CNR ISMAC

Institute for Macromolecular Studies

Biella

www.bi.ismac.cnr.it

Politecnico of Turin www.polito.it

Course of Textile Fibres and Technology

Unit 25
Dyeing of synthetic fibres
Claudio Tonin
AY 2014/15

c.tonin@bi.ismac.cnr.it

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Dyeing Polyamide fibres

The two important fibres to be considered are Nylon 6 and Nylon 6.6.
Because of their similar chemical composition and molecular weights, many of their
properties are alike.
They do not differ in basic dyeing mechanism but rather in some details which
are of importance to the dyer; for example, nylon 6 dyes faster than 6.6 and has a
lower glass transition point (Tg Nylon 6 = 40 C; Tg Nylon 6.6 = 50 C).
Differences in the dyeing behaviour are practically due to differences in the physical
structures.
Nylon 6.6 is more crystalline and dye migrability (levelling) is more difficult than
with Nylon 6.
This should be taken into consideration when selecting the type of dye to be applied:
- small molecules are more suitable for good levelling in dyeing Nylon 6.6;
- big molecules are suitable to obtain high fastness to wet treatments when dyeing
Nylon 6;
- there are no differences in fastness to light between the two fibres dyed with the
same dyestuff.
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Polyamide fibres contain both acid (-COOH) and basic (-NH2) functional groups.
Therefore, both anionic (acid) and cationic (basic) dyes may be used for dyeing Nylon
under appropriate process conditions. Moreover, also disperse dyes can be applied to Nylon.

Dye

Tone

Levelling

Wet fastness

Acid (pH 4 - 5)

Brilliant

Good - Very good

Medium - good

Wealky Acid - Neutral

(pH 6 - 7)

Brilliant

Medium - low

Good - very good

Metal complexes
(premetallised)

Dark - deep

Medium - low

Good - very good

Chrome

Dark - deep

Medium - low

Very good

Reactive

Brilliant

Medium - low

Very good

Disperse low
Molecular Weight

Brilliant

Very good

Medium - low

Disperse high
Molecular Weight

Brilliant

Medium - good

Medium - good

Direct

Brilliant

Medium - low

Good

Cationic (basic)

Medium

Medium

Medium - good
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Acid dyes are used to a considerable extent for dyeing Nylon, because of their higher
wash and light fasness compared with disperse dyes.
Although the end groups are not made up of equivalent acid and basic groups due to the
use of chain stoppers in the polymerisation (acetic or benzoic acid), as with wool
adsorption of simple acids may be used as a basis for discussing the adsorption of the
more complex dye molecules:
NH3+

NH3+
+ H3O+

Ny
COO-

Ny

+ H2O
COOH

Nylons have a limited number of amino terminals (0.05 meq/g for Nylon 6.6) with
respect to wool (0.8 - 0.9 meq/g).
In the acid pH range the maximum quantity of acid taken up reaches a plateau
which correspond approximately to the number of amino end groups in the polimer.

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Further reduction in pH (<2) leads to additional adsorption of acid, which is attributed to

association with amino groups until the cleavage of the amide bonds with degradation
of the fibre:

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The mechanism of dyeing is similar to that of wool with acid dyes:

NH3+ X-

NH3+ Col-SO3+ Col-SO3- Na+

Ny
COOH

+ Na+ X-

Ny
COOH

Dyes are first adsorbed on the fibre surface, then penetrate into the fibre core where they
bond with protonated amino groups (ionic bonds) and with secondary links (Van der Waals).
In general, the affinities are larger so that the
pH conditions required for dyeing Nylon are
correspondingly higher.
Acid dyes for Nylon are classified into two
groups:
1) level dyeing nylon, applied at pH 4 - 5 with
formic acid and 10% Glaubers salt
(sodium sulphate);

2) high affinity dyes (milling and super-milling

dyes), applied at pH 6 - 7, exhausted with
ammonium acetate.
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In general, dyeing is begun at 40 C, the temperature gradually raised to 90 - 95 C and

dyeing continued at this temperature for 45 min.
For high affinity dyes, the levelling properties are poor so that the initial application must
be as uniform as possible: this is usually achieved by control of temperature and acidity,
i.e. by using dyeing conditions which favour slow and even exhaustion of dye by the fibre.
One difficulty which detracts from acid dyes is that the irregularities in the Nylon yarns
tend to be emphasised, especially with high affinity dyes (larger molecules).
The irregularities may be intrinsic from the yarn itself but may well have been introduced by
non-uniform tensions which may occur during weaving or by non-uniform heat setting.
A way to reduce the problem is dyeing irregular Nylons with disperse dyes, which are
relatively insensitive to both chemical and physical changes, because of their very small
molecular size.

As for wool, Nylon can also be dyed with

reactive dyes, especially in blend with wool
or cotton.

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Dyeing Acrylic fibres

Fibres made from 100% acrylonitrile are difficult to dye because of their compact
structure.
To overcome this and to improve the solubilty in solvents so that the polymer may
be wet or dry spun, copolymers are used.
A wide range of comonomers are used, which may be vinyl acetate, acrylic acid,
allyl-sulfuric acid,....(CH2=CH-CH2-SO3H).
The groups introduced may be basic, e.g. 2-vinyl pyridine, when the fibre may be dyed
with acid dyes under rather acid conditions.
Normally, the polymerisation of acrylonitrile and its copolymers is carried out using redox
initiators (chain growth polymerisation), the residues of which, namely SO3H or SO4 are
attached to the chain end.
The polymer itself therefore carries acidic groups (anionic groups) capable of acting as sites
for cationic dyes (basic dyes).

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The capacity for these dyes is enhanced if the comonomer itself carries an acidic group,
i.e. acrilic acid: -CH2-CHCOOH

Because basic dyes are readly adsorbed by acrylic fibres and the dyed material possesses
good light fastness, interest in dyeing acrylic and modacrylic fibres with basic dyes is
considerable.
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Basic or cationic dyes are colored cationic salts (usually chlorides, but sometimes
oxalates) of amine derivatives.
They were among the earliest colouring to be manufactured, especially for cotton treated
with tannins as mordants.
They remain of great interest because of their very bright shades and high light fastness
and are the most widely used for acrylic fibres.
Basic dyes fall into roughly five chemical groups,
as derivatives of:

Azines
Thiazines

Oxazines

Anthraquinone
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Triphenyl methane

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Acrylic fibres possess glass transition temperature in the region of 70 - 80 C. Dyeing

below this temperature is extremely slow but, once exceeded, the rate of sorption
becomes rapid.
The importance of temperature is shown in figure, when the dye uptake shows a marked
increase over a relative narrow temperature range.
A typical procedure, the dissolved dye is added to the bath at 60 C set with with acetic acid
and sodium acetate to pH 5. The temperature is quickly raised to 80 C and then slowly
brought to the boil, say at 1C/3-5 min and dyeing continues for 2 h.
The liquor is cooled slowly to 50 C, the goods are then rinsed and added with cationic
softeners.
The dye adsorption is influenced also
by the pH of the liquor because of the
dissociations equilibrium:
Acr-H
Acr-H + Dye+

Acr -

H+

Acr-Dye + H+

Dyeing is carried out with the addition

of acetic acid and sodium acetate or
sulphate, to ensure that the pH is
slightly acid in order to avoid the
possibility of decomposition of the dye.

curve A: pH = 4
curve B: pH = 5.5

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Unlevelness may result from uneven temperature gradients, especially for pale shades when
the carefull control of temperature is strongly needed.
In fact, the affinity of basic dyes for acrylic fibre is high and the dye strikes rapidly onto
the fibre: levelling cannot therefore be achieved by migration

Bath exhaustion curves for various depths of shade. The figures on the curves
indicate the percentage of Basacryl Blue GL.
Note that the absolute amount of dye adsorbed doesnt depend from the dye
concentration in the dye liquor.
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Levelling is also improved by the addition of retarding agents, cationic retarders,

which are quaternised long chain amines, that diffuse at speeds at least equal to
those of the dyes. By occupying first some of the fibre sites, they effectively reduce
the rate of dyeing, the retarder gradually being replaced by the dye.
In a similar way can be explained the moderate retarding action of the Na+ ions from
the salts (sodium sulphate or acetate), in competition with the cationic dye.

Bath exhaustion curves for 0.8 % Basacryl Blue GL with different amount of
retarder Basacryl Salt G
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Because the number of anionic sites of the acrylic fibres is limited to some extent,
special attention must be paid to:
- the saturation factors of the fibre;
- the saturation power of the dye;
- the saturation power of the cationic retarder.
Saturation factors are given for commercial acrylic fibres and related dyes, in order
not to exceed the total amount the fibre can uptake.
Dyebath preparation should be done by selecting dyes with comparable dyeing speed,
in order to avoid changes of hue: dyeing speed of commercial basic dyes is given in an
arbitrary scale from 1 to 5 (1= max dyeing speed).
In addition, care must be taken since the material is very easily deformed at the dyeing
temperature and stretching and flattening of the cloths may occur.
Acrylic fibres are often dyed also with disperse dyes.

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Dyeing Polyester fibres

The hydrofobic Polyester fibre has a very compact structure, it is highly crystalline and
doesnt contain functional groups available for bonding with dyes.
In addition, the stiffness imparted to the chains by the phenyl residues of the
terephthalate group results in a high glass transition temperature.
Hence, in order to dye at a suitable rate, the temperature must be as high as possible
commensurate with the equipment available.
The choice of dyes for this fibre is limited, being confined to the disperse dye range.
Polyester can be dyed as loose stock, yarn or in the fabric form.
Pale shades may be obtained at the boil, but for deeper ones dyeing must be carried out
at temperatures up to 130 C.
The need of pressure dye equipments represents a plant complication and an
increase of the process costs.
For the actual dyeing operation, prior scouring is desirable.

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Disperse dyes are small coloured molecules belonging mostly to the following chemical
systems:
- nitrodiphenylamine, providing yellows and oranges (1);
- azo, for a wide range of colours (1, 2);
- anthraquinone [derivatives of 3-methoxy-benzanthrone (3) and -amino anthraquinone (4)]
providing orange to greenish blue colours.

These dyes carry no charged groups although they contain rather polar substituents
such as -OH, -CH2CH2OH, NO2, etc. and their molecules are relatively small (~ 300 Dalton)
to give them a small solubility.
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The dyebath can be made up with dispersing agents and dyeing commences at 60 - 70 C
raising the temperature to 120 - 130 C when dyeing is carried out for 30 - 45 min.
The role played by the dispersing agent is more that to ensure the stability of the dyebath.
The dispersing agent is used over the Critical Micellar Concentration; its chemical
composition is affine to the dye which dissolves into the micelles.
Thus, the dyebath contains dye in three states, namely a small amount of dissolved dye, dye
into the micelles and solid dye, a situation which could be written as being an equilibrium:

Dyesolid

Dyemicelle

Dyedissolved

Removal of the truly dissolved dye by effect of dyeing, will result in more dye being
solubilised.
The dye in micelle therefore may be considered to act as a reservoir.
The dye comes into contact with the fibre surface and dissolves into the fibre itself, because
of the physical affinity and small molecular size (disperse dyes are also called plastosoluble).
The suggestion that the dyes may be mixed with or dissolved in the polymer chains
leads to the idea that the location of the dye is not specific.
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Structural differencies on the fibres may be the main cause or drawback in polyester dyeing.
Heat treatments (drawing, setting) modify the microstructure of polyester fibres; in general,
continuous-filament woven fabrics are thermo-set at 170 - 190 C and warp-knitted fabrics
at 200 - 230 C.
Exposure to such temperatures causes further crystalisation of the polymer with subsequent
modification of the domains accesible to dye.

The dye uptake decreases as the heat-setting temperature increases, reaching a

minimum at 180 C after which the uptake increases, with increasing the amorphous volume.
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When pressure vessels are not available, an alternative to using high temperatures
(ca. 130 C) for speeding up the rate of dyeing is by the addition of carriers which
reduce the glass transition temperature of the fibre.
These substances are rapidly adsorbed by the fibre and are likely to form a film on
the surface of the fibre.
Since disperse dyes dissolve in the carrier, the dyeing rate is increased by the high local
concentration of dye in this film.
carrier

disperse dye

film

fibre

The word carriers was coined because they carry the dye molecules from the bath, where
the dye is dispersed, into the fibre.
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For polyester, the most popular carriers are

o-phenylphenol, diphenyl or chlorinated
benzenes; among the range of compounds
suggested, some are water soluble (phenol
or benzoic acid) whereas others are
insoluble (diphenyl) and are used as
emulsions.
Different carriers augment the rate of uptake
to different extents, the water soluble ones
requiring to be used in larger concentration.

Carriers in general suffer from the disavantage

that they are toxic (suspected carcinogenic)
and may remain in the fabric even after
washing. Being comparative small
molecules, residual carrier may volatilise
during drying.
Their use is subjected to concern for the
environment and thus progressively declining
for the more environment friendly pressure
dyeing.
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Continuos dyeing polyester with disperse dyes is also carried out with the Thermosol
process that involves sublimation of the dye under heat and partial vacuum into fibres.
Polyester containing solid disperse dye applied to the fibre surface is heated near 200 C
under partial vacuum for a short period of time.
At this temperature the molecular motion within the polyester is high, permitting the dye
vapor to penetrate into the fibre and the dye to be dissolved.
On cooling, the disperse dye is permanently trapped within the fibre, with good levellig and
performances on fastness.
Thermosol is recommended for delicate textiles.
Finally, research is in progress on the application of supercritical CO2 as a solvent for
general purposes (dyeing or dry cleaning) in the textile field because of its strong
solvation properties.
Experiments with polyester have shown applicability on industrial scale.

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