EP0882836A2 - Process for crosslinking cellulose containing fibrous materials - Google Patents

Abstract

Method of crosslinking fibrous cellulosic materials comprises treating natural or regenerated cellulose fibres with reactive aliphatic or (hetero)aromatic compound(s) of formula A-ÄRÜn (I). In (I), A = a colourless aliphatic or (hetero)aromatic group; R = a fibre-reactive group; n = 1, 2, 3 or 4; ÄRÜn contains NOTLESS 2 fibre-reactive groups. Also claimed are (a) the treated material; and (b) aqueous solutions or dispersions containing compound(s) (I).

Description

The present invention relates to a method for crosslinking cellulosic fiber materials. By networking the cellulose-containing fiber materials, high finishing effects, e.g. B. in the area of crease resistance, easy care, dimensional stability and No shrinkage achieved.

It is known to treat fiber materials, such as textiles, which contain cellulose fibers or consist of cellulose fibers, with products which impart high finishing effects, such as, for example, shrink and wrinkle-resistant properties. For this, z. B. used products that can be obtained by adding formaldehyde to amide groups. These N-methylol compounds normally still contain residues of free formaldehyde, and they release formaldehyde to a certain extent during thermal treatment, which can lead to unpleasant odors and intolerance. This disadvantage of the N-methylol compounds can be reduced or avoided by using low-formaldehyde or formaldehyde-free products as crosslinkers for cellulose. Products which have etherified N-methylol groups or products which do not contain any -N-CH ₂ -O groupings are suitable here. An example of the latter class of compounds are N, N'-dialkyl-4,5-dihydroxiimidazolidinones (N, N'-dialkyl-dihydroxyethylene ureas), which can be obtained by reacting N, N'-dialkylureas with glyoxal. Etherification products of the last-mentioned compounds with polyhydric alcohols are also known as crosslinking agents for cellulosic materials.

The disadvantage of previously known formaldehyde-free cellulose crosslinking agents is that the desired effect level is not achieved in all cases. In addition, known ones require Products for adequate cross-linking reaction with cellulose usually Temperatures of approximately 160 ° C or higher, which is undesirable. Previously known formaldehyde-free Crosslinkers also require relatively high or very high amounts to be used and conditions and often lead to undesirable yellowing of the treated fiber materials.

The object of the present invention is a method for crosslinking cellulose-containing To develop fiber materials, e.g. highly effective formaldehyde-free To achieve equipment of fiber materials, which does not have the disadvantages described having. The process should allow the reaction of the crosslinker with the Cellulose (condensation) at relatively low temperatures, i.e. H. Temperatures of less than 150 ° C, and should at a higher level of crease or Easy care effects have so far led to this with known formaldehyde-free crosslinkers is possible.

worin A ein farbloser aliphatischer, aromatischer oder heteroaromatischer Rest, R ein faserreaktiver Rest, und n die Zahl 1, 2, 3 oder 4 ist, mit der Bedingung, dass der Rest [R]_n mindestens zwei faserreaktiv wirkende Gruppen enthält.The object is achieved by a method for crosslinking cellulose-containing fiber materials, in particular those fiber materials which consist of 20 to 100% by weight of natural or regenerated cellulose fibers, which is characterized in that the cellulose-containing fiber materials, the cellulose fibers being natural or regenerated cellulose, at least one product of the general formula (1) is applied,

wherein A is a colorless aliphatic, aromatic or heteroaromatic radical, R is a fiber-reactive radical, and n is the number 1, 2, 3 or 4, with the condition that the radical [R] _{n contains} at least two fiber-reactive groups.

A is preferably an aromatic radical which is unsubstituted or substituted by C ₁ -C ₄ -alkyl, such as methyl or ethyl, C ₁ -C ₄ -alkoxy, such as methoxy or ethoxy, halogen, such as fluorine, bromine or especially chlorine, Carboxy or preferably one or more water solubilizing groups may be substituted. Sulfo groups (-SO ₃ H) are particularly suitable as water-solubilizing groups. An aromatic radical A is preferably a benzene radical which can be substituted by one or two sulfo groups. The aromatic radical A can preferably also be free of water-solubilizing groups if at least one of the radicals R contains a water-solubilizing group, such as a sulfato group.

The aliphatic radical for A is, for example, an optionally one or more heteroatoms, such as, for. B. the oxygen atom, interrupted C ₁ -C ₁₈ alkyl radical, preferably a C ₂ -C ₁₂ alkyl radical, which may be substituted by one or more water-solubilizing groups. Examples of suitable water-solubilizing groups are sulfo groups or hydroxyl groups.

The radical A as a heteroaromatic radical is, for example, a morpholino, pyrimidine or Triazine residue which may optionally be substituted, e.g. through halogen.

A fiber-reactive radical is to be understood as radicals which are associated with the hydroxyl groups of the Cellulose, the amino, carboxy, hydroxyl and thiol groups in wool and silk, or with the amino and possibly carboxy groups of synthetic polyamides to form covalent chemical bonds are able to react. The reactive groups are in the Usually bound to the colorless radical A directly or via a bridge link. Suitable Reactive groups are, for example, those which have at least one removable substituent contain an aliphatic, aromatic or heterocyclic radical or wherein said radicals are a radical suitable for reaction with the fiber material, such as e.g. a triazine residue.

A reactive group includes, for example, those by a removable atom or a removable group of substituted carbo- or heterocyclic 4-, 5- or 6-rings to understand contained residues. As heterocyclic radicals come e.g. such a Consider which at least one removable substituent on a heterocyclic Rest bound included; including those that have at least one reactive substituent contain bound to a 5- or 6-membered heterocyclic ring, such as a monoazine, diazine, triazine, pyridine, pyrimidine, pyridazine, pyrazine, thiazine, Oxazine or asymmetrical or symmetrical triazine ring. Furthermore, the mentioned heterocyclic fiber-reactive radicals via a direct bond or via a Other fiber-reactive residues, e.g. the listed residues.

As reactive groups there are also those which have at least one activated group unsaturated group, especially an unsaturated aliphatic group such as e.g. the Vinyl, halovinyl, styryl, acrylic or methacrylic group, or at least one polymerizable Show ring system. As such groups, e.g. the halogen atoms containing unsaturated groups, such as halogenomaleic acid and halogenopropiolic acid residues, the α- or β-bromo or chloroacrylic groups, halogenated vinyl cetyl groups, Halogencrotonyl or halogen methacrylic groups. Continue to come too those groups that are easily, e.g. by splitting off hydrogen halide, in halogen-containing unsaturated groups, e.g. the dichloro or dibromopropionyl group. Among halogen atoms here are fluorine, chlorine, bromine and iodine atoms as well Pseudohalogen atoms, e.g. to understand the cyano group. Good results will come after achieved the inventive method with compounds which have an α-bromoacrylic group contain. As compounds containing a polymerizable double bond, are preferably those which contain at least one acryloyl, methacryloyl, α-bromocryloyl, contain α-chloroacryloyl, vinyl or vinylsulfonyl radical; most notably preferably those which have at least one acryloyl, α-bromoacryloyl or vinylsulfonyl radical contain.

Other atoms or groups that can be removed are, for example, ammonium including hydrazinium, sulfato, thiosulfato, phosphato, acetoxy, propionoxy or Carboxypyridinium.

In formula (1) the one to four reactive residues are not necessarily all to the rest A bound, but there can also be two or three reactive residues directly or via Bridge elements must be connected to each other.

In addition to the direct bond, a wide variety of radicals can be considered as a bridge between the colorless radical A and the fiber-reactive radical or as a bridge between two or three fiber-reactive radicals. The bridge member is, for example, an aliphatic, aromatic or heterocyclic radical; Furthermore, the bridge member can also be composed of various such residues. The bridge member can contain at least one functional group, for example the carbonyl group or the amino group, the amino group being optionally substituted by halogen, hydroxy, cyano, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkoxycarbonyl, carboxy, sulfamoyl, sulfo or Sulfato substituted C ₁ -C ₄ alkyl may be further substituted. An aliphatic radical, for example, is an alkylene radical with 1 to 7 carbon atoms or its branched isomers. The carbon chain of the alkylene radical can be interrupted by a hetero atom, such as an oxygen atom. The aromatic radical is, for example, a phenyl radical which is substituted by C ₁ -C ₄ alkyl, such as methyl or ethyl, C ₁ -C ₄ alkoxy, such as methoxy or ethoxy, halogen, such as fluorine, bromine or, in particular, chlorine, carboxy or can be substituted by sulfo, and a heterocyclic radical, for example a piperazine radical. Examples of such bridge members are the following radicals: -CO-N (R ₁ ) - (CH ₂ ) _2-3 -; -CO-N (R ₁ ) - (CH ₂ ) ₂ -O- (CH ₂ ) ₂ -; -N (R ₁ ) -CO- (CH ₂ ) ₃ -; -N (R ₁ ) -; -N (R ₁ ) - (CH ₂ ) ₂ -O- (CH ₂ ) ₂ -; -O- (CH ₂ ) ₂ -; - CH ₂ -N (R ₁ ) -;

In the formulas given above, R _{1 is} hydrogen or C ₁ -C ₄ alkyl, which is substituted by halogen, hydroxy, cyano, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxycarbonyl, carboxy, sulfamoyl, sulfo or sulfato can be.

The radicals A and [R] _n in formula (1) are preferably connected to one another via a bridge member containing the amino group -N (R ₁ ), particularly preferably via the bridge member -N (R ₁ ) -, where R _{1 is} the one indicated Has meaning.

The condition that the radical [R] _{n contains} at least two fiber-reactive groups means that the compound of the formula (1) contains at least two of the fiber-reactive groups mentioned, for example for n = 1 the dichloro or difluorotriazine radical, the two which can be split off Has halogen atoms, both of which can react with the cellulose fiber, or z. B. for n = 2, a 4-monochloro or 4-monofluorotriazin-2-yl radical which in the 6 position contains a fiber-reactive group, for example a vinylsulfonyl group, bonded directly or via a bridge member.

Reactive residues R, one or two fluorine or chlorotriazine groups and optionally an aliphatic reactive group, in particular of the vinylsulfonyl type contain, or contain two vinylsulfonyl reactive groups. Important connections of the Formula (1) contain as the colorless radical A an unsubstituted or by Sulfo group substituted benzene radical and as fiber-reactive radical R one or two over a bridging member linked fluorine or chlorotriazine groups, via a bridging member contain a further reactive radical, in particular a vinylsulfonyl radical. Further important compounds of formula (1) contain an unsubstituted as colorless radical A. or a benzene radical substituted by a sulfo group and two as the fiber-reactive radical R. vinyl sulfonyl residues bonded directly or via a bridge member.

worin T₁ Fluor, Chlor oder Carboxypyridinium ist und wobei als Substituenten V₁ am Triazinring insbesondere zu nennen sind: Fluor, Chlor, -NH2, ein C₁-C₆-Alkylamino-, N,N-Di-C₁-C₆-Alkylamino-, Cyclohexylamino-, N,N-Dicyclohexylamino-, Benzylamino-, Phenäthylamino-, Phenylamino-, Naphthylamino-, N-C₁-C₆-Alkyl-N-cyclohexylamino- oder N-C₁-C₆-Alkyl-N-phenylaminorest, oder Morpholino, Piperidino, Piperazino, Hydrazino oder Semicarbazido, oder eine durch einen Furan-, Thiophen-, Pyrazol-, Pyridin-, Pyrimidin-, Chinolin-, Benzimidazol-, Benzthiazol- oder Benzoxazolrest substituierte Aminogruppe. Die genannten Alkyl-, Cycloalkyl-, Aralkyl- und Arylreste sowie die heterocyclischen Reste können weitersubstituiert sein, z.B. durch C₁-C₄-Alkyl, wie z.B. Methyl oder Aethyl, C₁-C₄-Alkoxy, wie z.B. Methoxy oder Aethoxy, Halogen, wie z.B. Fluor, Brom oder insbesondere Chlor, Carboxy oder Sulfo. Die oben angegebene Bedingung, dass der Rest [R]_n mindestens zwei faserreaktiv wirkende Gruppen enthält, bedeutet für den Fall n=1 und R ein Rest der Formel (2), dass V₁ Fluor oder Chlor ist.Interesting reactive groups are 1,3,5-triazine residues of the formula

in which T _{1 is} fluorine, chlorine or carboxypyridinium and the substituents V ₁ on the triazine ring which may be mentioned in particular are: fluorine, chlorine, -NH2, a C ₁ -C ₆ -alkylamino-, N, N-di-C ₁ -C ₆ Alkylamino, cyclohexylamino, N, N-dicyclohexylamino, benzylamino, phenethylamino, phenylamino, naphthylamino, NC ₁ -C ₆ alkyl, N-cyclohexylamino or NC ₁ -C ₆ alkyl-N-phenylamino radical , or morpholino, piperidino, piperazino, hydrazino or semicarbazido, or an amino group substituted by a furan, thiophene, pyrazole, pyridine, pyrimidine, quinoline, benzimidazole, benzothiazole or benzoxazole radical. The alkyl, cycloalkyl, aralkyl and aryl radicals mentioned and the heterocyclic radicals can be further substituted, for example by C ₁ -C ₄ -alkyl, such as methyl or ethyl, C ₁ -C ₄ -alkoxy, such as methoxy or ethoxy, Halogen, such as fluorine, bromine or especially chlorine, carboxy or sulfo. The above-mentioned condition that the radical [R] _{n contains} at least two fiber-reactive groups means that when n = 1 and R is a radical of the formula (2), V _{1 is} fluorine or chlorine.

V ₁ is particularly preferred in the remainder of the formula (2) fluorine, chlorine, phenylamino or NC ₁ -C ₄ -alkyl-N-phenylamino, the phenyl rings optionally being replaced by halogen, such as fluorine, chlorine or bromine, nitro, cyano, trifluoromethyl, Sulfamoyl, carbamoyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, acylamino groups such as acetylamino or benzoylamino, ureido, hydroxy, carboxy, sulfomethyl or in particular sulfo are substituted.

worin T₂ und T₃ unabhängig voneinander Fluor, Chlor oder Carboxypyridinium sind und B ein Brückenglied ist.Interesting fiber-reactive residues are e.g. B. also those of the formula

wherein T ₂ and T _{3 are} independently fluorine, chlorine or carboxypyridinium and B is a bridge member.

in Betracht, worin R₁' und R₁" unabhängig voneinander Wasserstoff oder gegebenenfalls durch Halogen, Hydroxy, Cyan, C₁-C₄-Alkoxy, C₁-C₄-Alkoxycarbonyl, Carboxy, Sulfamoyl, Sulfo oder Sulfato substituiertes C₁-C₄-Alkyl sind und X ein gegebenenfalls durch Hydroxy, Sulfo, Sulfato, C₁-C₄-Alkoxy, Carboxy oder Halogen substituierter C₂-C₆-Alkylen- oder C₅-C₉-Cycloalkylenrest oder ein gegebenenfalls durch C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Sulfo, Halogen oder Carboxy substituierter Phenylen-, Biphenylen- oder Naphthylenrest ist.A bridge of the formula (2 ') is, for example, a radical of the formula

into consideration, wherein R ₁ 'and R ₁ "independently of one another are hydrogen or C ₁ - substituted by halogen, hydroxy, cyano, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxycarbonyl, carboxy, sulfamoyl, sulfo or sulfato C ₄ alkyl and X is a C ₂ -C ₆ alkylene or C ₅ -C ₉ cycloalkylene radical which is optionally substituted by hydroxy, sulfo, sulfato, C ₁ -C ₄ alkoxy, carboxy or halogen or a radical which is optionally substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, sulfo, halogen or carboxy substituted phenylene, biphenylene or naphthylene.

worin T₄ Fluor, Chlor oder Carboxypyridinium ist und
V₂ ein Rest der Formel

ist, worin R₁ Wasserstoff oder C₁-C₄-Alkyl, das durch Halogen, Hydroxy, Cyan, C₁-C₄-Alkoxy, C₁-C₄-Alkoxycarbonyl, Carboxy, Sulfamoyl, Sulfo oder Sulfato substituiert sein kann; B₁ die direkte Bindung oder ein Rest

m=1, 2, 3, 4, 5 oder 6; und R' ein Rest der Formel

oder

ist, worin R" Wasserstoff oder C₁-C₆-Alkyl ist, alk einen Alkylenrest mit 1 bis 7 Kohlenstoffatomen darstellt, T Wasserstoff, Halogen, Hydroxy, Sulfato, Carboxy, Cyano, C₁-C₄-Alkanoyloxy, C₁-C₄-Alkoxycarbonyl, Carbamoyl oder einen Rest -SO₂-Z bedeutet, V Wasserstoff, gegebenenfalls substituiertes C₁-C₄-Alkyl oder ein Rest der Formel

ist, worin (alk) die zuvor angegebene Bedeutung hat, alk' unabhängig voneinander Polymethylenreste mit 2 bis 6 C-Atomen bedeutet, Z β-Sulfatoethyl, β-Thiosulfatoethyl, β-Phosphatoethyl, β-Acyloxyethyl, β-Halogenethyl oder Vinyl bedeutet, r und t unabhängig voneinander je die Zahl 1, 2, 3, 4, 5 oder 6 bedeuten und s die Zahl 2, 3, 4, 5 oder 6 ist; und der Benzolring in Formel (4) weitere Substituenten enthalten kann; oder worin V₂ ein direkt an den Triazinring gebundener Rest der Formel (4a), (4b), (4c), (4d), (4e), (4f) oder (4g) ist, worin R', T, alk, V, alk', Z, p, q, r, s und t die angegebenen Bedeutungen haben; oder worin V₂ ein Rest der Formel

ist, worin R₁ und Z die oben angegebenen Bedeutungen haben und der Benzolring weitersubstituiert sein kann.Other interesting reactive groups are those of the formula

wherein T _{4 is} fluorine, chlorine or carboxypyridinium and
V _{2 is} a radical of the formula

is wherein R _{1 is} hydrogen or C ₁ -C ₄ alkyl which may be substituted by halogen, hydroxy, cyano, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxycarbonyl, carboxy, sulfamoyl, sulfo or sulfato; B ₁ the direct bond or a residue

m = 1, 2, 3, 4, 5 or 6; and R 'is a radical of the formula

or

where R "is hydrogen or C ₁ -C ₆ alkyl, alk represents an alkylene radical having 1 to 7 carbon atoms, T is hydrogen, halogen, hydroxy, sulfato, carboxy, cyano, C ₁ -C ₄ alkanoyloxy, C ₁ - C ₄ -alkoxycarbonyl, carbamoyl or a radical -SO ₂ -Z, V is hydrogen, optionally substituted C ₁ -C ₄ -alkyl or a radical of the formula

where (alk) has the meaning given above, alk 'independently of one another means polymethylene radicals having 2 to 6 carbon atoms, Z is β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl, β-acyloxyethyl, β-haloethyl or vinyl, r and t each independently represent the number 1, 2, 3, 4, 5 or 6 and s is the number 2, 3, 4, 5 or 6; and the benzene ring in formula (4) may contain further substituents; or in which V _{2 is} a radical of the formula (4a), (4b), (4c), (4d), (4e), (4f) or (4g) bonded directly to the triazine ring, in which R ', T, alk, V, alk ', Z, p, q, r, s and t have the meanings given; or wherein V _{2 is} a radical of the formula

is in which R ₁ and Z have the meanings given above and the benzene ring may be further substituted.

Other possible substituents for the benzene rings of the compounds of the formulas (4) and (4 ') are halogen, such as fluorine, chlorine or bromine, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ -alkoxy, acylamino groups, such as acetylamino or benzoylamino, ureido, hydroxy, carboxy, sulfomethyl and sulfo.

darstellt, ist B₁ durch das Sauerstoffatom an den Benzolring gebunden. Vorzugsweise ist B₁ die direkte Bindung.The radical B ₁ contains 1 to 6, preferably 1 to 4, carbon atoms. Examples of B ₁ are: methylene, ethylene, propylene, butylene, methyleneoxy, ethyleneoxy, propyleneoxy and butyleneoxy. If B _{1 is} a remainder

B ₁ is bonded to the benzene ring through the oxygen atom. B ₁ is preferably the direct bond.

Z is especially the β-chloroethyl radical as β-haloethyl and β-acyloxyethyl in particular the β-acetoxyethyl radical into consideration. The alkylene radical alk is preferred Methylene, ethylene, methylmethylene, propylene or butylene. The substituent T is as Alkanoyloxy radical, in particular acetyloxy, propionyloxy or butyryloxy, and as an alkoxycarbonyl radical especially methoxycarbonyl, ethoxycarbonyl or propyloxycarbonyl. If V is an alkyl radical, this can be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or be tert-butyl. The radical R "is, for example, methyl, ethyl, propyl, isopropyl, butyl, Isobutyl, sec-butyl, tert-butyl, pentyl or hexyl, or preferably hydrogen. The Polymethylene residues alk 'are preferably ethylene, propylene or butylene. The index is t preferably 2, 3 or 4. The indices r and s are independently preferred 2nd

Preferred radicals V ₂ are those of the formula (4), in which B _{1 is} the direct bond and R is a radical of the formula (4a), or in which V _{2 is} a radical of the formula (4b), (4c) or which is bonded directly to the triazine ring (4f), or wherein V _{2 is} a radical of formula (4 ').

und

worin R₁ die oben angegebene Bedeutung hat und X₁ und X₂ Chlor, oder X₁ Chlor und X₂ Fluor sind, mit der Bedingung, dass der Rest [R]_n in Formel (1) mindestens zwei faserreaktiv wirkende Gruppen enthält.Reactive groups of the formulas are also interesting

and

wherein R _{1 has} the meaning given above and X ₁ and X _{2 are} chlorine, or X _{1 is} chlorine and X _{2 is} fluorine, with the condition that the radical [R] _n in formula (1) contains at least two groups which act in a fiber-reactive manner.

As aliphatic reactive groups are those of the formulas -SO ₂ Z. -SO ₂ -NH-Z -NH-CO- (CH ₂ ) ₃ -SO ₂ Z. -CO-NH-CH ₂ CH ₂ -SO ₂ Z. and -NH-CO-Z ₁ wherein Z has the meanings given above, Z _{1 has} the meanings of Z and may additionally be halomethyl or α, β-dihalogenethyl, is preferred.

For Z ₁ , in particular chlorine and bromine are suitable as halogen in the halomethyl, β-haloethyl and α, β-dihaloethyl groups.

Particularly preferred aliphatic reactive groups are those of the formula (5a) and furthermore those of the formulas (5c) and (5d). For these radicals, Z is in particular β-sulfatoethyl or β-haloethyl.

worin Q den Rest C-Y oder insbesondere ein Stickstoffatom bedeutet, Y Chlor, V₃ und W₃, unabhängig voneinander, je Fluor, Chlor, R₂-X₂'-, R₃-X₃'-, Hydroxy, R₂ und R₃, unabhängig voneinander, je ein farbloser aliphatischer, insbesondere ein gegebenenfalls durch Sauerstoffatome unterbrochener C₁-C₈-Alkylrest, ein aromatischer, insbesondere ein gegebenenfalls durch C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen oder Sulfo substituierter Phenylrest, oder heteroaromatischer Rest, X₁', X₂' und X₃', unabhängig voneinander, je -S-, -N(R₄)-, -NH-CO-Phen-NH- oder -NH-CO-Phen-CO-NH-, R₄ Wasserstoff, C₁-C₅-Alkyl, C₅-C₆-Cycloalkyl oder Phenyl, Phen eine unsubstituierte oder substituierte Phenylengruppe, und n die Zahl 1, 2, 3 oder 4 ist, mit der Bedingung, dass der Rest [R]_n in Formel (1) mindestens zwei faserreaktiv wirkende Gruppen enthält. Der Rest A in Formel (1a) hat die unter Formel (1) angegebenen Bedeutung.Compounds of the formula (1a) are preferred

wherein Q represents the radical CY or in particular a nitrogen atom, Y chlorine, V ₃ and W ₃ , independently of one another, each fluorine, chlorine, R ₂ -X ₂ '-, R ₃ -X ₃ ' -, hydroxy, R ₂ and R. ₃ , independently of one another, in each case a colorless aliphatic, in particular a C ₁ -C ₈ -alkyl radical which may be interrupted by oxygen atoms, an aromatic, in particular an where appropriate C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, halogen or sulfo substituted phenyl radical, or heteroaromatic radical, X ₁ ', X ₂ ' and X ₃ ', independently of one another, each -S-, -N (R ₄ ) -, -NH-CO-Phen-NH- or -NH-CO- Phen-CO-NH-, R _{4 is} hydrogen, C ₁ -C ₅ alkyl, C ₅ -C ₆ cycloalkyl or phenyl, phen is an unsubstituted or substituted phenylene group, and n is the number 1, 2, 3 or 4, with the condition that the radical [R] _n in formula (1) contains at least two fiber-reactive groups. The radical A in formula (1a) has the meaning given under formula (1).

worin X₄ -NR₅- oder -S- ist, A₁ einen aliphatischer Rest mit 1 bis 18 C-Atomen, der frei von Sulfogruppen ist, bedeutet, und R₅ Wasserstoff oder C₁-C₄-Alkyl ist oder die Bedeutung von A₁ unabhängig von A₁ hat.Preferred compounds of the formula (1a), in which A is an aliphatic radical, correspond, for example, to the formula

wherein X _{4 is} -NR ₅ - or -S-, A _{1 is} an aliphatic radical having 1 to 18 carbon atoms and is free of sulfo groups, and R _{5 is} hydrogen or C ₁ -C ₄ -alkyl or the meaning of A ₁ independently of A ₁ .

A ₁ as an aliphatic radical having 1 to 18 carbon atoms is, for example, a C ₁ -C ₁₈ alkyl radical, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl , Isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, heptadecyl or octadecyl, where the alkyl radical can be substituted, for example by hydroxy or alkoxy, and where the alkyl chain can be interrupted one or more times , such as by oxygen, sulfur, amino, carbonamido, aminocarbonyl, ureido, sulfonamido, aminosulfonyl, carboxy, and carbonyloxy.
R ₅ as C ₁ -C ₄ alkyl is methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl or iso-butyl.

A ₁ is preferably a linear or branched C ₁ -C ₁₈ alkyl, in particular a C ₁ -C ₈ alkyl, which is substituted by -OR ₆ , where the alkyl chain can be interrupted by one or more radicals -Q-, or a linear or branched C ₁ -C ₁₈ alkyl, in particular a C ₁ -C ₈ alkyl, the alkyl chain being interrupted by one or more radicals -Q ₁ -, in which -Q ₁ - -O-, -S-, -NR ₇ -, -CONR ₇ -, -NR ₇ CO-, -NR ₇ -CO-NR ₇ -, -SO ₂ NR ₇ -, -NR ₇ SO ₂ -, -COO-, -OCO-, -NR _{7 is} COO- or -OCOO-, R _{6 is} hydrogen or C ₁ -C ₄ alkyl and R _{7 is} hydrogen or C ₁ -C ₄ alkyl.

C ₁ -C ₁₈ alkyl or C ₁ -C ₈ alkyl as A ₁ can optionally be substituted one or more times, for example by carboxy, carbonamido or sulfonamido.

-NR ₅ - is preferred as X ₄ .

As R ₅ , methyl and especially hydrogen are preferred.

R ₆ as C ₁ -C ₄ alkyl is methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl or iso-butyl.

R ₇ as C ₁ -C ₄ alkyl are methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, or iso-butyl.

As R ₆ , methyl and especially hydrogen are preferred.

Hydrogen is preferred as R ₇ .

As -Q ₁ - -O-, -S- and -NH- is preferred.

Of particular interest for the process according to the invention are the compounds of the formula (6) in which -X ₄ -A _{1 represents the} following radicals: -NHCH ₂ CH ₂ SCH ₂ CH ₂ OH, -NHCH ₂ CH ₂ CONHCH ₂ CH ₂ OH, -NHCH ₂ CH ₂ CH ₂ CONHCH ₂ CH ₂ OH, -NHCH ₂ CONHCH ₂ CH ₂ CH ₂ OH, -NHCH ₂ CONHCH ₂ CH ₂ CH ₂ OH, -NHCH ₂ CON (CH ₂ CH ₂ OH) ₂ , -NHCH ₂ CH ₂ NHCOCH ₂ CH ₂ CH ₂ OH, -NHCH ₂ CH ₂ CH ₂ NHCOCH ₂ CH ₂ CH ₂ OH, -NHCH ₂ CH ₂ CH ₂ CONHCH ₂ CH ₂ CH ₂ OH.

The compounds of the formulas are particularly important for the process according to the invention

The compounds of. Are particularly important for the process according to the invention Formulas (6f) and (6g).

mit äquimolarer Menge einer Verbindung der Formel HX₄-A₁ worin X₄ und A₁ die unter der Formel (6) angegebene Bedeutung hat, umsetzt und das entstehende Endprodukt der Formel (6) isoliert.The compounds of the formula (6) used in the process according to the invention are prepared by methods known per se, for example by using a trichlorotriazine of the formula

with an equimolar amount of a compound of the formula HX ₄ -A ₁ wherein X ₄ and A _{1 has} the meaning given under the formula (6), and the resulting end product of the formula (6) is isolated.

The new compounds of the formulas (6a) to (6n) are prepared in an analogous manner by using a trichlorotriazine of the formula (7), for example with an amine of the formula NH ₂ -CH ₂ CH ₂ OCH ₂ CH ₂ OH NH ₂ -CH ₂ CH (OH) CH ₂ OH NH ₂ -CH ₂ CH ₂ CON (CH ₂ CH ₂ OH) ₂ NH ₂ -CH ₂ CH ₂ CH ₂ CONHCH ₂ CH ₂ CH ₂ OH NH ₂ -CH ₂ CH ₂ NHCONHCH ₂ CH ₂ OH NH ₂ -CH ₂ CH ₂ CH ₂ SO ₂ NHCH ₂ CH ₂ CH ₂ OH NH ₂ -CH ₂ CH ₂ NHSO ₂ CH ₂ CH ₂ CH ₂ OH or NH ₂ -CH ₂ CH ₂ NHSO ₂ CH ₂ CH ₂ CH ₂ CH ₂ OH implements.

The amines of the formulas (8a) to (8h) are partly known or can according to known Methods are made.

The compounds of the formula (1) very particularly preferably comprise at least one reactive group of the formulas (2), (2 '), (3), (4i) to (4l), (5a) to (5e) and (6), where for A, A ₁ R ₁ , T ₁ , T ₂ , T ₃ , T ₄ , V ₁ , V ₂ , B, X ₁ , X ₂ , X ₄ , Z and Z ₁ the meanings and preferences given above apply. Of particular interest are the compounds of the formula (1) which contain at least one reactive group of the formulas (2), (2 '), (3), (4i) to (4l) and (5a) to (5e), where for R ₁ , T ₁ , T ₂ , T ₃ , T ₄ , V ₁ , V ₂ , B, X ₁ , X ₂ , Z and Z ₁ the meanings and preferences given above apply.

worin T₅ Fluor oder insbesondere Chlor, und R₁ Wasserstoff, Methyl oder Aethyl ist.Compounds of the formula (1b) are also very particularly preferred

wherein T _{5 is} fluorine or especially chlorine, and R _{1 is} hydrogen, methyl or ethyl.

worin T₅ und R₁ die unter Formel (1b) angegebenen Bedeutungen haben. Eine besonders bevorzugte Ausführungsform des erfindungsgemässen Verfahrens ist dadurch gekennzeichnet, dass man als Verbindung der Formel (1c) eine Verbindung einsetzt, worin T₅ Chlor und R₁ Wasserstoff ist. Insbesondere sind die beiden -NR₁- Gruppen in m- oder p-Stellung an den Benzolkern gebunden.Further preferred compounds in the process according to the invention correspond to the formula (1c)

wherein T ₅ and R _{1 have} the meanings given under formula (1b). A particularly preferred embodiment of the process according to the invention is characterized in that a compound of the formula (1c) is used in which T _{5 is} chlorine and R _{1 is} hydrogen. In particular, the two -NR ₁ - groups are bonded to the benzene nucleus in the m- or p-position.

verwendet, worin A₂ ein gegebenenfalls durch Sulfo substituierter Benzolrest, R₁₀ ein Rest der Formel (2), (2') oder (3) ist, oder worin R₁₀ der Rest -SO₂-Z ist, wobei Z die angegebenen Bedeutung hat, und n die Zahl 1, 2, 3 oder 4 ist, mit der Bedingung, dass der Rest [R₁₀]_n mindestens zwei faserreaktiv wirkende Gruppen enthält.Compounds of the formula are preferably used in the process according to the invention

used, in which A _{2 is} a benzene radical optionally substituted by sulfo, R _{10 is} a radical of the formula (2), (2 ') or (3), or in which R _{10 is} the radical -SO ₂ -Z, where Z has the meaning given has, and n is the number 1, 2, 3 or 4, with the condition that the radical [R ₁₀ ] _{n contains} at least two fiber-reactive groups.

worin R₁ und Z die unter Formel (4) bzw. (4h) angegebenen Bedeutungen haben, und Hal Halogen, vorzugsweise Chlor ist. In Formel (1e) ist Hal insbesondere Chlor, R₁ bedeutet Wasserstoff und -SO₂-Z ist in m- oder p-Stellung zur Aminogruppe gebunden und bedeutet den β-Sulfatoäthylsulfonyl-Rest.Further interesting compounds which can be used in the process according to the invention in which A is a heteroaromatic radical correspond to the formula

wherein R ₁ and Z have the meanings given under formula (4) or (4h), and Hal is halogen, preferably chlorine. In formula (1e), Hal is especially chlorine, R ₁ is hydrogen and -SO ₂ -Z is bonded in the m- or p-position to the amino group and means the β-sulfatoethylsulfonyl radical.

The method according to the invention is suitable for achieving high finishing effects, especially to improve wrinkle-free, easy-care, dimensional stability and freedom from shrinkage of fiber materials which are at least 20% by weight natural or contain regenerated cellulose fibers. If the content is less than 20% by weight the effect of the equipment is too small to take advantage of the process allow. The fiber materials can be cellulose fibers in a mixture with other fibers, especially made of polyester or polyamide, or they can be made exclusively of Cellulose fibers exist. Both cellulose fibers come as cellulose fibers Cotton as well as fibers from regenerated cellulose such as viscose (cellulose) in Question. Furthermore, modal fibers such as e.g. Polynosic fibers and Cupro fibers called. In no lyocell fiber is used in the process according to the invention.

Suitable fiber materials which are treated by the process according to the invention, especially aftertreated, are mainly textile fabrics or Knitwear. However, yarns whose tensile strength with the Application of the inventive method can be increased. An important and preferred application is the application of the method according to the invention Terrycloth goods. When it comes to quality assessment of terry goods, there is a reduction in lint important, the abrasion of fibers, especially after application in Tumble dryers. In the case of viscose fibers, the process according to the invention can be used Change in fiber surface, e.g. through the dyeing process, prevented or at least be reduced.

The process according to the invention has a number of advantages: the fiber materials, to which the above products have been applied can be found at 80 to 130 ° C to achieve good easy care effects. Temperatures up to 150 ° C and more, as known in the case of use formaldehyde-free crosslinkers are not required. In which The method according to the invention can be used to apply a crosslinker Carry out alkaline liquor using the wet dwell process. This means that after Application and a squeezing process, e.g. B. as part of a padding, the Fiber material, e.g. in the form of a textile fabric, protected against drying out stored at room temperature and after a certain dwell time of e.g. B. 20 hours with Water is rinsed and dried. During wet storage here networking takes place at least partially.

Dry pilling, in particular, can also be carried out using the method according to the invention important for upholstery fabrics.

The finished and dried fiber materials have after application of the Crosslinkers in the wet crosslinking process often have a higher degree of whiteness than in the case of Implementation of known methods with heat fixation. Protection against decay of the finished fiber materials is often much better than known ones Method. The method according to the invention can also be advantageously used combine with other processes, e.g. B. with a reactive dye in alkaline Medium or other processes to be carried out in alkaline medium. The Combination of the method according to the invention together with the dyeing and fixing of reactive dyes is of great advantage. The method according to the invention offers also has the advantage of less impairment of light fastness Substantive and reactive stains than is the case with known methods.

In the method according to the invention, preference is given to the fiber materials Textile fabrics or knitted fabrics are applied, at least one product of formula (1). It However, mixtures of several products covered by formula (1) can also be used be applied. You can also use one or more products at the same time Formula (1) other desired products can be applied to the fiber materials, such as e.g. B. agents for water-repellent, oil-repellent or flame-retardant equipment.

The application of such product mixtures can be done using a single treatment liquor, e.g. B. done by padding, with the liquor absorption as a rule at least 50%, preferably 60 to 80%, if these product mixtures are homogeneous mixtures represent. It is particularly advantageous for economic and ecological reasons that to carry out the method according to the invention such that a product of the formula (1) or a Product mixture in the form of an alkaline aqueous solution or dispersion of this Product or these products applied to the fiber materials and the fiber materials then be dried. Drying is preferably carried out in a temperature range of 80 to 130 ° C, e.g. by means of hot air; can if necessary however, other temperatures can also be used, e.g. up to 140 ° C. Next to the mentioned addition of other products to the treatment fleet comes in a preferred Embodiment of the method according to the invention with a reactive dyeing in a single operation in question. In this case, the treatment fleet is excluded one or more products of the formula (1) and optionally further products added a reactive dye. This preferred embodiment of the The method according to the invention is particularly useful for alkaline treatment liquors Question whose pH value at 20 ° C is preferably in a range from 7 to 13.

With regard to the stability of the solutions or dispersions, it is normally advantageous if the solutions or dispersions to be used for the process according to the invention, preferably aqueous solutions or dispersions, have a pH during storage which is not below 7.0 and not above 10 , 0, in some cases does not exceed 9.0. Adjusting or stabilizing the desired pH, e.g. B. in the range of 7 to 10, z. B. by Na ₂ CO ₃ , K ₂ CO ₃ , KHCO ₃ or NaHCO ₃ . The amount of alkali, for example NaOH or KOH, which is required for the treatment of the fiber materials (crosslinking reaction with cellulose) and / or for the reactive dyeing should only be added shortly before use.

The metal salts present in the alkaline aqueous medium, which are classified under the formula (1) fall and are suitable for the inventive method, salts of be monovalent or multivalent metal cations. As monovalent metals or Metal cations, sodium and potassium are particularly preferred. The sodium or Potassium salts of the water-soluble compounds of formula (1) are particularly preferred. A preferred embodiment of the method according to the invention thus consists in to use water-soluble products of the formula (1); these are water soluble products especially Na or K salts, which are used in aqueous equipment fleets. If only these Na ― or K salts are used, this is preferably the case about alkaline aqueous solutions. In the presence of other additives that are insoluble in water, but are water dispersible, the inventive method is preferably under Performed using aqueous dispersions. The for the dispersion of such Additional dispersing agents required in water are known to the person skilled in the art known. The aqueous dispersions, which in addition to at least one compound of Formula (1) contain other products, preferably have alkaline pH values in the Range from pH 7 to 13.

The treatment of the fiber materials by the method according to the invention can be carried out according to generally known methods. An application of solutions is well suited or dispersions which contain at least one product of the formula (1), by means of Padding. This treatment is conveniently carried out with an aqueous liquor carried out, which 1 to 12 wt .-%, based on the entire fleet, on one or contains several products of formula (1). The fiber material normally contains the subsequent squeezing off about 1 to 6% by weight of product of the formula (1), based on the total weight of the finished fiber material. The subsequent one Drying can be done in known devices, e.g. using hot air and will preferably carried out in a temperature range of 80 to 130 ° C. During the There may be a temperature gradient during the drying process. Simultaneously with the drying there is a reaction (crosslinking) of the product of formula (1) with cellulose. This The reaction is achieved by the presence of an alkaline pH. In addition to drying with hot air, a treatment with saturated steam at temperatures such. B. between 98 and 105 ° C or the combination of the treatment with hot air and the treatment with Saturated steam can be considered.

The crosslinking with the OH groups of the cellulose is thus achieved by the presence alkaline compounds. Even if for the inventive method already alkaline compounds of formula (1), e.g. B. metal salts of water-soluble Compounds of formula (1) are used, the addition of other is recommended alkaline connections to the treatment liquors. In particular sodium hydroxide and Potassium hydroxide is well suited for this. Instead of adding this Alkaline compounds to the treatment liquors can be the inventive Carry out the procedure in two stages. This is done, for example, by looking in the first stage, a first aqueous treatment liquor is applied to the fiber materials which contains a product of formula (1) and has a pH at which this liquor has high stability, e.g. a pH of 7 to 10 This first aqueous treatment liquor may contain other products such as reactive dyes. Applying this first Treatment liquor can be done by padding. After squeezing it will Dried fiber material. In a second stage, a second aqueous treatment liquor applied which the amount required for crosslinking with cellulose contains alkaline compound. This alkaline compound is preferably sodium hydroxide or potassium hydroxide. After the second liquor has been applied, drying is carried out, for example at 80 up to 130 ° C, where the crosslinking takes place. The second treatment fleet can be, for example aqueous sodium hydroxide or potassium hydroxide solution of relatively high concentration, e.g. between 30 and 60% by weight.

At the applied temperatures of e.g. 80 to 130 ° C, alkaline takes place in the presence Connections a crosslinking (condensation) with cellulose instead. For this reason the treatment of the fiber materials with treatment liquid preferably in one pH in the range of 7 to 13 (measured at 20 ° C) carried out.

The fiber materials treated by the process according to the invention stand out due to good finishing effects, especially easy care, dimensional stability and Freedom from shrinking.

The compounds used in the process according to the invention can be apply in different ways to the fiber material and fix it on the fiber, especially in the form of aqueous solutions, preferably using the exhaust method. After fixing, the treated fiber materials are cold and hot Water, optionally with the addition of a dispersing and the diffusion of non-fixed portions of the agent thoroughly rinsed.

The compounds of formula (1) containing a water solubilizing group, such as. B. a sulfo or sulfato group, are either in the form of their free acid or preferably as their salts such as. B. the alkali, alkaline earth or ammonium salts or as Salts of an organic amine. Examples include sodium, potassium, lithium or Ammonium salts or the salt of triethanolamine called.

The compounds of formula (1) are known or can be used in analogy to known ones Connections are made. So the compounds of formula (1) z. B. Reactive dye precursors as they are or can be known from WO 96/00399 can be produced analogously.

For the process according to the invention, the amounts in which the compounds of Formula (1) in the treatment baths, in particular in the dye baths together with Dyes, preferably reactive dyes, are used in a wide range fluctuate, generally there are quantities from 0.01 to 20 percent by weight, in particular 0.1 to 15 percent by weight, based on the fiber material, as advantageous proven.

The process according to the invention is preferably carried out before or during dyeing, but especially applied after the production of the cellulose fiber.

Treatment according to the exhaust method is preferred for the method according to the invention. It is usually carried out in an aqueous medium with a liquor ratio of for example 1: 2 to 1:60, in particular 1: 5 to 1:20. This is where the treatment takes place for example at a temperature of 20 to 100 ° C, in particular 40 to 90 ° C, and preferably 55 to 80 ° C.

A particularly preferred embodiment of the method according to the invention is characterized in that the crosslinking of the cellulose-containing fiber materials along with the coloring.

The compounds of formula (1) used are characterized by high reactivity, good Fixing ability and a very good building ability. You can therefore after Pull-out dyeing processes can be used at low dyeing temperatures. The degrees of fixation are high and the unfixed portions can be easily washed out, the Difference between degree of extension and degree of fixation remarkably small, i.e. the soap loss is very low.

The following examples illustrate the invention. The temperatures are given in degrees Celsius. Parts mean parts by weight and percentages Percentages by weight, unless stated otherwise. Parts by weight are due Parts by volume in the ratio of kilograms to liters.

Example 1 : 10 g of viscose fabric is clamped at 50 ° C. in a pull-out dyeing machine with 100 ml of a liquor containing 8 g of Glauber's salt and 1 g of the colorless compound of the formula (100) according to Table 1. After 10 minutes of agitation at 50 ° C, 2 g of anhydrous sodium carbonate are added in two portions. The viscose fabric is kept in motion for a further 20 minutes. The liquor is heated to 60 ° C. and 0.2 ml of 30% sodium hydroxide solution are added. After 20 minutes, the bath is drained and the viscose fabric is rinsed cold, washed to the boil and rinsed again cold, and then dried. A viscose fabric with higher dimensional stability and higher wet abrasion resistance is obtained.

Example 2: 10 g of viscose fabric is at 50 ° C. in a pull-out dyeing apparatus with 100 ml of a liquor containing 8 g of Glauber's salt, 1 g of the colorless compound of the formula (100) according to Table 1 and 0.1 g of the dye of the formula (200) according to table 2, clamped. After 20 minutes of agitation at 50 ° C, 2 g of anhydrous sodium carbonate are added in two portions. The viscose fabric is kept in motion for a further 10 minutes. The liquor is heated to 60 ° C. and 0.2 ml of 30% sodium hydroxide solution are added. After 20 minutes, the bath is drained and the viscose fabric is rinsed cold, washed to the boil and rinsed again cold, and then dried. A navy-blue colored viscose fabric with higher dimensional stability and higher wet abrasion resistance is obtained.

When in Example 1 the compound of formula (100) is replaced by another of the ones in Table 1 specified compounds replaced, you also get a viscose fabric with the specified advantageous properties.

If in Example 2 the dye of formula (200) is replaced by the dye of formula (201) replaced, you get a red-colored viscose fabric with the specified advantageous properties.

If the compound of formula (100) in Example 2 is replaced by another of the compounds shown in Table 1, a viscose fabric with the advantageous properties indicated is also obtained.

Example 3:

18.5 g of cyanuric chloride are introduced into a mixture consisting of 100 g of finely ground ice and 50 ml of water, which contains 0.6 g of a commercially available surfactant, and wetted for 15 minutes. Then, with thorough stirring, 6.1 g of ethanolamine are added dropwise in such a way that the pH of the mixture is kept at about 8. After the addition of ethanolamine has ended, about 8 g of a 50% strength aqueous solution of NaOH are then added dropwise in such a way that the pH can be maintained at 8. The resulting fine suspension is filtered off and dried. 15.5 g of a white powdery compound of the formula are obtained

Examples 4:

If the procedure is as described in Example 3, but instead of 6.1 g of ethanolamine, the equivalent amount of one of the amines given in Table 3 is obtained, the compounds listed in Table 3 are obtained.

Example 5: 10 g of viscose fabric is clamped at 50 ° C. in a pull-out dyeing machine with 100 ml of a liquor containing 8 g of Glauber's salt, 1 g of the first compound in Table 3 and 0.1 g of the dye of the formula (200) according to Table 2 . After 20 minutes of agitation at 50 ° C, 2 g of anhydrous sodium carbonate are added in two portions. The viscose fabric is kept in motion for a further 10 minutes. The liquor is heated to 60 ° C. and 0.2 ml of 30% sodium hydroxide solution are added. After 20 minutes, the bath is drained and the viscose fabric is rinsed cold, washed to the boil and rinsed again cold, and then dried. A navy-blue colored viscose fabric with higher dimensional stability and higher wet abrasion resistance is obtained.

Example 6: An aqueous suspension containing 85 g per liter of the colorless compound of the formula (100) is mixed in equal parts by volume with an aqueous alkaline solution containing 140 ml of 38 ° Bé water glass and 20 g of sodium hydroxide per liter and then immediately after a cotton fabric is lined up, the liquor absorption being 70 to 75%. The fabric treated in this way is then immediately treated with hot air at 110 ° C. for 5 minutes, the alkali is removed by rinsing with cold and warm water, and the fabric is then dried again. A fabric with significantly improved creasing properties is obtained.

EXAMPLE 7 An aqueous suspension containing 85 g per liter of the colorless compound of the formula (100) is mixed in equal parts by volume with an aqueous alkaline solution containing 60 g of calcined sodium carbonate per liter and then immediately blotted onto a cotton fabric. the fleet absorption is 70 to 75%. The tissue treated in this way is then immediately dried with hot air at 130 ° C. for 2 minutes, treated with saturated steam at 102 ° C. for 8 minutes, the alkali is removed by rinsing with cold and warm water, and the tissue is then dried again. A fabric with significantly improved creasing properties is obtained.

Claims (15)

Process for crosslinking cellulosic fiber materials, characterized in that at least one product of the general formula (1) is applied to the cellulosic fiber materials, the cellulose fibers consisting of natural or regenerated cellulose,

wherein A is a colorless aliphatic, aromatic or heteroaromatic radical, R is a fiber-reactive radical, and n is the number 1, 2, 3 or 4, with the condition that the radical [R] _{n contains} at least two fiber-reactive groups. A method according to claim 1, characterized in that fiber materials are used are, which consist of 20 to 100 wt .-% of cellulose fibers. Method according to one of claims 1 and 2, characterized in that one uses a compound of formula (1), wherein R is a radical of the formula

where T _{1 is} fluorine, chlorine or carboxypyridinium and V _{1 is} fluorine, chlorine, -NH ₂ , a C ₁ -C ₆ alkylamino, N, N-Di-C ₁ -C ₆ alkylamino, cyclohexylamino, N, N-dicyclohexylamino, benzylamino, phenethylamino, phenylamino, naphthylamino, NC ₁ -C ₆ alkyl-N-cyclohexylamino or NC ₁ -C ₆ alkyl-N-phenylamino radical, or morpholino, piperidino, piperazino , Hydrazino or semicarbazido, or an amino group substituted by a furan, thiophene, pyrazole, pyridine, pyrimidine, quinoline, benzimidazole, benzothiazole or benzoxazole residue. Method according to one of claims 1 and 2, characterized in that one uses a compound of formula (1), wherein R is a radical of the formula

is in which T ₂ and T _{3 are} independently fluorine, chlorine or carboxypyridinium and B as a bridge member is a radical of the formula

wherein R ₁ 'and R ₁ "are independently hydrogen or optionally substituted by halogen, hydroxy, cyano, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxycarbonyl, carboxyl, sulfamoyl, sulfo or sulfato, C ₁ -C Are _4- alkyl and X is a C ₂ -C ₆ alkylene or C ₅ -C ₉ cycloalkylene radical which is optionally substituted by hydroxy, sulfo, sulfato, C ₁ -C ₄ alkoxy, carboxy or halogen or a radical which is optionally substituted by C ₁ - C ₄ alkyl, C ₁ -C ₄ alkoxy, sulfo, halogen or carboxy substituted phenylene, biphenylene or naphthylene. A method according to claim 1, characterized in that a compound of formula (1a)

used, wherein A has the meaning given in claim 1, Q is CY or a nitrogen atom, Y is chlorine, V ₃ and W ₃ , independently of one another, each fluorine, chlorine, R ₂ -X ₂ '-, R ₃ -X ₃ '-, Hydroxy, R ₂ and R ₃ , independently of one another, each have a colorless aliphatic, in particular a C ₁ -C ₈ -alkyl radical which is optionally interrupted by oxygen atoms, aromatic, in particular an where appropriate C ₁ -C ₄ -alkyl, C ₁ -C ₄ alkoxy, halogen or sulfo substituted phenyl radical, or heteroaromatic radical, X ₁ ', X ₂ ' and X ₃ ', independently of one another, each -S-, -N (R ₄ ) -, -NH-CO-Phen -NH- or -NH-CO-Phen-CO-NH-, R _{4 is} hydrogen, C ₁ -C ₅ alkyl, C ₅ -C ₆ cycloalkyl or phenyl, phen is an unsubstituted or substituted phenylene group, and n is the number 1 , 2, 3 or 4, with the condition that the compound of formula (1a) contains at least two fiber-reactive groups. A method according to claim 5, characterized in that compounds of the formula

used, wherein X _{4 is} -NR ₅ - or -S-, A _{1 is} an aliphatic radical having 1 to 18 carbon atoms, which is free of sulfo groups, and R _{5 is} hydrogen or C ₁ -C ₄ alkyl or has the meaning of A ₁ independently of A ₁ . Process according to one of claims 1 and 2, characterized in that a compound of the formula is used as the compound of the formula (1)

wherein T _{5 is} fluorine or especially chlorine, and R _{1 is} hydrogen, methyl or ethyl. Process according to Claim 1, characterized in that compounds of the formula (1c)

used, wherein T ₅ and R _{1 have} the meanings given in claim 7. Method according to one of claims 1 to 5, characterized in that uses a compound of formula (1), wherein A is an aromatic radical, especially a Is benzene residue. A method according to claim 9, characterized in that a connection of formula (1) used, wherein A is a by at least one water-solubilizing Group, in particular at least one sulfo group is substituted. Method according to one of claims 1 and 2, characterized in that one uses a compound of formula (1), wherein R is a radical of the formula

wherein T _{4 is} fluorine, chlorine or carboxypyridinium and
V _{2 is} a radical of the formula

is wherein R _{1 is} hydrogen or C ₁ -C ₄ alkyl which may be substituted by halogen, hydroxy, cyano, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxycarbonyl, carboxy, sulfamoyl, sulfo or sulfato; B ₁ the direct bond or a residue

m = 1, 2, 3, 4, 5 or 6; and R 'is a radical of the formula

or

where R "is hydrogen or C ₁ -C ₆ alkyl, alk represents an alkylene radical having 1 to 7 carbon atoms, T is hydrogen, halogen, hydroxy, sulfato, carboxy, cyano, C ₁ -C ₄ alkanoyloxy, C ₁ - C ₄ -alkoxycarbonyl, carbamoyl or a radical -SO ₂ -Z, V is hydrogen, optionally substituted C ₁ -C ₄ -alkyl or a radical of the formula

in which (alk) has the meaning given above, alk 'independently of one another means polymethylene radicals having 2 to 6 C atoms, Z is β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl, β-acyloxyethyl, β-haloethyl or vinyl, r and t each independently represent the number 1, 2, 3, 4, 5 or 6 and s is the number 2, 3, 4, 5 or 6; and the benzene ring in formula (4) may contain further substituents; or in which V _{2 is} a radical of the formula (4a), (4b), (4c), (4d), (4e), (4f) or (4g) bonded directly to the triazine ring, in which R ', T, alk, V, alk ', Z, p, q, r, s and t have the meanings given; or wherein V _{2 is} a radical of the formula

is in which R ₁ and Z have the meanings given above and the benzene ring may be further substituted. A method according to claim 1, characterized in that compounds of the formula

used, wherein A _{1 is} a benzene radical optionally substituted by sulfo, R _{10 is} a radical of the formula (2), (2 ') or (3), or wherein R _{10 is} the radical -SO ₂ -Z, where Z has the meaning given and n is the number 1, 2, 3 or 4. Method according to one of claims 1 to 12, characterized in that the compound of formula (1) is applied to the fiber together with reactive dyes. The cellulose-containing fiber material treated according to claim 1. Aqueous solution or dispersion containing at least one compound of the formula (1) according to claim 1.