EP0631008A1 - 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
EP0631008A1
EP0631008A1 EP94810282A EP94810282A EP0631008A1 EP 0631008 A1 EP0631008 A1 EP 0631008A1 EP 94810282 A EP94810282 A EP 94810282A EP 94810282 A EP94810282 A EP 94810282A EP 0631008 A1 EP0631008 A1 EP 0631008A1
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EP
European Patent Office
Prior art keywords
weight
alkyl
washing
detergent
independently
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EP94810282A
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German (de)
English (en)
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EP0631008B1 (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 prints or dyeings produced with dyes on cellulose-containing 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.
  • the polymeric compounds (a) are preferably polyvinylpyrrolidone homopolymers or copolymers which e.g. ⁇ 20 mol%, preferably ⁇ 50 mol% and in particular ⁇ 75 mol% of vinyl pyrrolidone units.
  • the comonomers are e.g. monomers containing carboxyl groups, sulfo groups or phosphoric acid groups or other ethylenically unsaturated monomers.
  • Suitable monomers containing sulfo groups are, for example: (Meth) acrylamidomethanesulfonic acid, Vinyl sulfonic acid, (Meth) allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 3- (meth) acrylamidopropanesulfonic acid, 3-sulfopropyl (meth) acrylate, Bis (3-sulfopropyl itaconate), 4-styrene sulfonic acid and 3-allyloxy-2-hydroxypropylsulfonic acid.
  • Suitable comonomers with a carboxyl function are, 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, allylacetic acid, allyloxyacetic acid, ⁇ , ⁇ -dimethylacrylic acid, allylmalonic acid, allyloxymalonic acid 2-methylene acid, methylene -Halogeno (meth) acrylic acid, ⁇ -ethyl acrylic acid, acrylamidoglycolic acid, citraconic acid, glutaconic acid, ⁇ -carboxyethyl acrylate, allyloxy-3-hydroxybutanoic acid and allylsuccinic acid.
  • Suitable comonomers with a phosphoric acid group are e.g. Vinylphosphonic acid, (meth) allylphosphonic acid and acrylamidomethylpropanephosphonic acid.
  • ethylenically unsaturated compounds are, for example, comonomers suitable: N-vinylformamide, N-vinyl-N-methyl-formamide, N-vinylacetamide, N-vinyl-N-methyl-acetamide, N-vinyl-N-ethyl-acetamide, N-vinylimidazole, N-vinyl-N- methyl-imidazole, N-vinylimidazoline, N-vinyl-2-methylimidazoline, N-vinylcaprolactam, vinyl acetate, vinyl propionate, vinyl butyrate, C1-C22-alkyl vinyl ketone, C1-C22-alkyl vinyl ether, olefins (ethylene, propylene, isobutene), 1.2 -Dimethoxyethylene, styrene derivatives, hydroxyethyl / propyl / butyl / - (meth) acrylate, (
  • the polymer (a) is a polyvinylpyrrolidone copolymer
  • acrylic acid, methacrylic acid, acrylamide, acrylic acid ester and methacrylic acid ester are preferred as comonomers.
  • Polyvinylpyrrolidone homopolymers have proven particularly suitable as constituent (a) of the detergents used according to the invention, and in particular those with an average molecular weight of e.g. 1000 to 1,000,000, and preferably 2,500 to 750,000.
  • the water softener (b) is an alkali silicate
  • silicates of any Me2O: SiO2 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 Me2O: SiO2 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 use of anhydrous sodium metasilicate or sodium metasilicate 5- or 9-hydrate as component (b) of the detergents according to the invention is particularly preferred.
  • the underlying monomers are e.g. the monomers previously mentioned as comonomers for the polyvinylpyrrolidone copolymers.
  • the underlying monomers are e.g. the monomers previously mentioned as comonomers for the polyvinylpyrrolidone copolymers.
  • homopolymers of acrylic acid, methacrylic acid or ⁇ -hydroxyacrylic acid are also suitable.
  • the molecular weight of the carboxyl group-containing homo- or copolymers is generally between 1000 and 1,000,000 and preferably between 5,000 and 500,000.
  • the polymeric carboxylic acids are preferably used in salt form, e.g. used as alkali, ammonium or amine salt.
  • 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) G3, G1, G2 and G3 each independently represent a C1-C4 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) G3, G1, G2 and G3 each independently represent a C1-C4 alkyl radical and t is a number from 1 to 14, and their water-soluble
  • 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. Post-washing agents present in liquid (aqueous) form or preferably in solid form is 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, based on the mixture, e.g. 5 to 50% by weight of component (a) and 95 to 50% by weight of component (b) and preferably 10 to 25% by weight of component (a) and 90 to 75% by weight of component (b).
  • the method according to the invention is particularly suitable for the washing of prints or dyeings on cellulose-containing fiber materials, pure cellulose fibers or mixed fabrics of cellulose and synthetic organic material, e.g. linear polyesters or modified cellulose (cellulose esters).
  • 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 in any processing stage, for example as a loose one Material (flake), as a doubled, pre-stretched staple fiber tape or in the form of threads, yarns, but especially as a woven or knitted fabric.
  • a loose one Material for example as a loose one Material (flake), as a doubled, pre-stretched staple fiber tape or in the form of threads, yarns, but especially as a woven or knitted fabric.
  • the cellulose-containing fiber materials can be printed or dyed by any method; as dyes are e.g. Vat dyes, e.g. from Color Index, 3rd edition (1971), volume 3, pages 3719 to 3837, direct dyes, such as those e.g. in Color Index, 3rd edition (1971), volume 2 on pages 2005 to 2478 as "Direct Dyes", or in particular reactive dyes, i.e. Dyes which have fiber-reactive radicals which are able to react with the hydroxyl groups of cellulose to form covalent chemical bonds are suitable.
  • dyes are e.g. Vat dyes, e.g. from Color Index, 3rd edition (1971), volume 3, pages 3719 to 3837, direct dyes, such as those e.g. in Color Index, 3rd edition (1971), volume 2 on pages 2005 to 2478 as "Direct Dyes", or in particular reactive dyes, i.e. Dyes which have fiber-reactive radicals which are able to react with the hydroxyl groups of cellulose to
  • the dyes used for dyeing or printing are reactive dyes, then e.g. Dyes, as described in the Color Index, 3rd edition (1971) volume 3 on pages 3391 to 3562 as "reactive dyes", into question.
  • the reactive dyes have e.g.
  • examples are e.g. the chromophores underlying the radicals A1 and A2 described below.
  • the reactive dyes have one or more sulfo groups and can also be further substituted.
  • substituents are: 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, acylamino groups with 1 to 8 carbon atoms , in particular alkanoylamino groups, such as acetylamino, propionylamino or benzoylamino, phenylamino, N, N-di- ⁇ -hydroxyethylamino, N, N-di- ⁇ -sulfatoethylamino, sulfobenzylamino, N, N-disulfobenzylamino, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy radical such as methoxycarbonyl or e
  • 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 radicals which may contain the chromophores directly or bonded via suitable bridge members are, for example, an alkanoyl or alkylsulfonyl radical which is substituted by a removable atom or a removable group, an alkenoyl or alkenesulfonyl radical which is optionally substituted by a removable atom or a removable group or an alkenoyl or alkenesulfonyl group containing a vinyl group.
  • the alkanoyl, alkylsulfonyl and alkenesulfonyl radicals mentioned generally contain 2 to 8 carbon atoms and the alkenoyl radicals generally contain 3 to 8 carbon atoms.
  • heterocyclic radicals come e.g. those which contain at least one removable substituent bound to a heterocyclic radical; inter alia those which contain at least one reactive substituent bound to a 5- or 6-membered heterocyclic ring, such as to a monoazine, diazine, triazine, pyridine, pyrimidine, pyridazine, pyrazine, thiazine, oxazine - Or asymmetrical or symmetrical triazine ring, or to such a ring system which has one or more fused aromatic rings, such as a quinoline, phthalazine, chinnoline, quinazoline, quinoxaline, acridine, phenazine and phenanthridine ring system .
  • Cleavable atoms or cleavable groups include, for example, 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 usually contains at least one functional group, for example the carbonyl group or the amino group, the amino group being substituted by C1 optionally substituted by halogen, hydroxy, cyano, C1-C4-acoxy, C1-C4-alkoxycarbonyl, carboxy, sulfamoyl, sulfo or sulfato -C4-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.
  • An aromatic radical is, for example, a phenyl radical which can be substituted by C1-C4-alkyl, such as methyl or ethyl, C1-C4-alkoxy, such as methoxy or ethoxy, halogen, such as fluorine, bromine or especially chlorine, carboxy or sulfo can, 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-chlorotria
  • Suitable leaving groups Y are e.g. -Cl, -Br, -F, -OSO3H, -SSO3H, -OCO-CH3, -OPO3H2, -OCO-CCl3, -OCO-CHCl2, -OCO-CH2Cl, -OSO2-C1-C4-alkyl, -OSO2- N (C1-C4-alkyl) 2 or -OCO-C6H5.
  • Y is preferably a group of the formula -Cl, -OSO3H, -SSO3H, -OCO-CH3, -OCO-C6H5 or -OPO3H2, in particular -OSO3H.
  • 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 C1-C4 alkylene radical and particularly preferably an ethylene radical.
  • R is preferably hydrogen or the group -SO2-Z, in which Z has the meanings given above.
  • R particularly preferably represents hydrogen.
  • R7 is preferably hydrogen, C1-C4-alkyl or a group -alk-SO2-Z, wherein alk and Z each have the meanings given above.
  • R8 is preferably a C1-C4 alkyl radical and particularly preferably hydrogen.
  • Arylene is preferably a 1,3- or 1,4-phenylene radical which is unsubstituted or, for example, 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 e.g. for fluorine, chlorine, bromine, sulfo, C1-C4-alkylsulfonyl or phenylsulfonyl and preferably for fluorine or chlorine.
  • T is a group which can be split off as an anion or denotes a non-reactive substituent.
  • T is a group which can be split off as an anion, this is e.g. fluorine, chlorine, bromine, sulfo, C1-C4 alkylsulfonyl or phenylsulfonyl and preferably fluorine or chlorine.
  • T stands for a non-reactive substituent, this can e.g. a hydroxy, C1-C4-alkoxy, C1-C4-alkylthio, amino, N-C1-C4-alkylamino or N, N-di-C1-C4-alkylamino, the alkyl optionally being e.g.
  • sulfo is substituted by sulfo, sulfato, hydroxy, carboxy or phenyl, cyclohexylamino, morpholino, or N-C1-C Alkyl-alkyl-N-phenylamino or phenylamino or naphthylamino radical, the phenyl or naphthyl optionally being e.g. is substituted by C1-C4-alkyl, C1-C4-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-methyl-
  • T preferably has the meaning amino, N-C1-C4-alkylamino, which is unsubstituted in the alkyl part or substituted by hydroxyl, sulfato or sulfo, morpholino, phenylamino or N-C1-C4-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 X1 is a group which can be split off as an anion and the other radical X1 has the meanings and preferences given for T as non-reactive substituents or a radical of the formulas (6a) to (6e) or a group which can be split off as an anion, X2 is a negative substituent and R8 independently has the meanings given under formula (5).
  • the radical X1 which can be split off as an anion is preferably fluorine or chlorine
  • suitable radicals X2 are nitro, cyano, C1-C4-alkylsulfonyl, carboxy, chlorine, hydroxy, C1-C4-alkoxysulfonyl, C1-C4-alkylsulfinyl, C1-C4-alkoxycarbonyl or C2-C4-alkanoyl, where the meanings chlorine, cyano and methylsulfonyl are preferred for X2.
  • 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 A1 is the remainder of a monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazane, azomethine, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone, nitroaryl, naphthoquinone, Pyrenequinone or perylene tetracarbimide dye, A2 is independently of A1 has the meanings of A1 or is hydrogen or a colorless organic radical, R1, R2, R3 and R4 are independently hydrogen or optionally substituted C1-C4-alkyl, B is an aliphatic or aromatic Bridge member and Y1 and Y2 independently of one
  • Another preferred dyeing process relates to the dyeing of fiber mixtures of cellulosic fiber materials and polyester fibers in the presence of reactive dyes and disperse dyes, which is characterized in that in the presence of an amount of a mineral acid salt of 0 to 40 g per liter of dye bath at a temperature of 80 up to 150 ° C and a pH of 5 to 11 colors and as Reactive dyes used at least one of the reactive dyes of the above formulas (1) and (2).
  • radicals A1 and A2 in the dye of the formula (1) can have the usual substituents in organic dyes, e.g. contain those as previously mentioned for reactive dye chromophores.
  • a colorless organic radical for A2 in the dye of formula (1) e.g. Hydrogen, C1-C6-alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, C1-C4-alkoxy, hydroxy, halogen or cyan substituted C1-C6-alkyl, cyclohexyl which is unsubstituted or substituted by C1-C4-alkyl, unsubstituted or substituted by C1-C4-alkyl, C1-C4-alkoxy, C2-C4-alkanoylamino, benzoylamino, ureido, carboxy, sulfo or halogen-substituted phenyl or naphthyl, pyridyl, benzthiazolyl, Oxazolyl or thiazolyl.
  • A2 and R4 in formula (1) together with the nitrogen atom connecting them can also form a heterocyclic ring, e.g. Piperidyl or morpholyl.
  • A2 is preferably a dye radical which, independently of A1, has the meanings given above for A1.
  • A1 and A2 independently of one another are particularly preferably the residue of a monoazo, disazo or formazan dye, in particular residues of the following formulas (8a) to (8t): wherein R10 represents 0 to 3 identical or different substituents from the group C1-C4-alkyl, C1-C4-alkoxy, halogen, carboxy and sulfo. wherein R10 represents 0 to 3 identical or different substituents from the group C1-C4-alkyl, C1-C4-alkoxy, halogen, carboxy and sulfo.
  • R10 represents 0 to 3 identical or different substituents from the group C1-C4-alkyl, C1-C4-alkoxy, halogen, carboxy and sulfo.
  • R12 is C1-C4 alkanoyl or benzoyl.
  • R12 is C1-C4 alkanoyl or benzoyl.
  • R13 represents 0 to 3 identical or different substituents from the group C1-C4-alkyl, C1-C4-alkoxy, halogen, carboxy and sulfo.
  • R14 and R16 are independently hydrogen, C1-C4 alkyl or phenyl, and R15 is hydrogen, cyano, carbamoyl or sulfomethyl.
  • R13 represents 0 to 3 identical or different substituents from the group C1-C4-alkyl, C1-C4-alkoxy, halogen, carboxy and sulfo.
  • R17 represents 0 to 2 identical or different substituents from the group C1-C4-alkyl, C1-C4-alkoxy, halogen, carboxy and sulfo; and Z 'is ⁇ -sulfatoethyl, ⁇ -thiosulfatoethyl, ⁇ -phosphatoethyl, ⁇ -acyloxyethyl, ⁇ -halogenoethyl or vinyl.
  • R18 represents 0 to 2 identical or different substituents from the group C1-C4-alkyl, C1-C4-alkoxy, halogen, carboxy and sulfo; and Z 'is ⁇ -sulfatoethyl, ⁇ -thiosulfatoethyl, ⁇ -phosphatoethyl, ⁇ -acyloxyethyl, ⁇ -halogenoethyl or vinyl.
  • R10 for 0 to 3 identical or different substituents from the group C1-C4-alkyl, C1-C4-alkoxy, halogen, carboxy and sulfo and R11 for 0 to 3 identical or different substituents from the group halogen, nitro, cyano, trifluoromethyl , Sulfamoyl, carbamoyl, C1-C4-alkyl, C1-C4-alkoxy, amino, acetylamino, ureido, hydroxy, carboxy, sulfomethyl and sulfo.
  • Remains of heavy metal complexes are also of interest; copper, nickel, cobalt or chromium are particularly suitable as complex-forming heavy metals.
  • residues of copper complex azo dyes in particular those of the formulas (8a) to (8k), which each contain the copper atom bonded via an oxygen atom in the ortho position to the azo bridge.
  • azo dyes which are suitable as residues of metal complexes are:
  • Cr and Co complexes can contain the azo compound of the formula given above once or twice, ie they can be symmetrical or with any other ligand be constructed asymmetrically.
  • Copper complexes such as, for example, are preferred and
  • the radicals R1, R2, R3 and R4 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, C1-C4alkoxy, C1-C4alkoxycarbonyl, carboxy, sulfamoyl, sulfo or sulfato.
  • R1, R2, R3 and R4 are independently hydrogen, methyl or ethyl, especially hydrogen.
  • the bridge member B in the dye of the formula (1) is particularly preferably a radical of the formula - (CH2 , Cyclohexylene optionally substituted by C1-C4-alkyl, optionally substituted by C1-C4-alkyl, C1-C4-alkoxy, C2-C4-alkanoylamino, sulfo, halogen or carboxy or a radical of the formula wherein the benzene ring III is optionally substituted by C1-C4-alkyl, C1-C4-alkoxy, C2-C4-alkanoylamino, sulfo, halogen or carboxy.
  • D in the dye of the formula (2) is, for example, the remainder of an aminobenzene, Aminonaphthalene, phenylazo-aminobenzene, naphthylazo-aminobenzene, phenylazo-aminonaphthalene or naphthylazo-aminonaphthalene, each of which may be 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-C1 -C4-alkylamino, where the alkyl may optionally be further substituted by -OH, -OCOCH3, -OSO3H, -CN or halogen, for example methylamino, ethylamino, n- or iso-propylamino or n-, sec- or tert-butylamino , N, N-dimethyl- or diethylamino, ⁇ -chloroethylamino, ⁇ -cyanoethylamino, ⁇ -acetyloxyethylamin
  • R5 or R6 in the dye of the formula (2) is a C1-C6 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 can be substituted by hydroxy, sulfo, sulfato, carboxy, cyano, halogen, C1-C4-alkoxycarbonyl, C1-C4-alkanoyloxy, carbamoyl or a reactive radical and the alkyl radical, with the exception of methyl, optionally interrupted by -O- or -NR'- is and R 'is hydrogen or C1-C4 alkyl.
  • alkyl radical R5 and R6 independently of one another are preferably hydrogen or a C1-C4-alkyl radical which is unsubstituted or substituted by hydroxyl, sulfo, sulfato, carboxy, cyano or the group -SO2-Z and is optionally interrupted by -O-; preferably one of the radicals R5 and R6 is hydrogen.
  • Examples of particularly preferred non-reactive alkylamino radicals V1 and V2 are: -NH-CH3, -NH-CH2-SO3H, -NH-CH2-COOH, -NH-C2H5, -NH-CH2-CH2-OH, -NH-CH2-CH2-SO3H, -NH-CH2-CH2-OSO3H, -NH-CH2-CH2-CN, -NH-CH2-CH2-COOH, -NH-CH2-CH2-CH2-OSO3H, -NH-CH2-CH2-OH, -NH-CH2-CH (OH) -CH2-CH3, -NH-CH2-CH2-O-CH2-CH2-OH, -NH-CH2-CH2-O-CH2-CH2-OSO3H.
  • Form R5 and R6 together with the nitrogen atom connecting them a heterocyclic radical this can be, for example, a piperidinyl, piperazinyl or pyrrolidinyl radical, each unsubstituted or, for example, by a radical of the formula - (alk) p -SO2-Z, in which alk C1-C6 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 pyridone, which e.g. is substituted by one or more identical or different of the substituents mentioned above for D.
  • V1 and V2 in the dye of the formula (2) very particularly preferably represent a radical of the formula (3) in which R5 and R6 independently of one another are hydrogen or an unsubstituted or substituted by hydroxyl, sulfo, sulfato, carboxy, cyano or the group -SO2-Z are substituted C1-C6-alkyl, the alkyl with the exception of methyl optionally interrupted by -O- or -NR'- and R 'and Z have the meanings and preferences given above, or optionally by C1-C4-alkyl, C1 -C4-alkoxy, C2-C4-alkanoylamino, sulfo, halogen or carboxy substituted phenyl or naphthyl.
  • at least one of V1 and V2 contains a group -SO2-Z.
  • Q in the dye of formula (2) is preferably optionally by C1-C4-alkyl, C1-C4-alkoxy, C2-C4-alkanoylamino, C1-C4-alkoxycarbonyl, C1-C4-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 phenyl which is unsubstituted or substituted by methyl, trifluoromethyl, methoxy, sulfo, nitro, chlorine or bromine, in particular unsubstituted phenyl.
  • dyes of the formula (2) are preferred which, in the radical V1, V2 or D, have at least one reactive group of the formulas (4), (4a), (4b), (4c), (4d), (4e) or ( 5), where T in the rest of the formula (5) is a group of the formula (6a), (6b), (6c), (6d) or (6e).
  • Dyes of the formula (2) which contain at least one reactive group of the formula (4) in the radical V1, V2 or D, in particular in the radical V1 or V2, are very particularly preferred.
  • a dye of the formula (1) is used in which A1 and A2 are independently the remainder of a monoazo, disazo or formazan dye, B is a C2-C12 alkylene radical which can be interrupted by 1, 2 or 3 members from the group -NH-, -N (CH3) - or -O-, optionally by C1-C4-alkyl, C1-C4-alkoxy, C2-C4-alkanoylamino, sulfo, halogen or carboxy-substituted C5-C9-cycloalkylene radical or phenylene radical or a radical of the formula is in which the benzene rings I and II are optionally substituted by C1-C4-alkyl, C1-C4-alkoxy, C2-C4-alkanoylamino, sulfo, halogen or carboxy and B1 is a C2-C10-alkylene radical which is represented by 1, 2 or 3 oxygen
  • radicals A1 and A2 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 the sodium, potassium, lithium or ammonium salts or the salt of triethanolamine.
  • the dyes of the formulas (1) and (2) are known or can be prepared analogously to known dyes.
  • Dyes of formula (1) are e.g. from GB-A-1,529,645 and dyes of formula (2) e.g. known from EP-A-298,041 or can be prepared analogously.
  • salts of mineral acids are, for example, alkali or alkaline earth halides and alkali or alkaline earth sulfates, such as e.g. Lithium, sodium or potassium chlorides and sulfates to understand.
  • the salts of mineral acids are preferably alkali metal chlorides or alkali metal sulfates, in particular sodium chloride or sodium sulfate.
  • the dyeing is carried out in the presence of an amount of the salt of a mineral acid, which depends on the total amount of the dye used.
  • an amount of the salt of a mineral acid of 0 to 5 g, in particular 0.01 to 5 g, per liter of dyebath is used, for medium shades an amount of 5 to 10 g and for deep shades an amount of 10 to 20 G.
  • Bright shades are to be understood as meaning those in which the amount of the dye used for dyeing is less than 1 percent by weight, based on the weight of the material to be dyed.
  • Medium shades are those in which the amount of the dye used 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.
  • dyeing takes place in the presence of an amount of a mineral acid salt of 0 to 10 g per liter of dyebath, in particular 0.01 to 10 g.
  • the dyeing can take place in the presence of an amount of the salt of a mineral acid, which depends on the total amount of the dye used.
  • an amount of the salt of a mineral acid of 0 to 5 g, in particular 0.01 to 5 g, per liter of dyebath can be used and in the case of deeper shades an amount of 5 to 10 g.
  • Light shades are here as defined above and the lower shades correspond to amounts of the dye used which are 1 percent by weight or greater, in particular 1 percent by weight to 10 percent by weight, preferably 1 percent by weight to 6 percent by weight.
  • the amounts in which the reactive dyes are used in the dye baths can vary depending on the desired depth of color. In general, amounts of 0.01 to 10 percent by weight, in particular 0.01 to 6 percent by weight, based on the material to be dyed, proven to be advantageous.
  • Dyeing by the exhaust method is preferred for the process for dyeing cellulose-containing fiber materials.
  • the dyeing is generally carried out in an aqueous medium with a liquor ratio of, for example, 1: 2 to 1:60, in particular a liquor ratio of 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 of larger amounts of salts of a mineral acid such as 50 to 100 g / l, can be dispensed with. This results in a reduction in wastewater pollution and greater efficiency of the process.
  • disperse dyes are suitable as disperse dyes for the process for dyeing fiber mixtures, e.g. the dyes mentioned in Color Index, 3rd edition (1971) Volume 2 on pages 2479 to 2742.
  • Suitable cellulosic fiber materials are natural cellulose fibers, such as cotton, linen and hemp, as well as cellulose and regenerated cellulose.
  • the dyeing of polyester / cotton blended fabrics is particularly preferred.
  • the process for dyeing fiber mixtures is particularly suitable for the exhaust process, in particular for a one-step, single-bath process using the exhaust 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 a range from 6 to 10, in particular in a range from 6 to 8.
  • polyester / cotton blend fabrics are dyed at a temperature of 90 to 140 ° C. and a pH of 6 to 10 in a one-step, single-bath process using the exhaust method.
  • 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.
  • the meanings and preferences given above apply to the reactive dyes of the formulas (1) and (2).
  • the dyeing liquors correspond in terms of the possible additives and the liquor ratio to those given above for the process for dyeing cellulosic fiber materials.
  • the meanings and preferences given above apply to the salts of a mineral acid.
  • the otherwise customary addition of large 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 results in a reduction in wastewater pollution and an easier treatment of the fabric after the dyeing process.
  • the washing process according to the invention advantageously follows the dyeing process or the printing process as an aftertreatment.
  • the cellulose-containing fiber material is then in a fresh liquor containing at least one detergent according to the invention at a temperature of e.g. 50 to 100 ° C, preferably 60 to 100 ° C and particularly preferably at cooking temperature, i.e. treated at a temperature of about 90 to 100 ° C.
  • the amount of detergent according to the invention depends on the water hardness, but is generally e.g. ⁇ 0.25 g / l liquor, preferably 0.25 to 5 g / l liquor and particularly preferably 0.5 to 2 g / l wash liquor.
  • the fiber material is then removed from the wash liquor and advantageously rinsed with fresh water until the wash liquor components have been completely removed.
  • An aqueous preparation can be prepared from this powdery mixture before use, but the product can also be used directly in the wash liquor be added.
  • polyvinylpyrrolidone e.g. Luviskol® K 30
  • a dust-binding agent containing the main constituents paraffin oil and an oleyl polyglycol ether mixture.
  • An aqueous preparation can be prepared from this powdery mixture before use, but the product can also be added directly to the wash liquor when used.
  • polyvinylpyrrolidone e.g. Luviskol® K 30
  • polyvinylpyrrolidone e.g. Luviskol® K 30
  • An aqueous preparation can be prepared from this powdery mixture before use, but the product can also be added directly to the wash liquor when used.
  • 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 treated in a fresh liquor containing 2 g / l of the detergent according to Example 1 for 20 minutes at cooking temperature (approx. 98 ° C.), then rinsed with cold water and dried.
  • a cotton fabric dyed in a brown shade is obtained with good fastness properties, in particular good wet fastness properties.
  • the dyed cotton fabric is then treated twice in a fresh liquor containing 1 g / l of the detergent according to Example 1 a at cooking temperature (approx. 98 ° C.) for 10 minutes, then rinsed with cold water and dried.
  • a cotton fabric dyed in a light brown shade is obtained with good fastness properties, in particular good wet fastness properties.
  • the dyed cotton fabric is then treated in a fresh liquor containing 1.5 g / l of the detergent according to Example 1a for 20 minutes at cooking temperature (approx. 98 ° C.), then rinsed with cold water and dried.
  • 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 treated in a fresh liquor containing 2 g / l of the detergent according to Example 1b for 20 minutes at cooking temperature (approx. 98 ° C.), then rinsed with cold water and dried.
  • a yellow-coloring reactive dye of the formula (101) 0.125 parts of a yellow-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.
  • 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 mixed fabric is then treated in a fresh liquor containing 2 g / l of the detergent according to Example 1 for 20 minutes at cooking temperature (approx. 98 ° C.), then rinsed with cold water and dried.
  • a polyester / cotton blend fabric dyed in a brown shade with good fastness properties is obtained.
  • the dyed fabric is then treated in a fresh liquor containing 2 g / l of the detergent according to Example 1a for 20 minutes at cooking temperature (approx. 98 ° C.), then rinsed with cold water and dried.
  • a cotton fabric dyed in a greenish-yellow shade with good fastness properties is obtained.
  • 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 treated in a fresh liquor containing 2 g / l of the detergent according to Example 1b for 20 minutes at cooking temperature (approx. 98 ° C.), then rinsed with cold water and dried.
  • a cotton fabric printed in an orange shade with good fastness properties is obtained.
  • 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 adjusted by adding aqueous sodium hydroxide solution kept constant. 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.
  • A1 is a radical of the formula and A2 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 hydrogenphosphate in 500 parts of water, 14 parts of cyanuric fluoride are added dropwise 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 freed of salt by dialysis and the dye is evaporated.

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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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Cited By (4)

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WO1998030664A1 (fr) * 1997-01-10 1998-07-16 Unilever Plc Compositions detergentes et copolymeres pour inhiber le transfert de teinture
EP0760030A4 (fr) * 1994-05-10 1998-12-02 Henkel Corp Procede de fixation de colorants dans des matieres textiles
EP0894890A1 (fr) * 1997-07-31 1999-02-03 Sybron Chemie Nederland B.V. Procédé de lavage de textiles teints
WO2014090769A1 (fr) * 2012-12-14 2014-06-19 Henkel Ag & Co. Kgaa Principes actifs polymères améliorant le pouvoir détergent primaire

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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
EP1584371A1 (fr) * 2004-04-07 2005-10-12 Urea Casale S.A. Procede et dispositif de granulation en lit fluidise
US8557758B2 (en) * 2005-06-07 2013-10-15 S.C. Johnson & Son, Inc. Devices for applying a colorant to a surface
US7727289B2 (en) * 2005-06-07 2010-06-01 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
US7776108B2 (en) 2005-06-07 2010-08-17 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
US20080282642A1 (en) * 2005-06-07 2008-11-20 Shah Ketan N Method of affixing a design to a surface
DE102006012018B3 (de) * 2006-03-14 2007-11-15 Henkel Kgaa Farbschützendes Waschmittel
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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FR2263298A1 (fr) * 1974-03-07 1975-10-03 Basf Ag
GB1529645A (en) * 1975-03-20 1978-10-25 Ciba Geigy Ag Fibre-reactive fluoro triazine dyes
EP0262897A2 (fr) * 1986-10-01 1988-04-06 Unilever Plc Composition détergente
EP0298041A2 (fr) * 1987-07-02 1989-01-04 Ciba-Geigy Ag Colorants réactifs, leur préparation et leur emploi

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JPS4839208B1 (fr) * 1968-11-18 1973-11-22
DE2903134C3 (de) * 1979-01-27 1981-07-02 Girmes-Werke Ag, 4155 Grefrath Verfahren zum Waschen von gefärbtem oder bedrucktem Textilgut
DE3213840C2 (de) * 1982-04-15 1985-02-07 Girmes-Werke Ag, 4155 Grefrath Verfahren zum Waschen oder Spülen von gefärbtem oder bedrucktem, kontinuierlich vorlaufendem, bahnförmigem Textilgut

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FR2263298A1 (fr) * 1974-03-07 1975-10-03 Basf Ag
GB1529645A (en) * 1975-03-20 1978-10-25 Ciba Geigy Ag Fibre-reactive fluoro triazine dyes
EP0262897A2 (fr) * 1986-10-01 1988-04-06 Unilever Plc Composition détergente
EP0298041A2 (fr) * 1987-07-02 1989-01-04 Ciba-Geigy Ag Colorants réactifs, leur préparation et leur emploi

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0760030A4 (fr) * 1994-05-10 1998-12-02 Henkel Corp Procede de fixation de colorants dans des matieres textiles
WO1998030664A1 (fr) * 1997-01-10 1998-07-16 Unilever Plc Compositions detergentes et copolymeres pour inhiber le transfert de teinture
EP0894890A1 (fr) * 1997-07-31 1999-02-03 Sybron Chemie Nederland B.V. Procédé de lavage de textiles teints
WO2014090769A1 (fr) * 2012-12-14 2014-06-19 Henkel Ag & Co. Kgaa Principes actifs polymères améliorant le pouvoir détergent primaire

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