EP0879916B1 - Process for the treatment of fibrous materials made from natural or synthetic polyamide - Google Patents

Process for the treatment of fibrous materials made from natural or synthetic polyamide Download PDF

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Publication number
EP0879916B1
EP0879916B1 EP98810430A EP98810430A EP0879916B1 EP 0879916 B1 EP0879916 B1 EP 0879916B1 EP 98810430 A EP98810430 A EP 98810430A EP 98810430 A EP98810430 A EP 98810430A EP 0879916 B1 EP0879916 B1 EP 0879916B1
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EP
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Prior art keywords
alkyl
hydrogen
radical
methyl
independently
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EP98810430A
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German (de)
French (fr)
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EP0879916A3 (en
EP0879916A2 (en
Inventor
Philippe Ouziel
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BASF Schweiz AG
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Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
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Classifications

    • 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
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02—After-treatment
    • D06P5/04—After-treatment with organic compounds
    • D06P5/06—After-treatment with organic compounds containing nitrogen
    • 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
    • D06P1/52—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 synthetic macromolecular substances
    • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D06P1/5214—Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
    • D06P1/5242—Polymers of unsaturated N-containing compounds
    • 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
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02—After-treatment
    • D06P5/04—After-treatment with organic compounds
    • D06P5/08—After-treatment with organic compounds macromolecular
    • 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
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/916—Natural fiber dyeing
    • Y10S8/917—Wool or silk
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/92—Synthetic fiber dyeing
    • Y10S8/924—Polyamide fiber

Definitions

  • the present invention relates to a method for the treatment of natural or synthetic polyamide fiber materials to improve the fastness properties.
  • R 1 , R 2 , R 3 , R 4 and R 6 as C 1 -C 6 alkylsulfonyl are independently, for example, methylsulfonyl, ethylsulfonyl, n- or iso-propylsulfonyl, n-, iso- or sec-butylsulfonyl, straight-chain pentylsulfonyl or hexylsulfonyl, preferably methylsulfonyl or ethylsulfonyl and especially methylsulfonyl.
  • R 1 , R 2 , R 3 , R 4 and R 6 as phenyl are unsubstituted or, for example, by halogen, such as chlorine or bromine; hydroxy; sulfamoyl; carbamoyl; sulfo; carboxy; C 1 -C 4 alkyl, such as methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert-butyl, preferably methyl or ethyl; C 1 -C 4 alkoxy, such as methoxy, ethoxy, n- or iso-propoxy, n-, iso-, sec- or tert-butoxy, preferably methoxy or ethoxy; Amino or C 2 -C 7 alkanoylamino, preferably C 2 -C 4 alkanoylamino, such as acetylamino, propionylamino or butyrylamino, especially
  • R 1 , R 2 , R 3 , R 4 and R 6 as benzoyl are unsubstituted or in the phenyl ring, for example by halogen, hydroxy, sulfamoyl, carbamoyl, sulfo, carboxy; C 1 -C 4 alkyl, C 1 -C 4 alkoxy, amino or C 2 -C 7 alkanoylamino substituted.
  • the benzoyl radical is preferably unsubstituted or substituted in the phenyl ring by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, amino or C 2 -C 4 alkanoylamino. In particular, the benzoyl radical is unsubstituted.
  • R 1 , R 2 , R 3 , R 4 and R 6 as phenylsulfonyl are unsubstituted or in the phenyl ring, for example by halogen, hydroxy, sulfamoyl, carbamoyl, sulfo, carboxy, C 1 -C 4 alkyl, C 1 -C 4 alkoxy , Amino or C 2 -C 7 alkanoylamino substituted.
  • the phenylsulfonyl radical is preferably unsubstituted or substituted in the phenyl ring by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, amino or C 2 -C 4 alkanoylamino.
  • R 1 -C 12 alkyl for R 1 , R 2 , R 3 , R 4 , R 5 and R 6 independently of one another are, for example, methyl, ethyl, n- or iso-propyl, n-, iso-, sec.- or tert-butyl or straight-chain pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl, where these alkyl radicals can each carry one or more identical or different of the aforementioned substituents.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 as C 1 -C 12 alkyl are, independently of one another, preferably a C 1 -C 6 alkyl radical optionally substituted as mentioned above and particularly preferably one optionally mentioned as above substituted C 1 -C 4 alkyl radical.
  • R 5 the C 1 -C 4 alkyl radical is preferably unsubstituted.
  • R 1 , R 2 , R 3 , R 4 and R 6 are substituted as C 1 -C 4 alkyl radicals as mentioned above.
  • R 7 as C 1 -C 4 alkyl is, for example, methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert-butyl, preferably methyl or ethyl and particularly preferably methyl.
  • R 8 and R 9 C 1 -C 6 -alkyl are, for example, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl or straight-chain or branched pentyl or hexyl, independently of one another, preferred C 1 -C 4 alkyl, particularly preferably methyl or ethyl and very particularly preferably methyl.
  • Y - can be any anion, such as sulfate or halide.
  • Y - preferably represents a halide anion, for example the bromide ion Br - or in particular the chloride ion Cl - .
  • C 1 -C 10 alkylene is, for example, methylene, ethylene or straight-chain or branched propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene or decylene.
  • the rest (alk) preferably represents straight-chain or branched C 1 -C 6 -alkylene, for example methylene, 1,1- or 1,2-ethylene, 1,2- or 1,3-propylene or straight-chain or branched butylene, Pentylene or hexylene, and particularly preferably for C 1 -C 4 alkylene.
  • T represents hydrogen or a radical -NH 2 , -NHR 9 , -N (R 9 ) 2 , -N (R 9 ) 3 + Y - , in which the abovementioned meanings and preferences apply to R 9 and Y - .
  • T is preferably hydrogen or a radical -NH 2 , -NHR 9 , -N (R 9 ) 2 or -N (R 9 ) 3 + Y - , where R 9 is methyl or ethyl and Y - is a halide anion.
  • T particularly preferably denotes a radical -N (R 9 ) 2 or -N (R 9 ) 3 + Y - , where R 9 is methyl or ethyl, in particular methyl, and Y - is bromide or chloride anion.
  • radicals R 1 , R 2 , R 3 , R 4 and R 6 in the phenyl ring are phenylsulfonyl substituted by amino or C 2 -C 7 -alkanoylamino
  • the amino group or the C 2 -C 7 -alkanoylamino group is, for example, in o- or m-position to the sulfo group and preferably bound in the p-position to the sulfo group.
  • radicals R 1 , R 2 , R 3 , R 4 , R 5 and R 6 mean substituted C 1 -C 12 alkyl, the amino group or the -NH-CO-R 8 group is bound, for example, in the o- or m-position to the sulfo group and preferably in the p-position to the sulfo group, with R 8 being the same as above meanings and preferences mentioned apply.
  • Y - is a bromide or chloride anion.
  • R 1 , R 3 and R 6 have the meanings and preferences given above and do not mean hydrogen.
  • R 5 is preferably hydrogen, benzyl or C 1 -C 4 alkyl, preferably hydrogen, methyl or ethyl, in particular hydrogen or methyl.
  • the homopolymers and copolymers used according to the invention as fixing agents containing recurring structures of the formulas (1), (2) and (3) given above, in which the meanings of R 1 , R 3 and R 6 are identical, and R 2 and R 4 are identical Meanings can be prepared, for example, by polymerizing N-vinylformamide or N-vinyl acetamide and, if appropriate, further copolymerizable monomers, then hydrolyzing and the free amino groups of the homo- or copolymer obtained in an alkylation reaction with an alkyl halide R 1 -X 1 and optionally R 2 -X 2 and R 5 -X 5 , in which R 1 , R 2 and R 5 each have the meanings given above and X 1 , X 2 and X 5 each independently represent a halide anion, preferably each the bromide or chloride ion, subjects.
  • the reaction of the amino groups of the homo- or copolymer instead of the alkylation reaction with a suitable alkyl
  • the homopolymers and copolymers used according to the invention as fixing agents containing recurring structures of the formulas (1), (2) and (3) given above, in which R 2 , R 4 , R 5 and R 7 are hydrogen and the meanings of R 1 , R 3 and R 6 are identical, can also advantageously be prepared by adding a suitable vinylformamido compound, for example of the formula (4) and where R 6 has the meaning given above, polymerized and then hydrolyzed acidic or alkaline.
  • the following copolymerizable monomers are suitable, for example: allylamine or diallylamine derivatives such as, for example, diallylamine, N-methyldiallylamine, N-ethyldiallylamine, N, N-dimethyldiallylamonium chloride; Monomers with carboxyl function, for example (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, vinyl acetic acid, vinyl oxyacetic acid, vinyl propionic acid, crotonic acid, aconitic acid, allyl acetic acid, allyloxyacetic acid, ⁇ , ⁇ -dimethylacrylic acid, allylmalmalonic acid, allyloxymalonic acid, meth) acrylic acid, 2-halogeno (meth) acrylic acid, ⁇ -ethyl acrylic acid, acrylamidoglycolic acid, glutaconic acid, ⁇ -
  • Preferred copolymerizable monomers in the fixing agents according to the invention are allylamine or diallylamine derivatives, (meth) acrylic acid, maleic acid, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylformamide, N-vinyl-N -methyl-acetamide, N-vinyl-N-ethyl-acetamide, N-vinylimidazole, vinyl acetate, vinyl propionate, hydroxy-C 2 -C 4 alkyl (meth) acrylate, (meth) acrylic acid-C 1 -C 22 alkyl ester , Acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N-mono / N, N-di-C 1 -C 10 -alkyl- (meth) acrylamide or N, N-di-C 1 -C 2 -alkylamino-C 2 -C
  • copolymerizable monomers in the fixing agents according to the invention are acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylformamide, N-vinyl-N-methyl-acetamide, N-vinyl-N-ethyl-acetamide, N-vinylimidazole, vinyl acetate, acrylamide, methacrylamide, N-mono or N, N-di-C 1 -C 4 alkyl- (meth) acrylamide.
  • Very particularly preferred as copolymerizable monomers in the fixing agents according to the invention are N-vinylpyrrolidone, N-vinylformamide, N-vinyl acetamide, N-vinyl-N-methylformamide, N-vinyl-N-methyl-acetamide, N-vinyl-N-ethyl -acetamide, N-vinylimidazole, vinyl acetate, acrylamide, methacrylamide, N-mono- or N, N-di-C 1 -C 4 alkyl- (meth) acrylamld.
  • the quotient Q is defined by the ratio of the structural units of the formulas (1a) and (1b) the total number of all structural units in the copolymer.
  • the total number of all Structural units in the copolymer result from the sum of the structural units of the Formulas (1a), (1b), (5) and (6).
  • R 1 and R 2 in the homo- or copolymers described in more detail above under (i) are particularly preferably each independently of the other hydrogen, -CH 2 -CH 2 -COO- (CH 2 ) 1-2 -CH 3 , -CH 2 - CH 2 -COOH, -CH 2 -CH 2 -OH, -CH 2 -CH 2 -CN, -CH 2 -CH 2 -N (CH 3 ) 2 or -CH 2 -CH 2 -N + (CH 3 ) 3 Y - , where Y - is a bromide or chloride anion.
  • R 1 and R 2 very particularly preferably have identical meanings in the homopolymers or copolymers described in more detail above under (i).
  • the previously included (i) specified homo- or copolymers 20 to 100 mol% recurring Structural units of the formulas (1a) and (1b) and 80 to 0 mol% recurring Structural units of the formulas (5) and (6), the condition for the quotient Q being Q 0.2 to 1 applies.
  • the 40 to 100 mol% of homo- or copolymers previously specified under (i) recurring structural units of the formulas (1a) and (1b) and 60 to 0 mol% recurring structural units of the formulas (5) and (6), where for the quotient Q the condition Q 0.4 to 1 applies.
  • the quotient Q is defined by the ratio of the structural units of the formulas (7) and (8) the total number of all structural units in the copolymer.
  • the total number of all Structural units in the copolymer result from the sum of the structural units of the Formulas (7), (8), (5) and (6).
  • Fixing agents are used.
  • the homopolymers or copolymers used as fixing agents have a medium one Molecular weight of 1,000 to 1,000,000, preferably 1,000 to 500,000 and in particular 5,000 to 200,000.
  • Another object of the present invention are homopolymers or copolymers, characterized in that they contain structural units of the formula (7).
  • the Polymers according to the invention can be produced as described above.
  • the polymers used as fixatives or the polymers according to the invention containing structural units of the formula (7) are prepared in a manner known per se, for example by ionically or preferably free-radically initiated polymerization of the corresponding monomers, for example in solution, suspension or emulsion, and, if appropriate, subsequent Hydrolysis.
  • the polymerization is preferably carried out in solution with a peroxide, persulfate or an azo compound, for example with potassium persulfate or azo-bis- (2-amidinopropane) hydrochloride, as a free-radical initiator, this in an amount of, for example, 0.005 to 10% by weight, based on the monomers used, is present.
  • a hydrolysis step this takes place under alkaline or preferably under acidic conditions.
  • polymers with structural units of the formula (2) given above are obtained, in which R 5 is hydrogen.
  • the homopolymer or copolymer used according to the invention as a fixing agent becomes independent fleet ratio e.g. in an amount of 0.05 to 10% by weight, preferably 0.2 to 4 % By weight and particularly preferably 0.5 to 2% by weight of active compound, based on the Weight of the polyamide fiber material used.
  • the treatment of the polyamide fiber material with the fixing agent can be before, during or preferably after dyeing. It is advantageous to carry out the process according to the invention Process by first dyeing the polyamide fiber material in the usual way and then a post-treatment with the fixative in the previously specified Amount containing fresh aqueous liquor. After that, the colored one Polyamide fiber material drained without further rinsing and in the usual way be dried. Post-fixation is usually done in a fresh liquor. But it is also Can be carried out directly in the dye bath, provided that the dye bath is largely pulled out at the end and is still sufficiently acidic. After the fixation is usually done with water briefly rinsed cold.
  • Natural polyamide fiber material such as e.g. Wool or Silk, or synthetic polyamide fiber material, e.g. Polyamide 6 or polyamide 6.6, or fiber mixtures such as Wool / cellulose or polyamide / cellulose mixed fibers or Polyamide / wool blended into consideration.
  • the textile can be used in any form, e.g. as fiber, yarn, woven or knitted fabric.
  • the dyeings are carried out, for example, with anionic dyes, all of the usual anionic dyes, e.g. in Color Index, 3rd edition (1971) and the Addenda to this under the heading "Acid Dyes" or in the patents US-A-5,725,606, US-A-5,691,459, US-A-5,650,497, US-A-5,630,851, US-A-5,527,889, US-A-5,234,467, US-A-5,131,919, US-A-5,094,665, US-A-5,092,905 and US-A-2,844,597 are described.
  • Examples are sulfo group-containing monoazo, polyazo, metal complex azo, anthraquinone, Phthalocyanine or formazan dyes.
  • the anionic dyes used to dye the polyamide fiber material lie either in the form of their free sulfonic acid or preferably as their salts.
  • the salts include, for example, the alkali, alkaline earth or ammonium salts or the salts an organic amine.
  • Examples include sodium, lithium, potassium or Ammonium salts or the salt of mono-, di- or triethanolamine called.
  • the anionic dyes used to dye the polyamide fiber material can other additives, e.g. Cooking salt or dextrin.
  • the dyeing of the polyamide fiber material with anionic dyes can be carried out according to the these dyes usual dyeing or printing processes, for example according to Pull-out procedure.
  • the dyeing liquors or printing pastes can also Water and the dyes further additives, for example wetting agents, anti-foaming agents, Leveling agents or agents influencing the property of the textile material, e.g. Plasticizers, additives for flame retardant or dirt, water and oil repellent Agents and water softening agents and natural or synthetic Thickeners, e.g. Alginates and cellulose ethers.
  • anionic dyes in the dye baths or printing pastes can be used within wide limits depending on the desired depth of color fluctuate, generally amounts have from 0.01 to 15% by weight, in particular 0.01 up to 10% by weight, based on the dye material or the printing paste, has been found to be advantageous.
  • the dyeing is preferably carried out with anionic dyes at a pH of 3 to 7, in particular 4 to 7.
  • the liquor ratio can be chosen within a wide range e.g. from 1: 5 to 1:50, preferably 1: 5 to 1:30. It is preferable to dye one Temperature from 70 to 110 ° C, especially 80 to 105 ° C.
  • the aftertreatment is preferably carried out using the exhaust method.
  • the fleet ratio can be selected within a wide range and is e.g. 1: 4 to 1: 100, preferably 1:10 to 1:40 and in particular 1: 5 to 1:40.
  • Dyeing machines e.g. open baths, reel runners, jigger or paddle, jet or Circulators can be used.
  • the treatment time can e.g. 10 to 60 minutes and preferably 15 up to 40 minutes, whereby also for dark shades, e.g. Black coloring 15 Minutes at 75 ° C are sufficient.
  • the pH of the liquor is usually 4 to 10, preferably 5 to 7 and in particular 4.5 to 6.
  • the liquor can contain other conventional additives, e.g. Electrolytes such as Sodium chloride or sodium sulfate, dispersing and wetting agents and defoamers.
  • Electrolytes such as Sodium chloride or sodium sulfate, dispersing and wetting agents and defoamers.
  • Another object of the present invention is the use of the above described method for improving the ozone fastness of dyeings natural or synthetic polyamide fiber materials.
  • the process according to the invention gives dyeings or prints of Dyes, e.g. anionic dyes, on polyamide fiber material, which a significant improvement in ozone fastness and wet fastness, e.g. the washing and Show water rights and especially chlorine without the Color yield, shade or light fastness can be adversely affected. Furthermore the treated dyeings and prints show no stiffening. On printed Polyamide fiber material prevents soiling of the white fund.
  • Dyes e.g. anionic dyes
  • Example 1 60 parts of vinylformamide and 60 parts of deionized water are placed in a reactor and heated to about 70 ° C. under nitrogen. A solution of 1.8 parts of sodium persulfate in 12 parts of water is then added dropwise within 90 minutes. The mixture is then left to polymerize at 75 ° C. for 6 hours. A solution of 83 parts of 37% hydrochloric acid in 90 parts of water is then added and the mixture is heated at about 80 ° C. for 4 hours. After setting an active content of 20%, a slightly viscous, clear polymer solution is obtained, the active substance of which is in the form of hydrochloride and essentially structural units of the formulas contains, the value Q (x / x + y) being approximately 0.8.
  • Example 2 135 parts of a 17.5% hydrolyzed polyvinylformamide solution (degree of hydrolysis approx. 80%) are neutralized to pH 9.5. After adding 0.5 parts of benzyltrimethylammonium hydroxide and 2.4 parts of vinylsulfonyl-4-aminobenzene, the mixture is heated at about 70 ° C. for 2 hours. After adjusting the pH to 6 and an active content of 20%, a slightly viscous, clear polymer solution is obtained, the active substance of which is partly present as hydrochloride and essentially contains structural units of the formulas (101), (102) and contains and has a viscosity of 2530 cP.
  • Example 3 21.3 parts of vinylformamide, 15.9 parts of acrylonitrile, 15.9 parts of a 30% strength acrylamide solution and 145 parts of water are placed in a reactor and heated to about 80 ° C. under nitrogen. A solution of 1.45 parts of azobis (amidinopropane) hydrochloride in 10 parts of water is then added dropwise within 90 minutes. Then allowed to polymerize for 4 hours at 80 ° C. After adding 29.5 parts of 37% hydrochloric acid, the mixture is heated at about 80 ° C. for a further 4 hours. After setting an active content of 20%, a slightly viscous, clear polymer solution is obtained, the active substance of which is in the form of hydrochloride and essentially structural units of the formulas contains.
  • Example 4 14.2 parts of vinylformamide, 11.4 parts of 3- (N-vinylformamido) propionic acid ethyl ester and 50 parts of water are placed in a reactor and heated to about 70 ° C. under nitrogen. A solution of 0.5 parts of azo-bis (amidinopropane) hydrochloride in 10 parts of water is then added dropwise within 60 minutes. The mixture is then left to polymerize at 70 ° C. for 6 hours. After adding a solution of 27 parts of 37% hydrochloric acid in 40 parts of water, the mixture is heated at about 80 ° C. for 4 hours. After setting an active content of 20%, a slightly viscous, clear polymer solution is obtained, the active substance of which is in the form of hydrochloride and essentially contains structural units of the formulas (101) and contains.
  • Example 5 111 parts of an 18% polyvinylamine hydrochloride solution (degree of hydrolysis approx. 80%) are adjusted to pH 10 with an NaOH solution. After adding 0.2 parts of benzyltrimethylammonium chloride, the mixture is heated to 80.degree. A solution of 58 parts of 1-chloro-2-dimethylaminoethane hydrochloride and 75 parts of water is then added dropwise within 2 hours. During the addition, the pH is kept at about 9.5. After 5 hours at approx. 85 ° C, the pH is adjusted to 2.5. The solution is concentrated, the salts are filtered and the polymer is precipitated in ethanol. A 33% aqueous solution of the polymer is then prepared, which essentially contains structural units of the formulas (101), contains and is present as hydrochloride.
  • Example 6 150 parts of an 18% polyvinylamine hydrochloride solution (degree of hydrolysis approx. 85%) are adjusted to pH 10 with an NaOH solution. After adding 0.5 parts of benzyltrimethylammonium chloride, the mixture is heated to 80.degree. Then 23.3 parts of chloroethanol are added dropwise within 3 hours. During the addition, the pH is kept at about 9.5. After 5 hours at approx. 85 ° C, the pH is adjusted to 2.5. The solution is concentrated and the polymer is precipitated in acetone. A 33% aqueous solution of the polymer is then prepared, which essentially has structural units of the formulas (101) and contains and is present as hydrochloride.
  • Example 7 100 parts of an 18% polyvinylamine hydrochloride solution (degree of hydrolysis approx. 80%) are adjusted to pH 10 with an NaOH solution. A solution of 42.6 parts of 3-chloro-2-hydroxypropyltrimethylammonium chloride in 42.6 parts of water is then added dropwise at about 75 ° C. in the course of 1 hour. During the addition, the pH is kept at about 9.5. After 4 hours at approx. 80 ° C, the pH is adjusted to 2. The solution is partially concentrated and the polymer is precipitated in ethanol. A 33% aqueous solution of the polymer is then prepared, which essentially has structural units of the formulas (101) and contains and is present as hydrochloride.
  • Example 8 25.6 parts of vinylformamide, 20 parts of vinypyrrolidone, 16.9 parts of vinylimidazole and 238 parts of water are placed in a reactor and heated to about 80 ° C. under nitrogen. A solution of 1.6 parts of azo-bis (amidinopropane) hydrochloride in 10 parts of water is then added dropwise within 90 minutes. Then allowed to polymerize for 4 hours at 80 ° C. After adding 53 parts of 37% hydrochloric acid, the mixture is heated at about 95 ° C. for a further 4 hours. The polymer is precipitated in ethanol. A 20% aqueous solution of the polymer is then prepared, which essentially contains structural units of the formulas (101), contains and is present as hydrochloride.
  • Example 9 40 parts of 3- (N-vinylformamido) propionitrile, 10.1 parts of vinylimidazole and 82 parts of water are placed in a reactor and heated to about 80 ° C. under nitrogen.
  • a solution of 0.95 parts of azo-bis (amidinopropane) hydrochloride in 10 parts of water is then added dropwise within 90 minutes. Then allowed to polymerize for 4 hours at 80 ° C. After adding 42.3 parts of 37% hydrochloric acid, the mixture is heated at about 95 ° C. for 5 hours. The polymer is precipitated in ethanol. A 33% aqueous solution of the polymer is then produced, which essentially has structural units of the formulas contains and is present as hydrochloride.
  • Example 10 45.3 parts of a 15% hydrolyzed polyvinylformamide solution (degree of hydrolysis approx. 85%) are diluted with 35 parts of water and neutralized to pH 8.5. After the addition of 0.1 part of benzyltrimethylammonium chloride and 45 parts of tetrahydrofuran, a solution of 3.6 parts of benzenesulfochloride in 11 parts of tetrahydrofuran is added dropwise within 15 minutes. The mixture is stirred for a further 4 hours at room temperature. After adjusting the pH to 6.5, tetrahydrofuran is distilled off and the active content is set to 15%. A cloudy, slightly viscous polymer solution is obtained, the active substance of which is partly present as hydrochloride and essentially has structural units of the formulas (101), (102) and contains.
  • Example 11 45.3 parts of a 15% hydrolysed polyvinylformamide solution (degree of hydrolysis approx. 85%) are diluted with 35 parts of water and neutralized to pH 8.5. After adding 0.1 part of benzyltrimethylammonium chloride and 45 parts of tetrahydrofuran, a solution of 2.8 parts of benzoyl chloride in 11 parts of tetrahydrofuran is added dropwise within 15 minutes. The mixture is stirred for a further 4 hours at room temperature. After adjusting the pH to 6.5, tetrahydrofuran is distilled off and the active content is set to 15%. A cloudy, slightly viscous polymer solution is obtained, the active substance of which is partly present as hydrochloride and essentially has structural units of the formulas (101), (102) and contains.
  • Example 12 45.3 parts of a 15% hydrolyzed polyvinylformamide solution (degree of hydrolysis approx. 85%) are diluted with 35 parts of water and neutralized to pH 10. After the addition of 60 parts of tetrahydrofuran, 3.1 parts of 4-acetaminobenzenesulfochloride are added within 5-10 minutes. The pH is kept constant at 10. The mixture is stirred at room temperature for a further 2 hours. After adjusting the pH to 6.5, tetrahydrofuran is distilled off and the active content is set to 15%. A slightly cloudy, medium-viscosity polymer solution is obtained, the active substance of which is partly present as hydrochloride and essentially has structural units of the formulas (101), (102) and contains.
  • Example 13 75 parts of the polymer solution from Example 12 are diluted with 80 parts of water. After adding 13.2 parts of 37% hydrochloric acid, the mixture is stirred at 95 ° C. for 6 hours. After adjusting the pH to 7, the polymer solution is desalted and the active content is set to 15%. A slightly cloudy, viscous polymer solution is obtained, the active substance of which is partly present as hydrochloride and essentially has structural units of the formulas (101), (102) and contains.
  • Example 14 80 parts of a 15% hydrolyzed polyvinylformamide solution (degree of hydrolysis approx. 85%) are diluted with 30 parts of water and neutralized to pH 9.5. After adding 0.5 parts of benzyltrimethylammonium hydroxide, the mixture is heated to 70.degree. Then a solution neutralized to pH 4.5 of 3.5 parts of ⁇ -sulfatoethylsulfonyl-4-aminobenzene and 8 parts of water is added dropwise within 5-10 minutes. The pH is kept constant at 9.5. The mixture is stirred at 70 ° C for 2 hours. After adjusting the pH to 7, the active content is set to 15%. A clear, slightly viscous polymer solution is obtained, the active substance of which is partially present as hydrochloride and essentially contains structural units of the formulas (101), (102) and (103) and has a viscosity of 1600 cP.
  • Example 15 100 g of a polyamide 6.6 texture tricot with an m 2 weight of 235 g are placed on a laboratory reel with a liquor ratio 1:20, with a liquor containing 1 g / l ammonium acetate and 0.5 g / l contains a commercial leveling agent, colored.
  • the liquor is first adjusted to pH 5 with acetic acid, heated to 50 ° C. and the polyamide tricot is treated at this temperature for 10 minutes. Then 3.0 g / l of the dye of the formula added and the bath kept at 50 ° C for a further 5 minutes. Then the dyeing temperature is raised to 98 ° C. within 30 minutes. The polyamide tricot is treated at this temperature for 60 minutes.
  • the polyamide tricot is then rinsed with cold water and treated with a fresh bath which contains 3.0 g / l of the polymer solution according to Example 1 with a liquor ratio of 1:20.
  • the liquor is first adjusted to pH 4 with acetic acid and the colored polyamide tricot is introduced into the fixing liquor at 25 ° C. and treated at this temperature for 10 minutes. Then increase the bath temperature to 75 ° C within 20 minutes and hold this temperature for a further 15 minutes.
  • the dyed and post-fixed polyamide tricot is then rinsed briefly with cold water and dried at 60 ° C. A dyeing with very good wet fastness properties is obtained without influencing the shade and light fastness.
  • Example 15 The procedure is as described in Example 15, but is used instead of the polymer solution according to Example 1, the equivalent amount by weight of one of the polymer solutions one of the examples 2 to 14, a polyamide 6.6 texture tricot is also used improved wet fastness properties, without influencing the shade and light fastness.
  • Example 16 100 g of a polyamide 6 woven tricot with an m 2 weight of 120 g are placed on a laboratory jet with a liquor ratio of 1:10 with a liquor which contains 1 g / l ammonium acetate and 0.5 g / l of a commercially available leveling agent contains, colored.
  • the liquor is first adjusted to pH 5.5 with acetic acid, heated to 40 ° C. and the woven tricot is treated at this temperature for 15 minutes. Then 0.6 g / l of the dye of the formula and 1.2 g / l of the dye of the formula added and the bath kept at 40 ° C for a further 5 minutes. Then the dyeing temperature is raised to 98 ° C. within 30 minutes.
  • the woven tricot is treated for 60 minutes.
  • the liquor is then cooled to 50 ° C. within 15 minutes.
  • 1.5 g / l of the polymer solution according to Example 2 are added directly to the dye bath and the liquor is adjusted to pH 5 with acetic acid.
  • the temperature of the liquor is then raised to 80 ° C. within 15 minutes and kept at this temperature for 10 minutes.
  • the dyed and refixed woven tricot is then rinsed briefly with cold water and dried at 60 ° C. A dyeing with very good wet fastness properties is obtained without influencing the shade and light fastness.
  • Example 16 The procedure is as described in Example 16, but is used instead of the polymer solution according to example 2, the equivalent amount by weight of one of the polymer solutions according to one of Examples 1 and 3 to 14, a polyamide 6 woven tricot is also used improved wet fastness properties, without influencing the shade and light fastness.
  • Example 17 A dyebath containing 600 parts of water 0.0108 parts of a dye of the formula 0.0135 parts of a dye of the formula and 0.033 parts of a dye of the formula is adjusted to a pH of 6.5 with 0.72 parts of sodium dihydrogenphosphate monohydrate and 0.6 part of disodium hydrogenphosphate dodecahydrate. This dye bath is mixed with 30 parts of polyamide carpet fabric (polyamide 6) at 30 ° C. The temperature is raised uniformly to the boiling point within 45 minutes and dyeing is then carried out for a further 30 minutes at this temperature. The gray colored carpet is then rinsed.
  • polyamide carpet fabric polyamide 6
  • the dyed carpet fabric is aftertreated in a fresh bath of 600 parts of water, 3 parts of the polymer solution according to Example 2, 0.6 part of sodium acetate and 0.7 part of acetic acid at a pH of 4.5 and a temperature of 75 ° C. for 15 minutes.
  • the carpet fabric is then rinsed and dried.
  • the ozone fastness of the dyeing obtained is carried out in accordance with the test specification ISO 105-G03. The comparison of the after-treated carpet fabric with a carpet fabric that was not after-treated shows a significant increase in the ozone resistance of the after-treated carpet fabric.

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Description

Die vorliegende Erfindung betrifft ein Verfahren zur Behandlung von natürlichen oder synthetischen Polyamidfasermaterialien zur Verbesserung der Echtheiten.The present invention relates to a method for the treatment of natural or synthetic polyamide fiber materials to improve the fastness properties.

Färbungen und Drucke mit Farbstoffen zeigen oft ungenügende Nassechtheiten, besonders Wasch- und Wasserechtheiten. Der Farbstoff, welcher an der Oberfläche der Polyamidfaser gebunden ist, kann durch wiederholte Waschoperationen entfernt werden und auf benachbartes Textilmaterial, welches im gleichen Waschgang gewaschen wird, wieder aufziehen. Man begegnet diesem Mangel im allgemeinen, Indem man an den Färbeprozess eine Nachbehandlung mit einem Fixiermittel auf der Basis von Phenol-Formaldehyd-Kondensaten anschliesst. Die bekannten Fixiermittel weisen jedoch Nachteile, z.B. eine mangelnde Wirksamkeit oder eine negative Beeinflussung anderer Echtheiten, z.B. der Lichtechtheit auf. Es besteht daher Bedarf nach verbesserten Fixiermitteln für die Behandlung von Insbesondere mit anionischen Farbstoffen gefärbten, natürlichen oder synthetischen Polyamidfasermaterialien, welche die genannten Nachteile nicht aufweisen.Dyes and prints with dyes often show inadequate wet fastness, especially Washing and water rights. The dye that is on the surface of the polyamide fiber bound, can be removed by repeated washing operations and on neighboring textile material, which is washed in the same wash, again raise. One meets this deficiency in general by looking at the dyeing process an aftertreatment with a fixative based on phenol-formaldehyde condensates adjoined. However, the known fixatives have disadvantages, e.g. a lack of effectiveness or a negative influence on other fastness properties, e.g. the Lightfastness on. There is therefore a need for improved fixatives for the Treatment of natural or dyed in particular with anionic dyes synthetic polyamide fiber materials which do not have the disadvantages mentioned.

Es wurde nun gefunden, dass man die Nassechtheiten von beispielsweise Färbungen anionischer Farbstoffe auf Polyamidfasermaterial ohne negative Beeinflussung anderer Echtheiten verbessern kann, wenn man sie einer Behandlung mit bestimmten Homo- oder Copolymeren unterzieht.It has now been found that the wet fastness properties of, for example, dyeings anionic dyes on polyamide fiber material without adversely affecting others Fastness can improve if you treat them with certain homo- or Undergoes copolymers.

Gegenstand der vorliegenden Erfindung ist daher ein Verfahren zur Fixierung von Farbstoffen auf natürlichen oder synthetischen Polyamidfasermaterialien, dadurch gekennzeichnet, dass man das Fasermaterial vor, während oder nach der Färbung mit einer Flotte behandelt, enthaltend ein Homo- oder Copolymer mit wiederkehrenden Struktureinheiten mindestens einer der Formeln (1), (2) und (3)

Figure 00010001
und
Figure 00020001
worin

  • R1, R2, R3, R4 und R6 unabhängig voneinander je Wasserstoff, C1-C6-Alkylsulfonyl, gegebenenfalls substituiertes Phenyl, gegebenenfalls im Phenylring substituiertes Benzoyl oder Phenylsulfonyl oder einen C1-C12-Alkylrest, der unsubstituiert oder durch Hydroxy, Carboxy, Cyano, Carbamoyl, einen Rest -CONH-(alk)-T, N,N-Di-C1-C4-Alkylcarbamoyl,
    Figure 00020002
    Amino oder einen Rest -NHR9, -N(R9)2, -N(R9)3 + Y- oder -COO-(alk)-T substituiert ist, sind,
  • (alk) einen geradkettigen oder verzweigten C1-C10-Alkylenrest bedeutet,
  • T für Wasserstoff oder für einen Rest -NH2, -NHR9, -N(R9)2, -N(R9)3 + Y- steht,
  • R8 und R9 C1-C6-Alkyl und
  • Y- ein Anion sind,
  • R5 Wasserstoff, Benzyl oder eine der oben für R1, R2, R3, R4 und R6 als C1-C12-Alkylrest angegebenen Bedeutungen hat und
  • R7 Wasserstoff oder C1-C4-Alkyl ist.
    • The present invention therefore relates to a process for fixing dyes on natural or synthetic polyamide fiber materials, characterized in that the fiber material is treated with a liquor before, during or after dyeing, containing a homo- or copolymer with recurring structural units of at least one of the formulas (1), (2) and (3)
    Figure 00010001
    and
    Figure 00020001
    wherein
  • R 1 , R 2 , R 3 , R 4 and R 6 each independently of one another are hydrogen, C 1 -C 6 -alkylsulfonyl, optionally substituted phenyl, optionally substituted in the phenyl ring, benzoyl or phenylsulfonyl or a C 1 -C 12 -alkyl radical which is unsubstituted or by hydroxy, carboxy, cyano, carbamoyl, a radical -CONH- (alk) -T, N, N-di-C 1 -C 4 -alkylcarbamoyl,
    Figure 00020002
    Amino or a radical -NHR 9 , -N (R 9 ) 2 , -N (R 9 ) 3 + Y - or -COO- (alk) -T are substituted,
  • (alk) denotes a straight-chain or branched C 1 -C 10 alkylene radical,
  • T represents hydrogen or a radical -NH 2 , -NHR 9 , -N (R 9 ) 2 , -N (R 9 ) 3 + Y - ,
  • R 8 and R 9 are C 1 -C 6 alkyl and
  • Y - are an anion,
  • R 5 has hydrogen, benzyl or one of the meanings given above for R 1 , R 2 , R 3 , R 4 and R 6 as C 1 -C 12 alkyl radical and
  • R 7 is hydrogen or C 1 -C 4 alkyl.

    • R1, R2, R3, R4 und R6 als C1-C6-Alkylsulfonyl sind unabhängig voneinander beispielsweise Methylsulfonyl, Aethylsulfonyl, n- oder iso-Propylsulfonyl, n-, iso- oder sec.-Butylsulfonyl, geradkettiges Pentylsulfonyl oder Hexylsulfonyl, vorzugsweise Methylsulfonyl oder Aethylsulfonyl und insbesondere Methylsulfonyl.R 1 , R 2 , R 3 , R 4 and R 6 as C 1 -C 6 alkylsulfonyl are independently, for example, methylsulfonyl, ethylsulfonyl, n- or iso-propylsulfonyl, n-, iso- or sec-butylsulfonyl, straight-chain pentylsulfonyl or hexylsulfonyl, preferably methylsulfonyl or ethylsulfonyl and especially methylsulfonyl.

    R1, R2, R3, R4 und R6 als Phenyl sind unsubstituiert oder beispielsweise durch Halogen, wie z.B. Chlor oder Brom; Hydroxy; Sulfamoyl; Carbamoyl; Sulfo; Carboxy; C1-C4-Alkyl, wie z.B. Methyl, Aethyl, n- oder iso-Propyl, n-, iso-, sec.- oder tert.-Butyl, vorzugsweise Methyl oder Aethyl; C1-C4-Alkoxy, wie z.B. Methoxy, Aethoxy, n- oder iso-Propoxy, n-, iso-, sec.- oder tert.-Butoxy, vorzugsweise Methoxy oder Aethoxy; Amino oder C2-C7-Alkanoylamino, vorzugsweise C2-C4-Alkanoylamino, wie z.B. Acetylamino, Propionylamino oder Butyrylamino, insbesondere Acetylamino, substituiert. Vorzugsweise ist der Phenylring unsubstituiert.R 1 , R 2 , R 3 , R 4 and R 6 as phenyl are unsubstituted or, for example, by halogen, such as chlorine or bromine; hydroxy; sulfamoyl; carbamoyl; sulfo; carboxy; C 1 -C 4 alkyl, such as methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert-butyl, preferably methyl or ethyl; C 1 -C 4 alkoxy, such as methoxy, ethoxy, n- or iso-propoxy, n-, iso-, sec- or tert-butoxy, preferably methoxy or ethoxy; Amino or C 2 -C 7 alkanoylamino, preferably C 2 -C 4 alkanoylamino, such as acetylamino, propionylamino or butyrylamino, especially acetylamino. The phenyl ring is preferably unsubstituted.

    Die angegebenen Bedeutungen und Bevorzugungen für Halogen, C1-C4-Alkyl, C1-C4-Alkoxy und C2-C7-Alkanoylamino gelten auch für die nachfolgend aufgeführten, entsprechend substituierten Benzoyl- und Phenylsulfonylreste R1, R2, R3, R4 und R6.The meanings and preferences given for halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy and C 2 -C 7 -alkanoylamino also apply to the correspondingly substituted benzoyl and phenylsulfonyl radicals R 1 , R 2 listed below, R 3 , R 4 and R 6 .

    R1, R2, R3, R4 und R6 als Benzoyl sind unsubstituiert oder Im Phenylring beispielsweise durch Halogen, Hydroxy, Sulfamoyl, Carbamoyl, Sulfo, Carboxy; C1-C4-Alkyl, C1-C4-Alkoxy, Amino oder C2-C7-Alkanoylamino substituiert. Vorzugsweise ist der Benzoylrest unsubstituiert oder im Phenylring durch C1-C4-Alkyl, C1-C4-Alkoxy, Amino oder C2-C4-Alkanoylamino, substituiert. Insbesondere ist der Benzoylrest unsubstituiert.R 1 , R 2 , R 3 , R 4 and R 6 as benzoyl are unsubstituted or in the phenyl ring, for example by halogen, hydroxy, sulfamoyl, carbamoyl, sulfo, carboxy; C 1 -C 4 alkyl, C 1 -C 4 alkoxy, amino or C 2 -C 7 alkanoylamino substituted. The benzoyl radical is preferably unsubstituted or substituted in the phenyl ring by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, amino or C 2 -C 4 alkanoylamino. In particular, the benzoyl radical is unsubstituted.

    R1, R2, R3, R4 und R6 als Phenylsulfonyl sind unsubstituiert oder im Phenylring beispielsweise durch Halogen, Hydroxy, Sulfamoyl, Carbamoyl, Sulfo, Carboxy, C1-C4-Alkyl, C1-C4-Alkoxy, Amino oder C2-C7-Alkanoylamino substituiert. Vorzugsweise ist der Phenylsulfonylrest unsubstituiert oder im Phenylring durch C1-C4-Alkyl, C1-C4-Alkoxy, Amino oder C2-C4-Alkanoylamino substituiert.R 1 , R 2 , R 3 , R 4 and R 6 as phenylsulfonyl are unsubstituted or in the phenyl ring, for example by halogen, hydroxy, sulfamoyl, carbamoyl, sulfo, carboxy, C 1 -C 4 alkyl, C 1 -C 4 alkoxy , Amino or C 2 -C 7 alkanoylamino substituted. The phenylsulfonyl radical is preferably unsubstituted or substituted in the phenyl ring by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, amino or C 2 -C 4 alkanoylamino.

    Als C1-C12-Alkyl kommen für R1, R2, R3, R4, R5 und R6 unabhängig voneinander beispielsweise Methyl, Aethyl, n- oder iso-Propyl, n-, iso-, sec.- oder tert.-Butyl oder geradkettiges Pentyl, Hexyl, Heptyl, Octyl, Nonyl, Decyl, Undecyl oder Dodecyl in Betracht, wobei diese Alkylreste Jeweils einen oder mehrere gleiche oder verschiedene der zuvor genannten Substituenten tragen können. R1, R2, R3, R4, R5 und R6 als C1-C12-Alkyl sind unabhängig voneinander bevorzugt ein gegebenenfalls wie zuvor genannt substituierter C1-C6-Alkylrest und besonders bevorzugt ein gegebenenfalls wie zuvor genannt substituierter C1-C4-Alkylrest. Für R5 ist der C1-C4-Alkylrest bevorzugt unsubstituiert. In einer besonderen Ausführungsform der vorliegenden Erfindung sind R1, R2, R3, R4 und R6 als C1-C4-Alkylrest wie zuvor genannt substituiert.As C 1 -C 12 alkyl for R 1 , R 2 , R 3 , R 4 , R 5 and R 6 independently of one another are, for example, methyl, ethyl, n- or iso-propyl, n-, iso-, sec.- or tert-butyl or straight-chain pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl, where these alkyl radicals can each carry one or more identical or different of the aforementioned substituents. R 1 , R 2 , R 3 , R 4 , R 5 and R 6 as C 1 -C 12 alkyl are, independently of one another, preferably a C 1 -C 6 alkyl radical optionally substituted as mentioned above and particularly preferably one optionally mentioned as above substituted C 1 -C 4 alkyl radical. For R 5 the C 1 -C 4 alkyl radical is preferably unsubstituted. In a particular embodiment of the present invention, R 1 , R 2 , R 3 , R 4 and R 6 are substituted as C 1 -C 4 alkyl radicals as mentioned above.

    R7 als C1-C4-Alkyl ist beispielsweise Methyl, Aethyl, n- oder iso-Propyl, n-, iso-, sec.- oder tert.-Butyl, bevorzugt Methyl oder Aethyl und besonders bevorzugt Methyl. R 7 as C 1 -C 4 alkyl is, for example, methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert-butyl, preferably methyl or ethyl and particularly preferably methyl.

    R8 und R9 C1-C6-Alkyl sind unabhängig voneinander beispielsweise Methyl, Aethyl, n- oder iso-Propyl, n-, iso-, sec.- oder tert.-Butyl oder geradkettiges oder verzweigtes Pentyl oder Hexyl, bevorzugt C1-C4-Alkyl, besonders bevorzugt Methyl oder Aethyl und ganz besonders bevorzugt Methyl.R 8 and R 9 C 1 -C 6 -alkyl are, for example, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl or straight-chain or branched pentyl or hexyl, independently of one another, preferred C 1 -C 4 alkyl, particularly preferably methyl or ethyl and very particularly preferably methyl.

    Bei Y- kann es sich um ein beliebiges Anion wie beispielsweise Sulfat oder Halogenid handeln. Bevorzugt steht Y- für ein Halogenidanion, beispielsweise für das Bromidion Br- oder insbesondere für das Chloridion Cl-.Y - can be any anion, such as sulfate or halide. Y - preferably represents a halide anion, for example the bromide ion Br - or in particular the chloride ion Cl - .

    Bei (alk) C1-C10-Alkylen handelt es sich beispielsweise um Methylen, Aethylen oder um geradkettiges oder verzweigtes Propylen, Butylen, Pentylen, Hexylen, Heptylen, Octylen, Nonylen oder Decylen. Der Rest (alk) steht bevorzugt für geradkettiges oder verzweigtes C1-C6-Alkylen, z.B. für Methylen, 1,1- oder 1,2-Ethylen, 1,2- oder 1,3-Propylen oder geradkettiges oder verzweigtes Butylen, Pentylen oder Hexylen, und besonders bevorzugt für C1-C4-Alkylen.(Alk) C 1 -C 10 alkylene is, for example, methylene, ethylene or straight-chain or branched propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene or decylene. The rest (alk) preferably represents straight-chain or branched C 1 -C 6 -alkylene, for example methylene, 1,1- or 1,2-ethylene, 1,2- or 1,3-propylene or straight-chain or branched butylene, Pentylene or hexylene, and particularly preferably for C 1 -C 4 alkylene.

    T bedeutet Wasserstoff oder einen Rest -NH2, -NHR9, -N(R9)2, -N(R9)3 +Y-, worin für R9 und Y- jeweils die zuvor genannten Bedeutungen und Bevorzugungen gelten. Bevorzugt steht T für Wasserstoff oder einen Rest -NH2, -NHR9, -N(R9)2 oder -N(R9)3 +Y-, worin R9 Methyl oder Aethyl und Y- ein Halogenidanlon bedeuten. Besonders bevorzugt bedeutet T einen Rest -N(R9)2 oder -N(R9)3 +Y-, worin R9 Methyl oder Aethyl, Insbesondere Methyl, und Y- das Bromid- oder Chloridanlon bedeuten.T represents hydrogen or a radical -NH 2 , -NHR 9 , -N (R 9 ) 2 , -N (R 9 ) 3 + Y - , in which the abovementioned meanings and preferences apply to R 9 and Y - . T is preferably hydrogen or a radical -NH 2 , -NHR 9 , -N (R 9 ) 2 or -N (R 9 ) 3 + Y - , where R 9 is methyl or ethyl and Y - is a halide anion. T particularly preferably denotes a radical -N (R 9 ) 2 or -N (R 9 ) 3 + Y - , where R 9 is methyl or ethyl, in particular methyl, and Y - is bromide or chloride anion.

    Bedeuten die Reste R1, R2, R3, R4 und R6 im Phenylring durch Amino oder C2-C7-Alkanoylamino substituiertes Phenylsulfonyl, so ist die Aminogruppe oder die C2-C7-Alkanoylaminogruppe z.B. in o- oder m-Stellung zur Sulfogruppe und bevorzugt in p-Stellung zur Sulfogruppe gebunden.If the radicals R 1 , R 2 , R 3 , R 4 and R 6 in the phenyl ring are phenylsulfonyl substituted by amino or C 2 -C 7 -alkanoylamino, the amino group or the C 2 -C 7 -alkanoylamino group is, for example, in o- or m-position to the sulfo group and preferably bound in the p-position to the sulfo group.

    Bedeuten die Reste R1, R2, R3, R4, R5 und R6 durch

    Figure 00040001
    Figure 00040002
    substituiertes C1-C12-Alkyl, so ist die Aminogruppe oder die -NH-CO-R8-Gruppe z.B. in o- oder m-Stellung zur Sulfogruppe und bevorzugt in p-Stellung zur Sulfogruppe gebunden, wobei für R8 die zuvor genannten Bedeutungen und Bevorzugungen gelten.The radicals R 1 , R 2 , R 3 , R 4 , R 5 and R 6 mean
    Figure 00040001
    Figure 00040002
    substituted C 1 -C 12 alkyl, the amino group or the -NH-CO-R 8 group is bound, for example, in the o- or m-position to the sulfo group and preferably in the p-position to the sulfo group, with R 8 being the same as above meanings and preferences mentioned apply.

    Bevorzugt bedeuten R1, R2, R3, R4 und R6 unabhängig voneinander je Wasserstoff, gegebenenfalls durch Halogen, Sulfo, C1-C4-Alkyl, C1-C4-Alkoxy, Amino oder C2-C4-Alkanoylamino substituiertes Phenyl, gegebenenfalls im Phenylring durch Halogen, C1-C4-Alkyl, C1-C4-Alkoxy, Amino oder C2-C4-Alkanoylamino substituiertes Benzoyl oder Phenylsulfonyl oder einen C1-C6-Alkylrest, der unsubstituiert oder durch Hydroxy, Carboxy, Cyano, Carbamoyl, einen Rest -CONH-(alk)-T, N,N-Di-C1-C4-Alkylcarbamoyl,

    Figure 00050001
    Amino oder einen Rest -NHR9, -N(R9)2, -N(R9)3 + Y- oder -COO-(alk)-T substituiert ist, worin

  • (alk) C1-C4-Alkylen bedeutet,
  • T die zuvor angegebene Bedeutung hat,
  • R8 und R9 C1-C4-Alkyl und
  • Y- ein Halogenidanion sind.
    • R 1 , R 2 , R 3 , R 4 and R 6 are each independently of the other hydrogen, optionally by halogen, sulfo, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, amino or C 2 -C 4 -Alkanoylamino-substituted phenyl, optionally substituted in the phenyl ring by halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, amino or C 2 -C 4 -alkanoylamino-benzoyl or phenylsulfonyl or a C 1 -C 6 -alkyl radical, which is unsubstituted or by hydroxy, carboxy, cyano, carbamoyl, a radical -CONH- (alk) -T, N, N-di-C 1 -C 4 -alkylcarbamoyl,
    Figure 00050001
    Amino or a radical -NHR 9 , -N (R 9 ) 2 , -N (R 9 ) 3 + Y - or -COO- (alk) -T is substituted, wherein
  • (alk) denotes C 1 -C 4 alkylene,
  • T has the meaning given above,
  • R 8 and R 9 are C 1 -C 4 alkyl and
  • Y - are a halide anion.

    • Besonders bevorzugt bedeuten R1, R2, R3, R4 und R6 unabhängig voneinander je Wasserstoff, gegebenenfalls durch Halogen, C1-C4-Alkyl oder C1-C4-Alkoxy substituiertes Phenyl, gegebenenfalls im Phenylring durch C1-C4-Alkyl, C1-C4-Alkoxy, Amino, Acetylamino oder Propionylamino substituiertes Benzoyl oder Phenylsulfonyl oder einen C1-C4-Alkylrest, der unsubstituiert oder durch Hydroxy, Carboxy, Cyano, einen Rest -CONH-(CH2)1-3-T,

    Figure 00050002
    Amino oder einen Rest -NHR9, -N(R9)2, -N(R9)3 +Y- oder -COO-(CH2)1-3-T substituiert ist, worin

  • T die zuvor angegebene Bedeutung hat,
  • R9 Methyl oder Aethyl und
  • Y- ein Halogenidanion sind.
    • Particularly preferably independently of one another, R 1, R 2, R 3, R 4 and R 6 each represents hydrogen, optionally halogen-, C 1 -C 4 alkyl or C 1 -C 4 alkoxy substituted phenyl, optionally substituted in the phenyl ring by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, amino, acetylamino or propionylamino substituted benzoyl or phenylsulfonyl or a C 1 -C 4 alkyl radical which is unsubstituted or by hydroxy, carboxy, cyano, a radical -CONH- (CH 2 ) 1-3 -T,
    Figure 00050002
    Amino or a radical -NHR 9 , -N (R 9 ) 2 , -N (R 9 ) 3 + Y - or -COO- (CH 2 ) 1-3 -T is substituted, wherein
  • T has the meaning given above,
  • R 9 is methyl or ethyl and
  • Y - are a halide anion.

    • Ganz besonders bevorzugt bedeuten R1, R2, R3, R4 und R6 unabhängig voneinander je Wasserstoff, Phenyl, gegebenenfalls im Phenylring durch Methyl, Aethyl, Amino oder Acetylamino substituiertes Benzoyl oder Phenylsulfonyl, Methyl, Aethyl, Hydroxy-C1-C2-Alkyl, Carboxy-C1-C2-Alkyl, Cyano-C1-C3-Alkyl,

    Figure 00060001
    (R9)2N-C1-C3-Alky Y-(R9)3N+-C1-C3-Alkyl, oder einen Rest der Formel -CH2-CH(OH)-(CH2)1-2-T, -CH2-CH(R10)-COO-(CH2)1-3-T, oder -CH2-CH(R10)-CONH-(CH2)1-3-T worin

  • T Wasserstoff, -N(R9)2 oder -N(R9)3 +Y-,
  • R9 Methyl oder Aethyl,
  • R10 Wasserstoff oder Methyl und
  • Y- ein Bromid- oder Chloridanion sind.
    • R 1 , R 2 , R 3 , R 4 and R 6 are very particularly preferably each independently of the other hydrogen, phenyl, benzoyl or phenylsulfonyl, methyl, ethyl, hydroxy-C 1 - which is optionally substituted by methyl, ethyl, amino or acetylamino in the phenyl ring. C 2 alkyl, carboxy-C 1 -C 2 alkyl, cyano-C 1 -C 3 alkyl,
    Figure 00060001
    (R 9 ) 2 NC 1 -C 3 alkyl Y - (R 9 ) 3 N + -C 1 -C 3 alkyl, or a radical of the formula -CH 2 -CH (OH) - (CH 2 ) 1-2 -T, -CH 2 -CH (R 10 ) -COO- (CH 2 ) 1-3 -T, or -CH 2 -CH (R 10 ) -CONH- (CH 2 ) 1-3 -T wherein
  • T is hydrogen, -N (R 9 ) 2 or -N (R 9 ) 3 + Y - ,
  • R 9 is methyl or ethyl,
  • R 10 is hydrogen or methyl and
  • Y - are a bromide or chloride anion.

    • Besonders wichtig sind für R1, R2, R3, R4 und R6 unabhängig voneinander je die Bedeutungen Wasserstoff, Benzoyl, Phenylsulfonyl, 4-Aminophenylsulfonyl, 4-Acetylaminophenylsulfonyl, -CH2-CH2-COO-(CH2)1-2-CH3, -CH2-CH2-COOH, -CH2-CH2-OH, -CH2-CH2-CN,

    Figure 00060002
    -CH2-CH2-N(CH3)2 oder -CH2-CH2-N+(CH3)3 Y-, worin
    Y- ein Bromid- oder Chloridanion ist.The meanings hydrogen, benzoyl, phenylsulfonyl, 4-aminophenylsulfonyl, 4-acetylaminophenylsulfonyl, -CH 2 -CH 2 -COO- (CH 2 ) are particularly important for R 1 , R 2 , R 3 , R 4 and R 6 independently of one another. 1-2 -CH 3 , -CH 2 -CH 2 -COOH, -CH 2 -CH 2 -OH, -CH 2 -CH 2 -CN,
    Figure 00060002
    -CH 2 -CH 2 -N (CH 3 ) 2 or -CH 2 -CH 2 -N + (CH 3 ) 3 Y - , wherein
    Y - is a bromide or chloride anion.

    Ganz besonders wichtig für R2 und R4 ist die Bedeutung Wasserstoff.The importance of hydrogen is particularly important for R 2 and R 4 .

    In einer besonderen Ausführungsform der vorliegenden Erfindung haben R1, R3 und R6 die zuvor angegebenen Bedeutungen und Bevorzugungen und bedeuten nicht Wasserstoff.In a particular embodiment of the present invention, R 1 , R 3 and R 6 have the meanings and preferences given above and do not mean hydrogen.

    R5 ist bevorzugt Wasserstoff, Benzyl oder C1-C4-Alkyl, vorzugsweise Wasserstoff, Methyl oder Aethyl, insbesondere Wasserstoff oder Methyl.R 5 is preferably hydrogen, benzyl or C 1 -C 4 alkyl, preferably hydrogen, methyl or ethyl, in particular hydrogen or methyl.

    Bevorzugt für das erfindungsgemässe Verfahren sind Homo- oder Copolymere, worin R1, R3 und R6 unabhängig voneinander je Wasserstoff, Benzoyl, Phenylsulfonyl, 4-Aminophenylsulfonyl, 4-Acetylaminophenylsulfonyl, -CH2-CH2-COO-(CH2)1-2-CH3, -CH2-CH2-COOH, -CH2-CH2-OH, -CH2-CH2-CN,

    Figure 00070001
    -CH2-CH2-N(CH3)2 oder -CH2-CH2-N+(CH3)3 Y- bedeuten,

  • Y- ein Bromid- oder Chloridanion ist,
  • R2 und R4 Wasserstoff bedeuten und
  • R5 Wasserstoff, Benzyl oder C1-C4-Alkyl, vorzugsweise Wasserstoff, Methyl oder Aethyl, insbesondere Wasserstoff oder Methyl ist.
    • Preferred for the process according to the invention are homopolymers or copolymers in which R 1 , R 3 and R 6 independently of one another are each hydrogen, benzoyl, phenylsulfonyl, 4-aminophenylsulfonyl, 4-acetylaminophenylsulfonyl, -CH 2 -CH 2 -COO- (CH 2 ) 1-2 -CH 3 , -CH 2 -CH 2 -COOH, -CH 2 -CH 2 -OH, -CH 2 -CH 2 -CN,
    Figure 00070001
    -CH 2 -CH 2 -N (CH 3 ) 2 or -CH 2 -CH 2 -N + (CH 3 ) 3 Y - ,
  • Y - is a bromide or chloride anion,
  • R 2 and R 4 are hydrogen and
  • R 5 is hydrogen, benzyl or C 1 -C 4 alkyl, preferably hydrogen, methyl or ethyl, in particular hydrogen or methyl.

    • Für das erfindungsgemässe Verfahren sind Homo- oder Copolymere bevorzugt, welche wiederkehrende Struktureinheiten mindestens einer der Formeln (1) oder (2) enthalten, worin
    R1, R2, R3, R4, R5 und Y- die zuvor angegebenen Bedeutungen und Bevorzugungen haben.    For the process according to the invention, preference is given to homopolymers or copolymers which contain recurring structural units of at least one of the formulas (1) or (2), in which
    R 1 , R 2 , R 3 , R 4 , R 5 and Y - have the meanings and preferences given above.

    Die erfindungsgemäss als Fixiermittel verwendeten Homo- und Copolymere enthaltend wiederkehrende Strukturen der zuvor angegebenen Formeln (1), (2) und (3), worin die Bedeutungen von R1, R3 und R6 identisch sind, und R2 und R4 identische Bedeutungen haben, können hergestellt werden, z.B. indem man N-Vinylformamid oder N-Vinylacetamid und gegebenenfalls weitere copolymerisierbare Monomere polymerisiert, anschliessend hydrolysiert und die freien Aminogruppen des erhaltenen Homo- oder Copolymers einer Alkylierungsreaktion mit einem Alkylhalogenid R1-X1 und gegebenenfalls R2-X2 und R5-X5, worin R1, R2 und R5 jeweils die zuvor angegebenen Bedeutungen haben und X1, X2 und X5 unabhängig voneinander je ein Halogenidanion, vorzugsweise je das Bromid- oder Chloridion, darstellen, unterwirft. Anstelle der Alkylierungsreaktion mit einem geeigneten Alkylhalogenid kommt auch die Umsetzung der Aminogruppen des Homo- oder Copolymers mit einem geeigneten Epoxid oder mit einer doppelbindungshaltigen ungesättigten Verbindung in Frage.The homopolymers and copolymers used according to the invention as fixing agents containing recurring structures of the formulas (1), (2) and (3) given above, in which the meanings of R 1 , R 3 and R 6 are identical, and R 2 and R 4 are identical Meanings can be prepared, for example, by polymerizing N-vinylformamide or N-vinyl acetamide and, if appropriate, further copolymerizable monomers, then hydrolyzing and the free amino groups of the homo- or copolymer obtained in an alkylation reaction with an alkyl halide R 1 -X 1 and optionally R 2 -X 2 and R 5 -X 5 , in which R 1 , R 2 and R 5 each have the meanings given above and X 1 , X 2 and X 5 each independently represent a halide anion, preferably each the bromide or chloride ion, subjects. Instead of the alkylation reaction with a suitable alkyl halide, the reaction of the amino groups of the homo- or copolymer with a suitable epoxide or with a double bond-containing unsaturated compound is also suitable.

    Die erfindungsgemäss als Fixiermittel verwendeten Homo- und Copolymere enthaltend wiederkehrende Strukturen der zuvor angegebenen Formeln (1), (2) und (3), worin R2, R4, R5 und R7 Wasserstoff sind und die Bedeutungen von R1, R3 und R6 identisch sind, können vorteilhaft auch hergestellt werden, Indem man eine geeignete Vinylformamido-Verbindung, die z.B. der Formel (4)

    Figure 00080001
    entspricht und worin R6 die zuvor angegebene Bedeutung hat, polymerisiert und anschliessend sauer oder alkalisch hydrolysiert.The homopolymers and copolymers used according to the invention as fixing agents containing recurring structures of the formulas (1), (2) and (3) given above, in which R 2 , R 4 , R 5 and R 7 are hydrogen and the meanings of R 1 , R 3 and R 6 are identical, can also advantageously be prepared by adding a suitable vinylformamido compound, for example of the formula (4)
    Figure 00080001
    and where R 6 has the meaning given above, polymerized and then hydrolyzed acidic or alkaline.

    Handelt es sich bei den erfindungsgemäss verwendeten Polymeren um ein Copolymer, so kommen z.B. die folgenden copolymerisierbaren Monomere in Frage: Allylamin- oder Diallylamin-Derivate wie z.B. Diallylamin, N-Methyldiallylamin, N-Ethyldiallylamin, N,N-Dimethyldiallylamoniumchlorid; Monomere mit Carboxylfunktion, z.B. (Meth)acrylsäure, Maleinsäure, Fumarsäure, Itaconsäure, Mesaconsäure, Citraconsäure, Vinylessigsäure, Vinyloxyessigsäure, Vinylpropionsäure, Crotonsäure, Aconitsäure, Allylessigsäure, Allyloxyessigsäure, α,β-Dimethylacrylsäure, Allylmalonsäure, Allyloxymalonsäure, Methylenmalonsäure, 2-Hydroxy(meth)acrylsäure, 2-Halogeno(meth)acrylsäure, α-Ethylacrylsäure, Acrylamidoglycolsäure, Glutaconsäure, β-Carboxyethylacrylat, Allyloxy-3-hydroxybutansäure oder Allylbernsteinsäure; oder stickstoffhaltige und nicht-ionische Comonomere, z.B. N-Vinylpyrrolidon, N-Vinylformamid, N-Vinylacetamid, N-Vinyl-N-methyl-formamid, N-Vinyl-N-methyl-acetamid, N-Vinyl-N-ethyl-acetamid, N-Vinylimidazol, N-Vinyl-N-methyl-imidazol, N-Vinylimidazolin, N-Vinyl-2-methylimidazolin, N-Vinylcaprolactam, Vinylacetat, Vinylpropionat, Vinylbutyrat, C1-C22-Alkylvinylketon, C1-C22-Alkylvinylether, Olefine (Ethylen, Propylen, Isobuten), 1,2-Dimethoxyethylen, Hydroxy-C2-C4-Alkyl-(meth)-acrylat, (Meth)acrylsäure-C1-C22-alkylester, (Meth)acrolein, (Meth)acrylnitril, (Meth)acrylamid, N-Mono/N,N-Di-C1-C10-Alkyl-(meth)acrylamid, (C1-C4)-Alkoxy-(meth)acrylate, oder N,N-Di-C1-C2-Alkylamino-C1-C4-alkyl-(meth)acrylate in Form der Salze oder in quaternierter Form, wobei geeignete Quaternierungsmittel z.B. Dimethyl/ethyl-sulfat, Methyl/ethyl-chlorid oder Benzylchlorid sind.If the polymers used according to the invention are a copolymer, the following copolymerizable monomers are suitable, for example: allylamine or diallylamine derivatives such as, for example, diallylamine, N-methyldiallylamine, N-ethyldiallylamine, N, N-dimethyldiallylamonium chloride; Monomers with carboxyl function, for example (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, vinyl acetic acid, vinyl oxyacetic acid, vinyl propionic acid, crotonic acid, aconitic acid, allyl acetic acid, allyloxyacetic acid, α, β-dimethylacrylic acid, allylmalmalonic acid, allyloxymalonic acid, meth) acrylic acid, 2-halogeno (meth) acrylic acid, α-ethyl acrylic acid, acrylamidoglycolic acid, glutaconic acid, β-carboxyethyl acrylate, allyloxy-3-hydroxybutanoic acid or allylsuccinic acid; or nitrogen-containing and non-ionic comonomers, for example N-vinylpyrrolidone, N-vinylformamide, N-vinyl acetamide, N-vinyl-N-methylformamide, N-vinyl-N-methyl-acetamide, N-vinyl-N-ethyl-acetamide , N-vinylimidazole, N-vinyl-N-methylimidazole, N-vinylimidazoline, N-vinyl-2-methylimidazoline, N-vinylcaprolactam, vinyl acetate, vinyl propionate, vinyl butyrate, C 1 -C 22 alkyl vinyl ketone, C 1 -C 22 -Alkyl vinyl ether, olefins (ethylene, propylene, isobutene), 1,2-dimethoxyethylene, hydroxy-C 2 -C 4 -alkyl- (meth) -acrylate, (meth) acrylic acid-C 1 -C 22 -alkyl ester, (meth) acrolein, (meth) acrylonitrile, (meth) acrylamide, N-mono / N, N-di-C 1 -C 10 alkyl (meth) acrylamide, (C 1 -C 4 ) alkoxy (meth) acrylates, or N, N-di-C 1 -C 2 -alkylamino-C 1 -C 4 -alkyl- (meth) acrylates in the form of the salts or in quaternized form, suitable quaternizing agents, for example dimethyl / ethyl sulfate, methyl / ethyl are chloride or benzyl chloride.

    Bevorzugt als copolymerisierbare Monomere in den erfindungsgemässen Fixiermitteln sind Allylamin- oder Diallylamin-Derivate, (Meth)acrylsäure, Maleinsäure, N-Vinylpyrrolidon, N-Vinylformamid, N-Vinylacetamid, N-Vinyl-N-methyl-formamid, N-Vinyl-N-methyl-acetamid, N-Vinyl-N-ethyl-acetamid, N-Vinylimidazol, Vinylacetat, Vinylpropionat, Hydroxy-C2-C4-Alkyl-(meth)acrylat, (Meth)acrylsäure-C1-C22-alkylester, Acrylnitril, Methacrylnitril, Acrylamid, Methacrylamid, N-Mono/N,N-Di-C1-C10-Alkyl-(meth)acrylamid oder N,N-Di-C1-C2-Alkylamino-C2-C4-alkyl-(meth)acrylate in Form der Salze oder in quaternierter Form, wobei geeignete Quaternlerungsmittel z.B. Dimethyl/ethyl-sulfat, Methyl/ethyl-chlorid oder Benzylchlorid sind.Preferred copolymerizable monomers in the fixing agents according to the invention are allylamine or diallylamine derivatives, (meth) acrylic acid, maleic acid, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylformamide, N-vinyl-N -methyl-acetamide, N-vinyl-N-ethyl-acetamide, N-vinylimidazole, vinyl acetate, vinyl propionate, hydroxy-C 2 -C 4 alkyl (meth) acrylate, (meth) acrylic acid-C 1 -C 22 alkyl ester , Acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N-mono / N, N-di-C 1 -C 10 -alkyl- (meth) acrylamide or N, N-di-C 1 -C 2 -alkylamino-C 2 -C 4 -alkyl- (meth) acrylates in the form of the salts or in quaternized form, suitable quaternizing agents being, for example, dimethyl / ethyl sulfate, methyl / ethyl chloride or benzyl chloride.

    Besonders bevorzugt als copolymerisierbare Monomere in den erfindungsgemässen Fixiermitteln sind Acrylsäure, Methacrylsäure, Acrylnitril, Methacrylnitril, N-Vinylpyrrolidon, N-Vinylformamid, N-Vinylacetamid, N-Vinyl-N-methyl-formamid, N-Vinyl-N-methyl-acetamid, N-Vinyl-N-ethyl-acetamid, N-Vinylimidazol, Vinylacetat, Acrylamid, Methacrylamid, N-Monooder N,N-Di-C1-C4-Alkyl-(meth)acrylamid.Particularly preferred as copolymerizable monomers in the fixing agents according to the invention are acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylformamide, N-vinyl-N-methyl-acetamide, N-vinyl-N-ethyl-acetamide, N-vinylimidazole, vinyl acetate, acrylamide, methacrylamide, N-mono or N, N-di-C 1 -C 4 alkyl- (meth) acrylamide.

    Ganz besonders bevorzugt als copolymerisierbare Monomere In den erfindungsgemässen Fixiermitteln sind N-Vinylpyrrolidon, N-Vinylformamid, N-Vinylacetamid, N-Vinyl-N-methyl-formamid, N-Vinyl-N-methyl-acetamid, N-Vinyl-N-ethyl-acetamid, N-Vinylimidazol, Vinylacetat, Acrylamid, Methacrylamid, N-Mono- oder N,N-Di-C1-C4-Alkyl-(meth)acrylamld.Very particularly preferred as copolymerizable monomers in the fixing agents according to the invention are N-vinylpyrrolidone, N-vinylformamide, N-vinyl acetamide, N-vinyl-N-methylformamide, N-vinyl-N-methyl-acetamide, N-vinyl-N-ethyl -acetamide, N-vinylimidazole, vinyl acetate, acrylamide, methacrylamide, N-mono- or N, N-di-C 1 -C 4 alkyl- (meth) acrylamld.

    Bevorzugte Ausführungsformen der erfindungsgemäss als Fixiermittel verwendeten Polymere betreffen:Preferred embodiments of the fixatives used according to the invention Polymers relate to:

    (i) Homo- oder Copolymere enthaltend 5 bis 100 Mol-% wiederkehrende Struktureinheiten der Formeln (1a) und (1b)(i) Homo- or copolymers containing 5 to 100 mol% of repeating structural units of the formulas (1a) and (1b)

    Figure 00090001
    und 95 bis 0 Mol-% wiederkehrende Struktureinheiten der Formeln (5) und (6)
    Figure 00090002
    , worin

  • R1 und R2 die zuvor angegebenen Bedeutungen und Bevorzugungen haben,
  • R11 und R13 unabhängig voneinander je Wasserstoff oder Methyl und
  • R12 und R14 unabhängig voneinander je 2-Pyrrolidon-1-yl, Amino, N-Methylamino, N-Ethylamino, -NH-CHO, -NH-CO-CH3, -N(CH3)-CHO, -N(CH3)-CO-CH3, -N(C2H5)-CO-CH3, lmidazol-1-yl, -O-CO-CH3, -CO-NH2, -CO-NH(CH3) oder -CO-N(CH3)2 sind und
  • w, x, y und z ganze Zahlen bedeuten, die gleich oder grösser 1 oder die Zahl 0 sind, wobei
    für den Quotienten Q = w+x w+x+y+z die Bedingung, Q = 0,05 bis 1 gilt.
    • Figure 00090001
    and 95 to 0 mol% of repeating structural units of the formulas (5) and (6)
    Figure 00090002
    , in which
  • R 1 and R 2 have the meanings and preferences given above,
  • R 11 and R 13 are each independently hydrogen or methyl and
  • R 12 and R 14 are each independently 2-pyrrolidon-1-yl, amino, N-methylamino, N-ethylamino, -NH-CHO, -NH-CO-CH 3 , -N (CH 3 ) -CHO, -N (CH 3 ) -CO-CH 3 , -N (C 2 H 5 ) -CO-CH 3 , imidazol-1-yl, -O-CO-CH 3 , -CO-NH 2 , -CO-NH (CH 3 ) or -CO-N (CH 3 ) 2 and
  • w, x, y and z mean integers which are equal to or greater than 1 or the number 0, where
    for the quotient Q = w + x w + x + y + z the condition Q = 0.05 to 1 applies.

    • Der Quotient Q ist definiert durch das Verhältniss der Struktureinheiten der Formeln (1a) und (1b) zu der Gesamtzahl aller Struktureinheiten im Copolymer. Die Gesamtzahl aller Struktureinheiten im Copolymer ergibt sich aus der Summe der Struktureinheiten der Formeln (1a), (1b), (5) und (6).The quotient Q is defined by the ratio of the structural units of the formulas (1a) and (1b) the total number of all structural units in the copolymer. The total number of all Structural units in the copolymer result from the sum of the structural units of the Formulas (1a), (1b), (5) and (6).

    Bevorzugt bedeuten R1 und R2 in den zuvor unter (i) näher bezeichneten Homo- oder Copolymeren unabhängig voneinander je Wasserstoff, Methyl, Aethyl, Hydroxy-C1-C2-Alkyl, Carboxy-C1-C2-Alkyl, Cyano-C1-C3-Alkyl, (R9)2N-C1-C3-Alkyl, Y-(R9)3N+-C1-C3-Alkyl, oder einen Rest der Formel -CH2-CH(OH)-(CH2)1-2-T, -CH2-CH(R10)-COO-(CH2)1-3-T, oder -CH2-CH(R10)-CONH-(CH2)1-3-T worin

  • T Wasserstoff, -N(R9)2 oder -N(R9)3 +Y-,
  • R9 Methyl oder Aethyl,
  • R10 Wasserstoff oder Methyl und
  • Y- ein Bromid- oder Chloridanlon sind.
    • R 1 and R 2 in the homo- or copolymers described in more detail under (i) preferably each independently represent hydrogen, methyl, ethyl, hydroxy-C 1 -C 2 -alkyl, carboxy-C 1 -C 2 -alkyl, cyano -C 1 -C 3 alkyl, (R 9 ) 2 NC 1 -C 3 alkyl, Y - (R 9 ) 3 N + -C 1 -C 3 alkyl, or a radical of the formula -CH 2 -CH (OH) - (CH 2 ) 1-2 -T, -CH 2 -CH (R 10 ) -COO- (CH 2 ) 1-3 -T, or -CH 2 -CH (R 10 ) -CONH- (CH 2 ) 1-3 -T wherein
  • T is hydrogen, -N (R 9 ) 2 or -N (R 9 ) 3 + Y - ,
  • R 9 is methyl or ethyl,
  • R 10 is hydrogen or methyl and
  • Y - are a bromide or chloride anion.

    • Besonders bevorzugt bedeuten R1 und R2 in den zuvor unter (i) näher bezeichneten Homo- oder Copolymeren unabhängig voneinander je Wasserstoff, -CH2-CH2-COO-(CH2)1-2-CH3, -CH2-CH2-COOH, -CH2-CH2-OH, -CH2-CH2-CN, -CH2-CH2-N(CH3)2 oder -CH2-CH2-N+(CH3)3 Y-, worin
    Y- ein Bromid- oder Chloridanion ist.
    Ganz besonders bevorzugt haben R1 und R2 in den zuvor unter (i) näher bezeichneten Homo- oder Copolymeren identische Bedeutungen.    R 1 and R 2 in the homo- or copolymers described in more detail above under (i) are particularly preferably each independently of the other hydrogen, -CH 2 -CH 2 -COO- (CH 2 ) 1-2 -CH 3 , -CH 2 - CH 2 -COOH, -CH 2 -CH 2 -OH, -CH 2 -CH 2 -CN, -CH 2 -CH 2 -N (CH 3 ) 2 or -CH 2 -CH 2 -N + (CH 3 ) 3 Y - , where
    Y - is a bromide or chloride anion.
    R 1 and R 2 very particularly preferably have identical meanings in the homopolymers or copolymers described in more detail above under (i).

    In einer wichtigen Ausführungsform der vorliegenden Erfindung enthalten die zuvor unter (i) näher bezeichneten Homo- oder Copolymere 20 bis 100 Mol-% wiederkehrende Struktureinheiten der Formeln (1a) und (1b) und 80 bis 0 Mol-% wiederkehrende Struktureinheiten der Formeln (5) und (6), wobei für den Quotienten Q die Bedingung, Q = 0,2 bis 1, gilt.In an important embodiment of the present invention, the previously included (i) specified homo- or copolymers 20 to 100 mol% recurring Structural units of the formulas (1a) and (1b) and 80 to 0 mol% recurring Structural units of the formulas (5) and (6), the condition for the quotient Q being Q = 0.2 to 1 applies.

    In einer besonders wichtigen Ausführungsform der vorliegenden Erfindung enthalten die zuvor unter (i) näher bezeichneten Homo- oder Copolymere 40 bis 100 Mol-% wiederkehrende Struktureinheiten der Formeln (1a) und (1b) und 60 bis 0 Mol-% wiederkehrende Struktureinheiten der Formeln (5) und (6), wobei für den Quotienten Q die Bedingung, Q = 0,4 bis 1, gilt.In a particularly important embodiment of the present invention, the 40 to 100 mol% of homo- or copolymers previously specified under (i) recurring structural units of the formulas (1a) and (1b) and 60 to 0 mol% recurring structural units of the formulas (5) and (6), where for the quotient Q the condition Q = 0.4 to 1 applies.

    Bedeutet w der unter (i) näher bezeichneten Homo- oder Copolymere die Zahl 0, so sind Copolymere bevorzugt, die 20 bis 80 Mol-% wiederkehrende Struktureinheiten der Formel (1b) und 80 bis 20 Mol-% wiederkehrende Struktureinheiten der Formeln (5) und (6) enthalten, wobei für den Quotienten Q die Bedingung, Q = 0,2 bis 0,8, gilt.Means w the under (i) specified homo- or copolymers have the number 0, are Copolymers preferred, the 20 to 80 mol% recurring structural units of the Formula (1b) and 80 to 20 mol% of repeating structural units of the formulas (5) and (6) included, where the condition, Q = 0.2 to 0.8, applies to the quotient Q.

    (ii) Homo- oder Copolymere enthaltend wiederkehrende Struktureinheiten mindestens einer der Formeln (7) und (8)(ii) Homopolymers or copolymers containing recurring structural units of at least one of formulas (7) and (8)

    Figure 00110001
    worin

  • R15 Phenyl oder gegebenenfalls im Phenylring durch Methyl, Aethyl, Amino oder Acetylamino substituiertes Benzoyl oder Phenylsulfonyl bedeutet;
    bevorzugt Copolymere enthaltend 1 bis 50 Mol-% wiederkehrende Struktureinheiten der Formeln (7) und (8) und 99 bis 50 Mol-% wiederkehrende Struktureinheiten der Formeln (5) und (6), worin
  • R11, R12, R13 und R14 unabhängig voneinander je die zuvor unter (i) genannten Bedeutungen haben und
  • w, x, y und z ganze Zahlen bedeuten, die gleich oder grösser 1 oder die Zahl 0 sind,
    • wobei
    für den Quotienten Q = w+x w+x+y+z die Bedingung gilt, Q = 0,01 bis 0,5.
    Figure 00110001
    wherein
  • R 15 is phenyl or benzoyl or phenylsulfonyl which is optionally substituted in the phenyl ring by methyl, ethyl, amino or acetylamino;
    preferably copolymers containing 1 to 50 mol% of repeating structural units of the formulas (7) and (8) and 99 to 50 mol% of repeating structural units of the formulas (5) and (6), in which
  • R 11 , R 12 , R 13 and R 14 each independently have the meanings given above under (i) and
  • w, x, y and z are integers which are equal to or greater than 1 or the number 0,
    • in which
    for the quotient Q = w + x w + x + y + z the condition applies, Q = 0.01 to 0.5.

    Der Quotient Q ist definiert durch das Verhältniss der Struktureinheiten der Formeln (7) und (8) zu der Gesamtzahl aller Struktureinheiten im Copolymer. Die Gesamtzahl aller Struktureinheiten im Copolymer ergibt sich aus der Summe der Struktureinheiten der Formeln (7), (8), (5) und (6).The quotient Q is defined by the ratio of the structural units of the formulas (7) and (8) the total number of all structural units in the copolymer. The total number of all Structural units in the copolymer result from the sum of the structural units of the Formulas (7), (8), (5) and (6).

    Bevorzugt enthalten die zuvor unter (ii) näher bezeichneten Homo- oder Copolymere 1 bis 25 Mol-% wiederkehrende Struktureinheiten der Formeln (7) und (8) und 99 bis 75 Mol-% wiederkehrende Struktureinheiten der Formeln (5) und (6), wobei für den Quotienten Q die Bedingung, Q = 0,01 bis 0,25, gilt.The homopolymers or copolymers described in detail above under (ii) preferably contain 1 to 25 mol% of repeating structural units of the formulas (7) and (8) and 99 to 75 Mol% recurring structural units of the formulas (5) and (6), wherein for the Quotient Q the condition, Q = 0.01 to 0.25, applies.

    Es können auch Gemische von mehreren der zuvor genannten Homo- oder Copolymere als Fixiermittel verwendet werden.Mixtures of several of the aforementioned homo- or copolymers can also be used as Fixing agents are used.

    Die als Fixiermittel verwendeten Homo- oder Copolymere weisen ein mittleres Molekulargewicht von 1 000 bis 1 000 000, vorzugsweise 1 000 bis 500 000 und insbesondere 5 000 bis 200 000 auf.The homopolymers or copolymers used as fixing agents have a medium one Molecular weight of 1,000 to 1,000,000, preferably 1,000 to 500,000 and in particular 5,000 to 200,000.

    Einen weiteren Gegenstand der vorliegenden Erfindung bilden Homo- oder Copolymere, dadurch gekennzeichnet, dass sie Struktureinheiten der Formel (7) enthalten. Die erfindungsgemässen Polymere können wie zuvor beschrieben hergestellt werden.Another object of the present invention are homopolymers or copolymers, characterized in that they contain structural units of the formula (7). The Polymers according to the invention can be produced as described above.

    Die Herstellung der als Fixiermittel verwendeten Polymere bzw. der erfindungsgemässen Polymere, enthaltend Struktureinheiten der Formel (7), erfolgt in an sich bekannter Weise, z.B. durch ionisch oder vorzugsweise radikalisch eingeleitete Polymerisation der entsprechenden Monomere z.B. in Lösung, Suspension oder Emulsion, und gegebenenfalls anschliessende Hydrolyse. Die Polymerisation erfolgt dabei bevorzugt in Lösung mit einem Peroxid, Persulfat oder einer Azoverbindung, z.B. mit Kaliumpersulfat oder Azo-bis-(2-amidinopropan)-hydrochlorid, als Radikalkettenstarter, wobei dieser z.B. in einer Menge von 0,005 bis 10 Gew.-%, bezogen auf die eingesetzten Monomere, anwesend ist. Schliesst sich an die Polymerisation ein Hydrolyseschritt an, so erfolgt dieser unter alkalischen oder vorzugsweise unter sauren Bedingungen. Im Fall einer sauren Hydrolyse erhält man vorwiegend Polymere mit Struktureinheiten der zuvor angegebenen Formel (2), worin R5 Wasserstoff bedeutet.The polymers used as fixatives or the polymers according to the invention containing structural units of the formula (7) are prepared in a manner known per se, for example by ionically or preferably free-radically initiated polymerization of the corresponding monomers, for example in solution, suspension or emulsion, and, if appropriate, subsequent Hydrolysis. The polymerization is preferably carried out in solution with a peroxide, persulfate or an azo compound, for example with potassium persulfate or azo-bis- (2-amidinopropane) hydrochloride, as a free-radical initiator, this in an amount of, for example, 0.005 to 10% by weight, based on the monomers used, is present. If the polymerization is followed by a hydrolysis step, this takes place under alkaline or preferably under acidic conditions. In the case of acidic hydrolysis, polymers with structural units of the formula (2) given above are obtained, in which R 5 is hydrogen.

    Das erfindungsgemäss als Fixiermittel verwendete Homo- oder Copolymer wird unabhängig vom Flottenverhältnis z.B. in einer Menge von 0,05 bis 10 Gew.-%, vorzugsweise 0,2 bis 4 Gew.-% und besonders bevorzugt 0,5 bis 2 Gew.-% Wirkstoffgehalt, bezogen auf das Gewicht des Polyamidfasermaterials, eingesetzt.The homopolymer or copolymer used according to the invention as a fixing agent becomes independent fleet ratio e.g. in an amount of 0.05 to 10% by weight, preferably 0.2 to 4 % By weight and particularly preferably 0.5 to 2% by weight of active compound, based on the Weight of the polyamide fiber material used.

    Die Behandlung des Polyamidfasermaterials mit dem Fixiermittel kann vor, während oder vorzugsweise nach dem Färben erfolgen. Vorteilhaft führt man das erfindungsgemässe Verfahren aus, indem man zunächst das Polyamidfasermaterial in üblicher Weise färbt und anschliessend eine Nachbehandlung mit einer das Fixiermittel in der zuvor angegebenen Menge enthaltenden frischen wässrigen Flotte anschliesst. Danach kann das gefärbte Polyamidfasermaterial ohne weiteren Spülvorgang entwässert und auf übliche Weise getrocknet werden. Die Nachfixierung erfolgt in der Regel in frischer Flotte. Sie ist aber auch direkt im Färbebad durchführbar, sofem das Färbebad am Ende weitgehend ausgezogen und noch genügend sauer Ist. Im Anschluss an die Fixierung wird in der Regel mit Wasser kurz kalt gespült.The treatment of the polyamide fiber material with the fixing agent can be before, during or preferably after dyeing. It is advantageous to carry out the process according to the invention Process by first dyeing the polyamide fiber material in the usual way and then a post-treatment with the fixative in the previously specified Amount containing fresh aqueous liquor. After that, the colored one Polyamide fiber material drained without further rinsing and in the usual way be dried. Post-fixation is usually done in a fresh liquor. But it is also Can be carried out directly in the dye bath, provided that the dye bath is largely pulled out at the end and is still sufficiently acidic. After the fixation is usually done with water briefly rinsed cold.

    Als Polyamidfasermaterial kommt natürliches Polyamidfasermaterial, wie z.B. Wolle oder Seide, oder synthetisches Polyamidfasermaterial, wie z.B. Polyamid 6 oder Polyamid 6.6, oder Fasermischungen wie z.B. Wolle/Cellulose- oder Polyamid/Cellulose-Mischfasern oder Polyamid/Wolle-Mischfasem In Betracht.Natural polyamide fiber material such as e.g. Wool or Silk, or synthetic polyamide fiber material, e.g. Polyamide 6 or polyamide 6.6, or fiber mixtures such as Wool / cellulose or polyamide / cellulose mixed fibers or Polyamide / wool blended into consideration.

    Das Textilgut ist in jeglicher Form anwendbar, z.B. als Faser, Garn, Gewebe oder Gewirke.The textile can be used in any form, e.g. as fiber, yarn, woven or knitted fabric.

    Die Färbungen erfolgen beispielsweise mit anionischen Farbstoffen, wobei alle üblichen anionischen Farbstoffe, wie sie z.B. in Colour Index, 3. Auflage (1971) sowie den Nachträgen dazu unter den Rubriken "Acid Dyes" oder in den Patentschriften US-A-5,725,606, US-A-5,691,459, US-A-5,650,497, US-A-5,630,851, US-A-5,527,889, US-A-5,234,467, US-A- 5,131,919, US-A-5,094,665, US-A-5,092,905 und US-A-2,844,597 beschrieben sind, in Frage kommen.The dyeings are carried out, for example, with anionic dyes, all of the usual anionic dyes, e.g. in Color Index, 3rd edition (1971) and the Addenda to this under the heading "Acid Dyes" or in the patents US-A-5,725,606, US-A-5,691,459, US-A-5,650,497, US-A-5,630,851, US-A-5,527,889, US-A-5,234,467, US-A-5,131,919, US-A-5,094,665, US-A-5,092,905 and US-A-2,844,597 are described.

    Beispiele sind sulfogruppenhaltige Monoazo-, Polyazo-, Metallkomplexazo-, Anthrachinon-, Phthalocyanin- oder Formazanfarbstoffe.Examples are sulfo group-containing monoazo, polyazo, metal complex azo, anthraquinone, Phthalocyanine or formazan dyes.

    Die zum Färben des Polyamidfasermaterials verwendeten anionischen Farbstoffe liegen entweder in der Form ihrer freien Sulfonsäure oder vorzugsweise als deren Salze vor.The anionic dyes used to dye the polyamide fiber material lie either in the form of their free sulfonic acid or preferably as their salts.

    Als Salze kommen beispielsweise die Alkali-, Erdalkali- oder Ammoniumsalze oder die Salze eines organischen Amins in Betracht. Als Beispiele seien die Natrium-, Lithium-, Kaliumoder Ammoniumsalze oder das Salz des Mono-, Di- oder Triäthanolamins genannt.The salts include, for example, the alkali, alkaline earth or ammonium salts or the salts an organic amine. Examples include sodium, lithium, potassium or Ammonium salts or the salt of mono-, di- or triethanolamine called.

    Die zum Färben des Polyamidfasermaterials verwendeten anionischen Farbstoffe können weitere Zusätze, wie z.B. Kochsalz oder Dextrin, enthalten.The anionic dyes used to dye the polyamide fiber material can other additives, e.g. Cooking salt or dextrin.

    Das Färben des Polyamidfasermaterials mit anionischen Farbstoffen kann gemäss den für diese Farbstoffe üblichen Färbe- bzw. Druckverfahren, beispielsweise nach dem Ausziehverfahren, durchgeführt werden. Die Färbeflotten oder Druckpasten können ausser Wasser und den Farbstoffen weitere Zusätze, beispielsweise Netzmittel, Antischaummittel, Egalisiermittel oder die Eigenschaft des Textilmaterials beeinflussende Mittel wie z.B. Weichmachungsmittel, Zusätze zum Flammfestausrüsten oder schmutz-, wasser- und ölabweisende Mittel sowie wasserenthärtende Mittel und natürliche oder synthetische Verdicker, wie z.B. Alginate und Celluloseäther, enthalten.The dyeing of the polyamide fiber material with anionic dyes can be carried out according to the these dyes usual dyeing or printing processes, for example according to Pull-out procedure. The dyeing liquors or printing pastes can also Water and the dyes further additives, for example wetting agents, anti-foaming agents, Leveling agents or agents influencing the property of the textile material, e.g. Plasticizers, additives for flame retardant or dirt, water and oil repellent Agents and water softening agents and natural or synthetic Thickeners, e.g. Alginates and cellulose ethers.

    Die Mengen, in denen anionische Farbstoffe in den Färbebädern oder Druckpasten verwendet werden, können je nach der gewünschten Farbtiefe in weiten Grenzen schwanken, im allgemeinen haben sich Mengen von 0,01 bis 15 Gew.-%, insbesondere 0,01 bis 10 Gew.-%, bezogen auf das Färbegut bzw. die Druckpaste, als vorteilhaft erwiesen.The amounts of anionic dyes in the dye baths or printing pastes can be used within wide limits depending on the desired depth of color fluctuate, generally amounts have from 0.01 to 15% by weight, in particular 0.01 up to 10% by weight, based on the dye material or the printing paste, has been found to be advantageous.

    Vorzugsweise erfolgt das Färben mit anionischen Farbstoffen bei einem pH-Wert von 3 bis 7, insbesondere 4 bis 7. Das Flottenverhältnis kann innerhalb eines weiten Bereichs gewählt werden, z.B. von 1:5 bis 1:50, vorzugsweise 1:5 bis 1:30. Vorzugsweise färbt man bei einer Temperatur von 70 bis 110°C, insbesondere 80 bis 105°C.The dyeing is preferably carried out with anionic dyes at a pH of 3 to 7, in particular 4 to 7. The liquor ratio can be chosen within a wide range e.g. from 1: 5 to 1:50, preferably 1: 5 to 1:30. It is preferable to dye one Temperature from 70 to 110 ° C, especially 80 to 105 ° C.

    Die Nachbehandlung erfolgt bevorzugt nach dem Ausziehverfahren. Das Flottenverhältnis kann dabei innerhalb eines weiten Bereichs gewählt werden und beträgt z.B. 1:4 bis 1:100, vorzugsweise 1:10 bis 1:40 und insbesondere 1:5 bis 1:40.The aftertreatment is preferably carried out using the exhaust method. The fleet ratio can be selected within a wide range and is e.g. 1: 4 to 1: 100, preferably 1:10 to 1:40 and in particular 1: 5 to 1:40.

    Besondere Vorrichtungen sind nicht erforderlich. Es können z.B. die üblichen Färbeapparate, z.B. offene Bäder, Haspelkufen, Jigger oder Paddel-, Düsen- oder Zirkulationsapparate, verwendet werden.Special devices are not required. For example, the usual Dyeing machines, e.g. open baths, reel runners, jigger or paddle, jet or Circulators can be used.

    Man arbeitet zweckmässig bei einer Temperatur von z.B. 20 bis 100°C und vorzugswelse 30 bis 80°C. Die Behandlungszeit kann z.B. 10 bis 60 Minuten betragen und vorzugsweise 15 bis 40 Minuten betragen, wobei auch für dunkle Farbtöne, wie z.B. Schwarzfärbungen 15 Minuten bei 75°C ausreichend sind. Der pH-Wert der Flotte liegt in der Regel bei 4 bis 10, vorzugsweise bei 5 bis 7 und insbesondere bei 4,5 bis 6.It is convenient to work at a temperature of e.g. 20 to 100 ° C and preferred catfish 30 up to 80 ° C. The treatment time can e.g. 10 to 60 minutes and preferably 15 up to 40 minutes, whereby also for dark shades, e.g. Black coloring 15 Minutes at 75 ° C are sufficient. The pH of the liquor is usually 4 to 10, preferably 5 to 7 and in particular 4.5 to 6.

    Die Flotte kann ausser dem Fixiermittel weitere übliche Zusätze, z.B. Elektrolyte wie z.B. Natriumchlorid oder Natriumsulfat, Dispergier- und Netzmittel sowie Entschäumer, enthalten.In addition to the fixative, the liquor can contain other conventional additives, e.g. Electrolytes such as Sodium chloride or sodium sulfate, dispersing and wetting agents and defoamers.

    Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung des oben beschriebenen Verfahrens zur Verbesserung der Ozonechtheit von Färbungen auf natürlichen oder synthetischen Polyamidfasermaterialien.Another object of the present invention is the use of the above described method for improving the ozone fastness of dyeings natural or synthetic polyamide fiber materials.

    Man erhält nach dem erfindungsgemässen Verfahren Färbungen oder Drucke von Farbstoffen, z.B. anionischen Farbstoffen, auf Polyamidfasermaterial, welche eine erhebliche Verbesserung der Ozonechtheit und der Nassechtheiten, wie z.B. der Waschund Wasserechtheiten und insbesondere der Chlorechtheit aufweisen, ohne dass die Farbausbeute, Nuance oder die Lichtechtheiten negativ beeinflusst werden. Ausserdem zeigen die behandelten Färbungen und Drucke keinerlei Versteifung. Auf bedrucktem Polyamidfasermaterial wird die Anschmutzung des Weissfonds verhindert.The process according to the invention gives dyeings or prints of Dyes, e.g. anionic dyes, on polyamide fiber material, which a significant improvement in ozone fastness and wet fastness, e.g. the washing and Show water rights and especially chlorine without the Color yield, shade or light fastness can be adversely affected. Furthermore the treated dyeings and prints show no stiffening. On printed Polyamide fiber material prevents soiling of the white fund.

    Die nachfolgenden Beispiele dienen zur Erläuterung der Erfindung. Die Temperaturen sind in Celsiusgraden angegeben, Teile sind Gewichtsteile, die Prozentangaben beziehen sich auf Gewichtsprozente, sofern nicht anders vermerkt. Gewichtsteile stehen zu Volumenteilen im Verhältnis von Kilogramm zu Liter.The following examples serve to explain the invention. The temperatures are stated in degrees Celsius, parts are parts by weight, the percentages refer percentages by weight, unless stated otherwise. Parts by weight relate to parts by volume in the ratio of kilograms to liters.

    HerstellungsbeispielePreparation Examples

    Beispiel 1: 60 Teile Vinylformamid und 60 Teile entionisiertes Wasser werden in einem Reaktor vorgelegt und unter Stickstoff auf ca. 70°C geheizt. Dann wird eine Lösung von 1,8 Teilen Natriumpersulfat in 12 Teilen Wasser innerhalb von 90 Minuten zugetropft. Anschliessend lässt man 6 Stunden bei 75°C nachpolymerisieren. Dann wird eine Lösung aus 83 Teilen 37%ige Salzsäure in 90 Teilen Wasser zugegeben und 4 Stunden lang bei ca. 80°C geheizt. Nach Einstellung eines Aktivgehalts von 20% wird eine leicht viskose, klare Polymerlösung erhalten, deren Wirksubstanz als Hydrochlorid vorliegt und im wesentlichen Struktureinheiten der Formeln

    Figure 00160001
    enthält, wobei der Wert Q (x/x+y) etwa 0,8 beträgt. Example 1: 60 parts of vinylformamide and 60 parts of deionized water are placed in a reactor and heated to about 70 ° C. under nitrogen. A solution of 1.8 parts of sodium persulfate in 12 parts of water is then added dropwise within 90 minutes. The mixture is then left to polymerize at 75 ° C. for 6 hours. A solution of 83 parts of 37% hydrochloric acid in 90 parts of water is then added and the mixture is heated at about 80 ° C. for 4 hours. After setting an active content of 20%, a slightly viscous, clear polymer solution is obtained, the active substance of which is in the form of hydrochloride and essentially structural units of the formulas
    Figure 00160001
    contains, the value Q (x / x + y) being approximately 0.8.

    Beispiel 2: 135 Teile einer 17,5%igen, hydrolysierten Polyvinylformamidlösung (Hydrolysegrad ca. 80%) werden bis pH 9,5 neutralisiert. Nach Zugabe von 0,5 Teilen Benzyltrimethylammoniumhydroxid und 2,4 Teilen Vinylsulfonyl-4-aminobenzol wird 2 Stunden bei ca. 70°C erhitzt. Nach Einstellung des pH auf 6 und eines Aktivgehalts von 20% wird eine leicht viskose, klare Polymerlösung erhalten, deren Wirksubstanz teilweise als Hydrochlorid vorliegt und im wesentlichen Struktureinheiten der Formeln (101), (102) und

    Figure 00160002
    enthält und eine Viskosität von 2530 cP aufweist. Example 2: 135 parts of a 17.5% hydrolyzed polyvinylformamide solution (degree of hydrolysis approx. 80%) are neutralized to pH 9.5. After adding 0.5 parts of benzyltrimethylammonium hydroxide and 2.4 parts of vinylsulfonyl-4-aminobenzene, the mixture is heated at about 70 ° C. for 2 hours. After adjusting the pH to 6 and an active content of 20%, a slightly viscous, clear polymer solution is obtained, the active substance of which is partly present as hydrochloride and essentially contains structural units of the formulas (101), (102) and
    Figure 00160002
    contains and has a viscosity of 2530 cP.

    Beispiel 3: 21,3 Teile Vinylformamid, 15,9 Teile Acrylnitril, 15,9 Teile einer 30%igen Acrylamidlösung und 145 Teile Wasser werden in einem Reaktor vorgelegt und unter Stickstoff auf ca. 80°C aufgeheizt. Dann wird eine Lösung von 1,45 Teilen Azobis(amidinopropan)-hydrochlorid in 10 Teilen Wasser innerhalb von 90 Minuten zugetropft. Anschliessend lässt man 4 Stunden bei 80°C nachpolymerisieren. Nach Zugabe von 29,5 Teilen 37%ige Salzsäure wird noch 4 Stunden bei ca. 80°C erhitzt. Nach Einstellung eines Aktivgehalts von 20% wird eine leicht viskose, klare Polymerlösung erhalten, deren Wirksubstanz als Hydrochlorid vorliegt und im wesentlichen Struktureinheiten der Formeln

    Figure 00170001
    enthält. Example 3: 21.3 parts of vinylformamide, 15.9 parts of acrylonitrile, 15.9 parts of a 30% strength acrylamide solution and 145 parts of water are placed in a reactor and heated to about 80 ° C. under nitrogen. A solution of 1.45 parts of azobis (amidinopropane) hydrochloride in 10 parts of water is then added dropwise within 90 minutes. Then allowed to polymerize for 4 hours at 80 ° C. After adding 29.5 parts of 37% hydrochloric acid, the mixture is heated at about 80 ° C. for a further 4 hours. After setting an active content of 20%, a slightly viscous, clear polymer solution is obtained, the active substance of which is in the form of hydrochloride and essentially structural units of the formulas
    Figure 00170001
    contains.

    Beispiel 4: 14,2 Teile Vinylformamid, 11,4 Teile 3-(N-Vinylformamido)propionsäureethylester und 50 Teile Wasser werden in einem Reaktor vorgelegt und unter Stickstoff auf ca. 70°C aufgeheizt. Dann wird eine Lösung von 0,5 Teilen Azo-bis(amidinopropan)-hydrochlorid in 10 Teilen Wasser innerhalb von 60 Minuten zugetropft. Anschliessend lässt man 6 Stunden bei 70°C nachpolymerisieren. Nach Zugabe einer Lösung aus 27 Teilen 37%ige Salzsäure in 40 Teilen Wasser wird noch 4 Stunden bei ca. 80°C erhitzt. Nach Einstellung eines Aktivgehalts von 20% wird eine leicht viskose, klare Polymerlösung erhalten, deren Wirksubstanz als Hydrochlorid vorliegt und im wesentlichen Struktureinheiten der Formeln (101) und

    Figure 00170002
    enthält. Example 4 : 14.2 parts of vinylformamide, 11.4 parts of 3- (N-vinylformamido) propionic acid ethyl ester and 50 parts of water are placed in a reactor and heated to about 70 ° C. under nitrogen. A solution of 0.5 parts of azo-bis (amidinopropane) hydrochloride in 10 parts of water is then added dropwise within 60 minutes. The mixture is then left to polymerize at 70 ° C. for 6 hours. After adding a solution of 27 parts of 37% hydrochloric acid in 40 parts of water, the mixture is heated at about 80 ° C. for 4 hours. After setting an active content of 20%, a slightly viscous, clear polymer solution is obtained, the active substance of which is in the form of hydrochloride and essentially contains structural units of the formulas (101) and
    Figure 00170002
    contains.

    Beispiel 5: 111 Teile einer 18%igen Polyvinylaminhydrochlorid-Lösung (Hydrolysegrad ca. 80%) werden mit einer NaOH-Lösung auf pH 10 gestellt. Nach Zugabe von 0,2 Teilen Benzyltrimethylammoniumchlorid wird auf 80°C geheizt. Anschliessend tropft man innerhalb von 2 Stunden eine Lösung aus 58 Teilen 1-Chlor-2-dimethylaminoethanhydrochlorid und 75 Teilen Wasser zu. Während der Zugabe wird der pH bei ca. 9,5 gehalten. Nach 5 Stunden bei ca. 85°C wird der pH-Wert auf 2,5 gestellt. Die Lösung wird aufkonzentriert, die Salze fitriert und das Polymer in Ethanol gefällt. Anschliessend wird eine 33%ige wässrige Lösung des Polymers hergestellt, welches im wesentlichen Struktureinheiten der Formeln (101),

    Figure 00180001
    enthält und als Hydrochlorid vorliegt. Example 5 : 111 parts of an 18% polyvinylamine hydrochloride solution (degree of hydrolysis approx. 80%) are adjusted to pH 10 with an NaOH solution. After adding 0.2 parts of benzyltrimethylammonium chloride, the mixture is heated to 80.degree. A solution of 58 parts of 1-chloro-2-dimethylaminoethane hydrochloride and 75 parts of water is then added dropwise within 2 hours. During the addition, the pH is kept at about 9.5. After 5 hours at approx. 85 ° C, the pH is adjusted to 2.5. The solution is concentrated, the salts are filtered and the polymer is precipitated in ethanol. A 33% aqueous solution of the polymer is then prepared, which essentially contains structural units of the formulas (101),
    Figure 00180001
    contains and is present as hydrochloride.

    Beispiel 6: 150 Teile einer 18%igen Polyvinylaminhydrochlorid-Lösung (Hydrolysegrad ca. 85%) werden mit einer NaOH-Lösung auf pH 10 gestellt. Nach Zugabe von 0,5 Teilen Benzyltrimethylammoniumchlorid wird auf 80°C geheizt. Anschliessend tropft man innerhalb von 3 Stunden 23,3 Teile Chlorethanol zu. Während der Zugabe wird der pH bei ca. 9,5 gehalten. Nach 5 Stunden bei ca. 85°C wird der pH-Wert auf 2,5 gestellt. Die Lösung wird aufkonzentriert und das Polymer in Aceton gefällt. Anschliessend wird eine 33%ige wässrige Lösung des Polymers hergestellt, welches im wesentlichen Struktureinheiten der Formeln (101) und enthält und als Hydrochlorid vorliegt. Example 6 : 150 parts of an 18% polyvinylamine hydrochloride solution (degree of hydrolysis approx. 85%) are adjusted to pH 10 with an NaOH solution. After adding 0.5 parts of benzyltrimethylammonium chloride, the mixture is heated to 80.degree. Then 23.3 parts of chloroethanol are added dropwise within 3 hours. During the addition, the pH is kept at about 9.5. After 5 hours at approx. 85 ° C, the pH is adjusted to 2.5. The solution is concentrated and the polymer is precipitated in acetone. A 33% aqueous solution of the polymer is then prepared, which essentially has structural units of the formulas (101) and contains and is present as hydrochloride.

    Beispiel 7: 100 Teile einer 18%igen Polyvinylaminhydrochlorid-Lösung (Hydrolysegrad ca. 80%) werden mit einer NaOH-Lösung auf pH 10 gestellt. Anschliessend tropft man bei ca. 75°C innerhalb von 1 Stunde eine Lösung aus 42,6 Teilen 3-Chlor-2-hydroxypropyltrimethylammoniumchlorid in 42,6 Teilen Wasser zu. Während der Zugabe wird der pH bei ca. 9,5 gehalten. Nach 4 Stunden bei ca. 80°C wird einen pH-Wert auf 2 gestellt. Die Lösung wird teilweise aufkonzentriert und das Polymer in Ethanol gefällt. Anschliessend wird eine 33%ige wässrige Lösung des Polymers hergestellt, welches im wesentlichen Struktureinheiten der Formeln (101) und

    Figure 00190001
    enthält und als Hydrochlorid vorliegt. Example 7 : 100 parts of an 18% polyvinylamine hydrochloride solution (degree of hydrolysis approx. 80%) are adjusted to pH 10 with an NaOH solution. A solution of 42.6 parts of 3-chloro-2-hydroxypropyltrimethylammonium chloride in 42.6 parts of water is then added dropwise at about 75 ° C. in the course of 1 hour. During the addition, the pH is kept at about 9.5. After 4 hours at approx. 80 ° C, the pH is adjusted to 2. The solution is partially concentrated and the polymer is precipitated in ethanol. A 33% aqueous solution of the polymer is then prepared, which essentially has structural units of the formulas (101) and
    Figure 00190001
    contains and is present as hydrochloride.

    Beispiel 8: 25,6 Teile Vinylformamid, 20 Teile Vinypyrrolidon, 16,9 Teile Vinylimidazol und 238 Teile Wasser werden in einem Reaktor vorgelegt und unter Stickstoff auf ca. 80°C aufgeheizt. Dann wird eine Lösung von 1,6 Teilen Azo-bis(amidinopropan)-hydrochlorid in 10 Teilen Wasser Innerhalb von 90 Minuten zugetropft. Anschliessend lässt man 4 Stunden bei 80°C nachpolymerisieren. Nach Zugabe von 53 Teilen 37%ige Salzsäure wird noch 4 Stunden bei ca. 95°C ehitzt. Das Polymer wird in Ethanol gefällt. Anschliessend wird eine 20%ige wässrige Lösung des Polymers hergestellt, welches im wesentlichen Struktureinheiten der Formeln (101),

    Figure 00190002
    enthält und als Hydrochlorid vorliegt. Example 8: 25.6 parts of vinylformamide, 20 parts of vinypyrrolidone, 16.9 parts of vinylimidazole and 238 parts of water are placed in a reactor and heated to about 80 ° C. under nitrogen. A solution of 1.6 parts of azo-bis (amidinopropane) hydrochloride in 10 parts of water is then added dropwise within 90 minutes. Then allowed to polymerize for 4 hours at 80 ° C. After adding 53 parts of 37% hydrochloric acid, the mixture is heated at about 95 ° C. for a further 4 hours. The polymer is precipitated in ethanol. A 20% aqueous solution of the polymer is then prepared, which essentially contains structural units of the formulas (101),
    Figure 00190002
    contains and is present as hydrochloride.

    Beispiel 9: 40 Teile 3-(N-vinylformamido)-propionitril, 10,1 Teile Vinylimidazol und 82 Teile Wasser werden in einem Reaktor vorgelegt und unter Stickstoff auf ca. 80°C aufgeheizt. Example 9 : 40 parts of 3- (N-vinylformamido) propionitrile, 10.1 parts of vinylimidazole and 82 parts of water are placed in a reactor and heated to about 80 ° C. under nitrogen.

    Dann wird eine Lösung von 0,95 Teilen Azo-bis(amidinopropan)-hydrochlorid in 10 Teilen Wasser innerhalb von 90 Minuten zugetropft. Anschliessend lässt man 4 Stunden bei 80°C nachpolymerisieren. Nach Zugabe von 42,3 Teilen 37%ige Salzsäure wird noch 5 Stunden bei ca. 95°C erhitzt. Das Polymer wird in Ethanol gefällt. Anschliessend wird eine 33%ige wässrige Lösung des Polymers hergestellt, welches im wesentlichen Struktureinheiten der Formeln

    Figure 00200001
    enthält und als Hydrochlorid vorliegt.A solution of 0.95 parts of azo-bis (amidinopropane) hydrochloride in 10 parts of water is then added dropwise within 90 minutes. Then allowed to polymerize for 4 hours at 80 ° C. After adding 42.3 parts of 37% hydrochloric acid, the mixture is heated at about 95 ° C. for 5 hours. The polymer is precipitated in ethanol. A 33% aqueous solution of the polymer is then produced, which essentially has structural units of the formulas
    Figure 00200001
    contains and is present as hydrochloride.

    Beispiel 10: 45,3 Teile einer 15%igen, hydrolysierten Polyvinylformamidlösung (Hydrolysegrad ca. 85%) werden mit 35 Teilen Wasser verdünnt und bis pH 8,5 neutralisiert. Nach Zugabe von 0,1 Teilen Benzyltrimethylammoniumchlorid und 45 Teilen Tetrahydrofuran wird eine Lösung aus 3,6 Teilen Benzolsulfochlorid in 11 Teilen Tetrahydrofuran innerhalb von 15 Miunuten zugetropft. Es wird noch 4 Stunden bei Raumtemperatur gerührt. Nach Einstellung des pH auf 6,5 wird Tetrahydrofuran abdestilliert und der Aktivgehalt auf 15% gestellt. Man erhält eine trübe, leicht viskose Polymerlösung, deren Wirksubstanz teilweise als Hydrochlorid vorliegt und im wesentlichen Struktureinheiten der Formeln (101), (102) und

    Figure 00200002
    enthält. Example 10 : 45.3 parts of a 15% hydrolyzed polyvinylformamide solution (degree of hydrolysis approx. 85%) are diluted with 35 parts of water and neutralized to pH 8.5. After the addition of 0.1 part of benzyltrimethylammonium chloride and 45 parts of tetrahydrofuran, a solution of 3.6 parts of benzenesulfochloride in 11 parts of tetrahydrofuran is added dropwise within 15 minutes. The mixture is stirred for a further 4 hours at room temperature. After adjusting the pH to 6.5, tetrahydrofuran is distilled off and the active content is set to 15%. A cloudy, slightly viscous polymer solution is obtained, the active substance of which is partly present as hydrochloride and essentially has structural units of the formulas (101), (102) and
    Figure 00200002
    contains.

    Beispiel 11: 45,3 Teile einer 15%igen, hydrolysierten Polyvinylformamidlösung (Hydrolysegrad ca. 85%) werden mit 35 Teilen Wasser verdünnt und bis pH 8,5 neutralisiert. Nach Zugabe von 0,1 Teilen Benzyltrimethylammoniumchlorid und 45 Teilen Tetrahydrofuran wird eine Lösung aus 2,8 Teilen Benzoylchlorid in 11 Teilen Tetrahydrofuran innerhalb von 15 Miunuten zugetropft. Es wird noch 4 Stunden bei Raumtemperatur gerührt. Nach Einstellung des pH auf 6,5 wird Tetrahydrofuran abdestilliert und der Aktivgehalt auf 15% gestellt. Man erhält eine trübe, leicht viskose Polymerlösung, deren Wirksubstanz teilweise als Hydrochlorid vorliegt und im wesentlichen Struktureinheiten der Formeln (101), (102) und

    Figure 00210001
    enthält. Example 11 : 45.3 parts of a 15% hydrolysed polyvinylformamide solution (degree of hydrolysis approx. 85%) are diluted with 35 parts of water and neutralized to pH 8.5. After adding 0.1 part of benzyltrimethylammonium chloride and 45 parts of tetrahydrofuran, a solution of 2.8 parts of benzoyl chloride in 11 parts of tetrahydrofuran is added dropwise within 15 minutes. The mixture is stirred for a further 4 hours at room temperature. After adjusting the pH to 6.5, tetrahydrofuran is distilled off and the active content is set to 15%. A cloudy, slightly viscous polymer solution is obtained, the active substance of which is partly present as hydrochloride and essentially has structural units of the formulas (101), (102) and
    Figure 00210001
    contains.

    Beispiel 12: 45,3 Teile einer 15%igen, hydrolysierten Polyvinylformamidlösung (Hydrolysegrad ca. 85%) werden mit 35 Teilen Wasser verdünnt und bis pH 10 neutralisiert. Nach Zugabe von 60 Teilen Tetrahydrofuran werden 3,1 Teile 4-Acetaminobenzolsulfochlorid innerhalb von 5-10 Minuten zugegeben. Der pH-Wert wird konstant bei 10 gehalten. Es wird noch 2 Stunden bei Raumtemperatur gerührt. Nach Einstellung des pH auf 6,5 wird Tetrahydrofuran abdestilliert und der Aktivgehalt auf 15% gestellt. Man erhält eine leicht trübe, mittel viskose Polymerlösung, deren Wirksubstanz teilweise als Hydrochlorid vorliegt und im wesentlichen Struktureinheiten der Formeln (101), (102) und

    Figure 00210002
    enthält. Example 12 : 45.3 parts of a 15% hydrolyzed polyvinylformamide solution (degree of hydrolysis approx. 85%) are diluted with 35 parts of water and neutralized to pH 10. After the addition of 60 parts of tetrahydrofuran, 3.1 parts of 4-acetaminobenzenesulfochloride are added within 5-10 minutes. The pH is kept constant at 10. The mixture is stirred at room temperature for a further 2 hours. After adjusting the pH to 6.5, tetrahydrofuran is distilled off and the active content is set to 15%. A slightly cloudy, medium-viscosity polymer solution is obtained, the active substance of which is partly present as hydrochloride and essentially has structural units of the formulas (101), (102) and
    Figure 00210002
    contains.

    Beispiel 13: 75 Teile der Polymerlösung aus Beispiel 12 werden mit 80 Teilen Wasser verdünnt. Nach Zugabe von 13,2 Teilen 37%iger Salzsäure wird 6 Stunden lang bei 95°C gerührt. Nach Einstellung des pH auf 7 wird die Polymerlösung entsalzt und der Aktivgehalt auf 15% gestellt. Man erhält eine leicht trübe, viskose Polymerlösung, deren Wirksubstanz teilweise als Hydrochlorid vorliegt und im wesentlichen Struktureinheiten der Formeln (101), (102) und

    Figure 00220001
    enthält. Example 13 : 75 parts of the polymer solution from Example 12 are diluted with 80 parts of water. After adding 13.2 parts of 37% hydrochloric acid, the mixture is stirred at 95 ° C. for 6 hours. After adjusting the pH to 7, the polymer solution is desalted and the active content is set to 15%. A slightly cloudy, viscous polymer solution is obtained, the active substance of which is partly present as hydrochloride and essentially has structural units of the formulas (101), (102) and
    Figure 00220001
    contains.

    Beispiel 14: 80 Teile einer 15%igen, hydrolysierten Polyvinylformamidlösung (Hydrolysegrad ca. 85%) werden mit 30 Teilen Wasser verdünnt und bis pH 9,5 neutralisiert. Nach Zugabe von 0,5 Teilen Benzyltrimethylammoniumhydroxid wird auf 70°C geheizt. Dann wird innerhalb von 5 - 10 Minuten eine bis pH 4,5 neutralisierte Lösung aus 3,5 Teilen β-Sulfatoethylsulfonyl-4-aminobenzol und 8 Teilen Wasser zugetropft. Der pH wird bei 9,5 konstant gehalten. Es wird noch 2 Stunden bei 70°C gerührt. Nach Einstellung des pH auf 7 wird der Aktivgehalt auf 15% gestellt. Man erhält eine klare, leicht viskose Polymerlösung, deren Wirksubstanz teilweise als Hydrochlorid vorliegt und im wesentlichen Struktureinheiten der Formeln (101), (102) und (103) enthält und eine Viskosität von 1600 cP aufweist. Example 14 : 80 parts of a 15% hydrolyzed polyvinylformamide solution (degree of hydrolysis approx. 85%) are diluted with 30 parts of water and neutralized to pH 9.5. After adding 0.5 parts of benzyltrimethylammonium hydroxide, the mixture is heated to 70.degree. Then a solution neutralized to pH 4.5 of 3.5 parts of β-sulfatoethylsulfonyl-4-aminobenzene and 8 parts of water is added dropwise within 5-10 minutes. The pH is kept constant at 9.5. The mixture is stirred at 70 ° C for 2 hours. After adjusting the pH to 7, the active content is set to 15%. A clear, slightly viscous polymer solution is obtained, the active substance of which is partially present as hydrochloride and essentially contains structural units of the formulas (101), (102) and (103) and has a viscosity of 1600 cP.

    Anwendungsbeispieleapplications

    Beispiel 15: 100 g eines Polyamid 6.6 Textur-Tricot mit einem m2-Gewicht von 235 g werden auf einem Labor-Haspel mit einem Flottenverhältnis 1:20, mit einer Flotte, welche 1 g/l Ammoniumacetat und 0,5 g/l eines handelsüblichen Egalisiermittels enthält, gefärbt. Zu diesem Zweck wird die Flotte mit Essigsäure zunächst auf pH 5 eingestellt, auf 50°C aufgeheizt und das Polyamid-Tricot 10 Minuten bei dieser Temperatur behandelt. Anschliessend werden 3.0 g/l des Farbstoffs der Formel

    Figure 00230001
    zugesetzt und das Bad weitere 5 Minuten bei 50°C gehalten. Danach erhöht man die Färbetemperatur innerhalb von 30 Minuten auf 98°C. Bei dieser Temperatur wird der Polyamid-Tricot 60 Minuten behandelt. Anschliessend wird das Polyamid-Tricot mit kaltem Wasser gespült und mit einem frischem Bad, welches 3.0 g/l der Polymerlösung gemäss Beispiel 1 enthält mit einem Flottenverhältnis 1:20 nachbehandelt. Zu diesem Zweck wird die Flotte zunächst mit Essigsäure auf pH 4 eingestellt und das gefärbte Polyamid-Tricot bei 25°C in die Fixierflotte eingebracht und 10 Minuten bei dieser Temperatur behandelt. Danach erhöht man die Badtemperatur innerhalb von 20 Minuten auf 75°C und hält diese Temperatur weitere 15 Minuten. Das gefärbte und nachfixierte Polyamid-Tricot wird danach mit kaltem Wasser kurz gespült und bei 60°C getrocknet. Man erhält eine Färbung mit sehr guten Nassechtheiten ohne Einfluss auf die Nuance und die Lichtechtheit. Example 15 : 100 g of a polyamide 6.6 texture tricot with an m 2 weight of 235 g are placed on a laboratory reel with a liquor ratio 1:20, with a liquor containing 1 g / l ammonium acetate and 0.5 g / l contains a commercial leveling agent, colored. For this purpose, the liquor is first adjusted to pH 5 with acetic acid, heated to 50 ° C. and the polyamide tricot is treated at this temperature for 10 minutes. Then 3.0 g / l of the dye of the formula
    Figure 00230001
    added and the bath kept at 50 ° C for a further 5 minutes. Then the dyeing temperature is raised to 98 ° C. within 30 minutes. The polyamide tricot is treated at this temperature for 60 minutes. The polyamide tricot is then rinsed with cold water and treated with a fresh bath which contains 3.0 g / l of the polymer solution according to Example 1 with a liquor ratio of 1:20. For this purpose, the liquor is first adjusted to pH 4 with acetic acid and the colored polyamide tricot is introduced into the fixing liquor at 25 ° C. and treated at this temperature for 10 minutes. Then increase the bath temperature to 75 ° C within 20 minutes and hold this temperature for a further 15 minutes. The dyed and post-fixed polyamide tricot is then rinsed briefly with cold water and dried at 60 ° C. A dyeing with very good wet fastness properties is obtained without influencing the shade and light fastness.

    Verfährt man wie in Beispiel 15 beschrieben, verwendet jedoch anstelle der Polymerlösung gemäss Beispiel 1 die äquivalente Gewichtsmenge einer der Polymerlösungen gemäss einem der Beispiele 2 bis 14, so wird ebenfalls ein Polyamid 6.6 Textur-Tricot mit verbesserten Nassechtheiten, ohne Einfluss auf die Nuance und die Lichtechtheit, erhalten.The procedure is as described in Example 15, but is used instead of the polymer solution according to Example 1, the equivalent amount by weight of one of the polymer solutions one of the examples 2 to 14, a polyamide 6.6 texture tricot is also used improved wet fastness properties, without influencing the shade and light fastness.

    Beispiel 16: 100 g eines Polyamid 6 Webtricot mit einem m2-Gewicht von 120 g werden auf einem Labor-Jet mit einem Flottenverhältnis 1:10 mit einer Flotte, welche 1 g/l Ammoniumacetat und 0,5 g/l eines handelsüblichen Egalisiermittels enthält, gefärbt. Zu diesem Zweck wird die Flotte zunächst mit Essigsäure auf pH 5,5 eingestellt, auf 40°C aufgeheizt und das Webtricot 15 Minuten bei dieser Temperatur behandelt. Anschliessend werden 0,6 g/l des Farbstoffs der Formel

    Figure 00240001
    und 1,2 g/l des Farbstoffs der Formel
    Figure 00240002
    zugesetzt und das Bad weitere 5 Minuten bei 40°C gehalten. Danach erhöht man die Färbetemperatur innerhalb von 30 Minuten auf 98°C. Bei dieser Temperatur wird das Webtricot 60 Minuten behandelt. Danach kühlt man die Flotte innerhalb von 15 Minuten auf 50°C ab. Zur Fixierung werden 1,5 g/l der Polymerlösung gemäss Beispiel 2 direkt ins ausgezogene Färbebad gegeben und die Flotte mit Essigsäure auf pH 5 eingestellt. Anschliessend wird die Temperatur der Flotte Innerhalb von 15 Minuten auf 80°C erhöht und 10 Minuten bei dieser Temperatur gehalten. Das gefärbte und nachfixierte Webtricot wird danach mit kaltem Wasser kurz gespült und bei 60°C getrocknet. Man erhält eine Färbung mit sehr guten Nassechtheiten ohne Einfluss auf die Nuance und die Lichtechtheit. Example 16 : 100 g of a polyamide 6 woven tricot with an m 2 weight of 120 g are placed on a laboratory jet with a liquor ratio of 1:10 with a liquor which contains 1 g / l ammonium acetate and 0.5 g / l of a commercially available leveling agent contains, colored. For this purpose, the liquor is first adjusted to pH 5.5 with acetic acid, heated to 40 ° C. and the woven tricot is treated at this temperature for 15 minutes. Then 0.6 g / l of the dye of the formula
    Figure 00240001
    and 1.2 g / l of the dye of the formula
    Figure 00240002
    added and the bath kept at 40 ° C for a further 5 minutes. Then the dyeing temperature is raised to 98 ° C. within 30 minutes. At this temperature, the woven tricot is treated for 60 minutes. The liquor is then cooled to 50 ° C. within 15 minutes. For fixation, 1.5 g / l of the polymer solution according to Example 2 are added directly to the dye bath and the liquor is adjusted to pH 5 with acetic acid. The temperature of the liquor is then raised to 80 ° C. within 15 minutes and kept at this temperature for 10 minutes. The dyed and refixed woven tricot is then rinsed briefly with cold water and dried at 60 ° C. A dyeing with very good wet fastness properties is obtained without influencing the shade and light fastness.

    Verfährt man wie in Beispiel 16 beschrieben, verwendet jedoch anstelle der Polymerlösung gemäss Beispiel 2 die äquivalente Gewichtsmenge einer der Polymerlösungen gemäss einem der Beispiele 1 und 3 bis 14, so wird ebenfalls ein Polyamid 6 Webtricot mit verbesserten Nassechtheiten, ohne Einfluss auf die Nuance und die Lichtechtheit, erhalten.The procedure is as described in Example 16, but is used instead of the polymer solution according to example 2, the equivalent amount by weight of one of the polymer solutions according to one of Examples 1 and 3 to 14, a polyamide 6 woven tricot is also used improved wet fastness properties, without influencing the shade and light fastness.

    Beispiel 17: Ein Färbebad enthaltend 600 Teile Wasser,
    0,0108 Teile eines Farbstoffs der Formel

    Figure 00250001
    0,0135 Teile eines Farbstoffs der Formel
    Figure 00250002
    und 0,033 Teile eines Farbstoffs der Formel
    Figure 00250003
    wird mit 0,72 Teilen Natriumdihydrogenphosphat-monohydrat und 0,6 Teilen Dinatriumhydrogenphosphat-dodecahydrat auf einen pH von 6,5 eingestellt. In dieses Färbebad geht man bei 30°C mit 30 Teilen Polyamidteppichgewebe (Polyamid 6) ein. Die Temperatur wird gleichmässig innerhalb von 45 Minuten bis zum Siedepunkt erhöht und man färbt anschliessend noch 30 Minuten bei dieser Temperatur. Der grau gefärbte Teppich wird danach gespült. Das gefärbte Teppichgewebe wird in einem frischen Bad aus 600 Teilen Wasser, 3 Teilen der Polymerlösung gemäss Beispiel 2, 0,6 Teilen Natriumacetat und 0,7 Teilen Essigsäure bei einem pH von 4,5 und einer Temperatur von 75°C 15 Minuten nachbehandelt. Das Teppichgewebe wird anschliessend gespült und getrocknet. Die Ozonechtheit der erhaltenen Färbung wird nach der Prüfvorschrift ISO 105-G03 durchgeführt. Der Vergleich des nachbehandelten Teppichgewebes mit einem Teppichgewebe, das nicht nachbehandelt wurde, zeigt eine deutliche Erhöhung der Ozonbeständigkeit des nachbehandelten Teppichgewebes. Example 17 : A dyebath containing 600 parts of water
    0.0108 parts of a dye of the formula
    Figure 00250001
    0.0135 parts of a dye of the formula
    Figure 00250002
    and 0.033 parts of a dye of the formula
    Figure 00250003
    is adjusted to a pH of 6.5 with 0.72 parts of sodium dihydrogenphosphate monohydrate and 0.6 part of disodium hydrogenphosphate dodecahydrate. This dye bath is mixed with 30 parts of polyamide carpet fabric (polyamide 6) at 30 ° C. The temperature is raised uniformly to the boiling point within 45 minutes and dyeing is then carried out for a further 30 minutes at this temperature. The gray colored carpet is then rinsed. The dyed carpet fabric is aftertreated in a fresh bath of 600 parts of water, 3 parts of the polymer solution according to Example 2, 0.6 part of sodium acetate and 0.7 part of acetic acid at a pH of 4.5 and a temperature of 75 ° C. for 15 minutes. The carpet fabric is then rinsed and dried. The ozone fastness of the dyeing obtained is carried out in accordance with the test specification ISO 105-G03. The comparison of the after-treated carpet fabric with a carpet fabric that was not after-treated shows a significant increase in the ozone resistance of the after-treated carpet fabric.

    Claims (22)

    1. A method of fixing dyes on natural or synthetic polyamide fibre materials, wherein the fibre material is treated, before, during or after dyeing, with a liquor comprising a homo- or co-polymer having structural repeating units of at least one of formulae (1), (2) and (3)
      Figure 00340001
      and
      Figure 00340002
      wherein
      R1, R2, R3, R4 and R6 are each independently of the others hydrogen; C1-C6alkylsulfonyl; unsubstituted or substituted phenyl; benzoyl or phenylsulfonyl each unsubstituted or substituted in the phenyl ring; or a C1-C12alkyl radical that is unsubstituted or substituted by hydroxy, carboxy, cyano, carbamoyl, a radical -CONH-(alk)-T, N,N-di-C1-C4alkylcarbamoyl,
      Figure 00340003
      amino or by a radical -NHR9, -N(R9)2, -N(R9)3 + Y- or -COO-(alk)-T,
      (alk) is a straight-chain or branched C1-C10alkylene radical,
      T is hydrogen or a radical -NH2, -NHR9, -N(R9)2 or -N(R9)3 + Y-,
      R8 and R9 are C1-C6alkyl and
      Y- is an anion,
      R5 is hydrogen or benzyl or has one of the meanings indicated above for R1, R2, R3, R4 and
      R6 as a C1-C12alkyl radical, and
      R7 is hydrogen or C1-C4alkyl.
    2. A method according to claim 1, wherein
      R1, R2, R3, R4 and R6 are each independently of the others hydrogen; phenyl that is unsubstituted or substituted by halogen, sulfo, C1-C4alkyl, C1-C4alkoxy, amino or by C2-C4- alkanoylamino; benzoyl or phenylsulfonyl each unsubstituted or substituted in the phenyl ring by halogen, C1-C4alkyl, C1-C4alkoxy, amino or by C2-C4alkanoylamino; or a C1-C6alkyl radical that is unsubstituted or substituted by hydroxy, carboxy, cyano, carbamoyl, a radical -CONH-(alk)-T, N,N-di-C1-C4alkylcarbamoyl,
      Figure 00350001
      Figure 00350002
      amino or by a radical -NHR9, -N(R9)2, -N(R9)3 +Y- or -COO-(alk)-T, wherein
      (alk) is C1-C4alkylene,
      T is as defined in claim 1,
      R8 and R9 are C1-C4alkyl and
      Y- is a halide anion.
    3. A method according to claim 1 or 2, wherein
      R1, R2, R3, R4 and R6 are each independently of the others hydrogen; phenyl that is unsubstituted or substituted by halogen, C1-C4alkyl or by C1-C4alkoxy; benzoyl or phenylsulfonyl each unsubstituted or substituted in the phenyl ring by C1-C4alkyl, C1-C4alkoxy, amino, acetylamino or by propionylamino; or a C1-C4alkyl radical that is unsubstituted or substituted by hydroxy, carboxy, cyano, a radical -CONH-(CH2)1-3-T,
      Figure 00350003
      amino or by a radical -NHR9, -N(R9)2, -N(R9)3 +Y- or -COO-(CH2)1-3-T, wherein
      T is as defined in claim 1,
      R9 is methyl or ethyl and
      Y- is a halide anion.
    4. A method according to any one of claims 1 to 3, wherein
      R1, R2, R3, R4 and R6 are each independently of the others hydrogen; phenyl; benzoyl or phenylsulfonyl each unsubstituted or substituted in the phenyl ring by methyl, ethyl, amino or by acetylamino; methyl; ethyl; hydroxy-C1-C2alkyl; carboxy-C1-C2alkyl; cyano-C1-C3alkyl;
      Figure 00360001
      (R9)2N-C1-C3alkyl; Y-(R9)3N+-C1-C3alkyl; or a radical of formula -CH2-CH(OH)-(CH2)1-2-T, -CH2-CH(R10)-COO-(CH2)1-3-T, or -CH2-CH(R10)-CONH-(CH2)1-3-T wherein
      T is hydrogen, -N(R9)2 or -N(R9)3 +Y-,
      R9 is methyl or ethyl,
      R10 is hydrogen or methyl and
      Y- is a bromide or chloride anion.
    5. A method according to any one of claims 1 to 4, wherein
      R1, R2, R3, R4 and R6 are each independently of the others hydrogen, benzoyl, phenylsulfonyl, 4-aminophenylsulfonyl, 4-acetylaminophenylsulfonyl, -CH2-CH2-COO-(CH2)1-2-CH3, -CH2-CH2-COOH, -CH2-CH2-OH, -CH2-CH2-CN,
      Figure 00360002
      -CH2-CH2-N(CH3)2 or -CH2-CH2-N+(CH3)3 Y-, wherein
      Y- is a bromide or chloride anion.
    6. A method according to any one of claims 1 to 5, wherein
      R2 and R4 are hydrogen.
    7. A method according to claim 1, wherein
      R5 is hydrogen, benzyl or C1-C4alkyl.
    8. A method according to any one of claims 1 to 7, wherein
      R1, R3 and R6 are each independently of the others hydrogen, benzoyl, phenylsulfonyl, 4-aminophenylsulfonyl, 4-acetylaminophenylsulfonyl, -CH2-CH2-COO-(CH2)1-2-CH3, -CH2-CH2-COOH, -CH2-CH2-OH, -CH2-CH2-CN,
      Figure 00370001
      -CH2-CH2-N(CH3)2 or -CH2-CH2-N+(CH3)3 Y-, wherein
      Y- is a bromide or chloride anion, and
      R2 and R4 are hydrogen, and
      R5 is hydrogen, benzyl or C1-C4alkyl.
    9. A method according to any one of claims 1 to 8, wherein
      the homo- or co-polymer comprises structural repeating units of at least one of formulae (1) and (2), wherein
      R1, R2, R3, R4, R5 and Y- are as defined in claim 1.
    10. A method according to any one of claims 1 to 6, 8 and 9, wherein the homo- or co-polymer contains from 5 to 100 mol % structural repeating units of formulae (1a) and (1b)
      Figure 00370002
      and from 95 to 0 mol % structural repeating units of formulae (5) and (6)
      Figure 00370003
      wherein
      R1 and R2 are as defined in claim 1,
      R11 and R13 are each independently of the other hydrogen or methyl and
      R12 and R14 are each independently of the other pyrrolidonyl, amino, N-methylamino, N-ethylamino, -NH-CHO, -NH-CO-CH3, -N(CH3)-CHO, -N(CH3)-CO-CH3, -N(C2H5)-CO-CH3, imidazolyl, -O-CO-CH3, -CO-NH2, -CO-NH(CH3) or -CO-N(CH3)2 and
      w, x, y and z are integers equal to or greater than 1 or are the number 0, the condition Q = from 0.05 to 1 applying to the quotient Q = w + x w + x + y + z
    11. A method according to claim 10, wherein
      R1 and R2 are each independently of the other hydrogen, methyl, ethyl, hydroxy-C1-C2alkyl, carboxy-C1-C2alkyl, cyano-C1-C3alkyl, (R9)2N-C1-C3alkyl, Y-(R9)3N+-C1-C3alkyl, or a radical of formula -CH2-CH(OH)-(CH2)1-2-T, -CH2-CH(R10)-COO-(CH2)1-3-T, or -CH2-CH(R10)-CONH-(CH2)1-3-T wherein
      T is hydrogen, -N(R9)2 or -N(R9)3 +Y-,
      R9 is methyl or ethyl,
      R10 is hydrogen or methyl and
      Y- is a bromide or chloride anion.
    12. A method according to claim 10 or 11, wherein
      R1 and R2 are each independently of the other hydrogen, -CH2-CH2-COO-(CH2)1-2-CH3, -CH2-CH2-COOH, -CH2-CH2-OH, -CH2-CH2-CN, -CH2-CH2-N(CH3)2 or -CH2-CH2-N+(CH3)3 Y- wherein
      Y- is a bromide or chloride anion.
    13. A method according to any one of claims 10 to 12, wherein
      R1 and R2 have identical meanings.
    14. A method according to any one of claims 10 to 13, wherein the homo- or co-polymer contains from 20 to 100 mol % structural repeating units of formulae (1a) and (1b) and from 80 to 0 mol % structural repeating units of formulae (5) and (6), the condition Q = from 0.2 to 1 applying to Q.
    15. A method according to any one of claims 1 to 6, 8 and 9, wherein the homo- or copolymer comprises structural repeating units of at least one of formulae (7) and (8)
      Figure 00390001
      wherein R15 is phenyl or is benzoyl or phenylsulfonyl each unsubstituted or substituted in the phenyl ring by methyl, ethyl, amino or by acetylamino.
    16. A method according to claim 15, wherein the homo- or co-polymer is a copolymer containing from 1 to 50 mol % structural repeating units of formulae (7) and (8) and from 99 to 50 mol % structural repeating units of formulae (5) and (6)
      Figure 00390002
      wherein
      R11 and R13 are each independently of the other hydrogen or methyl and
      R12 and R14 are each independently of the other pyrrolidonyl, amino, N-methylamino, N-ethylamino, -NH-CHO, -NH-CO-CH3, -N(CH3)-CHO, -N(CH3)-CO-CH3, -N(C2H5)-CO-CH3, imidazolyl, -O-CO-CH3, -CO-NH2, -CO-NH(CH3) or -CO-N(CH3)2 and
      w, x, y and z are integers equal to or greater than 1 or are the number 0,
      the condition Q = from 0.01 to 0.5 applying to the quotient Q = w + x w+x+y+z .
    17. A method according to any one of claims 1 to 16, wherein the homo- or co-polymer has an average molecular weight of from 1 000 to 1 000 000, preferably from 5 000 to 200 000.
    18. A method according to any one of claims 1 to 17, wherein the homo- or co-polymer is present in the liquor in an amount of from 0.2 to 4 % by weight active ingredient content, based on the weight of the polyamide fibre material.
    19. A method according to any one of claims 1 to 18, wherein the fibre material is treated after the dyeing.
    20. A method according to any one of claims 1 to 19, wherein the treatment with the liquor comprising the homo- or co-polymer is carried out in accordance with the exhaust process.
    21. A homo- or co-polymer, comprising structural units of formula (7)
      Figure 00400001
    22. A method according to any one of claims 1 to 20, for improving the fastness to ozone of dyeings and prints on natural or synthetic polyamide fibre materials.
    EP98810430A 1997-05-20 1998-05-12 Process for the treatment of fibrous materials made from natural or synthetic polyamide Expired - Lifetime EP0879916B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    CH117197 1997-05-20
    CH1171/97 1997-05-20
    CH117197 1997-05-20

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    EP0879916A2 EP0879916A2 (en) 1998-11-25
    EP0879916A3 EP0879916A3 (en) 2001-12-12
    EP0879916B1 true EP0879916B1 (en) 2003-06-25

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    EP (1) EP0879916B1 (en)
    JP (1) JP3938630B2 (en)
    CN (1) CN1199794A (en)
    CA (1) CA2237924A1 (en)
    DE (1) DE59808788D1 (en)

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    EP0957197B1 (en) 1998-05-13 2006-06-21 Ciba SC Holding AG Process for treating natural or synthetic polyamide fibrous materials
    JP2003110714A (en) * 2001-09-26 2003-04-11 Sanshin Ind Co Ltd Small-sized ship information system, server computer and method for providing small-sized ship information
    ES2265517T3 (en) * 2001-12-05 2007-02-16 Ciba Specialty Chemicals Holding Inc. METHOD OF TREATMENT OF NATURAL OR SYNTHETIC POLYAMIDE FIBER MATERIALS.
    US7214633B2 (en) * 2001-12-18 2007-05-08 Kimberly-Clark Worldwide, Inc. Polyvinylamine treatments to improve dyeing of cellulosic materials
    DE10256618A1 (en) * 2002-12-03 2004-06-17 Basf Ag Method for after-cleaning dyed textiles, i.e. to remove unfixed dye, involves using copolymers of at least two mono-unsaturated monomers containing nitrogen heterocycles, e.g. N-vinylpyrrolidone and N-vinylimidazole
    WO2004050982A1 (en) * 2002-12-03 2004-06-17 Basf Aktiengesellschaft Use of copolymers as auxiliaries for dyeing and printing textiles
    WO2009017781A2 (en) * 2007-08-02 2009-02-05 Hercules Incorporated Modified vinylamine-containing polymers as additives in papermaking
    CN107779975B (en) * 2017-11-08 2019-11-15 哈尔滨工业大学 The preparation method of the aromatic polyamide fibre of high-performance heterocyclic containing chlorine
    JPWO2022210717A1 (en) * 2021-03-30 2022-10-06
    WO2024071108A1 (en) * 2022-09-28 2024-04-04 三菱ケミカル株式会社 Pretreatment agents for inkjet textile printing and inkjet textile printing method

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    JPH09324373A (en) * 1996-06-10 1997-12-16 Toray Ind Inc Polyester fiber product and its production

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    US5948125A (en) 1999-09-07
    JP3938630B2 (en) 2007-06-27
    JPH10325084A (en) 1998-12-08
    CN1199794A (en) 1998-11-25
    EP0879916A3 (en) 2001-12-12
    DE59808788D1 (en) 2003-07-31
    CA2237924A1 (en) 1998-11-20
    EP0879916A2 (en) 1998-11-25

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