EP0696661A1 - Multifunctionnal textile agents compositions - Google Patents

Multifunctionnal textile agents compositions Download PDF

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Publication number
EP0696661A1
EP0696661A1 EP95810494A EP95810494A EP0696661A1 EP 0696661 A1 EP0696661 A1 EP 0696661A1 EP 95810494 A EP95810494 A EP 95810494A EP 95810494 A EP95810494 A EP 95810494A EP 0696661 A1 EP0696661 A1 EP 0696661A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
weight
acid
component
methyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP95810494A
Other languages
German (de)
French (fr)
Other versions
EP0696661B1 (en
Inventor
Rainer Hans Dr. Traber
Albert Stehlin
Vladimir Dr. Arnold
Rolf Kuratli
Werner Schreiber
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
Original Assignee
Ciba Geigy AG
Ciba Spezialitaetenchemie Holding AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Geigy AG, Ciba Spezialitaetenchemie Holding AG filed Critical Ciba Geigy AG
Publication of EP0696661A1 publication Critical patent/EP0696661A1/en
Application granted granted Critical
Publication of EP0696661B1 publication Critical patent/EP0696661B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/86—Mixtures of anionic, cationic, and non-ionic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2006—Monohydric alcohols
    • C11D3/2034—Monohydric alcohols aromatic
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C11D3/2048—Dihydric alcohols branched
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C11D3/2058—Dihydric alcohols aromatic
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2065—Polyhydric alcohols
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—Ethers
    • 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
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates
    • 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
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in 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
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in 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
    • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
    • 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
    • C11D3/3788—Graft polymers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D06L1/12—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
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    • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D06L1/12—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
    • D06L1/14—De-sizing
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    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives
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    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening
    • D06L4/614—Optical bleaching or brightening in aqueous solvents
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    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
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    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
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    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/144—Alcohols; Metal alcoholates
    • D06M13/148—Polyalcohols, e.g. glycerol or glucose
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    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/152—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen having a hydroxy group bound to a carbon atom of a six-membered aromatic ring
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    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
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    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/165—Ethers
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    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
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    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
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    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/192—Polycarboxylic acids; Anhydrides, halides or salts thereof
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    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
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    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
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    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
    • D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
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    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
    • D06M13/272—Unsaturated compounds containing sulfur atoms
    • D06M13/278—Vinylsulfonium compounds; Vinylsulfone or vinylsulfoxide compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/288—Phosphonic or phosphonous acids or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/44—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen containing nitrogen and phosphorus
    • D06M13/447—Phosphonates or phosphinates containing nitrogen atoms
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53—Polyethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
    • D06P1/613—Polyethers without nitrogen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/651—Compounds without nitrogen
    • D06P1/65106—Oxygen-containing compounds
    • D06P1/65118—Compounds containing hydroxyl groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/653—Nitrogen-free carboxylic acids or their salts
    • D06P1/6533—Aliphatic, araliphatic or cycloaliphatic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/667—Organo-phosphorus compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C11D3/2044—Dihydric alcohols linear

Definitions

  • the present invention relates to storage-stable, low-foaming, silicone-free, aqueous textile auxiliaries, their production and multiple uses, e.g. as wetting agents, detergents, dispersants or as stabilizers in peroxide bleaching liquors.
  • Components (a) to (g) can each consist of individual compounds or can also be composed of several individual compounds.
  • foam-suppressing agents in particular silicone-containing compounds
  • the substituents R1 and R2 in the formulas (1) and (2) advantageously represent the hydrocarbon radical of a saturated or unsaturated aliphatic monoalcohol having 8 to 22 carbon atoms.
  • the hydrocarbon radical can be straight-chain or branched.
  • R1 and R2 are preferably an alkyl or alkenyl radical having 9 to 14 carbon atoms.
  • natural alcohols such as e.g. Lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, as well as synthetic alcohols, e.g. 2-ethylhexanol, 1,1,3,3-tetramethylbutanol, octan-2-ol, isononyl alcohol, trimethylhexanol, trimethylnonyl alcohol, decanol, C9-C11 oxo alcohol, tridecyl alcohol, isotridecanol or linear primary alcohols (alfoles) with 8 to 22 carbon atoms in Come into consideration. Some representatives of these alfoles are Alfol (8-10), Alfol (9-11), Alfol (10-14), Alfol (12-13) or Alfol (16-18). (“Alfol" is a registered trademark).
  • Unsaturated aliphatic monoalcohols are, for example, dodecenyl alcohol, hexadecenyl alcohol or oleyl alcohol.
  • the alcohol residues can be present individually or in the form of mixtures of two or more components, e.g. Mixtures of alkyl and / or alkenyl groups derived from soy fatty acids, palm kernel fatty acids or tallow oils.
  • Alkylene-O chains are preferably divalent radicals of the formulas ( ⁇ CH2-CH2-O) ⁇ , R4 represents the straight-chain hydrocarbon radical of a saturated aliphatic monoalcohol with 8 to 14 carbon atoms, ie n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl or n-tetradecyl.
  • R5 in formula (3) in the meaning of C1-C8-alkyl is the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl radical.
  • R5 is preferably the n-butyl radical.
  • cycloaliphatic radical examples include cycloheptyl, cyclooctyl or preferably cyclohexyl.
  • nonionic surfactants which correspond to component (a) are the addition products of 2 to 60 mol, preferably 4 to 10 mol, of alkylene oxides, in particular ethylene oxide, individual ethylene oxide units being substituted by epoxides, such as propylene oxide and / or 1,2-butylene oxide , can be replaced, to higher unsaturated or saturated fatty alcohols with 8 to 22 carbon atoms, or mixtures of these compounds.
  • Suitable monomeric starting compounds for the preparation of the polymeric compounds of component (b) are ethylenically unsaturated monomeric sulfonic acids or carboxylic acids or their anhydrides. Both monocarboxylic acids and dicarboxylic acids and their anhydrides as well as sulfonic acids, each having an ethylenically unsaturated aliphatic radical and preferably at most 7 carbon atoms, can be used. Monocarboxylic acids having 3 to 5 carbon atoms, e.g. acrylic acid, methacrylic acid, ⁇ -haloacrylic acid, 2-hydroxyethylacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid and vinyl acetic acid.
  • Ethylenically unsaturated dicarboxylic acids are preferably fumaric acid, maleic acid or itaconic acid, furthermore mesaconic acid, citraconic acid, glutaconic acid and methylmalonic acid.
  • Maleic anhydride is particularly mentioned as the anhydride of these acids.
  • Suitable monomeric sulfonic acids which are used for the polymerization are vinylsulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid.
  • Organic catalysts which form free radicals are preferably used as catalysts for the preparation of component (b).
  • Suitable initiators for carrying out the radical polymerization are e.g. symmetrical aliphatic azo compounds such as azo-bis-isobutyronitrile, azo-bis-2-methylvaleronitrile, 1,1'-azo-bis-1-cyclohexanitrile and 2,2'-azo-bis-isobutyric acid alkyl ester; symmetrical diacyl peroxides, e.g.
  • Suitable peroxides are: tert-butyl hydroperoxide, di-tert-butyl peroxide, cumene hydroperoxide, di-cumene peroxide and tert-butyl perpivalate.
  • Another suitable compound is potassium persulfate, which is preferably used in the preparation of component (b).
  • the catalysts are generally used in amounts of 0.1 to 10% by weight, preferably 0.5 to 2% by weight, based on the starting products.
  • Component (b) is preferably in the form of a partially neutralized compound which has a pH of 3 to 6.
  • the polymeric compound is produced e.g. by reacting an ethylenically unsaturated sulfonic acid or carboxylic acid or its anhydride in the presence of a nonionic surfactant or in the presence of mixtures of nonionic surfactants of the formula (2).
  • the reaction product is then partially neutralized with an inorganic and / or organic base to a pH of 3 to 6, preferably 4 to 5.
  • bases one uses e.g. 1 to 8% by weight inorganic or organic bases, e.g.
  • the polymerization is advantageously carried out in an inert atmosphere, e.g. carried out in the presence of nitrogen.
  • organic acids mentioned can also be in the form of their water-soluble salts, such as the alkali metal, in particular sodium or potassium, salts or the amine salts.
  • alkyl sulfate is in the form of a salt
  • sodium, potassium or ammonium salts can be used, for example.
  • the sodium salt is preferred.
  • the aliphatic saturated R11 is derived from monoalcohols. Natural or synthetic alcohols can be used. As natural alcohols e.g. Lauryl, myristyl, cetyl, stearyl, arachidyl or behenyl alcohol. Preferred compounds are those in which R11 is derived from branched aliphatic synthetic alcohols having 4 to 12, in particular 4 to 8, carbon atoms, e.g.
  • alkyl sulfates can already be in the form of their salts and can be used alone or as a (technical) mixture with one another in the wetting agent according to the invention.
  • hydrotroping agents of the formula (7) are 2-ethylhexyl sulfate.
  • alkyl sulfates are prepared in a manner known per se by reacting the corresponding alcohols with e.g. Sulfuric acid, oleum, chlorosulfonic acid or sulfur trioxide.
  • amphoteric surfactants such as e.g. Sodium laurimino dipropionate, dihydroxyethyl tallow fat glycinate, disodium cocoamphodiacetate, disodium capryloamphodiacetate or preferably disodium dicarboxyethylcocopropylene diamine or tallow fat amphopolycarboxyglycinate
  • Examples of the end-capped nonionic surfactants of component (d) are C10-C12 fatty alcohol-ethylene oxide or ethylene oxide / propylene oxide addition products or the reaction product of one mole of a C10 fatty alcohol with 6 moles of ethylene oxide and 1 mole of butylene oxide, where the addition products can be end-capped with C1-C4-alkyl, preferably methyl or butyl.
  • the nonionic surfactants of the formulas (1) and (2) are prepared in a manner known per se, e.g. by reaction of the corresponding alkylene oxide addition products with thionyl chloride and subsequent reaction of the chlorine compound formed with a saturated or unsaturated aliphatic C8-C22 monoalcohol.
  • the end-capped nonionic surfactants of the formula (3) are produced in a manner known per se, e.g. by reaction of ethylene oxide and / or propylene oxide and / or butylene oxide in the corresponding molar ratios with one mole of the alcohol R4-OH, and subsequent reaction of the adduct formed with an alkyl halide R5-Hal, preferably C1-C4 alkyl chloride.
  • the magnesium salts of carboxylic acids with complexing properties corresponding to the optional component (e) are salts of gluconic acid, citric acid, malic acid, lactic acid, L-glutamic acid and L-aspartic acid.
  • the magnesium salts of gluconic acid are used as component (s), and very particularly magnesium mono- or magnesium digluconate.
  • the magnesium gluconate can be used as such and preferably as a solid in the composition according to the invention.
  • the gluconate can also be formed in situ from gluconic acid and magnesium oxide or preferably magnesium hydroxide.
  • Gluconic acid or its sodium salt can also be used in combination with a water-soluble magnesium salt.
  • water soluble Magnesium salt is the acetate, especially the sulfate or its heptahydrate and in particular the chloride or its hexahydrate.
  • the magnesium salt is usually used as a solid, with solid magnesium chloride hexahydrate in the foreground.
  • the mixture of monomeric and oligomeric compounds (f 1) is preferably a mixture of monomeric and oligomeric compounds of the formula wherein R15 methyl or ethyl and q2 are 1 to 13.
  • the mixtures of the monomeric and oligomeric compounds of the type indicated are known per se and are prepared by known methods.
  • the mixture of the formulas (10a) and (10b) is preferably prepared by reacting phosphorus trichloride, acetic acid and optionally acetic anhydride in an aqueous medium.
  • the oligomeric portions of component (f 1) are at least partially hydrolyzed to the corresponding monomeric compounds in the aqueous composition according to the invention in the presence of an alkali metal hydroxide. Accordingly, as component (f 1) of the compositions according to the invention, especially monomeric compounds of one of the formulas (9a) or (10a) are also suitable.
  • Component (f 1) is preferably used as 35 to 90, preferably 40 to 85, in particular 40 to 60 percent by weight, aqueous solution in the composition according to the invention.
  • component (f4) examples include nitrilotrimethylenephosphonic acid, the Na salt of ethylenediamine-tetramethylenephosphonic acid, the Na salt of diethylenetriamine-pentamethylenephosphonic acid or N, N-bis (phosphonomethyl) glutamic acid.
  • Compounds of component (f) act as complexing agents for alkaline earth metals and heavy metals in aqueous liquors which contain a per compound, for example hydrogen peroxide, in pretreatment, especially in bleaching processes of cellulosic fiber materials.
  • a per compound for example hydrogen peroxide
  • the presence of these components suppresses the decomposition of the per-compound by free, ie non-complex heavy metals, which may be present in the process water of the fiber material or in the alkali added.
  • Suitable as component (g) are dihydric or polyhydric alcohols.
  • dihydric alcohols are those having 2 to 6 carbon atoms in the alkylene part, such as ethylene glycol, 1,2- or 1,3-propanediol, 1,3-, 1,4- or 2,3-butanediol, 1,5-pentanediol and to name 1,6-hexanediol or 2-methyl-2,4-pentanediol.
  • the latter compound is preferably used in the composition according to the invention.
  • polyhydric alcohols examples include glycerol, erythritol, the pentites, e.g. Arabite, adonite and xylitol as well as the hexites, e.g. D-sorbitol, D-mannitol and dulcitol.
  • the textile auxiliaries according to the invention can be prepared by adding components (a), (b), (c), and optionally (d), (e), (f) and (g) in water (component (h)), or thereby that the corresponding components are mixed with stirring and deionized water is added until a homogeneous solution is obtained. It is a purely mechanical process, which is optionally carried out at elevated temperature, for example from 30 to 40 ° C. There is no chemical reaction.
  • a further embodiment of the preparation of the textile auxiliaries according to the invention is that component (b) is first reacted by reacting a monomeric ethylenically unsaturated sulfonic acid or carboxylic acid or its anhydride in the presence of one or more of the compounds of the nonionic surfactant of the formulas (1) and / or ( 2) in the presence of a catalyst, adjust the pH to about 4.5 and then add the remaining components until a homogeneous solution is obtained.
  • the finished textile auxiliaries have a pH of z. B. 2 to 5, preferably from 2.5 to 3.5.
  • the pH value always relates to a 1% aqueous solution of the formulation according to the invention.
  • Magnesium hydroxide, potassium hydroxide, mono-, di- or triethanolamine and especially sodium hydroxide are used, for example, to subsequently adjust the desired pH.
  • the new formulations represent storage-stable, single-phase, low-foam and silicone-free textile auxiliaries with good complexing and sequestering properties with a dirt-removing effect. They show good emulsifying power and are stable in an alkaline liquor. In alkaline bleaching liquors, they have no creams or deposits. They also have good peroxide-stabilizing properties and bring about good rewettability of the textile goods. In addition, the formulations are readily biodegradable. Due to their liquid commercial form, they are easy to handle, which is why they are particularly suitable for modern dosing systems.
  • the universal applicability of the formulations according to the invention enables various applications. They can be used, for example, as wetting agents, textile detergents, dispersants or as stabilizers in peroxide bleaching liquors. They are also ideal as a universal household detergent.
  • the present invention accordingly also relates to a process for wetting, washing and / or bleaching fiber materials, which is characterized in that these materials are treated in an aqueous medium in the presence of a textile auxiliary as defined in claim 1.
  • the amounts in which the textile auxiliaries according to the invention are added to the treatment liquors are 0.1 to 60, preferably 1 to 20 g per liter of treatment liquor.
  • These fleets can also contain other additives, e.g. Desizing agents, dyes, optical brighteners, alkalis such as sodium hydroxide and hydrogen peroxide.
  • Possible fiber materials are: cellulose, in particular untreated natural cellulose such as Hemp, linen, jute, rayon, viscose, acetate treyon, native cellulose fiber and especially raw cotton, wool, polyamide, polyacrylonitrile or polyester fiber materials as well as fiber mixtures, e.g. those made of polyacrylonitrile / cotton or polyester / cotton.
  • the fiber material to be treated can be in different processing stages, for example the cellulosic material as loose material, yarn, woven or knitted fabric. As a rule, these are always textile fiber materials which are produced from pure textile cellulose fibers or from mixtures of textile cellulose fibers with textile synthetic fibers.
  • the fiber material can be treated continuously or batchwise in an aqueous liquor.
  • the aqueous treatment liquors can be applied to the fiber materials in a known manner, advantageously by impregnation on the foulard, the liquor absorption being about 70 to 120% by weight.
  • the padding process is used in particular in the pad-steam and pad-batch processes.
  • the impregnation can be carried out at 10 to 60 ° C, but preferably at room temperature.
  • the cellulose material is optionally subjected to a heat treatment, e.g. Subject at temperatures from 80 to 140 ° C.
  • the heat treatment is preferably carried out by steaming at 95 to 140, in particular at 100 to 106 ° C. Depending on the type of heat development and the temperature range, the heat treatment can take 30 seconds to 60 minutes.
  • the impregnated goods are rolled up without drying and then optionally packed with a plastic film and stored at room temperature for 1 to 24 hours.
  • the treatment of the fiber materials can also be carried out in long liquors with a liquor ratio of e.g. 1: 3 to 1: 100, preferably 1: 4 to 1:25 and at 10 to 100, preferably 60 to 98 ° C for about 1/4 to 3 hours under normal conditions, i.e. under atmospheric pressure in conventional equipment, e.g. a jigger, jet or reel runner.
  • a liquor ratio of e.g. 1: 3 to 1: 100, preferably 1: 4 to 1:25 and at 10 to 100, preferably 60 to 98 ° C for about 1/4 to 3 hours under normal conditions, i.e. under atmospheric pressure in conventional equipment, e.g. a jigger, jet or reel runner.
  • the treatment up to 150 ° C, preferably 105 to 140 ° C under pressure in so-called high-temperature equipment (HT equipment) can be carried out.
  • HT equipment high-temperature equipment
  • the fiber materials are rinsed thoroughly with hot water at about 90 to 98 ° C. and then with warm and finally with cold water, neutralized if necessary and then preferably dried at elevated temperatures.
  • the formulation is used as a textile auxiliary for alkaline digestion processes, leaching and mercerizing.
  • the formulation is used as a textile auxiliary for alkaline digestion processes, leaching and mercerizing.
  • the formulation is used as a textile aid for cold storage peroxide bleaching.
  • the formulation is used as a textile aid for boiling and bleaching processes.
  • the formulation is used as a textile aid for pad-steam-peroxide bleaching.
  • the formulation is used as a textile aid for pad steam peroxide bleaching.
  • Example 14 Alkaline digestion using the pad-steam method
  • the fleet intake is 100%.
  • the goods are then fed into a steamer with saturated steam at 102 ° C for 10 minutes and then washed out with hot water.
  • the result is a desized product with high absorbency.
  • Example 1 5 Cold storage peroxide bleach
  • the fleet intake is 100%.
  • the moist goods are wound up on a dock, packed with plastic wrap and stored for 20 hours at room temperature with slow rotation of the dock.
  • the goods are then washed out with hot water.
  • the result is an absorbent fabric with a high degree of whiteness and little fiber damage.
  • the spraying takes place e.g. in a Raco-Yet system from Rimisch-Kleinwefers.
  • the order quantity is 140%.
  • the damp goods are treated for 2 hours in a steamer with saturated steam at 102 ° C and then washed out with hot water.
  • the result is an absorbent fabric with a high degree of whiteness and little fiber damage.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Emergency Medicine (AREA)
  • Health & Medical Sciences (AREA)
  • Detergent Compositions (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Paper (AREA)

Abstract

Multifunctional textile auxiliary (I) contains: (a) 10-60 wt.% nonionic surfactant of formula R1O-(Alkylene-O)m1- (I); (b) 10-60 wt.% of the reaction prod. of a nonionic surfactant of formula R2O-(Alkylene-O)n1- (II) and an unsatd. sulphonic or carboxylic acid or anhydride, (c) 4-20 wt.% hydrotropic additive, (d) 0-20 wt.% nonionic surfactant of formula R4O(C(Y1)HC(Y2)HO)p1(C(Y3)HC(Y4)HO)p2R5 (III), (e) 0-8 wt .% Mg carboxylate salt, (f) 0-30 wt.% complexing or sequestering agent, (g) 0-10 wt.% diol or polyol and (h) 0-60 wt.% water, components (e) - (g) always being present. In formulae, R1, R2 = 8-22C alkyl or 5-22C alkenyl; R3 = H, 1-4C alkyl, at least 6C cycloaliphatic gp., or benzyl; R4 = 9-14C alkyl; R5 = 1-8C alkyl, at least 5C cycloaliphatic gp., lower alkylphenyl or styryl; Y1-Y4 = H, Me or Et; one of the gps. in each pair Y1/Y2 and Y3/Y4 is always H; Alkylene = 2-4C alkylene; m1 = 1-40; n1 = 1-60; p1 = 4-10; p2 = 0-8. Also claimed is a process for the prodn. of (I) by reacting (1) and/or (2) with unsatd. acid or anhydride as above in presence of a catalyst to give (b), adjusting to pH 4.5 and adding the other components to give an homogeneous soln. Also claimed is a process for wetting, washing and/or bleaching fibre materials by treatment in aq. medium in the presence of (I), pref. in amts. of 0.1-60 (esp. pref. 1-20) g/l. Also claimed is fibre material treated by this process.

Description

Die vorliegende Erfindung betrifft lagerstabile, schaumarme, silikonfreie, wässrige Textilhilfsmittel, ihre Herstellung und vielfache Verwendung z.B. als Netzmittel, Waschmittel, Dispergiermittel oder als Stabilisatoren in Peroxid-Bleichflotten.The present invention relates to storage-stable, low-foaming, silicone-free, aqueous textile auxiliaries, their production and multiple uses, e.g. as wetting agents, detergents, dispersants or as stabilizers in peroxide bleaching liquors.

Die erfindungsgemässen Textilhilfsmittel enthalten

  • (a) 10 bis 60 Gew.% eines nichtionogenen Tensids der Formel
    Figure imgb0001
  • (b) 10 bis 60 Gew.% des Umsetzungsproduktes aus einem oder mehreren nichtionogenen Tensiden der Formel
    Figure imgb0002
     und einer ethylenisch ungesättigten Sulfonsäure oder Carbonsäure oder deren Anhydrid,
  • (c) 4 bis 20 Gew.% eines Hydrotropiermittels,
  • (d) 0 bis 20 Gew.% eines nichtionogenen Tensids der Formel
    Figure imgb0003
  • (e) 0 bis 8 Gew.% eines Magnesiumsalzes einer organischen Carbonsäure
  • (f) 0 bis 30 Gew.% eines Komplexier- oder Sequestriermittels
  • (g) 0 bis 10 Gew.% eines Diols oder Polyols und
  • (h) 0 bis 60% Wasser,

wobei eine der Komponenten (e) bis (g) im Textilhilfsmittel immer vorhanden sein muss, worin in den Formeln (1), (2) und (3)
R₁ und R₂,
unabhängig voneinander, C₈-C₂₂-Alkyl oder C₈-C₂₂-Alkenyl,
R₃
Wasserstoff, C₁-C₄-Alkyl, einen cycloaliphatischen Rest mit mindestens 6 C-Atomen oder Benzyl,
R₄
C₉ bis C₁₄-Alkyl,
R₅
C₁ bis C₈-Alkyl, einen cycloaliphatischen Rest mit mindestens 5 C-Atomen, Niederalkylphenyl oder Styryl
Y₁, Y₂, Y₃ und Y₄,
unabhängig voneinander Wasserstoff, Methyl oder Ethyl, wobei einer der Reste Y₁, Y₂ bzw. Y₃, Y₄ immer Wasserstoff ist,

"Alkylen" einen 2 bis 4 Kohlenstoffatome aufweisenden Alkylenrest,
m₁
eine Zahl von 1 bis 40,
n₁
eine ganze Zahl von 1 bis 60,
p₁
eine ganze Zahl von 4 bis 10 und
p₂
eine ganze Zahl von 0 bis 8,

bedeuten.The textile auxiliaries according to the invention contain
  • (a) 10 to 60% by weight of a nonionic surfactant of the formula
    Figure imgb0001
  • (b) 10 to 60% by weight of the reaction product from one or more nonionic surfactants of the formula
    Figure imgb0002
     and an ethylenically unsaturated sulfonic acid or carboxylic acid or its anhydride,
  • (c) 4 to 20% by weight of a hydrotroping agent,
  • (d) 0 to 20% by weight of a nonionic surfactant of the formula
    Figure imgb0003
  • (e) 0 to 8% by weight of a magnesium salt of an organic carboxylic acid
  • (f) 0 to 30% by weight of a complexing or sequestering agent
  • (g) 0 to 10% by weight of a diol or polyol and
  • (h) 0 to 60% water,

one of the components (e) to (g) must always be present in the textile auxiliary, in which formulas (1), (2) and (3)
R₁ and R₂,
independently of one another, C₈-C₂₂-alkyl or C₈-C₂₂-alkenyl,
R₃
Hydrogen, C₁-C₄-alkyl, a cycloaliphatic radical with at least 6 C atoms or benzyl,
R₄
C₉ to C₁₄ alkyl,
R₅
C₁ to C₈ alkyl, a cycloaliphatic radical with at least 5 C atoms, lower alkylphenyl or styryl
Y₁, Y₂, Y₃ and Y₄,
independently of one another hydrogen, methyl or ethyl, where one of the radicals Y₁, Y₂ or Y₃, Y₄ is always hydrogen,

"Alkylene" means an alkylene radical having 2 to 4 carbon atoms,
m₁
a number from 1 to 40,
n₁
an integer from 1 to 60,
p₁
an integer from 4 to 10 and
p₂
an integer from 0 to 8,

mean.

Die Komponenten (a) bis (g) können jeweils aus Einzelverbindungen bestehen oder auch aus mehreren Einzelverbindungen zusammengesetzt sein.Components (a) to (g) can each consist of individual compounds or can also be composed of several individual compounds.

Auf Grund der extremen Schaumarmut und des guten Dämpfungsvermögens von Prozeßschäumen kann bei den erfindungsgemässen Textilhilfsmitteln auf den Zusatz weiterer schaumdämpfender Mittel, insbesondere silikonhaltiger Verbindungen, verzichtet werden.Because of the extreme low foam and the good damping capacity of process foams, it is possible to dispense with the addition of further foam-suppressing agents, in particular silicone-containing compounds, to the textile auxiliaries according to the invention.

Die Substituenten R₁ und R₂ in den Formeln (1) und (2) stellen vorteilhafterweise den Kohlenwasserstoffrest eines gesättigten oder ungesättigten aliphatischen Monoalkohols mit 8 bis 22 Kohlenstoffatomen dar. Der Kohlenwasserstoffrest kann geradkettig oder verzweigt sein. Vorzugsweise bedeuten R₁ und R₂ einen Alkyl- oder Alkenylrest mit 9 bis 14 C-Atomen.The substituents R₁ and R₂ in the formulas (1) and (2) advantageously represent the hydrocarbon radical of a saturated or unsaturated aliphatic monoalcohol having 8 to 22 carbon atoms. The hydrocarbon radical can be straight-chain or branched. R₁ and R₂ are preferably an alkyl or alkenyl radical having 9 to 14 carbon atoms.

Als aliphatische gesättigte Monoalkohole können natürliche Alkohole, wie z.B. Laurylalkohol, Myristylalkohol, Cetylalkohol oder Stearylalkohol, sowie synthetische Alkohole, wie z.B. 2-Ethylhexanol, 1,1,3,3-Tetramethylbutanol, Octan-2-ol, Isononylalkohol, Trimethylhexanol, Trimethylnonylalkohol, Decanol, C₉-C₁₁-Oxoalkohol, Tridecylalkohol, Isotridecanol oder lineare primäre Alkohole (Alfole) mit 8 bis 22 Kohlenstoffatomen in Betracht kommen. Einige Vertreter dieser Alfole sind Alfol (8-10), Alfol (9-11), Alfol (10-14), Alfol (12-13) oder Alfol (16-18). ("Alfol" ist ein eingetragenes Warenzeichen).As aliphatic saturated monoalcohols, natural alcohols such as e.g. Lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, as well as synthetic alcohols, e.g. 2-ethylhexanol, 1,1,3,3-tetramethylbutanol, octan-2-ol, isononyl alcohol, trimethylhexanol, trimethylnonyl alcohol, decanol, C₉-C₁₁ oxo alcohol, tridecyl alcohol, isotridecanol or linear primary alcohols (alfoles) with 8 to 22 carbon atoms in Come into consideration. Some representatives of these alfoles are Alfol (8-10), Alfol (9-11), Alfol (10-14), Alfol (12-13) or Alfol (16-18). ("Alfol" is a registered trademark).

Ungesättigte aliphatische Monoalkohole sind beispielsweise Dodecenylalkohol, Hexadecenylalkohol oder Oleylalkohol.Unsaturated aliphatic monoalcohols are, for example, dodecenyl alcohol, hexadecenyl alcohol or oleyl alcohol.

Die Alkoholreste können einzeln oder in Form von Gemischen aus zwei oder mehreren Komponenten vorhanden sein, wie z.B. Mischungen von Alkyl- und/oder Alkenylgruppen, die sich von Soja-Fettsäuren, Palmkernfettsäuren oder Talg-Oelen ableiten.The alcohol residues can be present individually or in the form of mixtures of two or more components, e.g. Mixtures of alkyl and / or alkenyl groups derived from soy fatty acids, palm kernel fatty acids or tallow oils.

(Alkylen-O)-Ketten sind bevorzugt zweiwertige Reste der Formeln (̵CH₂-CH₂-O)̵,

Figure imgb0004

R₄ stellt den geradkettigen Kohlenwasserstoffrest eines gesättigten aliphatischen Monoalkohols mit 8 bis 14 Kohlenstoffatomen dar, also n-Octyl, n-Nonyl, n-Decyl, n-Undecyl, n-Dodecyl, n-Tridecyl oder n-Tetradecyl.(Alkylene-O) chains are preferably divalent radicals of the formulas (̵CH₂-CH₂-O) ̵,
Figure imgb0004
R₄ represents the straight-chain hydrocarbon radical of a saturated aliphatic monoalcohol with 8 to 14 carbon atoms, ie n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl or n-tetradecyl.

R₅ in Formel (3) in der Bedeutung von C₁-C₈-Alkyl ist der Methyl-, Ethyl-, n-Propyl-, Isopropyl-, n-Butyl-, sec.Butyl- oder tert.Butyl-Rest. Vorzugsweise bedeutet R₅ den n-Butylrest.R₅ in formula (3) in the meaning of C₁-C₈-alkyl is the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl radical. R₅ is preferably the n-butyl radical.

Beispiele für einen cycloaliphatischen Rest sind Cycloheptyl, Cyclooctyl oder vorzugsweise Cyclohexyl.Examples of a cycloaliphatic radical are cycloheptyl, cyclooctyl or preferably cyclohexyl.

Als Beispiele für nichtionogene Tenside, die der Komponente (a) entsprechen, seien die Anlagerungsprodukte von 2 bis 60 Mol, vorzugsweise 4 bis 10 Mol Alkylenoxiden, insbesondere Ethylenoxid, wobei einzelne Ethylenoxideinheiten durch substituierte Epoxide, wie Propylenoxid und/oder 1,2-Butylennoxid, ersetzt sein können, an höhere ungesättigte oder gesättigte Fettalkohle mit 8 bis 22 Kohlenstoffatomen, bzw. Gemische dieser Verbindungen genannt.Examples of nonionic surfactants which correspond to component (a) are the addition products of 2 to 60 mol, preferably 4 to 10 mol, of alkylene oxides, in particular ethylene oxide, individual ethylene oxide units being substituted by epoxides, such as propylene oxide and / or 1,2-butylene oxide , can be replaced, to higher unsaturated or saturated fatty alcohols with 8 to 22 carbon atoms, or mixtures of these compounds.

Vorzugsweise verwendet man als nichtionogenes Tensid der Komponente (a) eine oder mehrere der Verbindungen der Formel

Figure imgb0005

worin

R₆
C₈-C₁₃-Alkyl;
Y₅
Wasserstoff oder Methyl; und
m₂
3 bis 15

bedeuten.Preferably one or more of the compounds of the formula are used as the nonionic surfactant of component (a)
Figure imgb0005
wherein
R₆
C₈-C₁₃ alkyl;
Y₅
Hydrogen or methyl; and
m₂
3 to 15

mean.

Als monomere Ausgangsverbindungen zur Herstellung der polymeren Verbindungen der Komponente (b) sind ethylenisch ungesättigte monomere Sulfonsäuren oder Carbonsäuren oder deren Anhydride geeignet. Es können sowohl Monocarbonsäuren als auch Dicarbonsäuren und deren Anhydride sowie auch Sulfonsäuren, die jeweils einen ethylenisch ungesättigten aliphatischen Rest und vorzugsweise höchstens 7 Kohlenstoffatome aufweisen, eingesetzt werden. Bevorzugt sind Monocarbonsäuren mit 3 bis 5 Kohlenstoffatomen, z.B. die Acrylsäure, Methacrylsäure, α-Halogenacrylsäure, 2-Hydroxyethylacrylsäure, α-Cyanoacrylsäure, Crotonsäure und Vinylessigsäure. Ethylenisch ungesättigte Dicarbonsäuren sind vorzugsweise die Fumarsäure, Maleinsäure oder Itaconsäure, ferner die Mesaconsäure, Citraconsäure, Glutaconsäure und Methylmalonsäure. Als Anhydrid dieser Säuren sei insbesondere Maleinsäureanhydrid genannt.Suitable monomeric starting compounds for the preparation of the polymeric compounds of component (b) are ethylenically unsaturated monomeric sulfonic acids or carboxylic acids or their anhydrides. Both monocarboxylic acids and dicarboxylic acids and their anhydrides as well as sulfonic acids, each having an ethylenically unsaturated aliphatic radical and preferably at most 7 carbon atoms, can be used. Monocarboxylic acids having 3 to 5 carbon atoms, e.g. acrylic acid, methacrylic acid, α-haloacrylic acid, 2-hydroxyethylacrylic acid, α-cyanoacrylic acid, crotonic acid and vinyl acetic acid. Ethylenically unsaturated dicarboxylic acids are preferably fumaric acid, maleic acid or itaconic acid, furthermore mesaconic acid, citraconic acid, glutaconic acid and methylmalonic acid. Maleic anhydride is particularly mentioned as the anhydride of these acids.

Als monomere Sulfonsäuren, die zur Polymerisation verwendet werden, kommen beispielsweise Vinylsulfonsäure oder 2-Acrylamido-2-methylpropansulfonsäure in Frage.Examples of suitable monomeric sulfonic acids which are used for the polymerization are vinylsulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid.

Als Katalysatoren für die Herstellung der Komponente (b) werden vorzugsweise freie Radikale bildende organische Initiatoren verwendet. Geeignete Initiatoren zur Durchführung der radikalischen Polymerisation sind z.B. symmetrische aliphatische Azoverbindungen wie Azo-bis-isobuttersäurenitril, Azo-bis-2-methyl-valeronitril, 1,1'-Azo-bis-1-cyclohexanitril und 2,2'-Azo-bis-isobuttersäurealkylester; symmetrische Diacylperoxide, wie z.B. Acetyl-, Propionyl- oder Butyrylperoxid, Benzoylperoxid, brom-, nitro-, methyl- oder methoxy-substituierte Benzoylperoxide sowie Lauroylperoxid; symmetrische Peroxydicarbonate, wie z.B. Diethyl-, Diisopropyl-, Dicyclohexyl-, sowie Dibenzylperoxidicarbonat; tert.-Butylperoctoat, tert.-Butylperbenzoat oder tert.-Butylphenylperacetat sowie Peroxidicarbamate wie tert.-Butyl-N-(phenylperoxi)-carbamat oder tert.-Butyl-N-(2,3-dichlor- oder -4-chlorphenyl-peroxi)-carbamat. Weitere geeignete Peroxide sind: tert.-Butylhydroperoxid, Di-tert.-butylperoxid, Cumolhydroperoxid, Di-cumolperoxid und tert.-Butylperpivalat. Eine weitere geeignete Verbindung ist Kaliumpersulfat, das bei der Herstellung der Komponente (b) bevorzugt eingesetzt wird.Organic catalysts which form free radicals are preferably used as catalysts for the preparation of component (b). Suitable initiators for carrying out the radical polymerization are e.g. symmetrical aliphatic azo compounds such as azo-bis-isobutyronitrile, azo-bis-2-methylvaleronitrile, 1,1'-azo-bis-1-cyclohexanitrile and 2,2'-azo-bis-isobutyric acid alkyl ester; symmetrical diacyl peroxides, e.g. Acetyl, propionyl or butyryl peroxide, benzoyl peroxide, bromo, nitro, methyl or methoxy substituted benzoyl peroxides and lauroyl peroxide; symmetrical peroxydicarbonates, e.g. Diethyl, diisopropyl, dicyclohexyl and dibenzyl peroxidicarbonate; tert-butyl peroctoate, tert-butyl perbenzoate or tert-butylphenyl peracetate and peroxidicarbamates such as tert-butyl-N- (phenylperoxi) carbamate or tert-butyl-N- (2,3-dichloro- or -4-chlorophenyl- peroxi) carbamate. Other suitable peroxides are: tert-butyl hydroperoxide, di-tert-butyl peroxide, cumene hydroperoxide, di-cumene peroxide and tert-butyl perpivalate. Another suitable compound is potassium persulfate, which is preferably used in the preparation of component (b).

Die Katalysatoren werden in der Regel in Mengen von 0,1 bis 10 Gew.-%, vorzugsweise 0,5 bis 2 Gew.-%, bezogen auf die Ausgangsprodukte, eingesetzt.The catalysts are generally used in amounts of 0.1 to 10% by weight, preferably 0.5 to 2% by weight, based on the starting products.

Die Komponente (b) liegt vorzugsweise als teilneutralisierte Verbindung vor, die einen pH-Wert von 3 bis 6 aufweist. Die Herstellung der polymeren Verbindung erfolgt z.B. durch Umsetzung einer ethylenisch ungesättigten Sulfonsäure oder Carbonsäure oder deren Anhydrid in Gegenwart eines nichtionogenen Tensides oder in Gegenwart von Mischungen nichtionogener Tenside der Formel (2). Anschliessend wird das Umsetzungsprodukt mit einer anorganischen und/oder organischen Base auf einen pH-Wert von 3 bis 6, vorzugsweise 4 bis 5, teilneutralisiert. Als Basen verwendet man z.B. 1 bis 8 Gew.-%ige anorganische oder organische Basen, wie z.B. Natriumhydroxid, Magnesiumhydroxid, Ethanolamin, Triethanolamin,N,N,N,N-Tetrakis(2-hydroxypropyl)-ethylenamin oder 1-Amino-1-deoxysorbit oder Mischungen davon. Wasser wird ad 100 Gew.% hinzugefügt.Component (b) is preferably in the form of a partially neutralized compound which has a pH of 3 to 6. The polymeric compound is produced e.g. by reacting an ethylenically unsaturated sulfonic acid or carboxylic acid or its anhydride in the presence of a nonionic surfactant or in the presence of mixtures of nonionic surfactants of the formula (2). The reaction product is then partially neutralized with an inorganic and / or organic base to a pH of 3 to 6, preferably 4 to 5. As bases one uses e.g. 1 to 8% by weight inorganic or organic bases, e.g. Sodium hydroxide, magnesium hydroxide, ethanolamine, triethanolamine, N, N, N, N-tetrakis (2-hydroxypropyl) ethylene amine or 1-amino-1-deoxysorbitol or mixtures thereof. Water is added to 100% by weight.

Die Polymerisation wird vorteilhafterweise in inerter Atmosphäre, z.B. in Gegenwart von Stickstoff durchgeführt.The polymerization is advantageously carried out in an inert atmosphere, e.g. carried out in the presence of nitrogen.

Vorzugsweise entspricht die Komponente (b) dem Umsetzungsprodukt aus 45 bis 5 Gew.-% Acrylsäure oder Methacrylsäure und 5 bis 45 Gew.-% eines oder mehrerer nichtionogener Tenside der Formel

Figure imgb0006

worin

R₇
C₈-C₁₈-Alkyl;
Y₆
Wasserstoff, Methyl oder Ethyl; und
n₂
1 bis 40;

bedeuten.Component (b) preferably corresponds to the reaction product of 45 to 5% by weight of acrylic acid or methacrylic acid and 5 to 45% by weight of one or more nonionic surfactants of the formula
Figure imgb0006
wherein
R₇
C₈-C₁₈ alkyl;
Y₆
Hydrogen, methyl or ethyl; and
n₂
1 to 40;

mean.

Als Hydrotropiermittel entsprechend Komponente (c) kommen in Betracht:

  • Aromatische Alkohole der Formel
    Figure imgb0007
     worin
    X₁
    -(CH₂)₁₋₆-, -CH=CH-CH₂- oder -O-(CH₂)₂₋₆- und
    R₈, R₉ und R₁₀,
    unabhängig voneinander, Wasserstoff, Hydroxy, Halogen oder C₁-C₆-Alkoxy bedeuten.

    Als Beispielhafte Verbindungen der Formel (6) sind Benzylalkohol, 2,4-Dichlorbenzylalkohol, Phenylethanol, Phenoxyethanol, 1-Phenoxy-2-propanol (Phenoxyisopropanol) und Zimtalkohol.
  • Sulfonate von Terpenoiden oder ein- oder zweikernigen aromatischen Verbindungen, z.B. die Sulfonate des Camphers, Toluols, Xylols, Cumols und Naphthols;
  • Aliphatische gesättigte und ungesättigte C₁-C₁₁-Monocarbonsäuren, wie die Essigsäure, Propionsäure, Capronsäure oder Undecylensäure;
  • Gesättigte oder ungesättigte C₃-C₁₂-Di- oder Polycarbonsäuren, z.B. die Malon-, Bernstein-, Glutar-, Adipin-, Pimelin-, Kork-, Azelain- und Sebacinsäure, die Undecan- und Dodecandicarbonsäure, die Fumar-, Malein-, Wein- und Apfelsäure sowie die Citronen- und Aconitsäure.
Possible hydrotroping agents corresponding to component (c) are:
  • Aromatic alcohols of the formula
    Figure imgb0007
     wherein
    X₁
    - (CH₂) ₁₋₆-, -CH = CH-CH₂- or -O- (CH₂) ₂₋₆- and
    R₈, R₉ and R₁₀,
    independently of one another are hydrogen, hydroxyl, halogen or C₁-C₆alkoxy.

    Exemplary compounds of the formula (6) are benzyl alcohol, 2,4-dichlorobenzyl alcohol, phenylethanol, phenoxyethanol, 1-phenoxy-2-propanol (phenoxyisopropanol) and cinnamon alcohol.
  • Sulfonates of terpenoids or mononuclear or dinuclear aromatic compounds, for example the sulfonates of camphor, toluene, xylene, cumene and naphthol;
  • Aliphatic saturated and unsaturated C₁-C₁₁ monocarboxylic acids such as acetic acid, propionic acid, caproic acid or undecylenic acid;
  • Saturated or unsaturated C₃-C₁₂-di- or polycarboxylic acids, e.g. malonic, succinic, glutaric, adipic, pimelin, cork, azelaic and sebacic acid, undecanoic and dodecanedicarboxylic acids, fumaric, maleic, Tartaric and malic acid as well as citric and aconitic acid.

Alle erwähnten organischen Säuren können auch in Form ihrer wasserlöslichen Salze, wie der Alkalimetall-, insbesondere Natrium- oder Kaliumsalze oder der Aminsalze vorliegen.All of the organic acids mentioned can also be in the form of their water-soluble salts, such as the alkali metal, in particular sodium or potassium, salts or the amine salts.

Weiterhin werden erfindungsgemäss als Hydrotropiermittel der Komponente (c) Alkylsulfate der Formel

        (7)   R₁₁O-SO₃X₂,


verwendet, worin

R₁₁
einen aliphatischen gesättigten, verzweigten oder geradkettigen Rest mit 4 bis 24 Kohlenstoffatomen und
X₂
Wasserstoff, Alkalimetall oder Ammonium bedeutet.
Furthermore, according to the invention, alkyl sulfates of the formula are used as hydrotroping agents of component (c)

(7) R₁₁O-SO₃X₂,


used where
R₁₁
an aliphatic saturated, branched or straight chain radical having 4 to 24 carbon atoms and
X₂
Means hydrogen, alkali metal or ammonium.

Liegt das Alkylsulfat als Salz vor, so kommen beispielsweise Natrium-, Kalium- oder Ammoniumsalze in Betracht. Das Natriumsalz ist bevorzugt.If the alkyl sulfate is in the form of a salt, sodium, potassium or ammonium salts can be used, for example. The sodium salt is preferred.

Der aliphatische gesättigte Rest R₁₁ leitet sich von Monoalkoholen ab. Dabei kommen natürliche oder synthetische Alkohole in Betracht. Als natürliche Alkohole sind z.B. Lauryl-, Myristyl-, Cetyl-, Stearyl-, Arachidyl- oder Behenylalkohol zu nennen. Bevorzugt sind Verbindungen, bei denen sich R₁₁ von verzweigten aliphatischen synthetischen Alkoholen mit 4 bis 12, insbesondere 4 bis 8 Kohlenstoffatomen ableitet, z.B. Isobutylalkohol, sek.Butanol, tert.Butanol, Isoamylalkohol, 2-Ethylbutanol, 2-Methylpentanol, 5-Methylheptan-3-ol, 2-Ethylhexanol, 1,1,3,3-Tetramethylbutanol, Octan-2-ol, Isononylalkohol, Trimethylhexanol, Trimethylnonylalkohol, n-Decanol oder C₉-C₁₁-Oxoalkohol.The aliphatic saturated R₁₁ is derived from monoalcohols. Natural or synthetic alcohols can be used. As natural alcohols e.g. Lauryl, myristyl, cetyl, stearyl, arachidyl or behenyl alcohol. Preferred compounds are those in which R₁₁ is derived from branched aliphatic synthetic alcohols having 4 to 12, in particular 4 to 8, carbon atoms, e.g. Isobutyl alcohol, sec-butanol, tert-butanol, isoamyl alcohol, 2-ethylbutanol, 2-methylpentanol, 5-methylheptan-3-ol, 2-ethylhexanol, 1,1,3,3-tetramethylbutanol, octan-2-ol, isononyl alcohol, Trimethylhexanol, trimethylnonyl alcohol, n-decanol or C₉-C₁₁-oxo alcohol.

Die Alkylsulfate können dabei bereits in Form ihrer Salze vorliegen und allein oder als (technisches) Gemisch untereinander in dem erfindungsgemässen Netzmittel eingesetzt werden.The alkyl sulfates can already be in the form of their salts and can be used alone or as a (technical) mixture with one another in the wetting agent according to the invention.

Beispielhaft erwähnt für Hydrotropiermittel der Formel (7) sei 2-Ethylhexylsulfat.Examples of hydrotroping agents of the formula (7) are 2-ethylhexyl sulfate.

Die Herstellung dieser Alkylsulfate erfolgt nach an sich bekannter Weise durch Umsetzung der entsprechenden Alkohole mit z.B. Schwefelsäure, Oleum, Chlorsulfonsäure oder Schwefeltrioxid.These alkyl sulfates are prepared in a manner known per se by reacting the corresponding alcohols with e.g. Sulfuric acid, oleum, chlorosulfonic acid or sulfur trioxide.

Weitere erfindungsgemäss eingesetzte, bevorzugte Hydrotropiermittel sind amphotere Tenside wie z.B. Natriumlauriminodipropionat, Dihydroxyethyl-talgfettglycinat, Dinatriumcocoamphodiacetat, Dinatriumcapryloamphodiacetat oder vorzugsweise Dinatriumdicarboxyethylcocopropylendiamin oder TalgfettamphopolycarboxyglycinatFurther preferred hydrotroping agents used according to the invention are amphoteric surfactants such as e.g. Sodium laurimino dipropionate, dihydroxyethyl tallow fat glycinate, disodium cocoamphodiacetate, disodium capryloamphodiacetate or preferably disodium dicarboxyethylcocopropylene diamine or tallow fat amphopolycarboxyglycinate

Wichtige nichtionogene Tenside der fakultativen Komponente (d) entsprechen der Formel

Figure imgb0008

worin

R₁₂
C₉-C₁₄-Alkyl;
R₁₃
C₁-C₄-Alkyl;
Y₇, Y₈, Y₉ und Y₁₀,
unabhängig voneinander, Wasserstoff, Methyl oder Ethyl, wobei einer der Reste Y₇, Y₈ bzw. Y₉, Y₁₀ immer Wasserstoff ist;
p₃ und p₄,
unabhängig voneinander, eine ganze Zahl von 4 bis 8;

bedeuten.Important nonionic surfactants of the optional component (d) correspond to the formula
Figure imgb0008
wherein
R₁₂
C₉-C₁₄ alkyl;
R₁₃
C₁-C₄ alkyl;
Y₇, Y₈, Y₉ and Y₁₀,
independently of one another, hydrogen, methyl or ethyl, where one of the radicals Y₇, Y₈ or Y₉, Y₁₀ is always hydrogen;
p₃ and p₄,
independently of one another, an integer from 4 to 8;

mean.

Als Beispiele für die endgruppenverschlossenen nichtionogenen Tenside der Komponente (d) sind C₁₀-C₁₂-Fettalkohol-Ethylenoxid- oder -Ethylenoxid/Propylenoxid-Additionsprodukte oder das Umsetzungsprodukt aus einem Mol eines C₁₀-Fettalkohols mit 6 Mol Ethylenoxid und 1 Mol Butylenoxid zu nennen, wobei die Additionsprodukte jeweils mit C₁-C₄-Alkyl, vorzugsweise Methyl oder Butyl endgruppenverschlossen sein können.Examples of the end-capped nonionic surfactants of component (d) are C₁₀-C₁₂ fatty alcohol-ethylene oxide or ethylene oxide / propylene oxide addition products or the reaction product of one mole of a C₁₀ fatty alcohol with 6 moles of ethylene oxide and 1 mole of butylene oxide, where the addition products can be end-capped with C₁-C₄-alkyl, preferably methyl or butyl.

Die Herstellung der nichtionogenen Tenside der Formeln (1) und (2) geschieht in an sich bekannter Weise, so z.B. durch Umsetzung der entsprechenden Alkylenoxidanlagerungsprodukte mit Thionylchlorid und nachfolgender Umsetzung der entstandenen Chlorverbindung mit einem gesättigten oder ungesättigten aliphatischen C₈-C₂₂-Monoalkohol.The nonionic surfactants of the formulas (1) and (2) are prepared in a manner known per se, e.g. by reaction of the corresponding alkylene oxide addition products with thionyl chloride and subsequent reaction of the chlorine compound formed with a saturated or unsaturated aliphatic C₈-C₂₂ monoalcohol.

Die Herstellung der endgruppenverschlossenen nichtionogenen Tenside der Formel (3) geschieht in an sich bekannter Weise, so z.B. durch Umsetzung von Ethylenoxid und/oder Propylenoxid und/oder Butylenoxid in den entsprechenden molaren Verhältnissen mit einem Mol des Alkohols R₄-OH, und nachfolgender Umsetzung des entstandenen Anlagerungsproduktes mit einem Alkylhalogenid R₅-Hal, vorzugsweise C₁-C₄-Alkylchlorid.The end-capped nonionic surfactants of the formula (3) are produced in a manner known per se, e.g. by reaction of ethylene oxide and / or propylene oxide and / or butylene oxide in the corresponding molar ratios with one mole of the alcohol R₄-OH, and subsequent reaction of the adduct formed with an alkyl halide R₅-Hal, preferably C₁-C₄ alkyl chloride.

Bei den Magnesiumsalzen von Carbonsäuren mit komplexierenden Eigenschaften entsprechend der fakultativen Komponente (e) handelt es sich um Salze von Gluconsäure, Zitronensäure, Äpfelsäure, Milchsäure, L-Glutaminsäure und L-Asparaginsäure.The magnesium salts of carboxylic acids with complexing properties corresponding to the optional component (e) are salts of gluconic acid, citric acid, malic acid, lactic acid, L-glutamic acid and L-aspartic acid.

Insbesondere werden als Komponente (e) die Magnesiumsalze der Gluconsäure verwendet und ganz besonders Magnesiummono- oder Magnesiumdigluconat. Das Magnesiumgluconat kann dabei in der erfindungsgemässen Zusammensetzung als solches und vorzugsweise als Feststoff eingesetzt werden. In einer weiteren Ausführungsform kann das Gluconat aber auch in situ gebildet werden aus Gluconsäure und Magnesiumoxid oder vorzugsweise Magnesiumhydroxid. Ferner kann Gluconsäure oder dessen Natriumsalz in Kombination mit einem wasserlöslichen Magnesiumsalz eingesetzt werden. Als wasserlösliches Magnesiumsalz kommt dabei das Acetat, vor allem das Sulfat oder dessen Heptahydrat und insbesondere das Chlorid oder dessen Hexahydrat in Betracht. Das Magnesiumsalz wird in der Regel als Feststoff eingesetzt, wobei festes Magnesiumchlorid-Hexahydrat im Vordergrund steht.In particular, the magnesium salts of gluconic acid are used as component (s), and very particularly magnesium mono- or magnesium digluconate. The magnesium gluconate can be used as such and preferably as a solid in the composition according to the invention. In a further embodiment, the gluconate can also be formed in situ from gluconic acid and magnesium oxide or preferably magnesium hydroxide. Gluconic acid or its sodium salt can also be used in combination with a water-soluble magnesium salt. As water soluble Magnesium salt is the acetate, especially the sulfate or its heptahydrate and in particular the chloride or its hexahydrate. The magnesium salt is usually used as a solid, with solid magnesium chloride hexahydrate in the foreground.

Bevorzugte Komplexbildner entsprechend der Komponente (f) in der erfindungsgemässen Zusammensetzung sind Verbindungen, die ausgewählt sind aus

  • (f₁) einem Gemisch aus monomeren und oligomeren Verbindungen entsprechend der Formeln
    Figure imgb0009
    Figure imgb0010
        worin
       Y₇ Wasserstoff oder -COT₁,
       R₁₄, X₃ und T₁ unabhängig voneinander jeweils C₁-C₄-Alkyl und
       q₁ 1 bis 16
       bedeuten,
  • (f₂) D-Gluconsäure,
  • (f₃) Zitronensäure und
  • (f₄) Aminophosphonsäure.
Preferred complexing agents corresponding to component (f) in the composition according to the invention are compounds which are selected from
  • (f₁) a mixture of monomeric and oligomeric compounds according to the formulas
    Figure imgb0009
    Figure imgb0010
     wherein
    Y₇ is hydrogen or -COT₁,
    R₁₄, X₃ and T₁ are each independently C₁-C₄ alkyl and
    q₁ 1 to 16
    mean,
  • (f₂) D-gluconic acid,
  • (f₃) citric acid and
  • (f₄) aminophosphonic acid.

Bei dem Gemisch aus monomeren und oligomeren Verbindungen (f₁) handelt es sich vorzugsweise um ein Gemisch aus monomeren und oligomeren Verbindungen der Formel

Figure imgb0011
Figure imgb0012
worin
R₁₅ Methyl oder Ethyl und
q₂ 1 bis 13 bedeuten.The mixture of monomeric and oligomeric compounds (f 1) is preferably a mixture of monomeric and oligomeric compounds of the formula
Figure imgb0011
Figure imgb0012
wherein
R₁₅ methyl or ethyl and
q₂ are 1 to 13.

Die Gemische der monomeren und oligomeren Verbindungen der angegebenen Art sind an sich bekannt und werden nach bekannten Methoden hergestellt. So wird z.B. das Gemisch der Formel (10a) und (10b) vorzugsweise durch Umsetzung von Phosphortrichlorid, Essigsäure und gegebenenfalls Essigsäureanhydrid in wässrigem Medium hergestellt. Die oligomeren Anteile der Komponente (f₁) werden in der wässrigen, erfindungsgemässen Zusammensetzung in Gegenwart eines Alkalimetallhydroxids mindestens teilweise zu den entsprechenden monomeren Verbindungen hydrolisiert. Demgemäß kommen als Komponente (f₁) der erfindungsgemässe Zusammensetzungen vor allem auch monomere Verbindungen einer der Formeln (9a) bzw. (10a) in Frage.The mixtures of the monomeric and oligomeric compounds of the type indicated are known per se and are prepared by known methods. For example, the mixture of the formulas (10a) and (10b) is preferably prepared by reacting phosphorus trichloride, acetic acid and optionally acetic anhydride in an aqueous medium. The oligomeric portions of component (f 1) are at least partially hydrolyzed to the corresponding monomeric compounds in the aqueous composition according to the invention in the presence of an alkali metal hydroxide. Accordingly, as component (f 1) of the compositions according to the invention, especially monomeric compounds of one of the formulas (9a) or (10a) are also suitable.

Die Komponente (f₁) wird vorzugsweise als 35 bis 90, vorzugsweise 40 bis 85, insbesondere 40 bis 60 gewichtsprozentige, wässrige Lösung in der erfindungsgemässen Zusammensetzung eingesetzt.Component (f 1) is preferably used as 35 to 90, preferably 40 to 85, in particular 40 to 60 percent by weight, aqueous solution in the composition according to the invention.

Beispiele für die Komponente (f₄) sind Nitrilotrimethylenphosphonsäure, das Na-Salz der Ethylendiamin-tetramethylenphosphonsäure, das Na-Salz der Diethylentriamin-pentamethylenphosphonsäure oder N,N-Bis(phosphonmethyl)glutaminsäure.Examples of component (f₄) are nitrilotrimethylenephosphonic acid, the Na salt of ethylenediamine-tetramethylenephosphonic acid, the Na salt of diethylenetriamine-pentamethylenephosphonic acid or N, N-bis (phosphonomethyl) glutamic acid.

Verbindungen der Komponente (f) wirken als Komplexbildner für Erdalkali- und Schwermetalle in wässrigen Flotten, die eine Perverbindung, z.B. Wasserstoffperoxid enthalten, bei der Vorbehandlung, insbesondere bei Bleichprozessen von cellulosehaltigen Fasermaterialien. Insbesondere wird durch die Anwesenheit dieser Komponenten die Zersetzung der Perverbindung durch freie, d.h. nicht als Komplex vorliegende Schwermetalle, die im Betriebswasser des Fasermaterials oder im zugesetzten Alkali vorhanden sein können, unterdrückt.Compounds of component (f) act as complexing agents for alkaline earth metals and heavy metals in aqueous liquors which contain a per compound, for example hydrogen peroxide, in pretreatment, especially in bleaching processes of cellulosic fiber materials. In particular, the presence of these components suppresses the decomposition of the per-compound by free, ie non-complex heavy metals, which may be present in the process water of the fiber material or in the alkali added.

Als Komponente (g) kommen zwei- oder mehrwertige Alkohole in Betracht. Als zweiwertige Alkohole sind insbesondere solche mit 2 bis 6 C-Atomen im Alkylenteil wie Ethylenglykol, 1,2- oder 1,3-Propandiol, 1,3-, 1,4- oder 2,3-Butandiol, 1,5-Pentandiol und 1,6-Hexandiol oder 2-Methyl-2,4-pentandiol zu nennen. Die letztgenannte Verbindung wird in der erfindungsgemässen Zusammensetzung bevorzugt verwendet.Suitable as component (g) are dihydric or polyhydric alcohols. In particular, dihydric alcohols are those having 2 to 6 carbon atoms in the alkylene part, such as ethylene glycol, 1,2- or 1,3-propanediol, 1,3-, 1,4- or 2,3-butanediol, 1,5-pentanediol and to name 1,6-hexanediol or 2-methyl-2,4-pentanediol. The latter compound is preferably used in the composition according to the invention.

Beispiele für mehrwertige Alkohole sind Glycerin, Erythrit, die Pentite, wie z.B. Arabit, Adonit und Xylit sowie die Hexite, wie z.B. D-Sorbit, D-Mannit und Dulcit.Examples of polyhydric alcohols are glycerol, erythritol, the pentites, e.g. Arabite, adonite and xylitol as well as the hexites, e.g. D-sorbitol, D-mannitol and dulcitol.

Vorzugweise werden Textilhilfsmittel verwendet, welche

  • (a) 10 bis 60 Gew.% eines oder mehrerer nichtionogener Tenside der Formel
    Figure imgb0013
  • (b) 10 bis 60 Gew.% des Umsetzungsproduktes aus 5 bis 45 Gew.-% eines oder mehrerer nichtionogener Tenside der Formel
    Figure imgb0014
     und
    45 bis 5 Gew.-% Acrylsäure;
  • (c) 4 bis 20 Gew.% eines Hydrotropiermittels ausgewählt aus Natrium-cumol-4-sulfonat und Dodecyliminodipropionat-di-Na-Salz; und
  • (d) 0 bis 20 Gew.% eines nichtionogenen Tensids der Formel
    Figure imgb0015
  • (e) 0 bis 8 Gew.% Magnesiummono- oder Digluconat;
  • (f) 0 bis 30 Gew.% D-Gluconsäure; und
  • (g) 0 bis 10 Gew.% 2-Methyl-2,4-pentadiol;

wobei eine der Komponenten (e) bis (g) im Textilhilfsmittel immer vorhanden sein muss, worin
R₆
C₈-C₁₃-Alkyl;
R₇
C₈-C₁₈-Alkyl;
R₁₂
C₉-C₁₄-Alkyl;
R₁₃
C₁-C₄-Alkyl;
Y₅
Wasserstoff oder Methyl;
Y₆
Wasserstoff, Methyl oder Ethyl;
Y₇, Y₈, Y₉, Y₁₀,
unabhängig voneinander, Wasserstoff, Methyl oder Ethyl, wobei einer der Reste Y₇, Y₈ bzw. Y₉, Y₁₀ immer Wasserstoff ist;
m₂
4 bis 15;
n₂
1 bis 40; und
p₃ und p₄,
unabhängig voneinander, eine ganze Zahl von 4 bis 8;

bedeuten,
enthalten.Textile auxiliaries are preferably used, which
  • (a) 10 to 60% by weight of one or more nonionic surfactants of the formula
    Figure imgb0013
  • (b) 10 to 60% by weight of the reaction product from 5 to 45% by weight of one or more nonionic surfactants of the formula
    Figure imgb0014
     and
    45 to 5% by weight acrylic acid;
  • (c) 4 to 20% by weight of a hydrotroping agent selected from sodium cumene-4-sulfonate and dodecyliminodipropionate di-Na salt; and
  • (d) 0 to 20% by weight of a nonionic surfactant of the formula
    Figure imgb0015
  • (e) 0 to 8% by weight magnesium mono- or digluconate;
  • (f) 0 to 30% by weight D-gluconic acid; and
  • (g) 0 to 10% by weight 2-methyl-2,4-pentadiol;

where one of the components (e) to (g) must always be present in the textile auxiliary, in which
R₆
C₈-C₁₃ alkyl;
R₇
C₈-C₁₈ alkyl;
R₁₂
C₉-C₁₄ alkyl;
R₁₃
C₁-C₄ alkyl;
Y₅
Hydrogen or methyl;
Y₆
Hydrogen, methyl or ethyl;
Y₇, Y₈, Y₉, Y₁₀,
independently of one another, hydrogen, methyl or ethyl, where one of the radicals Y₇, Y₈ or Y₉, Y₁₀ is always hydrogen;
m₂
4 to 15;
n₂
1 to 40; and
p₃ and p₄,
independently of one another, an integer from 4 to 8;

mean,
contain.

Die erfindungsgemässen Textilhilfsmittel können durch Eintragen der Komponenten (a), (b), (c), und gegebenenfalls (d), (e), (f) und (g) in Wasser (Komponente (h)) hergestellt werden, oder dadurch, dass man die entsprechenden Komponenten unter Rühren mischt und deionisiertes Wasser hinzugibt, bis eine homogene Lösung vorliegt. Es handelt sich dabei um einen rein mechanischen Vorgang, der gegebenenfalls bei erhöhter Temperatur, beispielsweise von 30 bis 40°C durchgeführt wird. Eine chemische Reaktion findet dabei nicht statt.The textile auxiliaries according to the invention can be prepared by adding components (a), (b), (c), and optionally (d), (e), (f) and (g) in water (component (h)), or thereby that the corresponding components are mixed with stirring and deionized water is added until a homogeneous solution is obtained. It is a purely mechanical process, which is optionally carried out at elevated temperature, for example from 30 to 40 ° C. There is no chemical reaction.

Eine weitere Ausführungsform der Herstellung der erfindungsgemässen Textilhilfsmittel besteht darin, dass man zunächst die Komponente (b) durch Umsetzung einer monomeren ethylenisch ungesättigten Sulfonsäure oder Carbonsäure oder deren Anhydrid in Gegenwart einer oder mehrerer der Verbindungen des nichtionogenen Tensids der Formeln (1) und/oder (2) in Anwesenheit eines Katalysators herstellt, den pH-Wert auf ca. 4,5 einstellt und dann die restlichen Komponenten hinzugibt, bis eine homogene Lösung vorliegt.A further embodiment of the preparation of the textile auxiliaries according to the invention is that component (b) is first reacted by reacting a monomeric ethylenically unsaturated sulfonic acid or carboxylic acid or its anhydride in the presence of one or more of the compounds of the nonionic surfactant of the formulas (1) and / or ( 2) in the presence of a catalyst, adjust the pH to about 4.5 and then add the remaining components until a homogeneous solution is obtained.

Die fertig hergestellten Textilhilfsmittel weisen einen pH-Wert von z. B. 2 bis 5, vorzugsweise von 2,5 bis 3,5 auf. Der pH-Wert bezieht sich dabei immer auf eine 1%ige wäsrige Lösung der erfindungsgemässen Formulierung. Für eine gegebenenfalls nachträgliche Einstellung des gewünschten pH-Wertes verwendet man z.B. Magnesiumhydroxid, Kaliumhydroxid, Mono-, Di- oder Triethanolamin und vor allem Natriumhydroxid.The finished textile auxiliaries have a pH of z. B. 2 to 5, preferably from 2.5 to 3.5. The pH value always relates to a 1% aqueous solution of the formulation according to the invention. Magnesium hydroxide, potassium hydroxide, mono-, di- or triethanolamine and especially sodium hydroxide are used, for example, to subsequently adjust the desired pH.

Die neuen Formulierungen stellen lagerstabile, einphasige, schaumarme und silikonfreie Textilhilfsmittel mit guten komplexierenden und sequestrierenden Eigenschaften mit schmutzlösender Wirkung dar. Sie zeigen gutes Emulgiervermögen und sind in alkalischer Flotte stabil. In alkalischer Bleichflotte weisen sie keine Aufrahmungen oder Abscheidungen auf. Sie besitzen weiterhin gute peroxid-stabilisierende Eigenschaften und bewirken eine gute Wiederbenetzbarkeit des Textilguts. Ausserdem sind die Formulierungen gut biologisch abbaubar. Sie zeichnen sich auf Grund ihrer flüssigen Handelsform durch einfache Handhabung aus, weshalb sie besonders für moderne Dosiereinrichtungen geeignet sind. Die universelle Einsetzbarkeit der erfindungsgemässen Formulierungen ermöglicht verschiedene Anwendungen. Sie können beispielsweise als Netzmittel, Textilwaschmittel, Dispergiermittel oder als Stabilisator in Peroxid-Bleichflotten eingesetzt werden. Ferner eignen sie sich hervorragend als universelles Haushaltswaschmittel.The new formulations represent storage-stable, single-phase, low-foam and silicone-free textile auxiliaries with good complexing and sequestering properties with a dirt-removing effect. They show good emulsifying power and are stable in an alkaline liquor. In alkaline bleaching liquors, they have no creams or deposits. They also have good peroxide-stabilizing properties and bring about good rewettability of the textile goods. In addition, the formulations are readily biodegradable. Due to their liquid commercial form, they are easy to handle, which is why they are particularly suitable for modern dosing systems. The universal applicability of the formulations according to the invention enables various applications. They can be used, for example, as wetting agents, textile detergents, dispersants or as stabilizers in peroxide bleaching liquors. They are also ideal as a universal household detergent.

Gegenstand der vorliegenden Erfindung ist demnach auch ein Verfahren zum Netzen, Waschen und/oder Bleichen von Fasermaterialien, das dadurch gekennzeichnet ist, dass man diese Materialien in wässrigem Medium in Gegenwart eines in Anspruch 1 definierten Textilhilfsmittels behandelt.The present invention accordingly also relates to a process for wetting, washing and / or bleaching fiber materials, which is characterized in that these materials are treated in an aqueous medium in the presence of a textile auxiliary as defined in claim 1.

Die Einsatzmengen, in denen die erfindungsgemässen Textilhilfsmittel den Behandlungsflotten zugesetzt werden, betragen 0,1 bis 60, vorzugsweise 1 bis 20 g pro Liter Behandlungsflotte. Diese Flotten können noch weitere Zusätze enthalten, z.B. Entschlichtungsmittel, Farbstoffe, optische Aufheller, Alkalien wie Natriumhydroxid und Wasserstoffperoxid.The amounts in which the textile auxiliaries according to the invention are added to the treatment liquors are 0.1 to 60, preferably 1 to 20 g per liter of treatment liquor. These fleets can also contain other additives, e.g. Desizing agents, dyes, optical brighteners, alkalis such as sodium hydroxide and hydrogen peroxide.

Als Fasermaterialien kommen in Betracht: Cellulose, insbesondere unvorbehandelte natürliche Cellulose wie z.B. Hanf, Leinen, Jute, Zellwolle, Viskose, Azetatreyon, native Cellulosefaser und besonders Rohbaumwolle, Wolle, Polyamid-, Polyacrylnitril- oder Polyesterfasermaterialien sowie Fasermischungen, z.B. solche aus Polyacrylnitril/Baumwolle oder Polyester/Baumwolle.Possible fiber materials are: cellulose, in particular untreated natural cellulose such as Hemp, linen, jute, rayon, viscose, acetate treyon, native cellulose fiber and especially raw cotton, wool, polyamide, polyacrylonitrile or polyester fiber materials as well as fiber mixtures, e.g. those made of polyacrylonitrile / cotton or polyester / cotton.

Das zu behandelnde Fasermaterial kann in verschiedenen Verarbeitungsstufen vorliegen, so z.B. das cellulosehaltige Material als loses Material, Garn, Gewebe oder Gewirke. Hierbei handelt es sich also in der Regel stets um textile Fasermaterialien, die aus reinen textilen Cellulosefasern oder aus Gemischen von textilen Cellulosefasern mit textilen Synthesefasern hergestellt werden. Das Fasermaterial kann kontinuierlich oder diskontinuierlich in wässriger Flotte behandelt werden.The fiber material to be treated can be in different processing stages, for example the cellulosic material as loose material, yarn, woven or knitted fabric. As a rule, these are always textile fiber materials which are produced from pure textile cellulose fibers or from mixtures of textile cellulose fibers with textile synthetic fibers. The fiber material can be treated continuously or batchwise in an aqueous liquor.

Die wässrigen Behandlungsflotten können in bekannter Weise auf die Fasermaterialien aufgebracht werden, vorteilhaft durch Imprägnieren am Foulard, wobei die Flottenaufnahme etwa 70 bis 120 Gew.% beträgt. Das Foulardierverfahren kommt insbesondere beim Pad-Steam- sowie Pad-Batch-Verfahren zur Anwendung.The aqueous treatment liquors can be applied to the fiber materials in a known manner, advantageously by impregnation on the foulard, the liquor absorption being about 70 to 120% by weight. The padding process is used in particular in the pad-steam and pad-batch processes.

Die Imprägnierung kann bei 10 bis 60°C, vorzugsweise jedoch bei Raumtemperatur, vorgenommen werden. Nach der Imprägnierung und Abquetschung wird das Cellulosematerial gegebenenfalls einer Hitzebehandlung, z.B. bei Temperaturen von 80 bis 140°C unterworfen. Vorzugsweise erfolgt die Hitzebehandlung durch Dämpfen bei 95 bis 140, insbesondere bei 100 bis 106°C. Je nach Art der Hitzeentwicklung und des Temperaturbereiches kann die Hitzebehandlung 30 Sekunden bis 60 Minuten dauern. Bei dem PadBatch-Verfahren wird die imprägnierte Ware ohne Trocknung aufgerollt und anschliessend gegebenenfalls mit einer Plastikfolie verpackt, und bei Raumtemperatur 1 bis 24 Stunden gelagert.The impregnation can be carried out at 10 to 60 ° C, but preferably at room temperature. After impregnation and squeezing, the cellulose material is optionally subjected to a heat treatment, e.g. Subject at temperatures from 80 to 140 ° C. The heat treatment is preferably carried out by steaming at 95 to 140, in particular at 100 to 106 ° C. Depending on the type of heat development and the temperature range, the heat treatment can take 30 seconds to 60 minutes. In the PadBatch process, the impregnated goods are rolled up without drying and then optionally packed with a plastic film and stored at room temperature for 1 to 24 hours.

Die Behandlung der Fasermaterialien kann aber auch in langen Flotten bei einem Flottenverhältnis von z.B. 1:3 bis 1:100, vorzugsweise 1:4 bis 1:25 und bei 10 bis 100, vorzugsweise 60 bis 98°C während etwa 1/4 bis 3 Stunden unter Normalbedingungen, d.h. unter atmosphärischem Druck in üblichen Apparaturen, z.B. einem Jigger, Jet oder einer Haspelkufe erfolgen. Gegebenenfalls kann aber auch die Behandlung bis 150°C, vorzugsweise 105 bis 140°C unter Druck in sogenannten Hochtemperatur-Apparaturen (HT-Apparaturen) durchgeführt werden.The treatment of the fiber materials can also be carried out in long liquors with a liquor ratio of e.g. 1: 3 to 1: 100, preferably 1: 4 to 1:25 and at 10 to 100, preferably 60 to 98 ° C for about 1/4 to 3 hours under normal conditions, i.e. under atmospheric pressure in conventional equipment, e.g. a jigger, jet or reel runner. Optionally, however, the treatment up to 150 ° C, preferably 105 to 140 ° C under pressure in so-called high-temperature equipment (HT equipment) can be carried out.

Anschliessend werden die Fasermaterialien, wenn es das Verfahren verlangt, mit heissem Wasser von etwa 90 bis 98°C und dann mit warmem und zuletzt mit kaltem Wasser gründlich gespült, gegebenenfalls neutralisiert und hierauf vorzugsweise bei erhöhten Temperaturen getrocknet.Then, if the process so requires, the fiber materials are rinsed thoroughly with hot water at about 90 to 98 ° C. and then with warm and finally with cold water, neutralized if necessary and then preferably dried at elevated temperatures.

In den nachfolgenden Beispielen, die zur Veranschaulichung der Erfindung dienen, beziehen sich die Prozente stets auf das Gewicht.In the following examples, which serve to illustrate the invention, the percentages always relate to the weight.

Herstellung der Einzelkomponenten:Manufacture of the individual components: Beispiel 1: Herstellung der Komponente (b)Example 1: Preparation of component (b)

In einem Planschliffkolben mit Heizmantel werden

360,0 g
deionisiertes Wasser,
76,0 g
des Umsetzungsproduktes aus einem Mol eines C₁₃-Oxoalkohols und 9 Mol Ethylenoxid,
48 g
des Umsetzungsproduktes aus einem Mol eines C₁₃-Oxoalkohols und 10 Mol Ethylenoxid

bei 20 bis 30°C vorgelegt und auf 88 bis 92°C erwärmt. Es entsteht eine milchig trübe Emulsion.In a flat-bottomed flask with a heating jacket
360.0 g
deionized water,
76.0 g
the reaction product from one mole of a C₁₃ oxo alcohol and 9 moles of ethylene oxide,
48 g
of the reaction product from one mole of a C₁₃ oxo alcohol and 10 moles of ethylene oxide

submitted at 20 to 30 ° C and heated to 88 to 92 ° C. A milky, cloudy emulsion is formed.

Bei 90°C werden gleichzeitig
124,0 g Acrylsäure und eine Initiatorlösung, bestehend aus
0,75 g Kaliumpersulfat, gelöst in 60,0 g deionisiertem Wasser
zudosiert. Die Dosierzeit für die Acrylsäure beträgt 180 Minuten, die der Initiatorlösung 195 Minuten. Anschliessend wird die entstandene Polymerlösung noch etwa 15 bis 30 Minuten nachgerührt und danach auf 25°C abgekühlt. Während der Abkühlphase werden unterhalb 70°C
9,7 g 30%ige Natronlauge
unter gutem Rühren zugegeben.At 90 ° C at the same time
124.0 g of acrylic acid and an initiator solution consisting of
0.75 g potassium persulfate, dissolved in 60.0 g deionized water
added. The dosing time for acrylic acid is 180 minutes, that of the initiator solution 195 minutes. The resulting polymer solution is then stirred for a further 15 to 30 minutes and then cooled to 25 ° C. During the cooling phase are below 70 ° C
9.7 g 30% sodium hydroxide solution
added with good stirring.

Es entsteht ein klares, farbloses Produkt.The result is a clear, colorless product.

Beispiel 2: Herstellung der Komponente (b)Example 2: Preparation of component (b)

In einem Planschliffkolben mit Heizmantel werden

346,0 g
deionisiertes Wasser,
138,0 g
des Umsetzungsproduktes aus einem Mol eines C₁₃-Oxoalkohols und 9 Mol Ethylenoxid,

bei 20 bis 30°C vorgelegt und auf 88 bis 92°C erwärmt. Es entsteht eine milchig trübe Emulsion.In a flat-bottomed flask with a heating jacket
346.0 g
deionized water,
138.0 g
the reaction product from one mole of a C₁₃ oxo alcohol and 9 moles of ethylene oxide,

submitted at 20 to 30 ° C and heated to 88 to 92 ° C. A milky, cloudy emulsion is formed.

Bei 90°C werden gleichzeitig

124,0 g
Acrylsäure und eine Initiatorlösung, bestehend aus
0,75 g
Kaliumpersulfat, gelöst in 60,0 g deionisiertem Wasser

zudosiert. Die Dosierzeit für die Acrylsäure beträgt 180 Minuten, die der Initiatorlösung 195 Minuten. Anschliessend wird die entstandene Polymerlösung noch etwa 15 bis 30 Minuten nachgerührt.At 90 ° C at the same time
124.0 g
Acrylic acid and an initiator solution consisting of
0.75 g
Potassium persulfate, dissolved in 60.0 g of deionized water

added. The dosing time for acrylic acid is 180 minutes, that of the initiator solution 195 minutes. The resulting polymer solution is then stirred for a further 15 to 30 minutes.

Bei 85 bis 95°C wird nun

13,9 g
Magnesiumhydroxid

eingerührt und die entstandene homogene Lösung auf 25°C abgekühlt. Während der Abkühlphase werden unterhalb 70°C
321,6 g
deionisiertes Wasser unter gutem Rühren zugegeben.
At 85 to 95 ° C is now
13.9 g
Magnesium hydroxide

stirred in and the resulting homogeneous solution cooled to 25 ° C. During the cooling phase are below 70 ° C
321.6 g
Deionized water added with good stirring.

Es entsteht ein klares, farbloses, homogenes Produkt.The result is a clear, colorless, homogeneous product.

Herstellung der erfindungsgemässen FormulierungenPreparation of the formulations according to the invention Beispiel 3:Example 3:

Folgende Komponenten werden unter Rühren miteinander gemischt:

24 %
des Umsetzungsproduktes aus einem Mol eines C₁₃-Oxoalkohols und 6 Mol Ethylenoxid,
22 %
der Komponente (b) gemäss Beispiel 1,
2,4 %
Dinatriumdicarboxyethylcocopropylendiamin,
10 %
des Umsetzungsproduktes aus einem Mol eines C₁₂-Fettalkohols und 6 Mol Ethylenoxid/4 Mol Propylenoxid
7,2 %
1-Hydroxy-1,1-ethandiphosphonsäure,
3 %
D-Gluconsäure,
6 %
2-Methyl-2,4-pentandiol und
25,4 %
Wasser.
The following components are mixed together with stirring:
24%
the reaction product of one mole of a C₁₃ oxo alcohol and 6 moles of ethylene oxide,
22%
component (b) according to Example 1,
2.4%
Disodium dicarboxyethyl cocopropylene diamine,
10%
of the reaction product from one mole of a C₁₂ fatty alcohol and 6 moles of ethylene oxide / 4 moles of propylene oxide
7.2%
1-hydroxy-1,1-ethanediphosphonic acid,
3%
D-gluconic acid,
6%
2-methyl-2,4-pentanediol and
25.4%
Water.

Es entsteht ein niederviskoses, klares und homogenes Produkt.The result is a low-viscosity, clear and homogeneous product.

Die Formulierung findet Verwendung als Textilhilfsmittel für alkalische Aufschlussverfahren, Laugieren und Mercerisieren.The formulation is used as a textile auxiliary for alkaline digestion processes, leaching and mercerizing.

Beispiel 4:Example 4:

Folgende Komponenten werden unter Rühren miteinander gemischt:

32 %
des Umsetzungsproduktes aus einem Mol eines C₁₃-Oxoalkohols und 7 Mol Ethylenoxid,
8 %
des Umsetzungsproduktes aus einem Mol eines C₁₃-Oxoalkohols und 6 Mol Ethylenoxid,
28 %
der Komponente (b) gemäss Beispiel 1,
2,4 %
Dinatriumdicarboxyethylcocopropylendiamin,
4,8 %
1-Hydroxy-1,1-ethandiphosphonsäure,
3 %
D-Gluconsäure,
6 %
2-Methyl-2,4-pentandiol und
14,6 %
Wasser.
The following components are mixed together with stirring:
32%
the reaction product from one mole of a C₁₃ oxo alcohol and 7 moles of ethylene oxide,
8th %
the reaction product of one mole of a C₁₃ oxo alcohol and 6 moles of ethylene oxide,
28%
component (b) according to Example 1,
2.4%
Disodium dicarboxyethyl cocopropylene diamine,
4.8%
1-hydroxy-1,1-ethanediphosphonic acid,
3%
D-gluconic acid,
6%
2-methyl-2,4-pentanediol and
14.6%
Water.

Es entsteht ein niederviskoses, klares und homogenes Produkt.The result is a low-viscosity, clear and homogeneous product.

Die Formulierung findet Verwendung als Textilhilfsmittel für alkalische Aufschlussverfahren, Laugieren und Mercerisieren.The formulation is used as a textile auxiliary for alkaline digestion processes, leaching and mercerizing.

Beispiel 5:Example 5:

Folgende Komponenten werden unter Rühren miteinander gemischt:

32 %
des Umsetzungsproduktes aus einem Mol eines C₁₃-Oxoalkohols und 6 Mol Ethylenoxid,
40 %
der Komponente (b) gemäss Beispiel 2,
1,8 %
Dinatriumdicarboxyethylcocopropylendiamin,
4,8 %
1-Hydroxy-1,1-ethandiphosphonsäure,
3 %
D-Gluconsäure,
8 %
2-Methyl-2,4-pentandiol und
10,4 %
Wasser.
The following components are mixed together with stirring:
32%
the reaction product of one mole of a C₁₃ oxo alcohol and 6 moles of ethylene oxide,
40%
component (b) according to Example 2,
1.8%
Disodium dicarboxyethyl cocopropylene diamine,
4.8%
1-hydroxy-1,1-ethanediphosphonic acid,
3%
D-gluconic acid,
8th %
2-methyl-2,4-pentanediol and
10.4%
Water.

Es entsteht ein niederviskoses, klares und homogenes Produkt.The result is a low-viscosity, clear and homogeneous product.

Die Formulierung findet Verwendung als Textilhilfsmittel für die Kaltlager-Peroxidbleiche.The formulation is used as a textile aid for cold storage peroxide bleaching.

Beispiel 6:Example 6:

Folgende Komponenten werden unter Rühren miteinander gemischt:

15 %
des Umsetzungsproduktes aus einem Mol eines C₁₃-Oxoalkohols und 3 Mol Ethylenoxid,
15%
des Umsetzungsproduktes aus einem Mol eines C₁₃-Oxoalkohols und 5 Mol Ethylenoxid,
42 %
der Komponente (b) gemäss Beispiel 1,
4 %
Talgfettamphopolycarboxyglycinat,
12 %
des Umsetzungsproduktes aus einem Mol eines C₁₀-Fettalkohols und 6 Mol Ethylenoxid/1 Mol Butylenoxid, methylendgruppenverschlossen,
6 %
2-Methyl-2,4-pentandiol und
6 %
Wasser.
The following components are mixed together with stirring:
15%
the reaction product from one mole of a C₁₃ oxo alcohol and 3 moles of ethylene oxide,
15%
the reaction product from one mole of a C₁₃ oxo alcohol and 5 moles of ethylene oxide,
42%
component (b) according to Example 1,
4%
Tallow fat amphopolycarboxyglycinate,
12%
the reaction product of one mole of a C₁₀ fatty alcohol and 6 moles of ethylene oxide / 1 mole of butylene oxide, methyl end groups,
6%
2-methyl-2,4-pentanediol and
6%
Water.

Es entsteht ein niederviskoses, klares und homogenes Produkt.The result is a low-viscosity, clear and homogeneous product.

Die Formulierung findet Verwendung als Textilhilfsmittel für Abkoch- und Bleichprozesse.The formulation is used as a textile aid for boiling and bleaching processes.

Beispiel 7:Example 7:

Folgende Komponenten werden unter Rühren miteinander gemischt:

3,5 %
des Umsetzungsproduktes aus einem Mol eines C₁₃-Oxoalkohols und 5 Mol Ethylenoxid,
9,5 %
des Umsetzungsproduktes aus einem Mol eines C₁₃-Oxoalkohols und 6 Mol Ethylenoxid,
2 %
des Umsetzungsproduktes aus einem Mol eines C₁₃-Oxoalkohols und 9 Mol Ethylenoxid,
12,6 %
der Komponente (b) gemäss Beispiel 1,
4 %
des Natriumsalzes der Cumol-4-sulfonsäure,
2,5 %
Magnesiumdigluconat und
65,9 %
Wasser.
The following components are mixed together with stirring:
3.5%
the reaction product from one mole of a C₁₃ oxo alcohol and 5 moles of ethylene oxide,
9.5%
the reaction product of one mole of a C₁₃ oxo alcohol and 6 moles of ethylene oxide,
2%
the reaction product from one mole of a C₁₃ oxo alcohol and 9 moles of ethylene oxide,
12.6%
component (b) according to Example 1,
4%
the sodium salt of cumene-4-sulfonic acid,
2.5%
Magnesium digluconate and
65.9%
Water.

Es entsteht ein niederviskoses, klares und homogenes Produkt.The result is a low-viscosity, clear and homogeneous product.

Die Formulierung findet Verwendung als Textilhilfsmittel für die Pad-Steam-PeroxidBleiche.The formulation is used as a textile aid for pad-steam-peroxide bleaching.

Beispiel 8:Example 8:

Folgende Komponenten werden unter Rühren miteinander gemischt:

15 %
des Umsetzungsproduktes aus einem Mol eines C₁₃-Oxoalkohols und 6 Mol Ethylenoxid,
20,7 %
der Komponente (b) gemäss Beispiel 2,
4 %
des Natriumsalzes der Cumol-4-sulfonsäure,
2,4 %
Magnesiumdigluconat und
57,9 %
Wasser.
The following components are mixed together with stirring:
15%
the reaction product of one mole of a C₁₃ oxo alcohol and 6 moles of ethylene oxide,
20.7%
component (b) according to Example 2,
4%
the sodium salt of cumene-4-sulfonic acid,
2.4%
Magnesium digluconate and
57.9%
Water.

Es entsteht ein niederviskoses, klares und homogenes Produkt.The result is a low-viscosity, clear and homogeneous product.

Die Formulierung findet Verwendung als Textilhilfsmittel für die Pad-Steam-Peroxid-Bleiche.The formulation is used as a textile aid for pad steam peroxide bleaching.

Beispiel 9:Example 9:

Folgende Komponenten werden unter Rühren miteinander gemischt:

30 %
des Umsetzungsproduktes aus einem Mol eines C₁₁-Oxoalkohols und 4 Mol Ethylenoxid,
42 %
der Komponente (b) gemäss Beispiel 1, aber mit einem Umsetzungsprodukt aus einem Mol eines C₁₃-Oxoalkohols mit 6 Mol Ethylenoxid anstelle des Umsetzungsproduktes aus einem Mol eines C₁₅-Oxoalkohols mit 9 und 10 Mol Ethylenoxid,
12 %
des Umsetzungsproduktes aus einem Mol eines C₁₀-Fettalkohols und 6 Mol Ethylenoxid sowie 1 Mol Butylenoxid, methylendgruppenverschlossen,
3 %
Dodecyliminodipropionat-di-Na-Salz,
6 %
2-Methyl-2,4-pentandiol und
7 %
Wasser.
The following components are mixed together with stirring:
30%
the reaction product of one mole of a C₁₁ oxo alcohol and 4 moles of ethylene oxide,
42%
component (b) according to Example 1, but with a reaction product of one mole of a C₁₃ oxo alcohol with 6 moles of ethylene oxide instead of the reaction product of one mole of a C₁₅ oxo alcohol with 9 and 10 moles of ethylene oxide,
12%
the reaction product of one mole of a C₁₀ fatty alcohol and 6 moles of ethylene oxide and 1 mole of butylene oxide, methyl end groups,
3%
Dodecyliminodipropionate di Na salt,
6%
2-methyl-2,4-pentanediol and
7%
Water.

Es etnsteht eine klare, niederviskose Formulierung.A clear, low-viscosity formulation is created.

Beispiel 10:Example 10:

Folgende Komponenten werden unter Rühren miteinander gemischt:

30 %
des Umsetzungsproduktes aus einem Mol eines C₁₁-Oxoalkohols und 4 Mol Ethylenoxid
42 %
der Komponente (b) gemäss Beispiel 1, aber mit einem Umsetzungsprodukt aus einem Mol eines C₁₃-Oxoalkohols mit 8 Mol Ethylenoxid anstelle des Umsetzungsproduktes aus einem Mol eines C₁₅-Oxoalkohols mit 9 und 10 Mol Ethylenoxid,
12 %
des Umsetzungsproduktes aus einem Mol eines C₁₀-Fettalkohols und 6 Mol Ethylenoxid sowie 1 Mol Butylenoxid, methylendgruppenverschlossen,
3 %
Dodecyliminodipropionat-di-Na-Salz,
6 %
2-Methyl-2,4-pentandiol und
7 %
Wasser.
The following components are mixed together with stirring:
30%
of the reaction product from one mole of a C₁₁ oxo alcohol and 4 moles of ethylene oxide
42%
component (b) according to Example 1, but with a reaction product of one mole of a C₁₃-oxo alcohol with 8 moles of ethylene oxide instead of the reaction product of one mole of a C₁₅-oxo alcohol with 9 and 10 moles of ethylene oxide,
12%
the reaction product of one mole of a C₁₀ fatty alcohol and 6 moles of ethylene oxide and 1 mole of butylene oxide, methyl end groups,
3%
Dodecyliminodipropionate di Na salt,
6%
2-methyl-2,4-pentanediol and
7%
Water.

Es entsteht eine klare, niederviskose Formulierung.The result is a clear, low-viscosity formulation.

Beispiel 11:Example 11:

Folgende Komponenten werden unter Rühren miteinander gemischt:

30 %
des Umsetzungsproduktes aus einem Mol eines C₁₁-Oxoalkohols und 4 Mol Ethylenoxid
42 %
der Komponente (b) gemäss Beispiel 1, aber mit einem Umsetzungsprodukt aus einem Mol eines C₁₃-Oxoalkohols mit 4 Mol Ethylenoxid anstelle des Umsetzungsproduktes aus einem Mol eines C₁₅-Oxoalkohols mit 9 und 10 Mol Ethylenoxid,
12 %
des Umsetzungsproduktes aus einem Mol eines C₁₀-Fettalkohols und 6 Mol Ethylenoxid sowie 1 Mol Butylenoxid, methylendgruppenverschlossen,
3 %
Dodecyliminodipropionat-di-Na-Salz,
6 %
2-Methyl-2,4-pantandiol und
7 %
Wasser.
The following components are mixed together with stirring:
30%
of the reaction product from one mole of a C₁₁ oxo alcohol and 4 moles of ethylene oxide
42%
component (b) according to Example 1, but with a reaction product from one mole of a C₁₃ oxo alcohol with 4 moles of ethylene oxide instead of the reaction product from one mole of a C₁₅ oxo alcohol with 9 and 10 moles of ethylene oxide,
12%
the reaction product of one mole of a C₁₀ fatty alcohol and 6 moles of ethylene oxide and 1 mole of butylene oxide, methyl end groups,
3%
Dodecyliminodipropionate di Na salt,
6%
2-methyl-2,4-pantanediol and
7%
Water.

Es entsteht eine klare, niederviskose Formulierung.The result is a clear, low-viscosity formulation.

Beispiel 12:Example 12:

Folgende Komponenten werden unter Rühren miteinander gemischt:

30 %
des Umsetzungsproduktes aus einem Mol eines C₁₁-Oxoalkohols und 4 Mol Ethylenoxid
42 %
der Komponente (b) gemäss Beispiel 2,
12 %
des Umsetzungsproduktes aus einem Mol eines C₁₀-Fettalkohols und 6 Mol Ethylenoxid sowie 1 Mol Butylenoxid, methylendgruppenverschlossen,
3 %
Dodecyliminodipropionat-di-Na-Salz,
6 %
2-Methyl-2,4-pentandiol und
7 %
Wasser.
The following components are mixed together with stirring:
30%
of the reaction product from one mole of a C₁₁ oxo alcohol and 4 moles of ethylene oxide
42%
component (b) according to Example 2,
12%
the reaction product of one mole of a C₁₀ fatty alcohol and 6 moles of ethylene oxide and 1 mole of butylene oxide, methyl end groups,
3%
Dodecyliminodipropionate di Na salt,
6%
2-methyl-2,4-pentanediol and
7%
Water.

Es entsteht eine opale, niederviskose Formulierung.The result is an opal, low-viscosity formulation.

Beispiel 13:Example 13:

Folgende Komponenten werden unter Rühren miteinander gemischt:

38 %
des Umsetzungsproduktes aus einem Mol eines C₁₃-Oxoalkohols und 7 Mol Ethylenoxid,
24 %
der Komponente (b) gemäss Beispiel 1,
6 %
Citronensäure Monohydrat,
4,8 %
1-Hydroxy-1,1-ethandiphosphonsäure,
3 %
D-Gluconsäure,
6 %
2-Methyl-2,4-pentandiol und
18,2 %
Wasser.
The following components are mixed together with stirring:
38%
the reaction product from one mole of a C₁₃ oxo alcohol and 7 moles of ethylene oxide,
24%
component (b) according to Example 1,
6%
Citric acid monohydrate,
4.8%
1-hydroxy-1,1-ethanediphosphonic acid,
3%
D-gluconic acid,
6%
2-methyl-2,4-pentanediol and
18.2%
Water.

Es entsteht eine klare, niederviskose Formulierung.The result is a clear, low-viscosity formulation.

ApplikationsbeispieleApplication examples Beispiel 14: Alkalischer Aufschluss nach dem Pad-Steam-VerfahrenExample 14: Alkaline digestion using the pad-steam method

Rohbaumwollgewebe wird auf einem Foulard bei Raumtemperatur mit einer Behandlungsflotte der folgenden Zusammensetzung imprägniert:

2 g/l
des gemäss Beispiel 4 hergestellten Textilhilfsmittels und
30 g/l
NaOH (100%).
Raw cotton fabric is impregnated on a foulard at room temperature with a treatment liquor of the following composition:
2 g / l
of the textile auxiliary produced according to Example 4 and
30 g / l
NaOH (100%).

Die Flottenaufnahme beträgt 100%. Die Ware wird nun für 10 Minuten in einen Dämpfer mit Sattdampf von 102°C geführt und anschliessend mit heissem Wasser ausgewaschen.The fleet intake is 100%. The goods are then fed into a steamer with saturated steam at 102 ° C for 10 minutes and then washed out with hot water.

Es resultiert eine entschlichtete Ware mit hoher Saugfähigkeit.The result is a desized product with high absorbency.

Beispiel 15: Kaltlager-Peroxid-Bleiche Example 1 5 : Cold storage peroxide bleach

Rohbaumwollgewebe wird auf einem Foulard bei Raumtemperatur mit einer Behandlungsflotte der folgenden Zusammensetzung imprägniert:

12 g/l
des gemäss Beispiel 5 hergestellten Textilhilfmittels,
30 g/l
NaOH (100%) und
50 ml/l
Wasserstoffperoxid.
Raw cotton fabric is impregnated on a foulard at room temperature with a treatment liquor of the following composition:
12 g / l
the textile auxiliary produced according to Example 5,
30 g / l
NaOH (100%) and
50 ml / l
Hydrogen peroxide.

Die Flottenaufnahme beträgt 100%. Die feuchte Ware wird auf eine Docke aufgewickelt, mit Plastikfolie verpackt und mit langsamer Drehbewegung der Docke 20 Stunden bei Raumtemperatur gelagert. Anschliessend wird die Ware mit heissem Wasser ausgewaschen. Es resultiert ein saugfähiges Gewebe mit hohem Weissgrad und nur geringer Faserschädigung.The fleet intake is 100%. The moist goods are wound up on a dock, packed with plastic wrap and stored for 20 hours at room temperature with slow rotation of the dock. The goods are then washed out with hot water. The result is an absorbent fabric with a high degree of whiteness and little fiber damage.

Beispiel 16: Pad-Steam-Peroxidbleiche Example 1 6 : Pad-Steam Peroxide Bleach

Rohbaumwollgewebe wird mit einer Behandlungsflote der folgenden Zusammensetzung besprüht:

20 g/l
des gemäss Beispiel 8 hergestellten Textilhilfsmittels
40 g/l
NaOH (100%) und
30 ml/l
Wasserstoffperoxid (35%).
Raw cotton fabric is sprayed with a treatment liquor of the following composition:
20 g / l
of the textile auxiliary produced according to Example 8
40 g / l
NaOH (100%) and
30 ml / l
Hydrogen peroxide (35%).

Die Besprühung erfolgt z.B. in einer Raco-Yet-Anlage der Firma Rimisch-Kleinwefers. Die Auftragsmenge beträgt 140 %. Die feuchte Ware wird für 2 Stunden in einem Dämpfer mit Sattdampf von 102°C behandelt und anschliessend mit heissem Wasser ausgewaschen.The spraying takes place e.g. in a Raco-Yet system from Rimisch-Kleinwefers. The order quantity is 140%. The damp goods are treated for 2 hours in a steamer with saturated steam at 102 ° C and then washed out with hot water.

Es resultiert ein saugfähiges Gewebe mit hohem Weissgrad und nur geringer Faserschädigung.The result is an absorbent fabric with a high degree of whiteness and little fiber damage.

Claims (17)

Multifunktionelle Textilhilfsmittel, enthaltend (a) 10 bis 60 Gew.% ein nichtionogenes Tensid der Formel
Figure imgb0016
 (b) 10 bis 60 Gew.% des Umsetzungsproduktes aus einem nichtionogenen Tensid der Formel
Figure imgb0017
 und einer ethylenisch ungesättigten Sulfonsäure oder Carbonsäure oder deren Anhydrid, (c) 4 bis 20 Gew.% eines Hydrotropiermittels, (d) 0 bis 20 Gew.% eines nichtionogenen Tensids der Formel
Figure imgb0018
 (e) 0 bis 8 Gew.% eines Magnesiumsalzes einer organischen Carbonsäure (f) 0 bis 30 Gew.% eines Komplexier- oder Sequestriermittels (g) 0 bis 10 Gew.% eines Diols oder Polyols und (h) 0 bis 60 % Wasser, wobei einer der Komponenten (e) bis (g) im Textilhilfmittel immer vorhanden sein muss, worin in den Formeln (1), (2) und (3) R₁ und R₂,   unabhängig voneinander, C₈-C₂₂-Alkyl oder C₅-C₂₂-Alkenyl, R₃   Wasserstoff, C₁-C₄-Alkyl, einen cycloaliphatischen Rest mit mindestens 6 C-Atomen oder Benzyl, R₄   C₉ bis C₁₄-Alkyl, R₅   C₁ bis C₈-Alkyl, einen cycloaliphatischen Rest mit mindestens 5 C-Atomen, Niederalkylphenyl oder Styryl Y₁, Y₂, Y₃ und Y₄,   unabhängig voneinander Wasserstoff, Methyl oder Ethyl, wobei einer der Reste Y1, Y₂ bzw. Y₃, Y₄ immer Wasserstoff ist, "Alkylen" einen Alkylenrest von 2 bis 4 Kohlenstoffatomen, m₁   eine Zahl von 1 bis 40, n₁   eine ganze Zahl von 1 bis 60, p₁   eine ganze Zahl von 4 bis 10 und p₂   eine ganze Zahl von 0 bis 8, bedeuten.Multifunctional textile auxiliaries containing (a) 10 to 60% by weight of a nonionic surfactant of the formula
Figure imgb0016
 (b) 10 to 60% by weight of the reaction product from a nonionic surfactant of the formula
Figure imgb0017
 and an ethylenically unsaturated sulfonic acid or carboxylic acid or its anhydride, (c) 4 to 20% by weight of a hydrotroping agent, (d) 0 to 20% by weight of a nonionic surfactant of the formula
Figure imgb0018
 (e) 0 to 8% by weight of a magnesium salt of an organic carboxylic acid (f) 0 to 30% by weight of a complexing or sequestering agent (g) 0 to 10% by weight of a diol or polyol and (h) 0 to 60% water, one of the components (e) to (g) must always be present in the textile auxiliary, in which formulas (1), (2) and (3) R₁ and R₂, independently of one another, C₈-C₂₂-alkyl or C₅-C₂₂-alkenyl, R₃ is hydrogen, C₁-C₄ alkyl, a cycloaliphatic radical with at least 6 C atoms or benzyl, R₄ C₉ to C₁₄ alkyl, R₅ C₁ to C₈ alkyl, a cycloaliphatic radical with at least 5 C atoms, lower alkylphenyl or styryl Y₁, Y₂, Y₃ and Y₄, independently of one another hydrogen, methyl or ethyl, one the radicals Y1, Y₂ or Y₃, Y₄ is always hydrogen, "Alkylene" means an alkylene radical of 2 to 4 carbon atoms, m₁ is a number from 1 to 40, n₁ is an integer from 1 to 60, p₁ is an integer from 4 to 10 and p₂ is an integer from 0 to 8, mean. Textilhilfsmittel nach Anspruch 1, dadurch gekennzeichnet, dass als Komponente (a) ein oder mehrere nichtionogene Tenside der Formel
Figure imgb0019
 worin R₆   C₈-C₁₈-Alkyl; Y₅   Wasserstoff oder Methyl; und m₂   3 bis 15; bedeuten,
verwendet werden.Textile auxiliary according to claim 1, characterized in that as component (a) one or more nonionic surfactants of the formula
Figure imgb0019
 wherein R₆ C₈-C₁₈ alkyl; Y₅ is hydrogen or methyl; and m₂ 3 to 15; mean,
be used. Textilhilfsmittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass in Komponente (b) die ethylenisch ungesättigten Carbonsäuren Monocarbonsäuren mit 3 bis 5 Kohlenstoffatomen bedeuten.Textile auxiliaries according to claim 1 or 2, characterized in that in component (b) the ethylenically unsaturated carboxylic acids are monocarboxylic acids having 3 to 5 carbon atoms. Textilhilfsmittel nach Anspruch 3, dadurch gekennzeichnet, dass in Komponente (a) als Monocarbonsäure Acrylsäure verwendet wird.Textile auxiliary according to claim 3, characterized in that acrylic acid is used as the monocarboxylic acid in component (a). Textilhilfsmittel nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Komponente (b) das Umsetzungsprodukt aus 45 bis 5 Gew.-% Acrylsäure oder Methacrylsäure und 5 bis 45 Gew.-% eines oder mehrerer nichtionogener Tenside der Formel
Figure imgb0020
 worin R₇   C₈-C₁₈-Alkyl; Y₆   Wasserstoff, Methyl oder Ethyl; und n₂   1 bis 40; bedeuten, ist.Textile auxiliary according to one of claims 1 to 4, characterized in that component (b) is the reaction product of 45 to 5% by weight of acrylic acid or methacrylic acid and 5 to 45% by weight of one or more nonionic surfactants of the formula
Figure imgb0020
 wherein R₇ C₈-C₁₈ alkyl; Y₆ is hydrogen, methyl or ethyl; and n₂ 1 to 40; mean is. Textilhilfsmittel nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass als Komponente (c) Natrium-cumol-4-sulfonat verwendet wird.Textile auxiliary according to one of claims 1 to 5, characterized in that sodium cumene-4-sulfonate is used as component (c). Textilhilfsmittel nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass als Komponente (c) Dinatriumdicarboxyethylcocopropylendiamin oder Talgfettamphopolycarboxyglycinat verwendet wird.Textile auxiliary according to one of claims 1 to 5, characterized in that disodium dicarboxyethyl cocopropylene diamine or tallow fat amphopolycarboxyglycinate is used as component (c). Textilhilfsmittel nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass als Komponente (d) ein nichtionogenes Tensid der Formel
Figure imgb0021
 worin R₁₂   C₉-C₁₄-Alkyl; R₁₃   C₁-C₄-Alkyl; Y₇, Y₈, Y₉ und Y₁₀,   unabhängig voneinander, Wasserstoff, Methyl oder Ethyl, wobei einer der Reste Y₇, Y₈ bzw. Y₉, Y₁₀ immer Wasserstoff ist; p₃ und p₄,   unabhängig voneinander, eine ganze Zahl von 4 bis 8; bedeuten,
verwendet wird.Textile auxiliary according to one of claims 1 to 7, characterized in that a nonionic surfactant of the formula as component (d)
Figure imgb0021
 wherein R₁₂ C₉-C₁₄ alkyl; R₁₃ C₁-C₄ alkyl; Y₇, Y₈, Y₉ and Y₁₀, independently of one another, are hydrogen, methyl or ethyl, where one of the radicals Y₇, Y₈ or Y₉, Y₁₀ is always hydrogen; p₃ and p₄, independently of one another, are an integer from 4 to 8; mean,
is used. Textilhilfsmittel nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass als Komponente (e) Magnesiummono- oder Digluconat verwendet wird.Textile auxiliary according to one of claims 1 to 8, characterized in that magnesium mono- or digluconate is used as component (s). Textilhilfsmittel nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass als Komponente (f) Verbindungen verwendet werden, die ausgewählt sind aus (f₁) einem Gemisch aus monomeren und oligomeren Verbindungen entsprechend der Formel
Figure imgb0022
    worin Y₇ Wasserstoff oder -COT₁,
   R₁₄, X₃ und T₁, unabhängig voneinander, jeweils C₁-C₄-Alkyl und
   q₁ 1 bis 17
bedeuten, (f₂) d-Gluconsäure, (f₃) Zitronensäure und (f₄) Aminophosphonsäure. Textile auxiliary according to one of Claims 1 to 9, characterized in that compounds selected from component are used as component (f) (f₁) a mixture of monomeric and oligomeric compounds according to the formula
Figure imgb0022
 wherein Y₇ is hydrogen or -COT₁,
R₁₄, X₃ and T₁, independently of one another, are each C₁-C₄-alkyl and
q₁ 1 to 17
mean, (f₂) d-gluconic acid, (f₃) citric acid and (f₄) aminophosphonic acid. Textilhilfsmittel nach Anspruch 10, dadurch gekennzeichnet, dass als Komponnete (f) D-Gluconsäure verwendet wird.Textile auxiliary according to claim 10, characterized in that D-gluconic acid is used as component (f). Textilhilfsmittel nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, dass als Komponente (g) 2-Methyl-2,4-pentadiol verwendet wird.Textile auxiliary according to one of claims 1 to 11, characterized in that 2-methyl-2,4-pentadiol is used as component (g). Textilhilfsmittel nach einem der Ansprüche 1 bis 12, enthaltend (a) 10 bis 60 Gew.% eines oder mehrerer nichtionogener Tenside der Formel
Figure imgb0023
 (b) 10 bis 60 Gew.% des Umsetzungsproduktes aus 5 bis 45 Gew.-% eines oder mehrerer nichtionogener Tenside der Formel
Figure imgb0024
 und 45 bis 5 Gew.-% Acrylsäure; (c) 4 bis 20 Gew.% eines Hydrotropiermittels, ausgewählt aus Natrium-cumol-4-sulfonat und Dodecyliminodipropionat-di-Na-Salz; (d) 0 bis 20 Gew.% eines nichtionogenen Tensids der Formel
Figure imgb0025
 (e) 0 bis 8 Gew.% Magnesiummono- oder Digluconat; (f) 0 bis 30 Gew.% D-Gluconsäure; und (g) 0 bis 10 Gew.% 2-Methyl-2,4-pentadiol; wobei einer der Komponenten (e) bis (g) im Textilhilfmittel immer vorhanden sein muss, worin R₆   C₈-C₁₃-Alkyl; R₇   C₈-C₁₈-Alkyl; R₁₂   C₉-C₁₄-Alkyl; R₁₃   C₁-C₄-Alkyl; Y₅   Wasserstoff oder Methyl; Y₆   Wasserstoff, Methyl oder Ethyl; Y₇, Y₈, Y₉, Y₁₀,   unabhängig voneinander, Wasserstoff, Methyl oder Ethyl, wobei einer der Reste Y₇, Y₈ bzw. Y₉, Y₁₀ immer Wasserstoff ist; m₂   4 bis 15; n₂   1 bis 40; und p₃ und p₄,   unabhängig voneinander, eine ganze Zahl von 4 bis 8; bedeuten.Textile auxiliaries according to one of claims 1 to 12, containing (a) 10 to 60% by weight of one or more nonionic surfactants of the formula
Figure imgb0023
 (b) 10 to 60% by weight of the reaction product from 5 to 45% by weight of one or more nonionic surfactants of the formula
Figure imgb0024
 and 45 to 5% by weight acrylic acid; (c) 4 to 20% by weight of a hydrotroping agent selected from sodium cumene-4-sulfonate and dodecyliminodipropionate di-Na salt; (d) 0 to 20% by weight of a nonionic surfactant of the formula
Figure imgb0025
 (e) 0 to 8% by weight magnesium mono- or digluconate; (f) 0 to 30% by weight D-gluconic acid; and (g) 0 to 10% by weight 2-methyl-2,4-pentadiol; where one of the components (e) to (g) must always be present in the textile auxiliary, in which R₆ C₈-C₁₃ alkyl; R₇ C₈-C₁₈ alkyl; R₁₂ C₉-C₁₄ alkyl; R₁₃ C₁-C₄ alkyl; Y₅ is hydrogen or methyl; Y₆ is hydrogen, methyl or ethyl; Y₇, Y₈, Y₉, Y₁₀, independently of one another, hydrogen, methyl or ethyl, where one of the radicals Y₇, Y₈ or Y₉, Y₁₀ is always hydrogen; m₂ 4 to 15; n₂ 1 to 40; and p₃ and p₄, independently of one another, are an integer from 4 to 8; mean. Verfahren zur Herstellung der Textilhilfsmittel gemäss einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass man zunächst die Komponente (b) durch Umsetzung einer monomeren ethylenisch ungesättigten Sulfonsäure oder Carbonsäure oder deren Anhydrid in Gegenwart einer oder mehrerer nichtionogener Tenside der Formeln (1) und/oder (2) in Anwesenheit eines Katalysators herstellt, den pH-Wert auf ca. 4,5 einstellt und dann die restlichen Komponenten hinzugibt, bis eine homogene Lösung vorliegt.Process for the preparation of the textile auxiliaries according to one of Claims 1 to 13, characterized in that component (b) is first reacted by reacting a monomeric ethylenically unsaturated sulfonic acid or carboxylic acid or its anhydride in the presence of one or more nonionic surfactants of the formulas (1) and / or (2) in the presence of a catalyst, adjust the pH to about 4.5, and then adjust the add the remaining components until a homogeneous solution is obtained. Verfahren zum Netzen, Waschen und/oder Bleichen von Fasermaterialien, dadurch gekennzeichnet, dass man diese Materialien in wässrigem Medium in Gegenwart eines in Anspruch 1 definierten Textilhilfsmittels behandelt.Process for wetting, washing and / or bleaching fiber materials, characterized in that these materials are treated in an aqueous medium in the presence of a textile auxiliary as defined in claim 1. Verfahren nach Anspruch 15, dadurch gekennzeichnet, dass man das Textilhilfsmittel in einer Menge von 0,1 bis 60 g, vorzugsweise 1 bis 20 g pro Liter Flotte einsetzt.A method according to claim 15, characterized in that the textile auxiliary is used in an amount of 0.1 to 60 g, preferably 1 to 20 g, per liter of liquor. Das nach Anspruch 15 oder 16 behandelte Fasermaterial.The fiber material treated according to claim 15 or 16.
EP95810494A 1994-08-11 1995-08-02 Multifunctionnal textile agents compositions Expired - Lifetime EP0696661B1 (en)

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EP0744459A1 (en) * 1995-05-19 1996-11-27 Ciba-Geigy Ag Multifunctional detergent raw material
EP0940495A1 (en) * 1998-03-05 1999-09-08 Bayer Aktiengesellschaft Simultaneous washing and bleaching of natural fibres and textiles containing the same
WO2000037735A1 (en) * 1998-12-22 2000-06-29 Bayer Aktiengesellschaft Agents for treating textiles, method for producing them and their use
WO2000058547A1 (en) * 1999-03-29 2000-10-05 Bayer Aktiengesellschaft Treatment agents for textiles, method of producing same and their use
WO2000041500A3 (en) * 1999-01-11 2001-02-15 3M Innovative Properties Co Soil-resistant spin finish compositions
EP1081554A1 (en) * 1999-08-31 2001-03-07 Kodak Polychrome Graphics Company Ltd. Developing system for alkaline-developable lithographic printing plates
EP1092804A1 (en) * 1999-10-16 2001-04-18 Ciba Spezialitätenchemie Pfersee GmbH Composition for the pretreatment of textiles
WO2003006734A2 (en) * 2001-07-11 2003-01-23 Clariant International Ltd. Textile fibre degreasing agents, their production and their use
WO2005019519A1 (en) * 2003-08-21 2005-03-03 Clariant International Ltd Multifunctional textile-pretreating agent
CN102995468A (en) * 2012-11-26 2013-03-27 浙江安诺其助剂有限公司 Polyester fabric dyeing degreaser and preparation method thereof

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EP1149945A1 (en) * 2000-04-29 2001-10-31 Ciba Spezialitätenchemie Pfersee GmbH Composition for the pretreatment of fibrous materials
DE10118236A1 (en) * 2001-04-11 2002-10-17 Ciba Sc Pfersee Gmbh Composition useful for pretreating textiles before dyeing comprises sulfonate or polyol, ethoxylated alcohol, alkoxylated alcohol, poly(meth)acrylic or polymaleic acid and water
CN103492632B (en) * 2012-02-24 2015-07-08 日华化学株式会社 Agent and method for refining and bleaching
EP2928859A1 (en) * 2012-12-06 2015-10-14 Pandit, Sandeepak Amphoteric detergent compatible softeners based on alkyl ammonium backbone
GB2529138A (en) * 2014-07-02 2016-02-17 Basf Se Detergent
JP2018062548A (en) * 2016-10-11 2018-04-19 ライオン株式会社 Bleaching agent composition
JP6991048B2 (en) * 2017-12-01 2022-01-12 ライオン株式会社 Liquid detergent composition

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EP0744459A1 (en) * 1995-05-19 1996-11-27 Ciba-Geigy Ag Multifunctional detergent raw material
EP0940495A1 (en) * 1998-03-05 1999-09-08 Bayer Aktiengesellschaft Simultaneous washing and bleaching of natural fibres and textiles containing the same
US6096097A (en) * 1998-03-05 2000-08-01 Bayer Aktiengesellschaft Simultaneous washing and bleaching of native fibres and textile products therefrom
WO2000037735A1 (en) * 1998-12-22 2000-06-29 Bayer Aktiengesellschaft Agents for treating textiles, method for producing them and their use
WO2000041500A3 (en) * 1999-01-11 2001-02-15 3M Innovative Properties Co Soil-resistant spin finish compositions
US6537662B1 (en) 1999-01-11 2003-03-25 3M Innovative Properties Company Soil-resistant spin finish compositions
US6528576B1 (en) 1999-03-29 2003-03-04 Bayer Aktiengesellschaft Treatment agents for textiles, method of producing same and their use
WO2000058547A1 (en) * 1999-03-29 2000-10-05 Bayer Aktiengesellschaft Treatment agents for textiles, method of producing same and their use
EP1081554A1 (en) * 1999-08-31 2001-03-07 Kodak Polychrome Graphics Company Ltd. Developing system for alkaline-developable lithographic printing plates
US6802871B1 (en) 1999-10-16 2004-10-12 Ciba Specialty Chemicals Corporation Composition for pretreating fiber materials
EP1092804A1 (en) * 1999-10-16 2001-04-18 Ciba Spezialitätenchemie Pfersee GmbH Composition for the pretreatment of textiles
WO2003006734A2 (en) * 2001-07-11 2003-01-23 Clariant International Ltd. Textile fibre degreasing agents, their production and their use
WO2003006734A3 (en) * 2001-07-11 2003-05-15 Clariant Int Ltd Textile fibre degreasing agents, their production and their use
US6989360B2 (en) 2001-07-11 2006-01-24 Clariant Finance (Bvi) Limited Textile fiber degreasing agents, their production and their use
WO2005019519A1 (en) * 2003-08-21 2005-03-03 Clariant International Ltd Multifunctional textile-pretreating agent
CN102995468A (en) * 2012-11-26 2013-03-27 浙江安诺其助剂有限公司 Polyester fabric dyeing degreaser and preparation method thereof
CN102995468B (en) * 2012-11-26 2015-04-15 浙江安诺其助剂有限公司 Polyester fabric dyeing degreaser and preparation method thereof

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