Dyes Merged

A project On:
Reactive dyes
Presented By:
Alaa Ashraf Elawady
Supervised By:
Prof/Dr. Hassan Ali Ali Etman

Reactive Dye
Introduction:
A dye, whichh is capable of reacting chemically with a substrate
to form a covalent dye substrate linkage, is known as reactive
dye.
Here the dye contains a reactive group and this reactive group
makes covalent bond with the fiber polymer and act as an
integral part of fibre. This covalent bond is formed between the
dye molecules and the terminal -OH (hydroxyl) group of
cellulosic fibres on between the dye molecules and the terminal
-NH2 (amino) group of polyamide or wool fibres.
History of Reactive Dye:
On the occasion of 100 year's celebration of synthetic dye
manufacturing, two chemists of ICI company (UK) named
Stephen and Rattee tried to manufacture a new dyestuff. Thus
they succeed to invent a new dye in 1956, which was named
REACTIVE DYE. This was manufacture for dyeing cellulosic
fabrics. The first three reactive dyes were PROCION
YELLOWR, PROCION BRILLIANT RED 2B and PROCION
BLUE 3G. for this effort they were awarded gold medal of the
society of dyes and colorists for the year 1960.
General structure of reactive dyes:
The general structure of reactive dye Is: D-B-G-X. Here,
D= dye part or chromogen (color producing part) Dyes may be
direct, acid, disperse, premetallised dye etc .
B = bridging part.
Bridging part may be -NH- group or -NR-group.
G-reactive group bearing part .
X= reactive group
Reasons for so named:
Reactive dyes are so called because this is the only type of dye,
which has reactive group, and that reactive group reacts
chemically with fiber polymer molecules and form covalent
bond. This covalent bond is formed between the reactive group
and terminal -OH (Hydroxyl) group of cellulosic fiber or
between reactive group and terminal -NH2 (Amino) group of
polyamide and wool fiber polymer. The strength of this covalent
bond is more than ionic bond, hydrogen bond and Vander Waal's
force of attraction. Thus the reactive group becomes an integral
part of the fiber.
For this reasons the dyes are so called. They are also called fiber
reactive group
Fibers can be dyed with Reactive Dye:
By reactive dyes the following fibres can be dyed successfully:
1) Cotton, rayon, flax and other cellulosic fibres
)2Polyamide and wool fibres .
)3Silk and acetate fibres .
It covers a wide range of color spectrum and includes shades
varying from bright to heavy dark like,
• Violet
• Blue
• Green
• Red
• Black
• Yellow
• Etc
Chemical structure of reactive dyes
Trade names:
Some trade names of this dye are mentioned:
Popularity of reactive dye:
Reactive dyes are mostly used for dyeing cellulosic fibres. At

past cellulosic fibres were dyed with direct and vat dyes, but
after the introduction of reactive dyes there utility has become
limited. Reactive dyes are superior to direct dye in the following
aspects:
1) Ability to produce bright shade of wide range .
2) High leveling quality.
3) Good washing fastness.
4) Good light fastness.
And it is superior to vat dyes in the following aspects :
1) Simple dyeing method therefore one stage dyeing .
2) Low temperature dyeing(below 100°c)
3) Lower cost, I.e. cheaper.
Again its dyeing process is fast and gives brighter shades than
metalized azo dyes. For the above reasons reactive dyes are
more popular
Properties of reactive dye:
1) Reactive dyes are anionic dyes, which are used for dyeing
cellulose, protein and polyamide fibres .
2) Reactive dyes are found in powder, liquid and print paste
form.
3) During dyeing the reactive group of this dye forms
covalent bond with fibre polymer and becomes an integral
parts of the fibre.
4) Reactive dyes are soluble in water .
5) They have very good light fastness with rating about 6.
The dyes have very stable electron arrangement and can
protect the degrading effect of ultra-violet ray.
6) Textile materials dyed with reactive dyes have very good
wash fastness with rating Reactive dye gives brighter
shades and has moderate rubbing fastness.
7) Dyeing method of reactive dyes Is easy. It requires less
time and low temperature for dyeing .
8) Reactive dyes are comparatively cheap
9) Reactive dyes have good perspiration fastness with rating
4-5.
10) Reactive dyes have good perspiration fastness.
Classification of reactive dyes:
Reactive dyes may be classified in various ways as below :
1) On the basis of reactive group:
Two types-
1. Mono-functional dyes
2. Bi-functional dyes
1:Monofunctional dyes:
The mono-functional reactive systems of outstanding
importance contain only one possible reactive centre, such
as the halogeno substituent in the aminohalotriazine dyes,
or the activated terminal carbon atom in the vinylsulphone
system.
Two groups-
i. Halogenated heterocyclic compounds
II. Activated Vinyl compound Halogenated heterocyclic
compounds are – Three groups
Triazine group
a) Monochlorotriazine (MCT) dyes
b) Dichlorotriazine (DCT) dyes
c) Monofluorotriazine (MFT) dyes
ii. Pyrimidine derivatives

a) Trichloropyrimidine (TCP) dyes
b) Difluorochloropyrimidine (DFCP) dyes
d) Chloromethylpyrimidine (CMP) dyes
Quinaxoline dyes
II. Activated Vinyl compounds :
• Vinyl Sulphone (D-SO2-CH-CH2)
• Vinyl Sulphonamide (D-SO2-NH-CH2-CH2-)
• Vinyl Acrylamide (D-NH-CO-CH-CH2)
2:Bi-functional Dyes
The use of a reactive dye containing two reactive groups rather
than its analogue with only one reactive group per molecule
increases the fixation from a typical 60% to approximately 80%
on average in exhaust dyeing. In pad batch processes the
corresponding fixation efficiency levels are about 75% and 95%
respectively.
Bi-functional systems containing two different kinds of reactive
group are popular in exhaust dyeing and gaining ground,
especially on account of their relative insensitivity of fixation to
fluctuations in dyeing temperature.
On the basis of reactivity
a. Lower reactive dye: reactivity of these dyes is low. So highly
alkaline environment required for the fixation of these dyes with
substrate. Here ph is maintained 12-12.5 by using strong alkali
such as NaOH in dye bath.
b. Medium reactive dye: Reactivity of these dyes is medium.
Here ph is maintained 11-12 by using Na2CO3 in dye bath
c. Higher reactive dye: Reactivity of this dye is high. So fixation
of these dyes are easy and lower alkaline medium is kept. Here
ph Is maintained 10-11 by using NaHCO3 In dye bath.
On the basis of dyeing temperature:
A:Cold brand: These types of dyes contain reactive dye of high
reactivity. So dyeing can be done in lower temperature i.e. 32°-
60°c
For example: PROCION M, LIVAFIX E
b. Medium brand: These types of dyes contains reactive group
of moderate reactivity. So dyeing is done In higher temperature
than that of cold brand dyes I.c. 60°-70°c.
For example: Remazol, Livafix are medium brand dyes.
c. Hot brand:These types of dyes contain reactive groups of least
reactivity. Sohigh temperature is required for dyeing i.e. 72-93°c
is required for dyeing.
For example: PROCIONH, CIBACRON are hot brand dyes
Characteristics of reactive group of reactive dye:

The characteristics of reactive group of reactive dye are
mentioned below.
• Reactive groups do not contribute to the color of dye.
Chromogen group imparts it.
• The reactivity of vinyl sulphone group is less than that of
halogen group
• If no of reactive group increases, binding also increases
depending on dye structure
• Reactive dye absorb up to 90%.
• Molecular weight of reactive group 69-211gm/mole.
• If the molecular weight of reactive group increases,
reactivity also increases .
• Chlorine imparts medium reactivity, but it is cheap and
hydrolysis rate is medium
• Reactivity of Iodine is high but Its rate of hydrolysis is
also high.
• Reactivity of fluorine is the least and its rate hydrolysis is
also less.
• Reactivity of vinyl sulphone group increases with
increasing temperature and pH.
• Sulphone group has more solubility but it is not stable
• Generally low molecular weight dyes are of hot brand.
• Less affinity dyes are used for pad dyes
Criteria for a Suitable Dyestuff

• Cheap
• Non-toxic
• Better fastness
• Good levelness on the materials
• Better brightness
• High color strngth
• Compatible to other dyes and chemicals
Reaction manner of dye and cellulose:

The bonding behavior of dye and cellulose are mentioned
below:
1:Hydroxyl group of cotton polymer takes part in reaction with
reactive group of dye.
2:Reactive group of dye react preferably with the hydroxyl
group of cellulose than that of water.
3:The activation energy of dye-water reaction is 16.4-26.2 kcal
and that of dye cellulose Is 9,2-15.8 kcal. As the latter is less, so
that occur predominately.
4:Higher activation energy causes slower reaction.
5:The reaction with water and dye takes place in a smaller
extent
6:The strength of covalent bond formed between cellulose
polymer and reactive group is more than hydrogen bonding.
Vander wall's force of attraction and metal co-ordination bonds.
7:Extreme acidic and alkaline condition should be avoided,
otherwise hydrolysis will take place resulting bond breakage and
poor wash fastness.
Criteria for cellulose for attracting reactive dye :
The chemical structure of cellulose macromolecule is given
below:
In cellulose macromolecule glucose units are linked through

oxygen bridges formed between el position of one glucose and
c4 position of adjacent glucose unit. Each glucose unit contains
one primary hydroxyl group(at c6 position) and two secondary
hydroxylgroup=CHOH(at c2 and 3 positions). Again one end of
this glucose unit has an additional secondary hydroxyl group at
c4 position and the other end has an aldehyde or hemiacetal
group at el position. Now the following things are considered .
1:Primary hydroxyl group(-CH2OH) at c6 position is more
reactive then the secondary hydroxyl groups(-CHOH) at c2 and
c3 positions.
2:C2 hydroxyl group is supported to be more acedic than c3
hydroxyl group under suitable alkaline condition and hence is
more reactive.
3:The hemiacetal group at el position is the most active while
the additional hydroxyl group of c4 position is the least reactive.
4:The reaction between reactive group and cellulose takes place
predominantly with primary hydroxyl group to some extent.
5:Longer carbon chain lowers the rate of reaction.
6:Incase of monochloro triazinyl dyes, this reaction takes place
15 times more frequently with c6 hydroxyl group than with the
hydroxyl group at c2 or c3 position
7:Incase of dichloro triazinyl dyes, this reaction takes place 3-7
times more frequently with hydroxyl group at c2 position than
that with hydroxyl group at elor c3 position.
Assistants used for dyeing with reactive dyes:
The following assistants are used for dyeing in dye bath with
reactive dyes.
1:Salt:
As a salt NaCl Is widelyused. The salts do the following things
• Salts are used to increase the affinity of dye to fiber
• It decreases the hydrolysis rate of dyes
• It neutralizes the electro negativity of fiber surface when
immersed in solution.
• It puts extra energy to push the dye inside the fiber
polymer i.e. increase absorption of dye.
The amount of salt and used depends upon the shade to be
produced.
• For light shade- 10 gm/L salt Is used.
• For medium shade- 20 gm/L. salt is used.
• For dark shade - 30 gm/L salt Is used.
2:Alkali:
Alkali is used for the following purposes:
• Alkali is used to maintain proper pH in dye bath and thus
to create alkaline condition .
• Alkali is used as a dye fixing agent
• Without alkali no dyeing take place.
• The strength of alkali used depends on the reactivity of
dyes.
• As strong alkali caustic soda is used to create pH 12-12.5.
• As medium alkali soda ash(Na2CO3) is used to create pH
11-12 when dye is of medium reactivity.
• As weak alkali NaHCO3 is used to create pH 10-11 when
dye is highly reactive.
3:Urea:
Urea is used In continuous method of dyeing. It helps to get
required shade of dye. To get dark shade more urea is used and
to get light shade less amount of urea is used. Urea Is also used
in Printing to hold up the moisture.
4:Soaping:
By soaping, the extra color is removed from fibre surface. Thus
washing fastness I improved. Soaping increases the brightness
and stability of the dye.
Factors considered for selection of dyeing:
Dye selection depends upon the following factors
1:Selection of dyeing method: Dye selection depends on
dyeing method, which may be-
1:Batch wise/discontinuous method
2:Semi continuous method I.e.
• Pad-batch method
• Pad-jig method
• Pad-roll method
3:Continuous method i.e.
• Pad-steam method
• Pad-dry method
• Pad-thermofix method
This dyeing method selection depends on:
• Speed of dye diffusion on the fibre.
• Affinity of dye to fibre
• Reactivity to dye stuff.
2:Selection of dyeing method: Dye selection depends on
dyeing method, which may be-
a) Hot brand-Less reactive dye (temp 72-93)
b) Medium brand-Medium reactive dye.
c) Cold brand-Most reactive dye.
3:Economy of production
4:Availability of dyes
5:Storage of dyes
6:Fastness of dye ie, washes, light, rubbing fastness
7:Bond stability i.e. kind of bonding
8:Re-producibility
Dyeing mechanism of reactive dye:
Reactive dyes cover a full range of bright shades, with good to
excellent wash fastness, moderate to good light fastness. This
class of dye is mostly used to dye the cellulosic fibre; however,
suitable functional group of reactive dyes is used for wool and
man- made fibre. Dye containing a triazine or vinylesulphone
group could form covalent bond with -OH (hydroxyl) group of
cellulose fibresor -NH2 (amino group) of protein or woolfibres
at proper pH and at reasonable temperature between 30 – 100 ⁰
C. The overall dyeing mechanism consists of four stages :
i. Adsorption of dye on the fibresurface.
ii. Diffusion/exhaustion of dyes into the interior of fibre .
iii. Fixation of dyes in the fibre.
iv. Wash off.
1.Adsorption of dye on the fibresurface:
Adsorption is the movement of the dye from the solution phase
to the fibre phase, at the fibre surface. Basically, reactive dyes
and cellulose fibres show negative charge in dye bath and repel
each other reducing substantivity of dye. Once salt is added in
the dye bath to reduce the negative charge by decreasing its zeta
potential difference between the fibre phase and dye molecule
resulting better absorption. In fact, salt acts as exhaustion agent
and assist in movement of dye molecules from dye bath on to
the fibre surfaces. The rate of adsorption depends on dye
concentration, salt concentration and liquor ration of the dye
bath.
2:Diffusion/exhaustion of dyes Into the interior of fibre :
The diffusion of the dye means movement of dye molecules
from the fibre surface to the Interior of the fibre. Moreover, rate
of diffusion of the dye molecules depend on temperature of the
bath and size of dye molecules. Higher the temperature better Is
the rate of diffusion for dye molecules of lower size.
3:Fixation of dyes in the fibre:
Fixation of dye means the reaction of reactive group of dye with
terminal -OH or -NH2 group of fibre and thus forming strong
covalent bond with the fibre. This Is an Important phase, which
Is controlled by maintaining proper pH by adding alkali. The
good fastness to washing of dyeing with reactive dyes on the
cellulose fibres Is a result of the stable covalent bond formed
between the dye molecules and cellulose polymer. The covalent
bond can be formed between the dye and cellulose fibre by
substitution reaction with heterocyclic ring of triazine dyes
(scheme 1) and by addition reaction with vinyl sulphone
dyes .But both dyes are hydrolysed if they react with water
(Scheme 2)
4.Wash off:
After dyeing, a good wash must be applied to the material to
remove the unfixed and hydrolysed dyes as well as residual salt
and alkali from the material surface. This Is necessary for level
dyeing and good wash fastness. It is done by a series of hot
wash, cold wash and soaping wash.
How reactive dye link with fiber with covalent bond
1:Via trichlorotriazine
Example: synthesis of procian

Synthesis of procian
How procian link with cellulosic fibers

2:Via vinyl sulphone moiety
Example reactive black 5

Synthesis of reactive black 5
A Report on
Chemistry of azoic dyeing

Synthesis, properties, and Examples.
Under The Supervision of:
Prof. Dr. Hassan A. Etman

Prof. of Organic Synthesis, Chemistry Depart., Mansoura University, Egypt
Represented by:
Salma T. Alghalii
Pre-Masters Student in Organic Chemistry
2023-2024
Chemistry of Azoic Dyeing
Abstract
Azo dyes are the most used dyes and account for more than 60 % of total
dyes. Approximately 70 % of all the dyes used in industry are azo dyes.
These compounds are characterized by the functional group (-N=N-) uniting
two symmetrical and/or asymmetrical identical or non-azo alkyl or aryl
radicals.
Azo dyes are the most important synthetic colorants which have been widely
used in textile, printing, paper manufacturing, etc.
Azo dyes are called monoazo, disazo, trisazo, tetrakisazo, etc., and those
with three or more azo groups, polyazo dyes., Depending on the number of
azo groups.
Azo dyes can be classified either according to their characteristic chemical

groups or by their application in dye works, although a rigid assignment to
one of the two classification systems is possible, it’s not advisable because
of the overlapping.
Most azo dyes are synthesized by diazotization of an aromatic primary

amine, followed by coupling with one or more electron-rich nucleophiles
such as amino and hydroxy. There are other methods of synthesis of azo
dyes among these are reduction of nitroaromatic derivatives in alkaline
medium, reduction of nitroso compounds by AlLiH4, etc.
Some examples of Azo dyes include Congo Red dye, Butter Yellow dye,
and Disperse Red 60.
Unfortunately, some dyeing processes and the dye itself were found to be
toxic to both humans and the environment to a certain level. Some are even
considered carcinogenic.
1
Introduction
Azo dyes represent the largest production volume of dye chemistry today,
and their relative importance may even increase in the future. They play a
crucial role in the governance of the dye and printing market. These dyes are
synthesized from a simple method of diazotization and coupling. Different
routes and modifications are made to obtain the desired color properties,
yield, and particle size of the dye for improved dispersibility. [1]
Azo dyes are the type of dyes that is characterized by a chromophoric azo
group R−N=N−R′ that is responsible for the coloring, whose nitrogen atoms
are linked respectively to sp2-hybridized carbon atoms, meaning that R and
R′ are usually aryl and substituted aryl groups.
At least one of these carbon atoms belongs to an aromatic carbocycle

(usually a benzene or naphthalene derivative) or heterocycle (e.g.,
pyrazolone, thiazole), whereas the second carbon atom adjoining the azo
group may also be part of an enolizable aliphatic derivative (e.g., acetoacetic
acid). The most common types of azo dyes can thus be summarized as
follows: aryl−N=N−R, where R can be an aryl, heteroaryl, or
−CH=C(OH)−alkyl.
Due to the simple nature of the synthesis, usually in aqueous medium, and
the almost unlimited choice of starting products, an extremely wide variety
of azo dyes is possible. The number of combinations is further increased by
the fact that a dye molecule can contain several azo groups. This diversity of
inexpensively produced azo dyes permits a wide spectrum of shades and
fastness properties suitable for use on a variety of substrates. Naturally
occurring azo dyes are unknown (some containing azoxy groups are known),
but the azo dyes represent the most numerous and widely manufactured
synthetic dyes.
2
1. Nomenclature
Depending on the number of azo groups, the azo dyes are called monoazo,
disazo, trisazo, tetrakisazo, etc., dyes, and those with three or more azo
groups, polyazo dyes.
The structure of an azo dye can be described by means of a structural formula

(a), IUPAC nomenclature (b), or CI name (c).
1-Naphthol-8-
amino-3,6- H-Acid
disulfonic acid
(a) (b) (c)
All industrially important dyes are also classified according to the Colour
Index [2]. This catalog of dyes gives information about trade names,
coloristic properties, and, if published, the chemical constitution.
The Color Index (CI) is a widely used system for the identification and
classification of dyes and pigments, including azo dyes. The CI system
provides a standardized nomenclature for colorants, making it easier to
identify and communicate information about these substances. The
nomenclature includes a Color Index Generic Name (CIGN) and a Color
Index Constitution Number (CICN). Here are the key elements of the CI
nomenclature for azo dyes:
1. Color Index Generic Name (CIGN):
CIGN is a unique name assigned to each colorant, providing information

about its chemical structure and color. For azo dyes, the CIGN typically
includes terms related to the azo group and the specific color of the dye.
Example: C.I. Solvent Yellow 2 (CIGN) indicates a yellow azo dye soluble
in solvents.
3
2. Color Index Constitution Number (CICN):
CICN is a numerical identifier assigned to each colorant, facilitating

reference and identification. It provides a systematic code for organizing and
cataloging colorants.
Example: C.I. 11020 (CICN) is the Constitution Number for an azo dye,
which could have a specific color and chemical structure.
3. Use of Numerical Prefixes:
Numerical prefixes in the CIGN often denote the color shade or variation
within a particular color family. For example, C.I. Acid Orange 7 and C.I.
Acid Orange 10 may both be orange azo dyes, but the numerical difference
indicates distinctions in their chemical structures or color nuances.
4. Application Classifications:
In addition to the CIGN and CICN, the CI system may include information
about the application of the colorant. For example, C.I. Disperse Orange 1
indicates a disperse azo dye specifically used for coloring synthetic fibers.
Example:
C.I. Disperse Red 60 (CIGN) with CICN 60505 is an example of a red azo
dye with a specific identification number in the Color Index.
Fig. 1 C.I. Disperse Red 60.
4
2. Classification
Depending on other chemical features, Azo dyes fall into several categories
defined by the fibres for which they have affinity or by the methods by
which they are applied. These dyes can be classified either according to
chemical guidelines (characteristic chemical groups) or by color aspects
(application in dye works). A rigid assignment to one of the two
classification systems is possible, but not advisable because of overlapping.
There is therefore scarcely a chemical class of azo dyes that belongs to a
single color-class or vice versa. However, a compromise between the two
classification systems with emphasis on application in the dye works seems
to be the most appropriate. The importance of azo dyes is due to their mode
of application and to the fact that they represent a clearly defined concept.
The most easily applied azo dyes are those designated as direct: they are
anionic dyes that contain chemical substituents that make them soluble in
water, and they are absorbed from the solution by cotton (Cellulosic fiber).
The first direct dye was Congo red, discovered in 1884; it has been largely
replaced by dyes with superior resistance to acids and to fading.
Fig. 2.1 Congo red’s solid and aqueous form, and its chemical structure.
Acid azo dyes possess affinity for wool and silk and are applied by
essentially the same procedure used for the direct class. Tartrazine is a
yellow acid azo dye discovered in 1884 and still in common use.
5
Fig. 2.2 The yellow azoic Tartrazine dye’s color and chemical structure.
Other azo dyes contain chemical groups that bind metal ions. Among
numerous metal salts used with these dyes, chromium and copper are most
common; often, the metal ion also unites with the fibre, improving the
resistance of the dye to washing. The presence of the metal sometimes
produces important changes in shade. [5].
A few of the anthraquinone vat dyes and some disperse dyes are also azo
compounds; the latter are water-insoluble but can be suspended in water by
soap and in that state are adsorbed from the suspension by cellulose
acetate fibers.
3. Synthesis / Production
Most azo dyes are synthesized by diazotization of an aromatic primary

amine, followed by coupling with one or more electron-rich nucleophiles
such as amino and hydroxy [3]. There are other methods of synthesis of azo
dyes among these are [4, 6]: reduction of nitroaromatic derivatives in
alkaline medium, reduction of nitroso compounds by AlLiH4, oxidation of
primary amines by permanganate potassium or lead tetraacetate,
condensation of hydrazines and quinones, condensation of primary amines
with nitroso derivatives, etc.
The processes that are important in the production of azo dyes are classified
as follows: [5]
6
Processes involving synthesis of the azo group:
– Diazotization and coupling.
– Condensation of nitro compounds with amines.
– Reduction of nitro compounds
– Oxidation of amino compounds
Syntheses with compounds already containing the azo group:
– Exposure of concealed or protected amino groups.
– Acylation of aminoazo compounds.
– Alkylation and acylation of phenolic hydroxyl groups.
– Metal-complex formation.
Influence of Reaction Conditions on the synthesis process.
The success of azo dye synthesis is highly dependent on reaction conditions

such as pH and temperature. Optimal pH conditions and controlled
temperatures are crucial for achieving efficient reaction kinetics and desired
product yields. Additionally, catalysts and other reaction enhancements are
employed to improve overall reaction efficiency.
For instance, the diazotization reaction is usually carried out at very low
temperatures between 0-5 oC. This is due to the reason that at higher
temperature diazonium salt is unstable which resulted the formation of
unwanted side product. In contrast, diazonium salt undergoes crystallization
at very low temperature.
Choice of Starting Materials.
The chemical nature of starting materials, both aromatic amines and diazo
components, significantly influences the properties of the resulting azo dye.
7
A meticulous selection of these starting materials allows for tailoring the

dye's characteristics, such as color, solubility, and stability. Isomeric
considerations also play a role, affecting the synthesis pathway and the final
product.
Environmental Implications.
Green chemistry approaches are gaining prominence in azo dye synthesis.

Strategies such as using benign reaction conditions, reducing waste
generation, and incorporating sustainable practices contribute to minimizing
the environmental impact of these synthetic processes. Effective waste
management strategies are implemented to handle by-products and ensure a
sustainable synthesis pathway.
An efficient and green approach for the synthesis of azo dyes has been
developed via the Brønsted acidic ionic liquid (IL) promoted diazo coupling
reaction of naphthols with aryltriazenes. [7]
3.1. Diazotization
The synthesis of azo dyes relies heavily on the diazotization process, a

chemical transformation where aromatic amines are converted into
diazonium salts. This step is pivotal in determining the ultimate color,
stability, and application of the resulting azo dye.
Diazotization is defined as the reaction of primary aromatic amines with

nitrites, preferably with sodium nitrite, in a usually aqueous mineral acid
solution at around 0◦C, whereby the amine is converted into the
corresponding diazonium salt.
8
Fig. 3.1 Diazotization process of Aniline with NaNO2 and HCl.
The essential step in diazotization, as shown in (fig. 3.1.1), is the

electrophilic nitrosation of the amino group of the primary aromatic
amine. Formation of the diazonium ion, then follows via the
diazohydroxide.
Weakly basic amines require a higher acid concentration, since otherwise

diazoamino compounds Ar−N=N−HN−Ar may form. Very weakly basic
amines, i.e., amines with several negative (−I/−M) substituents (e.g., tetra
halogen anilines, di- and trinitroanilines, halogen nitroanilines) can only be
diazotized after being dissolved in concentrated sulfuric acid and
subsequently reacted with nitrosylsulfuric acid, HSO4NO. [5]
A further reason for using concentrated acids (concentrated sulfuric acid)

is the fact that diazonium salts of weakly basic amines are readily
hydrolysable in dilute acids.
Diazotization of aromatic diamines gives bisdiazonium compounds and

therefore is called bisdiazotization.
9
Diazotizing Methods. [5]
Considering the basicity and solubility of the amines being diazotized, the
following diazotization methods find industrial use:
a) Direct Diazotization. The primary aromatic amine is dissolved or

suspended in aqueous hydrochloric or sulfuric acid to which an aqueous,
concentrated sodium nitrite solution is added. An excess of 2.5 to 3
equivalents of acid per equivalent of amine is used. A temperature of 0 to 5
◦C is maintained by adding ice.
b) Indirect Diazotization. Amines with sulfonic or carboxylic acid groups

are often difficult to dissolve in diluted acid. Diazotization therefore takes
place as follows: the amine is dissolved in water or weak alkalis, and the
calculated amount of sodium nitrite solution is stirred into the ice-cooled
acid solution already in the vessel. The acid can also be added to the
amine–nitrite mixture already at hand.
c) Diazotization of Weakly Basic Amines. Weakly basic amines are

dissolved in concentrated sulfuric acid and diazotized with nitrosylsulfuric
acid, which is easily prepared from solid sodium nitrite and concentrated
sulfuric acid.
d) Diazotization in Organic Solvents. The water-insoluble or only

slightly soluble amine is dissolved in glacial acetic acid or other organic
solvents and, where necessary, diluted with water. After the addition of
acid, it is diazotized in the usual manner with sodium nitrite solution.
Temperature, pH, and the concentration of the diazotizing solution often
have a considerable effect on the progress of diazotization. Physical
properties (distribution, particle size) and the addition of emulsifiers and
dispersing agents influence the diazotization of slightly soluble amines.
10
3.2. Coupling
Also called diazo coupling, this process is a chemical reaction that occurs
between a diazonium salt and a coupling component.
Coupling components are aromatic systems with nucleophilic centers at the

aromatic nucleus, particularly phenols, naphthols, and amines or enolizable
compounds with reactive methylene groups. Phenols react as phenolates,
naphthols as napththolates, and amines as free bases. [5]
After formed, the diazonium salt undergoes a coupling reaction with another
aromatic compound, typically an aromatic amine called the coupling
component. The coupling component contains a nucleophilic group, often
an amino (NH2) group, which reacts with the diazonium salt.
Diazonium salt + Coupling component → Azo dye + By-products
Azo coupling can be summarized as follows: an aromatic amine is linked

to a nucleophilic partner RH (coupling component) in the presence of a
nitrosyl-eliminating compound XNO to form an aromatic azo
compound.
Of all the industrially important processes azo coupling, during which the
azo group is synthesized, is by far the most important. All other industrially
employed processes are advantageous only where azo coupling cannot be
utilized, for example, because of the unavailability of the starting
compounds.
11
Fig. 3.2 Coupling of diazonium salt with 2-naphthol to form scarlet red
dye.
4. Properties of Azo dyes
Generally, all azo dyes are water-soluble and can be synthetic or natural.
The wash-fastness properties of azoic dyed cellulosic materials are

excellent. All azoic combinations withstand soaping at the boil.
The dark shades exhibit excellent lightfastness. However, at medium and

pale shades lightfastness is good to fair. Like many other dyes, the
lightfastness of azoic dyed ground fabric or yarn is also affected by
environmental humidity.
Unlike Sulphur dyes most of the azoic dyes withstands chlorine bleaching.
Hence, azoic dyed fabrics may be bleached with chlorine containing
bleaching agents without any danger of color removal.
12
Most of the azoic combinations have excellent perspiration-fastness also.

Fastness to hydrogen peroxide is not adequate.
Many organic solvents affect most of the azoic dyed shades.
Rubbing-fastness problems are very common with azoic colors; this

problem can be overcome by adopting proper dyeing technology.
The dischargeability of azoic colors is good; hence they are suitable for
dyed ground shades intended for white or colored discharge prints.
The use of azoic colors has declined since the introduction of reactive dyes
and the subsequent developments of this dye class. Since many of the
components used in naphthol dyeing are known or suspected carcinogens,
they should not be used.
5. Examples of Azo dyes
Azo dyes are a large and diverse class of synthetic dyes, some of the most
significant examples of azo dyes will be noted in the following section.
Methyl Orange
Methyl orange is a commonly used azo dye in analytical chemistry with the
chemical formula C14H14N3O3C14H14N3O3. It is often used as a pH indicator.
In its pure form, it appears as a red solid, but it takes on a vibrant orange
color in acidic solutions and turns yellow in strongly basic solutions.
The color change is due to the fact that the protonation or deprotonation of
the nitrogen atoms in the molecule alters its electronic structure, affecting
its absorption of light and, consequently, its color.
13
Because it changes color at the pKa of a mid-strength acid, it is usually used

in titration of strong acids in weak bases that reach the equivalence point at
a pH of 3.1-4.4.[3] Unlike a universal indicator, methyl orange does not have
a full spectrum of color change, but it has a sharp end point.
Fig. 5.1 Structure and colors of Methyl Orange pH indicator.
Orange II (OII)
Also called acid orange 7, is an acid azo dye widely used in the dyeing of
textiles, food, and cosmetics. It is also used in histology for staining
purposes. It is produced by azo coupling of β-naphthol and diazonium
derivative of sulfanilic acid. [5]
Fig. 5.2 Structure of Orange II dye.
14
Tartrazine (Yellow 5)
Tartrazine is a bright yellow, water-soluble [15] azo dye, this vibrant yellow
hue makes it popular for various applications, particularly in the food
industry. It's commonly found in beverages, snacks, and desserts. It is also
known as E number E102, and Yellow 5. Tartrazine is produced from 4-
amino benzenesulfonic acid by diazotization and coupling with 4,5-dihydro-
5-oxo-1-(4-sulfophenyl)-1H-pyrazole-3-carboxylic acid or its esters. [17]
Tartrazine appears to cause the most allergic and intolerance reactions of all
the azo dyes.
Fig. 5.3 Structure of Tartrazine.
Congo Red
Congo red is the sodium salt of 3,3′-([1,1′-biphenyl]-4,4′-diyl) bis(4-

aminonaphthalene-1-sulfonic acid). Congo red is water-soluble, yielding a
red colloidal solution, though its solubility is greater in organic solvents. The
use of Congo red in the textile industry has long been abandoned, primarily
because of its carcinogenic properties,[5] but it is still used for histological
staining. It is prepared by azo coupling of the bis(diazonium) derivative of
benzidine with naphthionic acid. [16]
Fig. 5.4 Chemical structure of Congo Red dye.
15
Amaranth (Red 2)
Amaranth is an anionic azo dye. It can be applied to natural and synthetic

fibers, leather, paper, and phenol-formaldehyde resins. Amaranth is a red
azo dye that has been used in the food industry, although its use is restricted
or banned in some countries due to safety concerns.
Fig. 5.5 Chemical structure of Red 2 dye.
Solvent Yellow 14
Also known as Sudan I, this azo dye is soluble in organic solvents. It was
used in the coloring of various materials, including plastics and inks.
although the use of Sudan I in foods is now banned in many countries,
because it has been classified as category 3 carcinogens by the International
Agency for Research on Cancer. [18]
Fig. 5.6 Chemical structure of Solvent Yellow 14.
16
Direct Blue 1
Direct Blue 1 is an azo dye used in the textile industry for dyeing fabrics. It
belongs to the class of direct dyes. It used for dyeing textiles with high
contents of cellulose, i.e., cotton. It is prepared by the azo coupling of the
aminonaphthalene and diazotized derivative of o-dianisidine. [5]
Fig. 5.7 Chemical structure of Direct Blue 1.
Scarlet Red dye
Also known as Sudan IV, this diazo dye is a lysochrome (fat-soluble dye)
used for the staining of lipids, triglycerides, and lipoproteins on frozen
paraffin sections. fibers, such as wool and silk. Sudan IV is considered an
illegal dye, mainly because of its harmful effect over a long period of time,
as it is a carcinogen. [18]
Fig. 5.8 Chemical structure of Sudan IV.
17
6. Hazards and Diseases associated with Azo dyes
Commercial dyes are never 100% pure. Additional substances such as traces
of unreacted dye intermediates and catalysts (if used), dispersing agents,
diluents, etc., are always present to different extents. In addition to dyes any
dyeing operation will require chemicals/auxiliaries to facilitate the aqueous
dyeing under suitable dyeing conditions to meet the commercial
requirements. In the present section the effect of dyes and dyeing auxiliaries
on the environment are highlighted in terms of human toxicity and
environmental toxicity of dyes and dyeing auxiliaries. [5]
6.1 Azodyes as potential Carcinogens
Most toxic effects following oral ingestion are probably due to reduction of
the dyes by intestinal microflora, i.e., cleavage of azo bonds leading to
formation of aromatic amines, which may subsequently be N-hydroxylated
or N-acetylated. [19]
Fig. 6.1 Proposed mechanism of bacterial degradation of azo dyes. [20]
18
It is known that dye intermediates, dyes and even dyed fabrics can cause a
wide variety of health problems ranging from skin rashes, headaches, lack
of concentration, nausea, diarrhoea, fatigue, muscle and joint pain,
dizziness, difficulty in breathing, irregular heartbeat and seizures.
Symptoms in children include red cheeks and ears, dark circles under the
eyes, hyperactivity, and behavior or learning problems. In extreme cases
some dyes also show health hazards leading to cancer. [8] Human toxicity
of textile dyes can be considered in terms of acute toxicity and chronic or
genotoxicity. [9]
Azo dyes are by far the most important class of dye, accounting for over
50% of world annual production. Not surprisingly, the toxicity of azo dyes
has been studied extensively. As early as 1895 increased rates in bladder
cancer were observed in workers involved in dye manufacturing. Since that
time, many studies have been conducted showing the toxic potential of azo
dyes. A broader understanding of the problem can be found in the works of
Brown and DeVito as well as Levine. [10,11] The carcinogen may be the dye
itself, or it may be a metabolite of the dye. For water-insoluble, but solvent-
soluble dyes, such as solvent dyes and disperse dyes, the dye is normally the
carcinogen. For water-soluble dyes, it is a metabolite of the dye which is the
carcinogen. Water-soluble azo dyes based on H-acid, J-acid and Gamma-
acid represent a very important class of dyes for dyeing hydrophilic textiles
such as cotton and viscose rayon. Cotton is the world’s most widely
used textile fabric so the tonnages of these water-soluble dyes are extremely
large. The dyes are conveniently divided into two types:
1. Those which are capable of generating a carcinogenic metabolite.

2. Those that are not.
19
6.2 Environmental toxicity of Azodyes
The emission of effluents from textile industries has been a major concern
of the modern world, due to the great pollution that these effluents promote
on the water resources. Among the synthetic dyes released in effluents from
textile industries, azo dyes is one of the more detrimental classes because it
is highly persistent in the aquatic environment, due to its chemical
composition, involving aromatic rings, azoic linkages and amino groups.
The largest amount of azo dyes are consumed by the textile industry, but not
all the dye is adsorbed onto the fabric’s surface. Approximately 10%–15%
of the dye remains in the solution and generates colored wastewater which
may be released into water bodies without proper treatment [12]. Thus,
regular industrial effluents discharged with azo dye residuals become a
threat to human health and aquatic life as a few azo dyes or their
metabolites (e.g., arylamines) are highly toxic and carcinogenic [13].
Benzidine and its derivatives are one of the major azo reduction products of
the azo dyes, and these are potentially highly carcinogenic and toxic in
nature. Also, azo dyes are toxic to fishes, algae, aquatic plants, and other
organisms in the water.
Fig. 6.2 Azo reduction (cleavage) of Acid Black 077 dye to form the
Benzidine moiety. [21]
20
References
1. Shankarling G.S., Deshmukh P.P., Joglekar A.R. Process

intensification in azo dyes. J. Environ. Chem. Eng. 2017;5:3302–3308.
2. Society of Dyers and Colourists; American Association of Textile
Chemists and Colorists (1971) Colour Index (Prepared By) the
Society of Dyers and Colourists (And) the American Association of
Textile Chemists and Colorists 3rd ed., Bradford 1971, First Revision
1975, Second Revision 1982.
3. Gürses A., Açıkyıldız M., Güneş K., Gürses M.S. Dyes and
Pigments. Springer; 2016. Classification of dye and pigments; pp.
31–45.
4. Zhao R., Tan C., Xie Y., Gao C., Liu H., Jiang Y. One step synthesis of
azo compounds from nitroaromatics and anilines. Tetrahedron Lett.
2011;52:3805–3809.
5. Klaus Hunger, Peter Mischke, Wolfgang Rieper, Roderich Raue,
Klaus Kunde, Aloys Engel: "Azo Dyes" in Ullmann’s Encyclopedia of
Industrial Chemistry, 2005, Wiley-VCH, Weinheim.
6. Leriche G., Budin G., Brino L., Wagner A. Optimization of the
azobenzene scaffold for reductive cleavage by dithionite; development
of an azobenzene cleavable linker for proteomic applications. Eur. J.
Org. Chem. 2010;2010:4360–4364.
7. Manuel I. Velasco, Laura I. Rossi, et al. A green alternative to
synthetize azo compounds. (2011) Dyes and Pigments 90 259-264
8. Dyes and Chemical Sensitivities, http://organicclothing.blogs.com.
21
9. Gregory P (2007), Toxicology of textile dyes, in Environmental Aspects

of Textile Dyeing, Christie R M (Ed.), Woodhead Publishing Ltd,
Cambridge, UK, 44–73.
10. Brown M A and DeVito S C Predicting azo dye toxicity, Critical

Reviews in Environmental Science and Technology, 23 (3), (1993),
249–324.
11. Levine W G Metabolism of azo dyes: Implication for detoxication and

activation, Drug Metabolism Reviews, 23 (3–4), (1991), 253–309.
12. S. Benkhaya, O. Cherkaoui, M. Assouag, et al., Synthesis of a New

Asymmetric Composite Membrane with Bi-Component Collodion:
Application in the Ultra filtration of Baths of Reagent Dyes of Fabric
Rinsing/ Padding, J. Mater. Environ. Sci. 7 (12) (2016) 4556–4569.
13. L. Al-Rubaie, R.J. Mhessn, Synthesis and characterization of azo dye

para red and new derivatives, J. Chem. 9 (2012) 465–470.
14. I. D. Rattee, M. M. Breuer: The Physical Chemistry of Dye

Absorption, Academic Press, London – New York 1974.
15. Jain, Rajeev; Bhargava, et al. "Electrochemical Studies on a

Pharmaceutical Azo Dye: Tartrazine". Industrial & Engineering
Chemistry Research. 42 (2) (2003). 243–247.
16. Gerald Booth "Naphthalene Derivatives" in Ullmann's Encyclopedia

of Industrial Chemistry, 2005, Wiley-VCH, Weinheim.
17. König, J. Food colour additives of synthetic origin. Colour Additives

for Foods and Beverages (2014)., 35-60.
22
18. Refat NA, Ibrahim ZS, Moustafa GG, et al. "The induction of
cytochrome P450 1A1 by sudan dyes". J. Biochem. Mol. Toxicol.
(2008). 22 (2): 77–84.
19. Kaya, S.I., Cetinkaya, A., Ozkan, S.A., Latest advances on the
nanomaterials-based electrochemical analysis of azo toxic dyes Sunset
Yellow and Tartrazine in food samples. Food Chem. Toxicol. 156
(August) 2021. 112524
20. Pearce, C.I. et al. 2003. Dyes and Pigments 58: 179-196
21. Ahlström, L., Sparr Eskilsson, C., & Björklund, E. Determination

of banned azo dyes in consumer goods. TrAC Trends in Analytical
Chemistry (2004)., 24(1), 49-56.
23
An essay on
Cationic (basic) dyes
Under Supervision of: Prof.Dr/ Hassan Etman

Prepared by: Doha Khaled EL-Gendy
Abstract
• What dye is ?
Dye, substance used to impart colour to textiles, paper, leather, and other materials such that
the colouring is not readily altered by washing, heat, light, or other factors to which the material is
likely to be exposed. Dyes differ from pigments, which are finely ground solids dispersed in a liquid,
such as paint or ink, or blended with other materials. Most dyes are organic compounds (i.e., they
contain carbon), whereas pigments may be inorganic compounds (i.e., they do not contain carbon) or
organic compounds. Pigments generally give brighter colours than dyes. Colour has always fascinated
humankind, for both aesthetic and social reasons so Dyes play a pivotal role in various industries,
ranging from textile manufacturing to biological staining.
And Among the myriad classes of dyes, cationic (basic) dyes stand out for their
unique chemical properties and diverse applications. This essay aims to provide a detailed
exploration of cationic dyes, covering their chemical structure, properties, synthesis,
applications, and environmental implications.
Introduction
• What are cationic Dyes?

Basic dyes are also called cationic dyes because in solution the basic dye molecule
ionizes, causing its colored component to become an action of positively charged radical.
This a class of synthetic dyes, that act as bases and when made soluble in water, they form a
colored cationic salt, which can react with the anionic sites on the surface of the substrate.
The basic dyes produce bright shades with high tinctorial values, on textile materials. The
major application of basic dyes is in dyeing of acrylic fibers that have been copolymerised
in combination with anionic copolymers.
* Here are some common types of cationic dyes:
Basic Dyes: Basic dyes are the most common type of cationic dyes. They are synthetic
dyes that contain amino groups with a positive charge. These dyes are often used for
dyeing acrylic, silk, wool, and other protein-based fibers.
Methylene Blue: Methylene blue is a cationic dye that is commonly used in biological
staining procedures. It has applications in histology and microbiology for staining
tissues and cells.
Crystal Violet: Crystal violet is another cationic dye used in microbiology for staining
bacteria. It is often employed in the Gram staining method to differentiate between
Gram-positive and Gram-negative bacteria.
Safranin: Safranin is a cationic dye commonly used in histology and microbiology for
staining biological tissues and microorganisms. It is often used as a counterstain in
Gram staining.
Malachite Green: Malachite green is a cationic dye that is used in various

applications, including as a biological stain, a dye for silk and wool, and as an
antifungal agent in aquaculture.
Chemical structure and Properties of Cationic
Dyes
1. Chemical structure :
Cationic dyes are so named because of their positively charged chromophores.
These dyes consist of a chromophoric group that imparts color and a cationic functional
group responsible for the positive charge. The most common chromophores in cationic dyes
include triarylmethane, xanthene, and acridine derivatives. The cationic group is often a
quaternary ammonium salt, providing the positive charge necessary for effective dyeing.
The positive charge of cationic dyes allows them to interact strongly with negatively
charged substrates, such as cellulosic fibers in textiles or nucleic acids in biological tissues.
This electrostatic interaction is a key factor in their dyeing affinity and colorfastness.
2. properties :
1. Color Range: Cationic dyes are available in a variety of colors, and their shades can
be adjusted by modifying the chemical structure of the chromophore.
2. Solubility: Many cationic dyes are water-soluble, which makes them suitable for
dyeing processes that involve aqueous solutions.
3. Stability: Cationic dyes are generally stable, but their stability can vary depending
on the specific chemical structure and the environmental conditions.
4. Affinity to Substrates: Cationic dyes are particularly suitable for materials with a
negative charge, such as synthetic polymers like polyester and acrylic fibers.
5. Application Methods: Cationic dyes are often applied through methods like
padding, exhaustion, or printing, depending on the material being dyed.
3. Basic/Cationic dyes are available in:
 Powders
 Pearls
 Liquids
Synthesis of Cationic Dyes
The synthesis of cationic dyes is a complex process that involves the creation of both the
chromophoric and cationic components. One common method is the quaternization of amine-
containing chromophores with alkyl halides or other quaternizing agents. The reaction typically occurs
under carefully controlled conditions to ensure the desired product's purity and yield.
Another approach involves the synthesis of cationic dyes through condensation reactions. For example,
the reaction between diazonium salts and amines can lead to the formation of azo dyes with cationic
functionalities. The choice of synthetic route depends on the specific chromophore and cationic group
desired for the target application. . Recent advancements in green chemistry approaches for the
synthesis of cationic dyes, aiming for reduced environmental impact.
1. Selection of Chromophore:
Choose a suitable chromophore that will contribute to the color of the dye. Common chromophores
include azo, anthraquinone, and triarylmethane.
2. Introduction of Cationic Group:

Introduce a cationic group, typically amino groups (NH₂⁺), into the chromophore. This can be
achieved through various methods:
3. Diazotization/Coupling (for azo dyes):

 Start with an aromatic amine.
 Diazotize the amine with sodium nitrite and hydrochloric acid.
 Couple the resulting diazonium salt with another aromatic compound containing amino
groups.
4. Condensation (for anthraquinone dyes):

React anthraquinone with a diamine, forming a substituted anthraquinone.
5. Quaternization (for triarylmethane dyes):

 Start with a triarylmethane compound.
 React with a methylating agent (e.g., methyl iodide) to quaternize the amine groups.
6. Purification:
Purify the resulting dye compound through techniques like recrystallization or column
chromatography.
7. Characterization:
Analyze the structure of the synthesized cationic dye using spectroscopic techniques such as UV-Vis
spectroscopy, NMR, and mass spectrometry.
8. Application Testing:
Evaluate the dye's performance in intended applications, such as dyeing textiles or staining biological
samples.
Example Reaction for Quaternization:

As an example, consider the synthesis of a quaternary ammonium salt (cationic) from a triaryl methane
compound:
1. Starting Material:
 Triarylmethane compound with amine groups.
2. Quaternization:
 React with a methylating agent (e.g., methyl iodide) in the presence of a base.
 The amine groups are quaternized, forming a cationic dye.
3. Purification and Characterization:
 Purify the product and characterize its structure using analytical techniques.
Applications of Cationic Dyes
Cationic dyes find applications in diverse fields, showcasing their versatility. In

the textile industry, these dyes are widely used for dyeing natural fibers like cotton and
wool. The electrostatic attraction between the cationic dye and the anionic sites on the
fibers ensures efficient coloration and good wash fastness.
In the biological sciences, cationic dyes play a crucial role in staining cellular
components. For instance, methylene blue, a cationic dye, is commonly used to stain
cell nuclei in histology and cytology. The positive charge of the dye enables it to bind to
negatively charged cellular structures, aiding in microscopic examination and analysis.
Moreover, cationic dyes have applications in inkjet printing, where their affinity
for cellulose-containing paper ensures vivid and durable prints. They are also employed
in the formulation of markers and highlighters, providing vibrant and long-lasting colors
on various surfaces.
Here are some common applications of cationic basic dyes:
1. Textile Industry:
Cationic dyes are widely used in the textile industry for dyeing natural and synthetic fibers. They
are particularly effective for dyeing materials like wool, silk, and nylon, which have a negatively
charged surface.
2. Paper Industry:
Cationic dyes are employed in the paper industry for coloring paper and board. They are
especially useful for improving the wet fastness of the dyed paper.
3. Leather Industry:
In the leather industry, cationic dyes are utilized for dyeing leather and other related materials.
They provide good penetration and adhesion to the negatively charged surfaces of leather.
4. Ink and Printing:
Cationic dyes find applications in ink formulations, especially for printing on paper. They are also
used in inkjet printing, where they provide vibrant and fast-drying colors.
5. Biological Staining:
Cationic dyes are used in biological staining techniques. They can selectively stain various
biological specimens, such as cells and tissues, due to their affinity for certain cellular
components with negative charges.
6. Plastics:
Cationic dyes are applied in the coloration of plastics, providing a durable and vibrant coloration
to the polymer materials.
7. Cosmetics:
Some cationic dyes are used in cosmetics, including hair dyes and makeup products. They can
provide long-lasting and vibrant colors to cosmetic formulations.
8. Water Treatment:
Cationic dyes are employed in water treatment processes for detecting and quantifying anionic
impurities in water. The dyes can be used as indicators in chemical analyses.
9. Antistatic Agents:
Cationic dyes are sometimes used as antistatic agents in the textile industry. They can help reduce
static electricity in synthetic fabrics.
10. Research and Development:
Cationic dyes are used in laboratories for various research purposes, including studying molecular
interactions and surface charges.
Cationic Dyes in Textile Industry
Basic dyes are mainly applied the following type of fibers:
1. Acidic types of acrylic fibers
2. Mordanted cotton
3. Cationic dyeable polyester fiber (CDP)
Though basic dyes produce attractive, bright and highly intensive dyes, but their fastness to
light and wet on mordanted cotton, protein fibers and acrylic fibers are very low.
Dyeing of Acrylic Fiber with Basic Dyes:

Acrylic fiber has become the third largest produced synthetic fiber in the world. Regular acrylic
fibers are produced from polymers containing 85% or more of acrylonitrile monomer, the other
co-monomers usually being methacrylic acid, methylmethacrylate, vinyl acetate or a similar
vinyl compound which are incorporated in order to improve dyeability and mechanical p Initially,
acrylic fibers were very difficult to dye and, until acidic groups were incorporated as dye sites in the fiber,
basic dyestuffs were of little interest. Cationic dyes are currently used in large quantities to dye acrylics
(Orlon, Acrilan, Creslan, Zefran) and modified acrylics (Verel). Subsequent developments led to the
introduction of acidic groups to polyester and polyamide fibers, further increasing the market for these
dyes.
Basic dyes are water-soluble and dissociate into anions and coloured cations. The cations
have a strong affinity for the acidic group (sulfonic or carboxylic) and form salts. Because of
these strong bonds, wash fastness is usually outstanding, and lightfastness varies considerably,
depending on the dyestuff. Basic dyes are usually applied in a batch process with skein, stock,
and package dyeing more prevalent than piece dyeing on becks or jet dyeing machine.
The fundamental steps in the acrylic dying mechanism are: absorption of the basic dye at
the fiber surface, which occurs only when the glass transition point of the fiber is exceeded;
diffusion of the dye into the fiber as the fiber molecules acquire enough energy to move;
formation of the dye-fiber bond; and migration of dyestuff from the dyesite to another or from
within the fiber to the surface. The degree of migration varies considerably, depending on the
dyestuff, but generally basic dyes do not migrate well.
Leveling of basic dyestuffs can be a major problem which often can be traced partially to
differing exhaustion rates of individual dyestuffs which may occur in combination shades. Every
basic dyeable fiber has a saturation value, i.e., it has given number of acidic dye sites, which
limit the quantity of basic dyestuff that can be fixed. The dyestuff also has a saturation factor,
which is a measure of the relative molecular weight per caution in the dye. These two values
determine the depth of shade obtainable with a given dye and fiber.
Acrylic fibers also vary considerably in their rate of dyeing, depending on whether they
are of a dry-spun or a wet-spun fiber. Wet spun fibers dye at a higher rate than dry spun fibers.
Nonionic products must be present to act as antiprecipitants or to suspend particles

resulting from the reaction between the cationic dyes and anionic dyestuffs when blends of
basic-dyeable and disperse-dyeable polyester are dyed.
The most common anionic group attached to acrylic polymers is the sulphonate group, -
SO3-, closely followed by the carboxylate group, -CO2-. These are either introduced as a result of
co-polymerization, or as the residues of anionic polymerization inhibitors. It is this anionic
property which makes acrylics suitable for dyeing with cationic dyes, since there will be a strong
ionic interaction between dye and polymer (in effect, the opposite of the acid dye-protein fiber
interaction).
Dyeings on polyacrylic fibers can be obtained with high color depth, high brilliance and
good fastness. The cationic dyes can be applied in exhaust processes as well as in continuous
dyeing processes. In exhaust dyeing careful temperature control in the range of high dyestuff
absorption rate is required.
A scheme of a polyacrylic dyeing is shown in below Figure.
Figure: Functional scheme of a

dyeing with cationic dyes and retarders.
Retarders can be added to the dye bath to support levelling of a dying. Anionic retarders
reversibly form soluble adducts with the dye in solution. Thus, the effective concentration of
dyes in the concentration gradient for dye adsorption is lowered and the rate of dyestuff sorption
is reduced. The strength of the adduct must be lower than the binding strength between fiber and
dyestuff; otherwise, the dye will not be released completely from the adduct and substantially
lighter dyeing will be obtained. Condensation products between naphthalene sulphonic acid and
formaldehyde are chemical representatives for anionic retarders.
Cationic retarders (e.g. quaternary ammonium compounds) compete for the adsorption
and ionic binding at the fiber. Apparently, the number of binding sites on the fiber SF is reduced
and the rate of dyestuff sorption is lowered. The cationic retarder thus acts like a colourless dye,
which also blocks a share of the available binding sites. In the calculations of fiber saturation
through dyestuff binding, the concentration of cationic retarders used has to be considered. In
case the amount of retarder has been chosen to high, the dyestuff sorption will remain
incomplete.
As an example, the dyeing can be started at 60 °C and heated up to 70–75 °C rapidly. The
actual interval of temperature is dependent on the fiber type. Then very slow and well-
controlled increase in temperature with a gradient of 0.25–0.5 °C/min is required to maintain
rate of dyestuff sorption low. At the boil, the dyestuff absorption is completed within 20–60
min, based on concentration of dye and exact bath temperature.
Stripping of Basic Dyes:

Stripping and leveling: A degree of leveling can be achieved by treatment with a carefully
calculated amount of cationic retarder at the boil for 1–2 hours. For some stripping up to 10%
owg of a suitable anionic retarder can be used also at the boil. For severe or chemical stripping,
the goods should be treated with sodium hypochlorite acidified to pH ca. 6 with acetic acid for
30 minutes at the boil. Sodium nitrate (1 to 4 g/L) is required to passivate the stainless steel of
the vessel.
Advantages and limitations of cationic Dyes
 Advantages of Basic Dyes:

 High Tinctorial strength
 Moderate substantivity
 Relatively economical
 Wide shade range
 Includes some of the most brilliant synthetic dyes
 Shows good brightness
 Limitations of Basic Dyes:

 Poor shade stability
 High acid content
 colored backwaters
 Very poor lightfastness
 Preferential dyeing
Types / Classification of Basic Dyes
The conventional basic dyes belong to several chemical classes, such as:
1. Diphenylmethane or ketone imine (presence of C=NH group), e.g. C.I. Basic

Yellow 2.
2. Triphenylmethane, e.g. C.I. Basic Green 4, C.I. Basic Blue 5 and C.I. Basic
Violets 3 and 14.
3. Thiazine (nitrogen and sulphur atoms forming a ring with benzene carbons),
e.g. C.I. Basic Blue 9 and C.I. Basic Green 5.
4. Oxazine, similar to thiazine, but nitrogen and oxygen atoms form a ring with
benzene carbons, e.g. C.I. Basic Blue 12.
5. Azine, similar to thiazine, but two nitrogen atoms form a ring with benzene
carbons, e.g. C.I. Basic Red 5.
6. Xanthene (two benzene rings linked by oxygen atom and methylene bridge)
derivatives, e.g. C.I. Basic Violet 10.
7. Acridine (two benzene rings linked by a nitrogen atom and –CH= group)
derivatives, e.g. C.I. Basic Orange 14.
8. Azo groups, e.g. C.I. Basic Brown 1.

Examples
 C.I. Basic Yellow 2.
Molecular Formula:C17H22ClN3
Molecular Weight: 303.83
Manufacturing Methods :
(a) will be dissolved in 4-(4-Diethylamino)benzyl)-N,N-diethylbenzenamine, join

ammonium chloride and sodium chloride, ammonia gas flow in in 175 ℃ heat the
mixture, with hot water extraction dye, again salting-out (GP 53614)
(b) Bis(4-(dimethylamino)phenyl)methanone and ammonium chloride and zinc micro-

sphere in 15 (50-160 ℃ heating hot (GP 29060).
Properties and Applications:
yellow. Soluble in cold water, soluble in hot water for bright yellow, in boiling water
can decompose, soluble in ethanol for yellow. The strong sulfuric acid in colorless,
diluted into light yellow. Add hydrochloric acid in aqueous solution into deep yellow,
heated to a boiling is colorless; Sodium hydroxide solution to generate white
precipitation. Silk fiber in a bright yellow, in a red under tengsten lamp. Used for silk,
acrylic, tannin mordant dyeing cotton dyeing, also can be used for leather, paper, hemp
and glue directly printing and dyeing, the discharge printing. Can also be used in oil and
fat, paint color, also can be used in the preparation of color which used in.
 C.I. Basic Blue 5
Molecular Formula:C25H28Cl2N2
2-Chlorobenzaldehyde and N-cyclohexylnaphthalen-1-amine (2 Moore) condensation,

and then will product oxidation.
bright blue. Yellow-brown powder. Soluble in hot water and ethanol. The strong sulfuric
acid dyes for red light yellow, yellow green for diluted. The dye solution for green blue,
add sodium hydroxide solution into palm light yellow, precipitation. Acrylic fiber dyed
green light blue for colourful, tungsten filament in light and dark colored light slant
green. Used in acrylic, cotton, silk, vinegar fiber of dyeing and printing, also used for
paper, leather, grass products coloring and organic pigments and solvent dye.
 C.I. Basic Green 5.
Molecular Formula:C16H17ClN4O2S
commonly known as Methylene Green. (C.I.Basic Blue 9, C.I. 52015) in the first use
of hydrochloric acid sodium nitrite processing, and then treated with nitric acid and zinc
chloride double salt precipitation..
dark blue light green. Soluble in water for green light blue, slightly soluble in ethanol
for green light blue. In the dark for the strong sulfuric acid, diluted for green light blue.
Dye with sodium hydroxide solution for purple, have violet black precipitation.
 C.I. Basic Blue 12.
Molecular Formula:C20H20ClN3O
commonly known as the Nile Blue. 5-(Diethylamino)-2-
nitrosophenol and Naphthalen-1-amine hydrochloride reaction.
bright blue. Soluble in hot water and ethanol are blue. The strong sulfuric acid
for orange or brown, after dilute for blu-ray to green and then into a blue. The dye
solution to join sodium hydroxide have red precipitation (precipitation soluble in ethyl
ether for a green fluorescent light brown orange).
 C.I. Basic Red 5.
(a) N,N-dimethyl-4-nitrosobenzenamine and 4-Methylbenzene-1,3-
diamine reaction, form Toluylene Blue (Basic Dye, C.I. 49410), heating make
cyclization;
(b) oxidation N1,N1-dimethylbenzene-1,4-diamine , and 4-Methylbenzene-1,3-
diamine mixture.
red light purple and red. Soluble in water is cherry red, soluble in ethanol for
product red colour with red fluorescent light brown. The strong sulfuric acid
for green, blue for diluted, and then into a product red. The dye solution to join
strong sodium hydroxide solution have yellow brown precipitation.
 C.I. Basic Violet 10.
Molecular Formula:C28H31ClN2O3
commonly known as Rhodamine B.
(a) 3-(Diethylamino)phenol and Phthalic anhydride condensation, Alkali fusion, with
sulfuric acid, hydrochloric acid crystals;
(b) 2-(3,6-Dichloro-9H-xanthen-9-yl)benzoic acid and Diethylamine in the reaction
pressure (BP 960088).
red light purple. Light green flash small crystalline powder. Soluble in water and
alcohol with a strong fluorescence blue light red solution, easily soluble in soluble fiber
element, slightly soluble in acetone. The strong sulfuric acid for yellow brown, have
intense green fluorescent, diluted by the large red after change to blue light red, and
then into the orange; In nitric acid for golden brown. Dyes to join sodium hydroxide
solution for the roses red, after heating villous precipitation; Join the hydrochloric acid
have green subtle crystallization precipitation. In acetic acid dye in silk, used for
mordant dyeing cotton cloth dyeing tannins, mainly used for light wax paper, such as
typing paper, which is used in the manufacturing of the color, printing ink, painterly
dye, also can be used for hemp, straw and leather products color.
 C.I. Basic Orange 14.
4,4 ‘-Bis (N, N-dimethyl) aminodiphenylmethane obtained dinitration of 4,4′ – bis (N,
N-dimethyl) amino-2 ‘- dinitro-diphenyl methane reduction, and with an acid of heat,
so that the diamino compound is cyclized product is oxidized and then cyclized and
converted into zinc chloride double salt.
bright yellow orange. Soluble in water and ethanol for orange yellow,
with green fluorescent. The strong sulfuric acid in nearly colorless, a green fluorescent,
diluted for orange. The dye solution with strong sodium hydroxide solution have yellow
precipitation. And C.I. Solvent Orange 15 the same chemical structure (free base).
 C.I. Basic Brown 1.
Molecular Formula:C18H18N8
based in 2 Moore’s handling of the 3 moles Benzene-1,3-diamine hydrochloride (this
product in the above may double the azo dyes as the main component of the mixture,
and goods is usually two hydrochloric acid dyes by hydrates composition).
brown. Brown powder. Soluble in water for yellow brown, slightly soluble in ethanol
and soluble fiber element, insoluble in acetone, benzene, carbon tetrachloride, ceramic,
and solvent. The strong sulfuric acid for brown, diluted into a red light brown; In nitric
acid solution for orange, to yellow. The dye solution to join hydrochloric acid
discoloration; Add 10% sodium hydroxide solution have orange precipitation. Used for
wool, silk, leather, paper, bamboo, wood color, also used in the manufacture of color
and solvent dye deposit.
 References
1. Textile Dyes by N. N. Mahapatra
2. Handbook of Textile and Industrial Dyeing Volume 2: Applications of Dyes
Edited by M. Clark
3. Textile Dyes By Mansoor Iqbal
4. Physico-chemical Aspects of Textile Coloration by Stephen M. Burkinshaw
5. Textile Chemistry by Thomas Bechtold, Tung Pham
6. Textile Engineering-An Introduction Edited by Yasir Nawab
7. An Introduction to Textile Coloration: Principles and Practice By Roger H.

Wardman
8. https://www.worlddyevariety.com/
Name :- Raed Ahmed Mohamed
Course Name:- Applied Organic Chemistry 633
Under The Supervision Of
Professor Dr Hassan Ali Etman
Onium Dyes
A small range of dyes which owe their name to the fact
that they are either ammonium or sulphonium
compounds. They are water soluble cationic dyes and
hence must not be mixed with anionic dyes; otherwise
they will participate with each other. In the presence of
heat and alkali the solubilising groups split up to give a
very fast dye on the fibre. This is an example of a
temporarily solubilised dyestuff. Cotton is the most
important fibre for onium dyestuff. The ICI trademark is
‘Alcian’.
The history of onium dyes is closely tied to the

development of synthetic dyes and advancements in
organic chemistry. While the specific timeline may vary
based on the onium ion and dye type, here are key
points in the history of onium dyes:
1. **Late 19th Century:** The late 19th century saw the
rise of synthetic dye chemistry, with the discovery
of various classes of dyes. Early developments, such
as the synthesis of aniline dyes, paved the way for
the exploration of new dye structures.
2. **Early 20th Century:** Researchers began

investigating the synthesis of onium salts, including
ammonium, phosphonium, and up compounds.
These efforts laid the foundation for the later
development of onium dyes
3. **Mid-20th Century:** The mid-20th century

witnessed increased interest in the field of
fluorescence and the development of
fluorophosphores. This era saw the integration of
onium ions with fluorescent molecules to create
onium dyes with unique optical properties.
4. **Late 20th Century:** Onium dyes gained
prominence in various scientific disciplines,
including biology, materials science, and chemistry.
Researchers started exploring their applications in
fluorescence imaging, sensing, and other
technologies.
5. **Recent Decades:** Advances in organic synthesis

and materials science have led to the design of
tailored onium dyes with enhanced properties.
Their applications have expanded to include
cutting-edge technologies, such as advanced
imaging techniques and smart materials.
Throughout this history, the evolution of onium dyes

has been driven by the need for versatile and functional
dyes in research and technology. Today,
Onium dyes continue to play a crucial role in various
scientific and industrial applications due to their unique
properties and application
What is Onium Dye?

 Onium dye is a cationic dye, which is soluble by
sulphonium, phosphonium or oxonium substituent which
splits off during fixation to leave an insoluble colorant in
the fiber. They produce insoluble color on the fabric during
fixation process. Generally onium dyes are applied on
cotton and jute.
 They’re Salts and onium compounds of polymers are
named by placing the appropriate prefix or suffix together
with the name of the CRU in the enclosed part of the
polymer name, e.g. poly(sodium 1-carboxylatoethylene)
(57) and poly[(dimethyliminio)ethylene bromide]
Properties of Onium Dyes:

1. It is insoluble in water, but it can soluble by sulphonium,
phosphonium or oxoinum substituent.
2. It is a cationic dye.
3. It produce insoluble color on the fabric during fixation
process.
4. It’s structure like as pigment, but it’s application like as
dye.
5. Onium pigment always applied on acidic condition at
low temperature
Trade or Commercial Name of Onium Dyes:

1. Alcian Blue 8GS 300 [I.C.I – UK]
2. Alcian Blue 8GX 300 [I.C.I – UK]
3. Alcian Green 2GX [I.C.I – UK]
4. Alcian Green 3BX [I.Q.I – UK]
5. Alcian Yellow GXS [I.C.I -UK]
Classification of Dyeing Process of Onium

Dyes:
1. Phthalocymine.
2. Anthraquinone.
3. Azoic.
Application of Onium Dyes on Cotton Fabric (Continuous Dyeing

Process):
Onium dyes have diverse applications, including:
1. **Fluorescent Imaging:** Onium dyes are used in

fluorescence microscopy and imaging techniques to
label specific cellular structures, proteins, or other
biomolecules.
2. **Biological Staining:** They are employed in

biological and medical research for staining cells and
tissues, aiding in visualization and analysis under
microscopes.
3. **Polymer and Materials Science:** Onium dyes are

utilized in the study of polymers and materials, serving
as probes to monitor structural changes or to indicate
specific properties.
4. **Photodynamic Therapy (PDT):** Some onium dyes

have photosensitizing properties, making them
candidates for photodynamic therapy in treating certain
medical conditions, including cancer.
5. **Sensor Development:** Onium dyes can be

incorporated into sensors for detecting specific ions or
molecules, contributing to environmental monitoring or
medical diagnostics.
6 .**Electron Microscopy:** In electron microscopy,

onium dyes can be employed as contrast agents to
enhance the visibility of certain structures
7.**Photochromic Materials:** Certain onium

compounds exhibit photochromic behavior, meaning
they can change color
Dyeing Procedure:
Grey fabric
↓
Pretreatment of fabric
↓
Padding solution preparation [Acetic acid + water+dye+detergent]
↓
Padding [at 30-40oC]
↓
Steaming [at 120oC about 3-4 minute for fixation]
↓
Development [by using seven box open soaping system]
↓
Dyed fabric
Stripping Process of Onium Dye:
For stripping, the materials is treated at 50-60oC temperature in a solution

containing 2% sodium hydrosulphite (reducing agent) about 15 minute
Uses of Onium Dyes:

 It is generally use in cotton dyeing and printing process. It is also used
in jute dyeing process.
 Onium dye is a advance dye. We can also applied it on cotton fabric in

batch dyeing process by using winch dyeing machine.
Structure Of Onium Dyes

The structure of onium dyes varies depending on the specific onium ion incorporated.
Generally, an onium ion is a positively charged species derived from ammonium,
phosphonium, or sulfonium. Here are simplified representations of the structures for each:
1. **Ammonium-Based Onium Dye:**

- Structure: \[R_3N^+\]
- Example: \[CH_3)_3N^+\]
2. **Phosphonium-Based Onium Dye:**
- Structure: \[R_3P^+\]
- Example: \[CH_3)_3P^+\]
3. **Sulfonium-Based Onium Dye:**
- Structure: \[R_3S^+\]
- Example: \[CH_3)_3S^+\]
These structures represent the general onium ions. Onium dyes are typically derived from
these ions by attaching a chromophore or fluorophore group, which imparts the dye with its
specific optical properties. The choice of onium ion and the attached functional groups can be
tailored to achieve desired characteristics for different applications.
Properties of onium dyes

They can vary based on the specific onium ion and the attached chromophore or fluorophore. However,
some general properties include:
1. **Fluorescence:** Many onium dyes exhibit fluorescence, making them useful for
imaging and detection applications. The emission wavelength can be tuned based on
the attached fluorophore.
2. **Charge:** Onium dyes are positively charged due to the presence of onium ions
(ammonium, phosphonium, or sulfonium), which can influence their interactions with
negatively charged species in biological or material systems.
3. **Solubility:** Solubility can vary depending on the specific onium ion and the
attached functional groups. This property is crucial for the practical use of onium dyes
in different solvents or biological environments.
4. **Chemical Stability:** Onium dyes are designed to be chemically stable under

specific conditions to ensure their reliability and longevity in applications.
5. **Photostability:** Some onium dyes may exhibit photostability, resisting degradation

or fading when exposed to light over time. This is especially important in applications
involving prolonged imaging or exposure.
6. **Specificity:** Depending on the chosen onium ion and attached moieties, onium
dyes can be designed to target specific cellular structures, biomolecules, or chemical
environments, adding a level of molecular specificity to their applications
7. **Absorption Spectra:** The absorption spectra of onium dyes, influenced by the

chromophore or fluorophore, determine the wavelengths at which they can absorb
light.
8. **Photosensitivity:** Certain onium dyes may have photosensitive properties,
undergoing changes in their structure or properties upon exposure to light. This
feature is exploited in applications like photochromic materials.
These properties collectively contribute to the versatility of onium dyes across various
scientific and technological applications
While onium dyes offer various advantages, they also

have some potential disadvantages:
1. **Limited Penetration in Tissues:** The positive charge of onium dyes may hinder
their penetration into certain biological tissues or cells due to electrostatic
interactions, limiting their use in deep-tissue imaging.
2. **Cytotoxicity Concerns:** Some onium dyes may exhibit cytotoxic effects, impacting
cell viability. This aspect needs consideration, especially in live-cell imaging and other
biological applications.
3. **Sensitivity to Environmental Conditions:** The performance of onium dyes can be

sensitive to changes in environmental conditions such as pH and solvent polarity,
affecting their reliability in certain applications.
4. **Cost:** The synthesis of specialized onium dyes with unique properties can be
complex and may involve expensive reagents, impacting the overall cost of these dyes
compared to more common alternatives.
5. **Nonspecific Binding:** Depending on the specific design and application, onium

dyes may show nonspecific binding to cellular structures or molecules, leading to
potential background noise in imaging studies.
6. **Photobleaching:** Despite efforts to enhance photostability, onium dyes may still

be susceptible to photobleaching over extended periods of illumination, limiting their
utility in long-term imaging studies.
7. **Limited Commercial Availability:** Specialized onium dyes with unique properties

may not be readily available commercially, requiring researchers to synthesize them
in-house, which can be time-consuming.
8. **Phototoxicity in Photodynamic Therapy:** While onium dyes are used in

photodynamic therapy, the light exposure required for activation may cause
phototoxic effects on surrounding tissues.
It’s essential to consider these potential drawbacks and choose onium dyes carefully based on
the specific requirements of the intended application. Researchers often weigh the
advantages and disadvantages to select the most suitable dye for their experiments.
Dyes as Photoinitiators or
Photosensitizers of Polymerization
Reactions
A short but up-to-date review on the role of dyes in the
photoinitiation processes of polymerization reactions is
presented. Radical and cationic reactions are largely
encountered in the radiation curing and the imaging areas for
use in traditional coating applications as well as in high tech
sectors such as nanofabrication, computer-to-plate processing,
laser direct imaging, manufacture of optical elements, etc.
Recent promising developments concerned with the
introduction of the silyl radical chemistry that enhances the
polymerization efficiency are also discussed.
Radical and cationic photopolymerization reactions are largely

encountered in many industrial applications within the radiation
curing and imaging areas. Upon light exposure, a liquid
monomer/oligomer matrix leads to either a coating or an image
through a chain reaction. As known, this is still extensively growing in
traditional industrial sectors related to UV Curing (flooring, packaging,
release coatings, powder coatings, wood and medium density fiber
(MDF) panels, automotive items, optical fibers, pipe lining, adhesives,
graphic arts, dentistry and
medicine, etc.). On the other hand, the imaging area appears today as
a fantastic field of development for new applications in high-tech
sectors: microelectronics, Laser Direct Imaging (LDI) technology,
Computer-To-Plate processing, 3D modeling, holographic recording
and information storage, manufacture of optical elements, design of
structured materials on the nanoscale size.
One key factor in photopolymerization reactions is concerned with the

photoinitiating systems (PIS), which allow the starting resin
formulation to absorb the light and to create reactive species that are
further able to initiate the polymerization. A PIS for free radical
photopolymerization (FRP) can consist in (i) a photoinitiator (PI; e.g.,
suitable cleavable ketones), (ii) a photoinitiator (e.g., a ketone) and a
co-initiator (coI; e.g., an amine, a thiol, a silane, etc.), (iii) a
photosensitizer (PS) and a PI or (iv) more complex associations such as
PS/PI/coI/RS (where RS is a molecule that improves the efficiency
through additional by-side reactions). Basically, the created radicals
initiate the polymerization (see e.g., (1a)). In cationic
photopolymerization (CP), the PIS is based on a PI (e.g., an onium salt)
or a PS/PI couple (1b) (C+ in reaction 1b represents the initiating
cation); in free radical promoted cationic photopolymerization FRPCP
(1c), a radical is produced (e.g., from a usual radical photoinitiator)
and then oxidized by an onium salt to form a cation suitable for the
opening of the cationic monomer ring. Little is known in anionic
photopolymerization.
PIS + hν → → → R● → Polymer (1a)
PIS + hν → → → C+ → Polymer (1b)
PIS + hν → → → R● → C+ → Polymer (1c)
Most PIs for FRP, CP and FRPCP absorb in the UV wavelength range
and directly lead, e.g., (2a), upon excitation, to the desired initiating
species (R● or C+). Applications requiring the use of visible lights
delivered by lamps (Hg lamp, Xe lamp, Hg-Xe lamp, doped Hg lamp,
etc.), LED, sun or lasers (CW lasers, pulsed lasers, laser diodes, etc.)
have largely induced strong efforts to (i) search for colored molecules
(this has been done for a long time and, among them, dyes represent
an interesting class of PI), (ii) design new PIs with red-shifted
absorption (which requires much expensive or time-consuming work)
and (iii) find well selected PS structures which have to absorb the light
and transfer their excitation to a suitable and conventional PI (e.g., 2b,
2c in FRP). These PSs obviously include dyes, but also a lot of other
colored molecules that are not, strictly speaking a dye (“a substance
used to color materials”); the term “dye” is, however, very often used
in a broader sense: in the following, it will refer to any visible light
photosensitive PI or PS.
PI + hν (UV light) → PI* → R● (2a)

PS + hν (visible light) → PS* → PI* → R● (2b)
PS + hν (visible light) → PS* → PS●- + PI●+ → R′●
(2c)
Here we will give a short but general presentation of dye

photosensitized polymerization reactions together with some
examples of applications.
Overview of the Available Dye Based

Radical Photoinitiators
Dye based PIs can be operative in different photoinitiating systems;
review papers and original research papers describe the currently
available systems as well as the mechanisms involved in the excited
states.
(i) one-component (or Type I) systems where radicals are readily

produced through a homolytic bond cleavage (3a),
PI + hν → R1● + R2● (3a)
(ii) two-component (Type II) systems that involve energy (2b) or
electron (2c) transfer in PS/PI combination or electron/proton or
direct hydrogen transfer in PI/coI where coI is a hydrogen donating
compound AH (3b),
PI + AH + hν → PIH● + A● → Polymer (3b)
(iii) multi-component photoinitiating systems containing three or
more compounds and exhibiting a much more complex mechanism,
e.g. in (3b-c) in the case of a PI/AH/B system (where it very often
appears that A● is the initiating radical whereas PIH● is a terminating
radical of the growing polymer chain; B is an additive being able to
scavenge the detrimental radicals).
PIH● + B → PIH+ + A●− → PI + H+ + A●− (3c)
1-One-component photoinitiating systems

Examples of one-component photoinitiating systems include:
(i) bisacylphosphine oxides (absorbing up to 480 nm and working
through a C-P cleavage).
(ii) organoborates (composed of a borate anion and a visible light
absorbing counter cation which allows to tune the absorption).
(iii) organometallic compounds (the most widely used derivatives are

the titanocenes which exhibit an excellent absorption around 500
nm).
(iv) metal carbonyl derivatives centered on Mn, Fe, Mo, Cr, Os, Re, Ru.
(v) metal salts and metallic salt complexes based on Co, Fe, Ni, Cu, Cr.
(vi) light absorbing amines.
(vii) difunctional compounds containing two cleavable moieties (which

lead to a light absorption better than that of the parent
monofunctional compound).
(viii) mono-and di-benzoyl germanes (that absorb around 400 nm).
(ix) bis germyl ketones (the absorption at the Ar laser line is quite
good).
(x) group 14 di-metal compounds.

(xi) new transition metal carbonyls.
2-Two-component photoinitiating systems
Many colored molecules involved in two-component photoinitiating

systems have been reported (most of them work through
electron/proton transfer with an amine):
(i) carefully selected α-diketones (which allow an excellent efficiency
in the near UV-visible region for the photopolymerization of clear
thick molded objects or coatings under visible light and sun exposure).
(ii) substituted benzophenone, camphorquinone or thioxanthone and

related amino (or thiol) derivatives and thioxanthone-fluorenes.
(iii) various ketone families such as anthraquinone, fluorenone,

flavone, anthrone, quinone, naphtacenequinone, quinoline,
benzodioxinone.
(iv) xanthenic dyes…, thiazines (methylene blue…), acridines, N-

methylacridone, phenosafranines, thiopyronines, riboflavines,
phenoxazines, pyrromethenes, polymethines, fluorones, squarylium,
julolidine dyes, phenoxazones, quinolinones, phtalocyanines,
benzopyranones, rhodanines, crystal violet/benzofuranone
derivatives, dimethyl aminostyryl benzothiazolinium iodides. The
mechanisms involved in the different systems and the various
encountered or promising applications have been reported.
(v) bis-arylimidazole derivatives (for example, Cl-bis-imidazole

derivatives HABI are largely used in the laser imaging area; because of
the low bond energy between the two imidazoyl moieties, a very fast
cleavage occurs leading to two lophyl radicals which then react with
electron/hydrogen donors such as mercaptans or N-phenyl glycine).
(vi) coumarin and ketocoumarin derivatives.

(vii) pyrylium and thiopyrylium salts (that can decompose peresters;
addition of a diphenyl iodonium salt or a bromo compound such as
CBr4 to a thiopyrylium salt leads to the generation of radicals).
(viii) ketone/ketone based systems (a typical energy transfer is

encountered between a thioxanthone derivative and a morpholino
ketone derivative or between a mercaptothioxanthone and a bis
phosphineoxide derivative).
(ix) ketone/cleavable compounds (hydroxamic esters, thiohydroxamic

esters, etc.).
(x) organometallic compound/ketone based systems (e.g., in
ruthenium tris bipyridine/morpholinoketone).
(xi) photosensitizer linked photoinitiator or co-initiator based systems

(e.g., a dye linked to a triazine moiety or eosin linked to a O-
acyloxime).
(xii) miscellaneous systems (xanthene/thiol, carbazole/triazine,

photosensitizer/ketone, etc.).
3- Multi-component photoinitiating systems
Multi-component photoinitiating systems involve complex
combinations of well selected compounds and are very often used in
the design of high speed photopolymers. The mechanisms are rather
complex but a clever mixture of suitable compounds allows an
improvement in the performance of the PISs and their ability to work
in well defined conditions required by the applications.
(i) ketone (e.g., isopropylthioxanthone)/amine/bromo compound or

onium salt.
(ii) ketocoumarin/amine/onium salt.

(iii) eosin/amine/onium salt, bromo compound, THF or keto-oxime
derivative PDO; methylene blue/amine/onium salt.
(iv) dye (e.g., merocyanine, safranine)/amine/bromo compound or

onium salt.
(v) thioxanthene dye/amine/onium salt or bromo compound.
(vi) acridinium cation/dihydropyridine/onium salt.

(vii) ketone/amine/maleimide or maleic anhydride.
(viii) ketone (isopropylthioxanthone/benzophenone

sulfonylketone/amine).
(ix) dye/amine/triazine derivatives.
(x) dye (crystal violet, phenosafranine, methylene blue,

thiopyronine/amine/ketone) (acetophenone, benzophenone,
thioxanthone, 4,4’-bis-dimethylamino benzophenone).
(xi) (keto)coumarin/amine/ferrocenium salt.

(xii) coumarin, ketocoumarin or titanocene derivative/ bis-aryl
imidazole Cl-HABI/mercaptobenzoxazole.
(xiii) dye (methylene blue)/amine/cobalt salts.
(xiv) dye (Rose Bengal, eosin)/ferrocenium salt/amine/hydroperoxide.
(xv) coumarin or diethyl amino benzophenone/amine/bis-aryl

imidazole/onium salt, pyrromethene/amine/triazine, miscellaneous
systems (based on ruthenium derivatives, gold containing molecule,
etc.
Overview of the Available Dye Based

Cationic Photoinitiating Systems
1-Colored onium salts

Useful cationic photoinitiators generally belong to three main classes:
diazonium salts, onium salts and organometallic complexes. Iodonium
and sulfonium salts absorb in the near UV and represent the main and
largely used class of cationic photoinitiators in the radiation curing
area. Adequate structural modifications give rise to a red-shifted and
enhanced absorption. Alkyl phenyl (9-phenyl thioanthracenyl)-10-
sulfonium salts and arylbenzylmethylsulfonium derivatives are
sensitive up to 500 nm. The decomposition process is now well
established and involves either a heterolytic or homolytic cleavage of
the C-I or C-S bond that forms e.g., a singlet phenyliodide/phenyl
cation pair or a phenyliodinium cation/phenyl radical, respectively.
Then, in-cage or/and an out-of-cage process arises. In any case, a
strong acid is generated and initiates the cationic polymerization (CP).
The highly sensitive and potentially low cost acylsulfonium salts
containing aromatic moieties allows the possibility of a long
wavelength excitation. N-alkoxy pyridinium salts also allow efficient
photosensitized cationic polymerization reactions.
2-Organometallic complexes
Organometallic complexes are sensitive in the visible part of the

spectrum, e.g., dicarbonyl chelates of IIIa, IVa, Va group elements,
ferrocene, zirconocene, organoaluminium complexes, tri-carbonyl iron
complexes, various inorganic complexes and organo-metallic
transition-metal compounds (metal carbonyl, alkylcyclopentadienyl
iron dicarbonyl, etc.), non-transition metal complexes (diketone
chelates of boron or silicium), rhodium catalyst derivatives,
dicobaltoctacarbonyl derivatives, triaryl (1-pyrenyl) bismuthonium
salts, cyclopentadienyl arene complexes, bis arene ferrocenium salt
derivatives (η6−cumene).
3-Dye/onium salt systems

The possible sensitized decomposition of onium salts On+ in the
presence of a photosensitizer (PS) was shown to occur through (i)
energy transfer (only with a ketone exhibiting a high lying triplet state)
or (ii) electron transfer with hydrocarbons (anthracene, pyrene,
perylene, carbazole, etc.), phenothiazine derivatives, dyes, ketones
(camphorquinone, benzil, anthraquinone, thioxanthone, etc.).
Anthracene bound sulfonium salts appeared as highly efficient
photoinitiators. The electron transfer reactions occur both in the
singlet and the triplet states of dyes such as xanthene, thioxanthene
and merocyanine, acridone, flavin and acridine derivatives,
tetrabenzoporphyrine, curcumin. Aromatic amines, manganese
decacarbonyl/alkyl halides, and dithienothiophene act as good
electron donors. New recent and promising developments have been
published.
Photosensitization is also feasible through an electron transfer

between a radical that can be generated from a usual radical
photoinitiator and the iodonium salt: this way is referred to free
radical promoted cationic photopolymerization (FRPCP). This
mechanism was originally observed with radicals formed through a
fast α-cleavage process from the short-lived triplet state of benzoin
ethers, dialkoxyacetophenones or benzoyl phosphine oxides; the ketyl
radicals produced e.g., in benzophenone/dimethylaniline are also
efficient. This reaction was also achieved with other salts (allylic
sulfonium salts, phosphonium salts, polysilanes/pyridinium salts,
polysilanes/pyridinium salts/benzaldehyde, etc.).
Another photosensitizing method is concerned with the

addition/fragmentation reaction involving a radical source and a
cationic salt containing an allylic group (these two species can also be
linked in a single molecule): a careful selection of the radical source
allows the absorption to be tuned to higher wavelengths.
4- Photoacids PAG
Photoacid generators (PAG) are encountered in the imaging area. They
can involve ionic systems (such as the onium salts) or non-ionic
systems. The non-ionic photoacids generate sulfinic acid, sulfonic acid,
carboxylic acid, phosphoric acid. They involve several kinds of
structures e.g., (i) iminosulfonates (the sulfonic acid is
photochemically produced in a first step; in a second step, a thermal
process favors the crosslinking reactions of e.g., epoxides, a negative
image will thus be obtained under solvent development); (ii) esters of
sulfonic or carboxilic acids; (iii) arene sulfonate derivatives; (iv)
hydroxyimide sulfonates; (v) oxime sulfonates; (vi) sulfone derivatives;
(vii) triaryl phosphate derivatives; (viii) naphtalimides; their
photosensitized decomposition under visible lights is, however,
usually rather difficult. The photochemistry, photophysics,
photopolymerization activity and photoimaging applications of
naphthalimides in the presence of photosensitizers has been largely
explored.
Most of these systems are used in organic high speed photopolymers

that can be excited by visible laser lights. Sensitizer/PAG systems
containing dispersed photopolymers have been developed for micron-
scale photolithography. A chemistry based on a photochemical event
that requires one photon to produce one acid has obviously a limited
efficiency in photoresist applications. The chemical amplification
process where one photon is able to indirectly induce several
reactions was evidenced in negative photoresists but also in positive
photoresists (e.g., depolymerization of polyphthaldehyde or
deprotection of the acidic function of a polymer that will become
soluble in an alkali; a post baking treatment favors the acid diffusion
and the chemical amplification; this acid catalyzed reaction produces a
positive relief image).
‫االسم ‪:‬نورهان عبد الغنى السيد اسماعيل طه‬
‫المقرر‪Dyes :‬‬
‫تحت اشراف االستاذ الدكتور‪ :‬حسن عتمان‬

Sulfur dyes:
Sulphur dyes are complex heterocyclic molecules or mixtures formed by melting or

boiling organic compounds containing amino or nitro groups with Na-polysulphide and
Sulphur. Sulphur dyes are so called as they all contain Sulphur linkage within their
molecules. The sulphur dyes are named so because of the presence of sulphur atoms in
their molecules. Like direct dyes, sulphur dyes are also quite cheap for dyeing cellulosic
textiles with limited colour fastness properties. Different types of sulphur dyes include:
1. CI sulphur dyes
2. CI leuco sulphur dyes
3. CI solublized sulphur dyes
4. CI condensed sulphur dyes
Properties of Sulphur Dyes:

The main properties and characteristics features of Sulphur dyes are mentioned below:-
1. Sulphur dyes have Sulphur linkage within their molecules.

2. Sulphur dyes are highly colouerd water insoluble dyes. Some dyes are partially
soluble in water.
3. They have no direct affinity towards cellulosic fibres. To make them substantive
they are to be converted in to soluble lucoform by treating them with reducing
agents (Like dilute Na2S solution)
4. Sulphur dyes have good light fastness with rating about 4. This light fastness may be
improved by an after treatment with metallic salt.
5. These dyes have excellent wash fastness with rating about 3-4. This good wash
fastness is due to its larger molecular size & insolubility in water.
6. They are not applicable to wool due to strong alkaline condition.
7. They are exclusively amorphous, few of them show crystallinity.
8. Important for producing a wide range of shades on a varity of cotton and rayon.
9. Sulphur dyes are suitable for heavy & durable shades
10. Available in powder and soluble form
11. Sulphur dyes are cheap & easy to manufacture.
12. Heat and chemical resistance of Sulphur dyes are moderate to good. They have poor
fastness to chlorine and are not applied to goods which are bleached with
hypochlorite.
Features of Sulphur Dye
1. Amorphous Colloidal materials.

2. High molecular weight with various composition
3. Complex molecular structure –heterocyclic molecules containing Sulphur linkage.
4. Decomposed by acids, with the liberation of H2S.
5. Characterized by thiozine ring, containing Sulphur atom.
Sulphur dyes are highly coloured, water insoluble compounds and have to be converted in
to water soluble substantive forms (leucoforms) before application to the textile materials.
This conversion is carried out by a treatment with a reducing agent like dilute aqueous
Na2S. Since this leucoform of Sulphur dye is substantive to cellulosic materials. They are
absorbed on the fiber surface. Then they are reconverted original water insoluble form of
dye by oxidation. This oxidation is carried out by “airing” (exposure to air) or by using an
oxidizing agent like Na-dichromate (Na2Cr2O7). The reducing agents converts the “S” in
dye in to –SH group and the Sulphur linkages. Then inside the material the thiols containing
–SH groups are oxidized & thus reconverted to original form of dye.
Sulphur gives best result (Bright Tone) when they are used to produce black, Black and
brown shades but red shades cannot be obtained by Sulphur dyes.
Chemical Nature of Sulphur Dyes

The manufacturing method of Sulphur dyes may be shown as below:-
…………………………………………………Thionation Sulphorization
Aromatic Hydro Carbon —————————————————————-→ Sulphur
Dye
Containing Hydroxy amino or nitro group
This reaction is carried out in a closed vessel in the presence or absence of solvents. For
this (Thionisation/Sulphorisation) purpose Sulphur or Na- polysulphide is used. The
features of the products of thionation are controlled by organic compounds, conditions of
reaction (time, temp etc). Condition of separating dyes from reaction mixture etc.
After the reaction is over the dye is precipitated acidification or oxidation or

both.Generally Sulphur dyes are marketed in forms of powder pastes or liquid solutions.
The dyes are amorphous colloidal materials of high molecular weight and variable
composition. Their exact chemical composition is not yet established. However they are
complex in structure. Some amorphous present in Sulphur dyes are as
These in turn are subdivided in to 6 sub classes, depending on the method of application.
Namely–
1. Method i
2. Method ii
3. Method iii
4. Method iv
5. Method v
6. Method vi
Method-i:
Conventional Sulphur dyes (i.e. water insoluble Sulphur dyes) are dyed in method i. They
have slight affinity to textile fibers of cellulosic origin. Method is as below:-
Dye pasted with cold water,
Add required amount of Na-sulphide
Dissolved by adding boiling water
Boiled for 100 minutes to complete desolation
Taken in dye bath containing soda ash
Material immersed in dye bath
Raising temperature & adding Glauber’s salt for exhaustion.
Method-ii:
These dyes are also insoluble in water and are called specialized conventional Sulphur
dyes. Its application method is as below:-
Pasting of dye with 25-30 times soft water and reducing agent
Dissolved dye added to dye bath (mixture of soda ash & rongalite C) and boiled for
sometime
Material put in dye bath and dyeing carried out for 20 minutes
For exhaustion common salt or Glauber salt is added and dyeing continued for 30-40
minutes.
Method-iii:
This method is used for leuco Sulphur dyes; they have distinct affinity for cellulosic
fibres. These Sulphur dyes are dyed as in the case of method –I except that little or no
Na-sulphide is required for their volatilization.
Method-iv:
These dyes are soluble in water having substantivity to cellulosic fibres. They are mixture
of Sulphur dyes and Na- sulphide. The dyeing method is as below:
Dye pasted with little amount water at 300C
Diluted with 10-20 times water at same temperature
Dissolved dye is added to required quantity of water in dye vessel
Common or Glauber Salt and soda ash is added in dye bath
Material is put in dye bath and kept at 400-600C for 25-30 minutes.
Method-v:
These dyes are also soluble in water & are substantive to cellulosic fibres. They are dry
mixture of the dyes and Rongallite-C. The dyeing method is as below:
Dye pasted with water & dissolved by boiling at 10-20 times soft water
Solution is added to dye bath containing required amount of water
Temperature is raised to 900C
Material is entered in to the dye bath after 20 minutes
Glauber salt is added & dyeing continued for some times.
Method-vi:
These dyes are solubilized Sulphur dyes. They have no affinity towards cellulosic fibres.
Chemically they are thio-sulphuric acid derivatives and are applied either by Na-sulphite
method or by Na-Hydrosulphite method.
Reducing Steps of Sulphur Dyes
reducing step is the most important in the application of Sulphur dyes. Unless the dyes
are converted in to the completely soluble form, the full colour value cannot be achieved.
The solubility of reduced Sulphur dyes varies appreciably from dye to dyes. For example
yellow Sulphur dyes are the last soluble dyes (i.e. most insoluble dyes)
The reducing agents are used for Sulphur dyes are:-
1. Na-Sulphide.
2. Na-Hydro Sulphide.
3. Thioglycolic Acid.
4. Pseudo-Thio-Hydantion.
But Na Sulphide is the most widely used reducing agent for dissolving Sulphur dyes. They
may be replaced by Na-Hydrosulphide in some cases. But the latter is a more powerful
reducing agent. So, over reducing of the dye may take place, leading to a product having
lower affinity for cellulosic fibres. Hence lower colour yields are obtained along with
wastage of dyestuff. In some cases lower wash fastness results if Na-Hydrosulphide is used.
It also decreases the life time of the vessel. For dissolving the Sulphur dyes, reducing agent
is taken according to the weight of dye. In practice, they are taken at same weight. For
example, 10 gm dye is mixed with 10 gm reducing agent. Then the mixture is boiled after
adding necessary amount of water to get a good solution. For this wooden vessel or
enameled iron vessel are used but not iron vessels. Because iron reacts with Sulphur.
Oxidation Step of Sulphur Dye:

After dyeing the reduced water soluble form of the dyes have to be converted in to the
original water insoluble form by oxidation. The commonly used oxidizing agents are-
1. Potassium dichromate
2. Na-Perborate.
3. Na-percarborate.
4. Na-peroxide.
The method of oxidizing selection plays an important role in the development of correct
shades & their optimum fastness properties. Rinsing off the dyeing should be done
rapidly to remove as much as Na-Sulphide as possible. If even after washing some Na-
sulphide or Soda-ash stays on fabric, we use CH3-COOH to neutralize them. Using of
different oxidizing agents may give following results-
1. Use of perborate or percartborate in presence of acetic acid gives brighter shade.

2. Treating dyed material with dichromate without rinsing reduces colour losses but
causes dull shade.
Sulfur dyes mainly applied to cotton, viscose, cellious and staple fibers.
Dyeing of Cellulosic Fibres with Sulphur Dyes:
The sequence of dyeing with Sulphur dyes is as following:
Goods Preparation
Dye Solution preparation
Dyeing
Oxidation
After treatment
Dyed Goods
Typical Recipe:
The Typical recipe for dyeing is as below:-
 Sulphur Dye : 10% (On the weight of the fabric)

 Na2S (Reducing Agent) : 1.5% (On the weight of the Dye)
 Salt : 8 gm/litre (NaCl)
 Soda Ash (NaCO3) : 7 gm/litre
 Temperature : 1000C
 Time : 90 minutes
 Material: Liquor : 1:20
Sometimes a chelating agent EDTA is added to chelate any metal salt extracted from the
cotton goods & effectively remove these ions from the dye bath. This is necessary to
prevent a harsh texture forming on a textile.
Dyeing:
At first dye solution is taken in a dye bath & the fabric is immersed in that solution. Then
it is heated for 10-15 minutes. Then half of the total NaCl solution is added and temperature
is raised to boil & then the rest amount of NaCl is added. Dyeing at this temperature is
continued for about 30 minutes. Then the steaming is turned off and the application
continued in cooling liquor for a further half hour. This steaming helps to diffuse the dye
in to the fabric before fixing. Retained dye liquor should be rinsed out immediately from
the surface of the fabric.
Oxidation:
After dyeing the reduced water soluble form of the dye should be make insoluble by
oxidation, to fix it on the fabric permanently. For this oxidation, we may use K2Cr2O7,
CH3COOH. Na-perborate, Na2O2 etc.
After Treatment:
The dyed substance is soaped which makes the colour bright and makes shade permanent.
The light fastness property of Sulphur dyes which is generally good can be improved by
after treatment with certain metallic salts. Thus a treatment with CuSO4 & CH3COOH in
presence of K2Cr2O7 improves the light fastness. When the dichromate is also present the
washing fastness is slightly improved.
The following recipe is used for after treatment:
 CuSO4 Solution : 1-2% (on the weight of goods)

 CH3COOH (60%) : 1-2%
 Temperature : 700C
 Time : 20-30 Minutes
Precaution in the dyeing process:

The precautions in the dyeing process with the Sulphur dyes are mentioned below:
1. In the application of Sulphur dye, the dye bath should not contain Ca- Salts. If they
are present in the form of insoluble co-compounds with the Sulphur dyes which
precipitated easily in closed machines and form sludge when restrict the circulation
of the dye liquor.
2. The dye should be dissolved with soda.
3. Great care should be taken during reduction process because over reduction should
lower the affinity of dye towards the fibre. As a result dull shade will appear and a
lot of dye stuff will go to waste.
4. Fabric must not to expose to air during dyeing to prevent precipitation & oxidation.
This will cause uneven dyeing.
5. To prevent uneven dyeing in the fabric selvedge more amount of Na2S or NaOH
and salt should be added in case of the jigger dyeing machine.
6. To prevent the broziness the dye liquor should not be very worm.
7. Goods dyed with Sulphur black should be after treated with a solution of
K2Cr2O7 followed by rinsing. This will prevent Sulphur black tendering.
Control of Dyeing:
Reduced Sulphur dyes are similar to direct dyes. Because they can also be exhausted by
adding common salts (NaCl) or Glauber’s salt (Na2SO4.10H2O) to the dye bath.
Sodium bi sulphite (NaHSO3) and ammonium sulphate {(NH4)2SO4} may also act as
exhausting agents. Especially in dyeing combination shades. NaHSO3 is an acidic salt
and (NH4)2SO4 is an acid liberating agent. They reduce the pH of dye bath and produce
15-20% deeper shades than common salt, when used as the exhausting agent. But the
shades produced in presence of them are less bloomy and dull.
When NaHSO3 is used alone the rate of exhaustion is low but the produced shade is
brighter and bloomier than common salt (NaCl) dyeing.
The use of the exhausting agents causes wastage of dye but as the Sulphur dyes are
relatively cheap this wastage is not considered. Especially in case of medium & light
shades.
Topping of Sulphur Dyes:

Sulphur dyes act as mordents for the basic dyes. The cotton textile materials dyed with
Sulphur dyes can be topped with basic dyes for brightening the shades. So, topping of
Sulphur dyes is one kind of re dyeing by which required brighter shades are obtained.
For topping of Sulphur dyes, at first dyed materials (dyed with Sulphur dyes) is washed
thoroughly to remove the alkali from the fabric. Then the fabric is treated with basic dye
in a second dye bath containing acetic acid of alum. In this bath temperature is raised
about 600C to control the exhaustion of basic dye.
Defects of Sulphur Dyeing:

They are mainly two defects which are common in Sulphur dyed textile materials:-
1. Bronziness or Dullness of shades

2. Sulphur Black tendering
Now they are Described below:-
1. Bronziness of Shades:
This is a common defect found in Sulphur dyed textile materials.
Causes:
The causes are as below:-
 Excessive delay between lifting of the material from the dye bath and washing off.
 Exposure of goods to air while dyeing.
 Too much use of common salts as exhausting agents.
 Insufficient Na2S (i.e. reducing agent) in dye bath. As a result of which dye is
incompletely reduced.
Remedies:
The remedies are as below:-
1. Good washing and dilute solution of Na2S (0.1%) at 300C or,
2. A treatment with boiling soap solution or a strong Na2S solution or,
3. A treatment with a solution containing 10% salponified palm oil at 600C or,
 Ammonia : 125-200 gm/100 litre or, 1.25-2 gm/litre
 T.R Oil : 200-300gm/100litre or, 2-3 gm/litre.
 Time : 15 minutes
 Temperature : Water Bath
2. Sulphur Black Tendering:

If Sulphur dyed textile materials are stored (weakening) tentering effect is seen on the
cellulose. Due to storage a part of the Sulphur colour converts in to H2SO4 by oxidizing
which in turn causes degradation of cotton by hydrolysis. It is a serious problem of
Sulphur dyed goods.
Causes:
The causes are as below:-
 Gradual oxidation of Sulphur to H2SO4 on storage.

 After treatment with copper salts causes rapid tendering.
 Presence of iron as an impurity causes rapid tendering.
 The method of oxidation for the recon version to insoluble form influence tendering.
Remedies:
The remedies are as below:-
 Treatment of dyed material with 1-3% K2Cr2O7 and 1-3% CH3COOH at 600C
temperature for 30 minutes followed by through rinsing.
 Treatment with a little CH3COOH so that H2SO4 may be converted in to harmless
acetic acid.
 Using 5 gm/litre soda ash after dyeing followed by drying without rinsing.
Stripping of Sulphur Dyes:

Unevenly Dyed shades on cellulosic materials with Sulphur dyes may be corrected by a
treatment with a worm solution of Na2S in the presence of Albigen A (polyvinyl
pyrolodine)
If this method is found to be in effective then the uneven dyed material may be treated
with a solution of a NaOCl or bleaching powder (2-3 gm/Litre of available chlorine).
In some cases bleaching with KMnO4 solution may be effectively carried out. In other
cases the dyed material may be treated with worm NaOCl solution in the presence of
NaOH.
The uneven dyeing of material causes due to the following reasons:
 The oxidation of dye during dyeing when the material comes in contact with air.
 Presence of gummy material on the fabric.
 Defective Dye.
Uses of Sulphur Dye:
1. To dye Umbrella cloth with Sulphur black.

2. To dye cotton fabric eg-lining boot.
3. To dye rubber material hence after treatment by CuSO4 is necessary
S-Radical in Sulphur dye:

In case of tendering of Sulphur, due to storage lose of strength occurs and forms to
Sulphur radical. Three types of Sulphur radical are present in Sulphur dyes as below:-
Mechanically free Sulphur: Air+S= H2SO4Stable Sulphur: 70%-80%, not easily
oxidized.Chemically active Sulphur : 20-25%
Colors/Shades found from Sulphur dyes:
Red : Not good, not pure red color.

Black, blue, brown : Excellent Shade.
Others: Olive, Orange, green etc.
EXAMPLES OF SULFUR DYES:
Sulfur Black 1
2,4-Dinitrophenol or its Sodium salt (by 1-Chloro-2,4-dinitrobenzene alkaline

hydrolysis) and Sodium polysulfide heating, in 110 ~ 120 ℃ reflux heating 48 to 72 hours,
or in 130 ~ 140 ℃ under pressure to short time heating, then dilution melt, adding acid or
air oxidation make dye completely precipitated out. In the molten material to the
intermediate Sodium polysulfide proportion must be appropriate, such ability in reaction
end solution almost no dye residual.
green black and blue black. Black uniform powder. Insoluble in water and Etanol. In the
Sodium sulfide solution solubility is good, for green black; Add Sodium hydroxide and
Sodium sulfide solution of colour and lustre is blue; Add hydrochloric acid Sodium sulfide
solution to have green black precipitation; In the cold part of concentrated sulfuric acid
solution, after heating for deep green light blue, further heating into dark blue; In 25% of
fuming sulfuric acid for black blue, dilution after green black precipitation.
Sulphur Green 3
Green Aquamarine blue powder. Slightly soluble in water. In the Sodium sulfide solution
solubility is good, for olive; In concentrated sulfuric acid for dark blue, dark blue
precipitation after Dilution. Dyeing content in alkaline insurance powder solution for
dark orange, after oxidation can be restored to the original colour and lustre; In Sodium
hypochlorite solution all fade, join concentrated sulfuric acid into dark blue. Suitable for
cotton, hemp, viscose and vinylon/cotton blended fabric dyeing, also used for cotton
direct printing, a few used in leather
Solubilized Sulphur Black 7
Solubilized Sulphur Black 7, also known as Solubilized Sulfur Black B, is a derivative of

Sulphur Black dyes that has better solubility in water compared to the original Sulphur
Black dyes. The improved solubility allows for easier dyeing and application processes in
the textile industry.In terms of its chemical properties, Solubilized Sulphur Black 7
possesses similar structural features as other Sulphur Black dyes. It consists of carbon,
hydrogen, oxygen, nitrogen, and sulfur atoms arranged in a specific pattern, but with
modifications that enhance its solubility characteristics.Some key chemical properties of
Solubilized Sulphur Black 7 include:
1. Solubility: As the name suggests, Solubilized Sulphur Black 7 is highly soluble in

water. This property allows for easy formulation of dye solutions and even dye
distribution during the dyeing process.
2. Stability: Solubilized Sulphur Black 7 demonstrates good stability under normal

conditions, exhibiting resistance to light, heat, and various chemicals. This stability
ensures the dye retains its color shade and durability on the dyed fabric.
3. pH Sensitivity: The dye's solubility

.Sulphur Black 9
Sulphur Black 9" refers to the chemical compound called C.I. Sulphur Black 9 or Sulphur
Black B. It is a type of synthetic dye used in the textile industry to dye cotton fibers. Sulphur
Black 9 belongs to the class of sulfur dyes.
The chemical structure of Sulphur Black 9 consists of carbon, hydrogen, oxygen, nitrogen,
and sulfur atoms arranged in a specific pattern. The exact structure may vary depending on
the specific formulation used by different manufacturers.
Sulphur Black 9 has good solubility in water and is often used in combination with other
dyes to achieve a range of color shades. It is known for its dark black color and is
commonly used for dyeing denim and other dark-colored fabrics.
In terms of chemical properties, Sulphur Black 9 exhibits good color fastness properties,
meaning it has a high resistance to fading and washing. It is also resistant to light and heat,
ensuring the color remains stable and durable on the dyed fabric.
Overall, Sulphur Black 9 is an important dye in the textile industry, providing a deep black
color to various fabrics while maintaining good color fastness properties.
Leuco Sulphur Black 6
Leuco Sulphur Black 6, also known as Leuco Sulphur Black RL, is a reducing agent used
in the textile industry for the reduction and fixation of Sulphur Black dyes. It is the reduced
form of Sulphur Black dyes, which allows for easier application and better color fastness
on fabrics.
Leuco Sulphur Black 6 is typically used in combination with other dyes to achieve specific
color shades. It works by undergoing a chemical reaction with oxygen or air, where it is
oxidized back to its original Sulphur Black dye form. This oxidation process results in the
formation of strong color bonds with the fabric, creating long-lasting and intense color on
the textile.
In terms of chemical properties, Leuco Sulphur Black 6 is typically a water-insoluble
substance. It needs to be dissolved in a reducing agent, such as sodium hydrosulfite or other
reducing agents, to form a dye bath suitable for textile dyeing. The reduction reaction
allows for the dyeing process to occur effectively.
Additionally, Leuco Sulphur Black 6 has good light fastness, heat resistance, and chemical
stability, ensuring the color remains vibrant and durable even after exposure to various
environmental conditions.
Leuco Sulphur Black 2
Leuco Sulphur Black 2, also known as Leuco Sulphur Black HB or Leuco Sulphur Black
SBR, is a reducing agent and a color precursor used in the textile industry for the production
of Sulphur Black dyes. It is the reduced form of Sulphur Black 2, which allows for better
solubility and easier application on fabrics.
Leuco Sulphur Black 2 is typically used in combination with other color precursors and
chemicals to create customized Sulphur Black dyes for specific applications. It is
commonly employed in the dyeing of cellulose fibers like cotton and viscose.
In terms of chemical properties, Leuco Sulphur Black 2 is a water-insoluble compound but

can be dissolved in alkaline solutions. The reduction process converts it into a water-
soluble form, allowing for easy incorporation into dye baths.
Leuco Sulphur Black 2 undergoes an oxidation reaction with air or oxidizing agents,
resulting in the formation of the original Sulphur Black 2 dye. This dye reacts with the
fibers and forms intense color bonds, resulting in deep black shades.Additionally, Leuco
Sulphur Black 2 exhibits good light fastness, heat resistance, and chemical stability
Solubilized Sulphur Brown 97
Solubilized Sulphur Brown 97 Solubilized Sulphur Brown 97, also known as Solubilized
Sulfur Brown D, is a type of synthetic dye that belongs to the class of sulfur dyes. It is
primarily used in the textile industry for coloring cellulose fibers, particularly
cotton.Solubilized Sulphur Brown 97 is specifically formulated to have enhanced solubility
in water compared to traditional Sulphur Brown dyes. This improved solubility allows for
easier dyeing processes and effective color distribution on fabrics.Chemically, Solubilized
Sulphur Brown 97 consists of carbon, hydrogen, oxygen, nitrogen, and sulfur atoms
arranged in a specific molecular structure. The exact structure may vary depending on the
specific formulation used by different manufacturers. Some key properties of Solubilized
Sulphur Brown 97 include:
1. Solubility: As the name suggests, Solubilized Sulphur Brown 97 is highly soluble in

water. This property aids in the preparation of dye solutions and facilitates even coloration
during the dyeing process
2. Color fastness: Solubilized Sulphur Brown 97 demonstrates good color fastness

properties, meaning it retains its color and resists fading when exposed to light, washing
Sulphur Brown 52
Manufacturing Methods : Diacenaphtho[1,2-j:1′,2′-1]fluoranthene and sulfur mixture

for roasting (in 20 hours of roasting temperature up to 350 ℃, and keep the temperature
for more than 8 hour), the product with Sodium hydroxide in 100 ~ 110 ℃ processing,
then filtering, and taking sulfuric acid precipitation. Note: the Diacenaphtho[1,2-j:1′,2′-1]
fluoranthene and nitrocellulose derivatives (namely C.I. Sulphur Brown 60, C.I. 53325
and C.I. Sulphur Brown 51, C.I. 53327) the dye it has excellent resistance to sun fastness.
Properties and Applications: brown. Brown powder. Soluble in Sodium sulfide
solution. In the basic insurance powder solution for red brown; In Sodium hypochlorite
solution is partly by the bleaching. Used for cotton, hemp, viscose fabric dyeing.
Challenges of scientists to modification sulfur dye:
Sulfur dyes are inexpensive and are used mainly for dyeing textile cellulosic materials or
blends of cellulosic fibers. Sodium sulfide is fairly cheap and a traditional reducing agent
used for sulfur dyeing, but it is toxic and hazardous to handle. Its use may leave harmful
residues in finished fabrics and generate effluents that are difficult to treat and damaging
to the environment. Textile companies face the high costs of water and wastewater, as
well as strict environmental legislation. In this review, a variety of methods, including
physicochemical and biological methods, are surveyed for their application to the
treatment of water and wastewater containing sulfur dyes. This survey is followed by
suggestions for further actions that can be taken for the improvement of the treatment
processes from both economic and technical viewpoints.
The objective of this review is to compile the recent technological advances in the
development of water and wastewater treatment containing sulfur dyes. Moreover,
suggestions for further studies for the improvement of treatment processes from both
economic and technical viewpoints are presented.
Coagulation or precipitation processes

Some chemicals are rapidly dispersed in wastewaters, which can change the characteristics
of the suspended particles such that they tend to coalesce and form flocs that sink rapidly .
This process is called coagulation. Negatively charged colloidal suspensions are not
normally settled out and removed during conventional physical treatment; however, they
can be made simpler to remove when coagulation is employed. Coagulation is
accomplished by the addition of positive ions that reduce the
Biological methods
The ability of microorganisms to carry out dye decolorization has recently received much
attention. Microbial decolorization of dyes is a cost effective method for their removal
from wastewater . Bacteria are promising microorganisms for the degradation of a variety
of dyes Many bacteria are employed in dye decolorization,
including Brevibacillus sp., Klebsiella pneumoniae, Acetobacter liquefaciens,
and Pseudomonas desmolyticum. Yeasts have many advantages relative
Combined methods
Each process has its own advantages as well as disadvantages; therefore, various
combinations have been attempted to achieve the efficient treatment of sulfur dye effluents.
With the combination of coagulation and membrane processes, the black sulfur dye effluent
is initially pretreated with aluminum sulfate and thereafter by microfiltration (MF) using a
ceramic membrane . Aluminum sulfate is used as the coagulant and a polymer is used as
the flocculant. The supernatant is collected after Elimination of harmful substances in the
sulfur dyeing process
The major harmful substances in the sulfur dyeing process include conventional reducing
agents such as sodium sulfide and oxidizing agents such as dichromate, hydrogen peroxide,
and sodium hypochlorite. Sodium dithionate, thiourea dioxide, and indirect cathodic
reduction have been studied and tested as replacements for sodium sulfide . They are still
not commonly used in the textile industry because of their inconsistent results and higher
cost. Glucose, an eco-friendly reducing agent. From the articles surveyed in this study, it
is evident that substantial progress has been achieved in the treatment of wastewater
containing sulfur dyes, and there is also an indication that some of the approaches tend to
be more effective than others. Although the amounts of chemicals used are quite large and
the operating cost quite high, the physicochemical methods and/or their combined methods
are still often employed for color removal as well as for the elimination of sulfur dyes from
Mordant Dye
A mordant or dye fixative is a substance used to set (i.e.,
bind) dyes on fabrics.
It does this by forming a coordination complex with the

dye, which then attaches to the fabric (or tissue). It may be
used for dyeing fabrics or for intensifying stains in cell or
tissue preparations.
Although mordants are still used, especially by small batch

dyers, it has been largely displaced in industry by directs.
The term mordant comes from the Latin mordere, "to bite".
In the past, it was thought that a mordant helped the dye
bite onto the fiber so that it would hold fast during washing.
A mordant is often a polyvalent metal ion, and one example
is chromium (III). The resulting coordination complex of
dye and ion is colloidal and can be either acidic or alkaline.
The dye to be mordant dye must have
- The main chromophore –N=N- and auxochrome OH in

ortho position or N=O in ortho position to OH or C=O
in ortho position to OH
- Example 1 Mordant Yellow 3 OH in ortho position to
COOH.
- Example 2 CI Mordant Red 5 OH in ortho position to

azo group –N=N-
- Example 3 COOH in ortho position to azo group as in
CI Mordant Yellow 8
- Presence of OH make it confined with metal forming

lake dye
- If the dye is acidic dye, the mordant is formed in basic
medium as NaOH
- If the dye is basic dye, the mordant is formed in acidic
medium as tannic acid.
Examples of Common Mordants

Common mordants used in dyeing and tanning include
aluminum, chromium, iron, copper, iodine, potassium,
sodium, tin, and tungsten salts (usually oxides); sodium
chloride; alum, tannic acid, and chrome alum. Important
histotechnology mordants include alum hematoxylin and
Harris’ hematoxylin in the hematoxylin and eosin (H&E)
stain.
- Common dye mordants

Mordants include tannic acid, oxalic acid, alum, chrome
alum, sodium chloride, and certain salts of aluminium,
chromium, copper, iron, iodine, potassium, sodium,
tungsten, and tin.
Iodine is often referred to as a mordant in Gram stains, but

is in fact a trapping agent.
Mordant red 19 is a typical mordant dye. Like many mordant dyes, it

features the azo group (RN=NR) and various sites for chelating to
metal cations.
Dyeing methods
The three methods used for mordanting are:
- Pre-mordanting (onchrome): The substrate is treated

with the mordant and then the dye. The complex
between the mordant and dye is formed on the fibre.
- Meta-mordanting (metachrome): The mordant is
added in the dye bath itself. The process is simpler than
pre- or post-mordanting, but is applicable to only a few
dyes. Mordant red 19 shown above is applied in this
manner
- Post-mordanting (afterchrome): The dyed material is
treated with a mordant. The complex between the
mordant and dye is formed on the fibre.
The type of mordant used affects the shade obtained after

dyeing and also affects the fastness property of the dye. The
application of mordant, either pre-mordant, meta-mordant
or post-mordant methods, is influenced by:
The action of the mordant on the substrate: if the mordant

and dye methods are harsh (for example, an acidic mordant
with an acidic dye), pre-mordanting or post-mordanting
limits the potential for damage to the substrate.
The stability of the mordant or dye lake or both: the

formation of a stable dye lake means that the mordant can
be added in the dye without risk of losing the dye properties
(meta-mordanting).
Dye results can also rely on the mordant chosen as the

introduction of the mordant into the dye will have a marked
effect on the final color. Each dye can have different
reactions to each mordant. For example, cochineal scarlet,
or Dutch scarlet as it came to be known, used cochineal
along with a tin mordant to create a brilliant orange-hued
red.
Residual iron mordant can damage or fade fabric,

producing "dye rot".
A French Indienne, a printed or
painted textile in the manner of
Indian productions, which used
mordants to fix the dyes.
Examples of mordant dyes:
Metalized Mordant Dyes for polyamide fiber
a) 1:1 Complexes
It means that one mole of mordant dye is formed complex

with metal.
For example: CI Acid blue 159 (34) is prepared by coupling

the
diazo-oxide of 1-amino-2-naphthol-4-sulfonic acid with 1-
naphthol-8-sulfonic acid and heating the resulting azo dye
at 115°C with chromium sulfate solution.
Synthesis of CI Acid blue 159

b) 2: 1 Complexes.
It means that two moles of mordant dye is formed complex

with metal.
For example CI Acid Violet 78 (40)

Synthesis of CI Acid Violet 78
CI Acid Violet 78 is prepared by chroming the azo dye
obtained by coupling diazotised 2-amino-4-
hydroxyphenylmethylsulfone with 2-naphthol.
Another examples of mordant dyes include:
1. Tannic acid
2. Alum
3. Chrome alum
4. Sodium chloride
5. Certain salts of aluminum, chromium, copper, iron,

iodine, potassium, sodium, tungsten, and tin
Introduction
Dye, substance used to impart colour to textiles, paper,
leather, and other materials such that the colouring is not
readily altered by washing, heat, light, or other factors to
which the material is likely to be exposed. Dyes differ from
pigments, which are finely ground solids dispersed in a
liquid, such as paint or ink, or blended with other materials.
Most dyes are organic compounds (i.e., they contain
carbon), whereas pigments may be inorganic compounds
(i.e., they do not contain carbon) or organic compounds.
Pigments generally give brighter colours and may be dyes
that are insoluble in the medium employed.
Colour has always fascinated humankind, for both aesthetic

and social reasons. Throughout history dyes and pigments
have been major articles of commerce. Manufacture of
virtually all commercial products involves colour at some
stage, and today some 9,000 colorants with more than
50,000 trade names are used. The large number is a
consequence of the range of tints and hues desired, the
chemical nature of the materials to be coloured, and the fact
that colour is directly related to the molecular structure of
the dye.
History of dyes
Natural dyes
Until the 1850s virtually all dyes were obtained from

natural sources, most commonly from vegetables, such as
plants, trees, and lichens, with a few from insects. Solid
evidence that dyeing methods are more than 4,000 years old
has been provided by dyed fabrics found in Egyptian
tombs. Ancient hieroglyphs describe extraction and
application of natural dyes. Countless attempts have been
made to extract dyes from brightly coloured plants and
flowers; yet only a dozen or so natural dyes found
widespread use. Undoubtedly most attempts failed because
most natural dyes are not highly stable and occur as
components of complex mixtures, the successful separation
of which would be unlikely by the crude methods employed
in ancient times. Nevertheless, studies of these dyes in the
1800s provided a base for development of synthetic dyes,
which dominated the market by 1900.
Two natural dyes, alizarin and indigo, have major

significance. Alizarin is a red dye extracted from the roots
of the madder plant, Rubia tinctorium. Two other red dyes
were obtained from scale insects. These include kermes,
obtained from Coccus ilicis (or Kermes ilicis), which
infects the Kermes oak, and cochineal, obtained from
Dactylopius coccus, which lives on prickly pear cactus in
Mexico. One kilogram (2.2 pounds) of cochineal dye can be
obtained from an estimated 200,000 insects. The principal
coloured components in these dyes are kermesic and
carminic acids, respectively, whose similarity was
established by 1920. In their natural state many colorants
are rendered water-soluble through the presence of sugar
residues. These sugars, however, are often lost during dye
isolation
procedures.
Probably the oldest known dye is the blue dye indigo,
obtained in Europe from the leaves of the dyerswoad herb,
Isatis tinctoria, and in Asia from the indigo plant,
Indigofera tinctoria. Even by modern standards, both
alizarin and indigo have very good dyeing properties, and
indigo remains a favoured dye for denim, although
synthetic indigo has replaced the natural material.
With a process developed by the Phoenicians, a derivative

of indigo, Tyrian purple, was extracted in very small
amounts from the glands of a snail, Murex brandaris,
indigenous to the Mediterranean Sea. Experiments in 1909
yielded 1.4 grams (0.05 ounce) from 12,000 snails.
Historically, this dye was also called royal purple because
kings, emperors, and high priests had the exclusive right to
wear garments dyed with it, as is well documented in the
Hebrew Bible and illustrated for Roman emperors on
mosaics in Ravenna, Italy. By the 1450s, with the decline of
the Eastern Roman Empire, the Mediterranean purple
industry died out.
Natural yellow dyes include louting, from the leaves of

weld, Reseda luteola, and quercetin, from the bark of the
North American oak tree, Quercus tinctoria. These are in
the flavonoid family, a group of compounds occurring
almost exclusively in higher plants and producing the
colours of many flowers. In fact, these compounds can
produce all the colours of the rainbow except green.
Luteolin, a yellow crystalline pigment, was used with
indigo to produce Lincoln green, the colour associated with
Robin Hood and his merry men.
Another group of compounds, the carotenoids, present in all
green plants, produce yellow to red shades. Lycopene, from
which all carotenoids are derived, produces the red colour
of tomatoes. An ancient natural yellow dye, crocetin, was
obtained from the stigmas of Crocus sativus; this dye is
undoubtedly derived from lycopene in the plant. Few of the
flavonoid and carotenoid colorants would have survived
ancient extraction processes.
Logwood is the only natural dye used today. Heartwood
extracts of the logwood tree, Haematoxylon
campechianum, yield hematoxylin, which oxidizes to
hematein during isolation. The latter is red but in
combination with chromium gives shades of charcoal, gray,
and black; it is used mainly to dye silk and leather.
Mordants
Highly skilled craftsmen with closely guarded secret
formulas rendered dyeing a well-protected trade. The
formation of different colours by mixing red, blue, and
yellow dyes was well known in ancient times, as was the
use of metal salts to aid the retention of dyes on the desired
material and to vary the resultant colours. Natural dyes
cannot be applied directly to cotton, in contrast to wool and
silk, although cotton can be dyed by vatting or by
pretreatment with inorganic salts known as mordants (from
Latin mordere, meaning “to bite”). These are adsorbed on
the fibre and react with the dye to produce a less soluble
form that is held to the fabric. Alum, KAl(SO4)2 × H2O, as
well as iron, copper, and tin salts were common ancient
mordants. No doubt the secret processes included other
ingredients to improve the final results. Mordants also were
used to vary the colours produced from a single dye. For
example, treatment with aluminum hydroxide, Al(OH)3,
before dyeing with alizarin produces Turkey red, the
traditional red of British and French army uniforms.
Alizarin gives violet colours with magnesium mordants,
purple-red with calcium mordants, blue with barium
mordants, and black-violet with ferrous salts. Around 1850,
chromium salts, used as mordants, were found to provide
uperior dye retention and, in time, largely displaced the
others; chromium mordants are still widely used for wool
and, to some extent, for silk and nylon.
Mordant in the Gram Stain
Iodine is referred to as a mordant in the Gram stain in
microbiology. However, it’s actually a trapping agent. A
trapping agent inhibits dye removal during the decolorizing
step after staining. Similarly, sodium chloride in the Salt
Gram technique and picric acid in the Gram-Weigert
method are trapping agents rather than true mordants.
While mordants are metals with a valency of at least two,
trapping agents are usually nonmetals, typically used with
basic dyes, and are applied after the dye. Processes
involving trapping agents stain perfectly well if the step is
omitted. Processes requiring a mordant don’t stain unless
the mordant is used.
Mordant Dye
Prepared by:
Aml Mahmoud Eltantawy
Under Supervisor:
Prof. Dr. Hassan Ali Etman

‫نورهان ساىم محمد جنينة‬
‫‪Chem.633‬‬
4-hydroxy propiophenone
No 4: CH3 appear triplet at 1.1ppm
No3: CH2 appear quartet 2.9ppm more deshilded than CH3
No5: OH appear broad signal singlet at about 10.3 ppm
1
Flurbiprofen
No11: CH3 appear douplet at about 1.4ppm
No 1: OH appear broad singlet at about 12.4ppm
2
Indomethacin
No 1: OH appear broad at about 12.4ppm
No 11: CH3 appear singlet at about 2.3ppm
No 9: CH3 appear singlet at about 3.9ppm
3
A: CH3 appear triplet at about 1.5ppm
B: CH2 appear quartet at about 2.6ppm
4
CH3 appear triplet at about 1.3ppm
CH2 appear quartet at about 2.9ppm
CH3O appear singlet at about 3.8ppm
5
CH3 appear triplet at about 1.4ppm
CH2 appear quartet at about 4ppm deshilded
6
CH3 appear singlet of 6 protons at about 2.2ppm
7
.
CH3 appear singlet at about 2.2ppm of 6 protons
OH appear broad singlet at about 12.6ppm
8
.
CH3 appear triple at about 1.2ppm
CH2 appear quartet at about 2.5ppm
OH appear broad singlet at about 6 ppm
9
Introduction
A dye is a colored substance that chemically bonds to the substrate to
which it is being applied. This distinguishes dyes from pigments which
do not chemically bind to the material they color. Dye is generally applied
in an aqueous solution and may require a mordant to improve the fastness
of the dye on the fiber.[2]
The majority of natural dyes are derived
from non-animal sources such as roots,
berries, bark, leaves, wood, fungi
and lichens.[3] However, due to large-
scale demand and technological
improvements, most dyes used in the
modern world are synthetically produced
from substances such as
petrochemicals.[4] Some are extracted
from insects and/or minerals.[5]
Synthetic dyes are produced from various chemicals. The great majority
of dyes are obtained in this way because of their superior cost, optical
properties (color), and resilience (fastness, mordancy).[2] Both dyes and
pigments are colored, because they absorb only some wavelengths of
visible light. Dyes are usually soluble in some solvent, whereas pigments
are insoluble. Some dyes can be rendered insoluble with the addition
of salt to produce a lake pigment.
Chemical structure of indigo dye, the
blue coloration of blue jeans. Although
once extracted from plants, indigo dye
is now almost exclusively synthesized
industrially.
1
History of dyes:
Dyeing wool cloth, 1482: from a
French translation of Bartolomaeus
Anglicus.
Textile dyeing dates back to the Neolithic period.
Throughout history, people have dyed their textiles
using common, locally available materials. Scarce
dyestuffs that produced brilliant and permanent
colors such as the natural invertebrate dyes Tyrian
purple and crimson kermes were highly prized
luxury items in the ancient and medieval world. Plant-based dyes such
as woad, indigo, saffron, and madder were important trade goods in the
economies of Asia and Europe. Across Asia and Africa, patterned fabrics
were produced using resist dyeing techniques to control the absorption of
color in piece-dyed cloth. Dyes from the New World such
as cochineal and logwood were brought to Europe by
the Spanish treasure fleets, and the dyestuffs of Europe were carried by
colonists to America.
Dyed flax fibers have been found in the Republic of Georgia in a
prehistoric cave dated to 36,000 BP.[8][9] Archaeological evidence
shows that, particularly in India and Phoenicia, dyeing has been widely
carried out for over 5,000 years. Early dyes were obtained
from animal, vegetable or mineral sources, with no to very little
processing. By far the greatest source of dyes has been from the plant
kingdom, notably roots, berries, bark, leaves and wood, only few of which
are used on a commercial scale.
2
Early industrialization was conducted by J. Pullar and Sons in
Scotland.[10] The first synthetic dye, mauve, was
discovered serendipitously by William Henry Perkin in 1856.
The discovery of mauveine started a surge in synthetic dyes and in organic
chemistry in general. Other aniline dyes followed, such
as fuchsine, safranine, and induline. Many thousands of synthetic dyes
have since been prepared.
The discovery of mauve also led to developments
within immunology and chemotherapy. In 1863 the forerunner to Bayer
AG was formed in what became Wuppertal, Germany. In 1891, Paul
Ehrlich discovered that certain cells or organisms took up certain dyes
selectively. He then reasoned that a sufficiently large dose could be
injected to kill pathogenic microorganisms, if the dye did not affect other
cells. Ehrlich went on to use a compound to target syphilis, the first time
a chemical was used in order to selectively kill bacteria in the body. He
also used methylene blue to target the plasmodium responsible
for malaria.
Chemistry of dyes:
The color of a dye is dependent upon the ability of the substance to absorb
light within the visible region of the electromagnetic spectrum (380-
750 nm). An earlier theory known as Witt theory stated that a colored dye
had two components, a chromophore which imparts color by absorbing
light in the visible region (some examples are nitro, azo, quinoid groups)
and an auxochrome which serves to deepen the color. This theory has
been superseded by modern electronic structure theory which states that
the color in dyes is due to excitation of valence π-electrons by visible
light.
Types of dyes:
3
Dyes are classified according to their solubility and chemical properties.
Acid dyes are water-soluble anionic dyes that are applied to fibers such
as silk, wool, nylon and modified acrylic fibers using neutral to acid dye
baths. Attachment to the fiber is attributed, at least partly, to salt
formation between anionic groups in the dyes and cationic groups in the
fiber. Acid dyes are not substantive to cellulosic fibers. Most synthetic
food colors fall in this category. Examples of acid dye are Alizarine Pure
Blue B, Acid red 88, etc.
Basic dyes are water-soluble cationic dyes that are mainly applied
to acrylic fibers, but find some use for wool and silk. Usually acetic
acid is added to the dye bath to help the uptake of the dye onto the fiber.
Basic dyes are also used in the coloration of paper.
Direct or substantive dyeing is normally carried out in a neutral or

slightly alkaline dye bath, at or near boiling point, with the addition of
either sodium chloride (NaCl) or sodium sulfate (Na2SO4) or sodium
carbonate (Na2CO3). Direct dyes are used on cotton, paper, leather,
wool, silk and nylon. They are also used as pH indicators and
as biological stains.
Laser dyes are used in the production of some lasers, optical media
(CD-R), and camera sensors (color filter array).
Mordant dyes require a mordant, which improves the fastness of the dye
against water, light and perspiration. The choice of mordant is very
important as different mordants can change the final color significantly.
Most natural dyes are mordant dyes and there is therefore a large literature
base describing dyeing techniques.
The most important mordant dyes are the synthetic mordant dyes, or
chrome dyes, used for wool; these comprise some 30% of dyes used for
wool, and are especially useful for black and navy shades. The
mordant potassium dichromate is applied as an after-treatment. It is
4
important to note that many mordants, particularly those in the heavy
metal category, can be hazardous to health and extreme care must be taken
in using them.
Vat dyes are essentially insoluble in water and incapable of dyeing fibres
directly. However, reduction in alkaline liquor produces the water-
soluble alkali metal salt of the dye. This form is often colorless, in which
case it is referred to as a Leuco dye, and has an affinity for the textile fibre.
Subsequent oxidation reforms the original insoluble dye. The color of
denim is due to indigo, the original vat dye.
Reactive dyes utilize a chromophore attached to a substituent that is
capable of directly reacting with the fiber substrate. The covalent bonds
that attach reactive dye to natural fibers make them among the most
permanent of dyes. "Cold" reactive dyes, such as Procion MX, Cibacron
F, and Drimarene K, are very easy to use because the dye can be applied
at room temperature. Reactive dyes are by far the best choice for
dyeing cotton and other cellulose fibers at home or in the art studio.
Disperse dyes were originally developed for the dyeing of cellulose
acetate, and are water-insoluble. The dyes are finely ground in the
presence of a dispersing agent and sold as a paste, or spray-dried and sold
as a powder. Their main use is to dye polyester, but they can also be used
to dye nylon, cellulose triacetate, and acrylic fibers. In some cases, a
dyeing temperature of 130 °C (266 °F) is required, and a pressurized
dyebath is used. The very fine particle size gives a large surface area that
aids dissolution to allow uptake by the fiber. The dyeing rate can be
significantly influenced by the choice of dispersing agent used during the
grinding.
Azoic dyeing is a technique in which an insoluble Azo dye is produced
directly onto or within the fiber. This is achieved by treating a fiber with
both diazoic and coupling components. With suitable adjustment of
5
dyebath conditions the two components react to produce the required
insoluble azo dye. This technique of dyeing is unique, in that the final
color is controlled by the choice of the diazoic and coupling components.
This method of dyeing cotton is declining in importance due to the toxic
nature of the chemicals used.
Sulfur dyes are inexpensive dyes used to dye cotton with dark colors.
Dyeing is effected by heating the fabric in a solution of an organic
compound, typically a nitrophenol derivative, and sulfide or polysulfide.
The organic compound reacts with the sulfide source to form dark colors
that adhere to the fabric. Sulfur Black 1, the largest selling dye by volume,
does not have a well defined chemical structure.
Indigo dyes are derivatives of indigo. Thus, the selenium, sulfur and
oxygen homologues of indigo blue cause significant hypochromic effects
with colors ranging from orange to turquoise, some examples of which
are summarized in Table.
Chemical structures and λmax of some indigo dyes.
Natural dyes
6
Natural dyes and their use in dyeing is probably the most ancient art of all
times. People started using natural dye as their first intellectual tool to
portray their surroundings and themselves by this art. Though natural dyes
have been used to color textiles from ancient times, but in the 19th
century, synthetic dyes replaced natural dyes after discovery of mauve
colorant.
Natural dye is defined as any dye, pigment, or any other substance derived
from natural sources such as plants, animals and minerals are renewable
and sustainable bioresource products with minimum environmental
impact. They have been known since antiquity for their use in coloring of
textiles, food substrate, natural protein fibers like wool, silk and cotton,
and leather as well as food ingredients and cosmetics.
The term ‘natural dye’ is conventionally taken to apply to those products
that are derived from plant sources, although dyes derived from insects,
such as cochineal, kermes and lac, are also included. The natural dyes are
complex mixtures of components derived extracted from natural
substances such as plants, animals or minerals.
A large number of herbs, shrubs, trees, insects, animals, microbes and
minerals have been identified for extraction of coloring compounds. Red,
yellow, brown, blue, black, green and orange color can be obtained from
natural dyes.
Color fastness of natural dyes to washing and light is in general inferior
to well-selected and applied synthetic dyes, and normally does not meet
consumer demands.
The term ‘natural’ and ‘safe’ are not synonymous; there are many
naturally occurring substances, e.g. arsenic and asbestos, which are
harmful. Natural dyes are derived from plant, animal or mineral sources,
and while some dyes are quite safe to use, some are hazardous. For
example, indigo and logwood are skin and respiratory irritants, and plants
such as lily of the valley and bloodroot are toxic
7
Handling of natural dye and its dyeing process needs scientific
interventions at four main steps:
• Extraction
• Isolation of dye molecule
• Dyeing
• Dye fixing
Applications of natural dyed textile can be extended to a diverse field such
as sportswear and medicinal field due to its various functional properties
such as antimicrobial as well as UV protection.
Sources of Natural Dyes:
Natural dyes are basically elements of natural

resources, and these dyes are generally
classified as plant, animal, mineral, and
microbial dyes based on their source of origin,
although plants are the major sources of
natural dyes. Natural dyes are sustainable as
they are renewable and bbiodegradabl.q
Natural Dyes: Properties, Classification,
Production, Advantages and Disadvantages
October 22, 2022 by Mazharul Islam Kiron
Applications of natural dyed textile can be
extended to a diverse field such as sportswear
and medicinal field due to its various
functional properties such as antimicrobial as
well as UV protection.
Natural dyes are basically elements of natural resources, and these dyes
are generally classified as plant, animal, mineral, and microbial dyes
based on their source of origin, although plants are the major sources of
8
natural dyes. Natural dyes are sustainable as they are renewable and
biodegradable.
Natural dye can be classified in following groups on the basis of sources:
1. Plants: Roots, leaves, fruits, flowers and barks can be used as a source
of natural dyes. Different colors can be obtained from each part such as
Sappan-wood tree pods give red, barks give brown and root gives yellow
color. Many by-products of plants can also be used to form dyes.
2. Animals: Dyes can be obtained from dried body of insects for example,
Lac, Cochineal and Kermes. Cochineal is a brilliant red dye produced
from insects living on Cactus plants. Carmine and Tyrian purple dye
derived from cochineal, shellfish (Murex spp.) respectively.
3. Minerals: Mineral dyes include iron buff, iron black, manganese bistre,
chrome yellow, and Prussian blue.
4. Microorganisms: Natural colorant can be extracted from fungi, bacteria
and algae that are fast growing and have the potential of being
standardized commercially. Chitosan, Serratia spp., Trichoderma virens
and Alternaria alternata were used to obtained dyes. Natural Red color is
produced by Monascus anka and also from fungus Echinodontium
tinctorium. Phycocyanin is blue pigment extracted from Spirulina
plarensis algae.
Properties / Characteristics of Natural Dyes:
Natural dyes are organic and are derived or extracted from resources
found in nature. Natural dyes are mostly eco-friendly, biodegradable, less
toxic, and less allergenic as compared to synthetic dyes. However, studies
have shown that certain natural dyes may have detectable mutagenic
effects e.g., elderberry color and safflower yellow; others, like carmine,
can cause asthma by continuous inhalation.
9
Indigo dye
Indigo dye is an organic compound with a distinctive blue color. Indigo is

a natural dye extracted from the leaves of some plants of
the Indigofera genus, in particular Indigofera tinctoria; dye-
bearing Indigofera plants were commonly grown and used throughout the
world, in Asia in particular, as an important crop, with the production of
indigo dyestuff economically important due to the historical rarity of other
blue dyestuffs.
10
Most indigo dye produced today is synthetic, constituting several
thousand tons each year. It is most commonly associated with the
production of denim cloth and blue jeans, where its properties allow for
effects such as stone washing and acid washing to be applied quickly.
Uses:
The primary use for indigo is as a dye for cotton yarn, mainly used in the
production of denim cloth suitable for blue jeans; on
average, a pair of blue jeans requires 3 grams (0.11 oz) to
12 grams (0.42 oz) of dye. Smaller quantities are used in
the dyeing of wool and silk.
Indigo carmine, also known as indigo, is an indigo
derivative which is also used as a colorant. About 20,000
tonnes are produced annually, again mainly for the
production of blue jeans. It is also used as a food colorant, and is listed in
the United States as FD&C Blue No. 2.
Sources:
Natural sources
A variety of plants have provided indigo throughout history, but most
natural indigo was obtained from those in the genus Indigofera, which are
native to the tropics, notably the Indian Subcontinent. The primary
commercial indigo species in Asia was true indigo (Indigofera tinctoria,
also known as I. sumatrana). A common alternative used in the relatively
colder subtropical locations such as Japan's Ryukyu Islands and Taiwan
is Strobilanthes cusia.
Until the introduction of Indigofera species from the south, Polygonum
tinctorum (dyer's knotweed) was the most important blue dyestuff in East
Asia; however, the crop produced less dyestuff than the average crop of
indigo, and was quickly surpassed in favour of the more
11
economical Indigofera tinctoria plant. In Central and South America, the
species grown is Indigofera suffruticosa, also known as anil, and in India,
an important species was Indigofera arrecta, Natal indigo. In
Europe, Isatis tinctoria, commonly known as woad, was used for dyeing
fabrics blue, containing the same dyeing compounds as indigo, also
referred to as indigo.
Several plants contain indigo, which, when exposed to an oxidizing
source such as atmospheric oxygen, reacts to produce indigo dye;
however, the relatively low concentrations of indigo in these plants make
them difficult to work with, with the color more easily tainted by other
dye substances also present in these plants, typically leading to a greenish
tinge.
The precursor to indigo is indican, a colorless, water-soluble derivative of
the amino acid tryptophan, and Indigofera leaves contain as much as 0.2–
0.8% of this compound. Pressing cut leaves into a vat and soaking
hydrolyzes the indican, releasing β-d-glucose and indoxyl. The indoxyl
dimerizes in the mixture, and after 12-15 hours of fermentation yields the
yellow, water soluble leucoindigo.
Subsequent exposure to air forms the blue, water-insoluble indigo
dye. The dye precipitates from the fermented leaf solution upon oxidation,
but may also be precipitated when mixed with a strong base such as lye.
The solids are filtered, pressed into cakes, dried, and powdered. The
powder was then mixed with various other substances to produce different
shades of blue and purple.
Natural sources of indigo also include mollusks; the Murex genus of sea
snails produces a mixture of indigo and 6,6′-dibromoindigo (red), which
together produce a range of purple hues known as Tyrian purple. Light
exposure during part of the dyeing process can convert the dibromoindigo
into indigo, resulting in blue hues known as royal blue, hyacinth purple,
or tekhelet.
12
Chemical synthesis:
Given its economic importance, indigo has been prepared by many

methods. The Baeyer-Drewson indigo synthesis dates back to 1882. It
involves an aldol condensation of o-nitrobenzaldehyde with acetone,
followed by cyclization and oxidative dimerization to indigo. This route
was highly useful for obtaining indigo and many of its derivatives on the
laboratory scale, but proved impractical for industrial-scale synthesis.
Johannes Pfleger and Karl Heumann [de] eventually came up with
industrial mass production synthesis from aniline by using mercury as a
catalyst. The method was discovered by an accident by Karl Heumann in
Zurich which involved a broken thermometer.
The first commercially practical route of producing indigo is credited to
Pfleger in 1901. In this process, N-phenylglycine is treated with a molten
mixture of sodium hydroxide, potassium hydroxide, and sodamide. This
highly sensitive melt produces indoxyl, which is subsequently oxidized in
air to form indigo. Variations of this method are still in use today.
An alternative and also viable route to indigo is credited to Heumann in
1897. It involves heating N-(2-carboxyphenyl)glycine to 200 °C (392 °F)
in an inert atmosphere with sodium hydroxide. The process is easier than
the Pfleger method, but the precursors are more expensive.
13
Indoxyl-2-carboxylic acid is generated. This material readily
decarboxylates to give indoxyl, which oxidizes in air to form indigo. The
preparation of indigo dye is practised in college laboratory classes
according to the original Baeyer-Drewsen route.
History:
Indigo, historical dye collection of the Technical University of Dresden,
Germany The oldest known fabric dyed indigo, dated to 6,000 years ago,
was discovered in Huaca Prieta, Peru.[8] Many Asian countries, such
as India, China, Japan, and Southeast Asian nations have used indigo as a
dye (particularly for silk) for centuries.
The dye was also known to ancient civilizations
in Mesopotamia, Egypt, Britain, Mesoamerica, Peru, Iran, and West
Africa. Indigo was also cultivated in India, which was also the earliest
major center for its production and processing.[9] The Indigofera
tinctoria species was domesticated in India.[9] Indigo, used as a dye,
made its way to the Greeks and the Romans, where it was valued as a
luxury product.[9]
In Mesopotamia, a neo-Babylonian cuneiform tablet of the seventh
century BC gives a recipe for the dyeing of wool, where lapis-colored
wool (uqnatu) is produced by repeated immersion and airing of the
cloth.[10] Indigo was most probably imported from India. The Romans
used indigo as a pigment for painting and for medicinal and cosmetic
purposes. It was a luxury item imported to the Mediterranean from India
by Arab merchants.
India was a primary supplier of indigo to Europe as early as the Greco-
Roman era. The association of India with indigo is reflected in the Greek
word for the dye, indikón (Ἰνδικόν, Indian).[10] The
Romans latinized the term to indicum, which passed into Italian
dialect and eventually into English as the word indigo.
14
In Bengal indigo cultivators revolted against exploitative working
conditions created by European merchants and planters in what became
known as the Indigo revolt in 1859. The Bengali play Nil Darpan by
Indian playwright Dinabandhu Mitra was a fictionalized retelling of the
revolt.
Dyeing technology:
Indigo white:
Indigo is a challenging dye because it is not soluble in water. To be
dissolved, it must undergo a chemical change (reduction). Reduction
converts indigo into "white indigo" (leuco-indigo). When a submerged
fabric is removed from the dyebath, the white indigo quickly combines
with oxygen in the air and reverts to the insoluble, intensely colored
indigo.
When it first became widely available in Europe in the 16th century,
European dyers and printers struggled with indigo because of this
distinctive property.
It also required several chemical manipulations, some involving toxic
materials, and presented many opportunities to injure workers. In the 19th
century, English poet William Wordsworth referred to the plight of indigo
dye workers of his hometown of Cockermouth in his autobiographical
poem The Prelude. Speaking of their dire working conditions and the
empathy that he felt for them, he wrote:
15
Doubtless, I should have then made common cause With some who
perished; haply perished tooA poor mistaken and bewildered offering
Unknown to those bare souls of miller blue.
A pre-industrial process for production of indigo white, used in Europe,
was to dissolve the indigo in stale urine, which contains ammonia. A more
convenient reductive agent is zinc. Another pre-industrial method, used in
Japan, was to dissolve the indigo in a heated vat in which a culture
of thermophilic, anaerobic bacteria was maintained. Some species of such
bacteria generate hydrogen as a metabolic product, which convert
insoluble indigo into soluble indigo white. Cloth dyed in such a vat was
decorated with the techniques of shibori (tie-dye), kasuri, katazome,
and tsutsugaki. Examples of clothing and banners dyed with these
techniques can be seen in the works of Hokusai and other artists.
Direct printing:
Two different methods for the direct application of indigo were developed
in England in the 18th century and remained in use well into the 19th
century. The first method, known as 'pencil blue' because it was most often
applied by pencil or brush, could be used to achieve dark hues. Arsenic
trisulfide and a thickener were added to the indigo vat. The arsenic
compound delayed the oxidation of the indigo long enough to paint the
dye onto fabrics.
The second method was known as 'China blue' due to its resemblance to
Chinese blue-and-white porcelain. Instead of using an indigo solution
directly, the process involved printing the insoluble form of indigo onto
the fabric. The indigo was then reduced in a sequence of baths of iron(II)
sulfate, with air oxidation between each immersion. The China blue
process could make sharp designs, but it could not produce the dark hues
possible with the pencil blue method.
16
Around 1880, the 'glucose process' was developed. It finally enabled the
direct printing of indigo onto fabric and could produce inexpensive dark
indigo prints unattainable with the China blue method.
Since 2004, freeze-dried indigo, or instant indigo, has become available.
In this method, the indigo has already been reduced, and then freeze-dried
into a crystal. The crystals are added to warm water to create the dye pot.
As in a standard indigo dye pot, care has to be taken to avoid mixing in
oxygen. Freeze-dried indigo is simple to use, and the crystals can be stored
indefinitely as long as they are not exposed to moisture.
Chemical properties :
Indigo dye is a dark blue crystalline powder that sublimes at 390–392 °C
(734–738 °F). It is insoluble in
water, alcohol, or ether, but soluble
in DMSO, chloroform, nitrobenzene, and
concentrated sulfuric acid. The chemical
formula of indigo is C16H10N2O2.
The molecule absorbs light in the orange part of the spectrum (λmax =
613 nm).[30] The compound owes its deep color to the conjugation of
the double bonds, i.e. the double bonds within the molecule are adjacent
and the molecule is planar. In indigo white, the conjugation is interrupted
because the molecule is non-planar.
Indigo derivatives
17
The benzene rings in indigo can be modified to give a variety of related
dyestuffs. Thioindigo, where the two NH groups are replaced by S atoms,
is deep red. Tyrian purple is a dull purple dye that is secreted by a common
Mediterranean snail. It was highly prized in antiquity. In 1909, its
structure was shown to be 6,6'-dibromoindigo (red). 6-bromoindigo
(purple) is a component as well. It has never been produced on a
commercial basis. The related Ciba blue (5,7,5′,7′-tetrabromoindigo) is,
however, of commercial value.
Indigo and its derivatives featuring intra- and intermolecular hydrogen
bonding have very low solubility in organic solvents. They can be made
soluble using transient protecting groups such as the tBOC group, which
suppresses intermolecular bonding. Heating of the tBOC indigo results in
efficient thermal deprotection and regeneration of the parent H-bonded
pigment.
Treatment with sulfuric acid converts indigo into a blue-green derivative
called indigo carmine (sulfonated indigo). It became available in the mid-
18th century. It is used as a colorant for food, pharmaceuticals, and
cosmetics.
Indigo as an organic semiconductor:
Indigo and some of its derivatives are known to be ambipolar organic
semiconductors when deposited as thin films by vacuum evaporation.
18
Safety and the environment:
Indigo has a low oral toxicity, with an LD50 of 5 g/kg (0.5% of total mass)
in mammals. In 2009, large spills of blue dyes had been reported
downstream of a blue jeans manufacturer in Lesotho.
The compound has been found to act as an agonist of the aryl hydrocarbon
receptor.
Classification as a spectral color

The Early Modern English word indigo
referred to the dye, not to the color (hue)
itself, and indigo is not traditionally part
of the basic color-naming
system. Modern sources place indigo in
the electromagnetic spectrum between
420 and 450 nanometers, which lies on
the short-wave side of color wheel
(RGB) blue, towards (spectral) violet.
The correspondence of this definition
with colors of actual indigo dyes,
though, is disputed. Optical scientists
19
Hardy and Perrin list indigo as between 445 and 464 nm
wavelength,[20] which occupies a spectrum segment from roughly the
color wheel (RGB) blue extending to the long-wave side, towards azure.
Isaac Newton introduced indigo as one of the seven base colors of his
work. In the mid-1660s, when Newton bought a pair of prisms at a fair
near Cambridge, the East India Company had begun importing indigo dye
into England, supplanting the homegrown woad as source of blue dye. In
a pivotal experiment in the history of optics, the young Newton shone a
narrow beam of sunlight through a prism to produce a rainbow-like band
of colors on the wall.
In describing this optical spectrum, Newton acknowledged that the
spectrum had a continuum of colors, but named seven: "The originall or
primary colours are Red, yellow, Green, Blew, & a violet purple; together
with Orang, Indico, & an indefinite varietie of intermediate
gradations." He linked the seven prismatic colors to the seven notes of a
western major scale, as shown in his color wheel, with orange and indigo
as the semitones. Having decided upon seven colors, he asked a friend to
repeatedly divide up the spectrum that was projected from the prism onto
the wall:
20
I desired a friend to draw with a pencil lines cross the image, or pillar of
colours, where every one of the seven aforenamed colours was most full
and brisk, and also where he judged the truest confines of them to be,
whilst I held the paper so, that the said image might fall within a certain
compass marked on it. And this I did, partly because my own eyes are not
very critical in distinguishing colours, partly because another, to whom I
had not communicated my thoughts about this matter, could have nothing
but his eyes to determine his fancy in making those marks.
Indigo is therefore counted as one of the traditional colors of the rainbow,

the order of which is given by the mnemonics "Richard of York gave battle
in vain" and Roy G. Biv. James Clerk Maxwell and Hermann
von Helmholtz accepted indigo as an appropriate name for the color
flanking violet in the spectrum.
Later scientists concluded that Newton named the colors differently from
current usage. According to Gary Waldman, "A careful reading of
Newton's work indicates that the color he called indigo, we would
normally call blue; his blue is then what we would name blue-
green or cyan."[28] If this is true, Newton's seven spectral colors would
have been:
21
The human eye does not readily differentiate hues in the wavelengths
between what are now called blue and violet. If this is where Newton
meant indigo to lie, most individuals would have difficulty distinguishing
indigo from its neighbors.
According to Isaac Asimov, "It is customary to list indigo as a color lying
between blue and violet, but it has never seemed to me that indigo is worth
the dignity of being considered a separate color. To my eyes, it seems
merely deep blue."
Modern color scientists typically divide the spectrum between violet and
blue at about 450 nm, with no indigo.
22
In nature:
Male indigobirds are a very dark, metallic blue. native
to North America, is mostly bright cerulean blue with
an indigo head. The related blue grosbeak is, ironically,
more indigo than the indigo bunting.
Fungi:
An upturned Lactarius indigo mushroom Lactarius
indigo is one of the very few species
of mushrooms colored in tones of blue.
Snakes:
Eastern indigo snake The eastern indigo
snake, Drymarchon couperi, of the southeastern United
States, is a dark blue/black.
23
In cultur:
Business:
IndiGo is an Indian budget airline that uses an indigo logo and
operates only Airbus A320s. Indigo Books and Music uses an
indigo logo and has sometimes referred to the color as "blue" in
advertising.
The GameCube was initially released in 2 color variants,
including one bearing the title of 'Indigo', with the main console
and controllers in that color.
Computer graphics:
Electric indigo is sometimes used as a glow color for computer
graphics lighting, possibly because it seems to change color from
indigo to lavender when blended with white.
Dyes:
Indigo dye was used to dye denim, giving the original 'blue jeans'
their distinctive colour. The original Postal Worker uniform
contained indigo dye, partly due to the dye not running when wet.
Guatemala, as of 1778, was considered one of the world's
foremost providers of indigo.
In Mexico, indigo is known as añil.[40] After silver,
and cochineal to produce red, añil was the most important
product exported by historical Mexico.
24
The use of añil is survived in the Philippines, particularly in the
Visayas and Mindanao. The powder dye is mixed with vinegar to
be applied to the cheek of a person suffering from mumps.
Food:
Scientists discovered in 2008 that when a banana becomes ripe, it
glows bright indigo under a black light. Some insects, as well as
birds, see into the ultraviolet, because they are tetrachromats and
can use this information to tell when a banana is ready to eat. The
glow is the result of a chemical created as the green chlorophyll in
the peel breaks down.
Literature:
Marina Warner's novel Indigo (1992) is a retelling of
Shakespeare's The Tempest and features the production of indigo
dye by Sycorax.
Military:
The French Army adopted dark blue indigo at the time of
the French Revolution, as a replacement for the white uniforms
previously worn by the Royal infantry regiments. In
1806, Napoleon decided to restore the white coats because of
shortages of indigo dye imposed by the British continental
blockade. However, the greater practicability of the blue color led
to its retention, and indigo remained the dominant color of French
military coats until 1914.
Popular culture:
25
In the Better Call Saul episode "Hero", Howard Hamlin mentions
that his law firm Hamlin Hamlin & McGill trademarked a colour
called "Hamlindigo" whilst confronting Jimmy McGill over
trademark infringement in a billboard advertisement he produced
for his own legal services.
Spirituality:
The spiritualist applications use electric indigo, because the color
is positioned between blue and violet on the spectrum.
The color electric indigo is used in New Age philosophy to
symbolically represent the sixth chakra (called Ajna), which is
said to include the third eye. This chakra is believed to be related
to intuition and gnosis (spiritual knowledge).
Alice A. Bailey used indigo as the "second ray", representing
"Love-Wisdom", in her Seven Rays system classifying people
into seven metaphysical psychological types.
Psychics often associate indigo paranormal auras with an interest
in religion or with intense spirituality and intuition. Indigo
children are said to have predominantly indigo auras. People with
indigo auras are said to favor occupations such as computer
analyst, animal caretaker, and counselor.
In Wicca, it represents emotion, fluidity, insight, and
expressiveness. It is used to spiritually heal.
26
P age |0
0|Page
Contents
Abstract: ..................................................................................... 2
1. Introduction: ........................................................................... 3
2. Hair dye ingredients: .............................................................. 4
3. Hair Dye-Induced Toxicities and Adverse Health Effects ...... 13
3.1. Contact Allergy and Hair Loss .......................................... 13
3.2. Respiratory Sensitization, Allergies, And Other Diseases 16
3.3. Hair Dye Poisoning .......................................................... 16
3.4. Reproductive Toxicity and Disruption of Thyroid Hormone
Synthesis ................................................................................ 17
4. Conclusion ............................................................................ 18
References ................................................................................ 19
1|Page
Abstract:
Given the worldwide popularity of hair

dyeing, there is an urgent need to understand
the toxicities and risks associated with
exposure to chemicals found in hair dye
formulations. Hair dyes are categorized as
oxidative and nonoxidative in terms of their
chemical composition and ingredients. For
several decades, the expert panel’s Cosmetic
Ingredient Review (CIR) has assessed the
safety of many of the chemicals used in hair
dyes; however, a comprehensive review of hair dye ingredients and the risk of
exposure to hair dyeing has not been documented. Herein, we review the safety of
the various chemicals in oxidative and nonoxidative hair dyes, toxicities associated
with hair dyeing, and the carcinogenic risks related to hair dyeing. While many
compounds are considered safe for users at the concentrations in hair dyes, there
are conﬂicting data about a large number of hair dye formulations. The CIR expert
panel has ratified a number of coloring ingredients for hair dyes and banned a
series of chemicals as carcinogenic to animals and unsafe for this application.
The use of these chemicals as raw materials for producing hair dyes may result in
the synthesis of other contaminants with potential toxicities and increased risk of
carcinogenesis. It is an open question whether personal or occupational hair dyeing
increases the risk of cancer; however, in specific subpopulations, a positive
association between hair dye use and cancer occurrence has been reported. To
address this question, a better understanding of the chemical and mechanistic basis
of the reported toxicities of hair dye mixtures and individual hair dye ingredients is
needed. It is anticipated that in-depth chemical and systems toxicology studies
harnessing modern and emerging techniques can shed light on this public health
concern in the future.
2|Page
1. Introduction:
About 33% of women over the age of 18 and more than 10% of men over age 40 in
Europe and the United States dye their hair.1 Given this popularity, it is critical to
assess the toxicity and carcinogenicity of hair dyes and their ingredients. Thanks to
the expert panel’s Cosmetic Ingredient Review (CIR), a large number of candidate
coloring ingredients have undergone safety assessment prior to use in hair dyes.
Modern hair dyes are classified as oxidative or nonoxidative, and their color
durability is referred to as temporary (8−12 washings), semipermanent (∼24
washings), or permanent (until hair grows out), in terms of their formulation (Table
1).2 As far as the chemical composition is concerned, oxidative hair
dye products are often referred to as permanent or semipermanent, while

nonoxidative hair dye products are considered temporary or semipermanent.
Nonoxidative compounds are used in temporary and semipermanent hair dyes,
which are used to directly dye natural hair.2−4 Oxidative dyes were introduced as
permanent hair dyes at the end of the 19th century and experienced explosive
growth after 1970; a variety of new permanent oxidative chemical hair dyes
currently dominate the global hair dye market. Permanent hair dyes account for the
highest market share of all modern hair dyes in Asia, America, and Europe.5
Because of the increasing number of users and the growing economic share, hair
dyeing has been pinpointed as a public health concern, urgently needing evaluation
of the toxicity and carcinogenicity related to hair dyes. Because different hair dye
types with specific compounds have been employed, results of hair dye-induced
toxicity and carcinogenicity reported in the literature have been inconclusive. This
article reviewed the existing literature and available data on the safety and risks
associated with established chemicals in hair dyes. We related these compounds to
their reported toxicities and carcinogenic risks, identified the current gaps of
knowledge in the field, and proposed future directions.
3|Page
Hair dyeing
Dye category Composition Hair dyeing type
process
Water-soluble
acidic and basic
Temporary Non-oxidative dyes bearing azo Deposition on hair
or anthraquinone
groups
Acid and basic
dyes bearing azo
groups,
Ionic interactions
anthraquinones,
Semi-permanent Non-oxidative or van der waals
triphenylmethanes
forces
and nitro
Derivatives as
chromophores
Precursor agent,
Penetration into
Permanent Oxidative coupling agent and
hair
oxidizer
Table1. Category and Composition of Modern Hair Dyes
2. Hair dye ingredients:
2.2 Hair Dye Categories. The chemical ingredients of hair dyes vary among
formulations that involve oxidative reactions to achieve coloring and those
using nonoxidative processes.2 Temporary and semipermanent hair dyes
typically rely on nonoxidative processes, while permanent hair dyes rely on
oxidative reactions (Table 1). Temporary hair dyes are
4|Page
composed of water-soluble acidic and basic dyes bearing azo or anthraquinone
groups; they are generally regarded as more benign because they are deposited on
the hair surface and do not penetrate into the hair cortex. They do not require an
oxidizing agent and are typically removed by a single shampooing.3,4
Semipermanent hair dyes consist of acidic and basic dyes bearing azo groups,
anthraquinones, triphenyl methanes, or nitro derivatives as chromophores.
Figure 1. Chemical structures of hair dye ingredients
5|Page
Maximum
allowable Ld50
Year (mg/kg)
c Carcinog
Compound b concentratio Toxicity Ref
e-nicity
n (%)
Reduced body
weight;
darkened
thyroid glands;
N,N-
decreased
bis(hydroxyethyl)-
serum iron No
p- 1984 ≤5 264 (10)
concentration; evidence
phenylenediamine
delayed
5 sulfate salt
hypersensitivity
; allergic
contact
dermatitis
Reduced body
N-phenyl-p- weight;
phenylenediamine degenerated
No
4, N-phenyl-p- 1993 ≤1.7 464–1000 seminiferous (11)
evidence
phenylenediamine tubules; skeletal
hcl malformations;
skin irritation
Reduced body
Hydroxypropyl weight;
bis(N- degenerated
No
hydroxyethyl-p- NA ≤0.4 2186 seminiferous (12)
evidence
phenylenediamine tubules; skeletal
) 6 hcl malformations;
skin irritation
4-methoxy-m-
phenylenediamine
8, 4-methoxy-m-
Animal
phenylenediamine Skin irritation;
1978 NA 400–500 carcinogeni (13)
sulfate salt, 4- mutagenicity
city
methoxy-m-
phenylenediamine
hcl
6|Page
2-chloro-p-
Skin irritation;
phenylenediamine
reduced body No
7, 2-chloro-p- 1984 ≤1.0 NA (14)
weight; ocular evidence
phenylenediamine
irritation
sulfate salt
Skin irritation;
2-methyl-5-
mutagenicity; No
hydroxyethylamin NA ≤5 5700 (15)
allergic contact evidence
ophenol 10
dermatitis
Increased rate
P-
of formation of No
methylaminophen NA ≤1 NA (16)
methemoglobin; evidence
ol 9 sulfate salt
skin irritation
2,4-diaminophenol
Skin irritation;
11, 2,4-
severe ocular No
diaminophenol 1993 ≤0.2 240 (17)
irritation; evidence
dihydrochloride
mutagenicity
salt
Nephrotoxicity;
cytotoxicity;
skin irritation;
Animal
skin (18,1
Hydroquinone 12 1981 ≤1 627–743 carcinogeni
sensitization; 9)
city
skin
depigmentation;
mutagenicity
Reduced body
T-butyl No
1981 480–800 weights; (20)
hydroquinone 13 evidence
mutagenicity
Skin irritation;
skin
Toluene-2,5-
sensitization;
diamine 14,
ocular irritation; No (21−2
toluene-2,5- 1984 ≤4 98–102
reproductive evidence 3)
diamine sulfate
toxicity;
salt
skeletal
malformation
7|Page
Duodenal
lesions;
Toluene-3,4- No (21,2
1984 NA NA genotoxicity;
diamine 15 evidence 2)
skin
sensitization
Disperse Blue 7 No
2002 NA NA Mutagenicity (24)
16 evidence
Disperse Violet 1 No
1988 ≤1 NA Ocular irritation (25)
17 evidence
Nephrotoxicity;
chromosomal Animal
Disperse Yellow 3
1992 NA NA aberrations; carcinogeni (26)
18
allergic contact city
dermatitis
Nephrotoxicity;
chromosomal
No
Acid Violet 43 19 1984 ≤1 NA aberrations; (27)
evidence
allergic contact
dermatitis
No
Basic Blue 99 20 1992 ≤2 2000 Skin irritation (28)
evidence
1250– No
HC Blue no. 2 21 1993 ≤1.7 Mutagenicity (29)
5000 evidence
HC Yellow no. 5 No
2002 ≤1.6 555.56 Skin irritation (30)
22 evidence
Skin
No
HC Red no. 7 23 2005 ≤1 NA sensitization; (31)
evidence
mutagenicity
Table 2. Detailed of Major Hair Dye Ingredientsa Characteristics
8|Page
aFor chemical structures, refer to Figure 1.
bThe first yearly report by the Food and Drug Administration.
cThe oral LD50 in rats of aqueous solutions. Abbreviations: LD50, median lethal dose; NA, not
assessed.
Aromatic amines, such as p-phenylenediamine (PPD, 1) (Figures 1 and 2),

constitute the main class of compounds used as precursors in permanent hair dyes.
The multiple toxicological properties of PPD have been demonstrated in previous
studies; for instance, PPD induces apoptosis by increasing reactive oxygen
species. (28) During hair coloring, PPD can penetrate the skin and be absorbed by
the airway, (29) where it can then be biotransformed into N-monoacetyl-p-
phenylenediamine (MAPPD, 2) and N,N′-diacetyl-p-phenylenediamine
(DAPPD, 3) (Figure 2). A study of the transformation of PPD to MAPPD and
DAPPD using reconstituted human epidermis showed that the metabolite levels
produced depend on the dose of PPD. At concentrations of 250–1000 μM, the
formation of MAPPD was favored, while at doses below 250 μM, DAPPD was
preferentially formed. (30) PPD induces dendritic cell (DC) activation after in vitro
exposure to oxygen in air, and a positive local lymph node assay (LLNA) response
in vivo, demonstrating its intracorporeal sensitizing potential. The sensitizers
produced by PPD oxidation in both cases induced immune stimulation. In contrast,
MAPPD and DAPPD did not induce DC activation or give a positive LLNA
response. (31) The biotransformation of PDD to MAPPD or DAPPD and the
formation of sensitizers from PPD oxidation are two distinct competing pathways.
The formation of sensitizing agents is promoted when increased PPD
concentrations are present, leading to a series of PPD-related toxicities (Figure 2).
9|Page
Figure2. Mechanism of toxicity induced by p-phenylenediamine
An increase in reactive oxygen species is associated with PPD 1-induced

apoptosis. Dermal N-acetylation biotransforms PPD toward MAPPD 2 and
DAPPD 3; at concentrations up to 250 μM, it is beneficial to the MAPPD
formation, and at the concentration of 250–1000 μM, it is beneficial to the DAPPD
formation. MAPPD and DAPPD fail to activate DCs or cause a positive LLNA
response, which are considered the markers of extracorporeal and intracorporeal
sensitizing potential of chemical compounds. PPD can induce DC activation after
exposure to oxygen in air in vitro, and creates an LLNA response in vivo. The
sensitizing PPD oxidation provides some effective immune stimulation that is
associated with PPD-induced toxicity. Abbreviations: ROS, reactive oxygen
species.
N-Phenyl-p-phenylenediamine 4 (Figure 1, Table 2) is another common aromatic

amine present in hair dyes. It has been associated with toxic effects including body
weight reduction as a function of dose in rats, degeneration of the seminiferous
tubules, skeletal malformation, and skin sensitization (Table 2). (32) The EU
Scientific Committee on Consumer Products (SCCP) identified limitations in some
10 | P a g e
of these studies, such as inadequate data inclusion and noncompliance with the
Organization for Economic Cooperation and Development guidelines, but
confirmed the strong potential of N-phenyl-p-phenylenediamine to cause skin
sensitization. (33) Exposure to the structurally related N,N-bis(hydroxyethyl)-p-
phenylenediamine 5 (sulfate salt) is associated with reduction in body weight,
darkening of thyroid glands, decrease in serum iron concentration, delayed
hypersensitivity of guinea pig skin, and allergic contact dermatitis
(ACD). (6,34) Exposure to hydroxypropyl bis(N-hydroxyethyl-p-
phenylenediamine) hydrochloride salt 6 is linked to reduced body weight,
decreased mean serum glucose, attenuated total protein levels, and reproductive
and developmental problems, (8) while exposure to 2-chloro-p-
phenylenediamine 7 and its sulfate salt were linked to skin irritation, reduced body
weight and ocular irritation. (10) It should be noted that 4-methoxy-m-
phenylenediamine 8 and its hydrochloride and sulfate salts are unsafe for use in
cosmetic products due to their reported carcinogenicity in rats and mice (Table
2). (9)
Aminophenols are another class of ingredients that are widely used in hair dyes.
They are chemically synthesized by the reduction of nitrophenols and can be used
as primary intermediates in manufacturing sulfur and azo dyes. (11) They typically
undergo reactions with oxidants to produce corresponding imines that can
chemically react with coupling agents to produce indophenol dyes. (12) As a
primary intermediate, p-methylaminophenol 9 (sulfate salt) reacts with hemoglobin
at a more rapid rate than p-aminophenol to form methemoglobin, a form of
oxidized hemoglobin, and slightly irritates rabbit skin but is not considered a
dermal sensitizer. (12) The coupling agent, 2-methyl-5-
hydroxyethylaminophenol 10 is used in oxidative hair dyes at a concentration of
≤5%. It can be mutagenic, and exposure can cause skin irritation, and allergic
contact dermatitis. (11) The Food and Drug Administration (FDA) concluded that
the maximum allowable concentration of 2,4-diaminophenol 11 and its
dihydrochloride salt for use in hair dyes is 0.2%. Exposure to this compound can
lead to slight skin irritation, severe ocular irritation, and mutagenicity (Table
2). (13) Hydroquinone 12 is used as an antioxidant, fragrance, reducing agent, and
polymerization inhibitor in hair dyes, skincare products, and lipsticks. (14) Human
skin absorbs hydroquinone from both aqueous and alcoholic preparations, and
11 | P a g e
excretion of this compound involves the formation of glucuronide or sulfate
conjugates. (15) This chemical may cause nephrotoxicity, cytotoxicity, skin
irritation, skin sensitization, skin depigmentation, and mutagenicity. (14) The most
noteworthy data are related to its reported animal carcinogenicity, in which an
increased incidence of renal tubule cell tumors and leukemia was observed in F344
rats; but so far, such adverse effects on humans have not been described. (15) The
acid-catalyzed reaction of hydroquinone with isobutylene or t-butanol produces a
new crystalline solid, t-butyl hydroquinone 13, an ingredient which can cause mild
to moderate toxicity such as reduced body weight and mutagenicity in rats when
administered orally or intraperitoneally (Table 2). (16)
Diaminotoluene is chemically prepared from dinitrotoluene via a catalytic

hydrogenation procedure or from the reaction of iron, hydrochloric acid, and
dinitrotoluene. The two isomers, toluene-2,5-diamine 14 and toluene-3,4-
diamine 15, are primary intermediates that can impart different colors to permanent
hair dyes. (17) For example, toluene-2,5-diamine and its sulfate salt can color hair
black, brown, gold, or gray, and toluene-3,4-diamine makes hair brown, red, or
gold. (17) Toluene-2,5-diamine 14 can be readily absorbed through the skin, but
90% will be excreted within 24 h after absorption, with a half-time excretion of 8
h. (19) These two compounds manifested some adverse effects such as extreme
skin sensitization (35) and reproductive toxicity (Table 2); however, a maximum
concentration of 2% (calculated as free base) or 3.6% (calculated as sulfate salt)
applied to the head was considered safe with regard to systemic toxicity. (35) An
Ames test demonstrated that the presence of toluene-2,5-diamine in an oxidative
hair dye may cause mutagenicity in the TA98 test strain. (36) Further studies are
needed to determine the safety of toluene-3,4-diamine as a hair dye ingredient.
Many nonoxidative ingredients are used in temporary and semipermanent hair

dyes. (20−27) The CIR concluded that there is insufficient data available regarding
the safety of Disperse Blue 7. (20) Disperse Blue 7 16 is an anthraquinone-based
dye used as a hair ingredient in a few selected hair dyes. Disperse Violet 1 17 is a
diamino-anthraquinone dye used in temporary and semipermanent hair dyes at a
maximum concentration of 1%. To date, the only toxicity reported is ocular
irritation. (21) Acid Violet 43 19 can be used in any cosmetic product because it
showed no signs of significant toxicity. (23) Basic Blue 99 20 is the most
frequently used chemical product for hair tints. (13) HC Blue no. 2 21 is
12 | P a g e
exclusively used in hair dyes at a concentration of ≤1.7%. (25) Although this
compound is mutagenic, no carcinogenic outcomes were observed in exposure
studies with rats and mice. (25) Formulations containing HC Yellow no. 5 22 are
sold with a caution statement because of skin irritation. While some concern still
exists, the available safety test data from the CIR expert panel demonstrated that
HC Yellow no. 5 had no animal carcinogenicity as a hair dye ingredient at a
concentration of ≤1.6%; the oral LD50 in rats is 555.56 mg/kg. (26) HC Red no. 7
has been confirmed as suitable for use in hair dyes by the CIR expert panel up to
concentrations of 1% but may elicit skin irritation and mutagenicity (Table 2). (27)
3. Hair Dye-Induced Toxicities and Adverse Health Effects
3.1. Contact Allergy and Hair Loss
Hair dyeing-induced contact allergies occur frequently, which may further lead to
the occurrence of ACD and urticarial contact (Table 3). (37−40) ACD commonly
occurs on the scalp, face, and hands of hair dye users, manifesting as redness of the
skin with vesiculation or scaling (Table 3), (41,42) which reduces quality of life in
the affected individuals and can have negative socioeconomic impacts. The
presence of contact allergies is closely attributed to the potent skin sensitizers
contained in hair dyes, such as aromatic amines including PPD, a prevalent hair
dye ingredient. (43) However, using permanent hair dyes containing PPD at
concentrations ≤0.67% is unlikely to induce skin sensitization. (44) Recently,
Goebel and co-workers (45) found that a methoxymethyl side chain introduced into
PPD not only reduced the sensitizing intensity and the risk of allergic induction but
also resulted in excellent hair coloring performance.
Patch
Study Exposure Symptom test Positive
Toxicity Sex Age Ingredients Ref
duration route timing Conc. reaction
(%)
Acd 2015 F 50 Henna Hair dyeing 4d 0.01 1+ (40)
3-nitro-p-hydroxy
ethylaminophenol
Acd 2005 F 50 Hair dyeing 1d 1.00 1+ (43)
24 and 4-amino-
3-nitrophenol 25
Contact 2017 F 56 Basic blue 99 20 Hair dyeing 10 min 0.10 3+ (37)
13 | P a g e
anaphylaxis
4-amino-2-
Acd 2009 F 47 hydroxytoluene Hair dyeing Na 1.00 2+ (44)
26
Acd 2018 F 43 1-naphthol 27 Hair dyeing 2d 1.00 3+ (49)
P-
phenylenediamine
Dle 2016 F 32 Hair dyeing Na Na 2+ (55)
1 and toluene-2,5-
diamine 14
P-
Angioedema 2018 F 29 phenylenediamine Hair dyeing 1d 1.00 3+ (61)
1
P-
Neck and facial
2016 F 15 phenylenediamine Hair dyeing 3d Na 3+ (62)
swelling
1
P-
Severe facial
2014 F 33 phenylenediamine Hair dyeing 2d Na 4+ (63)
swelling
1
P-
Hair loss 2011 F 41 phenylenediamine Hair dyeing 1d 1.00 2+ (64)
1
19 P-
Pneumothorax 2011 2f ± phenylenediamine Consumption Na Na Na
(71)
1b 1
P-
Rhabdomyolysis 2013 M 3 phenylenediamine Consumption 2h Na Na (72)
1
8m 23.2 P-
2002–
Rhabdomyolysis + ± phenylenediamine Consumption Na 0.95 Na (73)
2006
2f 7.6b 1
Table 3. Hair Dye-Related Toxicity from a Case Report Study
aSymptom timing indicates the duration from exposure to symptoms.
bThese studies describe more than one case, and the age is the mean value.
cThe positive reaction is calculated in terms of the patch test of corresponding ingredients at the
patch test concentration. Abbreviations: F, female; M, male; NA, not assessed
As far as plant-based hair dyes are concerned, although the public perceives them
as safe, they can cause minor allergic reactions. For example, a small number of
case reports have documented rare cases of ACD in users of plant-based hair dyes
that contain pure henna, black tea, and indigo powder (Table 3). (46−48) There
may be several explanations for this finding. First, pure henna, black tea, and
indigo powder all contain about 15% tannins, large complex polyphenolic
14 | P a g e
molecules that could cause the observed ACD. Although allergens in tannins have
not been identified to date, the tannin-induced allergenic response is associated
with inhibition of IL-8, IL-6, and TNF-α secretion from stimulated human mast
cells. (49) The resulting color intensity that can be achieved by some plant
colorants, such as pure henna, is time dependent. (47) Some darkening substances
in proprietary formulas, such as lemon oil, vinegar, eucalyptus oil, or clove oil,
may be added along with PPD to shorten the time of application.
As hairdressers are exposed on a regular basis to hair dyes in all steps of the dyeing
process, (50) they face a significantly higher skin sensitization risk than personal
hair dye users. (51,52) The use of protective gloves during hair coloring and
warnings on the product labels that a sensitivity test is needed before application
have decreased the incidence of hair dye-induced allergies. With sufficient
protection against local and systemic exposure to oxidative hair dyes, hair coloring
is unlikely to pose a serious risk to human health. (53,54) The adoption of adequate
protective measures during the use of hair dye as well as appropriate education and
training of hairdressers are crucial for lowering occupational risks and preventing
hair dye-induced skin sensitization. (55)
Discoid lupus erythematosus (DLE) is an autoimmune skin disease that may be

caused by ACD (Table 3); it is characterized by the development of autoantibodies
that attack the skin at the interphase level. (56,57) Systemic lupus erythematosus
(SLE) is another autoimmune disease manifesting multisystem disorders in
addition to skin lesions. Although exposure to aromatic amines (such as PPD) may
give rise to the occurrence of lupus, several studies collectively confirm an
insignificant association between the use of hair dyes containing PPD and the
increased risk of SLE. (58−60) Nevertheless, skin exposure to hair dyes may
induce other severe but rare contact allergies, including neck and facial swelling
and angioedema (Table 3). (61−63) Angioedema is a type I hypersensitivity
reaction characterized by edema of the skin and subcutaneous tissues that damages
the airways and gastrointestinal tract and may even lead to life-threatening
laryngeal swelling.
Along with the increasing popularity of hair dye use, growing complaints about
hair dye-induced hair loss have been a concern of dermatologists. Isik et
al. (62) found that patients who experienced hair loss after hair dyeing presented
15 | P a g e
symptoms of ACD before or at the time of hair loss, suggesting a close correlation
between hair dye-induced ACD and hair loss (Table 3). H2O2, monoethanolamine,
and PPD in hair dyes have been proposed as the main causative ingredients of hair
dyeing-induced hair loss. (64,65) Based on histological examination conducted in
animal tests, oxidative stress may be the mechanism underlying hair-dye induced
dermatitis. (64,65) H2O2 and monoethanolamine, in particular, were shown to
synergistically induce oxidative stress and cytotoxicity in human keratinocytes, an
observation that is consistent with the histological data. (64,65)
3.2. Respiratory Sensitization, Allergies, And Other Diseases
Asthma and allergic rhinitis are common diseases that can result in
overwhelmingly negative socioeconomic impacts. (66) Hairdressers are at a high
risk of occupational rhinitis and asthma because, in daily work, they are frequently
exposed to irritants and allergens such as persulfate and PPD in hair
dyes. (67,68) A case-control study from Norway (69) showed that hairdressers
over 40 years of age were more likely to suffer asthma-like symptoms than
nonhairdressers due to their long occupational exposure to hair dye ingredients.
Therefore, hairdressers and hairdressing apprentices should undergo continuous
medical surveillance to monitor the risk factors and reduce the chance of
respiratory diseases linked to occupational exposure.
3.3. Hair Dye Poisoning
Due to the easy availability and high toxicity of PPD, people in the developing
world who want to commit suicide may attempt it by consuming this
agent. (70) Hair dye poisoning may trigger the occurrence of some urgent and fatal
outcomes, like pneumothorax, rhabdomyolysis, and acute kidney injury (AKI)
(Table 3). (71−73) Orally ingesting PPD causes severe trauma to the airway and
may lead to dyspnea, asphyxia, and other respiratory symptoms. If those ingesting
PPD suffer respiratory distress and chest pain, then caution is needed regarding the
occurrence of pneumothorax, which can be diagnosed by sonography or bedside
X-ray. The pathological underpinning of rhabdomyolysis involves calcium ions
leaking from the smooth endoplasmic reticulum, resulting in prolonged muscle
contraction and irreversible changes in muscle structure. (74) The most striking
laboratory characteristic of rhabdomyolysis is a concentration of creatine
16 | P a g e
phosphokinase in the plasma >10,000 U/L. If patients do not receive aggressive
treatment, they will eventually die. Globally, approximately 13.3 million humans
suffer from AKI per year, and more than 1 in 10 lose their life from this
disease. (75) Individuals with AKI are also at a 9-fold risk of developing chronic
kidney disease that can give rise to other organ dysfunctions. The characterized
pathological manifestations of AKI include glomerular hyperemia, acute tubular
necrosis, intratubular casts, and tubulointerstitial hemorrhages as well as mesangial
hyperplasia. Hair dye-induced AKI occurs in a dose-dependent manner, but even
with no intervention, the injured kidney may recover over time. (74)
3.4. Reproductive Toxicity and Disruption of Thyroid Hormone Synthesis
Zebrafish embryos are suitable animal models for studying how hair dyes affect
embryonic growth. Two studies by Manjunatha et al. (76,77) demonstrated that
exposure to hair dyes induced morphological and physiological abnormalities in
zebrafish embryos, which provoked interest in determining whether hair dyes
could affect human embryo development. Abnormal birth weight in humans (live
birth weight <2500 g or >4000 g) reflects the poor health of the fetus and mother,
which could contribute to the occurrence of obesity, malnutrition, hypertension,
cardiovascular diseases, and cancer in the child in the future. (78) In terms of hair
dyeing, the risk of infantile abnormal birth weight is elevated when mothers have
irregular menstruation or have used hair dyes before pregnancy; the risk is
increased if both factors exist. (79)
Resorcinol 28 is widely used as a component in hair dyes and cosmetics, and

administration to rodents at high doses (>520 mg/kg/d) over 2 years disrupted
thyroid hormone synthesis and caused goitrogenic effects. (80) Dermatological
clinical reports indicated that frequent external application of ointments containing
a high concentration of resorcinol (>34 mg/kg/d) to integrity-compromised human
skin for several months to years can also induce thyroid side effects. (80) However,
a risk assessment study concluded that under real-world conditions, exposure to
resorcinol contained in hair dyes and cosmetics was unlikely to cause human
thyroid dysfunction. (80)
17 | P a g e
4. Conclusion
Hair dyeing formulations are generally categorized into oxidative and

nonoxidative types. Based on the safety assessment by the CIR expert panel
and the FDA, a series of oxidative and nonoxidative chemicals have been
assessed as safe for use in hair dyes, and an important aspect of this safety is
based on the concentration of the compound(s) found in the hair dye. Personal or
occupational exposure to hair dyes may still cause several kinds of toxicity and
side effects, in which ACD is the most frequent with pneumothorax,
rhabdomyolysis, and AKI being the most life-threatening. Although evidence in
recent decades has not drawn a consistent conclusion about the correlation
between hair dye use and risk of carcinogenesis, we cannot overlook that a
positive association of hair dye use and cancer occurrence is reported in specific
subpopulations. Moreover, maternal hair dyeing during the month before
pregnancy, during pregnancy, or during breastfeeding is a risk factor for the
occurrence of leukemia, brain tumors, and MGCTs in the offspring. An increasing
body of studies indicates the need for ascertaining the association between hair
dyeing and the carcinogenic risks in more specific subpopulations and
investigating the molecular mechanism of hair dye chemical-induced toxicity and
carcinogenicity. Overall, the association between personal hair dye use and
cancer risk is likely to remain a debated topic. While the consensus opinion from
the major cancer research centers suggests that there is not adequate evidence
to link the practice of hair dyeing to cancer, several studies highlight hair dye-
related toxicity and carcinogenicity as a public health concern. Given the amount
of conflicting data, more in-depth chemical and systems toxicology studies are
needed to better understand the risks associated with exposure to hair dyes and
to address this important public health concern. Studies evaluating not only the
risk of exposure to isolated hair dye ingredients but also to these compounds in
the context of chemical mixtures will allow an assessment of the cumulative risk
(exposure to multiple agents) and the interaction of exposures to multiple
chemicals present in combination in hair dyes. Systems-based strategies,
involving quantitative modeling, can shed light on the exposure-induced cellular
and molecular alterations that might not be detected otherwise. It is anticipated
that these current and emerging methods in toxicology can allow for a
significantly superior assessment of complex mixtures such as hair dyes and
therefore further support data-driven and fact-based evaluation of this public
health concern.
18 | P a g e
References
Gera, R.; Mokbel, R.; Igor, I.; Mokbel, K. Does the Use of Hair Dyes Increase the
Risk of Developing Breast Cancer? A Meta-analysis and Review of the
Literature. Anticancer Res. 2018, 38 (2), 707– 716, DOI:
10.21873/anticanres.12276
Hedberg, Y. S.; Uter, W.; Banerjee, P.; Lind, M. L.; Skovvang Steengaard, S.; Teo,
Y.; Lidén, C. Non-oxidative hair dye products on the European market: What do
they contain?. Contact dermatitis 2018, 79 (5), 281– 7, DOI: 10.1111/cod.13074
Piérard, G. E.; Goffin, V.; Piérard-Franchimont, C. Corneosurfametry: a predictive

assessment of the interaction of personal-care cleansing products with human
stratum corneum. Dermatology (Basel, Switzerland) 2004, 189 (2), 152– 6, DOI:
10.1159/000246820
Diamante, C.; Bergfeld, W. F.; Belsito, D. V.; Klaassen, C. D.; Marks, J. G.,
Jr; Shank, R. C.; Slaga, T. J.; Snyder, P. W.; Alan Andersen, F. Final report on the
safety assessment of Basic Violet 1, Basic Violet 3, and Basic Violet 4. Int. J.
Toxicol. 2009, 28 (6 Suppl 2), 193S– 204S, DOI: 10.1177/1091581809354649
Zhang, Y.; Birmann, B. M.; Han, J.; Giovannucci, E. L.; Speizer, F. E.; Stampfer,
M. J.; Rosner, B. A.; Schernhammer, E. S. Personal use of permanent hair dyes
and cancer risk and mortality in US women: prospective cohort
study. BMJ. 2020, 370, m2942, DOI: 10.1136/bmj.m2942
6
19 | P a g e
Panel TCIRE Final Report on the Safety Assessment of N,N-Bis(Hydroxyethyl)-p-
Phenylenediamine Sulfate. Int. J. Toxicol. 1992, 11 (1), 129– 142, DOI:
10.3109/10915819209141994
Andersen, F. A. Final report on the safety assessment of N-Phenyl-p-

Phenylenediamine, N- Phenyl-p-Phenylenediamine hydrochloride, and N-Phenyl-
p-Phenylenediamine sulfate. Journal of the American college of
toxicology 1994, 13 (5), 374– 394, DOI: 10.3109/10915819409140613
Becker, L. C.; Bergfeld, W. F.; Belsito, D. V.; Hill, R. A.; Klaassen, C. D.; Liebler,
D. C.; Marks, J. G., Jr; Shank, R. C.; Slaga, T. J.; Snyder, P. W.; Andersen, F.
A. Safety Assessment of Hydroxypropyl Bis(N-Hydroxyethyl-p-
Phenylenediamine) HCl as Used in Cosmetics. Int. J. Toxicol. 2016, 35 (2
suppl), 5s– 11s, DOI: 10.1177/1091581816659258
Skinner, J. P. Final report on the safety assessment of 4-Methoxy-m-

Phenylenediamine, 4-Methoxy-m-Phenylenediamine sulfate, and 4-Methoxy-m-
Phenylenediamine-HCl. Journal of the American college of
toxicology 1992, 11 (4), 381– 422, DOI: 10.3109/10915819209141882
10
Willis, L. Final report on the safety assessment of 2-Chloro-p-Phenylenediamine

and 2-Chloro-p-Phenylenediamine Sulfate. Journal of the American college of
toxicology 1992, 11 (4), 521– 530, DOI: 10.3109/10915819209141890
11
20 | P a g e
Panel TCIRE Final Report on the Safety Assessment of 2-Methyl-5-
Hydroxyethylaminophenol. Int. J. Toxicol. 1990, 9 (2), 185– 202, DOI:
10.3109/10915819009078733
12
Panel TCIRE Final Report on the Safety Assessment of p-Methylaminophenol

Sulfate. International journal of toxicology 1991, 10 (1), 53– 65
13
Andersen, F. A. Final report on the safety assessment of 2,4-Diaminophenol and

2,4- Diaminophenol Dihydrochloride. Journal of the American college of
toxicology 1994, 13 (5), 330– 343, DOI: 10.3109/10915819409140610
14
Panel TCIRE Addendum to the final report on the safety assessment of

Hydroquinone. Journal of the American college of toxicology 1994, 13 (3), 167–
230, DOI: 10.3109/10915819409141000
15
Andersen, F. A.; Bergfeld, W. F.; Belsito, D. V.; Hill, R. A.; Klaassen, C.

D.; Liebler, D. C.; Marks, J. G., Jr; Shank, R. C.; Slaga, T. J.; Snyder, P. W. Final
amended safety assessment of hydroquinone as used in cosmetics. Int. J.
Toxicol. 2010, 29 (6), 274S– 87S, DOI: 10.1177/1091581810385957
16
Panel TCIRE Final Report on the Safety Assessment of t-Butyl

Hydroquinone. International journal of toxicology 1991, 10 (1), 1– 7, DOI:
10.3109/10915819109078618
17
Pang, S. N. J. Final report on the safety assessment of toluene-2,5-diamine,

toluene-2,5-diamine sulfate, and toluene-3,4-diamine. Journal of the American
college of toxicology 1992, 11 (4), 423– 445, DOI: 10.3109/10915819209141883
18
21 | P a g e
Burnett, C. L.; Bergfeld, W. F.; Belsito, D. V.; Klaassen, C. D.; Marks, J. G.,
Jr; Shank, R. C.; Slaga, T. J.; Snyder, P. W.; Alan Andersen, F. Final amended
report of the safety assessment of toluene-2,5-diamine, toluene-2,5-diamine
sulfate, and toluene-3,4-diamine as used in cosmetics. International journal of
toxicology 2010, 29 (3_suppl), 61S– 83S, DOI: 10.1177/1091581810361964
19
Schettgen, T.; Heinrich, K.; Kraus, T.; Gube, M. Determination of 2,5-

toluylenediamine (2,5-TDA) and aromatic amines in urine after personal
application of hair dyes: kinetics and doses. Archives of
toxicology 2011, 85 (2), 127– 33, DOI: 10.1007/s00204-010-0563-3
20
Panel TCIRE Final report on the safety assessment of disperse Blue

7. International journal of toxicology 2007, 26 (Suppl 2), 65– 77, DOI:
10.1080/10915810701351210
21
Panel TCIRE Final Report on the Safety Assessment of Disperse

Violet. International journal of toxicology 1991, 10 (1), 103– 111, DOI:
10.3109/10915819109078618
22
Andersen, F. A. Final report on the safety assessment of Disperse Yellow

3. Journal of the American college of toxicology 1996, 15 (4), 311– 319, DOI:
10.3109/10915819609008723
23
Fiume, M. Z. Final report on the safety assessment of Acid Violet 43. International
journal of toxicology 2001, 20 (Suppl 3), 1– 6, DOI:
10.1080/10915810152902547
22 | P a g e
24
Panel TCIRE Final report on the safety assessment of Basic Blue 99. International
10.1080/10915810701351202
25
Andersen, F. A. Final report on the safety assessment of HC Blue No. 2. Journal of

the American college of toxicology 1994, 13 (5), 361– 373, DOI:
10.3109/10915819409140612
26
Panel TCIRE Final report on the safety assessment of HC Yellow No.

5. International journal of toxicology 2007, 26 (Suppl 2), 113– 124, DOI:
10.1080/10915810701351244
27
Panel TCIRE Final report on the safety assessment of HC Red No. 7. International
10.1080/10915810802032438
28
Chye, S. M.; Tiong, Y. L.; Yip, W. K.; Koh, R. Y.; Len, Y. W.; Seow, H. F.; Ng,
K. Y.; Ranjit, D. A.; Chen, S. C. Apoptosis induced by para-phenylenediamine
involves formation of ROS and activation of p38 and JNK in chang liver
cells. Environmental toxicology 2014, 29 (9), 981– 990, DOI: 10.1002/tox.21828
29
Abd-ElZaher, M. A.; Fawzy, I. A.; Ahmed, H. M.; Abd-Allah, A. M.; Gayyed, M.

F. Some toxicological health hazards associated with subchronic dermal exposure
to paraphenylene-diamine (PPD): An experimental study. Egyptian journal of
forensic sciences 2012, 2 (3), 105– 11, DOI: 10.1016/j.ejfs.2012.06.003
30
23 | P a g e
Nohynek, G. J.; Duche, D.; Garrigues, A.; Meunier, P. A.; Toutain, H.; Leclaire,
J. Under the skin: Biotransformation of para-aminophenol and para-
phenylenediamine in reconstructed human epidermis and human
hepatocytes. Toxicology letters 2005, 158 (3), 196– 212, DOI:
10.1016/j.toxlet.2005.03.014
31
Aeby, P.; Sieber, T.; Beck, H.; Gerberick, G. F.; Goebel, C. Skin sensitization to p-
phenylenediamine: the diverging roles of oxidation and N-acetylation for dendritic
cell activation and the immune response. Journal of investigative
dermatology 2009, 129 (1), 99– 109, DOI: 10.1038/jid.2008.209
32
Singh, R. L.; Khanna, S. K.; Shanker, R.; Singh, G. B. Acute and short-term
toxicity studies on p-aminodiphenylamine. Veterinary and human
toxicology 1986, 28 (3), 219– 223
33
SCCP. Opinion on N-Phenyl-p-phenylenediamine; European

Commission: Brussels, 2006. https://ec.europa.eu/health/ph_risk/committees/04_sc
cp/docs/sccp_o_089.pdf (accessed).
34
Hagiwara, A.; Miyata, E.; Tamano, S.; Shibata, M.-A.; Sugiura, S.; Inoue,
M.; Hirose, M. Non-Carcinogenicity of 2,2′-[(4-Aminophenyl)imino]bisethanol
Sulfate in a Long-term Feeding Study Fischer 344 Rats. Food and chemical
toxicology 1996, 34 (6), 537– 546, DOI: 10.1016/0278-6915(96)00010-5
35
SCCP. Opinion on toluene-2,5-diamine and its sulfate; European

Commission: Brussels, 2012. https://op.europa.eu/en/publication-detail/-
/publication/68467996-7b0d-4bce-bf8f-cbd38adbd91d (accessed).
36
24 | P a g e
Zhou, S.; Li, R.; Zhang, Z.; Gu, M.; Zhu, H.; Fang, J.; Ji, Z.; Xu, X.; Tang,
L. Analysis of mutagenic components of oxidative hair dyes with the Ames
test. Human & experimental toxicology 2021, 40 (11), 1921– 1937, DOI:
10.1177/09603271211013433
37
Montgomery, R.; Wilkinson, M. Allergic contact urticaria secondary to hair dye

use. Contact dermatitis 2017, 77 (4), 257– 9, DOI: 10.1111/cod.12811
38
Søsted, H.; Menné, T. Allergy to 3-nitro-p-hydroxyethylaminophenol and 4-

amino-3-nitrophenol in a hair dye. Contact dermatitis 2005, 52 (6), 317– 9, DOI:
10.1111/j.0105-1873.2005.00583.x
39
Washio, K.; Ijuin, K.; Fukunaga, A.; Nagai, H.; Nishigori, C. Contact anaphylaxis
caused by Basic Blue 99 in hair dye. Contact dermatitis 2017, 77 (2), 122–
3, DOI: 10.1111/cod.12740
40
Ellis, R. A.; Wilkinson, S. M. Contact dermatitis to 4-amino-2-hydroxytoluene in

hair dye. Contact dermatitis 2009, 60 (2), 118– 9, DOI: 10.1111/j.1600-
0536.2008.01491.x
41
Søsted, H.; Agner, T.; Andersen, K. E.; Menné, T. 55 Cases of allergic reactions to
hair dye: A descriptive, consumer complaint-based study. Contact
dermatitis 2002, 47 (5), 299– 303, DOI: 10.1034/j.1600-0536.2002.470508.x
42
King, T.; Sabroe, R.; Holden, C. Allergic contact dermatitis caused by 1-naphthol,
a red coupler, in a purple permanent oxidative hair dye. Contact
dermatitis 2018, 79 (2), 99– 100, DOI: 10.1111/cod.12997
43
25 | P a g e
Gregoriou, S.; Mastraftsi, S.; Hatzidimitriou, E.; Tsimpidakis, A.; Nicolaidou,
E.; Stratigos, A.; Katsarou, A.; Rigopoulos, D. Occupational and non-occupational
allergic contact dermatitis to hair dyes in Greece. A 10-year retrospective
study. Contact dermatitis 2020, 83 (4), 277– 85, DOI: 10.1111/cod.13598
44
Towle, K. M.; Hwang, R. Y.; Fung, E. S.; Hollins, D. M.; Monnot, A. D. Hair dye
and risk of skin sensitization induction: a product survey and quantitative risk
assessment for para-phenylenediamine (PPD). Cutaneous and ocular
toxicology 2020, 39 (4), 311– 6, DOI: 10.1080/15569527.2020.1802740
45
Goebel, C.; Troutman, J.; Hennen, J.; Rothe, H.; Schlatter, H.; Gerberick, G.
F.; Blömeke, B. Introduction of a methoxymethyl side chain into p-
phenylenediamine attenuates its sensitizing potency and reduces the risk of allergy
induction. Toxicology and applied pharmacology 2014, 274 (3), 480– 7, DOI:
10.1016/j.taap.2013.11.016
46
Belhadjali, H.; Akkari, H.; Youssef, M.; Mohamed, M.; Zili, J. Bullous allergic
contact dermatitis to pure henna in a 3-year-old girl. Pediatric
dermatology 2011, 28 (5), 580– 1, DOI: 10.1111/j.1525-1470.2010.01201.x
47
Lestringant, G. G.; Bener, A.; Frossard, P. M. Cutaneous reactions to henna and

associated additives. British journal of dermatology 1999, 141 (3), 598–
600, DOI: 10.1046/j.1365-2133.1999.03086.x
48
Swan, B. C.; Tam, M. M.; Higgins, C. L.; Nixon, R. L. Allergic contact dermatitis
to substitute hair dyes in a patient allergic to para-phenylenediamine: Pure henna,
black tea and indigo powder. Australasian journal of
dermatology 2016, 57 (3), 219– 21, DOI: 10.1111/ajd.12454
49
26 | P a g e
Lorenz, P.; Heinrich, M.; Garcia-Käufer, M.; Grunewald, F.; Messerschmidt,
S.; Herrick, A.; Gruber, K.; Beckmann, C.; Knoedler, M.; Huber, R.; Steinborn,
C.; Stintzing, F. C.; Gründemann, C. Constituents from oak bark (Quercus robur
L.) inhibit degranulation and allergic mediator release from basophils and mast
cells in vitro. Journal of ethnopharmacology 2016, 194, 642– 50, DOI:
10.1016/j.jep.2016.10.027
50
Lind, M. L.; Johnsson, S.; Lidén, C.; Meding, B.; Boman, A. Hairdressers’ skin
exposure to hair dyes during different hair dyeing tasks. Contact
dermatitis 2017, 77 (5), 303– 10, DOI: 10.1111/cod.12833
51
Gube, M.; Heinrich, K.; Dewes, P.; Brand, P.; Kraus, T.; Schettgen, T. Internal
exposure of hairdressers to permanent hair dyes: a biomonitoring study using
urinary aromatic diamines as biomarkers of exposure. International archives of
occupational and environmental health 2011, 84 (3), 287– 92, DOI:
10.1007/s00420-010-0539-x
52
Takkouche, B.; Regueira-Méndez, C.; Montes-Martínez, A. Risk of cancer among

hairdressers and related workers: a meta-analysis. International journal of
epidemiology 2009, 38 (6), 1512– 31, DOI: 10.1093/ije/dyp283
53
Hueber-Becker, F.; Nohynek, G. J.; Dufour, E. K.; Meuling, W. J.; de Bie, A.

T.; Toutain, H.; Bolt, H. M. Occupational exposure of hairdressers to [14C]-para-
phenylenediamine-containing oxidative hair dyes: a mass balance study. Food and
chemical toxicology 2007, 45 (1), 160– 9, DOI: 10.1016/j.fct.2006.08.002
54
Hueber-Becker, F.; Nohynek, G. J.; Meuling, W. J.; Benech-Kieffer, F.; Toutain,

H. Human systemic exposure to a [14C]-para-phenylenediamine-containing
oxidative hair dye and correlation with in vitro percutaneous absorption in human
27 | P a g e
or pig skin. Food and chemical toxicology 2004, 42 (8), 1227– 36, DOI:
10.1016/j.fct.2004.02.020
55
Goebel, C.; Diepgen, T. L.; Blömeke, B.; Gaspari, A. A.; Schnuch, A.; Fuchs,
A.; Schlotmann, K.; Krasteva, M.; Kimber, I. Skin sensitization quantitative risk
assessment for occupational exposure of hairdressers to hair dye
ingredients. Regulatory toxicology and pharmacology 2018, 95, 124– 32, DOI:
10.1016/j.yrtph.2018.03.006
56
Kirchhof, M. G.; Dutz, J. P. The immunopathology of cutaneous lupus

erythematosus. Rheumatic diseases clinics of north America 2014, 40 (3), 455–
74, DOI: 10.1016/j.rdc.2014.04.006
57
Van Aerde, E.; Kerre, S.; Goossens, A. Discoid lupus triggered by allergic contact
dermatitis caused by a hair dye. Contact dermatitis 2016, 74 (1), 61– 4, DOI:
10.1111/cod.12496
58
Sanchez-Guerrero, J.; Karlson, E. W.; Colditz, G. A.; Hunter, D. J.; Speizer, F.

E.; Liang, M. H. Hair dye use and the risk of developing systemic lupus
erythematosus: A cohort study. Arthritis and rheumatism 1996, 39 (4), 657–
62, DOI: 10.1002/art.1780390418
59
Petri, M.; Allbritton, J. Hair product use in systemic lupus erythematosus. A case-
control study. Arthritis and rheumatism 1992, 35 (6), 625– 9, DOI:
10.1002/art.1780350605
60
28 | P a g e
Jiménez-Alonso, J.; Sabio, J. M.; Pérez-Alvarez, F.; Reche, I.; Hidalgo, C.; Jáimez,
L. Hair dye treatment use and clinical course in patients with systemic lupus
erythematosus and cutaneous lupus. Lupus 2002, 11 (7), 430– 434, DOI:
10.1191/0961203302lu231oa
61
Ngwanya, R. M.; Spengane, Z.; Khumalo, N. Angioedema, an unusual reaction to

hair dye. pan african medical journal 2018, 30, 103, DOI:
10.11604/pamj.2018.30.103.12061
62
Isik, S. M. D.; Caglayan-Sozmen, S. M. D.; Anal, O. M. D.; Karaman, O. M.

D.; Uzuner, N. M. D. Severe Neck and Face Edema in an Adolescent-Delayed
Hypersensitivity Reaction to Hair Dye. Pediatric emergency
care 2017, 33 (6), 422– 3, DOI: 10.1097/PEC.0000000000000898
63
van Genderen, M. E.; Carels, G.; Lonnee, E. R.; Dees, A. Severe facial swelling in
a pregnant woman after using hair dye. BMJ. case
reports 2014, 2014, bcr2013202562, DOI: 10.1136/bcr-2013-202562
64
Ishida, W.; Makino, T.; Shimizu, T. Severe Hair Loss of the Scalp due to a Hair
Dye Containing para-phenylenediamine. ISRN
dermatology 2011, 2011, 947284, DOI: 10.5402/2011/947284
65
Seo, J. A.; Bae, I. H.; Jang, W. H.; Kim, J. H.; Bak, S. Y.; Han, S. H.; Park, Y.
H.; Lim, K. M. Hydrogen peroxide and monoethanolamine are the key causative
ingredients for hair dye-induced dermatitis and hair loss. Journal of dermatological
science 2012, 66 (1), 12– 9, DOI: 10.1016/j.jdermsci.2011.12.015
66
29 | P a g e
Dulon, M.; Peters, C.; Wendeler, D.; Nienhaus, A. Trends in occupational airway
diseases in german hairdressers: Frequency and causes. American journal of
industrial medicine 2011, 54 (6), 486– 93, DOI: 10.1002/ajim.20947
67
Moscato, G.; Pignatti, P.; Yacoub, M. R.; Romano, C.; Spezia, S.; Perfetti,
L. Occupational asthma and occupational rhinitis in
hairdressers. Chest 2005, 128 (5), 3590– 8, DOI: 10.1378/chest.128.5.3590
68
Helaskoski, E.; Suojalehto, H.; Virtanen, H.; Airaksinen, L.; Kuuliala, O.; Aalto-
Korte, K.; Pesonen, M. Occupational asthma, rhinitis, and contact urticaria caused
by oxidative hair dyes in hairdressers. Annals of allergy, asthma &
immunology 2014, 112 (1), 46– 52, DOI: 10.1016/j.anai.2013.10.002
69
Hollund, B. E.; Moen, B. E.; Lygre, S. H.; Florvaag, E.; Omenaas, E. Prevalence of
airway symptoms among hairdressers in Bergen, Norway. Occupational and
environmental medicine 2001, 58 (12), 780– 5, DOI: 10.1136/oem.58.12.780
69
Hollund, B. E.; Moen, B. E.; Lygre, S. H.; Florvaag, E.; Omenaas, E. Prevalence of
airway symptoms among hairdressers in Bergen, Norway. Occupational and
environmental medicine 2001, 58 (12), 780– 5, DOI: 10.1136/oem.58.12.780
71
Senthilkumaran, S.; Ram, J.; Menezes, R. G.; Sweni,

S.; Thirumalaikolundusubramanian, P. Pneumothorax in hair dye poisoning: An
unrecognized danger. Lung India 2011, 28 (4), 323– 4, DOI: 10.4103/0970-
2113.85753
72
30 | P a g e
Elevli, M.; Civilibal, M.; Ersoy, O.; Demirkol, D.; Gedik, A. H. Paraphenylene
diamine hair dye poisoning: an uncommon cause of rhabdomyolysis. Indian
journal of pediatrics 2014, 81 (7), 709– 11, DOI: 10.1007/s12098-013-1074-z
73
Ram, R.; Swarnalatha, G.; Prasad, N.; Dakshinamurty, K. V. Paraphenylene

diamine ingestion: an uncommon cause of acute renal failure. Journal of
postgraduate medicine 2007, 53 (3), 181– 2, DOI: 10.4103/0022-3859.33860
74
Sandeep Reddy, Y.; Abbdul Nabi, S.; Apparao, C.; Srilatha, C.; Manjusha, Y.; Sri
Ram Naveen, P.; Krishna Kishore, C.; Sridhar, A.; Siva Kumar, V. Hair Dye
Related Acute Kidney Injury - A Clinical and Experimental Study. Renal
failure 2012, 34 (7), 880– 4, DOI: 10.3109/0886022X.2012.687346
75
Lewington, A. J.; Cerdá, J.; Mehta, R. L. Raising awareness of acute kidney injury:
a global perspective of a silent killer. Kidney international 2013, 84 (3), 457–
67, DOI: 10.1038/ki.2013.153
76
Manjunatha, B.; Han, L.; Kundapur, R. R.; Liu, K.; Lee, S. J. Herbul black
henna (hair dye) causes cardiovascular defects in zebrafish (Danio rerio)
embryo model. Environmental science and pollution research
international 2020, 27 (12), 14150– 9, DOI: 10.1007/s11356-020-07762-z
77
Manjunatha, B.; Wei-bing, P.; Ke-chun, L.; Marigoudar, S. R.; Xi-qiang, C.; Xi-
min, W.; Xue, W. The effects of henna (hair dye) on the embryonic development
of zebrafish (Danio rerio). Environmental science and pollution research
international 2014, 21 (17), 10361– 7, DOI: 10.1007/s11356-014-2968-7
78
31 | P a g e
Harder, T.; Roepke, K.; Diller, N.; Stechling, Y.; Dudenhausen, J. W.; Plagemann,
A. Birth weight, early weight gain, and subsequent risk of type 1 diabetes:
systematic review and meta-analysis. American journal of
epidemiology 2009, 169 (12), 1428– 36, DOI: 10.1093/aje/kwp065
79
Jiang, C.; Hou, Q.; Huang, Y.; Ye, J.; Qin, X.; Zhang, Y.; Meng, W.; Wang,
Q.; Jiang, Y.; Zhang, H.; Li, M.; Mo, Z.; Yang, X. The effect of pre-pregnancy hair
dye exposure on infant birth weight: a nested case-control study. BMC pregnancy
and childbirth 2018, 18 (1), 144, DOI: 10.1186/s12884-018-1782-5
80
Lynch, B. S.; Delzell, E. S.; Bechtel, D. H. Toxicology review and risk assessment
of resorcinol: thyroid effects. Regulatory toxicology and
pharmacology 2002, 36 (2), 198– 210, DOI: 10.1006/rtph.2002.1585
32 | P a g e
Dyes for LASER
Prof. Dr. Hassan A. Etman

Chemist : Fatma Ibrahim Ahmed Al-sharkawy
1. Introduction
Applications of lasers are wide and varied today. They are found
in communication techniques, in microsurgery and in many
spectroscopic applications such as Raman spectroscopy for
following photochemical reactions and ultra fast reaction kinetics,
in isotope separations, and in trace analysis, eg.,
detection of sodium atoms in concentrations as low as 0.003ng
cm–3. Dye lasers are the most versatile and one of the most
successful laser sources known today due to their significant
contribution to basic physics, chemistry, biology and other fields.
The first laser dye was reported in 1966. Traditional laser
technology utilizes a variety of inorganic materials to produce the
required emission. Several different types of inorganic lasers have
been developed to emit in ultraviolet,visible or infrared regions of
the electromagnetic spectrum.
Though inorganic lasers are of low cost and robust devices, they
have Some drawbacks. They emit only at very few specific
wavelengths and in very narrow bands, whereas dye lasers cover the
entire visible and near IR region and have far greater tunability
compared to inorganic lasers.
Dye lasers are contributing greatly to the progress in laser
technology.
The aim of this review is to give an overview of the different types
of dyes used in laser technology application. We have focused on
recent developments in liquid-state dye laser technology.
2. Principle
The term LASER is an acronym for Light Amplification

by Stimulated Emission of Radiation. A laser is a device
used for the amplification or generation of coherent light
waves in the UV,VIS, and near IR region.
The principle of stimulated emission (Figure 1)
is explained here.
a) Light absorption brings molecules from the ground

state S0 to the excited state S1.
b) The absorbed energy is lost, e.g., by fluorescence

which leads to no phase relationship between the emitted
photons.
c) When the excited molecules are irradiated by a light flash

corresponding to the energy difference between S1 and S0 , stimulated
emission occurs within the average lifetime of excited state S1.
This means that the excited molecule, when hit by such a
photon, emits a second photon of the same energy, intensity, phase
and direction (polarization).
A condition for stimulated emission to occur is that the number of

molecules in the excited state S1 is higher than that in the ground
state S0 at the moment of flash. The situation in which molecules
exist predominantly in an excited state rather than ground state is
known as population inversion and is brought about by pumping the
system with a source of energy.
A simple schematic representation of a technical laser is presented
in Figure 2.
The active medium (AM) is the
system that is responsible for
stimulated emission.
The light energy pump (EP)
provides the energy for the
inversion of the population, and
Mirror 1 and Mirror 2 are parallel
mirrors that amplify the stimulated
emission by multiple passages through the laser cavity. A small fraction
of the laser light leaves the cavity through Mirror 2 and is used for the
given application.
There are several ways in which we can classify the different

types of lasers. They can be classified on the basis of their mode
of operation or according to what material is used as the active
medium. Depending on their mode of operation, lasers are classi�fied as
• Continuous wave (CW) lasers and
• Pulsed wave lasers.
Lasers are also broadly divided into four categories on the basis of
the material used as an active medium. They are
• Solid lasers
• Liquid lasers
• Gas lasers
• Semiconductor lasers.
Dye lasers belong to the family of liquid lasers. The active
material is a dye dissolved in a liquid solvent. The approximate
working ranges of various laser dyes are shown schematically in
Figure 3.
Dye spectral emission characteristics.
3. Requirements of Dyes for Laser Application
For effective performance, dye molecules should have the following

characteristics:
• Strong absorption at excitation wavelength and minimal absorption at
lasing wavelength, i.e., minimum overlap between
absorption and emission spectra.
• High quantum yield (0.5–1.0).
• Good photochemical stability.
• A short fluorescence lifetime (5–10 ns).
• Low absorption in the first excited state at the pumping and
lasing wavelengths.
• Low probability of intersystem crossing to the triplet state.
• Laser dyes have to be very pure since impurities frequently
quench the laser output.
By appropriate dye selection it is possible to produce coherent
light of any wavelength from 320 to 1200 nm.
4. Different Classes of Laser Dyes
Generally, laser dyes are complex molecules containing a number
of ring structures, which lead to complex absorption and emission
spectra. The laser dyes can be categorized into different classes
by virtue of their structures that are chemically similar. Common
examples are the coumarins, xanthenes and dipyrromethanes. The
structure and composition of the molecule has an important
influence on spectral emission. The laser activity was first observed by
chloro-aluminum-phthalocyanine (1) by Sorokin and Lankard. and from
3,3-diethylthiatricarbocyanine (2) by Schmidt and Schafer.
Laser dyes are complex molecules containing a

number of ring structures, which lead to complex absorption and
emission spectra.
4.1 Coumarin Laser Dyes

A group of widely used laser dyes emitting in the blue-green regions of
the spectrum are derived from coumarins by substituting 7-position with
auxochromes such as –OH, –OCH3 ,–NH2, –NHCH3, –N(CH3)2 and
other electron-donating substituents.
The first coumarin laser dye was 7-diethylamino-4-
methylcoumarin (3) which exhibits laser action at about
460 nm under flash lamp excitation.
The amino analogue, 7-amino-4-methylcoumarin

(coumarin 120) (4) shows laser action at 440 nm.
In some coumarin dyes the basic chromophore is replaced

with its heterocyclic analogues like aza-coumarin,
quinolone, or aza-quinolone in order to enhance the dye
properties. AC3F dye (5) is an example for these class of
dyes.
Coumarin dyes have the tendency for low photostability.

Coumarins degrade due to laser light. The side products formed
after degradation also absorb in the laser region which may give
undesired effects. Coumarin molecule as such is non-fluorescent,
but it exhibits intense fluorescence on substitution of various
functional groups at different positions. In general, electron�donating
substituents tend to enhance emission intensity while
electron-withdrawing substituents tend to diminish it. The inten�sity of
the dye laser beam cannot be increased over a certain range
of the pump power and is limited by saturation. This is due to
photo-quenching effect. Studies on the photo-quenching properties in
various dyes have shown that the effect plays a crucial role
in the performance of pulsed laser pumped dye laser systems.
Some of the commercial coumarin laser dyes are listed in Table 1.
Examples of coumarin laser dyes

4.2 Xanthene Dyes
Xanthene dyes cover the wavelength
region from 500 to 700 nm and are
generally very efficient. Most of the
commercial dye lasers are from this class –
Fluorescein and Rhodamine B are the two
widely used laser dyes. The electron
distribution in the chromophore in the
xanthenes dyes can be described by the
following two identical mesomeric
structures, (22) and (23).
Rhodamine 6G (24) shows efficient laser
action in the 590 nm region and lases with
about one percent efficiency in most
flashlamp pumped dye lasers. It is used as
reference dye to measure the efficiencies
of other dyes.
Since Rhodamine 6G also exhibits good
photostability, This laser dye is one of the
most often used and studied.
Most of the xanthene laser dyes show
efficient laser action in the 560 to 800 nm
region. Rhodamine 700 (25) is another
efficient laser dye obtained by molecular
engineering. This efficient dye exhibits
laser action between 700 to 800 nm.
Rhodamine 700 has the ‘double butterfly’
structure, which enables the amino groups
to become more rigid and planar (25). Replacing the phenyl group
substituent of Rhodamine 6G by the –CF3
group enhances its photostability.
Table 2 shows some of the commercial xanthenes class laser dyes.
Table 2. Examples of Rhodamine laser dyes

4.3 Oxazine Dyes
Oxazine dyes are planer and are rigid like xanthene dyes.
All oxazine dyes are photochemically more stable than xanthenes.
Some of the well-known oxazine laser dyes are listed in Table 3.
A few commercial oxazine dyes such as cresyl violet, nile blue,
etc., used for textile applications are also used as laser dyes.
These are cationic dyes.
4.4 Dipyrromethanes
Boron-dipyrromethene dyes, also known as BODIPY, are fluo�rescent
dyes used for laser application. They are composed of
dipyrromethene complexed with a disubstituted boron atom,
typically a BF2 unit.
BODIPYs
are an important class of laser dyes. They are tunable in the
green–yellow visible region of the electromagnetic spectrum. They
exhibit high lasing efficiency, good photostability, high fluorescence
quantum yield, low rate constant of intersystem crossing and large molar
absorption coefficient. The photophysical properties of these dyes can be
modulated to some extent by incorporating the adequate substitution in
the molecular structure of the parent BODIPY chromophore. The
general structure of BODIPY complex is shown here (35).
Some of the BODIPY complexes are commercially available.

The 1,3,5,7,8-pentamethyl-BODIPYcomplex in ethanol exhibited laser
action at 546 nm and lased about three times more efficiently than
Coumarin 545 and about 10 percent less efficient than Rhodamine 6G.
The 1,3,5,7,8- pentamethyl-2,6-diethyl-BODIPY (37)
complex commercially known as Pyrromethene-567 lases at 567 nm and
has an output about three times higher than that of Rhodamine 560.
Other BODIFYs show similar efficiencies. Another typical BODIPY
complex is (36).
This dye (36) ranks among the more effi�cient BODIPY dyes. The
Molecular structures of three of the most important commercial
BODIPY dyes are shown in Table
4.New BODIPY dyes with
two 4-formyl phenyl,4-(2,2-methoxycarbonyl-vinyl) phenyl and
4-(2,2-dicyano-vinyl)phenyl groups at the 3- and 5-positions are listed.
in Table 5. Recently, the synthesis of 8-propargylamino BODIPY
laser dye (46) with emission in the blue spectral region has been
reported.
Apart from these classes, a number of other laser dyes are
described by Brackman in the book Lambdachrome Laser Dyes.
5. Designing a Laser Dye
In recent years, molecular engineering and suitable additives
have led to superior laser dyes with increased photostabilities.
For instance, replacement of 4-methyl group in Coumarin 125 (3)
by more stable trifluoromethyl group resulted in a thermally more
stable compound Coumarin 152. The compounds (47) and (48)
are an interesting class of fluorescent compounds. The compound

(47) is known as syn-biamine which gives rise to very high
fluorescent quantum yield of 0.7 to 0.9, whereas the corresponding
‘anti’ isomer(48) is however, only weakly fluorescent.T G
Pavlopoulos in his overview on laser dyes titled Laser dyes:
structure and spectroscopic properties [4], has discussed various
approaches to design laser dyes by molecular engineering and
spectroscopic studies.
Following are a few approaches to design better laser dyes.
• Following the classical methods of organic dyes, one can keep
the chromophore constant and change the auxochrome groups
to improve properties of the laser dye. For example, replacing
one or more carbons by a hetero-atom improves the laser
effect as shown below in coumarins (49) and azacoumarins (50).
• Enhancing molecular rigidity of the dye to improve its quantum
yield and laser action efficiency. Example Biphenyl (51) with QF =
0.18, whereas the >CH2
bridged fluorene (52) which has a QF = 0.80 in cyclohexane.
• The photostability of dyes (e.g., coumarin ) may be improved
by switching a –CH3 group to a –CF3 group.
• Planar molecules exhibit strong fluorescence because the
motion of electrons is not restricted in them. However, in case
of non-planar molecules, resonance is reduced or even lost due
to steric crowding. For example, to keep the amino group.
coplanar, it has been replaced by the single butterfly or double

butterfly system as shown in (53–55). By adopting the molecular
design theory, about 125 new coumarin derivatives have been
reported over the last 40 years.
6. Applications
Industrial applications of laser dyes include separation of isotopes of
important radioactive elements such as Uranium. Uranium is used as
fuel in the nuclear power reactors to generate electricity.
In nature, uranium exists as several isotopes: primarily
uranium-238, uranium-235, and a very small amount of
uranium-234. The medical applications of laser dyes include skin
treatments, including port-wine stain and tattoo removal, diagnostic
measurements, lithotripsy, activation of photosensitive
drugs for photodynamic therapy, etc. In the field of medical
applications, dye lasers have potential advantages over other lasers.
Dye lasers are unique sources of tunable coherent radiation, from
the ultraviolet to the near infrared, using hundreds of dye molecular
species. Broadly tunable lasers have a tremendous impact in diverse
fields of science and technology. A Costela and coworkers have
reviewed the medical applications of dye lasers [8]. Some of the
most important clinical applications of dye lasers are presented here.
6.1 Laser Treatment of Port-Wine Stains

Port-wine stains (PWS) were one of the first vascular malformations
to be treated with laser radiation. They are congenital
malformations consisting of superficial and deep dilated capillaries
in the skin. The swollen blood vessels cause a reddish discoloration
of the skin. Although PWS can appear in any part of the body, they
occur more often on the face and persist throughout life.
In the field of
medical applications, dye lasers have potential advantagesover
other lasers.
Optical fibers conduct light from the laser head to the malformed
area, and convex lenses focus the laser beam directly onto the skin
to a spot of at most 1cm diameter, to reach energy fluencies.
(radiant exposure) in the range 4–10 J/cm2 , depending on the age
of the patient and the region irradiated. Children, with smaller
overall lesions and more superficial vessels with smaller diameters,
require lower energy fluence than adults. Sensitive areas, such as
eyelids and hands, also require reduced energy fluency.
After successful treatment, no textural changes or damage to the
surrounding dermis is seen in treated skin.
After successful treatment, no textural changes or damage to the
surrounding dermis is seen in treated skin.
6.2 Lithotripsy
Lithotripsy is a medical procedure that uses shock waves
to break up stones that form in the kidney, bladder, and
gallbladder. There are several forms of lithotripsy. The
Most common is extracorporeal shock wave lithotripsy;
however, for typical stone types and restricted access,
laser lithotripsy acts as a complementary technique. In the
usual extracorporeal shock wave lithotripsy (ESWL)
technique, an externally applied, focused, high-intensity
acoustic pulse passes through the body to the area on the
stones. The successive shock wave pressure pulses break
the stones into tiny pieces that then can pass easily
through the ureters or the cystic duct.
When a laser is used, a train of laser pulses is guided by a
fiber to the application site which ignites plasma at the
surface of the stone. The breakdown of the plasma creates
a shock wave, which detaches some fragments. After
many repetitions, the stone will be fragmented into
smaller pieces, which then can pass spontaneously. The
laser parameters appropriate for lithotripsy have a wide
range, depending on fiber diameter, lasing wavelength,
location, and composition of stones, which define their
absorption bands. Typical operational parameters of
flashlamp-pumped dye lasers used in lithotripsy treatment
are: emission wavelength of 504 nm and 595 nm,
depending on stone composition; pulse energy in the
range 50–120mJ/pulse; pulse duration from 1–42.5 s; and
repetition rate of 1–10 Hz. The procedure requires
endoscopic control of laser effects and a system for stone
recognition. Since the laser light is green, there is minimal
tissue absorption and almost negligible tissue damage.
Because the energy effects take place on structures with
crystalline makeup, soft tissue is basically unaffected.
Thus, even if the laser fiber fires repeatedly against the
urethral wall, very little tissue damage takes place.
Lithotripsy is a medical procedure that uses shock waves
to break up stones that form in the kidney, bladder, and
gallbladder.
6.3. Laser Angioplasty
Arteries can become narrowed or blocked by deposits
called plaque. Plaque is made up of fat and cholesterol
that builds up on the inside of the artery walls. This
condition is called atherosclerosis. Angioplasty is a
medical procedure to open arteries that are obstructed by
atherosclerotic plaque. It involves different forms of
minimally invasive vascular interventions, which can be
exemplified by balloon angioplasty, a procedure in which
a balloon is used to open a blockage in an artery narrowed
by atherosclerosis.
Laser angioplasty is a promising alternative method to
open arteries obstructed by atherosclerotic plaque, with
potential advantages over surgery, balloon angioplasty,
and other forms of vascular interventions. Laser radiation
can be introduced into arteries via small optical fibers,
thus avoiding major surgery. The radiation can remove
plaque rather than displacing it, thus poten�tially
reducing the high rate of restenosis
(gradual re-narrowing of the artery during several
months following the procedure) that occurs with balloon
angioplasty. Laser radiation with the appropriate
wavelength is preferentially absorbed by plaque, thereby
adding an element of specificity and safety that does not
exist with mechanical devices.
6.4 Laser Treatment of Vascular Lesions

Most vascular abnormalities can be successfully treated
with lasers.
A theory of selective photothermolysis predicts that
selective destruction of blood vessels is possible by
matching the wavelength of light absorbed by hemoglobin
into the vessels.
Defining thermal relaxation time as the time required for
the target tissue to lose 50% of its heat, they proposed
using a pulsed laser with the appropriate wavelength and
with a temporal pulse length shorter than the calculated
thermal relaxation time for blood vessels. This led to the
development of flashlamp-pumped pulsed dye lasers
(FPDL) especially designed for treatment of cutaneous
vascular lesions. The first FPDL systems used in the
treatment of vascular lesions were tuned to yellow, at 577
nm, a wavelength in the region of the third absorption
spectral peak of oxyhemoglobin. The pulse duration was
in the range 300–500 ms, calculated to match the thermal
relaxation time of cutaneous blood vessels.
6.5 Prospects of Dye Lasers:
A number of research groups are working around the
world to develop dye laser technology for a wide range of
applications:
Nowadays the use of solid matrices containing laser dyes
are coming as an attractive alternative to the conventional
liquid dye solutions. The future of laser dyes continues to
be good. Currently the main challenge in the development
of dye lasers is to increase their photostability and to
extend the range of output of the dyes.
7. Summary:
Dye laser technology has advanced significantly over the
last 50 years since the first laser action was from
chloro-aluminum phthalocyanine. The laser dyes find
uses in many scientific, industrial, medical and military
applications, ranging from spectroscopy to potential
countermeasure devices.
The development of a new dye laser is related to the
development in terms of easy tunability, wide wavelength
coverage and synthetic simplicity. Changing of functional
groups within the classes of laser dyes having good laser
characteristics has proven to be a useful way of creating
new laser dyes.
Preliminary MA
Mansoura University
2023-2024
Essay in
(Acid Dye)
Submitted By
Sara Ismail Ibrahim
Under Supervision of
Prof.Dr. Hasan Etman

Table of Contents
INTRODUCTION................................................................................................................................ 3
❑ Classification of Acid Dyes ........................................................................................................... 4
1. Classification according to affinity ........................................................................................... 4
2. Classification according to dyeing characteristics ................................................................... 4
2.1. Levelling or equalizing acid dyes ....................................................................................... 5

2.2. Fast acid dyes ...................................................................................................................... 5
2.3. Milling acid dyes ................................................................................................................. 5
2.4. Super-milling acid dyes ...................................................................................................... 6
3. Classification according to chemical constitution .................................................................... 7
❑ Azo Acid Dyes................................................................................................................................ 7
1. Monoazo acid dyes ..................................................................................................................... 7
2. Disazo acid dyes ....................................................................................................................... 13
 Primary disazo dyes of the type A1 → Z ← A2 ..................................................................... 13

 Primary disazo acid dyes of the type C1 ← D →C2 ............................................................. 14
 Secondary disazo dyes of the type A1 → M → C ................................................................. 15
❑ Chrome Dyes ............................................................................................................................... 15
❑ Acid Dyes for Synthetic Polyamides ......................................................................................... 16
❑ Anthraquinone Dyes ................................................................................................................... 19
1) 1-Amino-4-(substituted)amino anthraquinone-2-sulphonic acids ........................................ 19
2) 1-Amino-2-aryloxy-4-(substituted)amino anthraquinones .................................................... 21
3) Diamino dihydroxy anthraquinone sulphonic acids .............................................................. 21
4) 1,4-Diaminoanthraquinones with external sulphonic acid groups ....................................... 21
5) 1-Amino-4-hydroxy anthraquinones with external sulphonic acid groups ........................... 22
6) Other acid anthraquinone dyes ............................................................................................... 23
❑ Acid Nitro Dyes ........................................................................................................................... 23
1
❑ Triphenylmethane Acid Dyes ..................................................................................................... 24
❑ Water-Repellent Dyes ................................................................................................................. 28
❑ Acid Dyes with Inherent Light Fastness ................................................................................... 28
❑ Acid Dyes Free From 1-Naphthylamine ................................................................................... 29
❑ Future Trends .............................................................................................................................. 29
REFERENCES................................................................................................................................... 29
LIST OF FIGURES
Figure 1: Monoazo acid dyes ................................................................................................... 8
Figure 2: Monoazo acid dyes with enhanced wash fastness. ................................................. 10
Figure 3: Bisazo acid dyes and their intermediates ................................................................11
Figure 4: Disazo acid dyes. .................................................................................................... 14
Figure 5: Monoazo metal-complex dyes ................................................................................ 17
Figure 6: Monoazo acid dyes with enhanced light fastness. .................................................. 18
Figure 7: Anthraquinone acid dyes ........................................................................................ 20
Figure 8: Anthraquinone acid dyes. ....................................................................................... 22
Figure 9: Nitrodiphenylamine acid dyes. ............................................................................... 24
Figure 10: Triarylmethane acid dyes ...................................................................................... 25
Figure 11: Triarylmethane acid dyes. ..................................................................................... 25
Figure 12: Pyronine acid dyes. ............................................................................................... 26
Figure 13: Pyronine and diazine acid dyes. ........................................................................... 27
Figure 14: Diazine acid dyes .................................................................................................. 28
2
INTRODUCTION
The name ‘acid dye’ originates from the dyeing process, which is carried out in acidic
(pH 2.0–6.0) aqueous solution. Acid dyes or anionic dyes include many compounds
from the most varied chromophoric systems which exhibit characteristic differences in
structure but possess as a common feature water-solubilizing ionic substituent.
Almost invariably the products that are manufactured and used are water-soluble
sodium salts of sulphonic acids, the main reason being that they are readily introduced
and, as strong electrolytes, are completely dissociated in the acidity range used in the
dyeing process. Recently sodium salts of carboxylic acids have become important as
dyes for ink-jet printing. These dyes are therefore anionic in solution. Most
premetallized and mordant dyes are also acid dyes.
The anionic dyes in principle include direct dyes, but, because of their characteristic
structures these are used to dye cellulose containing materials and are applied to the
fibre from a neutral dyebath. The group of anionic dyes also includes a large
proportion of reactive dyes, which in addition to the usual structural characteristics
also contain groups that can react with functional groups of the fi bre during the
dyeing process.
Acid dyes will dye fibres with cationic sites such as wool, silk and nylon. Protein
fibres contain amino and carboxyl groups, which in the isoelectric range (pH 5.0), are
ionised mostly to NH3+ and COO−. In the acid dyebath the carboxylate ions are
converted to undissociated carboxyl groups owing to the addition of acid giving the
positively charged fibre H3N+ − F─COOH to take an equivalent amount of acid
anions. Dyeing involves exchange of the anion associated with ammonium ion in the
fibre with a dye anion. The dye anions exhibit a greater affinity for the substrate than
the much smaller acid anions. The dye is thus bonded to the wool not only by
electrostatic attraction (salt formation) but also by its affinity for the fibre. Dyeing is
therefore not solely a consequence of simple ionic interaction.
3
❑ Classification of Acid Dyes
1. Classification according to affinity
The absorption of dyes by polyamide fibres involves the ionic interaction of the dye
with the hydrophobic groups in the fibre together with the electrostatic attraction.
Therefore, their differences in affinity are primarily a function of molecular size.
Based on the affinity three different classes are recognised:
1) Levelling dyes form a salt-like bond with the protein fibre and are relatively small
molecules.
2) Milling dyes for which salt formation with the fibre and the adsorption forces
between the hydrophobic regions of the dye molecules and those of the protein
fibre predominate. They are the large volume molecules.
3) Dyes which not only form a salt-like bond with the wool fibre but also bonded to
the fibre by intermolecular forces. They have properties lying in an intermediate
position between those of the levelling and milling dyes with intermediate
molecular size.
2. Classification according to dyeing characteristics

Dyeing characteristics of acid dyes allow them to be categorised into the following
four types:
1. Level dyeing or equalizing dyes

2. Fast acid dyes
3. Milling acid dyes
4. Super-milling acid dyes.
The molecular weight and degree of sulphonation of the dye molecule determine the
dyeing behaviour such as the pH of dyeing, migration ability to dyeing and their
washing fastness.
4
2.1. Levelling or equalizing acid dyes
These dyes require considerable amounts of strong acids along with Glauber’s salt to
achieve good exhaustion. Under the high concentration of acid high concentration of
cationic ammonium groups are generated in the
wool and the dyes have rapid strike for the wool. The dye molecules, however, are not
strongly bound to the sites. Initial non-uniformity in colour is evened out by their good
migration at the boil.
As a consequence of ease of migration these dyes have poor to moderate wash

fastness. The light fastness, however, ranges from fair to good. This group of dyes is
thus used for pale to medium depths on wool fabrics and yarn where a high degree of
levelness only is critical and not good fastness to washing. They are brighter compared
to mordant or metal-complex dyes. They have relatively small molecular size and
hence have good water solubility. They have good penetration into individual fibres of
tightly woven fabrics and high twist yarns. The dye molecules do aggregate in solution
and at higher temperatures enough individual molecules are present for good
penetration.
2.2. Fast acid dyes

Compared to the typical levelling dyes fast acid dyes are of somewhat higher
molecular weight and are usually monosulphonated ones. The dyeing method is also
similar. They have reasonable migration at boil, and sometimes a levelling agent is
recommended. Fast acid dyes are used when level dyeing is necessary with good
washing and perspiration fastness.
2.3. Milling acid dyes

Milling is the process in which a woollen material is treated in weakly alkaline
solution, with considerable mechanical action to promote felting. Dyes of good
fastness to milling are necessary to avoid bleeding of colour during the milling.
5
Milling dyes have higher molecular weights and greater substantivity for wool than
levelling or fast acid dyes. They have fewer sulphonate groups per dye molecule and
hence they have lower water solubility. They have a strong tendency to aggregate even
in boiling water giving colloidal solutions. Dyeing with milling dyes is usually started
in the presence of sodium acetate or ammonium sulphate and is carried out in the pH
range from 5.0 to 7.0. The exhaustion is increased by the addition of acetic acid. They
have low rates of diffusion in wool and hence poor levelling ability. Other than the
ionic bonding there exist intermolecular forces between the dye and the fibre. Milling
acid dyes give moderate to good washing fastness and as expected are better than the
levelling acid dyes. Specifically, they are fast to alkaline milling and have fairly good
light fastness.
Since they have poor migration properties, level dyeing initially depends upon
gradually increasing the dyebath temperature, and then lowering the pH of the dyebath
by the addition of a small amount of acetic acid. These dyes tend to stain cotton. They
are often preferred for self-shades as they have poor dyeing compatibility in mixtures.
2.4. Super-milling acid dyes

These are similar to milling dyes but much more hydrophobic. The hydrophobicity is
manifested due to the presence of long-chain alkyl groups in the molecule. They have
good wash fastness, and good to very good light fastness. They are used for yarn
dyeing when there is a requirement of scouring and milling of the final fabric.
Milling and super-milling dyes have very rapid absorption behaviour resulting in
unlevel dyeing, and they do not migrate easily. The rate of absorption of the dye needs
to be controlled by gradual increase in the dyebath, followed by gradual decrease in
the pH of the dyebath. The initial pH of the dyebath must be even higher than 7.0 for
dyeing pale shades to mitigate the initial strike. The pH can be lower in case of dyeing
loose fibre and tops where levelness is less critical since the fibre will be blended
together during spinning. Dyeing rate with these dyes increases rapidly above 70°C,
6
once the dye aggregates in solution begin to break up with increasing temperature. A
careful control of temperature at this critical stage gives even dyeing.
3. Classification according to chemical constitution
Acid dyes are drawn from many different chromophoric systems. They are as follows:
✓ Sulphonated azo dyes

✓ Anthraquinone dyes
✓ Nitrodiphenylamine dyes
✓ Triphenylmethane and xanthenes dyes.
Sulphonated copper phthalocyanine dyes provide bright turquoise shades.
❑ Azo Acid Dyes

Sulphonated azo dyes constitute the major group and are mainly mono- and bisazo
dyes ranging in colour from yellow, through red to violet and brown. There are some
navy blue bis azo dyes that can build up to give blacks. The substantivity of anionic
azo dyes for polyamides and protein fibres is greater the higher their molecular weight
and the lower the number of sulphonic acid groups in the dye molecule. There are
several acid mordant and metal- complex dyes.
There are a number of acid and direct dyes with similar structural features in the azo
class. These dyes will dye wool, nylon and cotton. An important feature that
distinguishes acid dyes from direct dyes, apart from their lower molecular weights, is
that molecular planarity is not essential for acid dyes while it is a requirement for
direct dyes.
1. Monoazo acid dyes

There are a number of monoazo acid dyes distinguished by brilliance of shade, very
good levelling power and particularly low cost. They possess no outstanding
colouristic properties and their light and wash fastness meet only low to medium
7
requirements. However, in recent years, partly influenced by the introduction of the
International Wool Label to label high quality wool articles, the fastness requirements
have gone up considerably, and several fast dyes have been developed.
Figure 1: Monoazo acid dyes
In the manufacture of monoazo acid dyes usually aniline derivatives are used as the
diazo components. The coupling components for orange to blue shades are usually
aniline, naphthol, naphthylamine and aminonaphthol derivatives, while N-
phenylpyrazol-5 ones are used for preparing yellow and orange dyes.
Azo dyes with free OH and NH 2 groups are sensitive to alkali and acid, respectively.
In commercial dyes these groups occur ortho to the azo group in order to form a
8
hydrogen bond with the latter. This hydrogen bond prevents a dissociation of the
hydroxyl groups or a protonation of the amino groups and hence they are not pH-
sensitive.
One of the oldest azo dyes is C.I. Acid Yellow 36, C.I. 13065 [487-98-4] (1). For
economic reasons 1 is used for dyeing wool and in special applications (leather and
paper) in spite of lower fastness to acid.
Coupling of diazotized H-acid to 1-(phenylamino) naphthalene-8sulphonic acid (N-

phenyl peri acid) yields C.I. Acid Blue 92, C.I. 13390 [3861-73-2] (6). It gives a pure
blue colour on wool with good light fastness, moderate wash fastness and adequate
levelling power.
A series of two important dyes with very similar structure comprises C.I. Acid Red 88,
C.I. 15620 [1658-56-6] (4), obtained from diazotised naphthionic acid and 2-naphthol,
and C.I. Acid Red 13, C.I. 16045 [2302-96-7] (2), from diazotised naphthionic acid
and Schaeffer’s acid. They give attractive red shades and are used in textile dyeing
and also as leather and paper dyes. They exhibit only moderate fastness properties.
C.I. Acid Orange 7, C.I. 15510 (3), popularly known as Orange II, is one of the oldest
dyes. It is used more in special areas like leather and paper dyeing. The dye C.I. Acid
Red 14, C.I. 14720 [3567-69-9] (5) is used for inexpensive articles in wool dyeing to a
limited extent.
Introduction of large volume substituents on these simple dyes improves the wet
fastness of the dyes at the expense of levelling ability. An example is C.I. Acid Orange
19, C.I. 14690 [3058-98-8] (7), which has good fastness properties together with good
levelling power on wool and polyamide.
Monoazo acid dyes derived from aminonaphthol sulphonic acids like gamma acid and
H-acid as coupling components exhibit very good light and wet fastness. Especially,
acid coupling of gamma acid yields dyes with very good light fastness, which is
9
presumably attributable to the formation of a hydrogen bond between the azo bridge
and hydroxyl group adjacent to the azo bridge. Two such dyes of outstanding light
fastness and good levelling power with moderate wash fastness are C.I. Acid Red 42,
C.I. 17070 [624560-9] (8) and C.I. Acid Red 37, C.I. 17045 [6360-07-2] (9). In this
series by the choice of suitable substituted diazo components, bluish red to blue wool
dyes with good light and wet fastness can be produced, for example, C.I. Acid Violet
14, C.I. 17080 [4404-39-1] (10). Further examples in this series are C.I. Acid Red 32,
C.I. 17065 [6360-10-7] (11) and C.I. Acid Blue 117, C.I. 17055 [10069-12-7] (9).
There is continued interest in acid dyes of this type (Blus,1999).
Figure 2: Monoazo acid dyes with enhanced wash fastness.
10
Alkaline coupling of gamma acid where amino group is either acylated or arylated
gives valuable dyes. An example is C.I. Acid Red 68, C.I. 17920 [6369-40-0] (13). N-
arylation of gamma acid gives a strong deepening of the shade. It gives mainly brown
to black dyes with good light fastness and milling fastness. An example is C.I. Acid
Brown 20, CI 17640 [6369-33-1] (14).
H-acid is an important coupling component in the synthesis of acid dyes. Acylation of

amino group in H-acid substantially improves the light fastness of the dyes obtained
therefrom. These dyes have good levelling power, and light fastness as well as wet
fastness. Valuable dyes are also obtained with N-benzoyl-H-acid and N-
toluenesulphonyl-H-acid. A relatively simple structure is exemplified by C.I. Acid Red
1, C.I. 18050 [3734-67-6] (15).
Figure 3: Bisazo acid dyes and their intermediates
11
Incorporation of long hydrophobic hydrocarbon residues yields dyes with neutral
affinity and good wet fastness properties as in C.I. Acid Red 138, C.I. 18073 [15792-
43-5] (16). Acid dyes with dodecyl or dodecyloxy groups (Carbolan dyes) were
developed by ICI and are characterised by high milline fastness, a property conferred
on the molecule by the long-chain alkyl groups (Abrahart, 1977, p. 97; Venkataraman,
1970, p. 268). It has been found that long-chain alkyl groups increase the water
repellency and decrease the substantivity of dyes on cotton and wool fibres through
steric hindrance (Chao and Yeh, 1993; DeWitt and Shroff, 1953). Acid dyes with
arylsulphonamide groups have been continuously studied (Blus and Kraska, 1988,
1992, 1993; Kraska and Blus, 1984). Dyes with an arylsulphonanilide group dye
polyamide and protein fibres from weakly acidic dyeing baths give a very high degree
of dyebath exhaustion. The colour and constitution relationships in C.I. Acid Red 138
and its homologues have been studied (Stoyanov et al., 1995).
Light-fast yellow dyes are obtained using 1-phenylpyrazol-5-one coupling

components (Schwander, 1 982). The first representative in this series is Tartrazine,
C.I. Acid Yellow 23, C.I. 19140 [1934-21-0]. Tartrazine is prepared from 1-(phenyl-4-
sulphonic acid)-3-carboxy-5-pyrazolone as the starting material which is prepared
from oxaloacetic ester and phenylhydrazine-4-sulphonic acid and coupling with
diazotised sulphanilic acid.
Dyes based on 1-aryl-3-methylpyrazol-5-ones and their derivatives are cheaper

compared to the corresponding 3-carboxypyrazolones. An example is C.I.
Acid Yellow 17, C.I. 18965 [6359-98-4] (18), which gives a clear, lightfast yellow
with good to very good general fastness properties.
C.I. Acid Yellow 76, C.I. 18850 [6359–88–2] (17) is a milling dye. It is obtained by
coupling diazotised 4-aminophenol into the pyrazolone component and then
esterifying with p-toluene sulphonic acid chloride in an alkaline medium. Better
milling fastness is due to the presence of toluene sulphonic ester group. Yellow acid
12
dyes derived from 1-phenyl-3-methyl 5-pyrazolone and containing two
arylsulphonamide groups have also been synthesised (Blus, 1992).
Monoazo dyes from heterocyclic diazo components as well as coupling components

are not so common in acid dyes of commercial importance except those derived from
pyrazolones. However, there is academic interest in this area. 5-Substituted-2-
thiobarbituric acid has been mentioned as a coupler and a series of acid dyes is known
(Akiyama etal., 1987). Monoazo acid dyes from 4-aminonaphthalimide
(Wojciechowski, 1 993) and 5.10-dihydroxyphenophosphazine (Zhi-Gang et al.,2009)
are reported. 2-Aminobenzothiazoles containing a sulphonic group has been
mentioned as a useful diazo component for acid dyes in the patent literature. It has
been claimed that these dyes are compatible with the anthraquinone based dyes
(Gerhard and Richard 1 975). N-Phenylindole based couplers have also been used in
obtaining yellow and orange dyes (Niegel, 1980a,b; Weaver, 1974 ). 3-Amino-7-nitro-
2H-1,2benzothiazine-1,1-dioxide has been used in obtaining acid dyes as well as
chromable dyes having high tinctorial strength.
2. Disazo acid dyes

Primary disazo dyes are obtained according to the scheme A1 → Z ← A2 from a
bifunctional coupling component Z and two identical or different diazo components A 1
and A2 or according to the scheme C1 ← D → C2 by coupling a bis diazotised diamine
D to the coupling components C1 and C2, which may be the same or different.
Secondary disazo dyes are obtained according to the scheme A1 → M → C (where M
is the middle component) from diazotised amino azo dyes (A → M) and a coupling
component C.
 Primary disazo dyes of the type A1 → Z ← A2

H -acid is an important dual coupling component used in the disazo acid dyes. The
shade variation is very little in this series; mainly black, dull brown and blue dyes are
obtained. They are the completely conjugated chromophores.
13
C.I. Acid Black 1, C.I. 20470 [1064-48-8] (32) is one of the important acid dyes. It
dyes wool in blue-black shades with very good light fastness and exhibits high affi
nity and good levelling power but only moderate wet fastness. It has remained an
important dye that forms the basis of black acid dyes.
 Primary disazo acid dyes of the type C1 ← D →C2

These dyes include many milling dyes. This is due to the fact that molecular size can
be varied by suitable variations. When phenols, pyrazolones, acetoacetic acid
arylamides or naphthol sulphonic acids are used as coupling components clear yellow
to red shades are obtained.
Diamino diphenyls substituted at 2,2′ positions give wash-fast and millingfast acid
dyes. An example is C.I. Acid Yellow 44, C.I. 23900 [2426-76-7] (21). C.I. Acid
Yellow 42, C.I. 22910 [6375-55-9] is also an important example of this type.
Figure 4: Disazo acid dyes.
14
Special diamines developed for the synthesis of disazo acid dyes of this type are 22,
23, 24, and 25. Dyes based on these compounds have good light fastness, and
excellent wet fastness. They are usually neutral dyeing but play an important role in
dyeing blended spun yarn and blended fabrics of wool and cotton or wool and viscose
staple. The neutral dyeing acid dyes can be used in combination with direct dyes.
Examples are C.I. Acid Yellow 56, C.I. 24825 [6548-24-9] (26), C.I. Acid Red 154,
C.I. 24800 [6507-79-5] (27) and C.I. Acid Red 134, C.I. 24810 [6459-69-4] (28). A
milling dye is exemplifi ed by C.I. Acid Yellow 38, C.I. 25135 [13390-47-1] (29).
Disazo acid dyes derived from 3,3′diaminodiphenylsulphone have been reported.
 Secondary disazo dyes of the type A1 → M → C

There exist much greater possibilities for variations than the primary disazo dyes. Red
dyes and, above all, navy blues and blacks are found in this series.
Black, and navy-blue wool dyes in this series contain 1-naphthylamine or 1-

naphthylamine-7-sulphonic acid as middle components and N-phenyl peri acid and N-
tolyl peri acid, and naphthol and 1-naphthylamine derivatives as coupling components.
They are the very wash-fast and light-fast dyes. Examples are C.I. Acid Black 24, C.I.
26370 [3071-73-6] (30), C.I. Acid Blue 113, C.I. 26360 [3351-05-1] (31) and C.I.
Acid Black 26, C.I. 27070 [6262-07-3].
❑ Chrome Dyes
The chroming of largely acid monoazo dyes with certain structural features converts
them into chromium complexes on the fibre which improves the light fastness as well
as wash fastness of the dyeing. It also results in a deepening and dulling of the shade.
The application of chrome dyes to the fibre involves after-chroming, wherein the dye
is allowed to go onto the fibre from an acid bath followed by treatment with dissolved
alkali metal dichromate. In some special cases a one-bath chroming method
(metachrome process) is followed. Chrome dyes are only of very limited commercial
importance today for ecological reasons.
15
Salicylic acid based dyes are mainly yellow and orange. Examples are C.I. Mordant
Yellow 1, C.I. 14025 [584-42-9] (33) and C.I. Mordant Yellow 5, C.I. 14130 [6054-98-
4] (34). The complex formation on the salicylic acid group has little infl uence on hue
and light fastness, as against the o,o′-disubstituted arylazo compounds.
Metal complexation of o,o′-disubstituted arylazo compounds brings about a

considerable deepening of shade and usually increases the light fastness. Examples are
C.I. Mordant Red 7, C.I. 18760 [3618-63-1] (35) and C.I. Mordant Red 19, C.I. 18735
[1934-24-3] (36). Two other important black dyes are C.I.
Mordant Black 3, C.I. 14640 [3564-14-5] (38) and C.I. Mordant Black 11, C.I. 14645
[1787-61-7] (40). Other examples are C.I. Mordant Blue 13, C.I. 16680 [1058-92-0]
(37) and C.I. Mordant Black 9, C.I. 16500 [2052-25-7].
The o,o′-dihydroxy aminoazo and o-hydroxy-o′-aminoazo compounds with phenols or

aniline derivatives as coupling components give mainly brown shades on after-
chroming. C.I. Mordant Brown 33, C.I. 13250 [361862-0] (41) is an example.
Some dyes that are suitable for the one-bath chroming method (metachrome process)
are C.I. Mordant Yellow 30, C.I. 19360 [6359-71-3] (43), C.I. Mordant Brown 48, C.I.
11300 [6232-53-7] (44) and C.I. Mordant Blue 7, C.I. 17940 [3819-12-3] (45).
Compared with the after-chrome method metachrome dyeing has the advantage of
simple application process. The hydrophilic character and its rate of complex
formation decide the suitability of the dye to the metachrome process.
❑ Acid Dyes for Synthetic Polyamides

Polyamide materials of synthetic origin can be dyed with disperse dyes, and with
selected acid dyes including metal-complex dyes. Synthetic polyamides have lower
acid-binding power and hence dyes with two or more sulphonic acid groups in the
molecule go onto the fibre much more slowly and to a much lower saturation value
than dyes with one sulphonic acid group.
16
 As with acid dyes for wool, the acid dyes for synthetic polyamides fall into two
classes:
✓ Group A consists of acid dyes with good levelling power and low sub-stantivity
for polyamide; they give reasonably good wet fastness.
✓ Group B consists of acid dyes with lower levelling power, higher sub-stantivity
and high wet fastness on polyamide.
Many of these acid dyes with inferior levelling power reveal clear differences in fi bre
structure (so-called streakiness), so that it is usually necessary to add levelling and
retarding agents.
Figure 5: Monoazo metal-complex dyes
17
A few representative structures of Group A are C.I. Acid Yellow 25, C.I. 18835 [6359-
85-9] (46), C.I. Acid Red 42, C.I. 17070 [6245-60-9] (47) and C.I. Acid Red 32, C.I.
17065 [6360-107] (48). The main application of Group A dyes is in carpet dyeing.
Some of the Group B dyes are C.I. Direct Yellow 65, C.I. 14170 [640898-8] (49) and
C.I. Acid Blue 113, C.I. 26360 [3351-05-1] (50). They are used exclusively for
clothing textiles, for which stringent requirements are placed on wet fastness. Some
secondary disazo dyes such as 51 and 1:2 metal-complex dyes are gaining importance
in the dyeing of synthetic polyamides.
Figure 6: Monoazo acid dyes with enhanced light fastness.
The chemometric approach has been employed in the structure optimisation in a series
of acid dyes for wool, and synthetic polyamides (Carpignano et al ., 1985 ; De Giorgi
and Carpignano, 1996 ; De Georgi et al ., 1997).
18
❑ Anthraquinone Dyes
Anthraquinone acid dyes are rich in violet through blue to green complementing the
azo dyes. They have very good light fastness. They may be subdivided into the
following types.
1. 1-Amino-4-(substituted) amino anthraquinone-2-sulphonic acids

2. Diamino dihydroxy anthraquinone sulphonic acids
3. 1,4-Diaminoanthraquinones with external sulphonic acids
4. 1-Amino-4-hydroxy anthraquinones with external sulphonic acid groups
5. Other acid anthraquinone dyes.
Anthraquinone acid dyes offer bright blue shades not obtainable in azo dyes. The red
and yellow anthraquinone dyes are of little importance. Green dyes obtained by the
combination of yellow and blue dyes have mostly inferior wash fastness. The
uniformly dyeing green dyes of the anthraquinone series have proved their special
value in this context. When synthetic polyamides were known some selected dyes
from this series were used. Special acid dyes of this class have been recently
developed for this purpose.
1) 1-Amino-4-(substituted)amino anthraquinone-2-sulphonic acids

These are obtained by the condensation of bromamine acid with aromatic or
cycloaliphatic amines, by an Ullmann reaction catalysed by copper or copper salts.
This group of blue acid dyes has important usage value and there are several reported
commercial structures. The shade, levelling characteristics and light fastness can be
varied over a wide range by selecting particular amines. Cycloaliphatic amines give
the same brightness as aliphatic amines but give greater light fastness. Arylamines
substituted with alkyl, halogen, aryl, aryloxy or sulphonic ester group provide dyes
with better wash fastness and affinity in neutral media but levelling is improved. The
brilliance is increased by the substituents at the o-position accompanied by
hypsochromic shift. The influence of methyl groups on the colour and dyeing
19
characteristics of acid dyes derived from 1-amino-4-bromoanthraquinone-2-sulphonic
acid and arylamines has been studied. A new method for the preparation of bromamine
acid directly from bromamine acid has been reported. A convenient and efficient
process for the manufacture of C.I. Acid Blue 78 from anthraquinone has been
reported.
Figure 7: Anthraquinone acid dyes
Some examples are C.I. Acid Blue 25, C.I. 62055 [6408-78-2] (52), C.I. Acid Blue 62,
C.I. 62045 [4368-56-3] (53), C.I. Acid Blue 129, C.I. 62058 [6397-02-0] (54), C.I.
Acid Blue 40, C.I. 62124 [6424-85-7] (55), and 56, and 57.
20
2) 1-Amino-2-aryloxy-4-(substituted)amino anthraquinones
These are the violet acid dyes with a brilliant hue and excellent fastness introduced
between 1960 and 1 970 (Peter and Gunthart 1 951; Swiss Patent, 1966 ). The violet
acid dyes of the copper complex azo type give dull shades while those of the
triphenylmethane type have very poor light fastness. The anthraquinone violet dyes of
this type can be used for dyeing natural and synthetic polyamide fi bres in bright
shades of high light fastness.
They are obtained by condensation of bromamine acid with a di- or trialkylaniline and
subsequent condensation with an alkylphenol followed by sulphonation. While the
general formula of such dyes is known, the exact number of sulphonic acid groups and
their orientation are not clearly elucidated. The structure and dyeing properties of such
anthraquinone violet acid have been reported
3) Diamino dihydroxy anthraquinone sulphonic acids

These are the oldest synthetic dyes for wool, but their importance has decreased
considerably. An example is C.I. Acid Blue 43, C.I. 63000 [2150-60-9] (58).
4) 1,4-Diaminoanthraquinones with external sulphonic acid groups

These are obtained by sulphonation of the corresponding dye base derived from
quinizarin or halo amino anthraquinones. The reaction products of quinizarin with
aromatic or araliphatic amines predominate in number and importance. The
introduction of hydroxy function into the 5- or the 5,8 positions causes the expected
red shift. Substituents infl uence the wash fastness and levelling.
The shade can be varied from brilliant blue to green by appropriate amines. Sterically
hindered amines, araliphatic and cycloaliphatic amines lead to brilliant blue shades.
Dyes in this series exhibit more light fastness than the derivatives of bromamine acid.
Among the unsymmetrically substituted dyes derived from 1-amino or 1-alkylamino-
4-haloaminoanthraquinones, 1-alkylamino anthraquinones have inferior light fastness.
21
Exceptions are the 1-sec-alkylamino-4-halo anthraquinones. Introduction of alkoxy or
aryloxy groups into the 2 position introduces a blue shift giving bright violet dyes.
Examples are C.I. Acid Green 25, C.I. 61570 [4403-90-1] (59), C.I. Acid Green 41,
C.I. 62560 [4430-16-4] (60), greenish blue dyes 61, 62 and C.I. Acid Violet 42, C.I.
62026 [64026 [6408-73-7] (63).
5) 1-Amino-4-hydroxy anthraquinones with external sulphonic acid groups

These are obtained by the partial reaction of quinizarin with arylamines, followed by
sulphonation. They are the violet level dyeing ones. Derivatives of 1-amino-4-
hydroxy-2-phenoxy anthraquinones were developed for polyamides of synthetic
origin.
Figure 8: Anthraquinone acid dyes.
Examples are C.I. Acid Violet 43, C.I. 60730 [4430–18–6] (64) and the bluish brilliant
red dye 65.
22
6) Other acid anthraquinone dyes
In addition to the classes mentioned above a whole series of specially developed dyes
are available. For example, derivatives of the anthrimide and carbazole series are
known to be very light-fast grey and brown wool dyes. The sulphonation products of
1,5- and 1,8-diarylamino anthraquinones are violet dyes commonly used as mixtures.
An example is C.I. Acid Black 48, C.I. 65005 [1328-24-1] (66).

A novel azo-anthraquinone dye made through innovative enzymatic process has been
the subject of a recent publication (Enaud et al ., 2010 ).
❑ Acid Nitro Dyes

These were first used in the colouration of wool. More recently, like the acid azo nitro
dyes, they have been used for the dyeing of synthetic polyamides. They have low
colour strength but higher light fastness.
The earliest anionic nitro dyes were produced by treating picryl chloride with aromatic
amino sulphonic acids. However, the dye 67A [1534752-1] obtained by the reaction of
2,4-dinitro chlorobenzene with 4-amino diphenylamine-2-sulphonic acid became
industrially important. The dye 67A gives light-fast yellow shades on wool and
synthetic polyamide fi bres. Relationships between the structure of nitrodiphenylamine
derived monoazo acid dyes and their spectroscopic and fastness properties have been
established (Szadowski and Przybylski, 1984).
A mixture of the dyes 67 [72829-30-2] and 68 [72829-29-9] is commercially available

as Nylosan Yellow Brown EGL (Sandoz). The dyes with sulphonate ester group 69
and many other functionally substituted derivatives are known. C.I. Acid Brown 13,
C.I. 10410 (70) is a bifunctional acid nitro dye produced by the reaction of 4,4′-
dichloro-3,3′-dinitrodiphenyl sulphone with 4-aminodiphenylamine-4-sulphonic acid.
The dye 71 gives brilliant yellow colour on synthetic polyamide. In this dye the
conjugation is interrupted by the methylene bridges.
23
Figure 9: Nitrodiphenylamine acid dyes.
❑ Triphenylmethane Acid Dyes

Acid dyes with triphenylmethane (blues and greens) and xanthenes (reds and violets)
chromophores are less important though they are very brilliant. They have poor light
fastness.
Triphenylmethane acid dyes were initially synthesised by sulphonation of the parent

cationic dyes. Alcohol soluble aniline blue was converted by Nicholson in 1862 into a
soluble form suitable for dyeing. Acid triphenylmethane dyes from benzylated aniline
were found to be good wool dyes. Introducing a sulphonic acid group ortho to the
methane carbon was found to have improved the alkali fastness. The fi rst dye of this
type was Patent Blue V obtained by Hermann in 1888 by sulphonation of the dye
obtained from 3-hydroxy benzaldehyde with diethyl aniline.
Patent Blue V, C.I. Acid Blue 3 [3536-49-0] (72) is a valuable dye for wool. A similar
good dye is Patent Blue VE, C.I. Acid Blue 1, C.I. 42045 [129-17-9] (73), which does
not contain a hydroxy group. If diethyl aniline is replaced by ethyl benzyl aniline in
the synthesis of Patent Blue VE, Patent Blue AF, C.I. Acid Blue 7, C.I. 42080 (74) is
obtained.
24
Derivatives of N-ethyl-N-(3-sulphobenzoyl) aniline are also important dyes in this
series. Examples are C.I. Acid Blue 9 (Patent Blue AE, C.I. Food Blue 2, C.I. 42090)
[3844-45-9] (75), C.I. Acid Green 3 (C.I. Food Green 1, C.I. 42085) [4680-78-8] (76)
and C.I. Acid Green 9, C.I. 42100 [4857-81-2] (77).
Figure 10: Triarylmethane acid dyes
Derivatives of naphthalene sulphonic acids are also found in this range. An example is
C.I. acid Green 16, C.I. 44025 (78), which is prepared by the condensation of 4,4′-bis
(diethyl amino) benzhydrol with 2,7-naphthalene disulphonic acid, and oxidation of
the leuco compound.
Figure 11: Triarylmethane acid dyes.
25
Arylated pararosaniline dyes with one sulphonic acid group are waterinsoluble
betaines and have pigment character. The more highly sulphonated triphenyl
pararosanilines are readily water-soluble acid dyes and find application in printing
inks. Examples are C.I. Acid Blue 93, C.I. 42780; C.I. Acid Blue 104, C.I. 42735 (79);
C.I. Acid Blue 49, C.I. 42640 [1694-09-3] (80); C.I. Acid Violet 17, C.I. Food Violet
1, C.I. 42650 [4129-84-4] (80A); C.I. Acid Blue 90, C.I. 42655 [6104-58-1] (82) and
C.I. Acid Blue 13, C.I. 42571 (83).
Figure 12: Pyronine acid dyes.
Hydroxy triarylmethane dyes with an adjacent carboxylic acid group find application
as mordant dyes. Examples are C.I. Mordant Blue 1, C.I. 43830 (84) and C.I. Mordant
Violet 16, C.I. 43865 (85).
26
Acid dyes of the rhodamine class are used more as laser dyes. Examples are
Sulphorhodamine B, C.I. Acid Red 52, C.I. 45100 [3520-42-1] (86), Sulphorhodamine
G, C.I. Acid Red 50 (87) and Fast Violet ARR, C.I. Acid Violet 9, C.I. 45190 (88).
Figure 13: Pyronine and diazine acid dyes.
Heterocyclic analogues or triarylmethane dyes like diazines are also converted into
acid dyes. An example of an acid safranine dye is Acid Cyanine BF, C.I. 50230 [6448-
97-1] (93); Indulines 6B (94); Wool Fast Blue FFG, C.I. 50330 [6837-47-4] (94);
Acilian Fast Violet FB or Wool Fast Violet B, C.I. 50325 (95); Supranol Fast Cyanine
B, C.I. 50335 [6378-89-8] (96); Fast Blue EB, C.I. 50300 [6471-74-5] (97); Supranol
27
EG, C.I. 50310 [6378-87-6] (98); Supranol Blue EG (99); Novazol Acid Blue GL
(100) and Polar Blue G (101).
Figure 14: Diazine acid dyes
❑ Water-Repellent Dyes
Water repellence is an important property required for comfort wear. For comfort wear
it is necessary for the fabric to be sufficiently porous to allow moist air to circulate.
Water-repellent finish is given to fabric by way of finishes which form a water-
repellent layer on the surface of the material without filling up the interstices. Several
fluorine containing acid dyes are known in the literature and recently dyes having
inherent water-repellent characteristics have been prepared.
❑ Acid Dyes with Inherent Light Fastness

Acid dyes with improved light fastness have become important particularly in
connection with the usage of acid dyes in information recording systems. The inferior
light fastness may be due to several reasons. Auto oxidation reaction of dyes is
generally considered to occur on exposure to ultraviolet (UV) radiation and prevented
by the addition of UV absorbers or antioxidants such as hindered phenols or
naphthylamines. In recent years as an approach to the photostabilisation of dyes
attempts have been made to prepare dyes with built-in photostabilising moiety.
28
❑ Acid Dyes Free From 1-Naphthylamine
1-Naphthylamine has long been established as a diazo component and an intermediate
component in dyes of the type:
amine → intermediate component → coupler, giving heavy shades on wool and
cotton.
Even though these dyes are known for their brilliance and fastness properties, the
pronounced carcinogenicity of 1-naphthylamine may restrict the use of such dyes in
the future. Interest has therefore developed in recent years in the replacement of toxic
diamines and amines. In this connection 3-acetamidoaniline derivatives with selected
substituents at 4 position have been suggested as suitable substitutes. Several monoazo
and disazo dyes have been prepared in these lines and they have been compared with
their 1-naphthylamine counterparts (Sekar, 1 995, 1996; Sekar and Nayar, 2006 ).
❑ Future Trends
Developments in the basic chromogenic systems seem to be more or less saturated.
However, functions other than imparting colour are being closely researched. There
are publications discussing acid dyes with additional functions such as water
repellency, inbuilt UV-absorbing units and antibacterial properties. These kinds of
dyes are envisaged to eliminate the additional finishing steps such as water-repellent
finish, antibacterial finish and other finishing treatments. It is likely that commercial
dyes will evolve in these lines.
REFERENCES
1. A brahart E N (1977), Dyes and Their Intermediates, 2nd edn., Edward Arnold, London.
2. Akiyama S, Nakashima K, Nakatsuji S, Suzuli M and Umekawa C (1987), Synthesis and
properties of 5-substituted 2-thiobarbituric acid dyes, Dyes and Pigments, 8, 459–463.
3. Blus K (1992), Synthesis and properties of acid dyes derived from 1-phenyl-3-methyl-5-
pyrazolone, Dyes and Pigments, 20 , 53–65.
4. Blus K (1999), Synthesis and properties of acid dyes derived from 7-amino-1
hydroxynaphthalene-3-sulphonic acid, Dyes and Pigments, 41, 149–157.
29
5. Blus K and Kraska J (1988), Synthesis and properties of aminoarylsulphonanilidesulphonic
acids, Dyes and Pigments, 9 , 305–313.
6. Blus K and Kraska J (1992), Synthenis and Properties of acid dyes derived from 1-Phenyl-3-
methyl-5-pyrazolone, Dyes and Pigments, 20, 53–65.
7. Blus K and Kraska J (1993), The infl uence of arylamide groups on the properties of acid dyes,
Dyes and Pigments , 22 , 163–172.
8. Carpignano R, Avarino P S and Barni E (1985), Quantitative structure–property relationships
study of azo dyes using partial least squares analysis in latent variables (PLS), Dyes and
Pigments , 6 , 189–212.
9. Chao Y C and Yeh C W (1993), The influence of long-chain alkyl groups on the colour, dyeing
and fastness properties of 2-(and 1-) phenylazo-1-(and 2-) naphthol acid dyes, Dyes and
Pigments , 23 , 285–296.
10. Chao Y C, Chang M J and Chang C H (1998), Water-repellent acid dyes: The influence of the
perfluorobutamido group on the colour, dyeing and fastness properties of 2-( p -alkyl) phenylazo-
1-naphthol acid dyes, Dyes and Pigments , 39 , 183–191.
11. Chengqin Z (1979), Dyestuff industry,Shenyang Research Institute of Chemical Technology,6,79.
12. Chunlong Z (1989), Acid Dyes and Mordant Dyes, Chemical Industry Press, Beijing.
13. Ciba-Geigy (1980), Water-soluble dyes of the 1-amino-2-phenoxy-4-phenylamino anthraquinone
series, Eur Patent Application 12111.
14. De Giorgi M R and Carpignano R (1996), Design of dyes of high technical proper-ties for silk by
a chemometric approach, Dyes and Pigments , 30 , 79–88.
15. De Giorgi M R, Carpignano R and Crisponi G (1997), Structure optimization in a series of acid
dyes for wool and nylon, Dyes and Pigments , 34 , 1–12.
16. DeWitt C C and Shroff P D (1953), Synthesis of water-repellent dyes, Industrial and
Engineering Chemistry, 45 , 302–307.
17. naud E, Trovaslet M, Bruyneel F, Billottet L, Karaaslan R, Sener M E, Coppens
18. P, Casas A, Jaeger I J, Hafner C, Onderwater R C A, Corbisier A M, MarchandBrynaert J and
Vanhulle S (2010), A novel azoanthraquinone dye made through innovative enzymatic process,
Dyes and Pigments , 85 , 99–108.
19. oris A (1977), NMR Spechosocopy of Synthetic Dyes, in The Analytical Chemistry of Synthetic
Dyes , Venkataraman K (Ed.), John Wiley and Sons, New York, 217–254.
20. Freeman H S, Esancy M K, Esancy J F and Claxlon L D (1991), Color, yes. Cancer, no,
Chemtech , 7 , 438–445.
30
Vat dyes
Wael Awad Hamouda
Why So Called Vat Dye?
• The word vat means, ‘Vessel’. The dyes take their name from vatting.
• The vat dyes are naturally coloring matter and kept in wooden vat and make solubilise
vat dyes by the process of fermentation – so it is called vat dye.
• They are applied in a special kind of a dyebath in which the dye is reduced to a soluble
form by means of a strong reducing agent, such as hydrosulphite.
• The vat dyes are insoluble and cannot be used directly and requires vatting.
• Among all the dyes, it has the best fastness properties. Vat dyes are among the most
expensive dyes used for dyeing cellulosic materials with best overall fastness properties,
including washing fastness, light fastness and chlorine fastness.
• They are preferred for dyeing workwear or uniforms, or where the textiles
Vat Dyes
Vat dyes are complex, water-insoluble dyes. They exhibit unique light and wash fastness. The most
significant vat dyes were invented in the 20th century (Epp, 1995). An important role is played by vat
dyes both in printing and dyeing of cellulosic or cotton fibers. Though these dyes are insoluble in
water, sodium hydroxide and sodium hydrogen sulfide allow them to be dissolved in water for 15–
20 min at 50°C. They are sold as water-insoluble pigments that, on dissolution within solution,
provide molecular ions, which are transported to the surface of the fiber and can be drawn as
appropriate fiber.
Vat Dyes
• Vat dyes exhibit superior color fastness. Examples of vat dyes include
amarnthrene, benzanthrene, carbenthrene, indanthrene, navinon and
solanthrene. Prior to vat dye use, they are vatted via the addition of
sodium hydroxide and sodium hydrosulfite. These dyes on dissolving in
water are ionized and therefore do not produce the same color as the
parent dye. Even these dyes are dissociated by the addition of common
salt in the dye bath during dyeing of cotton and cellulosic fibers
(Aspland,1992).
Properties of Vat Dye
• Vat dyes are natural coloring dyes.
• Vat dye is water insoluble and can’t be applied directly on textile material.
• Vatting process is needed for making the insoluble vat dyes into soluble
form.
• Mainly use for cellulose fibre dyeing but in protein fibre dyeing PH
should be controlled.
• Stability of the color in the fiber is excellent.
• Vat dyeing is carried on alkaline medium
• Various shades are found.
• Dyes are available in two physical forms – powder and paste)‫) لصق‬.
• Dyeing process is difficult.
• Exposure of dye bath to sunlight should be avoided as dyes are sensitive to
light, and ester groups are affected to develop dye prematurely.
• Dyes are costly, but the levelling property is excellent.
• Vat dyes are mainly used for coloring cellulosic fibers.
• Wide range of color can be achieved by these dyes.
• Washing fastness of vat dye is very good with rating 4-5.
• Rubbing )‫(فرك‬fastness is not good.
• Sometimes, can causes skin diseases
• Application of vat dyes is limited in practical life.
Structure of Vat Dye
• Vat dyes contain a quinoid structure as their characteristic sign.
• The dyestuff in its oxidized form is insoluble in water and most solvents, as no
solubilizing groups are present in the molecular structure.
• The reduction of the quinoid structure is an essential step in the application of vat
dyes, as the reduced (leuco) form of the dye is soluble in alkaline solution.
• The reduced form of the vat dye is the fiber form that exhausts from the dyebath
• The principal chemical classes of vat dyes are anthraquinone and indigoid.
Fig: Characteristic structures of vat dyes: (a) C.I. Vat

Yellow 1 and (b) C.I. Vat Blue 4.
Vat Blue 36 Vat Blue 30

• Vat Green 11 Vat Red 18
Classification of Vat Dyes
• The vat dyes are to be divided into several groups, depending
upon their chemical nature and origin, as follows:
1-Indigo, including both natural and Synthetic
2-Thio-indigo dyes, containing sulphur.
3-Indigo derivatives, such as the brom-indigos; usually not
derived directly from indigo itself, but built up synthetically.
Classification of Vat Dyes
4-Anthraquinone derivatives, including the various Indanthrene,
Marione and others.
5-Carbazol derivatives, of which Hydron Blue is the chief
representative
Indigo
• Indigo Many plants of the genus Indigofera have been cultivated for
production of indigo in India, China, Japan, Central America, West Indies,
Brazil, South and Central Mrica, Madagascar, Java and the Philippine
Islands. The colouring principle is present as a glucoside of indoxyl
known as indican, and this was hydrolysed to free indoxyl by enzyme
action; indigo (also known as indigotin) was obtained by oxidation of
indoxyl:
Indigo
Natural indigo contains a red isomer of indigo known as indirubin and other
impurities in varying proportions.
These constituents facilitate preparation of the vat, and were considered to
have a desirable effect on the dyed shade, but the variable properties were a
nuisance to the dyer. Woad, which was extracted from the plant Isatis
tinctoria, and used in Western Europe.
Vat dyes can be classified based on the following
• Chemical constitution
• Method of application
• a) Chemical constitution
• As per chemical constitution, vat dyes can be classified into following two
classes:
• Indigoid
• Anthraquinonoid
Chemical constitution
• Indigoid dyes have limited range of colors. These form of dyes can dye
nylon, wool and cotton. Whereas Anthraquinonoid vat dyes, i.e.
anthraquinonoid compounds with carbonyl groups are in the market since
the beginning of 20th century. Most of the vat dyes belong to
anthraquinone groups because indogoid have lost their practical
importance.
Do you know these advantages of vat
dye?
1.Most of vat dyes are middle colors
Vat dyes has a full range of characteristics from yellow to black and bright to
general colors.The most important feature of which is the majority of intermediate
colors, which are essentially single components, advanced reproducibility,
especially green, Olive green, flesh, brown and gray series.
For example, green reactive dyes are generally made of yellow and turquoise
colors. Dyeing control is extremely important for combining different performance
of reactive dyes. And in the reduction of dyes there are several single structure of
the green varieties, not only can meet the different needs, but also have an excellent
reproducibility of dyeing when compared with the reactive dyes.
2.Having excellent light fastness and various fastness to light fastness
At present Various fastness to light fastness on cotton fabric, Such as Perspiration - fastness to sunlight, perspiration -
daylight - washing fastness, perspiration - daylight - rubbing fastness, etc. Compared with other types of cotton dyes, vat
dyes have special properties Therefore, it is very suitable for dyeing and printing to work clothes, summer clothes,
sportswear, coats, curtains, furniture cover.
3. It has excellent chlorine resistance and wet fastness.
To compared with vat dyes and reactive dyes, the former one has better chlorine resistance, no matter the fastness of
chlorine water(20ppm) or chlorine(500ppm).In addition, Vat dyes have excellent washing fastness etc, so vat dyes are
applicable for the occasions with high requirements of chlorine disinfection and washing resistance, for example, printing
and dyeing for fabrics, bedding, covers, bed sheets, clothing, etc. in hotels and hospitals. Especially for the product of the
requirements of washing treatment which needs to be washed for many times, the advantage of using vat dyes is more
obvious. In addition, vat dyes are also applicable for dyeing and printing of textiles requiring the highest wet fastness. For
example, dyeing with reactive dyes and textile fabric dyed with vat dyes.
Also in order to reduce the use of washing water in the United States and Europe and other
countries and regions, using strong detergent is putting Four acetyl Ethylenediamine(TAED)
into oxide so that could make New detergent or Use a large amount of detergent and wash
with warm water in the washing water, through these we can see, Vat dyes also have an
advanced fastness.
4.The excellent stability of post processing on printing and dyeing fabric
Besides, vat dye has a very good stability developed in recent years during the improvements
of the functional changes in the fiber of the functional processing, such as shape memory
processing, morphological stability processing, deodorant processing, antibacterial
processing, etc.
5. One bath dyeing suitable for blended fabric
One bath dyeing for polyester/cotton, polyamide/cotton, vinylon/cotton and other blended fabric getting
more popular among dyeing and printing industry. Vat dye has this characteristic of the same color
dyeing and suitable for one bath continuous dyeing, printing and dyeing method. These fabrics can be
used to make student clothes, all kinds of uniforms, moisture permeability coats and special textiles,
especially military uniforms and combat suits (such as camouflage), but also has excellent fastness and
anti-infrared and other special properties.
6. Can be dyed with natural colors, and extremely clear color sense
Fabrics dyed with vat dyes can be showed colors and features of Europe style of natural plant, for
example: A variety of washing or cleaning(Stone washing and bleaching ) of indigo dyed and dyed
fabric with vat dyes could make a very clear and natural plant color sensitive textiles.
In a word, compared with vat dyes and other dyes for cotton, the former has a series of various of
obvious characters, particular reflected in the fastness properties, therefore, vat dyes is still a kind of
dyes for cotton that need to be paid good attention.
Method of application
Vat dyes are classified into four groups according to method of application,
depending on the solubility, ease of vatting, optimum conditions of dyeing etc. In
Germany, vat dyes are divided into four groups, according to the method of
application.
• IK Class (K for cold or Kalit in German)
• IW Class (W for warm)
• IN Class (N for normal)
• IN Spl Class (S for special dyes)
Vat dye printing
• Vat dye printing employs reduction-oxidation chemistry, where the reducing
agent becomes the fixing agent in the printing process. In the presence of a
reducing agent, an insoluble vat dye becomes soluble in the print paste. The most
popular reducing agent is sodium sulphoxylate-formaldehyde (commercial
names are Formosul and Rongalite).
• To fix the dyes after printing, the fabric is steamed, which initiates the chemical
reduction process and diffuses the dye further into the fibers. Afterward, washing
with an oxidation agent such as hydrogen peroxide converts the vat dye back to
an insoluble state. Lastly, the printed cloth is treated in a hot water bath with
detergent, which stabilizes the vat dye molecules and establishes maximum
fastness and optimum shades.
Application of Vat Dye:
• Three Stages in vat dyeing,
1. Vatting
2. Dying
3. Oxidation
• Theory of Vat Dyeing:
The simplest arrangement for dyeing fabric is to pull the textile material
through the dyebath so that the dye can exhaust on to the fabric surface.
• Low liquor ratios and the addition of common salt or Glauber’s salt both promote
such exhaustion.
• In some cases, the addition of acid also promotes exhaustion.
• If the dye is only partially soluble in water and likely to be exhausted
unevenly) ‫(بشكل غير متساوي‬, the addition of soap or sodium carbonate may
promote leveling.
• A dyeing is considered to be level if all parts of all fibers have been penetrated
evenly and completely. Machines for this type of dyeing are called batch
machines.
• If a dye is not soluble in water, as is the case with vats, it may be applied to the fabric as a
dispersion by a padder.
• Once the insoluble vat dye has been uniformly applied to the fabric surface, usually with
the aid of special dispersing agents (detergents), it can be solubilized by reaction with a
reducing agent, e.g., sodium hydrosulfite (“hydros”, Na2 S2 O4 ) in dilute NaOH.
• Once it has been converted to its soluble (LEUCO) form, the vat dye can penetrate into
the cotton fibers.
• After adequate time for penetration to occur, the fabric is withdrawn from the bath and
oxidized by air or an oxidizing agent such as sodium perborate or hydrogen peroxide.
This process is schematically represented below.
Chemical Alternatives
• Before chemical reducing agents were readily available, vat dyes were converted
to their soluble leuco form by fermentation of organic matter in wood tubs called
vats.
• This method of reduction and application is the source of the name for this class
of dyes.
• Once the vat dyes have been regenerated inside the fiber, they are very insoluble.
This accounts for their excellent wash fastness.
• Because they can be applied as a dispersion by padding, solubilized by
reduction, and finally reoxidized when inside the fibers, vats are well- suited to
continuous dyeing operations.
Such treatments exhibit a number of advantages
1. Very efficient use of the dye. All that is made up can be applied.
2. The insoluble vat is very evenly distributed over the fabric surface, leading
to level dyeings.
3. Continuous processes are normally more economical processes than batch
processes.
References
1. Textile Dyes by N. N. Mahapatra

2. Industrial Dyes: Chemistry, Properties, Applications Edited by Klaus Hunger
3. Textile Chemistry by Thomas Bechtold, Tung Pham
4. Cellulosics Dyeing Edited by John Shore
5. Textile Engineering-An Introduction Edited by Yasir Nawab
6. Textile Dyeing by N. N. Mahapatra
7. https://www.cncolorchem.com/news/862.html
8. https://www.sciencedirect.com/topics/materials-science/vat-
dyes#:~:text=Vat%20dyes%20are%20insoluble%20pigments,both%20water%2Dsoluble%20a
nd%20substantive.
An essay on:
Natural dyes “indigo dye”
Prepared by:
Farah Abd-elmoteleb Sadeek Harga
Pre-master degree in organic chemistry.
Faculty of science mansoura University.
Supervised by:
Prof: Hassan Ali Ali Etman
Prof of organic chemistry, chemistry department.

Dyes Merged

Uploaded by

Copyright:

Available Formats

Dyes Merged

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Dyes Merged

Uploaded by

Copyright:

Available Formats

A project On:

Alaa Ashraf Elawady

Prof/Dr. Hassan Ali Ali Etman

Popularity of reactive dye:

Reactive dyes are mostly used for dyeing cellulosic fibres. At

ii. Pyrimidine derivatives

Characteristics of reactive group of reactive dye:

Criteria for a Suitable Dyestuff

Reaction manner of dye and cellulose:

In cellulose macromolecule glucose units are linked through

Example: synthesis of procian

How procian link with cellulosic fibers

Example reactive black 5

Chemistry of azoic dyeing

Under The Supervision of:

Prof. Dr. Hassan A. Etman

Azo dyes can be classified either according to their characteristic chemical

Most azo dyes are synthesized by diazotization of an aromatic primary

At least one of these carbon atoms belongs to an aromatic carbocycle

The structure of an azo dye can be described by means of a structural formula

1. Color Index Generic Name (CIGN):

CIGN is a unique name assigned to each colorant, providing information

2. Color Index Constitution Number (CICN):

CICN is a numerical identifier assigned to each colorant, facilitating

3. Use of Numerical Prefixes:

Fig. 1 C.I. Disperse Red 60.

Most azo dyes are synthesized by diazotization of an aromatic primary

Processes involving synthesis of the azo group:

– Diazotization and coupling.

– Condensation of nitro compounds with amines.

– Reduction of nitro compounds

– Oxidation of amino compounds

Syntheses with compounds already containing the azo group:

– Exposure of concealed or protected amino groups.

– Acylation of aminoazo compounds.

– Alkylation and acylation of phenolic hydroxyl groups.

Influence of Reaction Conditions on the synthesis process.

The success of azo dye synthesis is highly dependent on reaction conditions

Choice of Starting Materials.

A meticulous selection of these starting materials allows for tailoring the

Green chemistry approaches are gaining prominence in azo dye synthesis.

The synthesis of azo dyes relies heavily on the diazotization process, a

Diazotization is defined as the reaction of primary aromatic amines with

Fig. 3.1 Diazotization process of Aniline with NaNO2 and HCl.

The essential step in diazotization, as shown in (fig. 3.1.1), is the

Weakly basic amines require a higher acid concentration, since otherwise

A further reason for using concentrated acids (concentrated sulfuric acid)

Diazotization of aromatic diamines gives bisdiazonium compounds and

Diazotizing Methods. [5]

a) Direct Diazotization. The primary aromatic amine is dissolved or

b) Indirect Diazotization. Amines with sulfonic or carboxylic acid groups

c) Diazotization of Weakly Basic Amines. Weakly basic amines are

d) Diazotization in Organic Solvents. The water-insoluble or only

Coupling components are aromatic systems with nucleophilic centers at the

Diazonium salt + Coupling component → Azo dye + By-products

Azo coupling can be summarized as follows: an aromatic amine is linked

4. Properties of Azo dyes

The wash-fastness properties of azoic dyed cellulosic materials are

The dark shades exhibit excellent lightfastness. However, at medium and

Most of the azoic combinations have excellent perspiration-fastness also.