US 2016.

0047087A1
(19) United States
(12) Patent Application Publication (10) Pub. No.: US 2016/0047087 A1
Crepet et al. (43) Pub. Date: Feb. 18, 2016
(54) PIGMENT-DYEING METHOD Publication Classification
(71) Applicant: S.P.C.M. SA, Andrezieux Boutheon (FR) (51) Int. Cl.
D06P I/52 (2006.01)
(72) Inventors: Bernard Crepet, Lyon (FR): Olivier D06P I/44 (2006.01)
Level, Cibubur (ID) (52) U.S. Cl.
(73) Assignee: S.P.C.M. SA, Andrezieux Boutheon (FR) CPC ............... D06P I/5242 (2013.01): D06P I/445
(2013.01)
(21) Appl. No.: 14/780,443

(86). PCT No.: PCT/FR2014/050738

S371 (c)(1) Pigment-dyeing method for individualised textile fibres or
(2) Date: s Sep. 25, 2015 textile supports obtained from the fibres consisting of pre
treating the fibres or the Support with at least one polymer,
(30) Foreign Application Priority Data then dying the thus pre-treated fibres or Support using pig
ments, characterised in that the polymer is a vinylamine
Apr. 9, 2013 (FR) ....................................... 1353179 based (co)polymer.
US 2016/0047087 A1
PGMENT DYEING METHOD
FIELD OF THE INVENTION
0001. The invention relates to the textiles domain. More
precisely, the invention relates to a novel pigment-dyeing
method for textile materials by exhaustion.
BACKGROUND OF THE INVENTION
0002 There are two types of products to colour textile
materials: the dyes and the pigments.
0003. The dyes are water-soluble compounds. They can be
of different classes, such as direct, reactive, Sulphur-based,
indigo, basic or acidic. The benefit of the dye is that it pen
etrates the fibre itself. However, using dyes requires addi
tional rinsing steps, which result in highly polluted water with
residual dyes, which can cause ecological problems. More
over, the colouration process is long and requires large quan
tities of water and energy.
0004. The pigments are chemically inert, are not soluble in
water nor in most of the solvents currently used and don’t
have an affinity for the fibres. Consequently, they cannot
penetrate in the fibre like the dye but remain on the surface
only. Their use involves the use of binders, generally of the
thermoplastic elastomer type, and the use of fixing agents in
order to obtain high quality of resistance of the colours to wet
testS.
0005. In the textile industry the pigments are certainly the
simplest and most used method for colouring textile materials
because they offer many benefits:
0006 a versatile aspect (all fibres),
0007 their capabilities of preserving the environment
(low amounts of waste, no Subsequent washing, etc.),
0008 their good resistance to light, water and solvents,
0009 a wide choice of shades,
0010 less expensive application method.
0011. It is known to a person skilled in the art that pig
ment-dyeing by exhaustion is possible by providing Substan
tivity to the pigments by adding a cationic charge auxiliary
which provides affinity to the pigments for the fibre. The
textile Supports are then cationised before the dyeing step
itself.
0012 A person skilled in the art have several cationisation
agents at its disposal which allow improving the affinity of the
fibre with the pigments.
0013 The patent U.S. Pat. No. 5,006,129 describes a
method of pigmenting which includes a textile pre-treatment
step with a cationisation agent which includes a quaternary
ammonium group. The patent U.S. Pat. No. 5.252,103 claims
a method of pigmenting using cationic components that
include a quaternary ammonium group. Among the compo
nents used, one can cite acrylamide/2-(Methacryloyloxy)
ethyl trimethylammonium chloride copolymer.
0014. However, the prior art is not completely satisfactory.
The current problem is thus finding a pigment-dyeing method
that allows dyeing cellulose-based textile Supports or a com
bination of cellulose and synthetic fibres with the following
advantages:
0015 complete exhaustion of the dye baths,
0016 extremely high colour yields,
0017 high affinity of the pigment for the fibre,
0018 extremely short method times and low water vol
umes needed,
Feb. 18, 2016
0019 extremely high solidity of the colours during wet
tests,
0020 very low DCO and DBO5 charges in the effluents.
SUMMARY OF THE INVENTION
0021. The problem that the invention purports to solve is to
provide a novel pigment-dyeing method for textile materials
by exhaustion showing the above-mentioned advantages
while eliminating the disadvantages of the prior art.
0022. The applicant has finalised a novel pigment-dyeing
method for individualised textile fibres or textile supports
obtained from the said fibres consisting of pre-treating the
fibres or the support with at least one polymer then of dying
the thus pre-treated fibres or Support using pigments.
0023 The method is characterised in that the polymer is a
VinylAmine-based (co)polymer.
0024. The invention is applicable in particular to the pig
ment-dyeing of natural and/or synthetic fibres. As natural
fibres, it is possible to cite natural cellulose-based vegetable
fibres, like cotton, linen, cellulose regenerated fibres like
Viscose, modal, modified cellulose like acetate and triacetate.
We can also mention animal fibres like wool and silk. As
synthetic fibres, examples include acrylic-based, modacrylic
based, polyester-based, polyamide-based fibres and their
combinations.
0025. The support obtained from the fibres can be a
woven, a non-woven or a knitted Support.
0026. VinylAmine (co)Polymers (PVA)
0027. The PVA used in the novel method can result from
the various methods known by a person skilled in the art. We
can cite the PVA resulting from hydrolysis of the homopoly
mers or copolymers of N vinylformamide, or even the PVA
resulting from Hofman degradation.
0028 PVA resulting from complete or partial hydroly
sis of a (co)N-vinylformamide (co)polymer
0029. In a first step, a N-Vinylformamide (co)polymer
(NVF) must be obtained; the NVF having the following pat
tern:
-CH2-CH
NH-C-H
0030 Consequently, this NVF patter must be converted,
by hydrolysis, into VinylAmine:
-CH2-CH
0031. The hydrolysis can be carried out by an acidic action
(acid hydrolysis) or a basic action (basic hydrolysis).
0032. Depending on the added quantity of acid or base, the
NVF polymer or copolymer will be partially or completely
converted into VinylAmine.
0033 PVA resulting from Hofman degradation
0034. Hofman degradation is a reaction discovered by
Hofmann at the end of the nineteenth century, which allows
converting an amide (even an acrylonitrile) into a primary
US 2016/0047087 A1
amine by elimination of carbon-dioxide. Details of the reac
tion mechanism are given below.
0035. In the presence of a base (soda), a proton is pulled
off from the amide.
O H O These monomers can show acrylic, vinylic, maleic, fumaric,
| -/ OH- | --
R-C-y -to R-C-N-H
H
0036. The resulting amidate ion then reacts with the active
chloride (Cl) of the hypochloride (for example: NaClO
which is in balance: 2 NaOH+Clk-NaClO--NaCl-HO) to
resultina N-chloramide. The basic solution (NaOH) pulls off
a proton from the chloramide to form an anion. The anion
loses a chlorine ion to form a nitrene which undergoes an
isocynate transposition.
NU
0037. Through a reaction between the hydroxide ion and
isocynate, a carbamate is formed.
0038. After decarboxylation (elimination of CO2) of the
carbamate, a primary amine is obtained.
H'
R-NH-CO, -CO R-NH
0039 For the conversion of all or part of the amide groups
ofan acrylamide (co)polymer in an amine group, two primary
factors intervene (expressed in molar ratio). It involves: —Al
pha=(alkaline hypohalite and/or alkaline earth metal/acryla
mide) and —Beta=(alkaline hydroxide and/or alkaline earth
metal/alkaline hypohalogenure and/or alkaline earth metal).
0040. According to certain embodiments the PVA-based
(co)polymers can include other ionic and non-ionic mono
CS.
0041. The non-ionic monomer(s) that can be used within
the scope of the invention can be selected, particularly, from
the group consisting of water-soluble vinylic monomers in
the room. Preferred monomers belonging to this class are, for
example, acrylamide, N-isopropylacrylamide, N,N-dimethy
lacrylamide. Also, it is possible to use N-vinylformamide,
and N-vinylpyrrolidone. A non-ionic monomer is preferred
over acrylamide.
0042. The cationic monomer(s) that can be used within the
Scope of the invention can be selected, particularly among the
acrylamide, acrylic, vinylic, allelic or maleic monomers that
possess a quaternary ammonium group. It is possible to cite,
in particular in a non-exhaustive matter, quaternised dimethy
laminoethyl acrylate (ADAME) and quaternised dimethy
laminoethyl methacrylate (MADAME), dimethylkdiallylam
Feb. 18, 2016
monium chloride (DADMAC),
acrylamidopropyltrimethylammonium chloride (APTAC)
and methylenebisacrylami
demethacrylamidopropyltrimethylammonium chloride
(MAPTAC). The anionic monomers that can be used within
the scope of the invention can be chosen in a large group.
allelic groups, and contain a carboxylate, phosphonate, phos
phate, Sulfate, Sulfonate group, or another group with an
anionic charge. The monomer can be acid or even in the form
of a salt or an alkaline-earth metal or alkaline-metal corre
sponding to Such a monomer. Suitable examples of mono
mers include acrylic acid, methacrylic acid, itaconic acid,
crotonic acid, maleic acid, fumaric acid and highly acidic
type monomers, for example having a Sulfonic acid or phos
phonic acid type group Such as 2-acrylamid 2-sulfonic meth
ylpropane acid, vinylsulphonic acid, vinylphosphonic acid,
allylsulphonic acid, allylphosphonic acid, Sulphonic styrene
acid and water-soluble salts of an alkaline metal, an alkaline
earth metal and ammonium.
0043. According to a preferred method the PVA-based
(co)polymer results from Hofmann degradation made on a
base (co)polymer that includes acrylamide or derivatives.
0044 According to another method of the invention, it is
possible to use (co)polymers obtained by Hofman degrada
tion made on a base (co)polymer comprising acrylamide or
derivatives and at least one polyfunctional component con
taining at least three heteroatoms each having at least one
mobile hydrogen atom.
0045 Preferably, the polyfunctional component is
selected from the group consisting of polyethyleneamine,
polyamine, polyallylamine
0046. In a general manner, polymers of the invention do
not need development of a particular polymerisation method.
Indeed, they can be obtained according to all polymerisation
techniques which are well known to a person skilled in the art.
They can particularly involve solution polymerisation; gel
polymerisation; precipitation polymerisation;
0047 emulsion polymerisation (aqueous or inverse); Sus
pension polymerisation; or micellar polymerisation.
DETAILED DESCRIPTION OF THE INVENTION
0048 Pre-treatment:
0049. In accordance with the invention, the textile material
first undergoes a pre-treatment step.
0050. This step consists of putting the textile material into
contact with at least one vinylamine-based (co)polymer
(PVA) in a bath that contains water.
0051. The PVA (co)polymer is used in dosages from 1 to
10% in weight of the material to be dyed, preferably from 3 to
8%.
0.052 The polymer/pigment ratio in weight is between
1:10 and 10:1, preferably between 3:1 and 7:5, and more
preferably the ratio is 5:3.
0053. The pre-treatment is generally done at a temperature
between 20 and 100° C., preferably between 30 and 80° C.
The duration of the pre-treatment is between 1 and 60 min
utes, preferably between 5 and 40 minutes.
0054 The bath ratio is the ratio in weight between the total
dry material and the total Solution constituting the bath. Thus,
for example, a bath ratio of 1:10 signifies 10 litres of water for
1 kg of textile material. According to the invention, the bath
ratio for pre-treatment is between 1:5 and 1:40, preferably
between 1:10 and 1:30.
US 2016/0047087 A1
0055. The pre-treatment step is done at a pH between 3 and
8, preferably the pH is between 5 and 7. The pH is maintained
by adding an acid or an acid pH buffering. One can cite, for
example, acetic acid, formic acid, ammonium sulfate, sodium
carbonate.
0056. After the pre-treatment the bath is emptied. The
textile material is rinsed at least once with water at a tempera
ture between 10 and 30° C.
0057. Other components can be introduced during the pre
treatment step. An example might be anti-foam agents and
anti-breakage agents.
0058. The pre-treatment can be carried out with the
resources known by a person skilled in the art. Preferably, the
pre-treatment can be carried out in a dyeing device Such as jet
flow, over flow, bark, jigger, autoclave, industrial drum, reel
and wire dyeing device or skeins.
0059. In order to facilitate the pre-treatment, the textile
material can optionally undergo at least one prior step known
to a person skilled in the art. An example might be the
degreasing, quenching or laundering.
0060. The pre-treatment step can be followed by a soften
ing, stonnage or even bio-polishing of the textile material
before the dyeing step.
0061) Dyeing:
0062. In accordance with the invention, after the pre-treat
ment step, the material undergoes a dyeing step. This step
consists of putting the pre-treated textile material into contact
with at least one pigment in a bath containing water.
0063 More specifically, the textile material is coloured
using the exhaustion pigmentation technique. This technique
consists of exhausting the pigment bath by transferring the
latter towards the textile material.
0064. The pigment(s) can be introduced in the bath in
powder or liquid form. In a preferential manner, the pigments
are introduced in liquid form.
0065. In case of liquid form, the pigments are spread in at
least one solvent. The concentration of pigments in the Sol
vent is between 10 and 50%, preferably between 25 and 35%.
Preferably the solvent is water.
0066. In a general manner, the pigment(s) are added to the
bath at 0.1% to 10% in weight of the material to be dyed.
0067. The dyeing is done at a temperature between 20 and
90° C., preferably between 40 and 80° C. The increase in
temperature is lower than 10° C. per minute, preferably
between 1 and 4°C. per minute.
0068. Once the target temperature is reached, this latter is
maintained for 1 to 60 minutes, preferably between 5 and 40
minutes. The bath ratio for dyeing is between 1:5 and 1:40,
preferably between 1:10 and 1:30.
0069. After dyeing, the bath is emptied. The textile mate
rial is rinsed at least once with water. Preferably the water is
at a temperature between 10 and 30° C.
0070. Other components can be present during the dyeing
step. An example might be anti-foam agents or anti-breakage
agents.
(0071 Post-treatment
0072. In order to improve the solidities of the textile mate
rial in the wettests, a post-treatment can optionally be imple
mented.
0073. This post-treatment consists of adding at least one
binder and/or at least one fixing agent.
0074 The binder is a composition that includes pre-poly
mers of low molecular weight. During the spinning and dry
ing steps (at high temperature), these pre-polymers will react
Feb. 18, 2016
to form a film that entraps and integrates the pigments in the
fibre. The binder is used at dosages between 0.1 and 15%,
preferably between 1 and 10% in material weight.
0075. The reticulation of the binder is done at a tempera
ture between 50 and 250° C., preferably between 100 and
2000 C.
0076. The high temperature exposure lasts between 1 and
20 minutes, preferably between 3 and 10 minutes.
0077. The binder can be acrylate-based, styrene acrylate
based, styrene butadiene based and vinyl-acrylate-based.
0078. The fixing agent reacts to form a three-dimensional
network around the fibre at the time of drying.
007.9 The fixing agent is used at dosages between 0.1 and
15% preferably between 1 and 10% in material weight.
0080. The fixing agent is used at a temperature between 10
and 90° C., preferably between 20 and 60° C. The pH of the
bathis maintained between 3 and 6 per day, by adding an acid
or an acid pH buffering.
I0081. Once the fixing agent is introduced, the bath is
heated. The increase in temperature is lower than 10° C. per
minute, preferably between 1 and 4°C. per minute. Once the
target temperature is reached, this latter is maintained for 1 to
60 minutes, preferably between 5 and 30 minutes.
I0082. The bath ratio is between 1:5 and 1:40, preferably
between 1:10 and 1:30.
I0083. The fixing agent can be polyisocynate-based,
melamine formol-based, dimethyl dihydroxyethylene urea
based (DMDHEU).
I0084. After the post-treatment, the bath is emptied. The
textile material is rinsed at least once with water having a
temperature between 10 and 30° C.
I0085. The post-treatment step can be followed by a soft
ening, Stonnage or bio-polishing step of the textile material.
I0086 One of the advantages of the invention is in the high
rate of exhaustion of the pigments in the dyeing bath, since the
baths emptied in the sewage do not have a high load of
pigments.
I0087. It was unexpectedly discovered that PVA allows
higher quality of pigment exhaustion compared to conven
tional cationisation products. Indeed, it is possible to obtain
exhaustion rates higher than 95% for light and medium
colours, and higher than 90% for dark colours.
I0088 Moreover, without propounding any theory, it
would appear that the high pigment/fibre binding avoids a
systematic use of binder and/or fixing agent. During Subse
quent softenings, high quality pigment content was observed,
with little or no disgorgement.
I0089. The following examples illustrate the invention in a
non-exhaustive manner.
EXAMPLES
I/ Preparation of the Polymer
0090 Polymer A is obtained by a Hofman degradation
reaction on a basic copolymer (20% of active substance) of
acrylamide (70% molar) and ramified (MBA: 1000 ppm/
active substance) ammonium dimethyldiallyl chloride
(DADMAC) (30% molar) modified with a polyethyleneimine
polymer (of the Polymin HM type from BASF), at 1% of the
active Substance. To do this, polyethyleneinmine is combined
with DADMAC monomer and MBA in the reactor.
0091 Acrylamide will be incorporated by continuously
pouring for 2 hours, in a reactional environment maintained at
85°C. The catalysis will be carried out with SPS and MBS,
US 2016/0047087 A1
catalysers well known by a person skilled in the art. The
precursor polymer thus obtained shows a viscosity of 5500
cps (LV3, 12 rpm). The Hofman degradation itself is carried
out in the same manner as in example 1 of the patent of the
applicant PCT/FR/2009/050456. The acrylamide derivative
copolymer A thus obtained shows an intrinsic viscosity of
0.72 (25°C., Brookfield LV1, 60 rpm) and a concentration of
8%.
II/ Carrying out of the Method
Example 1
0092. A 1:1 ratio of a knit cotton/viscose 50/50 of 150
g/m is degreased in a winch. The bath ratio is 1:25. 1g/l of a
wetting detergent is added to the bath. The bath is then heated
and maintained at 60° C. for 25 minutes. The bath is then
emptied and the material is then rinsed twice using cold water
at 15°C. The pre-treatment is then carried out with a bath ratio
of 1:25. The pH is adjusted at 9 with sodium carbonate and
5% in weight of polymer A material is added. The bath is
heated and maintained at 60° C. for 30 minutes. The bath is
emptied and the material is then rinsed twice using cold water
at 15°C. The dyeing is then carried out in a bath ratio of 1:25.
In the bath, which has an initial temperature of 15°C., 3% of
15/3 blue pigment is added. The heat is then set to 60°C., in
increments of 3° C. per minute. The temperature is main
tained for 30 minutes. The bath is emptied and the material is
then rinsed twice using cold water 15° C. The treated mate
rials is then softened with a nano-silicone emulsion type
softener dosed at 2% for 15 minutes, temperature of the bath
set to 40°C., pH 5 adjusted with acetic acid.
Example 2
0093. 100% cotton material trousers twill 3/1205 g/mare
firstly desized in an industrial drum machine. The bath ratio is
1:10. The pH is adjusted to 6 with acetic acid. 3 g/l of an
amylase is added to the bath. The desizing is done at 60° C. for
20 minutes. The material is then cold rinsed twice using water
at 15° C. The trousers are then cationised in a bath ratio of
1:10, at pH 6 adjusted with acetic acid. 5% in weight of the
polymer material is added to the bath. The bath is then heated
and maintained at 60° C. for 30 minutes. The material is then
cold rinsed twice using water 15° C. The dyeing is then
carried out in a bath ratio of 1:10. In the bath, which has an
initial temperature of 15° C., 3.5% of 7 green pigment is
added. The heat is then set to 60°C., in increments of 3° C. per
minute. The temperature is maintained for 40 minutes. The
bath is then emptied and the material is then cold rinsed twice
using water 15° C. Stonnage is then carried out on the mate
rial for 20 min at a bath ratio of 1:10 at pH 4.5 with 1.5% of
acid cellulase. The bath is emptied and the material is then
cold rinsed twice using water 15° C. The materials is then
softened with 1% of silicone micro emulsion and 1% of fatty
acid for 15 minutes, temperature of the bath set to 40°C., pH
6 adjusted with acetic acid, the material is then Squeezed and
dried.
Example 3
0094. A 100% cotton poplin cloth 105 g/m pre-desized is
firstly whitened on an overflow dyeing machine with a bath
ratio of 1:20. The following products are added to the whit
ening bath: anti-foam, anti-breakage, oxygenated water sta
biliser, oxygenated water, caustic Soda. The bath is then
Feb. 18, 2016
heated at 98°C. for 30 minutes. The bath is then cooled to 70°
C. and the material neutralised at pH 7 with acetic acid. The
bath is then emptied and the material is then cold rinsed once.
The cationisation is then carried out in a bath ratio of 1:20 at
pH 5.5 adjusted with a pH acid buffer. 5% in weight of a PVA
cationisation agent, an anti-breakage agent and an anti-foam
agent are added to the bath. The bath is then heated and
maintained at 60° C. for 30 minutes. The material is then
rinsed twice using cold water at 15° C. The dyeing is then
carried out in a bath ratio of 1:20 at pH 5.5.2% of orange
pigment 34, 1% of yellow pigment 83, an anti-foam agent, an
anti-breakage agent and a dispersant are added to the water at
a temperature of 15° C. The heat is then set to 70° C., in
increments of 1° C. per minute. The temperature is main
tained for 20 minutes. At 70° C. an acrylic binder is added to
the bath and dosed at 5%. The bath is then emptied and the
material is then cold rinsed. The material is then softened with
a silicone hydrophilic emulsion type softener dosed at 2% for
20 minutes, bath temperature at 40°C., pH 5 adjusted with an
acid buffer.
Example 4
0.095 The cotton cloth of example 3 is whitened continu
ously, rolled and dried. The cloth is then foulard finished on a
sizing foulard in a bath containing 75 g/l of polymer A, at pH
6. The dye exhaust percentage is maintained at 60-80%, the
material is then dried on a drying stenter at 100-120°C. The
cloth thus treated and is then dyed according to the same
protocol described in example 3.
Example 5
Counter-example
0096. Example 3 is reproduced identically by replacing
the polymer A by the PRECAT 3005 (homopolymer of chlo
romethyled MADAME) distributed by CHT, R BEITLICH
GMBH used at 3%.
0097. The bath exhaustion, colours and friction solidity
inspections are carried out.
III/Assessment Tests
0.098 Assessment of the Rate of Exhaustion:
0099. At the end of each dyeing a bath sample is taken in
order to control the rate of exhaustion E (%) of the dyeing bath
pigments using a visible UV spectrophotometer (spectral
range from 190 to 900 nm, quartz cell of 10 mm) This latter is
calibrated using Successive dilutions of the initial coloured
pigment solution.
0100 Assessment of the Dry and Wet Solidities:
0101. A final cloth sample is taken in order to inspect the
dry and wet friction solidities following the standard NF EN
ISO 105-X12(2003) and using a crockmeter. The colour fad
ings on the cotton samples are assessed using the gray scale
and the ISO standard 105-A03 (2005).
0102 Assessment of the Colour:
0103) The final cloth colour is compared in relation with
the standard using a spectrophotometer under the D65 illu
minate and at an angle of 10 degrees. The colour differences
are determined by calculating the Delta E (CIE 2000) and
coloured forces (%) compared to the counter-example.
US 2016/0047087 A1 Feb. 18, 2016

0104 Results degradation reaction carried out on a base (co)polymer com

prising acrylamide or derivatives.
4. The method according to claim3 characterised in that the
Friction solidities base (co)polymer further comprises at least one polyfunc
tional component comprising at least three heteroatoms that
Tests dry humid E (%) FC (%) each have at least one mobile hydrogen atom.
Example 1 4-5 4 93.5 1086 5. The method in accordance with claim 4, characterised in
Example 2 4 3-4 912 112.4 that the polyfunctional component is selected from the group
Example 3
Example 4
4-5
4-5
4
4
92.8
90.8
11O.S
109.8
consisting of polyethyleneimine, polyamine, and polyally
Example 5 3-4 3 86.4 100 lamine.
6. The method according to claim 1, characterised in that
the (co)polymer represents from 1 to 10% in weight of the
0105. It can be observed that the novel cationisation pre material to be dyed.
treatment allows obtaining, compared with a conventional 7. The method according to claim 1, characterised in that
method: the polymer/pigment ratio is between 1:10 and 10:1.
0106] 1 to 2 points in result on the dry and humid fric 8. The method according to claim 1, characterised in that
tion Solidities, the pigment represent 0.1% to 10% in weight of the material
0107 an increase in the rate of exhaustion E(%) of the to be dyed.
pigments from 5 to 10%, 9. The method according to claim 1, characterised in that
(0.108 an increase in the FC tone levels (%) from 5 to the weight ratio between total dry material and total solution
15%. is between 1:5 and 1:40.
1. A pigment-dyeing method for individualised textile 10. The method according to claim 1, characterised in that
fibres or textile supports obtained from the fibres consisting of the (co)polymer represents from 3 to 8% in weight of the
pre-treating the fibres or the Support with at least one polymer, material to be dyed.
then dying the pre-treated fibres or Support using pigments, 11. The method according to claim 1, characterised in that
characterised in that the polymer is a vinylamine-based (co) the polymer/pigment ratio is between 3:1 and 7:5.
polymer. 12. The method according to claim 1, characterised in that
2. The method according to claim 1, characterised in that the polymer/pigment ratio is equal to 5:3.
the vinylamine-based (co)polymer results from a total or 13. The method according to claim 1, characterised in that
partial hydrolysis of a N-vinylformamide (co)polymer. the weight ratio between total dry material and total solution
is between 1:10 and 1:30.
3. The method according to claim 1, characterised in that
the vinylamine-based (co)polymer results from a Hofman k k k k k