Indian Patents. 250753:METHOD OF DYEING OR PRINTING TEXTILE FIBRE MATERIALS USING REACTIVE DYES

Title of Invention	METHOD OF DYEING OR PRINTING TEXTILE FIBRE MATERIALS USING REACTIVE DYES
Abstract	A method of dyeing or printing textile fibre materials, which comprises bringing the fibre material into contact with (a) at least one reactive dye containing at least one anionic group, (b) at least one compound which reduces the ionic character of the anionic group, and (c) at least one nucleophilic compound, yields dyeings or prints having deep hues and very good fastness properties.

Full Text	Method of dyeing or printing textile fibre materials using reactive dves The present invention relates to a method of dyeing or printing textile fibre materials using reactive dyes. The problem underlying the present invention was to make available an easy to perform method of dyeing or printing textile fibre materials which results in dyeings or prints having a high depth of shade and very good fastness properties. It has been found, surprisingly, that when, for example, synthetic polyamkle ffcre materials are dyetf high depths of shade are obtained in conjunction with very good wet fastness and contact fastness properties when the fibre material is dyed using reacBve dyes in the presence of suitable salts which improve the uptake behaviour and the fibre material is treated with suitable nucleophiles in accordance with the present invention. The dyeings obtained solve the posed problem especially well. In particular, the dyeings obtained are distinguished by very good fastness properties, especially wet fastness properties, and by deep hues. The problem posed is solved in accordance with the invention by the method described hereinbelow. The present invention accordingly relates to a method of dyeing or printing texSe ftore materials, which comprises bringing the fibre material into contact with (a) at least one reactive dye containing at least one anionic group, (b) at least one compound which reduces the ionic character of the anionic 7019, and (c) at least one nudeophific compound. Reactive dyes contain at least one fibre-reactive radical. Fibre-reactive radicals are to be understood in general 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 sifc, or with the amino and possibly carboxy groups of synthetic potyamides to form covatent 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 containing at least one removable substltuent 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. Reactive dyes are known and are described in large numbers, for exampie in Venkataraman The Chemistry of Synthetic Dyes" Volume 6, Academic Press, New York, London 1972. For the method according to the invention there is used, for example, at least one reactive dye of formula A-{Z)k (1) wherein A is the radical of a monoazo, disazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan or dioxazine dye, Z independently denotes k fibre-reactive substituents, which may be identical or different from one another, selected from the group of the vinylsulfonyl, acryloyl and heterocyclic series, and kisa number 1,2 or 3. Fibre-reactive radicals Z from the group of the vinylsulfonyl series are, for example, aflc^ sulfonyl radicals substituted by a removable atom or by a removable group or altenyisulfonyl radicals which are unsubstituted or substituted by a removable atom or by a removable group. The mentioned alkyisulfonyl and alkenylsulfonyl radicals contain generafiy from 2 to 8, preferably from 2 to 4, and especially 2, carbon atoms. Fibre-reactive radicals Z from the group of the acryloyl series are, for exampie. akanoyl radicals substituted by a removable atom or by a removable group or alkenoyf radicals which are unsubstituted or substituted by a removable atom or by a removable group. The mentioned alkanoyl and alkenoyl radicals contain generally from 2 to 8, preferably 3 or 4, and especially 3V carbon atoms. Examples of fibre-reactive radicals Z from the group of the heterocycfic series include heterocycRc radicals that contain 4-, 5- or 6-membered rings and that are substituted by a removable atom or by a removable group. Suitable heterocyclic radicals are, for example, those that contain at least one removable substituent bonded to a heterocyclic radical, inter alia those that contain at least one reactive substituent bonded to a 5- or 6-membered heterocyclic ring, for example to a monoazine, diazine, pyridine, pyrimkline, pyridazine, pyrazine, thiazine, oxazine or asymmetrical or symmetrical triazine ring, or to sue* a ring system that has one or more fused-on aromatic rings, for example a quinofine, phfoalazine, quinazoline, qumoxafine, acridine, phenazine or phenanthridine ring system. Removable atoms and removable groups or leaving groups are, for example, halogen, e.g. fluorine, chlorine or bromine, ammonium, including hydrazinium, sufeto, tWosuialc, phosphato, acetoxy, propionyloxy, azido, carboxypyridinium and rhodankto. As a radical from the group of the vinylsulfonyl series, Z is preferably a radical of formula -SO2-CH=CH2 or SO2-CH2-CH2-U wherein U is a leaving group. As a radical from the group of the acryloyl series, Z is preferably a radical of formula -CO-CH(Hal)-CH2(Hal) or -CO-C(Hal)=CH2 wherein Hal is chlorine or bromine. As a radical from the group of the heterocyclic series, Z is preferably a halotriazffie or halopyrimidine radical, especially a halotriazine radical, wherein the halogen is fluorine or chlorine. Z is preferably -SO2-CH=CH2 or -SO2-CH2-CH2-U, wherein U is a leaving group, -CO-CH(HaJ)-CH2(HaJ) or -CO-C(Hal)=CH2, wherein Hal is chlorine or bromine, or a halotriazine radical, wherein the halogen is fluorine or chlorine. The fibre-reactive radicals Z and the dye radical A may be connected to one anofier by way of a bridging member. Suitable bridging members include, besides a direct bond or, for example, an amino group, a very wide variety of radicals. For example, the bridging member is an aliphatic, aromatic or heterocyclic radical; the bridging member may also be composed of various such radicals. The bridging member generally contains at feast one fcmctional group, for example the carbonyf group or the arnino group, it being possfcle for the amino group to be substituted by C1-C4aikyl which is unsubstftuted or further substituted by halogen, hydroxy, cyano, Ci^alkoxy, Ci-C4alkoxycarbonylf carboxy, sulfamoyf, sutfo or by sutfato. A suitable aliphatic radical is, for example, an alkylene radical having from 1 to 7 carbon atoms, or a branched isomer thereof. The carbon chain of the alkylene radical may be interrupted by a hetero atom, for example an oxygen atom. A suitable aromatic radical is, for example, a phenylene radical which may be substituted by Ci«C4alkyl, e.g. methyl or ethyl, d-C4alkoxy, e.g. methoxy or ethoxy, halogen, e.g. fluorine, bromine or, especially, chlorine, carboxy or by sulfo, and a suitable heterocydic radical is, for example, a piperazine radical. Such fibre-reactive radicals Z are known per se and large numbers of them are descrtoed, for example in Venkataraman The Chemistry of Synthetic Dyes" Volume 6, pages 1-2CS, Academic Press, New York, London 1972 or in EP-A-625 549 and US-Ar5 68413e. k preferably denotes a number 2 or 3, especially 2. When k denotes a number 2 or 3, preference is given to at least one of the fibre-reactive radicals Z being a radical from the group of the heterocydic series, for example a halotriazine radical. In an especially preferred embodiment of the method according to the invention, there is used a reactive dye of formula (1a) wherein Ri is hydrogen or unsubsttuted or substituted d-C4alkyl, X is halogen, A is as defined above, and V is a non-fibre-reactive substituent or is a fibre-reactive substituent crfformiia wherein R2 is hydrogen or unsubstituted or substituted CrC4aIkyl or a radical wherein R3 is as defined below, R3 is hydrogen, hydroxy, sulfo, sutfato, carboxy, cyano, halogen, Ct-C^aBcoDcycagbonyt, Ci-C alkanoyloxy, carbamoyl or a group -SO2-Y, R4 is hydrogen or d-C^cyl, alk and alk1 are each independently of the other linear or branched d-GsaJkytene, arylene is a phenyiene or naphthyiene radical which is unsubstihjted or substituted by sulfo carboxy, hydroxy, Ci-C4alkyl, Ci-C4alkoxy or by halogen, Y is vinyl or a radical -CH2-CHZ-U and U is a leaving group, Yn is a group -CH(Hal>CH2(HaI) or -C(Hal)=CH2 wherein Hal is chlorine or bromine, W is a group -SOr*V, -CONR4- or -NR4CO- wherein R4 is as defined above, Q is a radical -O- or -NR4- wherein R4 is as defined above, and n is a number 0 or 1. If desired, a fibre-reactive radical, for example having the definitions and preferred meanings given above for Z, is bonded to the dye radical A. In an interesting embodiment of the present invention, either the radical A of the reactive dyes of formula (1a) used according to the invention is substituted by a fibre-reac&ve radical or the radical V is a fibre-reactive radical of formula (2a), (2b), (2c), (2d), (2e) or (2f). A is preferably not substituted by a fibre-reactive radical. As Ci-C4alkyl for Ri, R2 and R4, each independently of the others, there come info consideration, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and isobutyl, preferably methyl and ethyl, and especially methyl. The mentioned radtcafs R1 and R2 are unsubstituted or substituted, for example by halogen, hydroxy, cyano, d-C4alkoxy, CrC4alkoxycarbonyl, carboxy, sulfamoyl, sulfo or by sulfato, preferably by hydroxy, sulfo, sulfato, carboxy or by cyano. The unsubstituted radicals are preferred. X is, for example, fluorine, chlorine or bromine, preferably fluorine or chlorine, and especially chlorine. RT is preferably hydrogen or Ci-C4alkyl, especially hydrogen, methyl or ethyl, and very especially hydrogen. When Y is a radical -CH2-CH2-U, the leaving group U may be, for example. -CL -Bar, -F, -OSO3H, -SSO3H, -OCO-CH3, OPO3H2l -OCO-CeHs, OSOrC^-C^afkyi Or -OSO2-N(C1-C4an^l)2. U is preferably a group of formula -Cl, -OSO3H, -SSO3K -OCO-CH3, -OCO-C6H5 or -OPO3H2, especially -Cl or -OSO3H, and more especially -OSCbR Y is preferably vinyl, P-chkxoethyf, fr-sulfatoethyl, fJ4hiosulfatoethyl, p-acetoxyeflT^, P-phenoxyethyl or ^-phc^phatoethyl, especially p-chloroethyl, ^-sulfetoethyl or vinyi, more especially $-sulfatoethyl or vinyl, and very especially vinyl. Hal is preferably bromine. alk and alki, each independently of the other, are, for example, methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene or a branched isomer thereof, alk and alki, each independently of the other, are preferably a d-C4alkylene radical, and especially an ethylene or propylene radical. Preferred meanings of arylene are a 1,3- or 1,4-phenylene radical which is unsubstituted or substituted by sutfo, methyl or by methoxy, and especially an unsubstituted 1,3- or 1,4-phenylene radical. R2 is preferably hydrogen, Ci-C4alkyl or a radical of formula wheran R3, Y and alk in each case are as defined above and have the preferred meanings given above. R2 is especially hydrogen, methyl or ethyl, and very especially hydrogen. R3 is preferably hydrogen. R4 is preferably hydrogen, methyl or ethyl, and especially hydrogen. The variable Q is preferably -NH- or -O-, and especially -O-. W is preferabfy a group of formula -CONH- or -NHCO-, especially the group of farmuia -CONH-. The variable n is preferably the number 0. Preferred fibre-reactive substituents V of formulae (2a) to (2f) are those virtierein Rj and R3 are each hydrogen, R4 is hydrogen, methyl or ethyl, Q is a radical -NH- or -O-, W is the group -CONH-, alk and alki are each independently of the other ethyiene or pnopytene, arylene is phenylene which is unsubstituted or substituted by methyl, methoxy or by sutfo, Y is vinyl, P-chloroethyl or fi-sutfatoethyl, especially vinyl or fJ-sulfatoethy!, and very especially vinyl, YT is -CHBr-CH2Br or -CBP=CH2 and n is the number 0; amongst those substituents special preference is given to the radicals of formulae (2c) and (2d). When V has the meaning of a fibre-reactive substituent, very special preference is given to V being a group of formula especially (2c1), wherein Y is as defined above and has the preferred meanings given above. In the radical of formula (2c1), the nitrogen atom can be substituted by methyl or ethyl instead of hydrogen. An especially important fibre-reactive substituent V is the radical of formula wherein Y is vinyl or p-sulfatoefhyl, especially vinyl. When V is a non-fibre-reactive substituent, it may be, for example, hydraxy; CrC^aBcoxy; Ci-C4aJkylthio which is unsubstituted or substituted by hydroxy, carboacy or by suSo; amino; amino mono- or di-substituted by Ci-Csalkyl, the alkyl being unsubsftided or further substituted by, for example, sutfo, sulfato, hydroxy, carboxy or by phenyl, especially by sulfo or by hydroxy, and being uninterrupted or interrupted by a racBcai -O; cyctohexytamino; morpbolino; N-C1-C4alkyt-N'phenylamino or phenytamino or naphthylamino, the phenyl or naphthyl being unsubstituted or substituted by, for example, d-C^alkyt C1-C4akoxy. carboxy, sulfo or by halogen. Examples of suitable non-fibre-reactive substituents V are amino, methylamino, ethyiamino, P-hydroxyethylamino, N,N-di-p-hydroxyethylamino, p-sulfoethylamino, cydohexylamino, morpholino, o-, m- or p-chlorophenylamino, o-, m- or p-methylphenylamino, o-, m- or p-methoxyphenylamino, o-, m- or p-sulfophenylamino, disulfophenylamino, o-carboxyphenyl-amino, 1- or 2-naphthytamino, 1-suffo-2-naphthylamino, 4,8-disuffo-2nrMphthyiamino, N-ethyl-N-phenylamino, N-^nethyl-N-phenylamino, methoxy, ethoxy, n- or iso-propoxy and hydroxy. As a non-fibre-reactrve racfical preference is given to V in the meaning of Ct-C4afescy, CrC4-alkylthio which is unsubstituted or substituted by hydroxy, carboxy or by sutfo, t^droxy, amino, N-mono- or N9N- Especially preferred non-fibre-reactive radicals V are amino, N-methylamino, N-ettiylamino, morpholino, phenylamino, 2-, 3-or4-sulfophenylamino, naphthylamino, 1-suttonapttth-2-yl-amino, 3,7-disulfonaphth-2-yl-amino or N-d-CAalkyl-N-phenylarnino. When A is the radical of a monoazo, polyazo or metal complex azo chromophorB, tie following radicals, especially, come into consideration: chromophore radicate of a mono- or dis-azo dye of formula wherein D is the radical 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 is the radical of a coupling component of the benzene, naphthalene, pyrazoione, 6-hydraxypyrid-2-one or acetoacetk: acid arylamtde series, and u is a number 0 or 1, wherein D, M and K may cany substituents customary for azo dyes, for example d-C4alkyl or Ci-C4alkoxy each of which is unsubstituted or further substituted by hydroxy, sulfo or by sulfato, halogen, carboxy, sulfo, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, amino, ureido, hydroxy, carboxy, sulfo-methyl, C2-C4alkanoylamino, benzoylamino which is unsubstituted or substituted in the phenyl ring by d-C4alkyI, Ci-C4alkoxy, halogen or by sulfo, phenyl which is unsubstituted or substituted by Ci-C4aikyl, Ci-C4alkoxy, halogen, carboxy or by sulfo, and also ffcre-reactive radicals. There also come into consideration the metal complexes derived from the dye radicals of formulae (3) and (4), especially dye radicals of a 1:1 copper complex azo dye or 1:2 chromium complex azo dye, of the benzene or naphthalene series, wherein the copper or chromium atom is in each case bonded, on each side in the position ortho to fee azc bridge, to a group capable of being metatlated. When the chromophore radicals of formula (3) or (4) carry a reactive radical, the reactive radical may correspond, for example, to formula wherein Y and Hal each are as defined above and have the preferred meanings given above, Vn independently has the definitions and preferred meanings given above for V, X, independently has the definitions and preferred meanings given above for X, Rnf independently has the definitions and preferred meanings given above for Ri, and p is a number 0 or 1,andl, m and q are each independently of the others an integer from 1 to 6. Preferably, p is the number 0,1 and m are each independently of the other a number 2 or 3, and q is a number 1, 2, 3 or 4. As reactive radicals for the chromophore radicals of formula (3) or (4) there comes into consideration, especially, a radical of formula (5a), (5d), (5f), (5g) or (5h) given above, especially of formula (5a) or (5h). Preferably, the chrorrophore radicals A of formula (3) or (4) do not carry a reacfive radical. Especially preferred radicate of a monoazo or disazo chromophore A are the foiowtng; wherein (Rsh-3 denotes from 0 to 3 identical or different substituents from the gro$ Ci-C4alkyl, d-C4alkoxy, halogen, carboxy and strffo, wherein (Re)o-3 denotes from 0 to 3 identical or different substituents from the group halogen, nitro, cyano, trifluorornethyl, suifamoyl, carbamoyl, Ci-C4alkyl, CrC4alkoxy, amino, C2-C4-alkanoylamino, urekto, hydroxy, carboxy, sulfomethyl and sulfo, (6f), (69). (6h) wherein R7 is amino, Ci^alkylamino, C2-C4alkanoylamino1 benzoylammo or a reactive radical of formula (5d) or (5h) given above, (6j) wherein (Ra)o-3 denotes from 0 to 3 identical or different substituents from the group Ci-C4alky1, C^-C^koxy, halogen, cartx>xy and sulfo, wherein R9 and R« are each independently of the other hydrogen, d-C^alkyl or phenyi and R10 is hydrogen, cyano, carbamcyl or sulfbmethyl, C/JT i)—N~N—\ /—N = N—\ 'f (HO3S)1.3 / ) T\ (6p), V J V_ Jf (R5)o-3 (R7')o-3 OH OH >—I (or)or (Rs)o-3 (R6)o-3 (R5')o-3 (R5)o-3 (R5')o-3 /T\_ _TT\ (6S) \ / N~N—\ v wherein the benzene nuclei contain no further substituents or are further substituted by Ci-C4alkyl, CrC4alkoxy, d-C4alkyIsulfonyl, halogen or by carboxy. When A is the radical of a phthalocyanine dye, it is preferably a radical of formula (3) wherein Pc is the radical of a metal phthalocyanine, especially the racfical of a copper or nickel phthalocyanine; R is -OH and/or -NR13R14; R13 and R14 are each independently of the other hydrogen or d-C4alkyl which is unsubstituted or substituted by hydroxy or by suffo; R12 is hydrogen or C^^alkyt; E is a phenylene radical which is unsubstituted or substituted by Ci-C4alkyl, halogen, carboxy or by sutfo or is a CrCealkylene radical; and t is 1 to 3. Rt3 and R14 are preferably hydrogen. E is preferably a phenylene radical which is unsubstituted or substituted by Ci-C4alkyl, halogen, carboxy or by sulfo. Pc is preferably the radical of a copper phthalocyanine. When A is the radical of a dioxazine dye, it is, for example, a radical of formula wherein E1 is a phenylene radical which is unsubstituted or substituted by Ci~C4alkyl, halogen, carboxy or by sulfo or is a Cr-Cealkylene radical, r, s, v and w are each independently of the others a number 0 or 1, and Y is as defined above. Preferably, E1 is C2-C4alkylene or is 1,3- or 1,4-phenylene which is unsubstituted or substituted by sulfo, r is the number 1, s is the number 0, v is the number 1, and w is a number 0 or 1. When A is the radical of an anthraquinone dye, it is preferably a radical of formula wherein G is a phenylene radical which is unsubstituted or substituted by Ci-C^aicyL CrC4alkoxy, halogen, carboxy or by sutfo or is a cydohexylene, phenyienemetftytene or C2-C6alkylene radical, the anthraquinone dye radical of formula (10) preferably containing at least 2 sulfo groups. G is preferably a phenylene radical which is unsubsBtuted or substituted by Ci-C^alkyl, Ci-C4alkoxy, halogen, carboxy or by sulfo. Special preference is given to A being a monoazo or dssazo chromophore racficai of formula (6a), (6b), (6d), formula (10) given above, especially of formula (6a), (6b), (6e), (6g), (6h), (6i), (6j), (6k), (6m), (6s) or (10). In the meanings given for the variables, Ci-C4alkyl is generally methyl, ethyl, n- or iso-propyl or n-, iso-, sec- or tert-butyl. Ci-C^koxy is generally methoxy, ethoxy, rv or Iso-propoxy or n-, iso-, sec- or tert-butoxy. Halogen is generally, for example, fluorine, chlorine or brorrtne. Examples of Cr-C4alkanoylamtno are acetylamino and proplonylamino. Examptes of Ci-C4hyclroxyalkoxy are hydroxymethoxy, p-hydroxyethoxy and £- and y-hydroxypropaxy. Examples of Ci-C4sulfatoalkoxy are sutfatomethoxy, (5-suIfatoethoxy and $- and y-sulfatopropoxy. Examptes erf Ci-C4afkylsutfonyl are methylsulfonyl, ethylsutfonyl and propylsulfonyl. For the method according to the invention preference is given to the use of dyes of formula (1 a) wherein Ri, X and A are as defined above and have the preferred meanings given above and V is a fibre-reactive substituent of formula (2a), (2b), (2c), (2d), (2e) or (2f) wherein R2, R3, R4, alk, alk1( arylene, Y, Yi, W, Q and n are each as defined above and have the preferred meanings given above. The reactive dyes of formula (1) contain at least one, preferably at least two, sulfo group(s), which is/are either in the form of the free acid or, preferably, in the form of a salt thereof. Suitable salts are, for example, the alkali metal, alkaline earth metal or ammonium safts, salts of an organic amine or mixtures thereof. As examples there may be mentioned sodium, lithium, potassium or ammonium salts, the salt of mono-, di- or tri-ethanolamine or NaftJ or Na/Li/NH4 mixed salts. Dyes that are suitable for the method according to the invention correspond, for example, to formulae O NH, \|\| \| ^ CO-NH-CH9CH9-SO--CH=CH9 L JL Jl .J N~{ /> T T iH* H /N=\ d2) TT ^ H3C>Y^CH3 ° SO3H HO3S a ^ I H-C-OONH 1 LA^>—N = N / V-HM—I^ jl_NH—/ V-SO2-CH=CH2 ^1-3j' HO3S a CH3 HO3S^. Ni.N r^^N = N-4^^N-WNi-N-^J>-SO2-CH=CH2 (1.4), I CH2CH3 a HN^^^^N HO HN N N'yS (13). Br\Ao ^VS^S H ^^ B^ HO3S'^^X^N"SO3H a ^^N HO HN^N^N^S^ (1.6). a on u 1 CO-NH-CH?CH:,-SO5-CH=CH, 9U3H .^^. / 2 2 2 2 J\| I I \—/ \—/ H N H \—/ (1.7), SO3H a HO3S NH, ^ ) ( , -k N N J y (\ /)—N = N—C />—N—U- J— N~— SO,-CH=CH, \ // \_J H N H \_/ 2 2 (1.8). HO3S a HO,S NH2 1 3W/ ^^^ N^N /=, V/ \_/ H N H \^ (1.9), I \— OH CONH-(CH2)2-SO2-(CH2)2-OSO3H HO3S a HO,S NH. 1 3W 2 N^N / V-N=N-^V-N-WN>-NH-(CH2)2-O-(CH2)2-SO2-(CH2)2-a HO3S a /=\ N^"N /={_/— N=N~{_^K^N^H \_/~S°2"CH=CH2 HO3S HJC-OC-NH a A HO3S HO3S KjC-oc-w r^+caca^cHj a 1 HO3S _ N^N W (1-13). )—' / NH-CO-CHBr-CH2Br HO,S H^-OC-NH a _ N^N 3\=, (1.14). )—^ / NH-CO-CHBr-CH^ HO3S H3C H3C ^ N=N-^_^_yrA (1.15), N n \=u CH2)2-O-(CH2)2-SO2-CH2CH2CI a 1 HO,S HO3S NH2 ^ N (>N=N-OK4^N^) (1.16), )—( NH-CO-CHBr-CH^r y_/-°H HO3S a HO3S NH2 ^ NJ^N ^=N^ )—( NH-CO-CHBr-CH^ HO3S H,C I n H N H \=/ S02-CH2CH2-OSO3H HO3S Nh^ HO3S 4 >— N=N—4 ^ X \_/ Y_f N^N (1.19), { }-0H N—U- JL-NH-{CH2)2-O-(CH2)2-SO2-(CH2)2-a V (/ H N HO3S HO3S a fr\ ^y^K N^N /=H03S NH-CO-CHBr-CHjBr 0 NH2 ^YVVS°3H UvU NJ-N H°3SV_ d-21). /—v 0 N — (CH-), — N U- J N f 7 H 2'3 H N H \—/ NH-CO-CHBr-CH2Br Cl N^ N , v ^ SO,H OH HN U- jJ—N—f V r^y I I N I \=/ (1^2) and J^JJ—N^N f^:;^[fS °2H5 NH-CO-CHBr-CH2Br HQ3S -^^^N^ SO3H O NH2 3 H ] 2-2 The reactive dyes used in the method accorrfing to the invention may comprise further additives such as, for example, socfium chloride or dextrin. The dyes used in accordance with the invention are known or can be prepared using methods known perse, such as those described, for example, in US-A-5 760 194, US-A-5 760 195, US-A-5 779 740 and EP-A-1 247 841. For the method according to the invention, the customary dyeing or printing methods may be used. The dye liquors or printing pastes may comprise, in addition to water and the dyes, further additives, for example wetting agents, antifoams, levelling agents or agents that influence the characteristics of the textile material, for example softeners, fiame-fetardam additives, or dirt-, water- aid oB-repeBents, and also water-softeners and natural or synthetic thickeners, for example akjinates and cellulose ethers. The amounts in which the individual dyes are used in the dye baths or printing pastes can vary within wide limits depending on the required depth of shade; in general, amounts of from 0.01 to 15 % by weight, especially from 0.1 to 10 % by weight, based on the material to be dyed or the printing paste, have proved to be advantageous. The dyes may be used singly, or mixtures of dyes, for example mixtures of two or three dyes (di- ortri-chromism), may be used. Suitable compounds which reduce the ionic character of the anionic group, that is to say which reduce the solubility product of the dye in the aqueous dye liquor, are, for example. alkaline earth metal salts, transition metal salts and aluminium salts. In this context, although the term salt also includes oxides and hydroxides, hydroxides and carbonates are preferably not used in the method according to the invention. There may be mentioned, by way of example, salts of polyvalent metals such as Mg2*** Ca2(+\ Sr+\ Ba2" Mn2". Cu2" Zn2(+\ Ni2" Cd2(+), Co1, Al3" Sn2" and Cr+> salts, e_g. in the form of a chloride, sulfate, nitrate, acetate, formate, tartrate or lactate, preferably in the form of a chloride, sulfate or nitrate and especially in the form of a chloride. Preference is given to Ca2, Ba2* and Al31 salts, especially Ca2* salts. Special preference is given to the use of CaCfe. Suitable nucleophilic compounds are compounds which are capable of reacting with the fibre-reactive groups of the reactive dyes in an addition or substitution reaction, e.g. aliphatic or aromatic compounds containing at least one amino, mercapto or hydroxy group. The term amino group in the present case includes both primary and secondary amino groups which are capable of entering into an addition or substitution reaction with fibre-reactive groups. Preference is given to compounds containing at least one amino group, for example two or three amino groups. Suitable aromatic amines are, for example, anilines or aminonaphthalenes. The mentioned anilines or aminonaphthalenes also include compounds substituted at the nitrogen by, for example, d-C4alkyl and are unsubstituted or substituted at the aromatic moiety by, for example, CrC18alkyl, C^dealkoxy, carboxy, carbamoyl, N-d-dsalkylcarbamoyl, sulfo, hydroxy or by halogen. Suitable aromatic amines also include those containing two amino groups such as, for example, compounds of formula H2N-B-NH2 (11), wherein B is unsubstituted or d-C4alkyh Ci-C4alkoxy-, C2-C4alkanoylamino-, sutfo-, halo- or carboxy-substituted Ci-C6alkytenephenylene, e.g. methylenephenylene, or unsubstituted or similarly substituted naphthylene or phenylene, or a radical of formula £\_L_/jA £VL^GX wherein the benzene rings I and II are unsubstituted or substituted by Cr^^aBcyl, Ct-Cr-alkoxy, C2-dalkanoyiamino, sulfo, halogen or by carboxy and L is a direct bond or a d-C«r alkylene radical which, with the exception of methytene, may be interrupted by 1, 2 or 3 oxygen atoms, or L is a bridging member of formula -CH=CH-, -NH-, -CO-, -NH-CO-, -NH-SOr, -NH-CO-m-, -O-, -S- or -SCV. The aromatic bridging members mentioned far B are preferably unsubstituted or substituted by sulfo. There may be mentioned, by way cf example: phenylenediamine, toluylenediamine, xylylenediamine and 4,4f-diaminodiphenyl-methane. The two amino groups in the compound of formula (11) may be further substituted by one substituent, for example by Ci-C4afkyl which may in turn be substituted by, for example, C2-C4alkanoylamino, e.g. acetylamino or propionylamino; Ci-C4alkoxy, e.g. methoxy or ethoxy; hydroxy; suffb; sutfato; carboxy; carbamoyl or by sulfamoyl. Suitable aliphatic amines are, for example, Cio-C&terpeneamines, preferably C2oditerpeneamines, that is to say an amino group monosubstituted by a terpene hydrocarbon radical. Suitable terpene hydrocarbon radicals are, for example, acyclic, monocyclic or bicyclic C10terpenes, acyclic, monocyclic, bicyclic or tricyclic Ci5sesqui-terpenes, acyclic, monocyclic or tricyclic C2oditerpenes, especially tricyclic C2oditerpenes and very especially dehydrogenated tricyclic C^diterpenes, for example those which are derived from dehydroabietic acid. An example of such a dehydrogenated tricyclic C^diterpeneamine is the compound of formula HJ (13). Suitable aliphatic amines also include, for example, N-mono- or N,N-dHd-C»aBcytamffi^T e.g. methylamine, ethylamine, N,N-dimethylamine, N.N-diethylamine, isopropylamine, n-butylamine, sec-butylamine, isobutylamine or tert-butylamine, linear or branched pentylamine, hexylamtne, heptyiamine, octylamine, nonylamine, decylamine, urxtecytacrme dodecylamine, tridecylamine ortetradecylamine. The mentioned amines are unstfosftuteri or substituted in the alkyl moiety, for example by phenyl which may in turn be subsfituted by C^-Ciaalkyl, Ci-Ciealkoxy, halogen, c^boxy, carbamoyl, sulfo or by suHamoyt; QTOIB-alkanoylamino, e.g. acetyfamrno or propionylamino; Ct-dsalkoxy, e.g. methoxy or effioxy; hydroxy; sulfo; sulfato; carboxy; carbamoyl or by sulfamoyl. The mentioned radicals are uninterrupted or interrupted in the alkyl moiety by oxygen or by -MR15-, wherein R15 is hydrogen, methyl or ethyl, preferably hydrogen. Suitable aliphatic amines also include those containing two amino groups, e.g. aliphatic diamines of formula (11) wherein B is Ci-C4alkylenephenylene-CrC4alkylene, e.g. methylenephenylenemethylene, or a Cr^alkylene radical which is unsubstltuted or substituted by hydroxy, sulfo, sulfato, cyano or by carboxy and which may be interrupted by from 1 to 12 moieties, e.g. 1,2, 3 or 4 moieties, from the group oxygen and -NR15-, wherein R15 is hydrogen, methyl or ethyl, preferably hydrogen. Preferred substituents of the aflcytene radicals mentioned for B are hydroxy, suffo or sulfato, especially hydroxy. By way erf exampte there may be mentioned: 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-butyJenedianwie, 1,5-pentamethytenediamine or 1,6-hexamethylenediamine, 3-amino-1-methylar™nopropane, N-hydroxyethylethylenediamine, N-methyf-bis(3-aminopropyl)amine, tetraethylenediamine, 1-aminoethyl-1,2-ethylenediamine, diethylenetriamine, tetraethylenepentamine and pentaethylenehexamine, especialfy 1,6-hexamethylenediamine. Also suitable are relatively high molecular weight polyamines such as, for example, polyethyleneimines containing more than 24 carbon atoms or polyvinylamine. Suitable aliphatic amines also include compounds containing three or more than three primary amino groups, e.g. tris(2-aminoethyl)amine. Suitable aliphatic amines also include, for example, aliphatic diamines of formula (11) wherein B is Cs-Cgcycloalkylene, e.g. cyclohexylene. The mentioned cycloalkylene racfic^ may be unsubstituted or substituted by Ci-C4afkyl, CrC4alkoxy, C2-C4alkanoy1amino1 suffo, halogen or by carboxy, especially by Ci-CAalkyl. Also suitable for B are methylene-cyclohexylene, ethylene-cyclohexytene and methylene-cyclohexylene-methylene radicate unsubstituted or substituted in the cyclohexylene ring by Ci-C4alkyl, especiaBy by meSTyl and the isophorone radical and the hydrogenated diphenylmethane radical. By way of example there may be mentioned: 1,4-diaminocyctohexane, isophoronedsamine, hydrogenated xylylenediamtne and hydrogenated 4,4l-diaminodiphenyknethane. An aromatic amine is understood to be a compound wherein the nitrogen atom erf the amino group is directly bonded to an aromatic carbon atom. Accordingly, the term aliphatic amine is understood to refer to a compound wherein the nitrogen atom of the amino group is cfirectfy bonded to an afiphatic carbon atom. In the method accortfing to the invention, preference is given to the use of aliphatic amines as the nucieophiiic compound, especially those containing at least two amino groups. Preferred nucieophiiic compounds are the aliphatic diamines of formula (11). Especially preferred nucieophiiic compounds are compounds of formula (11) wherein B is a CrCi2alkylene radical, especially a CrCealkytene radical, which may be interrupted by 1, 2 or 3 -O- moieties and which is unsubstituted or substituted by hydroxy or by suKato. Of special importance are compounds of formula (11) wherein B is a (VCealkyiene radical which is unsubstituted and is not interrupted by -O-. Advantageously, (b) and (c), that is to say treatment of the textile fibre material with the saft and treatment of the textile fibre material with the nucieophiiic compound, are carried out one after the other. Treatment of the textile fibre material with the salt (b) is advantageously carried out by first dyeing the fibre material in customary manner and then adding the salt in suitable form, e.g. in the form of an aqueous solution, to the dye liquor during the dyeing process, for example after a dyeing period of from 10 to 60 minutes, especially from 10 to 30 minutes, followed, where appropriate, by a farther period of dyeing of, for example, from 10 to 60 minutes, especially from 20 to 50 minutes. (b) can also be carried out by treating, for example impregnating, the textile fibre material with the salt before the dyeing or printing process, it being unimportant which technique is used to introduce the salt into the fibre material; for example, spray or foam appBcafioru immersion or a pad can be used. Dyeing or printing with the reactive dye according to (a) can be carried out thereafter. It is then unnecessary to add further salt during the dyeing or printing process. Treatment of the textile fibre material with the nucieophiiic compound (c) can be carried out directly in the dye liquor by adding the nucieophiiic compound in suitable form, e.g. in the form of an aqueous solution, or preferably in a separate after-treatment bath. When carrying out (c) in a separate after-treatment bath, the dyed material is removed from the dye Hquor after the actual dyeing process and after the performance of (b) and, where appropriate, is rinsed again in suitable manner before being introduced into the after-treatment liquor. When (c) is carried out in a separate after-treatment bath, the treatment with the nucleophilic compound is performed at a temperature of, for example, from 30 to 100°C and especially from 50 to 80°C. The compounds which reduce the ionic character of the anionic group are advantageously used in an amount of, for example, from 0.1 to 100 % by weight, preferably from 0.5 to 50 % by weight and especially from 2 to 40 % by weight, based on the weight of the substrate, thai is to say the textile fibre material. The nucleophilic compound is advantageously used in an amount of, for example, from 0.001 to 2 % by weight, especially from 0.01 to 1 % by weight, based on the weight of the dye liquor or on the weight of the after-treatment bath. The method according to the invention is suitable, for example, for dyeing or printing hydroxyl-group-containing or nitrogen-containing fibre materials. By way of example there may be mentioned silk, wool, cellulosic fibre materials of all kinds and polyurethanes and polyamide fibres. Cellulosic fibre materials are, for example, the natural cellutosic fibres, such as cotton, linen and hemp, and also cellulose and regenerated cellulose. The method according to the invention is also suitable for dyeing or printing hydroxyl-group-containing fibres present in blend fabrics, e.g. mixtures of cotton with polyester fibres or polyamide fibres. In a particular embodiment, the method according to the invention is not used for cellulosic or silk-containing fibre materials such as, for example, cellulose or silk. Preferably, the method according to the invention is suitable for dyeing or printing synthe&c polyamide fibre materials, such as, for example, polyamide-6 (poly-e-caprolactamX polyamide-6.6 (poly(hexamethylene adipamide)), polyamkJe-7, polyamide-6.12 (pofy(hexamethytene dodecanoamide)), polyamide-11 or polyamkle-12, copoJyamkJes with polyamide-6.6 or potyamide-6, for example polymers of hexamethyienecfiarrune, E-caprolactam and adipic acid and polymers of adipic add, hexamethytenediamine and isophthalic acid or of acfiptc acid, hexamethyienediamine and 2-methyipentamethytene- diamine or 2-ethyltetramethylenediamine, and is also suitable for dyeing or printing blend fabrics or yarns of synthetic polyamide and wool. The method according to the invention is advantageously also suitable for dyeing or printing microfibres of synthetic pofyamides. Mtcrofibres are understood to be fibre materials that are composed of filaments having an individual filament fineness of less than 1 denier (1.1 dTex). Such microfibres are known and are usually produced by melt-spinning. In order to improve further the fastness properties of synthetic polyamides, especially microfibres, the dyeing process according to the invention can be followed by customary after-fixing or alkaline after-treatment. The mentioned textile material can be in a very wide variety of processing forms, such as, for example, in the form of fibres, yam, woven fabric, knitted fabric and in the form of carpets. In the case of carpet fabrics, printing methods such as, for example, displacement printing, or space dyeing are of importance. Preference is given to dyeing which is especially carried out in accordance with the exhaust method and, in the case of carpet dyeing, may also be carried out in accordance with the continuous method. Preference is given to dyeing at a pH of from 2 to 7, especially from 2.5 to 5.5, and very especially from 3 to 4.5. The liquor ratio can be selected within a wide range, e.g. from 13 to 1:50, preferably from 1:5 to 1:30. Preference is given to dyeing at a temperature of from 80 to 130°C, especially from 85 to 120°C. Dyeings and printings with good all-round fastness properties, such as, for example, good fastness to chlorine, rubbing, wetting, wet-rubbing, washing, water, sea-water and perspiration, are obtained. Contact fastness properties especially, such as, for example, fastness to water and perspiration, exhibit very good values. The Examples given hereinbetow are intended to illustrate the invention without Imiting the invention to the Examples specifically mentioned. The temperatures are given in degrees Celsius, parts are parts by weight and percentages refer to % by weight, unless otherwise specified. Parts by weight relate to parts by volume in the same ratio as kilograms to litres. Example 1: 70 g of a blend fabric consisting of 72 % polyamide microfibres and 28 % elastane are treated in a dyeing apparatus with 1.5 litres of liquor containing 3 g of formic acid, 0.4 g of wetting agent and 0.7 of a levelling agent, for 10 minutes at 40°C. The pH of the liquor is 2.9. 5.8 g of the dye of formula (1.5), previously dissolved in a smaB amount of water, are then added. The material to be dyed is treated in the dye liquor at 40°C for 5 min and is then heated to 100°C and dyed for 20 min at that temperature. 14 g of calcium chloride are then added and dyeing is continued for 40 min. After dyeing, the material is treated with 1.5 litres of an after-treatment bath containing 2 g of 1,6-hexamethytenediamioe for 20 minutes at 70°C. Rinsing and finishing are then carried out in customary manner. A deep, level dyeing having good fastness properties is obtained. In order to improve the fastness properties further, customary after-fixing or alkaline after-treatment may follow. For alkaline after-treatment, the dyeing is treated in a fresh bath, which contains 2 g/l of soda and has a pH of 9.2, for 20 minutes at 60°C. The depth of shade of the dyeing is approximately three times that of a comparison dyeing carried out analogously to Example 1 but omitting the treatment with CaCI2 and 1,6-hexamethylenediamine. Example 2: 70 g of a fabric of polyamide-6.6 microfibres are treated in a dyeing apparatus with 1.5 litres of liquor containing 3 g of formic acid, 0.4 g of wetting agent and 0.7 g of a levelling agent, for 10 min at 40°C. The pH of the liquor is 2.9. 6.6 g of the dye of formula (1.23), previously dissolved in a small amount of water, are then added. The material to be dyed is treated in the dye liquor at 40°C for 5 min and is then heated to 100°C and dyed for 20 min at that temperature. 14 g of calcium chloride, previously dissolved in 70 g of water, are then added and dyeing is continued for 40 min. After dyeing, the material is treated w* 1.5 litres of an after-treatment bath containing 2 g of 1,6-hexamethylenediamine for 20 minutes at 70°C. Rinsing and finishing are then carried out in customary mamer. A deep, level dyeing having excellent fastness properties is obtained. The depth of shade of the dyeing is approximately twice that of a comparison dyeing carried out analogously to Example 2 but omitting the treatment with CaCI2 and 1,6-hexamethytenedianwe. By proceeding as described in Example 1 but using, instead of 5.8 g of the dye of formula (1.5), the same amount of the dye of formula (1.1), (1.2), (1.3), (1.4), (1.6), (1.7), (1.8), (1.9), (1.10), (1.11), (1.12), (1.13), (1.14), (1.15), (1.16), (1.17), (1.18), (1.19), (1.20), (1.21) or (1.22), a deep, level dyeing having very good fastness properties is likewise obtained. What is claimed is: 1. A method of dyeing or printing textile fibre materials, which comprises bringing the fibre material into contact with (a) at least one reactive dye containing at least one anionic group, (b) at least one compound which reduces the ionic character of the anionic group, and (c) at least one nudeophific compound. 2. A method according to claim 1, which comprises using at least one reactive dye erf formula A-(Z)k (1) wherein A is the radical of a monoazo, disazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan or dioxazine dye, Z independently denotes k fibre-reactive substituents, which may be identical or different from one another, selected from the group of the vinylsulfonyl, acryloyl and heterocyclic series, and k is a number 1, 2 or 3. 3. A method according to claim 2, wherein Z is -SO2-CH=CH2 or -SO2-CH2-CH2-U, wherein U is a leaving group, -CO-CH(Hal)-CH2(Hal) or -C0-C(Hal)=CH2, wherein Hal is chlorine or bromine, or a halotriazine radical wherein the halogen is fluorine or chlorine. 4. A method according to any one of claims 1 to 3, which comprises using a reactive dye of formula (1a) wherein Ri is hydrogen or unsubstituted or substituted Ci-C4alkyl, X is halogen, A is the radical of a monoazo, dtsazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan or dioxazine dye, and V is a non-fibre-reactive substituent or is a fibre-reactive substituent of formula wherein R2 is hydrogen or unsubstituted or substituted Ci-C4alkyl or a radical wherein R3 is as defined below, R3 is hydrogen, hydroxy, sulfo, sulfato, carboxy, cyano, halogen, d-C4aIkoxycarbonyt, C1-C4- alkanoyloxy, carbamoyi or a group -SO^Y, R4 is hydrogen or Ci^^alky!, alk and alki are each independently of the other linear or branched CrC6alkyIene, arylene is a phenylene or naphthylene radical which is unsubstituted or substituted by sulfo, carboxy, hydroxy, Ci-C4alkyl, C^-CAalkoxy or by halogen, Y is vinyl or a radical -CH2-CH2-U and U is a leaving group, Y1 is a group -CH(Hal)-CH2(HaI) or -C(Hal)=CH2 wherein Hal is chlorine or bromine, W is a group -SO2-NR4-, -CONR- or -NR4CO- wherein R4 is as defined above, Q is a radical -O- or -NR4- wherein R is as defined above, and n is a number 0 or 1. 5. A method according to any one of claims 1 to 4, which comprises using, as the compound which reduces the ionic character of the anionic group, an alkaline earth metal salt a transition metal salt or an aluminium salt. 6. A method according to any one of claims 1 to 5, which comprises using, as the compound which reduces the ionic character of the anionic group, an Mg2(+), Ca2(\ Sr2*', Ba2(+\ Mn2(+), Cu2(+), Zn2(+), Ni2(+), Cd2(+), Co3", AI3(+), Sn2(+) or Cr3" salt in the form of a chloride, sulfate, nitrate, acetate, formate, tartrate or lactate. 7. A method according to any one of claims 1 to 6, which comprises using, as nudeophttic compound, a compound of formula H2N-B-NH2 (11) wherein B is a C2-Ci2alkylene radical which may be interrupted by 1, 2 or 3 -O- moieties and which is unsubstituted or substituted by hydroxy or by sulfato. 8. A method according to any one of claims 1 to 7, wherein treatment of the fibre material with the nucleophilic compound is carried out in a separate after-treatment bath at a temperature of from 30 to 100X, especially from 50 to 80°C. 9. A method according to any one of claims 1 to 8, wherein the compound which reduces the ionic character of the anionic group is used in an amount of from 0.1 to 100 % by weight preferably from 0.5 to 50 % by weight and especially from 2 to 40 % by weight, based on the weight of the substrate. 10. A method according to any one of claims 1 to 9, wherein the nucleophilic compound is used in an amount of from 0.001 to 2 % by weight, especially from 0.01 to 1 % by weight, based on the weight of the dye liquor or on the weight of the after-treatment bath. 11. A method according to any one of claims 1 to 10, wherein synthetic polyamide fibre material is dyed.

Full Text

Method of dyeing or printing textile fibre materials using reactive dves
The present invention relates to a method of dyeing or printing textile fibre materials using reactive dyes.
The problem underlying the present invention was to make available an easy to perform method of dyeing or printing textile fibre materials which results in dyeings or prints having a high depth of shade and very good fastness properties.
It has been found, surprisingly, that when, for example, synthetic polyamkle ffcre materials are dyetf high depths of shade are obtained in conjunction with very good wet fastness and contact fastness properties when the fibre material is dyed using reacBve dyes in the presence of suitable salts which improve the uptake behaviour and the fibre material is treated with suitable nucleophiles in accordance with the present invention.
The dyeings obtained solve the posed problem especially well. In particular, the dyeings obtained are distinguished by very good fastness properties, especially wet fastness properties, and by deep hues.
The problem posed is solved in accordance with the invention by the method described hereinbelow.
The present invention accordingly relates to a method of dyeing or printing texSe ftore materials, which comprises bringing the fibre material into contact with
(a) at least one reactive dye containing at least one anionic group,
(b) at least one compound which reduces the ionic character of the anionic 7019, and
(c) at least one nudeophific compound.
Reactive dyes contain at least one fibre-reactive radical. Fibre-reactive radicals are to be understood in general 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 sifc, or with the amino and possibly carboxy groups of synthetic potyamides to form covatent 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 containing at least

one removable substltuent 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.
Reactive dyes are known and are described in large numbers, for exampie in Venkataraman The Chemistry of Synthetic Dyes" Volume 6, Academic Press, New York, London 1972.
For the method according to the invention there is used, for example, at least one reactive dye of formula
A-{Z)k (1)
wherein
A is the radical of a monoazo, disazo, polyazo, metal complex azo, anthraquinone,
phthalocyanine, formazan or dioxazine dye,
Z independently denotes k fibre-reactive substituents, which may be identical or different
from one another, selected from the group of the vinylsulfonyl, acryloyl and heterocyclic
series, and
kisa number 1,2 or 3.
Fibre-reactive radicals Z from the group of the vinylsulfonyl series are, for example, aflc^ sulfonyl radicals substituted by a removable atom or by a removable group or altenyisulfonyl radicals which are unsubstituted or substituted by a removable atom or by a removable group. The mentioned alkyisulfonyl and alkenylsulfonyl radicals contain generafiy from 2 to 8, preferably from 2 to 4, and especially 2, carbon atoms.
Fibre-reactive radicals Z from the group of the acryloyl series are, for exampie. akanoyl radicals substituted by a removable atom or by a removable group or alkenoyf radicals which are unsubstituted or substituted by a removable atom or by a removable group. The mentioned alkanoyl and alkenoyl radicals contain generally from 2 to 8, preferably 3 or 4, and especially 3V carbon atoms.
Examples of fibre-reactive radicals Z from the group of the heterocycfic series include heterocycRc radicals that contain 4-, 5- or 6-membered rings and that are substituted by a

removable atom or by a removable group. Suitable heterocyclic radicals are, for example, those that contain at least one removable substituent bonded to a heterocyclic radical, inter alia those that contain at least one reactive substituent bonded to a 5- or 6-membered heterocyclic ring, for example to a monoazine, diazine, pyridine, pyrimkline, pyridazine, pyrazine, thiazine, oxazine or asymmetrical or symmetrical triazine ring, or to sue* a ring system that has one or more fused-on aromatic rings, for example a quinofine, phfoalazine, quinazoline, qumoxafine, acridine, phenazine or phenanthridine ring system.
Removable atoms and removable groups or leaving groups are, for example, halogen, e.g. fluorine, chlorine or bromine, ammonium, including hydrazinium, sufeto, tWosuialc, phosphato, acetoxy, propionyloxy, azido, carboxypyridinium and rhodankto.
As a radical from the group of the vinylsulfonyl series, Z is preferably a radical of formula -SO2-CH=CH2 or SO2-CH2-CH2-U wherein U is a leaving group.
As a radical from the group of the acryloyl series, Z is preferably a radical of formula -CO-CH(Hal)-CH2(Hal) or -CO-C(Hal)=CH2 wherein Hal is chlorine or bromine.
As a radical from the group of the heterocyclic series, Z is preferably a halotriazffie or halopyrimidine radical, especially a halotriazine radical, wherein the halogen is fluorine or
chlorine.
Z is preferably -SO2-CH=CH2 or -SO2-CH2-CH2-U, wherein U is a leaving group, -CO-CH(HaJ)-CH2(HaJ) or -CO-C(Hal)=CH2, wherein Hal is chlorine or bromine, or a halotriazine radical, wherein the halogen is fluorine or chlorine.
The fibre-reactive radicals Z and the dye radical A may be connected to one anofier by way of a bridging member. Suitable bridging members include, besides a direct bond or, for example, an amino group, a very wide variety of radicals. For example, the bridging member is an aliphatic, aromatic or heterocyclic radical; the bridging member may also be composed of various such radicals. The bridging member generally contains at feast one fcmctional group, for example the carbonyf group or the arnino group, it being possfcle for the amino group to be substituted by C1-C4aikyl which is unsubstftuted or further substituted by halogen, hydroxy, cyano, Ci^alkoxy, Ci-C4alkoxycarbonylf carboxy, sulfamoyf, sutfo or by sutfato. A

suitable aliphatic radical is, for example, an alkylene radical having from 1 to 7 carbon atoms, or a branched isomer thereof. The carbon chain of the alkylene radical may be interrupted by a hetero atom, for example an oxygen atom. A suitable aromatic radical is, for example, a phenylene radical which may be substituted by Ci«C4alkyl, e.g. methyl or ethyl, d-C4alkoxy, e.g. methoxy or ethoxy, halogen, e.g. fluorine, bromine or, especially, chlorine, carboxy or by sulfo, and a suitable heterocydic radical is, for example, a piperazine radical.
Such fibre-reactive radicals Z are known per se and large numbers of them are descrtoed, for example in Venkataraman The Chemistry of Synthetic Dyes" Volume 6, pages 1-2CS, Academic Press, New York, London 1972 or in EP-A-625 549 and US-Ar5 68413e.
k preferably denotes a number 2 or 3, especially 2.
When k denotes a number 2 or 3, preference is given to at least one of the fibre-reactive radicals Z being a radical from the group of the heterocydic series, for example a halotriazine radical.
In an especially preferred embodiment of the method according to the invention, there is used a reactive dye of formula
(1a)
wherein
Ri is hydrogen or unsubsttuted or substituted d-C4alkyl,
X is halogen,
A is as defined above, and
V is a non-fibre-reactive substituent or is a fibre-reactive substituent crfformiia

wherein
R2 is hydrogen or unsubstituted or substituted CrC4aIkyl or a radical
wherein R3 is as defined below,
R3 is hydrogen, hydroxy, sulfo, sutfato, carboxy, cyano, halogen, Ct-C^aBcoDcycagbonyt, Ci-C
alkanoyloxy, carbamoyl or a group -SO2-Y,
R4 is hydrogen or d-C^cyl,
alk and alk1 are each independently of the other linear or branched d-GsaJkytene,
arylene is a phenyiene or naphthyiene radical which is unsubstihjted or substituted by sulfo
carboxy, hydroxy, Ci-C4alkyl, Ci-C4alkoxy or by halogen,
Y is vinyl or a radical -CH2-CHZ-U and U is a leaving group,
Yn is a group -CH(Hal>CH2(HaI) or -C(Hal)=CH2 wherein Hal is chlorine or bromine,
W is a group -SOr**V, -CONR4- or -NR4CO- wherein R4 is as defined above,
Q is a radical -O- or -NR4- wherein R4 is as defined above, and

n is a number 0 or 1.
If desired, a fibre-reactive radical, for example having the definitions and preferred meanings given above for Z, is bonded to the dye radical A.
In an interesting embodiment of the present invention, either the radical A of the reactive dyes of formula (1a) used according to the invention is substituted by a fibre-reac&ve radical or the radical V is a fibre-reactive radical of formula (2a), (2b), (2c), (2d), (2e) or (2f). A is preferably not substituted by a fibre-reactive radical.
As Ci-C4alkyl for Ri, R2 and R4, each independently of the others, there come info consideration, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and isobutyl, preferably methyl and ethyl, and especially methyl. The mentioned radtcafs R1 and R2 are unsubstituted or substituted, for example by halogen, hydroxy, cyano, d-C4alkoxy, CrC4alkoxycarbonyl, carboxy, sulfamoyl, sulfo or by sulfato, preferably by hydroxy, sulfo, sulfato, carboxy or by cyano. The unsubstituted radicals are preferred.
X is, for example, fluorine, chlorine or bromine, preferably fluorine or chlorine, and especially chlorine.
RT is preferably hydrogen or Ci-C4alkyl, especially hydrogen, methyl or ethyl, and very especially hydrogen.
When Y is a radical -CH2-CH2-U, the leaving group U may be, for example. -CL -Bar, -F, -OSO3H, -SSO3H, -OCO-CH3, OPO3H2l -OCO-CeHs, OSOrC^-C^afkyi Or -OSO2-N(C1-C4an^l)2. U is preferably a group of formula -Cl, -OSO3H, -SSO3K -OCO-CH3, -OCO-C6H5 or -OPO3H2, especially -Cl or -OSO3H, and more especially -OSCbR
Y is preferably vinyl, P-chkxoethyf, fr-sulfatoethyl, fJ4hiosulfatoethyl, p-acetoxyeflT^, P-phenoxyethyl or ^-phc^phatoethyl, especially p-chloroethyl, ^-sulfetoethyl or vinyi, more especially $-sulfatoethyl or vinyl, and very especially vinyl.
Hal is preferably bromine.

alk and alki, each independently of the other, are, for example, methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene or a branched isomer thereof, alk and alki, each independently of the other, are preferably a d-C4alkylene radical, and especially an ethylene or propylene radical.
Preferred meanings of arylene are a 1,3- or 1,4-phenylene radical which is unsubstituted or substituted by sutfo, methyl or by methoxy, and especially an unsubstituted 1,3- or 1,4-phenylene radical.
R2 is preferably hydrogen, Ci-C4alkyl or a radical of formula wheran R3, Y
and alk in each case are as defined above and have the preferred meanings given above. R2 is especially hydrogen, methyl or ethyl, and very especially hydrogen.
R3 is preferably hydrogen.
R4 is preferably hydrogen, methyl or ethyl, and especially hydrogen.
The variable Q is preferably -NH- or -O-, and especially -O-.
W is preferabfy a group of formula -CONH- or -NHCO-, especially the group of farmuia -CONH-.
The variable n is preferably the number 0.
Preferred fibre-reactive substituents V of formulae (2a) to (2f) are those virtierein Rj and R3 are each hydrogen, R4 is hydrogen, methyl or ethyl, Q is a radical -NH- or -O-, W is the group -CONH-, alk and alki are each independently of the other ethyiene or pnopytene, arylene is phenylene which is unsubstituted or substituted by methyl, methoxy or by sutfo, Y is vinyl, P-chloroethyl or fi-sutfatoethyl, especially vinyl or fJ-sulfatoethy!, and very especially vinyl, YT is -CHBr-CH2Br or -CBP=CH2 and n is the number 0; amongst those substituents special preference is given to the radicals of formulae (2c) and (2d).

When V has the meaning of a fibre-reactive substituent, very special preference is given to V being a group of formula

especially (2c1), wherein Y is as defined above and has the preferred meanings given above.
In the radical of formula (2c1), the nitrogen atom can be substituted by methyl or ethyl instead of hydrogen.
An especially important fibre-reactive substituent V is the radical of formula

wherein Y is vinyl or p-sulfatoefhyl, especially vinyl.
When V is a non-fibre-reactive substituent, it may be, for example, hydraxy; CrC^aBcoxy; Ci-C4aJkylthio which is unsubstituted or substituted by hydroxy, carboacy or by suSo; amino; amino mono- or di-substituted by Ci-Csalkyl, the alkyl being unsubsftided or further substituted by, for example, sutfo, sulfato, hydroxy, carboxy or by phenyl, especially by sulfo or by hydroxy, and being uninterrupted or interrupted by a racBcai -O; cyctohexytamino; morpbolino; N-C1-C4alkyt-N'phenylamino or phenytamino or naphthylamino, the phenyl or naphthyl being unsubstituted or substituted by, for example, d-C^alkyt C1-C4akoxy. carboxy, sulfo or by halogen.

Examples of suitable non-fibre-reactive substituents V are amino, methylamino, ethyiamino, P-hydroxyethylamino, N,N-di-p-hydroxyethylamino, p-sulfoethylamino, cydohexylamino, morpholino, o-, m- or p-chlorophenylamino, o-, m- or p-methylphenylamino, o-, m- or p-methoxyphenylamino, o-, m- or p-sulfophenylamino, disulfophenylamino, o-carboxyphenyl-amino, 1- or 2-naphthytamino, 1-suffo-2-naphthylamino, 4,8-disuffo-2nrMphthyiamino, N-ethyl-N-phenylamino, N-^nethyl-N-phenylamino, methoxy, ethoxy, n- or iso-propoxy and hydroxy.
As a non-fibre-reactrve racfical preference is given to V in the meaning of Ct-C4afescy, CrC4-alkylthio which is unsubstituted or substituted by hydroxy, carboxy or by sutfo, t^droxy, amino, N-mono- or N9N- Especially preferred non-fibre-reactive radicals V are amino, N-methylamino, N-ettiylamino, morpholino, phenylamino, 2-, 3-or4-sulfophenylamino, naphthylamino, 1-suttonapttth-2-yl-amino, 3,7-disulfonaphth-2-yl-amino or N-d-CAalkyl-N-phenylarnino.
When A is the radical of a monoazo, polyazo or metal complex azo chromophorB, tie following radicals, especially, come into consideration:
chromophore radicate of a mono- or dis-azo dye of formula

wherein D is the radical 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 is the radical of a coupling component of the benzene, naphthalene, pyrazoione, 6-hydraxypyrid-2-one or acetoacetk: acid arylamtde series, and u is a number 0 or 1, wherein D, M and K may cany

substituents customary for azo dyes, for example d-C4alkyl or Ci-C4alkoxy each of which is unsubstituted or further substituted by hydroxy, sulfo or by sulfato, halogen, carboxy, sulfo, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, amino, ureido, hydroxy, carboxy, sulfo-methyl, C2-C4alkanoylamino, benzoylamino which is unsubstituted or substituted in the phenyl ring by d-C4alkyI, Ci-C4alkoxy, halogen or by sulfo, phenyl which is unsubstituted or substituted by Ci-C4aikyl, Ci-C4alkoxy, halogen, carboxy or by sulfo, and also ffcre-reactive radicals. There also come into consideration the metal complexes derived from the dye radicals of formulae (3) and (4), especially dye radicals of a 1:1 copper complex azo dye or 1:2 chromium complex azo dye, of the benzene or naphthalene series, wherein the copper or chromium atom is in each case bonded, on each side in the position ortho to fee azc bridge, to a group capable of being metatlated.
When the chromophore radicals of formula (3) or (4) carry a reactive radical, the reactive radical may correspond, for example, to formula

wherein Y and Hal each are as defined above and have the preferred meanings given above, Vn independently has the definitions and preferred meanings given above for V, X, independently has the definitions and preferred meanings given above for X, Rnf independently has the definitions and preferred meanings given above for Ri, and p is a number 0 or 1,andl, m and q are each independently of the others an integer from 1 to 6. Preferably, p is the number 0,1 and m are each independently of the other a number 2 or 3, and q is a number 1, 2, 3 or 4.

As reactive radicals for the chromophore radicals of formula (3) or (4) there comes into consideration, especially, a radical of formula (5a), (5d), (5f), (5g) or (5h) given above, especially of formula (5a) or (5h).
Preferably, the chrorrophore radicals A of formula (3) or (4) do not carry a reacfive radical. Especially preferred radicate of a monoazo or disazo chromophore A are the foiowtng;

wherein (Rsh-3 denotes from 0 to 3 identical or different substituents from the gro$ Ci-C4alkyl, d-C4alkoxy, halogen, carboxy and strffo,

wherein (Re)o-3 denotes from 0 to 3 identical or different substituents from the group halogen, nitro, cyano, trifluorornethyl, suifamoyl, carbamoyl, Ci-C4alkyl, CrC4alkoxy, amino, C2-C4-alkanoylamino, urekto, hydroxy, carboxy, sulfomethyl and sulfo,
(6f),
(69).
(6h)
wherein R7 is amino, Ci^alkylamino, C2-C4alkanoylamino1 benzoylammo or a reactive radical of formula (5d) or (5h) given above,
(6j)
wherein (Ra)o-3 denotes from 0 to 3 identical or different substituents from the group Ci-C4alky1, C^-C^koxy, halogen, cartx>xy and sulfo,

wherein R9 and R« are each independently of the other hydrogen, d-C^alkyl or phenyi and R10 is hydrogen, cyano, carbamcyl or sulfbmethyl,

C/JT i)—N~N—\ /—N = N—\ 'f
(HO3S)1.3 / ) T\ (6p),
V J V_ Jf
(R5*)o-3 (R7')o-3
OH OH
>—I (or)or
(Rs)o-3 (R6)o-3 (R5')o-3
(R5)o-3 (R5')o-3
/T\_ _TT\ (6S)
\ / N~N—\ v

wherein the benzene nuclei contain no further substituents or are further substituted by Ci-C4alkyl, CrC4alkoxy, d-C4alkyIsulfonyl, halogen or by carboxy.
When A is the radical of a phthalocyanine dye, it is preferably a radical of formula
(3)
wherein Pc is the radical of a metal phthalocyanine, especially the racfical of a copper or nickel phthalocyanine; R is -OH and/or -NR13R14; R13 and R14 are each independently of the other hydrogen or d-C4alkyl which is unsubstituted or substituted by hydroxy or by suffo; R12 is hydrogen or C^^alkyt; E is a phenylene radical which is unsubstituted or substituted by Ci-C4alkyl, halogen, carboxy or by sutfo or is a CrCealkylene radical; and t is 1 to 3. Rt3 and R14 are preferably hydrogen. E is preferably a phenylene radical which is unsubstituted or

substituted by Ci-C4alkyl, halogen, carboxy or by sulfo. Pc is preferably the radical of a copper phthalocyanine.
When A is the radical of a dioxazine dye, it is, for example, a radical of formula

wherein E1 is a phenylene radical which is unsubstituted or substituted by Ci~C4alkyl, halogen, carboxy or by sulfo or is a Cr-Cealkylene radical, r, s, v and w are each independently of the others a number 0 or 1, and Y is as defined above. Preferably, E1 is C2-C4alkylene or is 1,3- or 1,4-phenylene which is unsubstituted or substituted by sulfo, r is the number 1, s is the number 0, v is the number 1, and w is a number 0 or 1.
When A is the radical of an anthraquinone dye, it is preferably a radical of formula

wherein G is a phenylene radical which is unsubstituted or substituted by Ci-C^aicyL CrC4alkoxy, halogen, carboxy or by sutfo or is a cydohexylene, phenyienemetftytene or C2-C6alkylene radical, the anthraquinone dye radical of formula (10) preferably containing at least 2 sulfo groups. G is preferably a phenylene radical which is unsubsBtuted or substituted by Ci-C^alkyl, Ci-C4alkoxy, halogen, carboxy or by sulfo.
Special preference is given to A being a monoazo or dssazo chromophore racficai of formula (6a), (6b), (6d),
formula (10) given above, especially of formula (6a), (6b), (6e), (6g), (6h), (6i), (6j), (6k), (6m), (6s) or (10).
In the meanings given for the variables, Ci-C4alkyl is generally methyl, ethyl, n- or iso-propyl or n-, iso-, sec- or tert-butyl. Ci-C^koxy is generally methoxy, ethoxy, rv or Iso-propoxy or n-, iso-, sec- or tert-butoxy. Halogen is generally, for example, fluorine, chlorine or brorrtne. Examples of Cr-C4alkanoylamtno are acetylamino and proplonylamino. Examptes of Ci-C4hyclroxyalkoxy are hydroxymethoxy, p-hydroxyethoxy and £- and y-hydroxypropaxy. Examples of Ci-C4sulfatoalkoxy are sutfatomethoxy, (5-suIfatoethoxy and $- and y-sulfatopropoxy. Examptes erf Ci-C4afkylsutfonyl are methylsulfonyl, ethylsutfonyl and propylsulfonyl.
For the method according to the invention preference is given to the use of dyes of formula (1 a) wherein Ri, X and A are as defined above and have the preferred meanings given above and V is a fibre-reactive substituent of formula (2a), (2b), (2c), (2d), (2e) or (2f) wherein R2, R3, R4, alk, alk1( arylene, Y, Yi, W, Q and n are each as defined above and have the preferred meanings given above.
The reactive dyes of formula (1) contain at least one, preferably at least two, sulfo group(s), which is/are either in the form of the free acid or, preferably, in the form of a salt thereof. Suitable salts are, for example, the alkali metal, alkaline earth metal or ammonium safts, salts of an organic amine or mixtures thereof. As examples there may be mentioned sodium, lithium, potassium or ammonium salts, the salt of mono-, di- or tri-ethanolamine or NaftJ or Na/Li/NH4 mixed salts.
Dyes that are suitable for the method according to the invention correspond, for example, to
formulae

O NH,
|| | ^ CO-NH-CH9CH9-SO--CH=CH9
L JL Jl .J N~{ />
T T iH* H /N=\ d2)
TT ^
H3C>Y^CH3 °
SO3H
HO3S a
^ I H-C-OONH 1
LA^>—N = N / V-HM—I^ jl_NH—/ V-SO2-CH=CH2 ^1-3j'
HO3S
a
CH3 HO3S^. Ni.N
r^^N = N-4^^N-WNi-N-^J>-SO2-CH=CH2 (1.4),
I CH2CH3
a
HN^^^^N HO HN N N'yS (13).
Br\Ao ^VS^S H ^^
B^ HO3S'^^X^N"SO3H
a
^^N HO HN^N^N^S^ (1.6).

a
on u 1 CO-NH-CH?CH:,-SO5-CH=CH,
9U3H *.^^. / 2 2 2 2
J| I I \—/ \—/ H N H \—/ (1.7),
SO3H
a
HO3S NH, ^
) ( , -k N N J y
(\ /)—N = N—C />—N—U- J— N~— SO,-CH=CH,
\ // \_J H N H \_/ 2 2 (1.8).
HO3S
a
HO,S NH2 1
3W/ ^^^ N^N /=,
V/ \_/ H N H \^ (1.9),
I \— OH CONH-(CH2)2-SO2-(CH2)2-OSO3H
HO3S
a
HO,S NH. 1
3W 2 N^N
/ V-N=N-^V-N-WN>-NH-(CH2)2-O-(CH2)2-SO2-(CH2)2-a
HO3S
a
/=\ N^"N /={_/— N=N~{_^K^N^H \_/~S°2"CH=CH2 HO3S HJC-OC-NH
a A HO3S
HO3S KjC-oc-w r^+caca^cHj

a
1 HO3S
_ N^N *W (1-13).
)—' / NH-CO-CHBr-CH2Br
HO,S H^-OC-NH
a
_ N^N 3\=, (1.14).
)—^ / NH-CO-CHBr-CH^
HO3S H3C
H3C
^ N=N-^_^_yrA (1.15),
N n \=u
CH2)2-O-(CH2)2-SO2-CH2CH2CI
a
1 HO,S
HO3S NH2 ^ N (>N=N-OK4^N^) (1.16),
)—( NH-CO-CHBr-CH^r
y_/-°H HO3S
a
HO3S NH2 ^ NJ^N ^=N^
)—( NH-CO-CHBr-CH^
HO3S
H,C
I n H N H \=/
S02-CH2CH2-OSO3H

HO3S Nh^ HO3S
4 >— N=N—4 ^ X
\_/ Y_f N^N (1.19),
{ }-0H N—U- JL-NH-{CH2)2-O-(CH2)2-SO2-(CH2)2-a
V (/ H N
HO3S
HO3S a
fr\ ^y^K N^N /=H03S NH-CO-CHBr-CHjBr
0 NH2
^YVVS°3H
UvU NJ-N H°3SV_ d-21).
/—v
0 N — (CH-), — N U- J N f 7
H 2'3 H N H \—/
NH-CO-CHBr-CH2Br
Cl
N^ N , v
^ SO,H OH HN U- jJ—N—f V
r^y I I N I \=/ (1^2) and
J^JJ—N^N f^:;^[fS °2H5
NH-CO-CHBr-CH2Br HQ3S -^^^N^
SO3H
O NH2
3 H ] 2-2
The reactive dyes used in the method accorrfing to the invention may comprise further additives such as, for example, socfium chloride or dextrin.

The dyes used in accordance with the invention are known or can be prepared using methods known perse, such as those described, for example, in US-A-5 760 194, US-A-5 760 195, US-A-5 779 740 and EP-A-1 247 841.
For the method according to the invention, the customary dyeing or printing methods may be used. The dye liquors or printing pastes may comprise, in addition to water and the dyes, further additives, for example wetting agents, antifoams, levelling agents or agents that influence the characteristics of the textile material, for example softeners, fiame-fetardam additives, or dirt-, water- aid oB-repeBents, and also water-softeners and natural or synthetic thickeners, for example akjinates and cellulose ethers.
The amounts in which the individual dyes are used in the dye baths or printing pastes can vary within wide limits depending on the required depth of shade; in general, amounts of from 0.01 to 15 % by weight, especially from 0.1 to 10 % by weight, based on the material to be dyed or the printing paste, have proved to be advantageous.
The dyes may be used singly, or mixtures of dyes, for example mixtures of two or three dyes (di- ortri-chromism), may be used.
Suitable compounds which reduce the ionic character of the anionic group, that is to say which reduce the solubility product of the dye in the aqueous dye liquor, are, for example. alkaline earth metal salts, transition metal salts and aluminium salts.
In this context, although the term salt also includes oxides and hydroxides, hydroxides and carbonates are preferably not used in the method according to the invention.
There may be mentioned, by way of example, salts of polyvalent metals such as Mg2*** Ca2(+\ Sr*+\ Ba2" Mn2". Cu2" Zn2(+\ Ni2" Cd2(+), Co*1, Al3" Sn2" and Cr*+> salts, e_g. in the form of a chloride, sulfate, nitrate, acetate, formate, tartrate or lactate, preferably in the form of a chloride, sulfate or nitrate and especially in the form of a chloride.
Preference is given to Ca2***, Ba2*** and Al3**1 salts, especially Ca2*** salts. Special preference is given to the use of CaCfe.

Suitable nucleophilic compounds are compounds which are capable of reacting with the fibre-reactive groups of the reactive dyes in an addition or substitution reaction, e.g. aliphatic or aromatic compounds containing at least one amino, mercapto or hydroxy group. The term amino group in the present case includes both primary and secondary amino groups which are capable of entering into an addition or substitution reaction with fibre-reactive groups. Preference is given to compounds containing at least one amino group, for example two or three amino groups.
Suitable aromatic amines are, for example, anilines or aminonaphthalenes. The mentioned anilines or aminonaphthalenes also include compounds substituted at the nitrogen by, for example, d-C4alkyl and are unsubstituted or substituted at the aromatic moiety by, for example, CrC18alkyl, C^dealkoxy, carboxy, carbamoyl, N-d-dsalkylcarbamoyl, sulfo, hydroxy or by halogen.
Suitable aromatic amines also include those containing two amino groups such as, for example, compounds of formula
H2N-B-NH2 (11),
wherein B is unsubstituted or d-C4alkyh Ci-C4alkoxy-, C2-C4alkanoylamino-, sutfo-, halo- or carboxy-substituted Ci-C6alkytenephenylene, e.g. methylenephenylene, or unsubstituted or similarly substituted naphthylene or phenylene, or a radical of formula
£\_L_/jA
£VL^GX wherein the benzene rings I and II are unsubstituted or substituted by Cr^^aBcyl, Ct-Cr-alkoxy, C2-dalkanoyiamino, sulfo, halogen or by carboxy and L is a direct bond or a d-C«r alkylene radical which, with the exception of methytene, may be interrupted by 1, 2 or 3 oxygen atoms, or L is a bridging member of formula -CH=CH-, -NH-, -CO-, -NH-CO-, -NH-SOr, -NH-CO-m-, -O-, -S- or -SCV. The aromatic bridging members mentioned far B are preferably unsubstituted or substituted by sulfo. There may be mentioned, by way cf

example: phenylenediamine, toluylenediamine, xylylenediamine and 4,4f-diaminodiphenyl-methane.
The two amino groups in the compound of formula (11) may be further substituted by one substituent, for example by Ci-C4afkyl which may in turn be substituted by, for example, C2-C4alkanoylamino, e.g. acetylamino or propionylamino; Ci-C4alkoxy, e.g. methoxy or ethoxy; hydroxy; suffb; sutfato; carboxy; carbamoyl or by sulfamoyl.
Suitable aliphatic amines are, for example, Cio-C&terpeneamines, preferably C2oditerpeneamines, that is to say an amino group monosubstituted by a terpene hydrocarbon radical. Suitable terpene hydrocarbon radicals are, for example, acyclic, monocyclic or bicyclic C10terpenes, acyclic, monocyclic, bicyclic or tricyclic Ci5sesqui-terpenes, acyclic, monocyclic or tricyclic C2oditerpenes, especially tricyclic C2oditerpenes and very especially dehydrogenated tricyclic C^diterpenes, for example those which are derived from dehydroabietic acid. An example of such a dehydrogenated tricyclic C^diterpeneamine
is the compound of formula HJ (13).
Suitable aliphatic amines also include, for example, N-mono- or N,N-dHd-C»aBcytamffi^T e.g. methylamine, ethylamine, N,N-dimethylamine, N.N-diethylamine, isopropylamine, n-butylamine, sec-butylamine, isobutylamine or tert-butylamine, linear or branched pentylamine, hexylamtne, heptyiamine, octylamine, nonylamine, decylamine, urxtecytacrme dodecylamine, tridecylamine ortetradecylamine. The mentioned amines are unstfosftuteri or substituted in the alkyl moiety, for example by phenyl which may in turn be subsfituted by C^-Ciaalkyl, Ci-Ciealkoxy, halogen, c^boxy, carbamoyl, sulfo or by suHamoyt; QTOIB-alkanoylamino, e.g. acetyfamrno or propionylamino; Ct-dsalkoxy, e.g. methoxy or effioxy; hydroxy; sulfo; sulfato; carboxy; carbamoyl or by sulfamoyl. The mentioned radicals are uninterrupted or interrupted in the alkyl moiety by oxygen or by -MR15-, wherein R15 is hydrogen, methyl or ethyl, preferably hydrogen.

Suitable aliphatic amines also include those containing two amino groups, e.g. aliphatic diamines of formula (11) wherein B is Ci-C4alkylenephenylene-CrC4alkylene, e.g. methylenephenylenemethylene, or a Cr^alkylene radical which is unsubstltuted or substituted by hydroxy, sulfo, sulfato, cyano or by carboxy and which may be interrupted by from 1 to 12 moieties, e.g. 1,2, 3 or 4 moieties, from the group oxygen and -NR15-, wherein R15 is hydrogen, methyl or ethyl, preferably hydrogen. Preferred substituents of the aflcytene radicals mentioned for B are hydroxy, suffo or sulfato, especially hydroxy. By way erf exampte there may be mentioned: 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-butyJenedianwie, 1,5-pentamethytenediamine or 1,6-hexamethylenediamine, 3-amino-1-methylar™nopropane, N-hydroxyethylethylenediamine, N-methyf-bis(3-aminopropyl)amine, tetraethylenediamine, 1-aminoethyl-1,2-ethylenediamine, diethylenetriamine, tetraethylenepentamine and pentaethylenehexamine, especialfy 1,6-hexamethylenediamine.
Also suitable are relatively high molecular weight polyamines such as, for example, polyethyleneimines containing more than 24 carbon atoms or polyvinylamine.
Suitable aliphatic amines also include compounds containing three or more than three primary amino groups, e.g. tris(2-aminoethyl)amine.
Suitable aliphatic amines also include, for example, aliphatic diamines of formula (11) wherein B is Cs-Cgcycloalkylene, e.g. cyclohexylene. The mentioned cycloalkylene racfic^ may be unsubstituted or substituted by Ci-C4afkyl, CrC4alkoxy, C2-C4alkanoy1amino1 suffo, halogen or by carboxy, especially by Ci-CAalkyl. Also suitable for B are methylene-cyclohexylene, ethylene-cyclohexytene and methylene-cyclohexylene-methylene radicate unsubstituted or substituted in the cyclohexylene ring by Ci-C4alkyl, especiaBy by meSTyl and the isophorone radical and the hydrogenated diphenylmethane radical. By way of example there may be mentioned: 1,4-diaminocyctohexane, isophoronedsamine, hydrogenated xylylenediamtne and hydrogenated 4,4l-diaminodiphenyknethane.
An aromatic amine is understood to be a compound wherein the nitrogen atom erf the amino group is directly bonded to an aromatic carbon atom. Accordingly, the term aliphatic amine is understood to refer to a compound wherein the nitrogen atom of the amino group is cfirectfy bonded to an afiphatic carbon atom. In the method accortfing to the invention, preference is

given to the use of aliphatic amines as the nucieophiiic compound, especially those containing at least two amino groups.
Preferred nucieophiiic compounds are the aliphatic diamines of formula (11).
Especially preferred nucieophiiic compounds are compounds of formula (11) wherein B is a CrCi2alkylene radical, especially a CrCealkytene radical, which may be interrupted by 1, 2 or 3 -O- moieties and which is unsubstituted or substituted by hydroxy or by suKato. Of special importance are compounds of formula (11) wherein B is a (VCealkyiene radical which is unsubstituted and is not interrupted by -O-.
Advantageously, (b) and (c), that is to say treatment of the textile fibre material with the saft and treatment of the textile fibre material with the nucieophiiic compound, are carried out one after the other.
Treatment of the textile fibre material with the salt (b) is advantageously carried out by first dyeing the fibre material in customary manner and then adding the salt in suitable form, e.g. in the form of an aqueous solution, to the dye liquor during the dyeing process, for example after a dyeing period of from 10 to 60 minutes, especially from 10 to 30 minutes, followed, where appropriate, by a farther period of dyeing of, for example, from 10 to 60 minutes, especially from 20 to 50 minutes.
(b) can also be carried out by treating, for example impregnating, the textile fibre material with the salt before the dyeing or printing process, it being unimportant which technique is used to introduce the salt into the fibre material; for example, spray or foam appBcafioru immersion or a pad can be used. Dyeing or printing with the reactive dye according to (a) can be carried out thereafter. It is then unnecessary to add further salt during the dyeing or printing process.
Treatment of the textile fibre material with the nucieophiiic compound (c) can be carried out directly in the dye liquor by adding the nucieophiiic compound in suitable form, e.g. in the form of an aqueous solution, or preferably in a separate after-treatment bath. When carrying out (c) in a separate after-treatment bath, the dyed material is removed from the dye Hquor

after the actual dyeing process and after the performance of (b) and, where appropriate, is rinsed again in suitable manner before being introduced into the after-treatment liquor.
When (c) is carried out in a separate after-treatment bath, the treatment with the nucleophilic compound is performed at a temperature of, for example, from 30 to 100°C and especially from 50 to 80°C.
The compounds which reduce the ionic character of the anionic group are advantageously used in an amount of, for example, from 0.1 to 100 % by weight, preferably from 0.5 to 50 % by weight and especially from 2 to 40 % by weight, based on the weight of the substrate, thai is to say the textile fibre material.
The nucleophilic compound is advantageously used in an amount of, for example, from 0.001 to 2 % by weight, especially from 0.01 to 1 % by weight, based on the weight of the dye liquor or on the weight of the after-treatment bath.
The method according to the invention is suitable, for example, for dyeing or printing hydroxyl-group-containing or nitrogen-containing fibre materials. By way of example there may be mentioned silk, wool, cellulosic fibre materials of all kinds and polyurethanes and polyamide fibres. Cellulosic fibre materials are, for example, the natural cellutosic fibres, such as cotton, linen and hemp, and also cellulose and regenerated cellulose. The method according to the invention is also suitable for dyeing or printing hydroxyl-group-containing fibres present in blend fabrics, e.g. mixtures of cotton with polyester fibres or polyamide fibres. In a particular embodiment, the method according to the invention is not used for cellulosic or silk-containing fibre materials such as, for example, cellulose or silk.
Preferably, the method according to the invention is suitable for dyeing or printing synthe&c polyamide fibre materials, such as, for example, polyamide-6 (poly-e-caprolactamX polyamide-6.6 (poly(hexamethylene adipamide)), polyamkJe-7, polyamide-6.12 (pofy(hexamethytene dodecanoamide)), polyamide-11 or polyamkle-12, copoJyamkJes with polyamide-6.6 or potyamide-6, for example polymers of hexamethyienecfiarrune, E-caprolactam and adipic acid and polymers of adipic add, hexamethytenediamine and isophthalic acid or of acfiptc acid, hexamethyienediamine and 2-methyipentamethytene-

diamine or 2-ethyltetramethylenediamine, and is also suitable for dyeing or printing blend fabrics or yarns of synthetic polyamide and wool.
The method according to the invention is advantageously also suitable for dyeing or printing microfibres of synthetic pofyamides. Mtcrofibres are understood to be fibre materials that are composed of filaments having an individual filament fineness of less than 1 denier (1.1 dTex). Such microfibres are known and are usually produced by melt-spinning.
In order to improve further the fastness properties of synthetic polyamides, especially microfibres, the dyeing process according to the invention can be followed by customary after-fixing or alkaline after-treatment.
The mentioned textile material can be in a very wide variety of processing forms, such as, for example, in the form of fibres, yam, woven fabric, knitted fabric and in the form of carpets.
In the case of carpet fabrics, printing methods such as, for example, displacement printing, or space dyeing are of importance.
Preference is given to dyeing which is especially carried out in accordance with the exhaust method and, in the case of carpet dyeing, may also be carried out in accordance with the
continuous method.
Preference is given to dyeing at a pH of from 2 to 7, especially from 2.5 to 5.5, and very especially from 3 to 4.5. The liquor ratio can be selected within a wide range, e.g. from 13 to 1:50, preferably from 1:5 to 1:30. Preference is given to dyeing at a temperature of from 80 to 130°C, especially from 85 to 120°C.
Dyeings and printings with good all-round fastness properties, such as, for example, good fastness to chlorine, rubbing, wetting, wet-rubbing, washing, water, sea-water and perspiration, are obtained. Contact fastness properties especially, such as, for example, fastness to water and perspiration, exhibit very good values.
The Examples given hereinbetow are intended to illustrate the invention without Imiting the invention to the Examples specifically mentioned. The temperatures are given in degrees

Celsius, parts are parts by weight and percentages refer to % by weight, unless otherwise specified. Parts by weight relate to parts by volume in the same ratio as kilograms to litres.
Example 1: 70 g of a blend fabric consisting of 72 % polyamide microfibres and 28 % elastane are treated in a dyeing apparatus with 1.5 litres of liquor containing 3 g of formic acid, 0.4 g of wetting agent and 0.7 of a levelling agent, for 10 minutes at 40°C. The pH of the liquor is 2.9. 5.8 g of the dye of formula (1.5), previously dissolved in a smaB amount of water, are then added. The material to be dyed is treated in the dye liquor at 40°C for 5 min and is then heated to 100°C and dyed for 20 min at that temperature. 14 g of calcium chloride are then added and dyeing is continued for 40 min. After dyeing, the material is treated with 1.5 litres of an after-treatment bath containing 2 g of 1,6-hexamethytenediamioe for 20 minutes at 70°C. Rinsing and finishing are then carried out in customary manner. A deep, level dyeing having good fastness properties is obtained.
In order to improve the fastness properties further, customary after-fixing or alkaline after-treatment may follow. For alkaline after-treatment, the dyeing is treated in a fresh bath, which contains 2 g/l of soda and has a pH of 9.2, for 20 minutes at 60°C. The depth of shade of the dyeing is approximately three times that of a comparison dyeing carried out analogously to Example 1 but omitting the treatment with CaCI2 and 1,6-hexamethylenediamine.
Example 2: 70 g of a fabric of polyamide-6.6 microfibres are treated in a dyeing apparatus with 1.5 litres of liquor containing 3 g of formic acid, 0.4 g of wetting agent and 0.7 g of a levelling agent, for 10 min at 40°C. The pH of the liquor is 2.9. 6.6 g of the dye of formula (1.23), previously dissolved in a small amount of water, are then added. The material to be dyed is treated in the dye liquor at 40°C for 5 min and is then heated to 100°C and dyed for 20 min at that temperature. 14 g of calcium chloride, previously dissolved in 70 g of water, are then added and dyeing is continued for 40 min. After dyeing, the material is treated w* 1.5 litres of an after-treatment bath containing 2 g of 1,6-hexamethylenediamine for 20 minutes at 70°C. Rinsing and finishing are then carried out in customary mamer. A deep, level dyeing having excellent fastness properties is obtained. The depth of shade of the dyeing is approximately twice that of a comparison dyeing carried out analogously to Example 2 but omitting the treatment with CaCI2 and 1,6-hexamethytenedianwe.

By proceeding as described in Example 1 but using, instead of 5.8 g of the dye of formula (1.5), the same amount of the dye of formula (1.1), (1.2), (1.3), (1.4), (1.6), (1.7), (1.8), (1.9), (1.10), (1.11), (1.12), (1.13), (1.14), (1.15), (1.16), (1.17), (1.18), (1.19), (1.20), (1.21) or (1.22), a deep, level dyeing having very good fastness properties is likewise obtained.

What is claimed is:
1. A method of dyeing or printing textile fibre materials, which comprises bringing the fibre
material into contact with
(a) at least one reactive dye containing at least one anionic group,
(b) at least one compound which reduces the ionic character of the anionic group, and
(c) at least one nudeophific compound.
2. A method according to claim 1, which comprises using at least one reactive dye erf formula
A-(Z)k (1)
wherein
A is the radical of a monoazo, disazo, polyazo, metal complex azo, anthraquinone,
phthalocyanine, formazan or dioxazine dye,
Z independently denotes k fibre-reactive substituents, which may be identical or different
from one another, selected from the group of the vinylsulfonyl, acryloyl and heterocyclic
series, and
k is a number 1, 2 or 3.
3. A method according to claim 2, wherein
Z is -SO2-CH=CH2 or -SO2-CH2-CH2-U, wherein U is a leaving group, -CO-CH(Hal)-CH2(Hal) or -C0-C(Hal)=CH2, wherein Hal is chlorine or bromine, or a halotriazine radical wherein the halogen is fluorine or chlorine.
4. A method according to any one of claims 1 to 3, which comprises using a reactive dye of
formula
(1a)

wherein
Ri is hydrogen or unsubstituted or substituted Ci-C4alkyl,
X is halogen,
A is the radical of a monoazo, dtsazo, polyazo, metal complex azo, anthraquinone,
phthalocyanine, formazan or dioxazine dye, and
V is a non-fibre-reactive substituent or is a fibre-reactive substituent of formula

wherein
R2 is hydrogen or unsubstituted or substituted Ci-C4alkyl or a radical
wherein R3 is as defined below,
R3 is hydrogen, hydroxy, sulfo, sulfato, carboxy, cyano, halogen, d-C4aIkoxycarbonyt, C1-C4-
alkanoyloxy, carbamoyi or a group -SO^Y,
R4 is hydrogen or Ci^^alky!,

alk and alki are each independently of the other linear or branched CrC6alkyIene,
arylene is a phenylene or naphthylene radical which is unsubstituted or substituted by sulfo,
carboxy, hydroxy, Ci-C4alkyl, C^-CAalkoxy or by halogen,
Y is vinyl or a radical -CH2-CH2-U and U is a leaving group,
Y1 is a group -CH(Hal)-CH2(HaI) or -C(Hal)=CH2 wherein Hal is chlorine or bromine,
W is a group -SO2-NR4-, -CONR*- or -NR4CO- wherein R4 is as defined above,
Q is a radical -O- or -NR4- wherein R* is as defined above, and
n is a number 0 or 1.
5. A method according to any one of claims 1 to 4, which comprises using, as the compound
which reduces the ionic character of the anionic group, an alkaline earth metal salt a
transition metal salt or an aluminium salt.
6. A method according to any one of claims 1 to 5, which comprises using, as the compound
which reduces the ionic character of the anionic group, an Mg2(+), Ca2(*\ Sr2**', Ba2(+\ Mn2(+),
Cu2(+), Zn2(+), Ni2(+), Cd2(+), Co3", AI3(+), Sn2(+) or Cr3" salt in the form of a chloride, sulfate,
nitrate, acetate, formate, tartrate or lactate.
7. A method according to any one of claims 1 to 6, which comprises using, as nudeophttic
compound, a compound of formula
H2N-B-NH2 (11)
wherein B is a C2-Ci2alkylene radical which may be interrupted by 1, 2 or 3 -O- moieties and which is unsubstituted or substituted by hydroxy or by sulfato.
8. A method according to any one of claims 1 to 7, wherein treatment of the fibre material
with the nucleophilic compound is carried out in a separate after-treatment bath at a
temperature of from 30 to 100X, especially from 50 to 80°C.
9. A method according to any one of claims 1 to 8, wherein the compound which reduces the
ionic character of the anionic group is used in an amount of from 0.1 to 100 % by weight
preferably from 0.5 to 50 % by weight and especially from 2 to 40 % by weight, based on the
weight of the substrate.

10. A method according to any one of claims 1 to 9, wherein the nucleophilic compound is
used in an amount of from 0.001 to 2 % by weight, especially from 0.01 to 1 % by weight,
based on the weight of the dye liquor or on the weight of the after-treatment bath.
11. A method according to any one of claims 1 to 10, wherein synthetic polyamide fibre
material is dyed.

Documents:

1577-CHENP-2006 AMENDED PAGES OF SPECIFICATION 07-06-2011.pdf

1577-CHENP-2006 AMENDED CLAIMS 07-06-2011.pdf

1577-CHENP-2006 ASSIGNMENT 11-08-2011.pdf

1577-chenp-2006 form-1 11-08-2011.pdf

1577-CHENP-2006 FORM-13 11-08-2011.pdf

1577-chenp-2006 form-13-1 11-08-2011.pdf

1577-CHENP-2006 FORM-2 11-08-2011.pdf

1577-chenp-2006 form-3 07-06-2011.pdf

1577-CHENP-2006 FORM-6 11-08-2011.pdf

1577-chenp-2006 form-6-1 11-08-2011.pdf

1577-CHENP-2006 OTHER PATENT DOCUMENT 07-06-2011.pdf

1577-CHENP-2006 POWER OF ATTORNEY 07-06-2011.pdf

1577-CHENP-2006 AMENDED PAGES OF SPECIFICATION 09-12-2011.pdf

1577-CHENP-2006 AMENDED CLAIMS 09-12-2011.pdf

1577-chenp-2006 correspondence others 11-08-2011.pdf

1577-chenp-2006 correspondence others 28-12-2010.pdf

1577-CHENP-2006 EXAMINATION REPORT REPLY RECEIVED 07-06-2011.pdf

1577-CHENP-2006 CORRESPONDENCE OTHERS 09-12-2011.pdf

1577-CHENP-2006 CORRESPONDENCE PO.pdf

1577-CHENP-2006 FORM-18.pdf

1577-chenp-2006-abstract.pdf

1577-chenp-2006-claims.pdf

1577-chenp-2006-correspondnece-others.pdf

1577-chenp-2006-description(complete).pdf

1577-chenp-2006-form 1.pdf

1577-chenp-2006-form 26.pdf

1577-chenp-2006-form 3.pdf

1577-chenp-2006-form 5.pdf

1577-chenp-2006-pct.pdf

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Patent Number

250753

Indian Patent Application Number

1577/CHENP/2006

PG Journal Number

04/2012

Publication Date

27-Jan-2012

Grant Date

24-Jan-2012

Date of Filing

09-May-2006

Name of Patentee

HUNTSMAN ADVANCED MATERIALS (SWITZERLAND) GmbH

Applicant Address

KLYBECKSTRASSE 200, CH-4057 BASEL

Inventors:

#	Inventor's Name	Inventor's Address
1	MUNDLE, WOLFGANG	MEIGERWEG 3, 79576 WEIL AM RHEIN
2	SCHMIEDL, JURGEN	BELCHENSTRASSE 17, 79585 STEINEN

PCT International Classification Number

D06Q1/00,D06P1/38,1/382,1/384,3/10,1/673

PCT International Application Number

PCT/EP2004/052742

PCT International Filing date

2004-11-01

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	03104150.2	2003-11-11	EUROPEAN UNION