Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
  • D06M13/35—Heterocyclic compounds
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
  • D06M13/35—Heterocyclic compounds
  • D06M13/352—Heterocyclic compounds having five-membered heterocyclic rings
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
  • D06M13/35—Heterocyclic compounds
  • D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
  • D06M13/35—Heterocyclic compounds
  • D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
  • D06M13/358—Triazines
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
  • D06P1/642—Compounds containing nitrogen
  • D06P1/6426—Heterocyclic compounds
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
  • D06M2101/02—Natural fibres, other than mineral fibres
  • D06M2101/04—Vegetal fibres
  • D06M2101/06—Vegetal fibres cellulosic
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/58—Material containing hydroxyl groups
  • D06P3/60—Natural or regenerated cellulose
  • D06P3/66—Natural or regenerated cellulose using reactive dyes

Definitions

• the present invention relates to a method for crosslinking cellulosic fiber materials.
• high finishing effects e.g. B. in the area of crease resistance, easy care, dimensional stability and No shrinkage achieved.
• 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.
• N-methylol groups 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 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.
• 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.
• 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.
• 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.
• the mentioned heterocyclic fiber-reactive radicals via a direct bond or via a Other fiber-reactive residues, e.g. the listed residues.
• 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.
• an unsaturated aliphatic group such as e.g. the Vinyl, halovinyl, styryl, acrylic or methacrylic group, or at least one polymerizable Show ring system.
• the halogen atoms containing unsaturated groups such as halogenomaleic acid and halogenopropiolic acid residues, the ⁇ - or ⁇ -bromo or chloroacrylic groups, halogenated vinyl cetyl groups, Halogencrotonyl or halogen methacrylic groups.
• halogen-containing unsaturated groups e.g. the dichloro or dibromopropionyl group.
• 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 ⁇ -bromoacrylic group contain.
• compounds containing a polymerizable double bond are preferably those which contain at least one acryloyl, methacryloyl, ⁇ -bromocryloyl, contain ⁇ -chloroacryloyl, vinyl or vinylsulfonyl radical; most notably preferably those which have at least one acryloyl, ⁇ -bromoacryloyl or vinylsulfonyl radical contain.
• atoms or groups that can be removed are, for example, ammonium including hydrazinium, sulfato, thiosulfato, phosphato, acetoxy, propionoxy or Carboxypyridinium.
• 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.
• 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.
• 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
• a heterocyclic radical for example a piperazine radical.
• 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 ) -;
• 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.
• 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.
• 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.
• 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,
• 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.
• 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.
• 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.
• 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 benzoy
• 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.
• 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.
• 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.
• the radical B 1 contains 1 to 6, preferably 1 to 4, carbon atoms.
• 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 ⁇ -chloroethyl radical as ⁇ -haloethyl and ⁇ -acyloxyethyl in particular the ⁇ -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.
• 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
• 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 ').
• 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.
• 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 ⁇ , ⁇ -dihalogenethyl, is preferred.
• Z 1 in particular chlorine and bromine are suitable as halogen in the halomethyl, ⁇ -haloethyl and ⁇ , ⁇ -dihaloethyl groups.
• Particularly preferred aliphatic reactive groups are those of the formula (5a) and furthermore those of the formulas (5c) and (5d).
• Z is in particular ⁇ -sulfatoethyl or ⁇ -haloethyl.
• 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.
• A is an aliphatic radical
• a 1 is an aliphatic radical having 1 to 18 carbon atoms and is free of sulfo groups
• 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.
• 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.
• R 6 methyl and especially hydrogen are preferred.
• Hydrogen is preferred as R 7 .
• -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 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 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.
• T 5 is fluorine or especially chlorine
• R 1 is hydrogen, methyl or ethyl
• 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.
• the two -NR 1 - groups are bonded to the benzene nucleus in the m- or p-position.
• 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.
• A is a heteroaromatic radical
• R 1 and Z have the meanings given under formula (4) or (4h)
• Hal is halogen, preferably chlorine.
• 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 ⁇ -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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• the inventive method is preferably under Performed using aqueous dispersions.
• 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.
• reaction Simultaneously with the drying there is a reaction (crosslinking) of the product of formula (1) with cellulose.
• This reaction is achieved by the presence of an alkaline pH.
• 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.
• alkaline compounds of formula (1) e.g. B. metal salts of water-soluble Compounds of formula (1)
• the addition of other is recommended alkaline connections to the treatment liquors.
• sodium hydroxide and Potassium hydroxide is well suited for this.
• this Alkaline compounds 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• Example 1 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.
• Example 2 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.
• Example 2 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.
• cyanuric chloride 18.5 g 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
• 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.

Landscapes

• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Coloring (AREA)

Applications Claiming Priority (3)

Publications (2)

Family

ID=4208125

Family Applications (1)

Country Status (6)

Cited By (6)

Families Citing this family (15)

Family Cites Families (19)

• 1998
  • 1998-05-19 US US09/081,429 patent/US6036731A/en not_active Expired - Fee Related
  • 1998-05-26 EP EP98810490A patent/EP0882836A3/fr not_active Withdrawn
  • 1998-05-28 JP JP10146807A patent/JPH1112928A/ja active Pending
  • 1998-06-02 BR BR9801749-7A patent/BR9801749A/pt not_active IP Right Cessation
  • 1998-06-03 CN CN98117262A patent/CN1210918A/zh active Pending
  • 1998-06-03 TR TR1998/01002A patent/TR199801002A2/xx unknown

Also Published As

Similar Documents

Legal Events