The present invention relates to a process for fixing dyes on organic materials using colourless cationic compounds that contain at least two polymerisable double bonds with ionising radiation or by irradiation with UV light in the presence of photoinitiators.

It is known that dyes, preferably those containing activated unsaturated groups, can be fixed on organic material, especially fibre material, by subjecting said material to ionising irradiation. Dyeing processes are also known in which there are used nonionic colourless compounds containing at least one polymerisable double bond and the subsequent dye fixation is effected by ionising electron beam radiation or by irradiation with UV light in the presence of photoinitiators. These dye fixation processes, however, have so far not been put into actual practice owing to the unsatisfactory fixation.

Hence it is the object of the present invention to provide a process for fixing dyes by ionising radiation or by irradiation with UN light in the presence of photoinitiators, which process makes it possible to achieve superior fixation.

It has been found that this object can be attained by the process described in this specification.

Accordingly, the invention relates to a process for dyeing or printing organic material, preferably fibre material, which comprises applying dyes together with a colourless cationic compound containing at least two polymerisable double bonds, as well as additional optional auxiliaries, to said organic material, preferably fibre material, and subsequently fixing the dyes thereon with ionising radiation, or applying said dyes, together with a colourless cationic compound containing at least two polymerisable double bonds, and at least one photoinitiator, as well as additional optional auxiliaries, to said organic material, preferably fibre material, and subsequently fixing the dyes thereon with UV light.

The distinguishing feature of the novel process is that dye and colourless cationic

compound are applied together so that only a single dyebath or only a single dye liquor is necessary, thereby achieving a markedly higher degree of fixation than in the known processes without a colourless cationic polymerisable compound. The colourless cationic compound can, however, also be applied separately before or after the actual dyeing process. A further advantage is that the process can be carried out at such a low radiation dose that less dye is destroyed, thereby resulting in great brilliance of the dyeing.

The fixation process consists in briefly subjecting a fibre material to be dyed, typically textile fibre material, after the treatment with a dye and in the presence of a colourless cationic compound that contains at least two polymerisable double bonds, as well as additional optional auxiliaries, in the wet, moist or dry state to ionising radiation or, in the presence of at least one photoinitiator, to irradiation with UV light The treatment of the fibre material to be dyed with a dye as defined herein can be carried out by a standard method. For example, if the material is a textile fabric, then treatment is carried out by impregnating said material with a dye solution in an exhaust bath, or by spraying or by padding the material with a pad liquor, or by printing the material on a roller printer or by the ink jet method.

Ionising radiation will be understood as meaning radiation which can be produced in an ionising chamber. It consists either of electrically charged, directly ionising particles which, in gases along their path, produce ions by impact, or of uncharged, indirectly ionising particles or photons which produce in matter directly ionising charged secondary particles, typically the secondary electrons of X-rays or γ-rays or the recoil nuclei (especially protons) of fast neutrons. Likewise indirectly ionising particles are slow neutrons which are able to produce energy-rich charged particles by nuclear reactions in part direct, in part via photons from (β,γ) processes. Suitable heavy charged particles are protons, atomic nuclei or ionised atoms. Of particular importance for the inventive process are light, charged particles, for example electrons. Suitable X-ray radiation is both braking radiation and characteristic radiation. Important particle radiation of heavy charged particles is typically α-radiation.

The ionising radiation can be produced by one of the standard methods. Thus, for example, spontaneous nuclear transformations and also nuclear reactions (enforced nuclear transformations) can be used to produce ionising radiation. Suitable sources of radiation are natural or synthetic radioactive substances and, more particularly, atomic reactors. The radioactive fission products produced by nuclear fission in such reactors are

a further important source of radiation.

A further possible method of producing radiation is that using an X-ray tube.

Of particular importance are beams which consist of particles accelerated in electric fields. Suitable sources of radiation here are thermal, electron impact, low tension arc, cold cathode and high-frequency ion sources.

Electron beams are of particular importance for the inventive process. These are produced by acceleration and bunching of electrons which are triggered by thermionic emission, field emission or photoemission a as well as by electron or ion bombardment from a cathode. Sources of radiation are electron guns and accelerators of conventional make. Typical sources of radiation are known from the literature, e.g. International Journal of Electron Beam & Gamma Radiation Processing, in particular 1/89 pages 11-15; Optik, 77 (1987), pages 99-104.

Sources of radiation for electron beams are also β-emitters such as strontium-90.

Suitable technically useful ionising beams are also γ-rays, which can be readily produced with caesium- 137 or cobalt-60 isotope sources.

When using ultraviolet radiation, the presence of a photoinitiator is necessary. The photoinitiator absorbs the radiation to produce free radicals that initiate the polymerisation. Illustrative examples of photoinitiators or photosensitisers suitable for use in the practice of this invention are carbonyl compounds such as 2,3-hexanedione, diacetyl acetophenone, benzoin and benzoin ethers such as dimethyl, ethyl and butyl derivatives, typically 2,2-diethoxyacetophenone and 2,2-dimethoxyacetophenone, benzophenone or a benzophenone salt and phenyl-(l-hydroxycyclohexyl)ketone or a ketone of formula

benzophenone in conjunction 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, azobisisobutyronitrile, hydrazine, phenylhydrazine as well as trimethylbenzylammonium chloride; and sulfur-containing compounds such as benzenesulfonate, diphenyl disulfide as well as tetramethylthiuram disulfide. Such photosensitisers are used singly or together with one another.

The amount of photosensitiser in the applied dye components directly before irradiation is 0.01 - 20 %, preferably 0.1 - 5 %, based on the total amount of colourless polymerisable compounds.

Water-soluble as well as water-insoluble photosensitisers are suitable. Furthermore, the copolymerisable photoinitiators mentioned, inter alia, in "Polymers Paint Colour Journal, 180, page 42f (1990)" are especially useful.

Also suitable are cationic photoinitiators such as triarylsulfonium salts, diaryliodonium salts, diaryl iron complexes or, quite generally, the structures described in "Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints" Vol. 3, published by SITA Technology Ltd., Gardiner House, Broomhill Road, London, 1991.

It is preferred to use acylphosphine oxides such as (2,4,6- trimethylbenzoyl)(diphenyl)- phosphine oxide or a photoinitiator of formula

or

(IB)

or the photoinitiator of formula

together with a co-initiator of formula (1A), (IB) or

or benzophenone together with a co-initiator of formula (1A), (1C) or (ID).

It is particularly preferred to use the photoinitiator of formula

Furthermore, it is also possible to add, besides the photosensitiser, polymerisation co-initiators such as peroxides or aliphatic azo compounds which are activated by an additional hot air process step and initiate the polymerisation.

The customary catalysts which form free radicals can be used for the polymerisation or copoylmerisation. Typical catalysts are hydrazine derivatives such as hydrazine hydrochloride, organometallic compounds such as tetraethyl lead, and, in particular, aliphatic azo compounds such as α,α'-azoisobutyrodinitrile and organic peroxides, chloroacetyl peroxide, trichloroacetyl peroxide, benzoyl peroxide, chlorobenzoyl peroxide, benzoyl acetylperoxide, propionyl peroxide, fluorochloropropionyl peroxide,

lauryl peroxide, cumene hydroperoxide, cyclohexanone hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, di-tert-amyl peroxide and p-methane hydroperoxide, and inorganic peroxide compounds such as sodium peroxide, alkali percarbonates, alkali persulfates or alkali perborates and, preferably, hydrogen peroxide, which can with advantage replace expensive benzoyl peroxide. The amount of catalyst to be added will depend in known manner on the desired reaction course or on the desired properties of the polymer. It is advantageous to use about 0.05 to 10 % by weight, based on the total amount of binder or binder mixture.

The UV light used is suitably radiation whose emission is in the range from 200 to 450 nm, preferably from 210 to 400 nm. The radiation is preferably produced artificially with high-pressure, medium-pressure or low-pressure mercury vapour lamps, halogen lamps, metal halide lamps, xenon or tungsten lamps, carbon arc lamps or fluorescent tubes, H- and D-lamps, superactinic fluorescent lamps and lasers.

It is advantageous to use capillary mercury high-pressure lamps or mercury high-pressure lamps or mercury low-pressure lamps. It is particularly advantageous to use mercury high-pressure lamps and mercury medium-pressure lamps which may also be doped with iron or gallium halide. These lamps can also be activated by microwaves or pulse-operated to concentrate the radiation in peaks. Pulsed operation is also possible when using xenon lamps if a higher proportion of long-wave UV light is required.

The standard UV sources of radiation are those described in "Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints", Vol. 1, published by SITA Technology, Gardiner House, Broomhill Road, London, 1991.

The precise radiation time of the dyeings or prints will depend on the intensity of the UV source, the distance from the light source, the type and amount of photosensitiser and the permeability of the formulation and the textile substrate to UV light.

Normal radiation times are from 1 second to 2 minutes, preferably from 2 seconds to 1 minute. The fixation can be terminated by discontinuing the irradiation so that it can also be carried out batchwise.

Irradiation may be carried out in an inert gas atmosphere to prevent oxygen inhibition; but this precautionary measure is usually not necessary. Oxygen inhibition can also be

effectively prevented by the addition of anti-blocking agents, i.e. amines and also, more particularly, aminoacrylates.

Dyes suitable for this fixation process are those whose chromophoric systems belong to a wide range of classes, typically the monoazo or polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan, azomethine, nitroaryl, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone, naphthoquinone, pyrenequinone or perylenetetracarbimide series.

Particularly suitable dyes include the direct dyes and the reactive dyes.

By direct dyes are meant those described in the Colour Index 3rd edition (3rd Revision 1987, including Additions and Amendments to No. 85) as "Direct Dyes".

By reactive dyes are meant those dyes that contain one or more than one reactive group, for example those described in the Colour Index 3rd edition (3rd Revision 1987, including Additions and Amendments to No. 85) as "Reactive Dyes".

Reactive groups will be understood as meaning fibre-reactive radicals that are able to react with the hydroxyl groups of celulose, the amino, carboxyl, hydroxyl and thiol groups of wool and silk, or with the amino and carboxyl groups of synthetic polyamides to form covalent chemical bonds. The reactive groups are usually bonded direct or through a linking group to the dye radical. Suitable reactive groups are typically those that contain at least one removable substituent present on an aliphatic, aromatic or heterocyclic radical or wherein the cited radicals carry a radical that is suitable for reaction with the fibre material, typically a triazine radical.

Reactive groups are typically radicals containing carbocyclic or heterocyclic 4-, 5- or 6-membered rings substituted by a removable atom or a removable group. Suitable heterocyclic radicals are typically those that carry at least one removable substituent attached to a heterocyclic radical, including those that carry at least one reactive substituent attached to a 5- or 6-membered heterocyclic ring, typically to a monoazine, diazine, triazine, pyridine, pyrimidine, pyridazine, pyrazine, thiazine, oxazine or asymmetric or symmetric triazine ring, or to such a ring system that contains one or more than one fused aromatic ring, typically a quinoline, phthalazine, quinoline, quinazoline,

quinoxaline, acridine, phenazine and phenanthridine ring system. In addition, the cited heterocyclic fibre-reactive radicals may contain further fibre-reactive radicals linked through a direct bond or through a linking group, for example the radicals listed above.

Further suitable reactive groups are those that contain at least one activated unsaturated group, preferably an unsaturated aliphatic group, typically the vinyl, halovinyl, styryl, acryloyl or methacryloyl group, or contain at least one polymerisable ring system. Such groups typically include the unsaturated groups that contain halogen atoms such as halomaleic acid and halopropiolic acid radicals, the α- or β-bromo- or chloroacryloyl groups, halogenated vinylacetyl groups, halocrotonyl or halomethacryloyl groups. Those groups are also suitable which are readily converted into halogen-containing unsaturated groups, conveniently by dehydrohalogenation, for example the dichloropropionyl group or the dibromopropionyl group. Halogen atoms in this context will be taken to mean fluorine, chlorine, bromine and iodine atoms as well as pseudohalogen atoms such as the cyano group. Good results are also obtained by the process of this invention with dyes that contain a α-bromoacryloyl group. Dyes that contain a polymerisable double bond are preferably those that contain at least one acryloyl, methacryloyl, α-bromoacryloyl, α-chloroacryloyl, vinyl or vinylsulfonyl radical. Most preferred are those dyes that contain at least one acryloyl, α-bromacryloyl or vinylsulfonyl radical. Suitable dyes that contain a polymerisable ring system are preferably those that contain at least one epoxide radical.

Further removable atoms or removable groups are typically ammonium including hydrazinium, sulfato, thiosulfato, phosphato, acetoxy, propionoxy or carboxypyridinium.

The linking group between the dye radical and the fibre-reactive radical, or the linking group between two fibre-reactive radicals, is suitably any radical in addition to the direct bond. The linking group is typically an aliphatic or heterocyclic radical, and may also be comprised of different radicals of this type. The linking group usually contains at least one functional group, typically the carbonyl group or the amino group, which amino group may be further substituted by Cι-C alkyl or C C ₄ alkyl which is substituted by halogen, hydroxy, cyano, C ₁ -C ₄ alkoxy, C _r C ₄ alkoxycarbonyl, carboxy, sulfamoyl, sulfo or sulfato. An aliphatic radical may typically be an alkylene radical of 1 to 7 carbon atoms or the branched isomers thereof. The carbon chain of the alkylene radical may be interrupted by a hetero atom, typically an oxygen atom. An aromatic radical may typically be a phenyl radical that may be substituted by C _j - alkyl such as methyl or ethyl, Cj- alkoxy such as methoxy or ethoxy, halogen such as fluoro, bromo or, preferably, chloro, carboxy or

sulfo; and a heterocyclic radical may suitably be a piperazino radical. Illustrative examples of such linking groups are:

-CO-N(R ₁ )-(CH ₂ ) ₂ . ₃ -; -CO-N(R ₁ )-(CH ₂ ) ₂ -O-(CH ₂ ) ₂ -;

-N(R ₁ )-CO-(CH ₂ ) ₃ -; -N^)-;

-N(R ₁ )-(CH ₂ ) ₂ -O-(CH ₂ ) ₂ -; -O-(CH ₂ ) ₂ -;

-CO- N N - (CH ₂ ) ₃ - _; -N(Rι)

In the above formulae R _j is hydrogen or C ₁ -C alkyl which may be substituted by halogen, hydroxy, cyano, C _r C alkoxy, -Qalkoxycarbonyl, carboxy, sulfamoyl, sulfo or sulfato.

Interesting reactive groups are 1,3,5-triazine radicals of formula

wherein Tj is fluoro, chloro or carboxypyridinium and preferred substituents V _x at the triazine ring are: fluoro, chloro, -NH ₂ , Ci-Cβalkylamino, N.N-di-Cj-Cgalkylamino, cyclohexylamino, N,N-dicyclohexylamino, benzylamino, phenethylamino, phenylamino, naphthylamino, N-Ci-Cgalkyl-N-cyclohexylamino or N-Cj-Cβalkyl-N-phenylamino, or morpholino, piperidino, piperazino, hydrazino or semicarbazido, or an amino group which is substituted by a furan, thiophene, pyrazole, pyridine, pyrimidine, quinoline, benzimidazole, benzothiazole or benzoxazole radical. The cited alkyl, cycloalkyl, aralkyl and aryl radicals and the heterocyclic radicals may be further substituted as indicated in

connection with formula (1).

Vi in the radical of formula (1) is most preferably fluoro, chloro, phenylamino or N-C ₁ -C ₄ alkyl-N-phenylamino, in which two last mentioned radicals the phenyl rings may be substituted by halogen such as fluoro, chloro or bromo, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C ₁ -C ₄ alkyl, C _r C alkoxy, acylamino groups such as acetylamino or benzoylamino, ureido, hydroxy, carboxy, sulfomethyl or, preferably, sulfo.

Interesting fibre reactive radicals typically include those of formula

wherein T ₂ and T ₃ are each independently of the other fluoro, chloro or carboxypyridinium and B is a linking group.

The linking group B may typically be a radical of formula

wherein Rj and R _x ' are each independently of the other hydrogen or C ₁ -C alkyl or C ₁ -C ₄ alkyl which is substituted by halogen, hydroxy, cyano, C ₁ -C alkoxy, C _r C alkoxycarbonyl, carboxy, sulfamoyl, sulfo or sulfato, and X is a or C ₅ -C ₉ cycloalkylene radical which is unsubstituted or substituted by hydroxy, sulfo, sulfato, C _r C alkoxy, carboxy or halogen, or is a phenylene, biphenylene or naphthylene radical, each unsubstituted or substituted by C C alkyl, C _j - alkoxy, sulfo, halogen or carboxy.

Further interesting reactive groups are those of formula

wherein T ₄ is fluoro, chloro or carboxypyridinium, and V ₂ is a radical of formula

wherein R _λ is hydrogen or C _r C ₄ alkyl which may be substituted by halogen, hydroxy, cyano, C ₁ -C alkoxy, C _j - alkoxycarbonyl, carboxy, sulfamoyl, sulfo or sulfato; Bj is a direct bond or a radical -(-CH ₂ -)^- or — O — (-CH ₂ -) — ; n = 1, 2, 3, 4, 5 or 6; and R is a radical of formula

-N-(alk)-CH ₂ -SO ₂ -Z (4a) V

-N-(alk)-CH ₂ -SO ₂ -Z (4b)

R ^* -N-(CH ₂ ) _p -O-(CH ₂ ) _q -SO ₂ -Z (4c)

R'

-N-(alk ^* )-NH-(alk ^* )-SO ₂ -Z (4d)

R' -N-(CH ₂ ) _r -N[(CH ₂ ) _s -SO ₂ -Z] ₂ (4e)

R' -N[(CH ₂ ) _s -SO ₂ -Z] ₂ (4f) or

^■ (CH ₂ ) -S0 ₂ -Z (4g)

wherein R ¹ is hydrogen or - alkyl, alk is an alkylene radical of 1 to 7 carbon atoms, T is hydrogen, halogen, hydroxy, sulfato, carboxy, cyano, C ₁ -C ₄ alkanoyloxy, C C ₄ alkoxy- carbonyl, carbamoyl or a radical -SO ₂ -Z, V is hydrogen, unsubstituted or substituted C ₁ -C ₄ alkyl or a radical of formula

-(alk)-CH ₂ -SO ₂ -Z (4h)

wherein (alk) is as previously defined, each alk' is independently polymethylene of 2 to 6 carbon atoms, Z is β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl, β-acyloxyethyl,

✓ ^R 30 β-haloethyl, vinyl or - CH ₂ - CH ₂ - N , wherein R ₃₀ and R ₃₁ are each

\ R ^• 31 independently of the other hydrogen or which is unsubstituted or substituted by SO ₃ H, p, q, r and t are each independently of one another 1, 2, 3, 4, 5 or 6, and s is 2, 3, 4, 5 or 6; and the benzene ring in formula (4) may contain further substituents; or wherein V ₂ is a radical of formula (4a), (4b), (4c), (4d), (4e), (4f) or (4g) which is attached direct to the triazine ring, wherein R', T, alk, V, alk', Z, p, q, r, s and t have the given meanings; or wherein V ₂ is a radical of formula

wherein Ri and Z have the given meanings and the benzene ring may be further substituted.

Further possible substituents of the benzene rings of the compounds of formulae (4) and (4') are halogen such as fluoro, chloro or bromo, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, Cj- alkyl, C ₁ -C ₄ alkoxy, acylamino groups such as acetylamino or benzoylamino, ureido, hydroxy, carboxy, sulfomethyl and sulfo.

The radical B _τ contains 1 to 6, preferably 1 to 4, carbon atoms. Typical examples of B ₂ are: methylene, ethylene, propylene, butylene, methyleneoxy, ethyleneoxy, propyleneoxy

and butyleneoxy. If B*. is a radical — O—(-CH ₂ -) — , then B _! is attached through the oxygen atom to the benzene ring. Preferably Bj is a direct bond.

Z as β-haloethyl is preferably β-chloroethyl and, as β-acyloxyethyl, is preferably β-acetoxyethyl. The alkylene radical alk is preferably methylene, ethylene, methylmethylene, propylene or butylene. The substituent T as alkanoyloxy is preferably acetoxy, propionyloxy or butyryloxy and, as alkoxycarbonyl radical, is preferably methoxycarbonyl, ethoxycarbonyl or propoxycarbonyl. An alkyl radical V may be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl. The radical R' is typically methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl or hexyl or, preferably, hydrogen. The polymethylene radicals alk' are preferably ethylene, propylene or butylene. The indices p, q and t are each independently of one another preferably 2, 3 or 4. The indices r and s are each independently of the other preferably 2.

Preferred radicals V ₂ are those of formula (4), wherein B _! is a direct bond and R is a radical of formula (4a), or wherein V ₂ is a radical of formula (4b), (4c) or (4f) which is attached direct to the triazine ring, or wherein V ₂ is a radical of formula (4').

Preferred aliphatic reactive groups are those of formulae

-SO ₂ Z (5a),

-SO ₂ -NH-Z (5b),

-NH-CO-(CH ₂ ) ₃ -SO ₂ Z (5c),

-CO-NH-CH ₂ CH ₂ -SO ₂ Z (5d) and

-NH-CO-Zx (5e),

wherein Z is as defined above, Zj has the meanings of Z and may additionally be α,β-dihaloethyl.

Halogen in the β-haloethyl, α,β-dihaloethyl and α-haloacryloyl groups represented by Z are preferably chloro and bromo.

Particularly preferred aliphatic reactive groups are those of formula (5a), as well as those of formulae (5c) and (5d). In these radicals, Z is preferably β-sulfatoethyl or β-haloethyl.

Most preferably the reactive dyes contain at least one reactive group of formulae (1), (2),

(3) and (5a) bis (5e), wherein T _lf T ₂ , T ₃ , T ₄ , V V ₂ , B, Z and Z _λ have the meanings and preferred meanings assigned to them above.

The reactive dyes are preferably derived from the radical of a monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan, azomethine, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone, nitroaryl, naphthoquinone, pyrenequinone or perylenetetracarbimide dye, preferably from the radical of a monoazo, disazo, metal complex azo, formazane-, anthraquinone, phthalocyanine or dioxazine dye. In addition to containing the reactive group, the reactive dyes may contain in the molecule the customary substituents of organic dyes as further substituents.

Typical examples of such further substituents of the reactive dyes are: alkyl groups of 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl or butyl, alkoxy groups of 1 to 4 carbon atoms, typically methoxy, ethoxy, propoxy, isopropoxy or butoxy, acylamino groups of 1 to 8 carbon atoms, preferably alkanoylamino groups and alkoxycarbonylamino groups such as acetylamino, propionylamino, methoxycarbonylamino, ethoxycarbonyl- amino or benzoylamino, phenylamino, N-N-di-β-hydroxyethylamino, N,N-di-β-sulfatoethylamino, sulfobenzylamino, N,N-disulfobenzylamino, alkoxycarbonyl containing 1 to 4 carbon atoms in the alkoxy moiety, typically methoxycarbonyl or ethoxycarbonyl, alkylsulfonyl of 1 to 4 carbon atoms, typically methylsulfonyl or ethylsul- fonyl, trifluoromethyl, nitro, cyano, halogen such as fluoro, chloro or bromo, carbamoyl, N-alkylcarbamoyl containing 1 to 4 carbon atoms in the alkyl moiety, typically N-methyl- carbamoyl or N-ethylcarbamoyl, sulfamoyl, N-alkylsulfamoyl of 1 to 4 carbon atoms, e.g. N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl or N-butylsulfamoyl, N-(β-hydroxyethyl)sulfamoyl, N,N-bis(β-hydroxyethyl)sulfamoyl, N-phenylsulfamoyl, ureido, hydroxy, carboxy, sulfomethyl or sulfo as well as further fibre-reactive radicals. The reactive dyes preferably contain one or more than one sulfonic acid group.

The reactive dyes are preferably derived from the following dye radicals:

a) Dye radicals of a 1 : 1 copper complex azo dye of the benzene or naphthalene series in which the copper atom is attached to a metallisable group on both sides in ortho-position to the azo bridge.

b) Particularly preferred dye radicals are the radicals of a mono- or disazo dye of formula

D _r N=N-(M-N=N) _u -K- (6a),

-D _r N=N-(M-N=N) _u -K (6b) or

-D _r N=N-(M-N=N) _u -K- (6C), or of a metal complex derived therefrom; D s the radical of a diazo component of the benzene or naphthalene series, M is the radical of a middle component of the benzene or naphthalene series, and K is the radical of a coupling component of the benzene, naphthalene, pyrazolone, 6-hydroxypyrid-2-one or acetoacetylarylamide series, and D^ M and K may carry the customary substituents of azo dyes, preferably hydroxy, amino, methyl, ethyl, methoxy or ethoxy groups, unsubstituted or substituted alkanoylamino groups of 2 to 4 carbon atoms, unsubstituted or substituted benzoylamino groups, halogen atoms, or a fibre-reactive radical, preferably a -SO ₂ -Z radical, wherein Z is β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl, β-acyloxyethyl, β-haloethyl or vinyl; u = 0 or 1; and D M and K together contain at least two sulfo groups, preferably three or four sulfo groups.

c) Particularly preferred dye radicals are also the dye radicals of a disazo dye of formula

-D _r N=N-K-N=N-D ₂ (7a) or

-D _r N=N-K-N=N-D ₂ - (7b), wherein D _x and D ₂ are each independently of the other the radical of a diazo component of the benzene or naphthalene series, and K is the radical of a coupling component of the naphthalene series; and D _l5 D ₂ and K may carry the customary substituents of azo dyes, preferably hydroxy, amino, methyl, ethyl, methoxy or ethoxy groups, unsubstituted or substituted alkanoylamino groups of 2 to 4 carbon atoms, unsubstituted or substituted benzoylamino groups, halogen atoms or a fibre-reactive radical, preferably a -SO ₂ -Z radical, wherein Z has the given meaning, and D _lt D ₂ and K together contain at least two sulfo groups, prfeerably three or four sulfo groups.

Important dye radicals are d) Dye radicals of a formazan dye of formula

(8a) or (8b)

(8c) or (8d), wherein the benzene nuclei may be further substituted by alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylsulfonyl of 1 to 4 carbon atoms, halogen or carboxy.

e) Dye radicals of an anthraquinone dye of formula

wherein G is a phenylene, cyclohexylene, phenylenemethylene or Cj-Cgalkylene radical; and the anthraquinone nucleus may be substituted by a further sulfo group, and a phenyl radical G may be substituted by alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, halogen, carboxy or sulfo, and the dye preferably contains at least 2 sulfo groups.

f) Dye radicals of a phthalocyanine dye of formula _y (S0 ₂ W) _k

Pc

\ S0 ₂ -N-E- (10),

R wherein Pc is the radical of a copper or nickel phthalocyanine; W is -OH and/or -NR ₅ R ₅ _; R ₅ and R ₅ . are each independentiy of the other hydrogen or alkyl of 1 to 4 carbon atoms which may be substituted by hydroxy or sulfo; R is hydrogen or alkyl of 1 to 4 carbon atoms; E is a phenylene radical which may be substituted by alkyl of 1 to 4 carbon atoms, halogen, carboxy or sulfo; or is an alkylene radical of 2 to 6 carbon atoms, preferably a sulfophenylene or an ethylene radical; and k = 1, 2 or 3.

g) Dye radicals of a dioxazine dye of formula

or

wherein E is a phenylene radical which may be substituted by alkyl of 1 to 4 carbon atoms, halogen, carboxy or sulfo; or is an alkylene radical of 2 to 6 carbon atoms; and the outer benzene rings in the formula (1 la) and (lib) may be further substituted by alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, acetylamino, nitro, halogen, carboxy, sulfo or -SO ₂ -Z in which Z is β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl,

β-acyloxyethyl, β-haloethyl, vinyl or - CH ₂ - CH ₂ - wherein R ₃₀ and R ₃₁ are each independently of the other hydrogen or C C ₃ alkyl which is unsubstituted or substituted by SO ₃ H.

It is also particularly preferred to use dyes containing the radical of formula (12a) to (12j)

wherein (R )ι_ ₃ denotes 1 to 3 substituents selected from the group consisting of C^alkyl, C^alkoxy, halogen, carboxy and sulfo;

wherein (R ₉ )ι. ₃ denotes 1 to 3 substituents selected from the group consisting of C^alkyl, C^alkoxy, halogen, carboxy and sulfo;

wherein (Rιo)i- ₃ denotes 1 to 3 substituents selected from the group consisting of halogen, carboxy and sulfo;

wherein R _π is C^alkanoyl or benzoyl;

wherein R ₁₂ is C^alkanoyl or benzoyl;

wherein (R ₁₃ ) ₀ - ₃ denotes 0 to 3 substituents selected from the group consisting of C^alkyl, ^alkoxy, halogen, carboxy and sulfo;

wherein R ₁₄ and R ₁₅ are each independently of the other hydrogen, or phenyl, and R ₁₆ is hydrogen, cyano, carbamoyl or sulfomethyl;

wherein (R ₁₇ ) ₁ denotes 1 to 4 substituents selected from the group consisting of hydrogen, halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C _1-4 alkyl, C^alkoxy, amino, acetylamino, ureido, hydroxy, carboxy, sulfomethyl and sulfo, each independently of one another; and

Particularly preferred dyes are those of formula

wherein

A ₂ is hydrogen or - C ₃ alkyl, T ₅ is a radical of formula

(16) (17) (18)

Z ₂ and Z ₃ are each independently of the other hydrogen or the radicals of formulae

O

- NH - C - (CH^ - SO ₂ - CH = CH _{2 •} X ₂ is chloro or fluoro, X _! and X^ are each independently of the other hydrogen, chloro, bromo or methyl, and

Ai is a direct bond, - jΑ~ O - C ₂ H ₄ - , or

Particularly suitable direct dyes are phthalocyanine dyes, dioxazine dyes and dyes of formula

A ₃ -B ₃ -A ₄ (34a)

in which dyes of formula (34a) B ₃ is a linking group and A ₃ and A ₄ are each independently of the other a radical of a monoazo, polyazo, metal complex azo, stilbene or anthraquinone dye, or wherein B ₃ and A ₃ have the given meanings and A is a phenyl or naphthyl radical which is substituted by a heterocyclic radical or a benzoylamino or phenylamino group, or a reactive group as defined above, or wherein B ₃ is a direct bond and A ₃ and A ₄ are each the radical of a metal complex azo dye, or dyes of formula

A ₅ - NH - L ₂ (34b),

wherein

A ₅ is the chromophoric radical of an organic dye, and

Lj is a radical of formula

-CO-R ₂ , -SO ₂ -R or , wherein

X ₄ and X ' are each independently of the other a direct bond, NH, NR, O or S, R ₂ and R ₂ ' are each independently of the other hydrogen, aromatic, aliphatic or cycloaliphatic radicals which are unsubstituted or substituted by halogen, OR", COOR", SO ₃ H or aralkyl which is unsubstituted or substituted by halogen, OR", COOR" or SO ₃ H, and R" is hydrogen or C _r C ₆ alkyl.

Suitable linking groups B ₃ in formula (34a) are typically the following groups:

-NH- (35a),

O

II _N — c — N— (35b),

R ₂₅ R ₂₅ "

O O

II II

_N_ _C -X ₃ -C-N — (35c),

^R 25 25'

N

_N — < S N — (35d),

1 I II 1

R ₂ 5 ^N * . ^{N R} 25'

Y

O — N →l — (35g),

-N=N- (35h) und

-CH=CH- (35i),

wherein R^ and R^ are each independently of the other unsubstituted or substituted C _r C ₈ alkyl or, preferably, hydrogen, X ₃ and X5 are linking groups and Y and Y' are each independentiy of the other hydroxy, C ₁ -C ₄ alkoxy, chloro, bromo, - alkylthio, amino, N-mono- or N,N-di-C ₁ -C alkylamino which are each unsubstituted or substituted in the alkyl moiety by hydroxy, sulfo, carboxy or C ₁ -C ₄ alkoxy, or cyclohexylamino, or phenylamino or N-C _r C alkyl-N-phenylamino which are each unsubstituted or substituted in the phenyl nucleus by C _r C ₄ alkyl, C ₁ -C ₄ alkoxy, carboxy, sulfo and/or halogen, or are morpholino or 3-carboxy- or 3-carbamoylpyridin-l-yl.

R;25 and R^ as Cj-Cgalkyl may be unsubstituted or substituted by e.g. halogen, hydroxy, cyano, - alkoxy, Ci- alkoxycarbonyl, carboxy, sulfamoyl, sulfo or sulfato.

The linking group X ₃ in formula (35c) is preferably a or C ₅ -C9cycloalkylene radical which is unsubstituted or substituted by hydroxy, sulfo, sulfato, C _r C ₄ alkoxy, carboxy or halogen, or a phenylene, biphenylene or naphthylene radical, each unsubstituted or substituted by C C ₄ alkyl, C C alkoxy, sulfo, halogen or carboxy. X ₃ is preferably an unsubstituted or a sulfo-substituted phenylene radical.

Suitable linking groups X ₅ in formula (35e) are typically the following radicals of formulae:

-NR ₂₅ -(CH ₂ ) ₂ ^-NR ₂₅ .- (36a),

— N N — (36b),

\_/

and, preferably,

in which R^ and R^ have the meanings and preferred meanings given previously.

The radicals R ₂ and R ₂ ' in formula (34b) are preferably - alkyl or C^Cgalkylene radicals, typically methyl ethyl and isopropyl, which may be substituted by carboxy or phenyl; and also phenols which may be substituted by carboxy; and unsubstituted or substituted benzyl radicals; as well as radicals of formulae

— N N — R" and — N O

wherein R" is as defined in connection with formula (34b).

Particularly preferred dyes are those of formula (34a), wherein B ₃ and A ₃ have the given meanings and A is a phenyl radical which is substituted by benzothiazolyl, benzisothiazolyl or naphthotriazolyl, and the phenyl radical and the benzothiazolyl, benzisothiazolyl and naphthotriazolyl substituents of the phenyl radical may each independently of one another be substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, carboxy, hydroxy, sulfo, sulfamoyl, ureido, amino which may be further substituted by C _j - alkyl or C _j - hydroxyalkyl, or by C^-Cgalkanoyl or C^-Cgalkanoylamino which

may be further substituted in the alkyl moiety by hydroxy.

Particularly preferred dyes are also the direct dyes of formula (34b), wherein Li is a radical of formula

R"

COCH ₃ , -COCH ₂ CH ₂ COOH, - CO- - CO - CH = CH ι--f

wherein X ₆ is halogen and R" is as defined for formula (34b).

The reactive dyes as well as the direct dyes preferably contain at least one water-solubilising group, typically a sulfo or sulfato group, and are in this case in the form of the free acid or, preferably, of salts thereof such as alkali metal, alkaline earth metal or ammonium salts or as salts of an organic amine. Illustrative examples of such salts are the sodium, potassium, lithium or ammonium salts or the salt of triethanolamine.

The reactive dyes and direct dyes are known or can be obtained by methods analogous to those for preparing known dyes.

The cationic compounds eligible for use in the practice of this invention are conveniently colourless or almost colourless quaternary ammonium salts that additionally carry at least two polymerisable double bonds. Preferred cationic compounds are those of the general formula

(R ₂ R ₃ R ₃ .R ₃ ..N) _m ⁺ (Ar- , (40),

wherein R ₂ is a radical of formula

CH ₂ -= CX ₇ - Y ₁ - Q ₄ - (40a),

wherein

X ₇ is hydrogen, halogen or Cj- C^alkyl,

Yi is - CO - O - oder - CO - NH - ,

Q ₄ is - CH ₂ - CHOH - CH ₂ - or - (CH ₂ ) _Z - ,

A is an anion selected from the group consisting of the halides, sulfates and C

C ₂ alkylsulfates,

R ₃ is allyl or R ₂ ,

R ₃ . and R ₃ - are each independently of the other hydrogen, allyl or R ₂ , or the quaternary nitrogen atom in formula (40) may also be a member of a N-heterocyclic ring which may be unsubstituted or substituted and may contain further hetero atoms, m is 1, 2 or 3, and z is an integer from 1 to 3.

Quaternary ammonium salts containing two and three polymerisable double bonds are preferred.

Particularly preferred quaternary ammonium salts are those of formulae

wherein

R ₄₁ and R ₄₂ are each independently of the other hydrogen or methyl and

R* and R** are each independently of the other methyl or ethyl.

In addition to containing dye and novel polymerisable cationic compounds, the print pastes and dye liquors may contain the customary auxiliaries such as thickeners, dyeing assistants, fillers, dispersants, lubricants, antioxidants and polymerisation inhibitors. These last mentioned compounds are usually also added as stabilisers to the polymerisable compounds.

The novel process is applicable to the most diverse fibres, including fibres of animal origin such as wool, silk, hairs (e.g. as felt) or regenerated fibres such as protein fibres, man-made fibres, including polyvinyl, polyacrylonitrile, polyester, polyamide or polyurethane fibres, polypropylene and, more particularly, cellulosic materials such as bast fibres, including linen, hemp, jute, ramie and, preferably, cotton, as well as cellulosic fibres such as viscose or modal fibres, copper, nitrate or saponified acetate fibres, or cellulose acetate fibres , for example secondary acetate fibres, or cellulose triacetate fibres such as Arnel®, Trilan®, Courpleta® or Tricel®.

The above fibres can be in any of the forms of presentation used especially in the textile industry, typically filaments, yarns, woven fabrics, knitted fabrics or nonwovens such as felts.

Prefeired fibre material in the process of this invention is wool, silk, hairs, polyvinyl, polyacrylonitrile, polyester, polyamide, aramide, polypropylene or polyurethane fibres or cellulosic fibres.

It is especially preferred to use cellulose fibres, woven and knitted polyester/cellulose blends as well as intimate polyester/cellulose blends.

The treatment of the material to be dyed with a dye as defined herein can be effected in conventional manner, for example if the material is a textile fabric by impregnating the material with a dye solution in an exhaust bath or by spraying or padding with a pad solution, or by printing on a knife-coater or by the ink-jet printing method. The dye and colourless cationic compound can be applied together as homogeneous solution, suspension, emulsion or foam by standard methods.

The dyed material can be irradiated in the wet, moist or dry state.

Usually the colourless cationic compounds and the other auxiliaries are applied together with the dye to the material to be dyed. It is, however, also possible to apply the colourless cationic compounds and/or the photoinitiators as well as the optional polymerisation co-initiators separately, conveniently in the form of a pre- or aftertreatment. If a water-insoluble photoinitiator is used and dyeing is carried out by the exhaust process or by padding, it is useful to impregnate the woven or knitted fabric first with the photoinitiator and then to dye the fabric with the dye liquor which may also contain the photoinitiator.

The process is particularly suitable for carrying out continuous dyeing and fixing processes. However, the process, or partial steps thereof, can also be carried out batchwise.

The novel process is carried out by passing the dyed textile material which has been treated with a solution of a colourless cationic compound at room temperature, through the beam of an electron accelerator. The speed at which the material is passed through the beam is such that a radiation dose of specific intensity is achieved. The radiation doses normally employed are in the range from 0.1 to 15 Mrad, but the radiation dose is preferably in the range from 0.1 to 4 Mrad. At a dose of less than 0.1 Mrad the fixation is

usually insufficient, whereas at a dose of more than 15 Mrad the fibre material and the dye suffer damage. The concentrations of the dye solutions or print pastes can be chosen as in conventional dyeing and printing processes, conveniently 0.001 to 20 percent by weight, based on the fibre material. Dye fixation is high, typically more than 90 %. The dyeings obtained in the novel process have good allround fastness properties, typically good fastness to water and light.

When carrying out the novel process, regard must naturally be had to the particular technical requirements. Thus the special embodiment of the process will depend in particular on the kind of ionising beams used for radiation and on how they are produced. If it is desired, for example, to irradiate a roll of yarn impregnated with dye solution and a solution of the colourless compound with γ-rays, then said roll is subjected to radiation sealed in a cell. If higher radiation doses are desired at a lower radiation intensity, the material can be subjected to radiation in several passes.

To prevent destructive oxidation of the dye, it is useful to carry out the irradiation in an inert gas atmosphere, conveniently under nitrogen.

A preferred embodiment of the invention comprises carrying out both fixation of the fibre material with appropriate dyes as well as dyeing or printing continuously.

The invention further relates to colourless cationic compounds that contain at least two polymerisable double bonds and have the formulae

wherein

R ₁ and R ₄₂ are each independentiy of the other hydrogen or methyl, and

R* and R** are each independently of the other methyl or ethyl, with the exception of the compound of formula

The compounds of formulae (50) to (53) are prepared in accordance with the following Examples.

Parts and percentages are by weight, and the relationship between parts by weight and parts by volume is the same as that between the gram and the cubic centimetre.

Example 1: 55.5 parts by weight of N-methyldiallylamine are charged to 300 parts by weight of water at a temperature of 0°C, and then 1.5 parts by weight of tetrabutylammonium bromide, 0.1 part by weight of sodium hydrogenphosphate and 0.2 part by weight of hydroquinone monomethyl ether are added.

Then 50 parts by volume of concentrated hydrochloric acid are added dropwise and the pH is adjusted to 6. The reaction mixture is heated to 60°C and 75 parts by weight of glycidyl methacrylate are added dropwise over 20 minutes and the temperature is raised to 75°C. The reaction mixture is stirred at this temperature for a further 30 minutes, while keeping a constant pH of 6 by addition of 2N hydrochloric acid. Complete conversion of the amine is determined by titration with NaOH. A clear solution of the cation of formula

in the form of the chloride is obtained.

Example 2: The procedure of Example 1 is repeated, but replacing 55.5 parts by weight of N-methyldiallylamine with 85 parts by weight of dimethylaminopropylmethacrylamide, to give a clear solution of the cation of formula

in the form of the chloride.

Example 3: 28.13 parts by weight of a 40 % aqueous solution of dimethylamine together with 300 parts by weight of water, 0.3 part by weight of sodium dihydrogenphosphate and an amount of surfactant are charged to a reactor at 0°C and the mixture is adjusted with 25 parts by volume of concentrated hydrochloric acid to pH 4. Then 0.2 part by weight of hydroquinone monomethyl ether are added and the reaction mixture is heated to 70°C. Then 78 parts by weight of glycidyl methacrylate are added dropwise over 15 minutes and the pH is kept constant at 6.5 by the addition of 2N hydrochloric acid. The reaction is complete after c. 2 hours, The contents of the reactor arc cooled and extracted with diethyl ether at room temperature, in the process of which a minor amount of oily substance is removed. A solution of the cation of the formula

in the form of the chloride is obtained.

In the following working Examples, the radiation doses are normally expressed in Mrad (megarad), 1 rad corresponding to an absorption of 10" ² J/kg (joule/kg).

The UV irradiation is carried out with a 120 watt/cm mercury medium-pressure lamp at a transport speed of 8 m/min, unless otherwise indicated.

The fabric specified in the following Examples is printed on one side or dyed by the pad-batch process and irradiated in an inert gas atmopshere. Dyeings are irradiated on both sides in two passes.

The percentage fixation is determined from the dye content of the extracts of an irradiated and unwashed sample and a non-irradiated punched sample, both measuring (2.5 cm) ² . The samples are treated once at room temperature for 20 minutes with in 25 ml of a solution of 600 ml/1 of phosphate buffer (pH 7) and 40 ml/1 of tetramethylurea in deionised water and thereafter once with 25 ml of this solution for 20 minutes at 100°C. Both extracts of each sample are combined and measured spectroscopically. The percentage fixation is determined from the extinction (at _m ^) of the extracts of the samples.

Parts and percentages are by weight, and the relationship between parts by weight and parts by volume is the same as that between the gram and the cubic centimetre.

Example 4: A cotton cretonne fabric is padded with a liquor consisting of 450 g/1 of the aqueous solution of the cation of formula (52a) prepared according to Example 1, 30 gl of a dye of formula

and 100 g 1 of urea (pick-up c. 70 %). The fabric is dried and then irradiated on both sides with accelerated electrons at a dose of 1 Mrad per side to give a brilliant red dyeing. The dye fixation is 97 %.

Example 5: A cotton cretonne fabric is padded with a liquor consisting of 475 g/1 of the aqueous solution of the cation of formula (50a) prepared according to Example 2, 30 gl of a dye of formula (100) and 100 g/1 of urea (pick-up c. 70 %). The fabric is dried and then irradiated on both sides with accelerated electrons at a dose of 1 Mrad per side to give a brilliant red dyeing. The dye fixation is 98 %.

Example 6: A blue dyeing with a fixation of 97 % is obtained by repeating the procedure

of Example 5, but replacing 30.0 g/1 of the dye of formula (100) with 26.0 g/1 of a dye of formula ₂

Example 7: The procedure of Example 5 is repeated, but without drying the fabric before irradiation, to give a brilliant red dyeing with 98 % dye fixation.

Example 8: The procedure of Example 7 is repeated, but without adding urea to the liquor, to give a brilliant red dyeing with 98 % dye fixation.

Example 9: A cotton cretonne fabric is padded with a liquor consisting of 475 g/1 of the aqueous solution of the cation of formula (50a) prepared according to Example 2, 30 gl of a dye of formula (100), 10 g 1 of the photoinitiator of formula (1 A) and 100 g/1 of urea (pick-up c. 70 %). The fabric is dried and then irradiated with UV light to give a red dyeing. The dye fixation is 100 %.

Example 10: The procedure of Example 9 is repeated, replacing 30 g/1 of the dye of formula (100) with 26.7 g/1 of a dye of formula (101), to give a blue dyeing with 100 % dye fixation.

Example 11: The procedure of Example 10 is repeated, but without adding urea to the liquor, to give a blue dyeing with 100 % dye fixation.