WO1998001615A1

WO1998001615A1 - Process for dyeing and printing fibre materials

Info

Publication number: WO1998001615A1
Application number: PCT/EP1997/003363
Authority: WO
Inventors: Peter Scheibli
Original assignee: Ciba Specialty Chemicals Holding Inc.
Priority date: 1996-07-08
Filing date: 1997-06-26
Publication date: 1998-01-15
Also published as: DE19781859T1; AU3437897A

Abstract

This invention relates to a process for dyeing or printing fibre materials, in particular textile fibre materials, which comprises treating the fibre materials with an aqueous dye formulation comprising: a) at least one pigment dye as component (A); b) at least one disperse dye as component (B); c) a water-soluble cross-linking resin as component (C); d) a pigment dye binder as component (D) and; e) optionally, further assistants, subsequently drying the fibre materials and at the same time fixing the pigment and disperse dye by a heat treatment, as well as to dye formulation comprising the components (A), (B), (C) and (D).

Description

Process for dyeing and printing fibre materials

The present invention relates to a process for dyeing or printing fibre materials with pigment and disperse dyes as well as to the dye formulations used for this process.

Processes for dyeing or printing fibre materials with pigment dyes have been known for a long time. However, these processes do not fully meet today's requirements, e.g. as regards the ecological requirements concerning the use of organic solvent systems and, in particular, owing to their handle which is often too hard.

Accordingly, there is a need for an improved pigment dyeing and printing process.

Surprisingly, it has now been found possible with the process of this invention to avoid the above-mentioned disadvantages as the amounts of pigment and pigment binder can be reduced, no organic solvents are used and the dyeings and prints obtained have a soft handle.

Accordingly, this invention relates to a process for dyeing or printing fibre materials, in particular textile fibre materials, which comprises treating the fibre materials with an aqueous dye formulation comprising a) at least one pigment dye as component (A), b) at least one disperse dye as component (B), c) a water-soluble crosslinking resin as component (C), d) a pigment dye binder as component (D) and, e) optionally, further assistants.

This invention also relates to an aqueous dye formulation comprising a) at least one pigment dye as component (A), b) at least one disperse dye as component (B), c) a water-soluble crosslinking resin as component (C), d) a pigment dye binder as component (D) and, e) optionally, further assistants. Pigment dyes suitable as component (A) in the novel process are inorganic pigments, such as carbon black, titanium oxide or iron oxide, as well as organic pigments, preferably those of the phthalocyanine, anthraquinone, perinone, indigoid, thioindigoid, dioxazine, diketo- pyrrolopyrrole, isoindolinone, perylene, azo, quinacridone and metal complex series, typically metal complexes of azo, azomethine or methine dyes, and also classic azo dyes of the β- oxynaphthoic acid and acetoacetarylide series, or metal salts of azo dyes. It is also possible to use mixtures of different organic pigments or mixtures of one or several inorganic pigments with one or several organic pigments. Illustrative examples of such pigment dyes are listed in Colour Index, 3rd Edition (3rd Revision 1987 including Additions and Amendments up to No. 85) under "Pigments".

Preferred components (A) are pigment dyes of formulae

wherein

R is hydrogen, halogen, C C₄alkyl, d-C-jalkoxy, nitro or cyano,

Ri is hydrogen, halogen, nitro or cyano,

R₂ is hydrogen, halogen or phenylaminocarboxy,

R₃ is hydrogen or hydroxy,

R₄ is hydrogen or a radical of formula _ wherein R₅ is hydrogen,

C₁-C₄alkyl or C C₄alkoxy, R₆ is hydrogen or halogen, and R₇ is hydrogen, C C₄alkyl or C C alkoxy,

wherein

R₈ and R₉ are each independently of the other C C₄alkyl, and R₁₀and Rn are halogen,

the rings A, B, D and E being unsubstituted or substituted once or several times by halogen,

wherein

R,₂ is C C₄alkyl,

R₁₃ is hydrogen, halogen, Cι-C₄alkyl, Cι-C alkoxy, nitro or cyano,

Rι is hydrogen, halogen, nitro or cyano,

Ris is hydrogen, halogen, C_rC₄alkyl, Cι-C₄alkoxy, nitro or cyano, and

the rings A' and B' being unsubstituted or substituted once or several times by halogen. The pigment dyes of formulae (1) to (5) are known or can be prepared by known methods.

Disperse dyes suitable as component (B) in the novel process are those described in Colour Index, 3rd Edition (3rd Revision 1987 including Additions and Amendments up to No. 85) under "Disperse Dyes". Examples thereof are nitro, amino, amino ketone, ketone imine, methine, polymethine, diphenylamine, quinoline, benzimidazole, xanthene, oxazine or coumarine dyes which are free of carboxylic acid groups and/or of sulfonic acid groups, and, preferably, anthraquinone and azo dyes, such as mono- or diazo dyes.

Disperse dyes preferably used as component (B) are those of formulae

wherein

Ri6 is halogen, nitro or cyano,

R₁ is hydrogen, halogen, nitro or cyano,

R_IΘ is halogen or cyano,

R₁9 is hydrogen, halogen, CrC₄alkyl or C_rC alkoxy,

R₂₀ is hydrogen, halogen or acylamino, and

R-₂1 and R₂₂ are each independently of the other C C₄alkyl which is unsubstituted or substituted by hydroxy or acetoxy,

wherein

R₂₃ is hydrogen, phenyl or phenylsulfoxy, the benzene ring in phenyl and phenylsulfoxy being unsubstituted or substituted by C--C₄alkyl or CrC₄alkylsulfo,

R₂₅ is amino or hydroxy,

R₂₆ is hydrogen or C C alkoxy, and

R₂₇ is hydrogen or the radical -O-C₆H5-SO₂-NH-(CH₂)3-O-C₂H₅,

wherein

R_2β is d-C alkyl which is unsubstituted or hydroxy-substituted,

R₂₉ is C C₄alkyl,

R₃₀ is cyano,

R₃₁ is the radical of formula -(CH₂)₃-O-(CH₂)₂-O-C₆H₅,

R₃₂ is halogen, nitro or cyano, and

R33 is hydrogen, halogen, nitro or cyano,

O

wherein R₃₄ and R₃₅ are each independently of the other C₁-C₄alkyl,

the rings A" and B" being unsubstituted or substituted once or several times by halogen, and

wherein

R₃ is Cι-C₄alkyl which is unsubstituted or substituted by CrC alkoxy or hydroxy.

The disperse dyes of formulae (6) to (1 1) are known or can be prepared by known methods.

Water-soluble crosslinking resins suitable as component (C) are, for example, water-soluble melamine, formaldehyde/melamine and formaldehyde/urea resins, or precondensates, such as trimethylol melamine, hexamethylol melamine or dimethylol urea, or water-soluble formal- dehyde/(pre)condensates with formamide, thiourea, guanidine, cyanamide, dicyanodiamide and/or water-soluble organic sulfonates, such as the sodium salt of the naphthalenesulfonic acid, or glyoxalurea derivatives, e.g. the compound of formula

CH- \ ³

>^{N "}-CH OH

0=C I _N-CH OH

/ CH, and, preferably, N-methylol derivatives of nitrogen-containing compounds, such as melamine/formaldehyde condensates or N-methylol urea compounds which may be etherified.

Typical examples for the melamine/formaldehyde condensates which may be etherified are the compounds of formulae

The N-methylol urea compounds which may be etherified are, for example, reaction products of formaldehyde with urea or urea derivatives which may be subsequently etherified, the urea derivates typically being cyclic ethylene urea or propylene urea which may also contain substituents such as hydroxyl groups in the alkylene group, urones or unsubstituted or substituted triazone resins.

Typical examples of corresponding N-methylol urea compounds are N-methylol hydroxy- ethylene urea products which may be modified, e.g. the compounds of formula

CH₂OH CH₂OH

\ ' \

>^N"-CH— OH -^{N ^}CH— OCH

0=C I 0=C 3 _N-CH — OH "^CH — ^0CH3

/ /

CH,OH CH,OH

2 or ²

?H₃

H₃COH₂C - NHCO - N - CH₂- C - CH(OH) - NHCONH - CH₂OCH₃ , or methylolation products

CH₂OH CH₃

based on propylene urea or ethylene urea/melamine. Preferred components (C) are optionally modified N-methylol hydroxyethylene urea compounds, methylolation products based on propylene urea or ethylene urea/melamine and, preferably, melamine/formaldehyde condensates which may be etherified. It is also possible to use mixtures of two or more different water-soluble crosslinking agents as component (C), for example a mixture consisting of an unetherified and of an only partially etherified melamine/formaldehyde condensate.

Pigment dye binders suitable as component (D) in the novel process are, for example, acryl polymers, such as poly(meth)acrylate, poly(meth)acrylamide or the mixed polymers of (meth)acrylates or (meth)acrylamide with suitable comonomers, such as maleic acid, fuma- ric acid, itaconic acid, mesaconic acid, citraconic acid, vinylacetic acid, vinyloxyacetic acid, vinylpropionic acid, crotonic acid, aconitic acid, allylacetic acid, allyloxyacetic acid, allylma- lonic acid, 2-acrylamido-2-methylpropanesulfonic acid, glutaconic acid or allylsuccinic acid, or with esters of these acids, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, (meth)acrolein, N-vinyl-N-methylacetamide, vinyl caprolactam, styrene derivatives or vinyl- phosphonic acid; polyamide derivatives; latices; mixed polymers based on vinyl; diamide/al- dehyde precondensates; mixed polymers containing N-vinyllactam, or polymers based on butadiene.

Suitable comonomers are, in particular, the esters of the above acids with C C₆alcohols, typically methyl alcohol, ethyl alcohol, isopropyl alcohol or butyl alcohol.

The pigment or disperse dyes are conveniently used in disperse form in the dye liquors or printing pastes.

In this process the dyes are advantageously ground together with the dispersant, such as to give a dye particle size of 0.05 - 0.5 μm.

For the preparation of the dye dispersions it is preferred to use the customary dispersants, preferably nonionic dispersants.

Suitable nonionic dispersants are, in particular, compounds selected from the group consisting of the

(ca) alkylene oxide adducts of formula

wherein Y* is Cι-C₁₂alkyl, aryl or aralkyl,

"alkylene" denotes the ethylene radical or propylene radical, and m-j is 1 to 4, and n-, is 4 to 50,

(cb) alkylene oxide adducts with

(cba) saturated or unsaturated 1 -6-valent aliphatic alcohols, (ebb) fatty acids,

(cbc) fatty amines,

(cbd) fatty amides,

(cbe) diamines,

(cbf) sorbitan ester,

(cc) alkylene oxide condensates (block polymers)

(cd) polymers of vinyl pyrrolidone, vinyl acetate or vinyl alcohol, and

(ce) co- or terpolymers of vinyl pyrrolidone with vinyl acetate and/or vinyl alcohol.

Very suitable components (ca) are polyadducts of 4 to 40 mol ethylene oxide with 1 mol of a phenol which contains at least one C₄-Cι₂alkyl group, one phenyl group, one tolyl group, one α-tolylethyl group, one benzyl group, one α-methylbenzyl group or one α,α-dimethyl- benzyl group, typically butylphenol, tnbutylphenol, octylphenol, nonylphenol, dinonylphenol, o-phenylphenol, benzylphenol, dibenzylphenol, α-tolylethylphenol, dibenzyl(nonyl)phenol, α-methylbenzylphenol, bis(α-methylbenzyl)phenol or tris(α-methylbenzyl)phenol, which adducts can be used singly or in admixture.

Particularly interesting adducts suitable for use as component (ca) are adducts of 6 to 30 mol of ethylene oxide with 1 mol of 4-nonylphenol, with 1 mol of dinonylphenol or, preferably, with 1 mol of compounds which are prepared by addition of 1 to 3 mol of styrenes with 1 mol of phenols.

The styrene addition products are prepared in known manner, preferably in the presence of a catalyst such as sulfuric acid, p-toluenesulfonic acid or, preferably, of zinc chloride. Suitable styrenes are conveniently styrene, α-methylstyrene or vinyl toluene (4-methyl- styrene). The phenols are typically phenol, cresols or xylenols.

Very particularly preferred adducts are ethylene oxide adducts of formula (21)

wherein m₃ is 1 to 3, and n₃ is 8 to 30.

Also preferred are ethylene oxide adducts of formula

wherein Y₂ is C₄-C₁₂alkyl, phenyl, tolyl, tolyl-Cι-C₃alkyl or phenyl-C--C₃alkyl, such as α-methylbeπzyl or α,α-dimethylbenzyl, m₂ is 1 to 3, and n₂ is 4 to 40.

The nonionic component (cb) is conveniently

- an alkylene oxide addition product of 1 to 100 mol of alkylene oxide, such as ethylene oxide and/or propylene oxide, with 1 mol of an aliphatic monoalcohol containing at least 4 carbon atoms, of a trihydric to hexahydric aliphatic alcohol or of a phenol which may be substituted by alkyl, phenyl, α-tolylethyl, benzyl, α-methylbenzyl or α,α-dimethylbenzyl (cba);

- an alkylene oxide addition product of 1 to 100, preferably of 2 to 80 mol, of ethylene oxide with higher unsaturated or saturated monoalcohols (cba), fatty acids (ebb), fatty amines (cbc) or fatty amides (cbd) of 8 to 22 carbon atoms, individual ethylene oxide units of which addition products may be replaced by substituted epoxides such as styrene oxide and/or propylene oxide;

- an alkylene oxide addition product, preferably of ethylene oxide and propylene oxide, with ethylene diamine (cbe);

- an ethoxylated sorbitan ester containing long-chain ester groups, such as polyoxy- ethylene sorbitan monolaurate containing 4 to 20 ethylene oxide units, or polyoxyethylene sorbitan trioleate containing 4 to 20 ethylene oxide units (cbf).

Preferred components (cc) are ethylene oxide/polypropylene oxide adducts (EO-PO block polymers) and propylene oxide/polyethylene oxide adducts (reversed EO-PO block polymers).

Particularly preferred ethylene oxide/propylene oxide block polymers are those having molecular weights, based on polypropylene oxide, of 1700 to 4000, and containing 30-80%, preferably 60-80%, of ethylene oxide in the entire molecule.

The novel dye formulations can be applied to the fibre material in different manner, preferably in the form of aqueous dye baths and printing pastes. They are particularly suitable for dyeing by the pad-dyeing process and for printing.

The amounts of pigment and disperse dyes used in the dye baths or printing pastes may vary depending on the desired tinctorial strength. In general, advantageous amounts have been found to be in the range from 0.01 to 15 % by weight, preferably from 0.1 to 10 % by weight, based on the total sum of the dyes and on the weight of the goods to be dyed, or 0.01 to 400 g, preferably 0.5 to 300 g, most preferably 1 to 200 g, of the pigment and disperse dyes per kg of printing paste. The ratio of component (A) (pigment dye) to component (B) (disperse dye) can vary from 90:10 to 10:90, preferably from 33:67 to 50:50.

In addition to components (A), (B), (C) and (D), the dye liquors can contain further customary assistants, for example acid donors, typically aliphatic amine chlorides or magnesium chloride, the aqueous solutions of inorganic salts, e.g. of alkali metal chlorides or of alkali metal sulfates, alkali metal hydroxides, urea, thickeners, such as alginate thickeners, water- soluble cellulose alkyl ether as well as levelling agents, antifoam agents and/or deaerators, penetration accelerators, migration inhibitors and also wetting agents.

The novel dye formulations are preferably used in a printing paste.

This printing paste typically comprises 1 to 100 g, preferably 10 to 50 g, of component (C) and 1 to 300 g, preferably 50 to 200 g of component (D) per kg of printing paste.

In addition to components (A), (B), (C) and (D), the printing paste can contain further customary assistants, for example as component (E) preferably thickeners of natural or synthetic origin, such as commercially available alginate thickeners, starch ether or carob bean gum ether, preferably sodium alginate by itself or mixed with modified cellulose, in particular with preferably 20 to 25 % by weight of carboxy methyl cellulose.

It is preferred to use synthetic thickeners in the novel printing pastes, for example those based on poly(meth)acrylic acids, poly(meth)acrylamides, and also the co- or terpolymers thereof.

If desired, the printing pastes can also contain acid donors such as butyrolactone or sodium hydrogen phosphate, preservatives, sequestrants, emulsifiers, water-insoluble solvents, oxidants or deaerators.

Suitable preservatives are, in particular, formaldehyde-donating agents, such as para- formaldehyde and trioxane, preferably aqueous solutions of c. 30 to 40 % by weight of formaldehyde; suitable sequestrants are, for example, nitrilotracetic sodium, sodium ethylene- diaminetetraacetic acid, preferably sodium polymethaphosphate, in particular sodium hexa- methaphosphate; suitable emulsifiers are, in particular, adducts consisting of an alkylene oxide and a fatty alcohol, preferably of a adduct consisting of oleyl alcohol and ethylene oxide; suitable water-insoluble solvents are high-boiling saturated hydrocarbons, preferably paraffins having a boiling range of about 160 to 210°C (so-called white spirits); suitable oxidants are e.g. an aromatic nitro compound, preferably an aromatic mono- or dinitrocarboxy- lic acid or mono- or dinitrosulfonic acid which may be present as alkylene oxide adduct, in particular a nitrobenzenesulfonic acid; and suitable deaerators are e.g. high-boiling solvents, preferably turpentine oils, higher alcohols, preferably C₈- to C₁₀alcohols, terpene alcohols or deaerators based on mineral oils and/or silicone oils, in particular commercial formulations consisting of about 15 to 25 % by weight of a mineral oil/silicone oil mixture and of about 75 to 85 % by weight of a C₈alcohol such as 2-ethyl-n-hexanol.

For printing fibre materials, the printing paste is applied directly on the fibre material on the entire surface area or only in some places, conveniently using printing machines of conventional make, such as rotogravure, rotary screen printing and surface screen printing machines.

After printing, the fibre material is dried at temperatures of up to 150°C, preferably in the range from 80° to 120°C.

The subsequent fixation of the fibre material is normally effected by dry heating (thermo- fixation) or superheated steam under atmospheric pressure (HT fixation). The fixation is carried out under the following conditions:

- thermofixation: 1 to 2 minutes at 190 to 230°C

- HT fixation: 4 to 8 minutes at 170 to 180°C.

The novel dye formulations can be applied to different fibre materials. Polyester-containing fibre materials are preferred.

Suitable polyester-containing fibre materials are those consisting entirely or partially of polyester. Illustrative examples are cellulose ester fibres, such as cellulose secondary acetate fibres and cellulose secondary triacetate fibres, and, preferably, linear polyester fibres which may also be acid-modified and which are obtained, for example, by condensing terephthalic acid with ethylene glycol, or from isophthalic acid or terephthaiic acid with 1 ,4- bis(hydroxymethyl)cyclohexane, as well as fibres consisting of mixed polymers of terephthalic acid and isophthalic acid with ethylene glycol. Also suitable are polyester-containing blended fibre materials, i.e. blends of polyester and other fibres, preferably cotton/polyester fibre materials. Wovens, knits or webs of these fibres are mainly used.

The prints obtainable by the novel process on polyester-containing fibre materials have good allround fastness properties; they have e.g. good fastness to light as well as to wet treatments, such as fastness to washing, water, sea water, cross-dyeing and sweat, good fastness to chlorine, rubbing, ironing and pleating. They are particularly distinguished by high tinctorial strength and a brilliant shade.

The following Examples illustrate the invention in more detail. Temperatures are given in degrees centigrade, and parts and percentages are by weight, unless otherwise stated. The relationship of parts by weight to parts by volume is the same as that of the kilogramme to the litre.

Example 1 :

A blended fabric consisting of 50% of cotton and 50% of polyester fibres is printed with a printing paste containing per 100 g of the printing paste 2.5 g of a commercial dye formulation consisting of 1.6 g of the disperse dye of formula

0.1 g of the disperse dye of formula

0.73 g of the disperse dye of formula

0.013 g of a commercial dispersant, and 0.057 g of water, 3.0 g of a commercial form of pigment Black 7, C.I. 77266

10.0 g of a commercial acrylate binder,

3.0 g of a water-soluble crosslinking melamine resin,

0.5 g of a 25% aqueous ammonia solution,

3.0 g of a commercial softener,

0.3 g of a commercial wetting agent, and

2.0 g of the ammonium salt of a polyacrylic acid as synthetic thickener.

The printed fabric is dried and then thermosoled for 1 minute at 210° C, giving a black print having a soft handle.

Example 2:

The general procedure of Example 1 is repeated, using the commercial products "Alcoprint PBA as acrylate binder and ^®Alcoprint PTF as synthetic thickener, as well as the compound of formula

as water-soluble crosslinking melamine resin, which also gives a black print having a soft handle.

Example 3:

A blended fabric consisting of 33% of cotton and 67% of polyester fibres is printed with a printing paste containing per 100 g of the printing paste

3.3 g of a commercial dye formulation consisting of

2.112 g of the disperse dye of formula (100),

0.132 g of the disperse dye of formula (101),

0.964 g of the disperse dye of formula (102),

0.017 g of a commercial dispersant, and

0.075 g of water 2.0 g of a commercial pigment Black 7, C.I. 77266, 7.0 g of a commercial acrylate binder, 2.0 g of a water-soluble crosslinking melamine resin, 0.5 g of a 25% aqueous ammonia solution,

3.0 g of a commercial softener,

0.3 g of a commercial wetting agent, and

2.0 g of the ammonium salt of a polyacrylic acid as synthetic thickener.

Example 4:

The general procedure of Example 3 is repeated, using the commercial products *Alcoprint PBA as acrylate binder and "Alcoprint PTF as synthetic thickener, as well as the compound of formula (50) as water-soluble crosslinking melamine resin. This also gives a black print having a soft handle.

Example 5:

A blended fabric consisting of 50% of cotton and 50% of polyester fibres is printed with a printing paste containing per 100 g of the printing paste

0.29 g of the disperse dye of formula

0.79 g of the disperse dye of formula

1.5 g of the pigment dye of formula

10.0 g of the acrylate binder "Alcoprint PBA,

3.0 g of a water-soluble crosslinking melamine resin of formula (50),

0.5 g of a 25% aqueous ammonia solution,

3.0 g of a commercial softener,

0.3 g of a commercial wetting agent, and

2.0 g of the ammonium salt of a polyacrylic acid ("Alcoprint PTF) as synthetic thickener.

The printed fabric is dried and then thermosoled for 1 minute at 210° C. This gives a red print having a soft handle.

Example 6:

0.39 g of the disperse dye of formula (103)

1.06 g of the disperse dye of formula (104)

1.3 g of the pigment dye of formula (105)

7.0 g of the acrylate binder *Alcoprint PBA,

2.0 g of a water-soluble crosslinking melamine resin of formula (50)

0.5 g of a 25% aqueous ammonia solution,

3.0 g of a commercial softener,

0.3 g of a commercial wetting agent, and

Example 7:

A blended fabric consisting of 50% of cotton and 50% of polyester fibres is printed with a printing paste containing per 100 g of the printing paste 0.8 g of the disperse dye of formula (100)

0.05 g of the disperse dye of formula (101 )

0.36 g of the disperse dye of formula (102)

3.0 g of a commercial form of pigment Black 7, C.I. 77266

10.0 g of the acrylate binder "Alcoprint PBA,

3.0 g of a water-soluble crosslinking melamine resin of formula (50)

0.5 g of a 25% aqueous ammonia solution,

3.0 g of a commercial softener,

0.3 g of a commercial wetting agent, and

The printed fabric is dried and then thermosoled for 1 minute at 210° C. This gives a black print having a soft handle.

Example 8:

1.06 g of the disperse dye of formula (100),

0.07 g of the disperse dye of formula (101),

0.48 g of the disperse dye of formula (102),

2.0 g of a commercial pigment Black 7, C.I. 77266,

7.0 g of the acrylate binder "Alcoprint PBA,

2.0 g of a water-soluble crosslinking melamine resin of formula (50)

0.5 g of a 25% aqueous ammonia solution,

3.0 g of a commercial softener,

0.3 g of a commercial wetting agent, and

The printed fabric is dried and then thermosoled for 1 minute at 210° C. This gives a black print having a soft handle. Examples 9 - 12:

The general procedure of Examples 2, 4, and 5 to 8 is repeated, but replacing the compound of formula (50) as water-soluble crosslinking melamine resin with the same amount of the compound of formula

CH, - OH

<^N-CH - OH 0=C I (51 )_, ^v _N-CH - OH ^κ '

/

CH₂ - OH

This also gives prints having a soft handle.

Claims

What is claimed is

1. A process for dyeing or printing fibre materials, in particular textile fibre materials, which comprises treating the fibre materials with an aqueous dye formulation comprising a) at least one pigment dye as component (A), b) at least one disperse dye as component (B), c) a water-soluble crosslinking resin as component (C), d) a pigment dye binder as component (D) and, e) optionally, further assistants, subsequently drying the fibre materials and at the same time fixing the pigment and disperse dye by a heat treatment.

2. A process according to claim 1 , which comprises printing the fibre materials.

3. A process according to claim 2, which comprises printing the fibre materials with a printing paste comprising a) at least one pigment dye as component (A), b) at least one disperse dye as component (B), c) a water-soluble crosslinking resin as component (C), d) a pigment dye binder as component (D), and e) a thickener as component (E).

4. A process according to claim 3, which comprises formulating component (A) with a nonionic dispersant.

5. A process according to either claim 3 or claim 4, which comprises formulating component (B) with a nonionic dispersant.

6. A process according to any one of claims 3 to 5, which comprises using an acid donor.

7. A process according to any one of claims 3 to 6, wherein component (E) is a synthetic thickener.

8. A process according to any one of claims 1 to 3, wherein the fibre materials are polyester-containing fibre materials.

9. A process according to claim 8, wherein the polyester-containing fibre material is a cellulose/polyester blended fabric.

10. An aqueous dye formulation, comprising a) at least one pigment dye as component (A), b) at least one disperse dye as component (B), c) a water-soluble crosslinking resin as component (C), d) a pigment dye binder as component (D) and, e) optionally, further assistants.