Dyestuff Chemistry

Direct Dyes
Introduction

 They can be dyed directly on cellulosic

fibers. Without the presence of salt, when
the fibers are immerged in water, it will show
anionic charge which repels the dyes.
Adding salt into the dye bath, it will reduce
anionic on the fibers so the dyes can get
closer and adsorb into the fibers.
 Few examples are cotton, viscose rayon
 Easily applied on cellulosic fibers
 They can be directly died from simple
solutions in water
That’s why these dyes are called direct dyes
 They have an affinity for cellulose so can
also be known as substantive dyes
 DIRECT DYES

Features
 Presence of sulphonic acid groups
 Water soluble
 Anionic in nature
 Substantivity/affinity to cotton
 Applied from aqueous dye bath containing electrolyte
 Simple dyeing operation
 Low wash fastness
 Wash fastness improved to some extent after treatment with
cationic dye fixing agent
 Wash fastness still not adequate compared to other dye classes
such as reactive dyes
Congo Red (Direct Dye)
 Congo red was the first direct dye which was
discovered in 1894
 Introduction of reactive dyes was welcomed
because its was not expensive to implement.
 Direct dyes are marketed under different
brand names by different dyestuff
manufactures.
 DYEING OF COTTON WITH DIRECT
DYES

 TYPICAL DYE STRUCTURE

NH2
NH2

N N N N

Na2SO3 Na2SO3

CONGO RED
Properties of a solution
 direct dyes are water soluble
 They ionize in water
 That give dye anions (negative ions) and sodium
cations (positive ions)
 Dyes are manufactured as sulphonic acids and are
converted into their sodium salts
 Sulphonic acids are less soluble in water and have less
affinity for cellulose than their sodium salts.
 Small amount of soda ash is added to the solution to
convert sulphonic acid to convert into sodium salt.
Properties of a solution

 Reason to convert sulphonic acid into salt is

that then some of the dye will be wasted
during their application to the textiles
 The dye will not be fixed properly on the fiber
Chemical Structure

DYE SO3H
Dyeing with direct dyes

• Dissolving in the water

Dye Fiber Interaction
 Cellulose is not ionic in nature so ionic bonds that exist
between acid dyes and wool are not possible between
direct dyes and cellulose.
 Cellulose is not ionic in nature so ionic bonds that exist
between acid dyes and wool are not possible between
direct dyes and cellulose.
 Direct dyes attaches themselves to the fiber through the
formation of large number of weak attractions
 These consist of hydrogen bonds and van der waals
forces
Dye Fiber Interaction

 Polar dye Polar Fibers

 Dye applied from a hot water solution

H
DYE N HO
Hydrogen Bond
Polar group H Polar group

• Cotton and cellulose-based fibers

Dyeing Cellulose with direct dyes
 Dyeing with direct dyes

Addition of salt: the

edition of electrolyte
to the dye liquor is
essential to obtain
adequate exhaustion
of the dye molecules
by the fiber polymer
system.

Application of the heat: to the dye liquor increases the

energy of the components of the dye liquor, swells the
fibers and accelerate the rate at which dyeing occurs.
Dyeing with direct dyes
Dyeing with direct dyes
Classification of direct dyes

Depending on the effect of salt and

temperature on the dyeing , direct dyes are
classified into three groups
 Group A
 Group B
 Group C
Group A

Group A
 Migrate well
 Have high leveling power
 When dyeing these dyes, dyeing can be
uneven first but continued dyeing levels the
shade
 These do not need salt for exhaustion
Group B

Group B
 Poor leveling properties ( not self leveling
dyes)
 Need controlled addition of salt for the
exhaustion
 Also known as salt controllable dyes
Group B

 If these are not taken up uniformly by the

fiber in initial stage of dyeing then its very
difficult to even out the shade
Group C

Group C
 These are temperature controllable dyes
 Have poor leveling power ( not self- leveling
dyes)
 These are highly sensitive to salt
 Exhaustion cannot be controlled by the
addition of salt alone
 Need temperature control
Application of Direct dyes

They can be applied by two methods

 Exhaust method
 Continuous method
Dyeing Method for Cotton and other Cellulosics

Exhaust Application
 Application of Azonine and Durantine Dyes to Cellulosic
fiber
 Azonine dyes are an economical range of direct dyes with
good color values for users where specific fastness properties
are not the prime requirement.
 Durantine dyes may be used to dye most cellulosic fibres and
its blend by exhaust, continuous and printing techniques.
Dyeing Procedure
 At A add Azonine or Durantine Dye (predissolved)
0.1 to 0.5g/l Neutrasol CR (for shades difficult to
level)
 At B add y g/l Glaubers salt (anhydrous)
(1/5th of total amount required).
 At C add z g/l Glaubers salt (anhydrous)
(4/5th of total amount required).
 At D rinse twice cold.
 Thoroughly rinse after dyeing to remove loose colour
Dyeing Procedure
Dyeability of cellulosic fibers

 The addition of electrolyte to a solution of direct

dye tends to lowers the electrostatic repulsion
between the negatively charged dye anions and
promote aggregation or exhaustion.
 The effect of the presence of an inorganic salt
when dyeing cellulosic is to overcome the long-
range forces of repulsion between the dye
anions and the negatively charged fiber surface
Dyeability of cellulosic fibers

 The closer approach then allows the hydrogen

bonding and other short-range attractive forces
to operate between the dye molecules and the
glucoside units of the fibrous polymer
 Hydrogen bonding that forms between the
hydroxyl groups of cellulose and centers of
electronegativity ( nitrogen, oxygen and sulphur
atoms) in the dye molecule.
Dyeability of cellulosic fibers

 Hydrogen bonding that forms between the

hydroxyl groups of cellulose and centers of
electronegativity ( nitrogen, oxygen and
sulphur atoms) in the dye molecule.
 The most hydrogen bonds that a dye can
form with the glucosidic polymer, the more
readily it can compete with and rupture the
fiber-fiber hydrogen bonds in order to
penetrate more deeply into the amorphous
structure of the polymer
Dyeability of cellulosic fibers

 Especially those substituted with hydrogen

atoms such as (=N-NH-, NH2, -OH,)
 This is widely acknowledged as it contributes to
adsorption and the retention of dye molecule.
 Many direct dyes with high affinity for cellulose
are disazo or triazo azo structures
 The molecules of almost all direct dyes possess
flexible chains of aryl nuclei linked by azo or
other groups
Ability to cover neps in cotton fabric

 Pale flecks in dyed cotton fabrics can be

caused by immature or dead cotton
 This causes poor dyeability
 Poor dye penetration may leave undyed
areas if the neps of loosely attached
immature fiber changes position after dyeing
 Directdyes containing more than one amino
or amide group in their structure were found
most likely to achieve relatively good
coverage of neps.
 Dye enters cellulose as single molecules and
then aggregates inside the cellulose
 A decisive factor in determining the rate of
dyeing of many direct dyes from aqueous
salt solutions is their tendency to aggregate
Application of direct dyes

Direct dyes can be applied to cellulosic fibers

by the following methods
 Batchwise
 Semi and fully continuous methods
Batchwise method

 Direct dyes are water soluble dyes

 A solution can be made by adding them into
cold water and then put hot water while
stirring
 A wetting agent should be added to the dye
bath to assist penetration and level dyeing
 They are normally applied at the boil
 Dye-bath is set at 40C and the temperature
is raised 2C per min and maintained at the
boil for 35-45 minutes
 During which salt is added according to the
recipe
 Pastel shades are preferably dyed without
the addition of salt
 Many direct dyes suitable for application by
combined scouring and dyeing of either
woven fabrics on jigs or knitted fabrics on
jets or winches
 In this process usual practice is to employ
soda ash and a nonionic detergent.
 Combined peroxide bleaching and dyeing
with selected direct dyes is another long
established process
 Itoffers savings of a process time and
energy but more care is necessary to ensure
good results
 Sodium carbonate is preferred over caustic
soda as there is a risk of oxidative
degradation of direct dyes at higher PH.
Semi and Fully Continuous method

 They are less suitable for continuous

application than for batchwise dyeing
 Wet fastness of direct dyes may be lowered
when they are applied by continuous
processes
 Thiscan be overcome by adding electrolyte
or by increasing the impregnation
temperature
 The pad-roll process is probably the most
suitable semi-continuous method for dyeing
cellulosic fibers with direct dyes
 The temperature range should be 80-100C
 It is very important to control the fabric
moisture content and pad-liquor temperature,
dye selection for optimum compatibility and
the use of appropriate auxiliaries
 Its more versatile in production than the
steaming methods
After treatment processes

The wet fastness properties of all direct dyes

are inadequate for many end uses but it can
be improved by different types of after
treatments.
Diazotization and development

 Many long-established direct dyes containing

primary amino groups could be diazotized
and coupled onto the fiber with a variety of
developers, including napthols, diamines and
phenols to give larger molecules with
improved wet fastness properties.
Metal salt treatments

 Treatment with acidified copper salt solution

(0.25-2% copper sulphate and 1% acetic
acid for 20-30 minutes at 60C) results in a
marked improvement in the light fastness of
certain direct dyes.
 Washing and alkaline treatments removes
the copper and light fastness becomes
normal
Cationic fixing agents

 These compounds interact with the

sulphonate groups present in direct dyes,
conferring increased wet fastness in all tests
at temperatures below 60C
 They will also precipitate direct dyes from
solution and therefore the dyed material must
be cleared of loosely held dye before
treatment.
 Color changes may occur and in some cases
light fastness may be reduced
Formaldehyde treatment

 Treatment of certain direct dyes mainly

blacks, with 2-3% formaldehyde (30%) 1%
acetic acid (30%) for 30 minutes at 70-80C
improves the wet fastness to both water and
washing.
 A drop of light fastness may occur
Cross linking agents and resin
treatments

 Improvements in wet fastness properties can

be ensured by treatment with cellulose
reactants or amide-formaldehyde resins
 Subsequent removal of resin by acid
hydrolysis (formic acid at 90C or HCL at 60C)
leaves the unfixed direct dye on the fiber with
its originally low level of wet fastness.
 Treatment with cross linking agents in resin
finishing improves the wet fastness but color
and light fastness may be affected
Stripping of direct dyes

 Itis very easy to strip the direct dyes if these

have not been after treated.
 The colors can be destroyed by boiling with
sodium dithionite Na2S2O4.H2O
 Or by bleaching with hypochlorite solution
containing 1-2gm/l of available chlorine
 Ifa cationic agent has been used as an after
treatment, it is removed by boiling with 1-2%
formic acid before destroying color with
either reduction or oxidation
 Formaterials after treated with metal salts,
the metal is first removed by boiling with a
metal sequestering agent like sodium salt of
ethylene diamine tetra acetic acid (EDTA) in
a concentration of 3g/l and then the dye is
decomposed by the usual treatment with
hydros or chlorine