EP0631008B1 - Procédé de lavage d'impressions ou de teintures sur des matériaux textiles contenant de la cellulose - Google Patents

Procédé de lavage d'impressions ou de teintures sur des matériaux textiles contenant de la cellulose Download PDF

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Publication number
EP0631008B1
EP0631008B1 EP94810282A EP94810282A EP0631008B1 EP 0631008 B1 EP0631008 B1 EP 0631008B1 EP 94810282 A EP94810282 A EP 94810282A EP 94810282 A EP94810282 A EP 94810282A EP 0631008 B1 EP0631008 B1 EP 0631008B1
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Prior art keywords
weight
radical
alkyl
dye
process according
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EP94810282A
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German (de)
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EP0631008A1 (fr
Inventor
Christian Guth
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BASF Schweiz AG
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Ciba Geigy AG
Ciba Spezialitaetenchemie 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
    • D06P5/08—After-treatment with organic compounds macromolecular
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/66—Natural or regenerated cellulose using reactive dyes
    • D06P3/663—Natural or regenerated cellulose using reactive dyes reactive group directly attached to heterocyclic group
    • 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
    • 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

Definitions

  • the present invention relates to a method for washing with dyes produced prints or dyeings on cellulosic textile materials.
  • Dyes or prints on cellulose-containing fiber materials are usually subjected to a hot washing treatment after the dye has been fixed and then rinsed in order to remove the unfixed dye component as completely as possible.
  • this washing treatment is crucial for the fastness properties, in particular the wet and rub fastness properties of the dyeings. It is therefore an important part of the entire dyeing process.
  • EP-A-0 262 897 describes a detergent preparation containing an anionic detergent, a nonionic compound with an HBL value ⁇ 10.5 and polyvinylpyrrolidone.
  • the polymeric compounds (a) are preferably Polyvinylpyrrolidone homopolymers or copolymers, e.g. ⁇ 20 mol%, preferably ⁇ 50 mol% and in particular ⁇ 75 mol% vinylpyrrolidone units contain.
  • the polymer (a) is a polyvinylpyrrolidone copolymer, then come as comonomers e.g. carboxyl-containing, sulfo-containing or monomers containing phosphoric acid groups or other ethylenically unsaturated Monomers in question.
  • comonomers e.g. carboxyl-containing, sulfo-containing or monomers containing phosphoric acid groups or other ethylenically unsaturated Monomers in question.
  • Suitable comonomers with carboxyl function are e.g. (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, Allylacetic acid, allyloxyacetic acid, ⁇ , ⁇ -dimethylacrylic acid, allylmalonic acid, Allyloxymalonic acid, methylene malonic acid, 2-hydroxy (meth) acrylic acid, 2-halogeno (meth) acrylic acid, ⁇ -ethyl acrylic acid, acrylamidoglycolic acid, citraconic acid, Glutaconic acid, ⁇ -carboxyethyl acrylate, allyloxy-3-hydroxybutanoic acid and Allylsuccinic acid.
  • (Meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid
  • Suitable comonomers with a phosphoric acid group are e.g. Vinylphosphonic acid, (Meth) allylphosphonic acid and acrylamidomethylpropanephosphonic acid.
  • ethylenically unsaturated compounds are also suitable as comonomers: N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, 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, styrene derivatives, hydroxyethyl / propyl / butyl / - (meth) acrylate, (meth) acrylic acid alky
  • the polymer (a) is a polyvinylpyrrolidone copolymer, the following are: as comonomers acrylic acid, methacrylic acid, acrylamide, acrylic acid ester and Methacrylic acid ester preferred.
  • polyvinylpyrrolidone homopolymers have proven to be, and in particular those with an average molecular weight of e.g. 1000 to 1000000 and preferably 2500 to 750,000.
  • water softening agents (b) there are e.g. Alkali silicates, zeolites, carboxyl-containing homo- or copolymers, polyphosphates or polyphosphonates in Question. It is also possible to mix different water softeners use.
  • the water softener (b) is an alkali silicate
  • silicates of any Me 2 O: SiO 2 composition can be used.
  • examples are water glasses, anhydrous metasilicates and metasilicate hydrates.
  • the focus is on water-soluble alkali silicates, preferably water-soluble sodium or potassium silicates and in particular water-soluble sodium silicates.
  • the alkali silicates have, for example, a Me 2 O: SiO 2 ratio of 0.5 to 3.5 and preferably 1 to 3.5, in which Me is an alkali metal cation, for example the lithium, potassium or in particular the sodium cation.
  • Preferred alkali silicates are anhydrous potassium or sodium metasilicates or Potassium or sodium metasilicate 5 to 10 hydrates.
  • the underlying monomers are e.g. the before as Comonomers for the monomers called polyvinylpyrrolidone copolymers come into question.
  • the The focus is on homopolymers of acrylic acid, methacrylic acid or ⁇ -hydroxyacrylic acid.
  • Homopolymers of crotonic acid are also suitable, Maleic acid, itaconic acid, mesaconic acid, aconitic acid, methylene malonic acid or Citraconic acid and copolymers of the aforementioned carboxylic acids with one another or with other ethylenically unsaturated compounds mentioned above, e.g.
  • the molecular weight of the carboxyl group-containing homo- or copolymers is generally between 1,000 and 1,000,000 and preferably between 5,000 and 500,000.
  • the polymeric carboxylic acids are preferably in salt form, e.g. as alkali, Ammonium or amine salt used.
  • Suitable polyphosphates (b) are sodium diphosphate or Sodium tripolyphosphate.
  • Suitable phosphonates are amino-trimethylenephosphonic acid (ATMP), diethyltriamine-pentamethylenephosphonic acid (DPPA), 1-hydroxyethane-1,1-diphosphonic acid (HEDP), water-soluble salts of the acids mentioned and monomeric and oligomeric compounds of the formula wherein U is hydrogen or -C (O) G 3 , G 1 , G 2 and G 3 each independently represent a C 1 -C 4 alkyl radical and t is a number from 1 to 14, and their water-soluble salts.
  • ATMP amino-trimethylenephosphonic acid
  • DPPA diethyltriamine-pentamethylenephosphonic acid
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • water-soluble salts of the acids mentioned and monomeric and oligomeric compounds of the formula wherein U is hydrogen or -C (O) G 3 , G 1 , G 2 and G 3 each independently represent a C 1 -C 4 alkyl radical and t is a
  • Components (a) and (b) of the after-washing agents used according to the invention are known per se or can be obtained by known methods.
  • the after-washing agents used according to the invention can contain further auxiliaries and additives customary in washing agents.
  • Anhydrous detergents according to the invention can be used as a further constituent e.g. contain a dust extractor.
  • Usual dedusting agents e.g. those based on paraffin oil, oleyl polyglycol ethers and / or polyethylene glycols are known to the person skilled in the art.
  • the dedusting agent is e.g. present in an amount of 0 to 5% by weight and preferably 0 to 1% by weight, based in each case on the anhydrous detergent.
  • the content of components (a) and (b) in the e.g. After-washing agents present in liquid (aqueous) form or preferably in solid form are advantageously> 50% by weight, preferably> 75% by weight and particularly preferably ⁇ 85% by weight, based on the total solids content.
  • the after-washing agents according to the invention can be prepared by simply mixing components (a) and (b), giving homogeneous mixtures.
  • Anhydrous after-washing agents according to the invention preferably contain 10 to 25% by weight of component (a) and 90 to 75% by weight of component (b).
  • the method according to the invention is in particular for the washing of prints or dyeings on cellulosic fiber materials, where pure Cellulose fibers or blends of cellulose and synthetic organic Material, e.g. linear polyesters or modified cellulose (cellulose esters), in question come.
  • Cellulose is to be understood here as natural and regenerated cellulose, e.g. Hemp, linen, jute, viscose silk, rayon or especially cotton.
  • the coloring material can be at any stage of processing, e.g. as loose Material (flake), as duplicated, pre-stretched staple fiber tape or in the form of threads, Yarns, but especially as a woven or knitted fabric.
  • the printing or dyeing of the cellulosic fiber materials can be done by any Procedures take place; as dyes are e.g. Vat dyes, e.g. out Color Index, 3rd edition (1971), volume 3, pages 3719 to 3837, Direct dyes such as in Color Index, 3rd edition (1971), volume 2 on the pages 2005 to 2478 are described as "Direct Dyes", or in particular reactive dyes, i.e. Dyes, which have fiber-reactive radicals that with the hydroxyl groups Cellulose is able to react to form covalent chemical bonds, suitable.
  • dyes are e.g. Vat dyes, e.g. out Color Index, 3rd edition (1971), volume 3, pages 3719 to 3837
  • Direct dyes such as in Color Index, 3rd edition (1971), volume 2 on the pages 2005 to 2478 are described as "Direct Dyes", or in particular reactive dyes, i.e. Dyes, which have fiber-reactive radicals that with the hydroxyl groups Cellulose is able to
  • the dyes used for dyeing or printing are reactive dyes
  • dyes such as those described in the Color Index, 3rd edition (1971) volume 3 on pages 3391 to 3562 as "reactive dyes” are suitable .
  • the reactive dyes have, for example, a monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazane, azomethine, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone, nitroaryl, naphthoquinone, Pyrenequinone or perylene tetracarbimide chromophore and preferably a monoazo, disazo, metal complex azo, formazan, anthraquinone, phthalocyanine or dioxazine chromophore.
  • examples are, for example, the chromophores on which the radicals A 1 and A 2 described below are based.
  • the reactive dyes have one or more sulfo groups and can be further substituted.
  • substituents called: alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, propyl, Isopropyl or butyl, alkoxy groups with 1 to 4 carbon atoms, such as methoxy, Aethoxy, propoxy, isopropoxy or butoxy, acylamino groups with 1 to 8 Carbon atoms, especially alkanoylamino groups, such as acetylamino, Propionylamino or benzoylamino, phenylamino, N, N-di- ⁇ -hydroxyethylamino, N, N-di- ⁇ -sulfatoethylamino, sulfobenzylamino, N, N-disulfobenzylamino, Alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy radical, such as methoxycarbonyl or Ae
  • the reactive dyes preferably contain one or more Sulfonic acid groups; further preferred substituents on the chromophore are methyl, Ethyl, methoxy, ethoxy, acetylamino, benzoylamino, amino, chlorine, bromine, ureido, Hydroxy, carboxy, sulfomethyl or sulfo.
  • suitable fiber-reactive residues that the chromophores directly or over suitable bridge members can contain bound, for example, one by one cleavable atom or a cleavable group of substituted alkanoyl or Alkylsulfonyl, optionally by a removable atom or a removable Substituted alkenoyl or alkenesulfonyl group or a vinyl group containing alkenoyl or alkenesulfonyl.
  • the alkanoyl-, alkylsulfonyl- and alkenesulfonyl radicals usually contain 2 to 8 carbon atoms and the Alkenoyl residues usually 3 to 8 carbon atoms.
  • heterocyclic radicals come e.g. such into consideration which have at least one removable substituent on one contain bound heterocyclic radical; including those that have at least one reactive substituents attached to a 5- or 6-membered heterocyclic ring contain, such as on a monoazine, diazine, triazine, pyridine, pyrimidine, pyridazine, Pyrazine, thiazine, oxazine or asymmetrical or symmetrical triazine ring, or on such a ring system, which has one or more fused aromatic rings has, such as a quinoline, phthalazine, chinnoline, quinazoline, quinoxaline, acridine, Phenazine and phenanthridine ring system.
  • Cleavable atoms or cleavable groups are, for example, among others Halogen, such as fluorine, chlorine or bromine, ammonium including hydrazinium, sulfato, Thiosulfato, phosphato, acetoxy, propionoxy, azido, carboxypyridinium or Rhodanido.
  • Halogen such as fluorine, chlorine or bromine, ammonium including hydrazinium, sulfato, Thiosulfato, phosphato, acetoxy, propionoxy, azido, carboxypyridinium or Rhodanido.
  • the bridge member is, for example, an aliphatic, aromatic or heterocyclic radical; Furthermore, the bridge member can also be composed of various such residues.
  • the bridge member generally contains at least one functional group, for example the carbonyl group or the amino group, the amino group being optionally substituted by halogen, hydroxy, cyano, C 1 -C 4 -alkoxy, C 1 -C 4 -alkoxycarbonyl, carboxy, sulfamoyl, Sulfo or sulfato substituted C 1 -C 4 alkyl may be further substituted.
  • An aliphatic radical for example, is an alkylene radical with 1 to 7 carbon atoms or its branched isomers.
  • the carbon chain of the alkylene radical can be interrupted by a hetero atom, such as an oxygen atom.
  • the aromatic radical is, for example, a phenyl radical which is substituted by C 1 -C 4 alkyl, such as methyl or ethyl, C 1 -C 4 alkoxy, such as methoxy or ethoxy, halogen, such as fluorine, bromine or, in particular, chlorine, carboxy or can be substituted by sulfo, and a heterocyclic radical, for example a piperazine radical.
  • Fiber-reactive residues may also be mentioned, for example: Mono- or dihalo-symmetrical-triazinyl residues, for example 2,4-dichlorotriazinyl-6-, 2-amino-4-chlorotriazinyl-6-, 2-alkylamino-4-chlorotriazinyl-6-, such as 2-methylamino-4- chlorotriazinyl-6, 2-ethylamino or 3-propylamino-4-chlorotriazinyl-6-, 2- ⁇ -oxethylamino-4-chlorotriazinyl-6-, 2-di- ⁇ -oxethylamino-4-chlorotriazinyl-6- and the corresponding sulfuric acid semiesters, 2-diethylamino-4-chlorotriazinyl-6-, 2-morpholino- or 2-piperidino-4-chlorotriazinyl-6-, 2-cyclohexylamino-4-chlorotriazinyl
  • Suitable leaving groups Y are, for example, -Cl, -Br, -F, -OSO 3 H, -SSO 3 H, -OCO-CH 3 , -OPO 3 H 2 , -OCO-CCl 3 , -OCO-CHCl 2 , -OCO -CH 2 Cl, -OSO 2 -C 1 -C 4 alkyl, -OSO 2 -N (C 1 -C 4 alkyl) 2 or -OCO-C 6 H 5 .
  • Y is preferably a group of the formula -Cl, -OSO 3 H, -SSO 3 H, -OCO-CH 3 , -OCO-C 6 H 5 or -OPO 3 H 2 , in particular -OSO 3 H.
  • Alk and alk ' are independent of each other e.g. a methylene, Ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene or 1,6-hexylene radical or their branched isomers.
  • Alk and alk ' are preferably a C 1 -C 4 alkylene radical and particularly preferably an ethylene radical.
  • R is preferably hydrogen or the group -SO 2 -Z, where Z has the meanings given above. R particularly preferably represents hydrogen.
  • R 7 is preferably hydrogen, C 1 -C 4 alkyl or a group -alk-SO 2 -Z, where alk and Z each have the meanings given above.
  • R 8 is preferably a C 1 -C 4 alkyl radical and particularly preferably hydrogen.
  • Arylene is preferably a 1,3- or 1,4-phenylene radical which is unsubstituted or e.g. by Sulfo, methyl, methoxy or carboxy is substituted.
  • E preferably represents -NH- and particularly preferably -O-.
  • W preferably denotes a group of the formula -CONH- or -NHCO-.
  • X stands for example for fluorine, chlorine, bromine, sulfo, C 1 -C 4 -alkylsulfonyl or phenylsulfonyl and preferably for fluorine or chlorine.
  • T is an anion is cleavable group or means a non-reactive substituent.
  • T is a group which can be split off as an anion, this is, for example, fluorine, chlorine, bromine, sulfo, C 1 -C 4 -alkylsulfonyl or phenylsulfonyl and preferably fluorine or chlorine.
  • T stands for a non-reactive substituent, this can be, for example, a hydroxy, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, amino, NC 1 -C 4 alkylamino or N, N -Di-C 1 -C 4 alkylamino, where the alkyl is optionally substituted, for example by sulfo, sulfato, hydroxy, carboxy or phenyl, cyclohexylamino, morpholino, or NC 1 -C 4 alkyl-N-phenylamino or Phenylamino or naphthylamino radical, where the phenyl or naphthyl is optionally substituted, for example by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, carboxy, sulfo or halogen.
  • non-reactive substituents T are amino, methylamino, Ethylamino, ⁇ -hydroxyethylamino, N, N-di- ⁇ -hydroxyethylamino, ⁇ -sulfoethylamino, Cyclohexylamino, morpholino, o-, m- or p-chlorophenylamino, o-, m- or p-methylphenylamino, o-, m- or p-methoxyphenylamino, o-, m- or p-sulfophenylamino, disulfophenylamino, o-carboxyphenylamino, 1- or 2-naphthylamino, 1-sulfo-2-naphthylamino, 4,8-disulfo-2-naphthylamino, N-ethyl-N-phenylamino, N-methyl-N-
  • T preferably has the meaning amino, NC 1 -C 4 -alkylamino, which is unsubstituted in the alkyl part or substituted by hydroxyl, sulfato or sulfo, morpholino, phenylamino or NC 1 -C 4 -alkyl-N-phenylamino, wherein the phenyl is in each case unsubstituted or substituted by sulfo, carboxy, methyl or methoxy.
  • pyrimidine or quinoxaline residues each of which has at least one group which can be split off as an anion.
  • examples are the 2,3-dichloroquinoxaline-6-carbonylamino residue, 2,4-dichloropyrimidine-5-carbonylamino residue and the rest of the formula wherein one of the radicals X 1 is a group which can be split off as an anion and the other radical X 1 has the meanings and preferences given for T as non-reactive substituents or is a radical of the formulas (6a) to (6e) or a group which can be split off as an anion , X 2 is a negative substituent and R 8 independently has the meanings given under formula (5).
  • the radical X 1 which can be split off as an anion is preferably fluorine or chlorine
  • suitable radicals X 2 are nitro, cyano, C 1 -C 4 -alkylsulfonyl, carboxy, chlorine, hydroxy, C 1 -C 4 -alkoxysulfonyl, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkoxycarbonyl or C 2 -C 4 alkanoyl, where the meanings chlorine, cyano and methylsulfonyl are preferred for X 2 .
  • the cellulose-containing fiber materials are preferably dyed by a process which is characterized in that dyeing in the presence of an amount of a mineral acid salt of from 0 to 20 g per liter of dyebath and at least one of the reactive dyes of the formulas wherein A 1 is the residue of a monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazane, azomethine, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone, nitroaryl, naphthoquinone , Pyrenchinone or perylene tetracarbimide dye, A 2 independently of A 1 has the meanings of A 1 or is hydrogen or a colorless organic radical, R 1 , R 2 , R 3 and R 4 are independently hydrogen or optionally substituted C 1 - C 4 alkyl, B is an aliphatic or aromatic bridge member and Y 1 and Y 2 independently
  • Another preferred dyeing process relates to the dyeing of fiber mixtures cellulosic fiber materials and polyester fibers in the presence of reactive dyes and disperse dyes, which is characterized in that in the presence an amount of the salt of a mineral acid from 0 to 40 g per liter of dyebath, in one Temperature of 80 to 150 ° C and a pH of 5 to 11 colors and as Reactive dyes at least one of the reactive dyes of the formulas given above (1) and (2) are used.
  • radicals A 1 and A 2 in the dye of the formula (1) can contain, on their backbone, the substituents customary in organic dyes, for example those as mentioned above for reactive dye chromophores.
  • a reactive group in the radical A 1 or A 2 in the dye of the formula (1) and in the radical V 1 , V 2 or D in the dye of the formula (2) can be one of the fiber-reactive radicals mentioned above.
  • a colorless organic radical for A 2 in the dye of the formula (1) is, for example, hydrogen, C 1 -C 6 -alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl C 1 -C 4 alkoxy, hydroxy, halogen or cyano substituted C 1 -C 6 alkyl, unsubstituted or substituted by C 1 -C 4 alkyl, cyclohexyl, unsubstituted or C 1 -C 4 alkyl, C 1 -C 4 -alkoxy, C 2 -C 4 -alkanoylamino, benzoylamino, ureido, carboxy, sulfo or halogen-substituted phenyl or naphthyl, pyridyl, benzthiazolyl, oxazolyl or thiazolyl.
  • a 2 and R 4 in formula (1) together with the nitrogen atom connecting them can likewise form a heterocyclic ring, such as, for example, piperidyl or morpholyl.
  • a 2 is preferably a dye radical which, independently of A 1, has the meanings given above for A 1 .
  • a 1 and A 2 are particularly preferably, independently of one another, the residue of a monoazo, disazo or formazan dye, in particular residues of the following formulas (8a) to (8t): wherein R 10 represents 0 to 3 identical or different substituents from the group C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxy and sulfo. wherein R 10 represents 0 to 3 identical or different substituents from the group C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxy and sulfo.
  • R 10 represents 0 to 3 identical or different substituents from the group C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxy and sulfo.
  • R 11 for 0 to 4 identical or different substituents from the group halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, amino, acetylamino, ureido, hydroxy, Carboxy, sulfomethyl and sulfo.
  • R 12 is C 1 -C 4 alkanoyl or benzoyl.
  • R 12 is C 1 -C 4 alkanoyl or benzoyl.
  • R 13 represents 0 to 3 identical or different substituents from the group C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxy and sulfo.
  • R 14 and R 16 are independently hydrogen, C 1 -C 4 alkyl or phenyl, and R 15 is hydrogen, cyano, carbamoyl or sulfomethyl.
  • R 13 represents 0 to 3 identical or different substituents from the group C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxy and sulfo.
  • R 17 represents 0 to 2 identical or different substituents from the group C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxy and sulfo; and Z 'is ⁇ -sulfatoethyl, ⁇ -thiosulfatoethyl, ⁇ -phosphatoethyl, ⁇ -acyloxyethyl, ⁇ -halogenoethyl or vinyl.
  • R 18 represents 0 to 2 identical or different substituents from the group C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxy and sulfo; and Z 'is ⁇ -sulfatoethyl, ⁇ -thiosulfatoethyl, ⁇ -phosphatoethyl, ⁇ -acyloxyethyl, ⁇ -halogenoethyl or vinyl.
  • R 10 for 0 to 3 identical or different substituents from the group C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxy and sulfo and R 11 for 0 to 3 identical or different substituents from the group halogen , Nitro, cyan, trifluoromethyl, sulfamoyl, carbamoyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, amino, acetylamino, ureido, hydroxy, carboxy, sulfomethyl and sulfo.
  • benzene nuclei in which the benzene nuclei can further be substituted by alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylsulfonyl having 1 to 4 carbon atoms, halogen or carboxy.
  • Remains of heavy metal complexes are also of interest; as complex-forming Heavy metals are primarily copper, nickel, cobalt or chromium. Residues of copper complex azo dyes are preferred, in particular those of Formulas (8a) to (8k), each of which positions the copper atom in the ortho position via an oxygen atom Azo bridge bound included.
  • azo dyes which are suitable as residues of metal complexes are:
  • Cr- and co-complexes may be the azo compound of the above formula once or included twice, i.e. they can be symmetrical or with any other ligand be constructed asymmetrically.
  • Copper complexes such as, for example, are preferred and
  • the radicals R 19 to R 21 are hydrogen or C 1 -C 4 alkyl.
  • the radicals R 19 to R 21 are preferably hydrogen, methyl or ethyl.
  • the aromatic rings in the above dyes of the formulas (9a) to (9f) and (10a) and (10b) can be further substituted, the benzene rings especially by methyl, ethyl, methoxy, ethoxy, methylsulfonyl, ethylsulfonyl, carboxy, acetylamino or chlorine , and the naphthalene rings in particular by methoxy, carboxy, acetylamino, nitro or chlorine.
  • the benzene rings are preferably not further substituted.
  • radicals A 1 and A 2 in the dye of the formula (1) are identical and have the meanings and preferences given above.
  • the radicals R 1 , R 2 , R 3 and R 4 in the dye of the formula (1) are straight-chain or branched as alkyl radicals; the alkyl radicals can be further substituted, for example by halogen, hydroxy, cyano, C 1 -C 4 alkoxy, C 1 -C 4 alkoxycarbonyl, carboxy, sulfamoyl, sulfo or sulfato.
  • R 1 , R 2 , R 3 and R 4 are preferably, independently of one another, hydrogen, methyl or ethyl, in particular hydrogen
  • the aliphatic or aromatic bridge member B in the dye of the formula (1) is preferably a C 2 -C 12 -alkylene radical which has 1, 2 or 3 members from the group -NH-, -N (CH 3 ) - or -O- can be interrupted, an optionally substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 2 -C 4 alkanoylamino, sulfo, halogen or carboxy C 5 -C 9 cycloalkylene radical or phenylene radical or a radical of formula wherein the benzene rings I and II are optionally substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 2 -C 4 alkanoylamino, sulfo, halogen or carboxy and B 1 is a C 2 -C 10 alkylene radical which can be interrupted by 1, 2 or 3 oxygen atoms, or in which B 1 is a bridge member of the formula -CH
  • the bridge member B in the dye of the formula (1) is particularly preferably a radical of the formula - (CH 2 , Optionally substituted by C 1 -C 4 alkyl-substituted cyclohexylene, optionally substituted by C 1 -C 4 alkyl C 1 -C 4 alkoxy, C 2 -C 4 alkanoylamino, sulfo, halogen or carboxyl-substituted phenylene or a radical of formula wherein the benzene ring III is optionally substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 2 -C 4 alkanoylamino, sulfo, halogen or carboxy.
  • radicals Y 1 and Y 2 in the dye of the formula (1) independently of one another are in particular fluorine or carboxypyridinium, preferably fluorine.
  • D in the dye of formula (2) is e.g. around the rest of an aminobenzene, Aminonaphthalene, phenylazo-aminobenzene, naphthylazo-aminobenzene, Phenylazo-aminonaphthalene or naphthylazo-aminonaphthalene, each of which unsubstituted or, preferably, substituted as indicated below.
  • D is preferably an optionally substituted residue of an aminobenzene or Aminonaphthalene.
  • Suitable substituents on the D radical are, for example: Alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl or butyl, alkoxy groups with 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy or butoxy, amino, N-mono- or N, N-Di-C 1 -C 4 alkylamino, where the alkyl may optionally be further substituted by -OH, -OCOCH 3 , -OSO 3 H, -CN or halogen, for example methylamino, ethylamino, n- or iso-propylamino or n-, sec.- or tert-butylamino, N, N-dimethyl- or diethylamino, ⁇ -chloroethylamino, ⁇ -cyanoethylamino, ⁇ -acetyloxyethyla
  • R 5 or R 6 in the dye of the formula (2) is a C 1 -C 6 -alkyl radical, it is, for example, a methyl, ethyl, n- or iso-propyl, n-, sec.- or tert-butyl or a straight-chain or branched pentyl or hexyl radical, these radicals, for example by hydroxy, sulfo, sulfato, carboxy, cyano, halogen, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkanoyloxy, carbamoyl or a reactive radical can be substituted and the alkyl radical, with the exception of methyl, is optionally interrupted by -O- or -NR'- and R 'is hydrogen or C 1 -C 4 -alkyl.
  • alkyl radical R 5 or R 6 is substituted by a reactive group, it can be one of the reactive groups mentioned above. Preferred is the rest of the formula -SO 2 -Z, wherein Z has the meanings and preferences given above.
  • the alkyl radical R 5 and R 6 independently of one another are preferably hydrogen or a C 1 -C 4 -alkyl radical which is unsubstituted or substituted by hydroxyl, sulfo, sulfato, carboxy, cyano or the group -SO 2 -Z and optionally by -O - is interrupted; preferably one of the radicals R 5 and R 6 is hydrogen.
  • Examples of particularly preferred non-reactive alkylamino radicals V 1 and V 2 are: -NH-CH 3 , -NH-CH 2 -SO 3 H, -NH-CH 2 -COOH, -NH-C 2 H 5 , -NH- CH 2 -CH 2 -OH, -NH-CH 2 -CH 2 -SO 3 H, -NH-CH 2 -CH 2 -OSO 3 H, -NH-CH 2 -CH 2 -CN, -NH-CH 2 -CH 2 -COOH, -NH-CH 2 -CH 2 -CH 2 -OSO 3 H, -NH-CH 2 -CH 2 -CH 2 -OH, -NH-CH 2 -CH (OH) -CH 2 - CH 3 , -NH-CH 2 -CH 2 -O-CH 2 -CH 2 -OH, -NH-CH 2 -CH 2 -O-CH 2 -CH 2 -OSO 3 H.
  • R 5 and R 6 form a heterocyclic radical together with the nitrogen atom connecting them, this can be, for example, a piperidinyl, piperazinyl or pyrrolidinyl radical, each of which is unsubstituted or, for example, by a radical of the formula - (alk) p -SO 2 -Z , wherein alk C 1 -C 6 alkylene, p is the number 0 or 1 and Z has the meanings and preferences given above, is substituted.
  • K preferably represents the remainder of a benzene, naphthalene, 1-phenyl-5-pyrazolone or pyridons, e.g. by one or more of the same or different ones previously for substituents mentioned D is substituted.
  • K particularly preferably corresponds to one of the formulas listed below:
  • V 1 and V 2 in the dye of the formula (2) very particularly preferably represent a radical of the formula (3) in which R 5 and R 6 independently of one another are hydrogen or an unsubstituted or substituted by hydroxyl, sulfo, sulfato, carboxy, cyano or the group -SO 2 -Z are substituted C 1 -C 6 -alkyl radicals, the alkyl with the exception of methyl optionally being interrupted by -O- or -NR'- and R 'and Z have the meanings and preferences given above, or optionally by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 2 -C 4 alkanoylamino, sulfo, halogen or carboxy are substituted phenyl or naphthyl.
  • at least one of the radicals V 1 and V 2 contains a group -SO 2 -Z.
  • Q in the dye of the formula (2) is preferably optionally C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 2 -C 4 alkanoylamino, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkylsulfonyl, halogen, sulfo, trifluoromethyl, nitro or cyano substituted phenyl, 1- or 2-naphthyl or furanyl, thienyl or benzthiazolyl.
  • Q in the dye of the formula (2) is particularly preferably unsubstituted or methyl; Trifluoromethyl, methoxy, sulfo, nitro, chlorine or bromine substituted phenyl, especially unsubstituted phenyl.
  • dyes of the formula (2) are preferred which contain at least one reactive group of the formulas (4), (4a), (4b), (4c), (4d), (4e) in the radical V 1 , V 2 or D or (5), wherein T in the remainder of formula (5) is a group of formula (6a), (6b), (6c), (6d) or (6e).
  • Particularly preferred dyes of the formula (2) are those which contain at least one reactive group of the formula (4) in the V 1 , V 2 or D radical, in particular in the V 1 or V 2 radical.
  • a dye of the formula (1) is used in which A 1 and A 2 are independently the residue of a monoazo, disazo or formazan dye, B is a C 2 -C 12 alkylene radical which can be interrupted by 1, 2 or 3 members from the group -NH-, -N (CH 3 ) - or -O-, optionally by C 1 -C 4 - Alkyl, C 1 -C 4 alkoxy, C 2 -C 4 alkanoylamino, sulfo, halogen or carboxy substituted C 5 -C 9 cycloalkylene radical or phenylene radical or a radical of the formula is in which the benzene rings I and II are optionally substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 2 -C 4 alkanoylamino, sulfo, halogen or carboxy and B 1 is a C 2 -C 10 alkylene radical, which may be
  • radicals A 1 and A 2 in the dye of the formula (1) and the radical D in the dye of the formula (2) contain no reactive group.
  • the dyes of the formulas (1) and (2) are either in the form of their free acid or preferably as their salts such as e.g. the alkali, alkaline earth or ammonium salts or as salts of an organic amine. Examples include sodium, potassium, Lithium or ammonium salts or the salt of triethanolamine called.
  • the dyes of the formulas (1) and (2) are known or can be used in analogy to known dyes are produced.
  • Dyes of formula (1) are e.g. from the GB-A-1,529,645 and dyes of formula (2) e.g. known from EP-A-298,041 or can be produced analogously.
  • salts of mineral acids are alkali or alkaline earth metal halides as well as alkali or alkaline earth sulfates, e.g. Lithium, sodium or potassium chlorides and -sulfates, to understand.
  • the salts of mineral acids are preferably Alkali chlorides or alkali sulfates, especially around sodium chloride or sodium sulfate.
  • the cellulose-containing Fiber materials are dyed in the presence of an amount of a salt Mineral acid, which depends on the total amount of the dye used. So with light shades, a quantity of the salt of a mineral acid from 0 to 5 g, in particular 0.01 to 5 g, used per liter of dye bath, one for medium shades Quantity of 5 to 10 g and for deep shades an amount of 10 to 20 g. Under bright Shades are understood to be those in which the amount of that used for coloring Dye less than 1 percent by weight, based on the weight of the dye Dyeing good, is. Medium shades are those in which the amount of used Dye is 1 to 3 percent by weight and deep shades are those in which the amount of the dye used is greater than 3 percent by weight, in particular greater than 3 Percent by weight and up to 10 percent by weight.
  • a salt Mineral acid which depends on the total amount of the dye used. So with light shades, a quantity of the salt of a mineral acid from 0 to 5 g, in particular 0.01 to 5 g, used per liter
  • dyeing takes place in the presence of an amount of mineral acid salt of 0 to 10 g per liter Dye bath, in particular 0.01 to 10 g.
  • the dyeing in Presence of an amount of the salt of a mineral acid, which of the Total amount of dye used depends. So with light shades one can Amount of the salt of a mineral acid of 0 to 5 g, in particular 0.01 to 5 g, per liter Dye bath can be used and for deeper shades an amount of 5 to 10 g.
  • Bright Nuances are defined as above and the lower nuances correspond to quantities of the dye used, which is 1 percent by weight or greater, in particular 1 % By weight to 10% by weight, preferably 1% by weight to 6 Percent by weight.
  • the amounts in which the reactive dyes in the Dye baths are used vary depending on the desired depth of color, in in general, amounts of 0.01 to 10 percent by weight, in particular 0.01 to 6 Percentage by weight, based on the material to be dyed, has proven to be advantageous.
  • the dyeing liquors can contain the generally customary additives, for example those aqueous solutions of alkali hydroxides, urea, thickeners, e.g. Alginate thickening, water-soluble cellulose alkyl ether, methyl cellulose, starch ether, Emulsion thickenings, preferably an alginate, e.g. Sodium alginate, as well Dispersing aids, leveling aids, wetting agents, migration aid inhibitors and Sodium m-nitrobenzenesulfonate.
  • alkali hydroxides urea
  • thickeners e.g. Alginate thickening, water-soluble cellulose alkyl ether, methyl cellulose, starch ether, Emulsion thickenings, preferably an alginate, e.g. Sodium alginate, as well Dispersing aids, leveling aids, wetting agents, migration aid inhibitors and Sodium m-nitrobenzenesulfonate.
  • the dyeing is usually done in aqueous Medium, with a liquor ratio of, for example, 1: 2 to 1:60, in particular one Fleet ratio from 1: 5 to 1:20.
  • the dyeing is carried out, for example, at a temperature of 20 to 100 ° C, in particular 40 to 90 ° C, and preferably 60 to 80 ° C.
  • the usual addition can be larger Amounts of salts of a mineral acid, e.g. 50 to 100 g / l. This will result in a reduction in wastewater pollution as well as a larger one Efficiency of the process achieved.
  • the disperse dyes for the process for dyeing fiber mixtures are suitable disperse dyes, such as the in Color Index, 3rd edition (1971) Volume 2 on pages 2479 to 2742.
  • the cellulosic fiber materials are, for example, the natural ones Cellulose fibers such as cotton, linen and hemp, as well as cellulose and regenerated Cellulose into consideration.
  • the coloring of is particularly preferred Polyester / cotton blended fabrics.
  • the process for dyeing fiber mixtures is particularly suitable for Extraction process, especially for a one-step, single-bath process according to the Extension method.
  • the dyeing is preferably carried out at a temperature of 90 to 140 ° C., in particular 100 to 130 ° C, and preferably 110 to 130 ° C.
  • the pH is preferably in one Range from 6 to 10, especially in a range from 6 to 8.
  • dyeing is carried out in the presence of an amount of a mineral acid salt of 0 to 30 g per liter of dye bath, in particular 0 to 20 g.
  • dyeing fiber mixtures When dyeing fiber mixtures, the following applies to the reactive dyes of the formulas (1) and (2) the meanings and preferences given above.
  • the dyeing liquors correspond with regard to the possible additions and the fleet ratio the above for the Process for dyeing cellulosic fiber materials specified.
  • a mineral acid has the meanings and preferences given above.
  • the usual addition can be larger Amounts of alkali metal hydroxides for fixing the reactive dyes can be dispensed with. Smaller amounts of salts of a mineral acid can also be used. This will reduce wastewater pollution as well as simpler Treatment of the fabric reached after the dyeing process.
  • the washing process according to the invention advantageously follows the dyeing process or the printing process as post-treatment.
  • the cellulose-containing fiber material is in a fresh, at least one according to the invention
  • Detergent-containing liquor at a temperature of preferably 60 to 100 ° C and particularly preferably at cooking temperature, i.e. at a temperature of approx. 90 up to 100 ° C, treated.
  • the amount of detergent according to the invention is from Water hardness depends, but is preferably 0.25 to 5 g / l liquor and especially preferably 0.5 to 2 g / l wash liquor.
  • the fiber material is then from the Washing liquor removed and advantageously with fresh water until the complete removal of the Wash liquor components rinsed.
  • Example 1 In a ball mill, 125 g of polyvinylpyrrolidone (for example Luviskol® K 30) and 875 g of sodium metasilicate are mixed homogeneously in anhydrous form.
  • polyvinylpyrrolidone for example Luviskol® K 30
  • 875 g of sodium metasilicate are mixed homogeneously in anhydrous form.
  • An aqueous preparation of this powdery mixture can be used before use
  • the product can also be used directly in the wash liquor be added.
  • Example 1a 18.75 g of polyvinylpyrrolidone (for example Luviskol® K 30) are premixed anhydrous with 130.5 g of sodium metasilicate and then mixed homogeneously with 0.75 g of a dust-binding agent containing as main constituents paraffin oil and an oleyl polyglycol ether mixture.
  • polyvinylpyrrolidone for example Luviskol® K 30
  • Example 1b 37.5 g of polyvinylpyrrolidone (for example Luviskol® K 30) are premixed anhydrous with 111.75 g of sodium metasilicate and then mixed homogeneously with 0.75 g of the dedusting agent according to Example 1a).
  • polyvinylpyrrolidone for example Luviskol® K 30
  • a yellowing reactive dye of the formula 1 part of a red-coloring reactive dye of the formula and 0.5 part of a blue-coloring reactive dye of the formula dissolved in 1000 parts of water with the addition of 10 parts of sodium chloride at a temperature of about 70 ° C.
  • the dyebath prepared in this way is mixed with 100 parts of a cotton fabric and the temperature is kept at 70 ° C. for about 50 minutes.
  • 10 parts of calcined sodium carbonate and 3 parts of sodium hydroxide (30%) are added. The temperature is held at 70 ° C for a further 50 minutes.
  • the liquor is then drained off and the cotton fabric is rinsed with cold water for about 10 minutes.
  • the dyed cotton fabric is then in a fresh liquor, the 2 g / l of Contains detergent according to Example 1, 20 minutes at cooking temperature (approx. 98 ° C) treated, then rinsed with cold water and dried. You get one in one brown shade dyed cotton fabric with good fastness properties, especially good wet fastness properties.
  • Example 3 0.2 part of the yellow-dyeing reactive dye of the formula (101), 0.025 part of the red-dyeing reactive dye of the formula (102) and 0.05 part of the blue-dyeing reactive dye of the formula (103) in 1000 parts of water with the addition of 5 parts Sodium sulfate dissolved at a temperature of approx. 70 ° C.
  • the dyebath prepared in this way is mixed with 100 parts of a cotton fabric and the temperature is kept at 70 ° C. for about 50 minutes. Then 10 parts of calcined sodium carbonate and 3 parts of sodium hydroxide (30%) are added. The temperature is held at 70 ° C for a further 50 minutes. The liquor is then drained off and the cotton fabric is rinsed with cold water for about 10 minutes.
  • the dyed cotton fabric is then in a fresh liquor, the 1 g / l of Contains detergent according to example la, twice for 10 minutes at cooking temperature (approx. 98 ° C) treated, then rinsed with cold water and dried. You get one in one light brown shade dyed cotton fabric with good fastness properties, especially good wet fastness properties.
  • Example 4 1.5 parts of the orange-reactive dye of the formula dissolved in 1000 parts of water with the addition of 6 parts of sodium sulfate at a temperature of about 70 ° C.
  • the dyebath prepared in this way is mixed with 100 parts of a cotton fabric and the temperature is kept at 70 ° C. for about 50 minutes.
  • 10 parts of calcined sodium carbonate and 3 parts of sodium hydroxide (30%) are added.
  • the temperature is held at 70 ° C for a further 50 minutes.
  • the liquor is then drained off and the cotton fabric is rinsed with cold water for about 10 minutes.
  • the dyed cotton fabric is then in a fresh liquor, the 1.5 g / l of Contains detergent according to example 1a, 20 minutes at cooking temperature (approx. 98 ° C) treated, then rinsed with cold water and dried. You get one in one orange shade dyed cotton fabric with good fastness properties, especially good wet fastness properties.
  • Example 5 There are 2.5 parts of the red-coloring reactive dye of the formula (102) and 2.5 parts of the blue-coloring reactive dye of the formula wherein B is a bridge member of the formula -CH 2 CH 2 - and A is a radical of the formula is, dissolved in 1000 parts of water with the addition of 10 parts of sodium sulfate at a temperature of about 70 ° C.
  • the dyebath prepared in this way is mixed with 100 parts of a cotton fabric and the temperature is kept at 70 ° C. for about 50 minutes. Then 10 parts of calcined sodium carbonate and 3 parts of sodium hydroxide (30%) are added.
  • the temperature is held at 70 ° C for a further 50 minutes. Then the fleet drained and the cotton fabric rinsed with cold water for about 10 minutes.
  • the dyed cotton fabric is then in a fresh liquor, the 2 g / l of Contains detergent according to Example 1b, 20 minutes at cooking temperature (approx. 98 ° C) treated, then rinsed with cold water and dried. You get one in one dark purple shade of dyed cotton fabric with good fastness properties, especially good wet fastness properties.
  • Example 6 There are 0.125 parts of a yellow-coloring reactive dye of the formula (101), 0.125 parts of a red-coloring reactive dye of the formula (102), 0.125 parts of a blue-coloring reactive dye of the formula (103), 0.075 parts of a yellow-colored disperse dye of the formula 0.075 part of a red-colored disperse dye of the formula and 0.075 part of a blue-colored disperse dye of the formula dissolved or dispersed in 300 parts of demineralized water. Then 0.2 parts of an anionic dispersant and 40 g / l sodium sulfate are added and the pH is adjusted to 7 with disodium hydrogen phosphate buffer.
  • the dyebath prepared in this way is mixed with 25 parts of a polyester / cotton blend (50/50), the dyebath is heated to a temperature of 130 ° C. at a heating rate of 1.5 ° C./minute and the dyebath is left for 30 minutes at this temperature. After cooling to a temperature of approx. 80 ° C, the liquor is drained off and the mixed fabric is rinsed with cold water for approx. 10 minutes.
  • the dyed blended fabric is then in a fresh liquor, the 2 g / l of Contains detergent according to Example 1, 20 minutes at cooking temperature (approx. 98 ° C) treated, then rinsed with cold water and dried. You get one in one brown shade dyed polyester / cotton blend with good Authenticity properties.
  • the dyed fabric is then in a fresh liquor, the 2 g / l of Contains detergent according to example 1a, 20 minutes at cooking temperature (approx. 98 ° C) treated, then rinsed with cold water and dried. You get one in one greenish-yellow shade of dyed cotton fabric with good fastness properties.
  • Example 8 3 parts of the reactive dye of the formula are sprinkled with rapid stirring into 100 parts of a stock thickener containing 50 parts of 5% sodium alginate thickener, 27.8 parts of water, 20 parts of urea, 1 part of sodium m-nitrobenzenesulfonate and 1.2 parts of sodium hydrogen carbonate.
  • a cotton fabric is printed with the printing paste thus obtained, and the printed material obtained is dried and steamed in saturated steam at 102 ° C. for 2 minutes. The printed fabric is then rinsed with cold water.
  • the dyed fabric is then in a fresh liquor, the 2 g / l of Contains detergent according to Example 1b, 20 minutes at cooking temperature (approx. 98 ° C) treated, then rinsed with cold water and dried. You get one in one orange shade printed cotton fabric with good fastness properties.
  • Examples 9-12 If the procedure is as described in Example 2 and instead of the dye mixture used there, the equivalent amount of one of the reactive dyes mentioned in the table below, similarly good results are obtained. 11 dye mixture containing the dyes of the formulas and wherein A 1 and A 2 are each a radical of the formula are in a ratio of approx. 1: 1.
  • the mixture can be prepared as follows: To a neutral solution of 42 parts of 7-amino-4-hydroxy-3- (2-sulfophenylazo) naphthalene-2-sulfonic acid and 5 parts of disodium hydrogenphosphate in 500 parts of water are added at a temperature below 2 ° C 14 parts of cyanuric fluoride added dropwise; the pH is kept constant by adding aqueous sodium hydroxide solution. When the reaction has ended, a solution of 1.8 parts of 1-methylethane-1,2-diamine and 1.8 parts of propane-1,3-diamine in 30 parts of water is added dropwise such that the pH does not have a value of 9.5 exceeds and keeps the pH constant at a value of 9.5 by adding sodium hydroxide solution. The mixture is allowed to warm to room temperature, the solution is dialyzed, and the product obtained is evaporated.
  • a 1 is a radical of the formula and A 2 is a radical of the formula is.
  • the compound can be prepared as follows: To a neutral solution of 53 parts of 1-amino-4- (3-amino-2,4,6-trimethyl-5-sulfo-phenyl) -anthraquinone-2-sulfonic acid and 5 parts of disodium hydrogen phosphate 14 parts of cyanuric fluoride are added dropwise to 500 parts of water at a temperature below 2 ° C .; the pH is kept constant by adding sodium hydroxide solution. When the reaction has ended, 6 parts of ethylenediamine in 54 parts of water are added dropwise in such a way that the temperature does not exceed 5 ° C. and the pH remains at a value of 6. The pH is then kept at a value of 6.
  • Solution 2 is added to solution 1, the pH is raised to a value of 8.5 and maintained. The mixture is allowed to warm to room temperature, the solution is dialyzed freed of salt and evaporates the dye.

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Claims (20)

  1. Procédé pour le lavage d'impressions ou teintures produites avec des colorants sur des matières fibreuses contenant de la cellulose, caractérisé en ce que l'on traite les matières fibreuses imprimées ou teintes dans un bain de lavage aqueux avec un agent de lavage contenant
    (a) 5 à 50% en poids d'un homo- ou copolymère de polyvinylpyrrolidone et
    (b) 95 à 50% en poids d'un agent adoucissant l'eau.
  2. Procédé selon la revendication 1, caractérisé en ce qu'il s'agit pour l'homo- ou copolymère (a) de polyvinylpyrrolidone, d'un homopolymére de polyvinylpyrrolidone ou d'un copolymère qui contient ≥ 20% en moles.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce qu'il s'agit pour l'homo- ou copolymère (a) de polyvinylpyrrolidone, d'un homopolymérisat de polyvinylpyrrolidone avec un poids moléculaire moyen de 1000 à 1000000.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce qu'il s'agit pour l'agent adoucissant l'eau (b), d'un silicate alcalin, d'une zéolithe, d'un homo- ou copolymère contenant un groupe carboxyle, d'un polyphosphate ou d'un polyphosphonate.
  5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que l'on utilise un silicate alcalin en tant qu'agent adoucissant l'eau (b).
  6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que l'on utilise un silicate alcalin avec un rapport Me2O: SiO2 de 0,5 à 3,5.
  7. Procédé selon l'une des revendications 1 à 6, caractérisé en ce que l'on utilise un métasilicate de sodium anhydre ou un métasilicate de sodium 5 ou 9 hydraté en tant qu'agent adoucissant l'eau (b).
  8. Procédé selon l'une des revendications 1 à 7, caractérisé en ce que l'on utilise un agent de lavage contenant
    (a) un homopolymére de polyvinylpyrrolidone et
    (b) un silicate alcalin
  9. Procédé selon l'une des revendications 1 à 8, caractérisé en ce que l'on utilise un agent de lavage se composant de
    (a) 5 à 50% en poids d'un homopolymère de polyvinylpyrrolidone avec un poids moléculaire moyen de 2500 à 750 000,
    (b) 95 à 50% en poids d'un métasilicate de potassium ou de sodium et
    (c) 0 à 5% en poids d'un agent de dépoussiérage.
  10. Procédé selon l'une des revendications 1 à 9 pcur le lavage d'impressions ou teintures produites avec des colorants réactifs.
  11. Procédé selon l'une des revendications 1 à 10, caractérisé en ce que l'on teint les matières fibreuses en présence d'une quantité du sel d'un acide minéral de 0 à 20 g par litre du bain de teinture et on utilise au moins l'un des colorants réactif des formules (1)
    Figure 00600001
    où A1 est le résidu d'un colorant monoazo, polyazo, complexe métallique azo, anthraquinone, phtalocyanine, formazan, azométhine, dioxazine, phénazine, stilbène, triphénylméthane, xanthène, thioxanthone, nitroaryle, naphtoquinone, pyrénequinone ou pérylènetétracarbimide, A2 indépendamment de A1 a les significations de A1 ou bien est hydrogène ou un résidu organique incolore, R1, R2, R3 et R4 indépendamment les uns des autres sont de l'hydrogène ou alkyle C1-C4, le cas échéant substitué, B est un organe de pontage aliphatique ou aromatique et Y1 et Y2 signifient indépendamment l'un de l'autre fluor ou carboxypyridinium,
    ou
    Figure 00610001
    où D est le résidu d'un composant diazo, Q signifie un résidu phényle ou naphtyle, le cas échéant substitué ou bien un résidu hétérocyclique aromatique, le cas échéant substitué et V1 et V2 indépendamment l'un de l'autre signifient un résidu de la formule
    Figure 00610002
    où R5 et R6 indépendamment l'un de l'autre indiquent hydrogène, aryle le cas échéant substitué ou bien alkyle C1-C6 le cas échéant substitué, où l'alkyle, à l'exception du méthyle, peut le cas échéant être interrompu par -O- ou -NR'- et R' est hydrogène ou alkyle C1-C4, ou bien R5 et R1 avec l'atome d'azote qui les relie forment un cycle hétérocyclique à 5 ou 6 membres, éventuellement plus amplement substitué, à la condition qu'au moins l'un des résidus V1, V2 et D présente un groupe réactif avec les fibres.
  12. Procédé selon l'une des revendications 1 à 11, caractérisé en ce que l'on utilise 0,25 à 5 g de l'agent de lavage par litre du bain de lavage.
  13. Procédé selon l'une des revendications 1 à 12, caractérisé en ce que l'on traite les matières fibreuses contenant de la cellulose à une température de 60 à 100°C avec l'agent de lavage.
  14. Procédé selon l'une des revendications 1 à 13 pour le lavage d'impressions ou teintures produites avec un colorant sur du coton ou des tissus mélangés de coton/polyester.
  15. Procédé pour le lavage d'impressions ou teintures produites avec des colorants réactifs sur des matières fibreuses contenant de la cellulose selon la revendication 1, caractérisé en ce que l'on traite les matières fibreuses imprimées ou teintes dans un bain aqueux de lavage avec 0,25 à 5 g/l du bain de lavage, d'un agent de lavage contenant
    (a) 5 à 50% en poids d'un homopolymére de polyvinylpyrrolidone et
    (b) 95 à 50% en poids d'un silicate alcalin à une température de 60 à 100°C.
  16. Utilisation d'un agent de lavage contenant
    (a) 5 à 50% en poids d'un homo- ou copolymère de polyvinylpyrrolidone et
    (b) 95 à 50% en poids d'un agent adoucissant l'eau,
       pour le post-lavage d'impressions ou teintures produites avec des colorants sur des matières textiles contenant de la cellulose.
  17. Agent de post-lavage pour la teinture et l'impression sur des matières fibreuses contenant de la cellulose contenant
    (a) 5 à 50% en poids d'un homo- ou copolymère de polyvinylpyrrolidone et
    (b) 95 à 50% en poids d'un agent adoucissant l'eau.
  18. Agent de post-lavage selon ia revendication 17, caractérisé en ce que l'agent adoucissant l'eau (b) est un silicate alcalin.
  19. Agent de post-lavage selon la revendication 17, caractérisé en ce que le composant (a) est un homopolymére de polyvinylpyrrolidone.
  20. Agent de post-lavage selon la revendication 17 se composant de
    (a) 10 à 25% en poids d'un homopolymére de polyvinylpyrrolidone avec un poids moléculaire moyen de 2500 à 750000 et
    (b) 90 à 75% en poids d'un métasilicate de sodium anhydre ou d'un métasilicate de sodium 5 ou 9 hydraté et
    (c) 0 à 1% en poids d'un agent de dépoussiérage.
EP94810282A 1993-05-24 1994-05-11 Procédé de lavage d'impressions ou de teintures sur des matériaux textiles contenant de la cellulose Expired - Lifetime EP0631008B1 (fr)

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CH155493 1993-05-24
CH1554/93 1993-05-24
CH155493 1993-05-24

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EP0631008B1 true EP0631008B1 (fr) 1999-08-18

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EP0812949A3 (fr) * 1996-06-11 1998-07-22 Ciba SC Holding AG Procédé pour traiter des matériaux fibreux cellulosiques teints
US5820638A (en) * 1996-06-26 1998-10-13 Burlington Chemical Co., Inc. Stain blocking agent
CA2277484A1 (fr) * 1997-01-10 1998-07-16 Robert Polywka Compositions detergentes et copolymeres pour inhiber le transfert de teinture
NL1006703C2 (nl) * 1997-07-31 1999-02-02 Sybron Chemie Nederland B V Werkwijze voor het nawassen van gekleurd textiel.
EP1584371A1 (fr) * 2004-04-07 2005-10-12 Urea Casale S.A. Procede et dispositif de granulation en lit fluidise
US7776108B2 (en) * 2005-06-07 2010-08-17 S.C. Johnson & Son, Inc. Composition for application to a surface
US8061269B2 (en) 2008-05-14 2011-11-22 S.C. Johnson & Son, Inc. Multilayer stencils for applying a design to a surface
US8557758B2 (en) * 2005-06-07 2013-10-15 S.C. Johnson & Son, Inc. Devices for applying a colorant to a surface
US20080282642A1 (en) * 2005-06-07 2008-11-20 Shah Ketan N Method of affixing a design to a surface
US7727289B2 (en) * 2005-06-07 2010-06-01 S.C. Johnson & Son, Inc. Composition for application to a surface
US8846154B2 (en) 2005-06-07 2014-09-30 S.C. Johnson & Son, Inc. Carpet décor and setting solution compositions
DE102006012018B3 (de) * 2006-03-14 2007-11-15 Henkel Kgaa Farbschützendes Waschmittel
DE102012024442A1 (de) 2012-12-14 2014-06-18 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Die Primärwaschkraft verbessernde polymere Wirkstoffe
CN104088167B (zh) * 2014-07-04 2016-08-17 常州大学 一种提高天然染料染色织物颜色深度和日晒牢度的方法
CN105886131B (zh) * 2016-04-18 2018-08-31 广东湛丰精细化工有限公司 一种棉质活性染料清洗剂及其制备方法

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JPH06330481A (ja) 1994-11-29
US5490866A (en) 1996-02-13
EP0631008A1 (fr) 1994-12-28

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