The practice of dyeing using reactive dyes has recently led to higher demands being made of the quality of the dyeings and the profitability of the dyeing process. As a result, there is still a need for novel reactive dyes having improved properties, especially in respect of their application.

Dyeing nowadays requires reactive dyes that have sufficient substantivity and at the same time have good ease of washing off of unfixed dye. They should also have a good tinctorial yield and high reactivity, the objective being to provide especially dyeings having high degrees of fixing. The known dyes do not satisfy these requirements in all properties.

The problem underlying the present invention is accordingly to find, for the dyeing and printing of fibre materials, improved reactive dyes having the qualities characterised above to a high degree. The dyes should especially be distinguished by high fixing yields and high fibre-dye binding stability; it should also be possible for dye that. is not fixed to the fibre to be washed off easily. The dyes should also yield dyeings having good all-round fastness properties, for example light-fastness and wet-fastness properties.

It has been shown that the problem posed is largely solved by the dyes defined below.

The present invention accordingly relates to reactive dyes of formula wherein A is the radical of a monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan or dioxazine chromophore, Q1 and Q2 are each independently of the other hydrogen or unsubstituted or substituted C-C4alkyl, (Q3) denotes n substituents selected from the group C,-C4alkyl, C1-C4alkoxy, halogen and sulfo, X is halogen, 3-carboxypyridin-1-yl, 3-carbamoylpyridin-1-yl, hydroxy, C1-C4alkoxy unsubstituted or substituted in the alkyl moiety, phenoxy unsubstituted or substituted in the phenyl moiety, Ci-C4alkylthio unsubstituted or substituted in the alkyl moiety, unsubstituted or substituted amino, or an N-heterocycle which may or may not contain further hetero atoms, Y is vinyl or a radical-CH2-CH2-U and U is a group removable under alkaline conditions, k is a number 2, 3,4, 5 or 6, m is a number 0 or 1, and n is a number 0,1 or 2, with the proviso that when A denotes a monoazo chromophore it is not directly linked to the triazinyl radical through a hydroxynaphthalenesulfonic acid coupling component and does not denote a radical of formula The radicals Q1 and Q2 as alkyl radicals are straight-chained or branched and may be further substituted, for example by hydroxy, sulfo, sulfato, cyano or carboxy. The following radicals may be mentioned as examples : methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, and the corresponding substituted radicals. As substituents, preference is given to hydroxy, sulfo, sulfato or carboxy, especially hydroxy or sulfato.

Q, and Q2 preferably are each independently of the other hydrogen or C1-C4alkyl, especially hydrogen, methyl or ethyl and very especially hydrogen.

Q3 as halogen is, for example, fluorine, chlorine or bromine, preferably chlorine or bromine and especially chlorine.

Q3 as C1-C4alkyl is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, preferably methyl or ethyl and especially methyl.

Q3 as C,-C4alkoxy may be, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy or isobutoxy, preferably methoxy or ethoxy and especially methoxy.

Q3 is preferably sulfo.

X as halogen is, for example, fluorine, chlorine or bromine and especially chlorine or fluorine.

X as C1-C4alkoxy is, for example, methoxy, ethoxy, n-or iso-propoxy, n-, sec-, iso-or tert- butoxy, preferably methoxy, ethoxy or isopropoxy and especially methoxy. The radicals mentioned are unsubstituted or substituted in the alkyl moiety, for example by C1-C4alkoxy, hydroxy, sulfo or carboxy. Preference is given to the unsubstituted radicals.

X as phenoxy is unsubstituted or substituted in the phenyl moiety, for example by C-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, hydroxy, sulfo or carboxy. Preference is given to the unsubstituted or sulfo-substituted radicals.

X as C1-C4alkylthio is, for example, methylthio, ethylthio, n-propylthio, isopropylthio or n-butylthio, especially methylthio or ethylthio. The radicals mentioned are unsubstituted or substituted in the alkyl moiety by hydroxy, carboxy or sulfo. Preference is given to the unsubstituted radicals.

X as unsubstituted or substituted amino is amino which is unsubstituted or substituted at the nitrogen atom, for example being one of the following radicals: N-mono-or N, N-di-C,-C4alkylamino, which includes-both the unsubstituted radicals and the radicals which are uninterrupted or interrupted in the alkyl moiety or moieties by oxygen as well as those which are substituted in the alkyl moiety or moieties, for example by C2-C4alkanoylamino, C1-C4alkoxy, hydroxy, sulfo, suifato, carboxy, cyano, carbamoyl or sulfamoyl, preferably by C,-C4alkoxy, hydroxy, sulfo or sulfato ; preference is given to the radicals substituted in the alkyl moiety or moieties; as examples there may be mentioned N-methylamino, N-ethylamino, N-propylamino, N, N-di-methylamino and N, N-di-ethylamino, N-ß-hydroxyethylamino, N, N-di-p-hydroxyethylamino, N-2-(ß-hydroxy-ethoxy)ethylamino, N-2-[2-(ß-hydroxyethoxy)ethoxy]ethylamino, N-ß-sulfatoethylamino, N-ß-sulfoethylamino, N-carboxymethylamino, N-p-carboxy-ethylamino, N-a, ß-dicarboxy-ethylamino, N-a, y- dicarboxypropylamino, N-ethyl-N-ß-hydroxyethylamino and N-methyl-N-ß-hydroxyethylamino ; C5-C7cycloalkylamino, which includes both the unsubstituted radicals and the radicals substituted in the cycloalkyl ring, for example by C1-C4alkyl, especially methyl, or carboxyl ; preference is given, as such radicals, to the corresponding cyclohexyl radicals ; phenylamino or N-C1-C4alkyl-N-phenylamino, which includes both the unsubstituted radicals and the radicals substituted in the phenyl ring, for example by Ci-C4alkyl, Cl-C4alkoxy, C2-C4alkanoylamino, carboxy, carbamoyl, sulfo or halogen, for example 2-, 3-or 4-chloro- phenylamino, 2-, 3-or 4-methylphenylamino, 2-, 3-or 4-methoxyphenylamino, 2-, 3-or 4- sulfophenylamino, disulfophenylamino, or 2-, 3-or 4-carboxyphenylamino ; preference is given to such radicals being unsubstituted or substituted in the phenyl ring by sulfo ; naphthylamino, which is unsubstituted or substituted in the naphthyl ring system, for example by sulfo ; preference is given to the radicals substituted by from 1 to 3 sulfo groups, for example 1-or 2-naphthylamino, 1-sulfo-2-naphthylamino, 1, 5-disulfo-2-naphthylamino or 4,8- disulfo-2-naphthylamino ; or benzylamino, which is unsubstituted or substituted in the phenyl moiety, for example by C,-C4alkyl, C1-C4alkoxy, carboxy, sulfo or halogen.

X as an N-heterocycle which may or may not contain further hetero atoms is, for example, morpholino or piperidin-1-yl.

X is preferably fluorine, chlorine, C1-C4alkoxy, C1-C4alkylthio, hydroxy, amino, N-mono-or N, N-di-C1-C4alkylamino unsubstituted or substituted in the alkyl moiety or moieties by hydroxy, sulfato or sulfo, phenylamino unsubstituted or substituted in the phenyl ring by sulfo, carboxy, acetylamino, chlorine, methyl, ethyl, methoxy or ethoxy, or N-C :-C4alkyl-N- phenylamino wherein the alkyl is unsubstituted or substituted by hydroxy, sulfo or sulfato, naphthylamino which is unsubstituted or substituted by from 1 to 3 sulfo groups, or morpholino.

X is especially fluorine, chlorine, amino, N-methylamino, N-ethylamino, N-ß-hydroxyethyl- amino, N-methyl-N-P-hydroxyethylamino, N-ethyl-N-p-hydroxyethylamino, N, N-di-p-hydroxy- ethylamino, morpholino, 2-, 3-or 4-sulfophenylamino or N-C1-C4alkyl-N-phenylamino.

X is very especially fluorine, chlorine, amino, N-ß-hydroxyethylamino, N,N-di-ß-hydroxyethyl- amino, morpholino or 2-, 3-or 4-sulfophenylamino.

Of very special importance for X is the meaning fluorine or chlorine, especially chlorine.

As a group U removable under alkaline conditions there come into consideration, for example, -Cl, -Br, -F, -OSO3H, -SSO3H, -OCO-CH3 -OPO3H2, -OCO-C6H5, -OSO2-C1-C4alkyl or -OSO2-N (C1-C4alkyl)2. U is preferably a group of formula-Cl,-OS03H,-SSO3H, -OCO-CH3, -OCO-C6H5 or -OPO3H2, especially -Cl or -OSO3H.

Examples of suitable radicals Y are accordingly vinyl, ß-bromo- or (3-chloro-ethyl, (3-acetoxy- ethyl, ß-benzoyloxyethyl, ß-phosphatoethyl, ß-sulfatoethyl and ß-thiosulfatoethyl. Y is preferably vinyl, ß-chloroethyl or ß-sulfatoethyl. k is preferably a number 2 or 3, especially 3. m is preferably the number 1. n is preferably the number 1.

As substituents for A there come into consideration the customary substituents for dyes. The following may be mentioned as examples: C,-C4alkyl, which is understood to be methyl, ethyl, n-or iso-propyl, n-, iso-, sec-or tert-butyl ; C,-C4alkoxy, which is understood to be methoxy, ethoxy, n-or iso-propoxy or n-, iso-, sec-or tert-butoxy; hydroxy-C,-C4alkoxy ; phenoxy; C2-C6alkanoylamino unsubstituted or substituted in the alkyl moiety by hydroxy or C,-C4alkoxy, for example acetylamino, hydroxyacetylamino, methoxyacetylamino or propionylamino ; benzoylamino unsubstituted or substituted in the phenyl moiety by hydroxy, sulfo, halogen, C-C4alkyl or Ci-C4alkoxy ; Ci-C6alkoxycarbonylamino unsubstituted or substituted in the alkyl moiety by hydroxy, C,-C4alkyl or C,-C4alkoxy ; phenoxycarbonylamino unsubstituted or substituted in the phenyl moiety by hydroxy, C1-C4alkyl or C1-C4alkoxy ; amino; N-C,-C4alkyl-or N, N-di-C1-C4alkyl-amino unsubstituted or substituted in the alkyl moiety or moieties by hydroxy, C,-C4alkoxy, carboxy, cyano, halogen, sulfo, suffato, phenyl or sulfophenyl, for example methylamino, ethylamino, N, N-dimethylamino, N, N-diethylamino, ß-cyanoethylamino, ß-hydroxyethylamino, N,N-di-ß-hydroxyethylamino, ß-sulfoethylamino, <BR> <BR> <BR> y-sulfo-n-propylamino, Fsulfatoethylamino, N-ethyl-N-(3-sulfobenzyl)-amino, N-(*sulfoethyl)- N-benzylamino ; cyclohexylamino ; N-phenylamino or N-C1-C4alkyl-N-phenylamino unsubstituted or substituted in the phenyl moiety by nitro, C,-C4alkyl, C-C4alkoxy, carboxy, halogen or sulfo ; C,-C4alkoxycarbonyl, for example methoxy-or ethoxy-carbonyl ; trifluoromethyl ; nitro; cyano; halogen, which is understood in general to be, for example, fluorine, bromine or, especially, chlorine ; ureido; hydroxy; carboxy; sulfo ; sulfomethyl ; carbamoyl ; carbamido; sulfamoyl ; N-phenylsulfamoyl or N-C-C4alkyl-N-phenylsulfamoyl unsubstituted or substituted in the phenyl moiety by sulfo or carboxy; methyl-or ethyl- sulfonyl.

Fibre-reactive radicals also come into consideration as substituents for A.

Fibre-reactive radicals are to be understood as being those which are capable of reacting with the hydroxy groups of cellulose, with the amino, carboxy, hydroxy and thiol groups in wool and silk or with the amino and possibly carboxy groups of synthetic polyamides to form covalent chemical bonds. The fibre-reactive radicals are generally bonded to the dye radical directly or via a bridging member. Suitable fibre-reactive radicals are, for example, those having at least one removable substituent at an aliphatic, aromatic or heterocyclic radical or those wherein the mentioned radicals contain a radical suitable for reaction with the fibre material, for example a vinyl radical.

A fibre-reactive radical present in A corresponds, for example, to formula - SO2-Y -NH-CO(CH2)k-SO2-Y (2b), -CONR2-(CH2) l-S02-Y (2c), -NH-CO-CH (Hal)-CH2-Hal (2d), -NH-CO-C(Hal)=CH2 (2e), wherein Hal is chlorine or bromine, Xi is halogen, 3-carboxypyridin-1-yl or 3-carbamoylpyridin-1-yl, T, has independently the same definitions as Xi, or is a non-fibre-reactive substituent or a fibre-reactive radical of formula -N-arylene-SO 2Y I (3c), - N-arylene- (alk) t W-alk S02 Y I (3d), Ksi Narylene-NHCOY1 1 (3, 1 wherein Ri, Ria and Rob are each independently of the others hydrogen or C1-C4alkyl, R2 is hydrogen, C1-C4alkyl unsubstituted or substituted by hydroxy, sulfo, sulfato, carboxy or cyano, or a radical R3 is hydrogen, hydroxy, sulfo, sulfato, carboxy, cyano, halogen, C,-C4alkoxycarbonyl, C,-C4alkanoyloxy, carbamoyl or a group-S02-Y, alk and alk, are each independently of the other linear or branched C1-C6alkylene, arylene is a phenytene or naphthylene radical unsubstituted or substituted by suifo, carboxy, C,-C4alkyl, C,-C4alkoxy or halogen, Q is a radical-O-or-NR,-wherein R, is as defined above, W is a group-SO2-NR2-,-CONR2-or-NR2CO-wherein R2 is as defined above, Y has the definitions and preferred meanings given above, Y, is a group-CH (Hal)-CH2-Hal or-C (Hal) =CH2, Hal being as defined above, and k and I are each independently of the other an integer from 1 to 6 and t is a number 0 or 1, and X2 is halogen or C1-C4alkylsulfonyl, X3 is halogen or C-C4alkyl, and T2 is hydrogen, cyano or halogen.

Ri, Ria and R, b preferably are each independently of the others hydrogen, methyl or ethyl, especially hydrogen.

R2 is preferably hydrogen or C1-C4alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, and especially hydrogen, methyl or ethyl. R2 is more especially hydrogen.

R3 is preferably hydrogen. k and I preferably are each independently of the other a number 2,3 or 4, especially a number 2 or 3.

Very especially, k is the number 3 and I is the number 2.

For a non-fibre-reactive substituent T, there come into consideration, for example, hydroxy or one of the radicals indicated above for X in the meaning of C,-C4aikoxy unsubstituted or substituted in the alkyl moiety, phenoxy unsubstituted or substituted in the phenyl moiety, C,-C4alkylthio unsubstituted or substituted in the alkyl moiety, unsubstituted or substituted amino, or an N-heterocycle which may or may not contain further hetero atoms.

As a non-fibre-reactive radical, T, is preferably C,-C4ålkoxy, C1-C4alkylthio, hydroxy, amino, N-mono-or N, N-di-C1-C4alkylamino unsubstituted or substituted in the alkyl moiety or moieties by hydroxy, suffato or sulfo, morpholino, or phenylamino or N-Ci-C4alkyl-N- phenylamino (wherein the alkyl is unsubstituted or substituted by hydroxy, sulfo or sulfato) each unsubstituted or substituted in the phenyl ring by sulfo, carboxy, acetylamino, chlorine, methyl or methoxy, or naphthylamino unsubstituted or substituted by from 1 to 3 sulfo groups.

Especially preferred non-fibre-reactive radicals Ti are amino, N-methylamino, N-ethylamino, N-ß-hydroxyethylamino, N-methyl-N-ß-hydroxyethylamino, N-ethyl-N-ß-hydroxyethylamino, N, N-di-p-hydroxyethylamino, morpholino, 2-, 3-or 4-carboxyphenylamino, 2-, 3-or 4-sulfo- phenylamino or N-C,-C4alkyl-N-phenylamino.

X, is preferably halogen, for example fluorine, chlorine or bromine and especially chlorine or fluorine.

T2, X2 and X3 as halogen are, for example, fluorine, chlorine or bromine, especially chlorine or fluorine.

X2 as C,-C4alkylsulfonyl is, for example, ethylsulfonyl or methylsulfonyl and especially methylsulfonyl.

X3 as C1-C4alkyl is, for example, methyl, ethyl, n-or iso-propyl, n-, iso-or tert-butyl and especially methyl.

X2 and X3 preferably are each independently of the other chlorine or fluorine.

T2 is preferably cyano or chlorine.

Hal is preferably bromine. alk and alk, are each independently of the other, for example, a methylene, ethylene, 1,3- propylene, 1, 4-butylene, 1, 5-pentylene or 1, 6-hexylen radical or a branched isomer thereof. alk and alk, preferably are each independently of the other a C1-C4alkylene radical and especially an ethylene radical or propylene radical. arylene is preferably a 1, 3- or 1, 4-phenylene radical unsubstituted or substituted, for example, by sulfo, methyl, methoxy or carboxy, and especially an unsubstituted 1, 3- or 1,4- phenylen radical.

Q is preferably-NH-or-O-and especially-0-.

W is preferably a group of formula-CONH-or-NHCO-, especially a group of formula -CONH-. t is preferably the number 0.

The reactive radicals of formulae (3a) to (3 are preferably those wherein W is a group of formula-CONH-, Ri, Rz and R3 are each hydrogen, Q is a radical -O- or -NH-, alk and alk, are each independently of the other ethylene or propylene, aryiene is phenylen unsub- stituted or substituted by methyl, methoxy, carboxy or sulfo, Y is vinyl or ß-sulfatoethyl, Y1 is - CHBr-CH2Br or-CBr=CH2 and t is the number 0.

A fibre-reactive radical present in A corresponds especially to a radical of formula (2a), (2c), (2d), (2e) or (20 wherein Y is vinyl, p-chioroethy) or ß-sulfatoethyl, Hal is bromine, R2 and R1a are hydrogen, I is a number 2 or 3, Xi is halogen, T, is C1-C4alkoxy, C1-C4alkylthio, hydroxy, amino, N-mono-or N, N-di-Ci-C4alkylamino unsubstituted or substituted in the alkyl moiety or moieties by hydroxy, sulfato or sulfo, morpholino, or phenylamino or N-C1-C4alkyl-N- phenylamino (wherein the alkyl is unsubstituted or substituted by hydroxy, sulfo or sulfato) each unsubstituted or substituted in the phenyl ring by sulfo, carboxy, acetylamino, chlorine, methyl or methoxy, or naphthylamino unsubstituted or substituted by from 1 to 3 sulfo groups, or is a fibre-reactive radical of formula (3a'), (3b'), (3c'), (3d') or (3f) - NH- (CH2) 2-3-S02Y (3a'), -NH-(CH2)2-3-O-(CH2)2-3-SO2Y (3b'), especially (3c') or (3d'), wherein Y is as defined above, and Y1 is a group-CH (Br)-CH2-Br or-C (Br) =CH2.

In the case of the radicals of formulae (3a') and (3b'), Y is preferably p-chioroethyi. ! n the case of the radicals of formulae (3c') and (3d'), Y is preferably vinyl or Fsulfatoethyl.

A denotes, for example, the following dye radicals : a) Dye radicals of a 1: 1 copper complex azo dye, of the benzene or naphthalene series, wherein the copper atom is in each case bonded, on each side in the position ortho to the azo bridge, to a group capable of being metallated. b) Dye radicals of a mono-or dis-azo dye of formula Di-N=N- (M-N=N) u-Kr (4) or -D2-N=N-(M-N=N) u-K2 (5) or of a metal complex derived therefrom, wherein D1 and Da are each independently of the other radicals of a diazo component, of the benzene or naphthalene series, M is the radical of a central component, of the benzene or naphthalene series, K, and K2 are each independently of the other the radical of a coupling component, of the benzene, naphthalene, pyrazolone, 6-hydroxypyrid-2-one or acetoacetic acid arylamide series, u is a number 0 or 1, and D1, D2, M, K1 and K2 may carry substituents customary for azo dyes, wherein K2 in the meaning of a radical from the naphthalene series does not carry a radical of formula (2b).

When u is the number 0, K, is preferably the radical of a coupling component, of the benzene, pyrazolone, 6-hydroxypyrid-2-one or acetoacetic acid arylamide series. c) Dye radicals of a disazo dye of formula -D3-N=N-K3-N=N-D4 (6) wherein D3 and D4 are each independently of the other radicals of a diazo component, of the benzene or naphthalene series, and K3 is the radical of a coupling component, of the naphthalene series; wherein D3, D4 and K3 may carry substituents customary for azo dyes.

The expression"substituents customary for azo dyes"is intended to include both fibre- reactive and non-fibre-reactive substituents, for example the substituents mentioned above. d) Dye radicals of a formazan dye of formula wherein the benzene rings contain no further substituents or are further substituted by C1-C4alkyl, C1-C4alkoxy, C1-C4alkylsulfonyl, halogen or carboxy. e) Dye radicals of an anthraquinone dye of formula (8) wherein G is a phenylen radical unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, halogen, carboxy or sulfo or is a cyclohexylene, phenylenemethylene or C2-C6alkylene radical. f) Dye radicals of a phthalocyanine dye of formula wherein Pc is the radical of a metal phthalocyanine, especially the radical of a copper or nickel phthalocyanine, W is-OH and/or-NQsQ6, Q5 and Q6 are each independently of the other hydrogen or G1-C4alkyl unsubstituted or substituted by hydroxy or sulfo, Q4 is hydrogen or C1-C4alkyl, E is a phenylen radical unsubstituted or substituted by C1-C4alkyl, halogen, carboxy or sulfo or is a C2-C6alkylene radical, and q is from 1 to 3. g) Dye radicals of a dioxazine dye of formula (10) wherein E'is a phenylen radical unsubstituted or substituted by C,-C4alkyl, halogen, carboxy or sulfo or is a C2-C6alkylene radical, s and v are each independently of the other a number 0 or 1, and the outer benzene rings in formula (10) may be further substituted by C,-C4alkyl, C1-C4alkoxy, acetylamino, nitro, halogen, carboxy, sulfo or a fibre-reactive radical of formula (2a), Y having the definitions and preferred meanings given above.

For A as a radical of a mono-or dis-azo dye of formula (4), (5) or (6) in the dyes of formula (1) according to the invention, preference is given to the dye radicals of formulae (11a), (11b), (11c), (11d), (11e), (110, (11g), (11h), (11i), (11j), (11k), (111), (11m), (11n), (110), (11 p), (11 q) and (11r) given below : wherein (R4) 0 3 denotes from 0 to 3 identical or different substituents from the group C1-C4alkyl, C,-C4alkoxy, halogen, carboxy and sulfo, (R5) 0 3 denotes from 0 to 3 identical or different substituents from the group halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C1-C4alkyl ; C1-C4alkoxy unsubstituted or substituted by hydroxy, sulfato or C1-C4alkoxy ; amino, C2-C4alkanoylamino, ureido, hydroxy, carboxy, sulfomethyl, C-C4alkylsulfonylamino and sulfo, and Zi is a radical of formula (2a), (2c), (2d), (2e) or (2f), preferably (2a), (2c), (2d) or (2e) and especially (2a), the mentioned radicals having the definitions and preferred meanings given above, wherein R6 is hydrogen, C,-C4alkyl, sulfophenyl, C2-C4alkanoyl, benzoyl or a radical of formula (2 given above, wherein the radicals have the definitions and preferred meanings given above, wherein (R7) 0 3 denotes from 0 to 3 identical or different substituents from the group C,-C4alkyl, C,-C4alkoxy, halogen, carboxy and sulfo, wherein R8 and R10 are each independently of the other hydrogen, C1-C4alkyl or phenyl, and Rg is hydrogen, cyano, carbamoyl or sulfomethyl, wherein (R4) 0-3 and Z1 each have the definitions and preferred meanings given above, wherein (R4) o-3, (R5) o-3 and (R7) 0 3 each have the definitions and preferred meanings given above, (R11)0-3 and (R12)0-3 each independently of the other denote from 0 to 3 identical or different substituents from the group C,-C4alkyl, C1-C4alkoxy, halogen, carboxy and sulfo, and Z1 has the definitions and preferred. meanings given above.

The numbers on the naphthyl rings ofthe radicals offormulae (11a), (11b), (11c), (11f), (11g), (11h), (11l), (11m), (11n) and (110) indicate the possible bonding positions.

(R4) 0-3 in the disazoamino radicals of formulae (11 q) and (11 s) preferably denotes from 1 to 3 sulfo groups.

Z, in the indicated dye radicals A is especially hydrogen.

Examples of suitable dye radicals A in the reactive dyes according to the invention are listed in US-A-5 484 899 (columns 13 to 40 and 47 to 71).

For A as the radical of a mono-or dis-azo dye of formula (4), (5) or (6), special preference is given to the radicals of formulas (11d), (11e), (11f), (11g), (11h), (11i), (11j), (11k), (11l), (11 m), (11 n), (110), (11 p), (11 q) and (11r).

Very especially preferred radicals of a mono-or dis-azo dye of formula (4), (5) or (6) correspond to formulae (11d), (11e), (11f), (11g), (11i), (11j), (11k), (11l), (11m), (11p), and (11q).

A is preferably the radical of a mono-or dis-azo dye.

In an especially preferred embodiment of the dyes according to the invention, A is a mono-or dis-azo dye radical of formula (11d), (11e), (11f), (11g), (11i), (11j), (11k), (11l), (11m), (11p), or (11q), wherein (R4) o-3, (R5) o-3, Re, (R7) o-3, Rs, Rg, Rio, (Rn) o-3 and Z, each have the definitions given above, and (R4) o-3 preferably denotes from 0 to 3 identical or different substituents from the group methyl, methoxy and sulfo, (R5) o-3 preferably denotes from 0 to 3 identical or different substituents from the group methyl, ethyl, methoxy, ethoxy, (3-hydroxy- ethoxy, ß-sulfatoethoxy, sulfo, acetylamino and ureido, R6 is preferably hydrogen, methyl, ethyl, acetyl, propionyl, benzoyl or a radical of formula (2 given above, wherein the definitions and preferred meanings are as given above, (R7) 0-3 preferably denotes from 0 to 3 identical or different substituents from the group methyl, methoxy, chlorine, carboxy and sulfo, R8 and Rio are each independently of the other hydrogen, methyl or ethyl, (R, 1) 0-3 preferably denotes from 0 to 3 identical or different substituents from the group methyl, ethyl, methoxy, ethoxy, carboxy and sulfo, and ZI, when present, is preferably a fibre-reactive radical of formula (2a) wherein Y is vinyl or ß-sulfatoethyl.

The reactive dye of formula (1) is preferably a dye of formula (1a) wherein A, Qi, Q2, X, Y and k each have the definitions and preferred meanings given above.

An especially preferred embodiment of the present invention relates to reactive dyes of formula (1a) wherein Q1 and Q2 are hydrogen, A is a mono-or dis-azo dye radical of formula (11d), (11e), (11fl, (11g), (11i), (11j), (11k), (111), (11 m), (11 p) or (11 q) wherein (R4) 0-3, (R5)0-3, R6, (R7)0-3, R8, R9, R10, (R11)0-3 and Z1 each have the definitions and preferred meanings given above, X is fluorine or chlorine, Y is vinyl"Ochloroethyl or p-sulfatoethyl, preferably vinyl or p-chtoroethyt, and k is a number 2 or 3.

The present invention relates also to a process for the preparation of the reactive dyes according to the invention, wherein approximately one molar equivalent of a compound of formula approximately one molar equivalent of a compound of formula A-NHQ2 (1 3) or suitable precursors of the compounds of formula (12) or (13), and approximately one molar equivalent of a compound of formula are reacted with one another step-wise, in any order, or, if using precursors of compounds of formula (12) or (13), the intermediates obtained are converted into the desired dyes and, where appropriate, a further transformation reaction is subsequently carried out, A, Q1, Q2, Q3, Y, k, m and n in each case having the definitions and preferred meanings given above and X being halogen, for example chlorine or fluorine, preferably chlorine.

For example, in a first condensation step, a compound of formula (12) is reacted with a compound of formula (14) and then, in a second condensation step, the intermediate obtained is reacted with a compound of formula (13), or, in a first condensation step, a compound of formula (13) is reacted with a compound of formula (14) and then, in a second condensation step, the intermediate obtained is reacted with a compound of formula (12).

When the use of precursors of compounds of formula (12) or (13) requires the transformation of intermediates into the final dyes, such a transformation involves especially coupling reactions that result in azo dyes.

A process variant comprises, for example, reacting approximately one molar equivalent of a compound of formula (13) and approximately one molar equivalent of a compound of formula (15) step-wise, in any order, with approximately one molar equivalent of a compound of formula (14) to form a compound of formula (16), diazotising a compound of formula and coupling to the compound of formula (16).

A further, preferred, process variant is distinguished by reacting approximately one molar equivalent of a compound of formula (15) with approximately one molar equivalent of a compound of formula (14) to form a compound of formula (18), diazotising a compound of formula (17) and coupling to the compound of formula (18), whereupon the compound of formula (19) is obtained, and reacting the compound of formula (19) with a compound of formula (13).

The diazotisation of the compounds of formula (17) is effected in customary manner, for example using a nitrite, e. g. an alkali metal nitrite, such as sodium nitrite, in a mineral acid medium, for example a hydrochloric-acid-containing medium, at temperatures of, for example, from-5 to 40°C, preferably from-5 to 10°C and especially from 0 to 5°C.

The condensation reactions between the compounds of formulae (12), (13) and (14) are generally effected analogously to known methods, such as those described, for example, in US-A-4 841 049, usually in aqueous solution at temperatures of, for example, from 0 to 50°C and at a pH value of, for example, from 2 to 10.

The halogen atom X on the triazine can be replaced by condensing the compound of formula (1) obtained wherein X is halogen, preferably fluorine or chlorine, with a compound X*-H wherein X* has the meanings given above for X except for halogen.

The compounds of formulae (12), (13) and (15) are known or can be obtained in a manner known per se.

Compounds of formula (17) are also known and are described, for example, in GB-A-1 155 149.

The end product may optionally be subjected to a further transformation reaction. In such a transformation reaction, for example, a group Y capable of being vinylated or a group, contained in A, capable of being-vinylated is converted into its vinyl form by treatment with dilute sodium hydroxide solution, e. g. conversion of the 8-sulfatoethylsulfonyl or (3-chloro- ethylsulfonyl group into the vinylsulfonyl radical. Such reactions are known per se.

The reactive dyes according to the invention are present either in the form of their free acid or, preferably, in the form of their salts. Suitable salts are, for example, alkali metal, alkaline earth metal or ammonium salts or salts of an organic amine. Examples that may be mentioned are sodium, lithium, potassium or ammonium salts or a mono-, di-or tri- ethanolamine salt.

The reactive dyes according to the invention are suitable for dyeing and printing a wide variety of materials, especially hydroxyl-group-containing or nitrogen-containing fibre materials. Examples include paper, silk, leather, wool, polyamide fibres and polyurethanes, and especially all types of cellulosic-fibre materials. Such fibre materials are, for example, natural cellulose fibres, such as cotton, linen and hemp, and cellulose and regenerated cellulose. The dyes according to the invention are also suitable for dyeing or printing hydroxyl-group-containing fibres present in blend fabrics, for example blends of cotton and polyester fibres or polyamide fibres.

The present invention accordingly relates also to the use of reactive dyes of formula (1) in the dyeing or printing of hydroxyl-group-containing or nitrogen-containing, especially cotton- containing, fibre materials.

The reactive dyes according to the invention can be applied to the fibre material and fixed to the fibre in a variety of ways, especially in the form of aqueous dye solutions or dye print pastes. They are suitable both for the exhaust process and for dyeing in accordance with the pad-dyeing process ; they can be used at low dyeing temperatures and require only short steaming times in the pad-steam process. The degrees of fixing are high and unfixed dye can be washed off readily, the difference between the degree of exhaust and the degree of fixing being remarkably small, that is to say the soaping loss is very small. The reactive dyes according to the invention are also suitable for printing, especially on cotton, and also for printing nitrogen-containing fibres, for example wool or silk or blend fabrics that contain wool.

The dyeings and prints produced using the reactive dyes according to the invention have a high tinctorial strength and a high fibre-dye binding stability in both the acidic and the alkaline range, and also good fastness to light and very good wet-fastness properties, such as fastness to washing, to water, to seawater, to cross-dyeing and to perspiration. The dyeings obtained exhibit fibre levelness and surface levelness.

The present invention relates also to aqueous inks which comprise a reactive dye of formula (1), wherein A, Qi, Qz, Qs, X, Y, k, m and n have the definitions and preferred meanings given above.

The dyes used in the inks should preferably have a low salt content, that is to say should have a total salt content of less than 0.5 % by weight, based on the weight of the dyes. Dyes which, as a result of their preparation and/or the subsequent addition of diluents, have higher salt contents can be desalted, for example, by membrane separation processes, such as ultrafiltration, reverse osmosis or dialysis.

The inks preferably have a total dye content of from 1 to 35 % by weight, especially from 1 to 30 % by weight and more especially from 1 to 20 % by weight, based on the total weight of the ink. The preferred lower limit is 1. 5 % by weight, especially 2 % by weight, more especially 3 % by weight.

The inks may comprise water-miscible organic solvents, for example C-C4alcohols, for example methanol, ethanol, n-propanol, isopropanot, n-butanol, sec-butanol, tert-butanol or isobutanol ; amides, for example dimethylformamide or dimethylacetamide ; ketones or ketone alcohols, for example acetone, diacetone alcohol ; ethers, for example tetrahydrofuran or dioxane; nitrogen-containing heterocyclic compounds, for example N-methyl-2-pyrrolidone or 1, 3-dimethyl-2-imidazolidone ; polyalkylene glycols, for example polyethylene glycol or polypropylene glycol ; C2-C6alkylene glycols and thioglycols, for example ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, thiodiglycol, hexylene glycol and diethylene glycol ; other polyols, for example glycerol or 1,2, 6-hexanetriol ; and C1-C4alkyl ethers of polyhydric alcohols, for example 2-methoxyethanol, 2- (2-methoxyethoxy) ethanol, 2-(2-ethoxyethoxy) ethanol, 2-l2-(2-methoxyethoxy) ethoxy] ethanol or 2- [2- (2-ethoxyethoxy)- ethoxy] ethanol ; preferably N-methyl-2-pyrrolidone, diethylene glycol, glycerol or, especially, 1, 2-propylene glycol, usually in an amount of from 2 to 30 % by weight, preferably from 5 to 30 % by weight and especially from 10 to 25 % by weight, based on the total weight of the ink.

The inks may also comprise solubilisers, for example £-caprolactam.

The inks may comprise thickening agents of natural or synthetic origin, inter alia for the purpose of adjusting the viscosity.

Examples of thickening agents which may be mentioned are commercially available alginate thickeners, starch ethers or locust bean gum ethers, especially sodium alginate on its own or in admixture with a modified cellulose, for example methyl-, ethyl-, carboxymethyl-, hydroxy- ethyl-, methylhydroxyethyl-, hydroxypropyl-or hydroxypropylmethyl-cellulose, especially with preferably from 20 to 25 % by weight carboxymethylcellulose. There may be mentioned as synthetic thickening agents also, for example, those based on poly (meth) acrylic acids or poly (meth) acrylamides.

The inks comprise such thickening agents, for example, in an amount of from 0.01 to 2 % by weight, especially from 0.01 to 1 % by weight and preferably from 0.01 to 0.5 % by weight, based on the total weight of the ink.

The inks may also comprise buffer substances, for example borax, borates, phosphates, polyphosphates or citrates. Examples which may be mentioned include borax, sodium borate, sodium tetraborate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium tripolyphosphate, sodium pentapolyphosphate, as well as sodium citrate. They are used especially in amounts of from 0.1 to 3 % by weight, preferably from 0.1 to 1 % by weight, based on the total weight of the ink, in order to establish a pH value of, for example, from 4 to 9, especially from 5 to 8.5.

The inks may comprise surfactants or humectants as further additives.

There come into consideration as surfactants commercially available anionic or non-ionic surfactants. In the inks according to the invention, there come into consideration as humectants, for example, urea or a mixture of sodium lactate (advantageously in the form of a 50 to 60 % aqueous solution) and glycerol and/or propylene glycol in amounts of preferably from 0.1 to 30 % by weight, especially from 2 to 30 % by weight.

Preference is given to inks having a viscosity of from 1 to 40 mPa-s, especially from 1 to 20 mPa-s and preferably from 1 to 10 mPa-s.

The inks may also comprise further conventional additives, for example antifoam agents or, especially, substances inhibiting fungal and/or bacterial growth. Such substances are usually used in amounts of from 0.01 to 1 % by weight, based on the total weight of the ink.

The inks can be prepared in a conventional manner by mixing the individual constituents in the desired amount of water.

The inks according to the invention are suitable especially for use in recording systems in which the ink is expressed in the form of droplets from a small aperture and is directed towards a substrate on which an image is produced. Suitable substrates are, for example, paper, textile fibre materials or plastics films. Suitable recording systems are, for example, commercially available inkjet printers for use in the printing of paper or textiles, or writing implements such as fountain pens or ball-point pens, and especially inkjet printers.

Depending on the nature of its use, it may be necessary for e. g. the viscosity or other physical properties of the ink, especially those properties affecting the affinity to the substrate in question, to be modified as appropriate.

As examples of paper that can be printed with the inks according to the invention there may be mentioned commercially available inkjet paper, photo paper, glossy paper, plastics-coated paper, for example Epson inkjet paper, Epson photo paper, Epson glossy paper, Epson glossy film, HP special inkjet paper, Encad photo gloss paper and llford photo paper. Plastics films that can be printed with the inks according to the invention are, for example, transparent or milky/opaque. Suitable plastics films are, for example, 3M transparency film.

As textile fibre materials there come-into consideration, for example, nitrogen-containing or hydroxy-group-containing fibre materials, e. g. textile fibre material of cellulose, silk, wool or synthetic polyamides, especially cellulose.

The present invention accordingly relates also to a method of printing textile fibre materials, paper or plastics films, preferably textile fibre materials or paper and especially textile fibre materials, by the inkjet printing method, which comprises using an aqueous ink comprising a reactive dye of formula (1), wherein A, Q1, Q2, Q3, X, Y, k, m and n have the definitions and preferred meanings given above.

In the inkjet printing method, individual droplets of the ink are sprayed onto a substrate in a controlled manner from a nozzle. For this purpose, predominantly the continuous inkjet method and the drop-on-demand method are used. ! n the continuous inkjet method, the droplets are produced continuously and any droplets not required for the printing are conveyed to a collecting vessel and recycled, whereas in the drop-on-demand method droplets are produced and printed as required; that is to say, droplets are produced only when required for the printing. The production of the droplets can be effected, for example, by means of a piezo-inkjet head or by means of thermal energy (bubble jet). For the method according to the invention, printing by means of a piezo-inkjet head is preferred. Also preferred for the method according to the invention is printing in accordance with the continuous inkjet method.

The recordings, e. g. prints, that are produced are distinguished especially by high tinctorial strength and brilliance of colour and also by good light-fastness and wet-fastness properties.

The following Examples serve to illustrate the invention. Unless otherwise indicated, the temperatures are given in degrees Celsius, parts are parts by weight and percentages relate to percent by weight. Parts by weight relate to parts by volume in a ratio of kilograms to litres.

Example 1: a) 25.6 parts of 1, 3-phenylenediamine-4-sulfonic acid are dissolved in 200 parts of water at neutral pH and 4.6 parts of sodium acetate are added. To the resulting solution there are added, at 10°C and with vigorous stirring, 31 parts of y- (p-chloroethylsulfonyl) butyryl chloride, the pH of the reaction mixture being maintained at 5 by the simultaneous addition of aqueous sodium hydroxide solution. The pH of the reaction mixture is then adjusted to 1.8 and the precipitate obtained is filtered off and dried, yielding 38.5 parts of an amine of formula b) The amine obtained according to a) is dissolved in 400 parts of water at neutral pH and 25 parts of a 4N sodium nitrite solution are added. The solution obtained is added dropwise, at 0 to 3°C, to a mixture of ice and 25 parts of concentrated hydrochloric acid. Stirring is carried out for 1 hour at that temperature. c) 19 parts of cyanuric chloride are dispersed in 75 parts of ice and 75 parts of water, with addition of a wetting agent. To the resulting dispersion there is added a neutral solution of 31.9 parts of 1-amino-8=naphthol-3, 6-disulfonic acid in 350 parts of water. After a few hours, the pH of the reaction mixture is adjusted to a value from 4 to 5.5 by addition of aqueous sodium hydroxide solution. d) The diazo compound obtained according to b) is coupled, at a pH from 2 to 5.5 and a temperature from 0 to 5°C, to the condensation product contained in the reaction mixture according to c). e) To the solution obtained according to d) there are added, in portions and at 10°C, 51.9 parts of the azo dye of formula the pH of the reaction mixture being maintained at 4 by the simultaneous addition of aqueous sodium hydroxide solution. After about one hour, the pH of the reaction mixture is adjusted to 5 by the successive addition of aqueous sodium hydroxide solution. The reaction mixture is heated to 50°C and stirred until the reaction is complete. The resulting solution is then clarified by filtration, freed of the salt by dialysis and freeze-dried. There are obtained 140 parts of a compound which in the form of the free acid corresponds to formula By treating the Fchloroethylsulfenyl form of formula (101) in dilute NaOH at pH 10 to 12, the vinylsulfonyl form is obtained, which in the form of the free acid corresponds to formula The dyes of formulae (101) and (102) dye cotton and wool a red shade with good all-round fastness properties.

Examples 2 to 38: By proceeding as described in Example 1 but using, instead of the azo dye according to Example 1 e), an equimolar amount of a dye of formula Ax-NH2, there is obtained, in each case, a compound which in the form of the free acid corresponds to formula wherein Ax in each case denotes a dye radical indicated in Table 1. By treating the p- chloroethylsulfonyl form in dilute NaOH at pH 10 to 12, the vinylsulfonyl form is obtained, which in the form of the free acid corresponds to formula wherein Ax in each case denotes a dye radical indicated in Table 1. The dyes dye cotton and wool the shades indicated in each case with good all-round fastness properties.

Table 1: Ex. Ax Shade SO3H H2N N=N 2/ red HO SOgH C3 /\. CH. SOaH SO3H CH3 3 N=N CH2so3H orange HO J L I C2H5 SO, H cH, /*. JL. CONH. S03H CH3 CONHz C SOt HO 4 HO3S N=N<CONH2 orange HO N O 'hoot C2H5 L ; 2H5 S03H. HO 5 N S03H orange N=N I HOOC S03H HO ci 6 N=N S03H orange CRI cri So3H HO SO3H orange ZON HOOC NHCOCH3 SO3H 3 8--b-N=N I orange i i SOgH NHCONH2 OH 3 9 N=N orange H03S S03H NHCONH2 10 N=N vS03H orange HOgS SO3H CH3 CHaS03H 11 N-N I3H orange HO HO IN O C2H5 NHCONH2 CH3 SOgH 12.. N=N N=N orange H3C HOgS NHCOCH3 OH 3 3 N=NSo3H orange S03H 3 SOgH CH3 S03H 14/\ N=N N-N i \ \ red S03H HOgS SOgH OH NHCOCH2CH3 15 N-N I w w red H03S S03H / HOgSSOgH OH NHCOCH3 16 N-N I red HO 3s S03H SOgH OH HNCO < 7 S N=N < red H03S soch A HO, S"SO, H SO, OH UNCO-0 18 I N-N red i H03S S03H HO, S"SO, H CH2 S03H OH HNCO < 19 I N-N red i i i i - CN S03H 2 0 II Cru f \ H03S N N S03H N N 0 0 0 il "CC//Q j cru H03S \ N \N \ S03H 21 N N viole-t N ZON S03H HO S O /CO/O/ co ^^ 3"'violet 22 N N H03S H03S O ll 0 oc H03S N N 23 1 | violet N N S03H t" rYT" O NH2 S03H 24 violet o HN 0 NH SO3H O NH2 S03H \/ 0 CH2 25 o HN » violet S03H O NH2 S03H c* Y CH3 26 0 HN 4 SO3H violet I O NH2 27 S03H violet violet 27 "TT P L H-CH2-lC-CH2 ci Cl CH3 28 SO3H OH HN N NHCH3 red N=N I H03 S03H SO3H CI violez 29 HN/ o/N I/ 29 r Y r r) 1} vio) et \ N/O H-CHa) s ci S03H SO3H OH NH2 30 N=N I N=N-O-SO2 (CH2) 2oSo3H violet H03 S03H H03S S03H SOgH OH NH2 /- JL J 31 N=N N-N-o-so 3H violet H03S S03H H03S S03H S03H OH NH2 HO3S 32 N=N N=N violet r HO3S SO3H SO3H 3 SO3H OH NH2 S03H I \ \ N-N I \ \ violet H03S S03H SOgH SO3H NH2 OH SO3H \ violez SO, H 03H SO3H SOgH N=N N=N 35 ,, red S03H H03S S03H OH HNCO-0- 36 N=N I red H03S S03H S03H O (CH2) OH OH 37 N=N-OL NH red H03S es HO, SO3H /\ SsHX N N (S02NH2) y zu \ N-Cu-N turquoise \ N i N-S02NH S03H], x x+y=2-3 - u-z= 1-2 Examples 39 to 41: Also in analogy to the procedure described in Example 1 it is possible to prepare the compounds which in the form of the free acid correspond to formulae (103), (104) and (105) and dye cotton and wool the shades indicated with good all-round fastness properties.

Shade 39 F ! SO, H H, N SO, H 39 F S03H H2N 03H N'ion S03H hi0 HN---N J--H N=N H HO (103) red OtC-NH HO3S SO3H SO3H cl (Ci H2) 3 so2-(CH2) 2-Cl 40 SO3H HO ci N=N"L S03H H2N S03H OC-NH H03S HN N=N (C-NH N H PO so2-(CH2) 2-Cl S03H 41 ci 1 SO, H H, N SO, H N"N S03H H2N S03H S03H HO HN--NJ--H N=N ßNN<SO H HOX (105) red O IC-NH °3 3 SO3H i S03H (CH2) 3 SO (CHZ) 2 OS03H Dyeing procedure I 100 parts of cotton fabric are placed at 60°C in 1500 parts of a dyebath containing 45 g/l of sodium chloride and 2 parts of the reactive dye obtained according to Example 1. After 45 minutes at 60°C, 20 g/l of calcined soda are added. Dyeing is continued at that temperature for a further 45 minutes. The dyed goods are then rinsed, soaped at the boil for a quarter of an hour with a non-ionic detergent, rinsed again and dried.

As an alternative to that procedure, dyeing can be carried out at 80°C instead of at 60°C.

Dyeing procedure)) 0.1 part of the dye according to Example 1-is dissolved in 200 parts of water, and 0.5 part of sodium sulfate, 0.1 part of a levelling agent (based on the condensation product of a higher aliphatic amine and ethylene oxide) and 0.5 part of sodium acetate are added. The pH is then adjusted to a value of 5.5 with acetic acid (80 %). The dyebath is heated at 50°C for 10 minutes and then 10 parts of a woollen fabric are added. The dyebath is heated to a temperature of 100°C in the course of about 50 minutes and dyeing is carried out at that temperature for 60 minutes. The dyebath is then cooled to 90°C and the dyed goods are removed. The woollen fabric is washed with hot and cold water, then spun and dried.

Printing procedure While stirring rapidly, 3 parts of the dye obtained according to Example 1 are sprinkled into 100 parts of a stock thickener containing 50 parts of 5 % sodium alginate thickener, 27.8 parts of water, 20 parts of urea, 1 part of sodium m-nitrobenzenesulfonate and 1.2 parts of sodium hydrogen carbonate. The print paste so obtained is used to print a cotton fabric; drying is carried out and the resulting printed fabric is steamed in saturated steam at 102°C for 2 minutes. The printed fabric is then rinsed, if desired soaped at the boil and again rinsed, and then dried.