EP0879916B1 - Verfahren zur Behandlung von natürlichen oder synthetischen Polyamidfasermaterialien - Google Patents

Verfahren zur Behandlung von natürlichen oder synthetischen Polyamidfasermaterialien 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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Prior art keywords
alkyl
hydrogen
radical
methyl
independently
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EP98810430A
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German (de)
English (en)
French (fr)
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EP0879916A2 (de
EP0879916A3 (de
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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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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Coloring (AREA)
EP98810430A 1997-05-20 1998-05-12 Verfahren zur Behandlung von natürlichen oder synthetischen Polyamidfasermaterialien Expired - Lifetime EP0879916B1 (de)

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CH1171/97 1997-05-20

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JP2003110714A (ja) * 2001-09-26 2003-04-11 Sanshin Ind Co Ltd 小型船舶情報システム、サーバコンピュータ、小型船舶情報提供方法
ES2265517T3 (es) * 2001-12-05 2007-02-16 Ciba Specialty Chemicals Holding Inc. Metodo de tratamiento de materiales de fibra de poliamida natural o sintetica.
US7214633B2 (en) * 2001-12-18 2007-05-08 Kimberly-Clark Worldwide, Inc. Polyvinylamine treatments to improve dyeing of cellulosic materials
DE10256618A1 (de) * 2002-12-03 2004-06-17 Basf Ag Verfahren zum Nachreinigen von gefärbtem Textil
ATE434076T1 (de) * 2002-12-03 2009-07-15 Basf Se Pfropfpolymerisaten als hilfsmittel für die textilfärberei und den textildruck
WO2006045721A1 (en) * 2004-10-28 2006-05-04 Huntsman Advanced Materials (Switzerland) Gmbh Method of improving thermal stability
US8604134B2 (en) * 2007-08-02 2013-12-10 Hercules Incorporated Modified vinylamine-containing polymers as additives in papermaking
CN107779975B (zh) * 2017-11-08 2019-11-15 哈尔滨工业大学 含氯高性能杂环芳香族聚酰胺纤维的制备方法
WO2022210717A1 (ja) * 2021-03-30 2022-10-06 三菱ケミカル株式会社 インクジェット捺染用前処理剤及びインクジェット捺染方法
EP4596786A1 (en) * 2022-09-28 2025-08-06 Mitsubishi Chemical Corporation Pretreatment agents for inkjet textile printing and inkjet textile printing method
CN116988325A (zh) * 2023-06-27 2023-11-03 宿迁市纤维检验所 一种提高靛蓝染色牛仔织物耐臭氧牢度的方法

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EP0387201B1 (de) * 1989-03-10 1994-02-02 Ciba-Geigy Ag Farbstoffmischung und deren Verwendung
GB2236542B (en) * 1989-10-06 1992-04-15 Sandoz Ltd Dye mixtures and their use in trichromatic dyeing processes
DE59009878D1 (de) * 1989-10-23 1995-12-21 Ciba Geigy Ag Farbstoffmischungen und deren Verwendung.
ES2100327T3 (es) * 1991-07-19 1997-06-16 Ciba Geigy Ag Mezclas de colorantes y su utilizacion.
JP2697996B2 (ja) * 1992-06-17 1998-01-19 日華化学株式会社 染料固着剤
DE4233040A1 (de) * 1992-10-01 1994-04-07 Basf Ag Verfahren zum Färben von Papier
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DE59409028D1 (de) * 1993-07-28 2000-02-03 Ciba Sc Holding Ag Verfahren zum Färben von wollhaltigen Fasermaterialien
JP2751806B2 (ja) * 1993-12-03 1998-05-18 日華化学株式会社 染料固着剤
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JPH09324373A (ja) * 1996-06-10 1997-12-16 Toray Ind Inc ポリエステル系繊維製品およびその製造方法

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

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