Wool Bleaching
Wool Bleaching
Wool Bleaching
Dr Rex Brady
Deakin University
Topics
1. The effect of sunlight on wool
2. Why bleach wool?
3. Why wool becomes yellow in sunlight
4. Oxidiative bleaches
5. Bleaching of pigmented wool
6. Reductive bleaches
7. Combined process ‘full’ bleaching
8. Photobleaching by light
9. Fluorescent brightening agents
10.Pastel shades with reductive bleach and FWA
11.The future for bleached wool
1. The effect of sunlight on wool
The effect of sunlight on wool
§ Sunlight causes wool to change colour and lowers the
strength and abrasion resistance of wool.
§ Initially, wool is bleached by sunlight (photobleaching);
subsequently, photoyellowing predominates.
§ Prolonged exposure to sunlight leads to a loss in strength
and abrasion resistance, resulting in photo-tendering.
§ The shortest wavelengths present in solar radiation (290-
320 nm) are the most damaging to wool, and they cause
both photo-yellowing and photo-tendering.
§ Although window glass cuts out the wavelengths below
320 nm, the transmitted UV light (320-400 nm) still
causes photoyellowing and phototendering, at a reduced
rate.
Poor light stability of wool limits the range
of products in some areas of application
§ The photo degradation of wool limits the use of wool in
markets where requirements for light fastness are
stringent.
§ These include car upholstery, curtains, and apparel
requiring bleached and lightfast bright pastel shades.
§ Particularly with car upholstery, dyeing with selected 2:1
premetallised dyes (mostly cobalt complexes) in heavy to
medium depths, enhances the light fastness and
photo-stability of wool, but only a limited range of shades
is available.
§ Pale shades and particularly bright pale shades are
limited to product areas where relatively low lightfastness
can be tolerated.
2. Why bleach wool?
Why bleach wool?
§ Very bright colours cannot be obtained on wool because it does not
have a white base, and yellows readily in sunlight, especially when
wet.
§ As a result, markets requiring vivid colours, bright whites and
pastel shades such as women’s wear, baby wear, sports and
leisure wear are dominated by polyester, nylon, acrylic and cotton,
and are almost totally lost to wool.
§ Nonetheless, around 10% of the total world production of wool is
bleached.
§ Dyebath yellowing of wool may be counteracted by including a
small amount of a reduction bleaching agent in the dyebath.
§ At point of sale, some degree of brightness is desirable even if it is
lost early during wear.
§ A great deal of bleaching is carried out as a top-up whitening
process in the scour. Hydrogen peroxide is added to the last bowl
and some degree of bleaching takes place in the drier. This comes
about because the whiteness of scoured wool is taken into
consideration in determining the value of the product.
3. Why wool becomes yellow in
sunlight
Why does wool become yellow?
§ The most likely candidates for the formation of yellow chromaphores in
wool are the amino acids with aromatic rings. Colouration theory tells us
that conjugated systems are required for the development of colour.
§ The most likely amino acid to be involved is tryptophan but phenylalanine,
tyrosine and cystine residues are also involved. To date, 14 yellow
chromophores (some of which have similar structures) have been
identified within the proteins of yellowed wool.
§ One of these compounds is 3-hydroxykynurenine. It is bright yellow and
contains a chromophore that is utilised as a yellow pigment in nature,
such as in brightly coloured butterfly wings.
+
O N O N
H H
Eumelanin O + O
(suggested structure) N
H
N
H
O O O O
+
O N O N
H H
HOOC NH2 OH H OH
N R O N
O HO COOH
Pheomelanin
(suggested structures) N N S S
COOH
O H2N COOH
O
NH2
Xanthommatin Trichochromes
Principle of mordant bleaching
§ When the wool is treated (mordanted) with ferrous sulphate solution,
ferrous ions become bound to the melanin granules in the pigmented fibres.
§ The ferrous irons not bound to the pigment are removed by washing.
§ When the wool is treated with hydrogen peroxide, the bleaching reaction is
catalysed mainly within the melanin granules and they are bleached
selectively.
§ The melanin is broken down by hydroxyl radicals into colourless or less
coloured compounds.
Fe
Fe Fe Fe
Fe
Fe Fe
Fe Fe
Fe Fe Fe
Fe Fe
Fe Fe
Fe Fe
Pigmented Mordanted, rinsed
fibre fibre
Fe
Fe Fe
Fe Fe FeFeFe Fe Fe Fe
Fe Fe Fe
Fe Fe
Fe FeFe
Fe Fe Fe Fe
Fe FeFeFe
Fe Fe
Fe
Fe Fe
Mordanted Bleached
fibre fibre
Activated bleaching of Alpaca fibre
Brown
alpaca top Method II Method II used
slightly higher
Method I
concentrations
of reagents.
Oxidation bleaching with sodium
percarbonate
§ Another source of hydrogen peroxide is sodium
percarbonate: 2Na2CO3.3H2O2.
§ When this solid is dissolved in water it
dissociates into sodium carbonate and hydrogen
peroxide.
§ A 1% solution of sodium percarbonate has a pH
of 10.5 which is appropriate for bleaching.
§ The main disadvantage of this chemical is that
it will slowly decompose during storage if
exposed to moisture, thus releasing the oxygen
prematurely.
Damage caused by oxidative bleaching
§ Hydrogen peroxide and peroxy compounds damage wool fibres
as a side effect to their bleaching reactions.
§ This is caused by progressive oxidation of disulphide bonds to
cysteic acid residues. Destruction of disulphide crosslinks in
keratin produces loss of fibre strength.
§ Subsequent dyeing processes can aggravate this initial damage
so pre-bleached wool should be dyed at as low a temperature as
possible.
§ Since pastel shades are normally produced on bleached
grounds, dyeing at around 80°C is adequate.
§ Oxidatively bleached wool should not be boiled since it
undergoes hydrothermal yellowing at a greater rate than
unbleached wool.
6. Reductive bleaches
Reductive bleaching
§ The most commonly used compounds are:
§ sodium dithionite (hydrosulphite),
§ sodium and zinc formaldehyde sulphoxylate
(e.g. Formosul)
§ sodium metabisulphite (e.g. Erioclarite B)
§ hydroxylamine sulphate (e.g. Lanalbin B)
§ thiourea dioxide
§ sodium tetraborate.
§ The whitening effect is not as great as with
oxidation bleaching but the bleached colour is
more durable.
Hydroxylamine sulphate (NH3OH)2 SO4
§ This has a mild bleaching action and it can be used to facilitate the
dyeing of bright paler colours.
§ Lanalbin B (Clariant):
§ its application level is 1.0-2.0% depending on the colour of the
wool. Its reaction is acidic and it may be necessary to adjust the pH
with ammonia or sodium acetate when applying neutral-dyeing
dyes.
§ Lanalbin BE (Clariant):
§ this product is similar to Lanalbin B but does not need to be
neutralised. The application level is 1.0-4.0%
§ when applying reactive dyes, Lanalbin B or Lanalbin BE should be
added to the exhausted dyebath rather than at the start of dyeing,
to avoid adverse effects on fastness and shade.
§ Lufibrol FW (BASF) is a mild reducing agent with complexing properties.
Quantities of 0.5-1.0 % are added at the start of dyeing. Most acid dyes
are unaffected but BASF Technical Information Bulletin No. TX177 lists a
few that are.
Sodium metabisulphite
§ Erioclarite B (Ciba) is a mixture of sodium metabisulphite
with the sodium salt of ethylenediamine tetraacetic acid
(EDTA).
§ The recommended application level of Erioclarite B is 0.5
- 1.0 g/l.
§ Dyeing at 80-85°C is recommended for pale shades.
§ If higher dyeing temperatures or prolonged treatment are
necessary, a further addition of 0.5 g/l Erioclarite B may
be required.
§ To maintain maximum fastness of Lanasol reactive dyes,
Erioclarite B should not be added until the bath has been
at maximum temperature for 15-20 minutes.
Sodium dithionite (hydrosulphite)
§ Na2S2O4 CI Reducing Agent 1
§ This is the most common compound for wool reductive bleaching. Many
companies offer stabilised products optimised for use on wool.
§ Typical recipe:
§ 2-5 g/1 stabilised dithionite (Hydros)
§ 0.5 g/l wetting agent
§ pH 5-6
§ 45-65°C
§ up to one hour
§ Typical products
§ Blankit AN (BASF)
§ Blankit IN (BASF). Binds iron and heavy-metal ions and leaves wool
soft
§ Leucophor PC (Clariant).
Sodium and zinc formaldehyde
sulphoxylates
§ Bleaching is usually carried out at pH 3, with
the temperature raised to 90°C and maintained
at this level for 30 minutes.
§ This process tends to harshen the handle of the
wool fibre and also leaves a sulphurous odour.
§ These products are commonly used for
discharge printing on wool.
Thiourea dioxide reductive bleach
§ Thiourea dioxide (Thiox) is applied at 70-80°C at pH 7 for
one hour (1-3 g/1) at pH 6.5.
§ A sequestering agent such as EDTA (0.25 g/l) must be
included in the bath to prevent heavy metal-catalysed
decomposition of this reducing bleach.
§ This compound is claimed to have less effect on the
physical properties of the fibre than other reducing
bleaches.
§ The active bleaching species in thiourea dioxide bleaching
is sulphinic acid (H2SO2).
Sodium borohydride bleach
§ COLORCLEAR® SOLUTION (Rohm and Haas) is a solution
of stabilised sodium borohydride, NaBH4.
§ Sodium borohydride as a source of the nucleophile H-
(hydride), which attacks partially positively charged
carbonyl carbon atoms of aldehydes and ketones and
converts them to alcohols. One mole of sodium
borohydride supplies four moles of hydride.
§ Recently it has been reported that sodium borohydride is
superior to both thiourea dioxide and sodium
hydrosulphite bleaching systems on wool,
chlorine/Hercosett wool and wool/cotton fabric.
§ The best bleached white was produced on wool and
chlorine/Hercosett wool with a combined
oxidative/reductive procedure using the new technology
in the reductive step.
§ The reducing agent technology gave acceptable damage
on wool, which was comparable with bisulphite bleaching.
Sodium borohydride bleach
§ ColorClear Method (Rohm and Haas).
§ Set bath at 40°C with:
§ ColorClear 2.0 g/l
§ catalyst 100 8.0 g/l
§ wetting agent/detergent 0.5 g/l
§ acetic acid to pH 5.5.
§ Run 10 minutes.
§ Raise temperature to 60°C and hold for 60
minutes.
§ Drain and rinse.
7. Combined process ‘full’ bleaching
Combined oxidation and reduction
bleaching
§ The textile industry prefers the neutral white colour
obtained by an oxidation bleach followed by a reduction
bleaching step (so-called ‘full’ bleach). Peroxide-bleached
wools often have a reddish cast whereas reductive-
bleached wools have a greenish tinge so the net result is
a more neutral white.
§ The greatest problem is the poor lightfastness of the
white produced.
§ Arifoglu and Marmer have described a novel oxidative-
reductive bleaching system which involves first bleaching
with hydrogen peroxide and then adding thiourea to
generate thiourea dioxide in situ.
Combined oxidation and reduction
bleaching
§ The best available technology at present for
producing a bleached white on wool and
chlorine/Hercosett wool is with a combined
oxidative/reductive procedure using Tinoclarite
WO and hydrogen peroxide (as recommended
by Woolmark), followed by the ColorClear
reductive bleaching treatment (Rohm and
Haas).
§ Both methods have been given in previous
slides.
Ref: ‘ColorClear technology, a new method of whitening of wool, machine washable wool and
wool/cotton blends’, S. M. Smith, D. J. Westmoreland & H. P. Schoots, Proc 11th Int. Wool Text
Conf., Leeds, UK (2005).
8. Photobleaching by light
Photobleaching by light
The problem of ‘first fade’
§ All wools become bleached to some extent when
exposed to sunlight, even behind glass.
§ Such photobleaching may be perceptible within a few
hours of exposure.
§ This is a particular problem with carpets if the shade is
sensitive to small changes in the light yellow colour of
the wool.
§ Photoyellowing is also caused by ultraviolet light, but
this is an unrelated problem, so photobleached wools
re-yellow slowly on prolonged exposure to light behind
glass.
Photobleaching by light
• The figure shows the rate of photobleaching of a number of wools
with different initial yellowness indices, when exposed to sunlight.
• A change in yellowness index (Y-Z) of 1.5 or more is easily
apparent to the human eye, so it is clear the yellower wools, if
used in ecru or pale colours, are likely to give rise to consumer
complaints.
• The initial rate of bleaching is relatively rapid.
• The yellower the wool, the greater the total change in yellowness.
Treatment to counteract the effects
of photobleaching
§ Lanalbin APB (Clariant) is a
colourless dye, was developed by
WRONZ, to eliminate the
problem of photobleaching by
undergoing a photoyellowing
reaction which counteracts the
photobleaching effect.
§ stilbene or bis-stilbine
derivatives, which make up the
majority of brightening agents.
Uvitex NFW
Lightfastness of bleached and optically
brightened wool
§ Some fluorescent whiteners, such as the
coumarin derivatives, give white wools that
have light fastness ratings of 1 on the SDC blue
scale. The most stable products (maximum light
fastness rating 2-3) seem to be based on bis-
stilbenes.
§ However, stilbene derivatives contain an
aliphatic carbon-carbon double bond (C=C
outside the aromatic rings) which is sensitive to
sunlight, oxidation, weathering, etc. Therefore,
these compounds do not have good light
fastness properties, and tend to loose their
effectiveness rapidly in use.
Why does wool yellow in sunlight?
§ The role of free-radical mechanisms in the photoyellowing of
wool, especially bleached and FWA-treated wool has been
extensively studied.
§ As with normal wool, yellowing appears to be the result of
reactions with specific amino acid residues in the wool protein
structure, such as tryptophan, phenylalanine, tyrosine and
cystine. These residues produce photo-oxidation products such
as kynurenine, N-formylkynurenine, 3-hydroxykynurenine, o-
tyrosine, m-tyrosine, and 3, 4-dihydroxyphenylalanine that are
possible contributors to the yellow chromophores in irradiated
wool.
§ Yellowing is accelerated by FWAs. Oxygen must also be present.
The suggested mechanism is:
10. Pastel shades with reductive
bleach and FWA
The current situation with pastel
colours
§ A completely effective solution to the problem
of rapid yellowing of bleached, and particularly
bleached and optically whitened, wool in
sunlight of has not been found.
§ The best current technology is to dye pastel
shades in the presence of a reduvtive bleach
and to similtaneously apply a FWA.
§ A typical procedure and the results obtained are
illustrated in the next few slides.
Pastel shades with reductive bleach
and FWA
CSIRO process
§ Prescour:
§ 1% (owf) nonionic detergent
§ 2% (owf) ammonia
§ 70oC, 15 minutes
§ LR 30:1
§ Dye: 85oC
20-30 min.
§ 10% (owf) ammonium sulphate
§ 1% Albegal B
§ 0.3% Albegal FFA 60oC
10 min.
§ 0.2-1.0% FWA
§ 4% Erioclarite B 40oC
10 min.
20oC
10 min.
Pastel shades with reductive bleach
and FWA
Dye % Xenotest Sunlight Sunlight Machine Alkaline
(o.w.f.) dry wet washing perspiration
fastness
Lanasol Bed B 0.015 4 4 3 3 5
Lanasol Red 6G 0.01 4 3-4 3 3-4 5
Lanasol Blue 3G 0.05 4 4 3-4 3 5
Reactofil 0.2 3-4 3-4 1-2 3 5
Turquoise Blue
8058 80%
Required amount
§ exhaustion:
§ 3-4 % CIBAFAST® W liquid, depending on liquor ratio
and requirements
§ continuous steaming:
§ 7.5 g/l CIBAFAST® W liquid, at 400% pick-up
§ aftertreatment:
§ 3-4 % CIBAFAST® W liquid.
Cibafast W
Dyeing Lightfastness
addition
Pale grey Rose Pale violet Pale blue