AU8105498A - Process for fixing pigment prints and pigment dyeings with ionising radiation or UV radiation - Google Patents

Description

WO 98/54399 PCT/EP98/02954 Process for fixing pigment prints and pigment dyeings with ionising radiation or UV radiation. The present invention relates to a process for fixing pigment prints and pigment dyeings on fibre material with ionising radiation or by irradiation with UV radiation in the presence of photoinitiators. Printing or dyeing fibre materials with pigment dyes by the so-called pigment printing or pig ment dyeing process is one of the oldest known processes for the production of coloured textile goods. Nevertheless, the current printing and dyeing processes do not yet meet all the requirements made on them today, especially not regarding environmental impact and energy consumption. Surprisingly, it has now been found that by the inventive process described hereinafter it is possible to achieve significant energy saving and thus to contribute to the required improve ment of the pigment printing or pigment dyeing process. Accordingly, this invention relates to a process for printing or dyeing fibre material with pig ment dyes, which comprises applying to the fibre material a dye formulation comprising at least one pigment dye and at least one pigment dye binder as well as optional further auxili aries and then fixing it with ionising radiation, or applying to the fibre material a dye formula tion comprising at least one pigment dye, at least one pigment dye binder and at least one photoinitiator as well as optional further auxiliaries and then fixing it with UV radiation. One advantage of the novel processs is that it dispenses with the energy-consuming heat setting required in the conventional pigment printing and pigment dyeing processes. The fixing process consists in briefly irradiating the fibre material to be printed or dyed, e.g. textile fibre material, with ionising radiation or with UV radiation in the presence of at least one photoinitiator after printing or dyeing in the moist or dry state. The printed or dyed fibre material is advantageously irradiated and fixed at elevated tempe ratures, for example from 40 to 1200 C, preferably from 60 to 1000 C. The irradiation can be carried out either immediately after the drying process or the cold printed fibre material may be heated to the desired temperature before irradiation, using e.g. an infrared heater.

WO 98/54399 PCT/EP98/02954 -2 lonising radiation is to be understood as being radiation which can be detected in an ionisa tion chamber. It consists either of electrically charged and directly ionising particles which produce ions by impact in gases along their path, or of uncharged and indirectly ionising par ticles or photons which produce directly ionising charged secondary particles in matter, such as secondary electrons of X- or y-rays or the recoil nuclei (in particular protons) of high-speed neutrons; other indirectly ionising particles are slow neutrons which can produce energy-rich charged particles by nuclear reactions in part directly and in part via photons from (0,y)-pro cesses. Suitable heavy charged particles are protons, atom nuclei or ionised atoms. Light charged particles, e.g. electrons, are particularly important for the process of this invention. Suitable X-rays are bremsstrahlung and also characteristic radiation. a-Radiation is to be mentioned as important particle radiation of heavy charged particles. The ionising radiation can be produced by one of the customary methods. Thus it is possible to use, for example, spontaneous nuclear transformations and also nuclear reactions (forced nuclear transformations) for the production of ionising radiation. Correspondingly, suitable radiation sources are natural or synthetic radioactive substances and, especially, atom reac tors. The radioactive fission products obtained from nuclear fission are another important radiation source. Another suitable radiation-producing method is that using an X-ray tube. Particularly important rays are those consisting of particles which are accelerated in electric fields. Suitable radiation sources in this connection are thermo, electron impact, low-voltage arc, cold cathode and high frequency ion sources. Electron beams are particularly important for the process of this invention. These are pro duced by accelerating and concentrating electrons which are emitted via thermionic, field or photo emission and also via electron or ion bombardment from a cathode. Radiation sources are electron guns and accelerators of conventional make. Examples of radiation sources are known from the literature, inter alia from the International Journal of Electron Beam & Gamma Radiation Processing, in particular 1/89 pages 11-15; Optik, 77 (1987), pages 99-104. Other radiation sources for electron beams are -emitters, e.g. strontium-90.

WO 98/54399 PCT/EP98/02954 -3 The y-emitters, which can easily be produced using, in particular, cesium-137- or cobalt-60 isotopic sources, are also to be mentioned as ionising radiation which can be of advanta geous technical use. The use of ultraviolet radiation requires the presence of a photoinitiator. The photoinitiator absorbs the radiation to produce free radicals which initiate the polymerisation. Typical exam ples of photoinitiators used according to this invention or of photoinitiators are carbonyl com pounds, such as 2,3-hexanedione, diacetylacetophenone, benzoin and benzoin ether, such as dimethyl derivatives, ethyl derivatives and butyl derivatives, e.g. 2,2-diethoxyacetophe none and 2,2-dimethoxyacetophenone, benzophenone or a benzophenone salt, and phenyl (1-hydroxycyclohexyl)ketone or a ketone of formula O CH 3 I I I C-C-OH(1)

OH

3 HO - CH 2 - CH 2 -O benzophenone in combination with a catalyst such as triethylamine, N,N'-dibenzylamine and dimethylaminoethanol and benzophenone plus Michler's ketone; acylphosphine oxides; nitrogen-containing compounds such as diazomethane, azo-bisisobutyronitrile, hydrazine, phenylhydrazine and also trimethylbenzylammonium chloride; and sulfur-containing com pounds such as benzene sulfonate, diphenyl disulfide and also tetramethylthiuram disulfide, as well as phophorus-containing compounds, such as phosphine oxides. Such photoinitiators are used by themselves or in combination with each other. Directly before irradiation, the photoinitiator component in the applied dye components is 0.01-20%, preferably 0.1-5%, based on the total amount of the colourless polymerisable compounds used. Suitable photoinitators may be water-soluble or water-insoluble. Particularly advantageous photoinitiators are also copolymerisable photoinitiators such as those mentioned, inter alia, in "Polymers Paint Colour Journal, 180, p42 et seq. (1990)".

WO 98/54399 PCT/EP98/02954 -4 It is also suitable to use cationic photoinitiators such as triarylsulfonium salts, diaryliodonium salts, diaryliron complexes or in general structures such as those described in "Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints", Vol. 3, edited by SITA Technology Ltd., Gardiner House, Broomhill Road, London, 1991. It is preferred to use acylphosphine oxides, such as (2,4,6 trimethylbenzoyl)(diphenyl)phos phine oxide, or photoinitiators of formula (1) or of formula c 1 (2) 11 OH 0 or a photoinitiator of formula

CH

3 I+ CH-N-OCH C C H (3) II ci 0 together with a photoinitiator of formula (1) or (2) or with a photoinitiator of formula

/CH

2 - CH 2 -OH H3C-N (4)

CH

2

-CH

2 -OH or benzophenone together with a photoinitiator of formula (1) or (2) or (3). The use of a photoinitiator of formula (1) is particularly preferred. It is very particularly preferred to use the following photoinitiators in the process of this inven tion: WO 98/54399 PCT/EP98/02954 -5 & 0 OCH 3 a) -C (1 b) // I1 /CH, OCH 3 O N C-C-N, i "CH, CH2-CH,

CH

3 O C II C O /1 1 j O (1id)

H

3 C-S C-C-N O (1c) H 3 C H H H (d) C I 3 H 3 H3C' C 3

CH

3 and also the mixture of the compounds of formulae S OCH 3 O 0 CH 0 CH 3 III II / \ I O -OH -H-H -- H C4~adId t2ke -0-OH (1fiatweight I~ ~ P 2,-- -- f- -- HC -C H2'C -C3 (1 e) and C - I U0H 3

OHH

3 L OCH3 ' ratio of 50:50 to 10:90, as well as the mixture of the compound of formula (1f) and 2,4,6-tri methylbenzoyldiphenyl phosphine at a weight ratio of 20:80 to 60:40. The UV radiation to be used has an emission from 200 and 450 nm, preferably from 210 and 400 nm. The radiation is preferably produced artificially using high-, medium- or low-pressure mercury vapour lamps, halogen lamps, metal halide, xenone or tungsten lamps, carbon arc or fluorescent lamps, H - and D - lamps, superactinic fluorescent tubes and laser. It is advantageous to use capillary high-pressure mercury lamps or high- or low-pressure mercury lamps. It is very particularly advantageous to use high- and medium-pressure mercury lamps which may be doped e.g. with iron halide or gallium halide. These lamps may also be excited via microwaves or may be pulsed to concentrate the radiation in peaks. It is also possible to work with pulsed xenone lamps if a higher component of longwave UV radiation is required.

WO 98/54399 PCT/EP98/02954 -6 The customary UV radiation sources are generally suitable, such as those described in "Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints", Vol. 1, edited by SITA Technology, Gardiner House, Broomhill Road, London, 1991. The exact irradiation time of the prints depends on the luminosity of the UV source, the distance from the radiation source, the kind and amount of photoinitiator used and on the transmissivity of the formulation and the textile substrate to UV radiation. Conventional irradiation times with UV radiation are from 1 second to 20 minutes, preferably from 5 seconds to 2 minutes. The fixing can be terminated by interrupting the irradiation so that it can also be carried out discontinuously. The irradiation can be carried out in an inert gas atmosphere, e.g. under nitrogen, to prevent inhibition by oxygen. The oxygen-inhibition can also be effectively prevented by adding so called "antiblocking agents", i.e. amines and, in particular, aminoacrylates. Pigment dyes suitable for the novel process are inorganic pigments, such as carbon black, titanium dioxide or iron oxides, as well as organic pigments, in particular those of the phthalo cyanine, anthraquinone, perinone, indigoid, thioindigoid, dioxazine, diketopyrrolopyrrole, iso indolinone, perylene, azo, quinacridone and metal complex series, for example metal com plexes of azo, azomethine or methine dyes, as well as classic azo dyes of the p-oxynaphthoic acid and acetoacetarylide series, or the metal salts of azo dyes. It is also possible to use mix tures 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 inclusive Additions and Amendments up to No. 85) under "pigments". Preferred pigment dyes are those of formula R R 3

R

4 R / N = N (5)

R/

WO 98/54399 PCT/EP98/02954 -7 wherein R is hydrogen, halogen, C 1

-C

4 alkyl, Cl-C 4 alkoxy, nitro or cyano,

R

1 is hydrogen, halogen, nitro or cyano,

R

2 is hydrogen, halogen or phenylaminocarboxy,

R

3 is hydrogen or hydroxy, Rs

R

4 is hydrogen or a radical of formula - CONH/ , wherein R 5 is hydrogen, R 7 R 6

C,-C

4 alkyl or C,-C 4 alkoxy, R. is hydrogen or halogen, and R 7 is hydrogen, Cl-C 4 alkyl or Cj

C

4 alkoxy, RR

R

9 R0 N N 6) N 0 N R R wherein

R

8 and R 9 are each independently of the other Cl-C 4 alkyl, and R 1 0 and R 11 are halogen, /E N N+ N / 2 A N- Cu -N I D (7), N N+ N B the rings A, B, D and E being unsubstituted or mono- or polysubstituted by halogen, WO 98/54399 PCT/EP98/02954 -8

R

5 HO cR 12 RS R N = N-C-C-NH O wherein

R

12 is C 1

-C

4 alkyl,

R

13 is hydrogen, halogen, C,-C 4 alkyl, C-C4alkoxy, nitro or cyano,

R

14 is hydrogen, halogen, nitro or cyano,

R

1 5 is hydrogen, halogen, Cl-C 4 alkyl, Cl-C 4 alkoxy, nitro or cyano, and N _ N - 7 (9), A' NH HN B' O O the rings A' and B' being unsubstituted or mono- or polysubstituted by halogen. The pigment dyes of formulae (5) to (9) are known or can be prepared by known methods. Pigment dye binders suitable for the novel process are, for example, acryl homopolymers, such as poly(meth)acrylic acid, poly(meth)acrylate or poly(meth)acrylamide. Other pigment dye binders suitable for the novel process are the mixed polymers (co- or ter polymers) of (meth)acrylic acid, (meth)acrylates or (meth)acrylamide with suitable comono mers, such as maleic, fumaric, itaconic, mesaconic, citraconic, vinylacetic, vinyloxyacetic, vi nylpropionic, crotonic, aconitic, allylacetic, allyloxyacetic, allylmalonic, 2-acrylamido-2-methyl propanesulfonic, glutaconic or allylsuccinic acid or with esters of these acids, N-vinylpyrroli done, N-vinylformamide, N-vinylacetamide, (meth)acrolein, N-vinyl-N-methylacetamide, vinyl caprolactam, styrene derivatives or vinylphosphonic acid. Suitable comonomers are, in particular, the esters of the above acids with C-C 6 alcohols, such as methyl alcohol, ethyl alcohol, isopropyl alcohol or butyl alcohol.

WO 98/54399 PCT/EP98/02954 -9 Other pigment dye binders suitable for the novel process are, for example, polyamide deriva tives, latices, mixed polymers based on vinyl, diamide-aldehyde precondensates, mixed poly mers containing N-vinyllactam, or polymers based on butadiene. Pigment dye binders preferably used in the novel process are poly(meth)acrylic acid, poly (meth)acrylate and poly(meth)acrylamide. The pigment dyes are conveniently used in disperse form in the dye liquors or printing pastes. In this process the dyes are advantageously ground with the dispersant such as to give a dye particle size of 0.05 - 0.5 sm. 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 con sisting of the (ca) alkylene oxide adducts of formula /_\-0o alkylene -0--- H (10), (Y) M wherein Y 1 is C 1

-C

12 alkyl, aryl or aralkyl, "alkylene" denotes the ethylene radical or propylene radical, m, is 1 to 4, and n 1 is 4 to 50, (cb) alkylene oxide adducts with (cba) saturated or unsaturated 1-6-valent aliphatic alcohols, (cbb) fatty acids, (cbc) fatty amines, (cbd) fatty amides, (cbe) diamines, (cbf) sorbitan esters, (cc) alkylene oxide condensates (block polymers) WO 98/54399 PCT/EP98/02954 -10 (cd) polymers of vinylpyrrolidone, vinyl acetate or vinyl alcohol and (ce) co- or terpolymers of vinylpyrrolidone with vinyl acetate and/or vinyl alcohol. Very suitable component (ca) are polyadducts of 4 to 40 mol ethylene oxide with 1 mol of a phenol which contains at least one C4-C 12 alkyl group, one phenyl group, one tolyl group, one a-tolylethyl group, one benzyl group, one a-methylbenzyl group or one a,a-dimethylbenzyl group, for example butylphenol, tributylphenol, octylphenol, nonylphenol, dinonylphenol, o phenylphenol, benzylphenol, dibenzylphenol, a-tolylethylphenol, dibenzyl-(nonyl)phenol, a methylbenzylphenol, bis(a-methylbenzyl)phenol or tris(a-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 to 1 mol with phenols. The styrene addition products are prepared in known manner, preferably in the presence of catalysts such as sulfuric acid, p-toluenesulfonic acid or, preferably, of zinc chloride. Suitable styrenes are usefully styrene, a-methylstyrene or vinyltoluene (4-methylstyrene). The phenols are typically phenol, cresols or xylenols. Very particularly preferred adducts are ethylene oxide adducts of formula (21)

-O-(-CH

2

-CH

2 -O- H / \ H/(11),

CH

3 m 3 wherein m 3 is 1 to 3, and n 3 is 8 to 30. Other preferred ethylene oxide adducts are those of formula WO 98/54399 PCT/EP98/02954 -11 / O- (-

CH

2 -H 2 - O-

)

-H S(12), 2 m2 wherein Y 2 is C 4

-C

12 alkyl, phenyl, tolyl, tolyl-C,-C 3 alkyl or phenyl-C 1

-C

3 alkyl, for example a-methylbenzyl or a,a-dimethylbenzyl, m 2 is 1 to 3, and n 2 is 4 to 40. The nonionic component (cb) is preferably - 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 3- to 6-valent aliphatic alcohol or of a phenol which may be substituted by alkyl, phenyl, a-tolylethyl, benzyl, a-methylbenzyl or a,a-dimethylbenzyl (cba); - an alkylene oxide addition product of 1 to 100 mol, preferably of 2 to 80 mol, of ethylene oxide with higher unsaturated or saturated monoalcohols (cba), fatty acids (cbb), fatty amines (cbc) or fatty amides (cbd) containing 8 to 22 carbon atoms, individual ethylene oxide units of which addition products may be replaced with substituted epoxides such as styrene oxide and/or propylene oxide; - an alkylene oxide addition product, preferably an ethylene oxide/propylene oxide adduct, with ethylene diamine (cbe); - an ethoxylated sorbitan ester containing long-chain ester groups, such as polyoxyethylene 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 (so-called EO PO block polymers) and propylene oxide/polyethylene oxide adducts (so-called reversed EO-PO block polymers). Particularly preferred ethylene oxide/propylene oxide block polymers are those having mole cular weights, based on polypropylene oxide, of 1700 to 4000, and containing 30-80%, pre ferably 60-80%, of ethylene oxide in the entire molecule.

WO 98/54399 PCT/EP98/02954 -12 The novel dye formulations can by applied to the fibre material in different manner, in particu lar 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 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 weight of the goods to be dyed, or from 0.05 to 200 g, preferably from 1.0 to 100 g, of the pigment dyes per kg of printing paste. The novel dye formulations are preferably used in the form of a printing paste. This printing paste typically comprises 1 to 400 g, preferably 50 to 250 g, of the pigment dye binder per kg of printing paste. In addition to the pigment dye and pigment dye binder, the printing paste advantageously also comprises thickeners of synthetic origin, e.g. those based on poly(meth)acrylic acids, poly(meth)acrylamides, and the co- or terpolymers thereof. It is preferred to use thickeners based on the potassium or sodium salts of poly(meth)acrylic acids as their use advantageously makes it possible to partially or completely forego the addition of ammonia or ammonium salts. The printing paste can also comprise other auxiliaries customarily used for pigment printing, for example usefully crosslinkers. Suitable crosslinkers are, for example, water-soluble melamine resins, formaldehyde/mela mine resins and formaldehyde/urea resins or precondensates, such as trimethylolmelamine, hexamethylolmelamine or dimethylol urea, or water-soluble formaldehyde (pre)condensates with formamide, thiourea, guanidine, cyanamide, dicyandiamide and/or water-soluble organic sulfonates, such as the sodium salt of naphthalenesulfonic acid, or glyoxalurea derivatives, such as the compound of formula WO 98/54399 PCT/EP98/02954 - 13 CH 3 IN-CH -OH O=C I N-CH-OH /

CH

3 and, in particular, N-methylol derivatives of nitrogen-containing compounds, such as optio nally etherified melamine/formaldehyde condensates or N-methylol urea compounds. Typical examples of the optionally etherified melamine/formaldehyde condensates are the compounds of formula HOH2C\ /CH 2 0CH3 N(CH 2

H)

2 N \ N-CH 2 0CH 3 N H N \>-N(CH 2 0H), N

HOH

2 C CH 2 0CH 3 or NH-CH 2 0H The optionally etherified N-methylol urea compounds are typically reaction products of for maldehyde with urea or urea derivatives which may be subsequently etherified, suitable urea derivatives 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 sub stituted triazone resins. Typical examples of the corresponding N-methylol urea compounds are N-methylolhydroxy ethylene urea products which may be modified, e.g. the compounds of formula

CH

2 0H CH 2 0H N- CH-OH N- CH-OCH3 O=C I O=C I N- CH-OH 'N- CH-OCH 3 CH20H or /H20H CH 2 OH or CH 2

OH

WO 98/54399 PCT/EP98/02954 -14

CH

3

H

3 COH C - NHCO - N - CH 2 - C - CH(OH) - NHCONH - CH 2

OCH

3 , or methylolation products I I

CH

2 OH CH 3 based on propylene urea or ethylene urea/melamine. Preferred crosslinkers are optionally modified N-methylolhydroxyethylene urea compounds, methylolation products based on propylene urea or ethylene urea/melamine and, in particu lar, optionally etherified melamine/formaldehyde condensates. It is also possible to use mix tures of two or more than two water-soluble crosslinkers, for example a mixture consisting of an unetherified and of an only partially etherified melamine/formaldehyde condensate. If desired, the printing paste can also comprise 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 paraformal dehyde and trioxane, preferably aqueous solutions of about 30 to 40 % by weight of formal dehyde; suitable sequestrants are, for example, nitrilotriacetic sodium, ethylenediaminetetra acetic sodium, preferably sodium polymethaphosphate, in particular sodium hexamethaphos phate; suitable emulsifiers are, in particular, adducts consisting of an alkylene oxide and a fatty alcohol, preferably of an 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 2100 C (so-called white spirits); suitable oxidants are e.g. an aromatic nitro compound, preferably an aromatic mono- or dinitrocarboxylic or mono- or dini trosulfonic acid which may be present as alkylene oxide adduct, in particular a nitrobenzene sulfonic acid, and suitable deaerators are e.g. high-boiling solvents, preferably turpentine oils, higher alcohols, preferably C8- to C 1 0 alcohols, terpene alcohols or deaerators based on mine ral 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 Caalcohol such as 2-ethyl-n-hexanol. For printing fibre materials, the printing paste is applied directly to the fibre material on the entire surface or only in some places, conveniently using printing machines of conventional WO 98/54399 PCT/EP98/02954 -15 make, such as rotogravure, rotary screen printing, roller printing and flat screen printing machines. Printing can also be carried out by the ink jet printing technique. After printing, the fibre material is advantageously dried, preferably in the temperature range from 800 to 12000. The printing paste used according to this invention can be applied to different fibre materials, such as wool, silk, cellulose, polyvinyl, polyacrylonitrile, polyamide, aramide, polypropylene, polyester or polyurethane. Cellulosic fibre materials are preferred. Suitable cellulosic fibre materials are those which consist entirely or partially of cellulose. Typical examples are natural fibre materials, such as cotton, linen or hemp, regenerated fibre materials, such as viscose, polynosic or cuprammonium rayon. Also suitable are cellulosic blended fibre materials, i.e. mixtures of cellulose and other fibres, in particular cotton/polyes ter fibre materials. Wovens, knits or webs of these fibres are mainly used. The novel process is carried out, for example, in such a manner that the textile material print ed and dried according to this invention is passed through the beam of an electron accelera tor at temperatures from 60 to 1000 C. This is done at such a speed as to reach a certain ra diation dosage. The radiation dosages normally to be used are from 0.1 to 15 Mrad at an accelerator voltage from 160 to 300 kV, the radiation dosage advantageously being from 0.1 to 4 Mrad. At a dosage of less than 0.1 Mrad, the degree of fixing is generally too low and at a dosage of more than 15 Mrad the fibre material and the dye are often damaged. The novel process gives prints having good allround fastness properties, e.g. good fastness to water and light. When carrying out the novel process, the respective technical preconditions must of course be considered. The special embodiment of this invention depends especially on the kind of ionising radiation to be used and its manner of production. If, for example, the printed fibre material is to be irradiated with y-rays, then the material is exposed to the radiation enclosed in a cell. If higher radiation dosages are desired at lower radiation intensity, then the material to be irradiated can be exposed to the radiation in several passages.

WO 98/54399 PCT/EP98/02954 -16 A preferred embodiment of this invention is that, wherein the printing as well as the fixing of the fibre material with the pigment dyes are carried out continuously. The prints obtainable by the novel process on cellulosic fibre material have good allround fastness properties; they have, for example, good fastness to light, wetting, such as to wash ing, water, seawater, cross-dyeing and perspiration, good fastness to chlorine, rubbing, iron ing and pleating and are distinguished in particular by high tinctorial strength and a brilliant shade. In the following Working Examples, the radiation dosages are given in conventional manner in Mrad (megarad), 1 rad corresponding to an absorption of 10 2 J/kg (joule/kg). The UV irradiation is carried out using a 120 watt/cm medium-pressure mercury lamp at transport speeds of 10 m/min. The fabric referred to in the following Examples is printed on one side and is irradiated under an inert gas atmosphere. Parts and percentages are by weight and temperatures are given in degrees Celsius. The relationship between parts by weight and parts by volume is the same as that between the gramme and the cubic centimetre. Example 1: A cotton fabric is printed with a printing paste containing per 1 kg of printing paste 20 g of a commercial pigment formulation of the pigment dye of formula

OCH

3

OCH

3 HO CONH CI c3 / (13), N = N

OCH

3

HNOC

WO 98/54399 PCT/EP98/02954 -17 120 g of a commercial acrylate binder (®Alcoprint PBA), 13 g of a commercial synthetic thickener (®Alcoprint PTF), 5 g of a 30% aqueous ammonia solution, and 3 g of a commercial deaerator, and is then dried at 1200 C for 90 seconds. It is then immediately irradiated with a dosage of 3 Mrad using an electron gun at an accelerator voltage of 180 kV. A red pigment print is obtained having good fastness to wetting and light. Example 2: The procedure of Example 1 is repeated, but the dried print, which is temporarily stored cold, is heated in an infrared predrier to 1000 C before irradiation. The subsequent irradiation also gives a red pigment print having good fastness to wetting and light. Example 3: A cotton fabric is printed with a printing paste containing per 1 kg of printing paste 20 g of a commercial pigment formulation of the pigment of formula (13) 120 g of a commercial acrylate binder (®Alcoprint PBA), 100 g of the photoinitiator of formula (1), 13 g of a commercial synthetic thickener (®Alcoprint PTF), 5 g of a 30% aqueous ammonia solution, and 3 g of a commercial deaerator, and is then dried at 1200 C for 90 seconds. It is then passed immediately at a speed of 10 m/min under a high-pressure mercury lamp of 120 watt/cm. A red pigment print is obtained having good fastness to wetting and light. Example 4: A cotton fabric is printed with a printing paste containing per 1 kg of printing paste 24 g of a commercial pigment formulation of the pigment dye of formula WO 98/54399 PCT/EP98/02954 - 18 N- CU-N (14), N N 120 g of a commercial acrylate binder (®Alcoprint PBA), 13 g of a commercial synthetic thickener (®Alcoprint PTF), and 3 g of a commercial deaerator, and is then dried at 1200 C for 90 seconds. It is then immediately irradiated with a dosage of 3 Mrad using an electron gun at an accelerator voltage of 180 kV. A blue pigment print is obtained having good fastness to wetting and light. Example 5: The general procedure of Example 4 is repeated, but the dried print, which is temporarily stored cold, is heated in an infrared predrier to 1000 C before irradiation. The subsequent irradiation also gives a blue pigment print having good fastness to wetting and light. Example 6: A cotton fabric is printed with a printing paste containing per 1 kg of printing paste 24 g of a commercial pigment formulation of the pigment of formula (14) 120 g of a commercial acrylate binder (®Alcoprint PBA), 100 g of the photoinitiator of formula (1), 13 g of a commercial synthetic thickener (®Alcoprint PTF), and 3 g of a commercial deaerator, and is then dried at 1200 C for 90 seconds. It is then immediately passed at a speed of 10 m/min under a high-pressure mercury lamp of 120 watt/cm. A blue pigment print is obtained having good fastness to wetting and light.

Claims (15)

1. A process for printing or dyeing fibre material with pigment dyes, which comprises apply ing to the fibre material a dye formulation comprising at least one pigment dye and at least one pigment dye binder as well as optional further auxiliaries and then fixing it with ionising radiation, or applying to the fibre material a dye formulation comprising at least one pigment dye, at least one pigment dye binder and at least one photoinitiator as well as optional further auxiliaries and then fixing it with UV radiation.

2. A process according to claim 1, which comprises carrying out the fixing with ionising radiation.

3. A process according to claim 1, which comprises carrying out the fixing with UV radiation in the presence of at least one photoinitiator.

4. A process according to any one of claims 1 to 3, which comprises formulating the pigment dye with a nonionic dispersant.

5. A process according to any one of claims 1 to 4, which comprises applying the dye formu lation to the fibre material from an aqueous dye bath by the pad-dyeing process.

6. A process according to any one of claims 1 to 4, wherein the dye formulation is a printing paste.

7. A process according to claim 6, wherein the printing paste comprises an acid donor.

8. A process according to either claim 6 or claim 7, wherein the printing paste comprises a synthetic thickener.

9. A process according to claim 8, which comprises using a thickener based on the potas sium or sodium salts of poly(meth)acrylic acids. WO 98/54399 PCT/EP98/02954 - 20

10. A process according to any one of claims 6 to 9, wherein the printing paste comprises a crosslinker.

11. A process according to any one of claims 1 to 10, wherein the fibre material is cellulosic fibre material.

12. A process according to claim 11, wherein the cellulosic fibre material is a cellulose/poly ester blend.

13. A process according to any one of claims 1 to 12, which comprises carrying out the fixing in the temperature range from 40 to 1200 C, preferably from 60 to 1000 C.

14. A process according to any one of claims 1 to 13, which comprises carrying out the fixing by irradiation in an inert gas atmosphere.

15. A process according to any one of claims 1 to 14, which comprises drying the printed or dyed fibre material prior to fixing.