EP1805289B1 - Liquid detergent comprising a dye fixing agent - Google Patents

Liquid detergent comprising a dye fixing agent Download PDF

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Publication number
EP1805289B1
EP1805289B1 EP05798081A EP05798081A EP1805289B1 EP 1805289 B1 EP1805289 B1 EP 1805289B1 EP 05798081 A EP05798081 A EP 05798081A EP 05798081 A EP05798081 A EP 05798081A EP 1805289 B1 EP1805289 B1 EP 1805289B1
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EP
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Prior art keywords
weight
washing
cleaning composition
ffm
alkyl
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EP05798081A
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German (de)
French (fr)
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EP1805289A1 (en
Inventor
Frank-Peter Lang
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Clariant Produkte Deutschland GmbH
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Clariant Produkte Deutschland GmbH
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Classifications

    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C11D1/831—Mixtures of non-ionic with anionic compounds of sulfonates with ethers of polyoxyalkylenes without phosphates
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0021—Dye-stain or dye-transfer inhibiting 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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides
    • 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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or 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
    • C11D1/02—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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the invention relates to liquid laundry detergents and cleaners for textiles containing one or more color fixing agents.
  • liquid detergents are today a very important product group among laundry detergents for textiles.
  • Liquid detergents contain surfactants as their main constituent.
  • surfactants are used simultaneously in modern detergents.
  • anionic surfactants used are linear alkylbenzenesulfonates (LAS), fatty alcohol sulfates (FAS), secondary alkanesulfonates (SAS) and, in some cases, fatty alcohol ether sulfates (FAES).
  • LAS linear alkylbenzenesulfonates
  • FAS fatty alcohol sulfates
  • SAS secondary alkanesulfonates
  • FAES fatty alcohol ether sulfates
  • Nonionic surfactants used are ethoxylates of long-chain, synthetic alcohols, for example the oxo alcohols, or of native fatty alcohols.
  • additive ingredients such as polycarboxylates and solubilizers such as ethanol, glycerol or propanediol are used.
  • additive ingredients which are generally included in low use concentrations and which may be grouped together under the term washing aids and which comprise such different active ingredient groups as foam regulators, grayness inhibitors, soil release polymers, enzymes, optical brighteners, dye transfer inhibitors and dye fixing agents are generally included.
  • the color fixing agents prevent the fading of colored textiles, which occurs especially in dark-colored textiles made of cotton and cotton blends over several washing cycles away. In the case of high-quality dyed textiles, the colors fade over a longer period of use.
  • EP 1236793 discloses a liquid detergent containing soap, a nonionic surfactant, a secondary alkanesulfonate and a color fixing agent.
  • the purpose of the present invention is to provide liquid washing and cleaning agent formulations for textiles which contain one or more color fixing agents in combination with an anionic surfactant and which are physically and chemically stable despite the potential incompatibility of the components.
  • the invention relates to liquid detergents and cleaners according to claim 1.
  • the mass ratio of anionic surfactants to nonionic surfactants is generally from 1: 4 to 4: 1, preferably from 1: 2 to 2: 1, in particular from 0.8 to 1 to 1.5: 1.
  • color fixing agents which can be incorporated in liquid detergents according to the invention are nonionic or cationic and are described below:
  • Polycondensates which can be used as dye fixing agents are prepared by the reaction of cyanamides with aldehydes and ammonium salts and / or monoamines (eg dye fixing agent FFM 3), by the reaction of monoamines and / or polyamines with epichlorohydrin (eg dye fixing agents FFM 2 and FFM 4). , or by the reaction of polyamines with cyanamides and amidosulfuric (eg color fixing FFM 1) obtained.
  • the monoamines used may be primary, secondary and tertiary amines. These may be aliphatic amines, e.g. Dialkylamines, especially dimethylamine, alicyclic amines, e.g. Cyclohexylamine and aromatic amines such as e.g. Aniline act. However, the amines used can also have aliphatic, alicyclic and aromatic substituents at the same time. Furthermore, heterocyclic compounds such as e.g. Pyridine can be used.
  • polyamines here includes, for example, diamines, triamines, tetraamines, etc, as well as the analogous N-alkyl-polyamines or the N, N-dialkyl-polyamines.
  • ammonium salts are salts of ammonia, in particular ammonium chloride or the above-mentioned amines or polyamines with various inorganic or organic acids or quaternary ammonium salts.
  • the cyanamides may be cyanamide or dicyandiamide.
  • Aldehydes that can be used to synthesize the color fixing agents include, for example, aliphatic aldehydes, e.g. Formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde; Dialdehydes, e.g. glyoxal; unsaturated aldehydes, e.g. Acrolein, crotonaldehyde and aromatic aldehydes, e.g. Benzaldehyde. Particularly preferred are the aliphatic aldehydes, in particular formaldehyde.
  • DADMAC diallyl-dimethylammonium chloride
  • FFM 5 dye-fixing agents
  • FFM 7 dye-fixing agents
  • Copolymers based on DADMAC contain as other components other vinylic monomers such as vinylimidazole, vinylpyrrolidone, vinyl alcohol, vinyl acetate, (meth) acrylic acid (ester), acrylamide, styrene, styrenesulfonic acid, acrylamidomethylpropane-sulfonic acid (AMPS), etc.
  • homopolymers based on DADMAC also available under the trade names Dodigen ® 3954, Dodigen 4033 and Genamin ® PDAC (Fa. Clariant).
  • the dye fixing agents are generally used in the liquid detergents in amounts of from 0.25 to 5% by weight, preferably from 0.5 to 3% by weight and more preferably from 0.5 to 1% by weight.
  • the liquid detergents according to the invention are preferably liquid and have a viscosity of max. 500 mPas. But they can also be higher viscosity, still flowable gels or spreadable pastes.
  • the detergents and cleaners according to the invention contain as solvent propanediol, glycerol or ethanol in a concentration of 1 to 10% by weight, preferably 1 to 5% by weight.
  • the pH of the formulations is adjusted to a value between 5 and 12 by the addition of acidic or alkaline substances.
  • Acidic substances may e.g. inorganic or organic acids, e.g. Sulfuric acid, phosphonic acids, citric acid.
  • Alkaline substances are e.g. Caustic soda, caustic soda and soda.
  • Acid to neutral liquid detergents are e.g. Wool detergents, neutral to weak alkaline liquid detergents are e.g. Detergents and alkaline detergents are so-called heavy-duty detergents.
  • Liquid detergents and cleaners containing the surfactant-dye fixative combination of the present invention may further contain other ingredients conventional in such compositions. These are described below.
  • the total surfactant content of the detergent formulations according to the invention may be from 10 to 70% by weight, preferably from 10 to 55% by weight and very particularly preferably from 20 to 50% by weight.
  • Suitable further anionic surfactants are alkyl ester sulfonates and alkyl ether sulfonates, suitable cations being alkali metals, for example sodium or potassium or alkaline earth metals, for example calcium or magnesium, and also ammonium, substituted Ammonium compounds, including mono-, di- or Triethanolammoniumkationen, and mixtures thereof.
  • Alkyl ester sulfonates include linear esters of C 8 -C 20 carboxylic acids (ie, fatty acids) which are sulfonated by means of gaseous SO 3 .
  • Suitable starting materials are natural fats such as tallow, coconut oil and palm oil, but may also be synthetic in nature.
  • Preferred alkyl ester sulfonates are compounds of the formula wherein R 1 is a C 8 -C 20 hydrocarbon radical, preferably alkyl, and R is a C 1 -C 6 hydrocarbon radical, preferably alkyl.
  • M is a cation which forms a water-soluble salt with the alkyl ester sulfonate. Suitable cations are sodium, potassium, lithium or ammonium cations, such as monoethanolamine, diethanolamine and triethanolamine.
  • R 1 is C 10 -C 16 -alkyl and R is methyl, ethyl or isopropyl. Particularly preferred are methyl ester sulfonates in which R 1 is C 10 -C 16 alkyl.
  • Alkyl ether sulfates are water-soluble salts or acids of the formula RO (A) m SO 3 M, where R is an unsubstituted C 10 -C 24 -alkyl or hydroxyalkyl radical, preferably a C 12 -C 20 -alkyl or hydroxyalkyl radical, more preferably C 12 -C 18 represents alkyl or hydroxyalkyl.
  • A is an ethoxy or propoxy moiety
  • m is a number greater than 0, preferably between about 0.5 and about 6, more preferably between about 0.5 and about 3
  • M is a hydrogen atom or a cation such as Sodium, potassium, lithium, calcium, magnesium, ammonium or a substituted ammonium cation.
  • substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine or mixtures thereof.
  • Examples C 12 were - to C 18 called fatty alcohol ether sulfates wherein the content of EO is 1, 2, 2.5, 3, or 4 mol per mol of fatty alcohol ether sulfate, and in which M is sodium or potassium. Due to their strong foam development, the use concentration of the alkyl ether sulfates depends on the intended use. Detergent laundry detergents use lower concentrations than laundry detergents. The ones encountered in practice Concentrations are between 1 to 20 wt .-%. Concentrations of from 1 to 10% by weight and preferably from 1 to 5% by weight are preferred for the present invention.
  • Nonionic surfactants which can be used in addition to those mentioned above.
  • the hydrophobic part of these compounds preferably has a molecular weight between about 1500 and about 1800.
  • the addition of ethylene oxide to this hydrophobic part leads to an improvement in water solubility.
  • the product is liquid up to a polyoxyethylene content of about 50% of the total weight of the condensation product, which corresponds to a condensation with up to about 40 moles of ethylene oxide.
  • Commercially available examples of this product class are the Pluronic ® brands from BASF and the ® Genapol PF brands from Clariant GmbH.
  • the hydrophobic moiety of these compounds consists of the reaction product of ethylenediamine with excess propylene oxide and generally has a molecular weight of about 2500 to 3000. Ethylene oxide is added to this hydrophobic unit to a content of about 40 to about 80 wt .-% polyoxyethylene and a molecular weight of about 5000 to 11000.
  • Commercially available examples of this class of compounds are the ® Tetronic brands of BASF and the ® Genapol PN brands of Clariant GmbH. Polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols.
  • These compounds include the condensation products of alkylphenols having a C 6 to C 20 alkyl group, which may be either linear or branched, with alkene oxides. Preference is given to compounds having about 5 to 25 mol of alkene oxide per mole of alkylphenol.
  • Commercially available surfactants of this type include Igepal ® CO-630, Triton ® X-45, X-114, X-100 and X102, and the Arkopal N ® brands from Clariant GmbH. These surfactants are referred to as Alkylphenolalkoxilate, eg Alkylphenolethoxilate.
  • nonionic compounds includes water-soluble amine oxides, water-soluble phosphine oxides, and water-soluble sulfoxides each having an alkyl group of from about 8 to about 18 carbon atoms.
  • Semi-polar nonionic surfactants are also amine oxides of the formula
  • R here is an alkyl, hydroxyalkyl or alkylphenol group having a chain length of about 8 to about 22 carbon atoms
  • R 2 is an alkylene or hydroxyalkylene group having about 2 to 3 carbon atoms or mixtures thereof
  • each R 1 is an alkyl or hydroxy alkyl group having from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about - 3 ethylene oxide units
  • x denotes a number from 0 to about 10.
  • the R 1 - Groups may be linked to each other via an oxygen or nitrogen atom and thus form a ring.
  • Particularly preferred amine oxides are C 8 -C 18 -alkyl-dimethyl-amine oxides and C 8 -C 12 -alkoxy-diethyl-dihydroxyethyl-amine oxides and C 8 -C 18 fatty acid-amidoalkyl-dimethyl-amine oxides.
  • Amine oxides can be used in use concentrations of 0.5 to 10 wt .-%, and preferably between 1 and 5 wt .-%.
  • Fatty acid amides have the formula
  • R is an alkyl group having from about 7 to about 21, preferably about 9 to about 17 carbon atoms and each R 1 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl or (C 2 H 4 O) x H, where x varies from about 1 to about 3.
  • nonionic surfactants are alkyl and Alkenyloligoglycoside and Fettchurepolyglykolester or Fettaminpolyglykolester having in each case 8 to 20, preferably 12 to 18 carbon atoms in the fatty alkyl, alkoxylated triglycamides, mixed ethers or Mischformyle, Alkyloligoglycoside, Alkenyloligoglycoside, fatty acid N-alkylglucamides, phosphine oxides, dialkyl sulfoxides and protein.
  • detergent ingredients that may be included in the present invention include inorganic and / or organic builders to reduce the degree of hardness of the water.
  • Inorganic builders include, for example, alkali, ammonium and alkanolammonium salts of polyphosphates such as tripolyphosphates, pyrophosphates and glassy polymeric metaphosphates, phosphonates, silicates, carbonates including bicarbonates, and sesquicarbonates and aluminosilicates, as described below:
  • Aluminosilicate builders particularly zeolites having the formula Na z [(AlO 2 ) z (SiO 2 ) y ] .xH 2 O, where z and y are integers of at least 6, the ratio of z to y is between 1.0 and about 0 , 5, and x is an integer from about 15 to about 264.
  • Suitable aluminosilicate-based ion exchangers are readily available. These aluminosilicates may be of crystalline or amorphous structure and may be naturally occurring or synthetically produced.
  • Preferred ion exchangers based on synthetic crystalline aluminosilicates are obtainable under the name of zeolite A, zeolite P (B) and zeolite X. Preference is given to aluminosilicates having a particle diameter of between 0.1 and 10 ⁇ m.
  • Suitable organic builders include polycarboxylic compounds such as ether polycarboxylates and oxydisuccinates. Likewise on “TMS / TDS" equipment from US 4,663,071 to get expelled.
  • Suitable builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, the alkali, ammonium and substituted ammonium salts of polyacetic acids such as e.g. Ethylenediamine-tetraacetic acid and nitrilotriacetic acid, and polycarboxylic acids, such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and their soluble salts.
  • polyacetic acids such as e.g. Ethylenediamine-tetraacetic acid and nitrilotriacetic acid
  • polycarboxylic acids such as mellitic acid, succinic acid, oxydisucc
  • Preferred organic builders are the polycarboxylates based on acrylic acid and / or maleic acid, e.g. the Sokalan CP brands (BASF) or the Acusol brands (Rhom and Haas), as well as citrate-based builders, e.g. the citric acid and its soluble salts, in particular the sodium salt.
  • BASF Sokalan CP brands
  • Rhom and Haas Acusol brands
  • citrate-based builders e.g. the citric acid and its soluble salts, in particular the sodium salt.
  • Phosphorus-based builders are alkali metal phosphates such as sodium tripolyphosphate, sodium pyrophosphate, and sodium orthophosphate.
  • Phosphonates such as ethane 1-hydroxy-1,1-diphosphonate (HEDP) and other known phosphonates are preferably suitable for the present invention.
  • HEDP ethane 1-hydroxy-1,1-diphosphonate
  • liquid detergents according to the invention which contain the surfactant system and a color fixing agent, may further contain the usual auxiliaries which enhance the cleaning action, serve to care for the textile to be washed or change the performance properties of the detergent composition.
  • Suitable adjuvants include, for example, enzymes, in particular proteases, lipases, cellulases, amylases and mannanases; Enzyme stabilizers; Foam boosters; Foam inhibitors, such as silicone oils or paraffins; Corrosion inhibitors; Color transfer inhibitors; optical brighteners; UV absorbers; Bleach; Preservatives; alkalis; hydrotrope compounds; antioxidants; Solvents or solubilizers, such as ethanol, glycerol, propanediol; dispersant; Anti-redeposition agents; graying; plasticizers; antistatic agents; Dyes and perfumes.
  • enzymes in particular proteases, lipases, cellulases, amylases and mannanases
  • Enzyme stabilizers Foam boosters
  • Foam inhibitors such as silicone oils or paraffins
  • Corrosion inhibitors Corrosion inhibitors
  • Color transfer inhibitors optical brighteners
  • UV absorbers Bleach; Preservatives;
  • dyes here includes both water-soluble dyes and insoluble color pigments.
  • water-soluble dyes are preferably used in liquid detergents. These include the groups of acid dyes, direct dyes and reactive dyes. These groups can be e.g. Represent representatives of azo dyes, metal complex dyes and polycyclic dyes.
  • fragrance or perfume oils individual perfume compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used.
  • mixtures of different fragrances are used, which together produce an attractive fragrance.
  • Perfume oils may also contain natural fragrance mixtures and lower-volatility essential oils.
  • polyamine N-oxides such as poly (4-vinylpyridine-N-oxide), poly (4-vinylpyridine-betaine), polyvinylpyrrolidone, and copolymers of N-vinylpyrrolidone with N-vinylimidazole and optionally other monomers, polyvinylimidazole, as well Cyclodextrins and cyclodextrin derivatives.
  • the detergents and cleaning agents according to the invention are characterized in that they are clear or at least opaque translucent to slightly cloudy. It is essential that these formulations are stable and do not flocculate. They provide a color-retaining and color transfer inhibiting effect, a softening effect, an anti-wrinkle effect and protection of mechanical wear.
  • Comparative Examples 1 to 4 demonstrate the incompatibility of anionic surfactants with the color fixing agents (FFM) and the problem of preparing stable anionic liquid detergents.
  • Examples 1 and 2 describe stable, liquid detergent formulations based on the anionic surfactant alkylbenzenesulfonate and polymeric color fixing agents (FFM) according to the invention.
  • Aqueous solutions having an anionic surfactant content of 5% and 15% (active ingredient) and containing 1% (active ingredient) of the color fixing agents were prepared and visually evaluated (see Tables 1 and 2).
  • the pH was not regulated.
  • the surfactant solutions without color fixing agents served as reference.
  • Table 1 Incompatibility of anionic surfactants, 5%, pH tq. with color fixatives 5% surfactant solutions with 1% FFM added ... surfactants without FFM FFM 1 FFM 2 FFM 3 FFM 4 Sec.
  • An anionic liquid detergent formulation having a total surfactant content of 26% (active ingredient) was prepared.
  • anionic surfactants linear alkyl benzene sulfonate and soap, nonionic surfactant C 12/14 alkyl 7EO ethoxylate, and color dye FFM 5 were used.
  • Table 6 Anionic, 26% liquid detergent containing FFM 5 Composition: Formulation: A Lin. alkylbenzenesulfonate 6.3% Kali and coconut soap 3.3% C12 / 14-alkyl-7EO ethoxylate 16.3% 1,2-propanediol 5% FFM 5 1 % water ad 100% Evaluation: Dim, homogeneous
  • An anionic liquid detergent formulation having a total surfactant content of 26% (active ingredient) was prepared.
  • anionic surfactants linear alkyl benzene sulfonate and soap, nonionic surfactant C 12/14 alkyl 7EO ethoxylate and color fixing agent FFM 7 were used.
  • Table 7 Anionic, 26% liquid detergent containing FFM 7 Composition: Formulation: A Lin. alkylbenzenesulfonate 6.3% Kali and coconut soap 3.3% C12 / 14-alkyl-7EO ethoxylate 16.3% 1,2-propanediol 5% FFM 7 1 % water ad 100% Evaluation: Dim, homogeneous

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Description

Die Erfindung betrifft flüssige Wasch- und Reinigungsmittel für Textilien, die ein oder mehrere Farbfixiermittel enthalten.The invention relates to liquid laundry detergents and cleaners for textiles containing one or more color fixing agents.

Neben den Waschpulvern stellen heute Flüssigwaschmittel eine sehr wichtige Produktgruppe unter den Waschmitteln für Textilien dar.
Flüssigwaschmittel enthalten als Hauptbestandteil Tenside. Dabei werden in modernen Waschmitteln in der Regel mehrere Tenside gleichzeitig eingesetzt. Bewährt hat sich hierbei die Kombination von anionischen und nichtionischen Tensiden.
Üblicherweise werden als anionische Tenside lineare Alkylbenzolsulfonate (LAS), Fettalkoholsulfate (FAS), sekundäre Alkansulfonate (SAS) und zum Teil auch Fettalkoholethersulfate (FAES) eingesetzt. Als nichtionische Tenside kommen Ethoxylate von langkettigen, synthetischen Alkoholen, z.B. der Oxoalkohole, oder von nativen Fettalkoholen zum Einsatz.
Als weitere wesentliche Bestandteile werden Gerüststoffe wie z.B. Polycarboxylate und Lösungsvermittler wie z.B. Ethanol, Glyzerin oder Propandiol verwendet.
Ferner sind in der Regel in geringen Einsatzkonzentrationen additive Bestandteile enthalten, die man unter dem Begriff Waschhilfsstoffe zusammenfassen kann und die so unterschiedliche Wirkstoffgruppen wie Schaumregulatoren, Vergrauungsinhibitoren, Soil Release Polymere, Enzyme, optische Aufheller, Farbübertragungsinhibitoren und Farbfixiermittel umfassen.
Die Farbfixiermittel verhindern das Verblassen farbiger Textilien, welches besonders bei dunkel gefärbten Textilien aus Baumwolle und Baumwollmischgeweben über mehrere Waschzyklen hinweg auftritt. Im Falle hochwertig gefärbter Textilien findet das Verblassen der Farben über einen längeren Gebrauchszeitraum statt.
Wenn dagegen die Farbstoffe eines gefärbten Textils schlecht fixiert sind, also das Textil "ausblutet", wirken die Farbfixiermittel gleichzeitig als Farbübertragungsinhibitoren und verhindern ein Anfärben von mitgewaschenen, andersfarbigen oder weißen Textilien.
Leider ist die Verwendung von Farbfixiermitteln in Flüssigwaschmitteln in der Praxis auf nichtionische Formulierungen beschränkt, also auf Formulierungen, die keine Aniontenside enthalten. Der Grund hierfür liegt in der mangelnden Verträglichkeit der anionischen Tenside mit den Farbfixiermitteln, die zu einer Flockung, Fällung oder Phasentrennung der Komponenten führt.In addition to washing powders, liquid detergents are today a very important product group among laundry detergents for textiles.
Liquid detergents contain surfactants as their main constituent. As a rule, several surfactants are used simultaneously in modern detergents. The combination of anionic and nonionic surfactants has proven useful here.
Usually, anionic surfactants used are linear alkylbenzenesulfonates (LAS), fatty alcohol sulfates (FAS), secondary alkanesulfonates (SAS) and, in some cases, fatty alcohol ether sulfates (FAES). Nonionic surfactants used are ethoxylates of long-chain, synthetic alcohols, for example the oxo alcohols, or of native fatty alcohols.
As further essential ingredients builders such as polycarboxylates and solubilizers such as ethanol, glycerol or propanediol are used.
In addition, additive ingredients which are generally included in low use concentrations and which may be grouped together under the term washing aids and which comprise such different active ingredient groups as foam regulators, grayness inhibitors, soil release polymers, enzymes, optical brighteners, dye transfer inhibitors and dye fixing agents are generally included.
The color fixing agents prevent the fading of colored textiles, which occurs especially in dark-colored textiles made of cotton and cotton blends over several washing cycles away. In the case of high-quality dyed textiles, the colors fade over a longer period of use.
If, on the other hand, the dyestuffs of a dyed textile are poorly fixed, ie the fabric "bleeds", the dye fixatives act simultaneously as Color transfer inhibitors and prevent staining mitgewaschenen, other colored or white textiles.
Unfortunately, the use of dye fixing agents in liquid detergents in practice is limited to nonionic formulations, that is, to formulations which contain no anionic surfactants. The reason for this is the lack of compatibility of the anionic surfactants with the color fixing agents, which leads to flocculation, precipitation or phase separation of the components.

Auf der anderen Seite kann man nicht auf anionische Tenside verzichten, wenn die Waschmittelformulierung ein möglichst gutes Waschvermögen besitzen soll.On the other hand, one can not do without anionic surfactants if the detergent formulation should have the best possible detergency.

EP 1236793 offenbart ein flüssiges Waschmittel enthaltend Seife, ein nichtionisches Tensid, ein sekundäres Alkansulfonat und ein Farbfixiermittel. EP 1236793 discloses a liquid detergent containing soap, a nonionic surfactant, a secondary alkanesulfonate and a color fixing agent.

Der Zweck der vorliegenden Erfindung ist es, flüssige Wasch- und Reinigungsmittel-formulierungen für Textilien zur Verfügung zu stellen, welche ein oder mehrere Farbfixiermittel in Kombination mit einem anionischen Tensid enthalten und welche, trotz der potentiellen Unverträglichkeit der Komponenten, physikalisch wie chemisch stabil sind.The purpose of the present invention is to provide liquid washing and cleaning agent formulations for textiles which contain one or more color fixing agents in combination with an anionic surfactant and which are physically and chemically stable despite the potential incompatibility of the components.

Es wurde nun überraschenderweise gefunden, dass dieses Ziel durch ein Tensidsystem erreicht werden kann, in welchem als Aniontensid Alkylbenzolsulfonat und/oder Olefinsulfonat und/oder Alkylsulfat in Kombination mit Seife und einem nichtionischen Tensid enthalten ist.It has now surprisingly been found that this object can be achieved by a surfactant system in which the anionic surfactant is alkylbenzenesulfonate and / or olefinsulfonate and / or alkylsulfate in combination with soap and a nonionic surfactant.

Gegenstand der Erfindung sind flüssige Wasch- und Reinigungsmittel nach Anspruch 1.The invention relates to liquid detergents and cleaners according to claim 1.

Die einzelnen Komponenten werden im folgenden beschrieben:

  • a1) Alkylbenzolsulfonat. Die Alkylgruppe kann verzweigt oder linear und gegebenenfalls mit einer Hydroxylgruppe substituiert oder ungesättigt (= Alkenyl) sein. Die bevorzugten Alkylbenzolsulfonate enthalten lineare Alkylketten mit ca. 9 bis 25 Kohlenstoffatomen, bevorzugt von ca. 10 bis ca. 13 Kohlenstoffatome, das Kation ist Natrium, Kalium, Ammonium, Mono-, Di- oder Triethanolammonium, Calcium oder Magnesium und Mischungen davon. Für milde Tensidsysteme ist Magnesium als Kation bevorzugt, für Standardwaschanwendungen dagegen Natrium.
  • a2) Olefinsulfonate werden durch Sulfonierung von C8-C24-, vorzugsweise C14-C16-α-Olefinen mit Schwefeltrioxid und anschließende Neutralisation erhalten. Bedingt durch das Herstellverfahren, können diese Olefinsulfonate kleinere Mengen an Hydroxyalkansulfonaten und Alkandisulfonaten enthalten. Spezielle Mischungen von α-Olefinsulfonaten sind in US-3,332,880 beschrieben.
  • a3) Alkylsulfate sind hier wasserlösliche Salze oder Säuren der Formel ROSO3M, worin R ein C10-C24-Kohlenwasserstoffrest, bevorzugt ein C10-C20-Alkyl- oder Hydroxyalkylrest, besonders bevorzugt ein C12-C18 Alkyl- oder Hydroxyalkylrest ist.
    M ist Wasserstoff oder ein Kation, z.B. ein Alkalimetallkation (z.B. Natrium, Kalium, Lithium) oder Ammonium oder substituiertes Ammonium, z.B. Methyl-, Dimethyl- und Trimethyl-ammoniumkationen, Alkanolammonium, z.B. Triethanolammonium und quaternäre Ammoniumkationen, wie Tetramethylammonium- und Dimethylpiperidinium-kationen und quartäre Ammoniumkationen, abgeleitet von Alkylaminen wie Ethylam in, Diethylamin, Triethylamin und Mischungen davon.
    Alkylketten mit C12-C16 sind für niedrige Waschtemperaturen (z.B. unter ca. 50°C) und Alkylketten mit C16-C18 für höhere Waschtemperaturen (z.B. oberhalb ca. 50°C) bevorzugt.
The individual components are described below:
  • a1) alkylbenzenesulfonate. The alkyl group can be branched or linear and optionally substituted by one hydroxyl group or unsaturated (= alkenyl). The preferred alkylbenzenesulfonates contain linear alkyl chains of about 9 to 25 carbon atoms, preferably from about 10 to about 13 carbon atoms, the cation being sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium and mixtures thereof. For mild surfactant systems, magnesium is preferred as a cation, whereas sodium is preferred for standard washing applications.
  • a2) Olefinsulfonates are obtained by sulfonation of C 8 -C 24 -, preferably C 14 -C 16 -α-olefins with sulfur trioxide and subsequent neutralization. Due to the preparation process, these olefin sulfonates may contain minor amounts of hydroxyalkanesulfonates and alkanedisulfonates. Specific mixtures of α-olefin sulfonates are in US 3,332,880 described.
  • a3) Alkyl sulfates here are water-soluble salts or acids of the formula ROSO 3 M, wherein R is a C 10 -C 24 -hydrocarbon radical, preferably a C 10 -C 20 -alkyl or hydroxyalkyl radical, particularly preferably a C 12 -C 18 -alkyl or Hydroxyalkyl radical.
    M is hydrogen or a cation, for example an alkali metal cation (for example sodium, potassium, lithium) or ammonium or substituted ammonium, for example methyl, dimethyl and trimethylammonium cations, alkanolammonium, for example triethanolammonium and quaternary ammonium cations, such as tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof.
    Alkyl chains with C 12 -C 16 are preferred for low wash temperatures (eg below about 50 ° C) and alkyl chains with C 16 -C 18 for higher wash temperatures (eg above about 50 ° C).

Die Komponenten a1, a2 und a3 werden einzeln oder in Kombination in Konzentrationen von insgesamt 3 bis 30 Gew.-%, bevorzugt zu 5 bis 20 Gew.-%, besonders bevorzugt zu 7 bis 17 Gew.-% und ganz besonders bevorzugt zu 7 bis 15 Gew.-% eingesetzt.

  • b) Bei Seife handelt es sich um die Salze langkettiger, nativer Fettsäuren mit 10 bis 22 C-Atomen. Als Fettsäure für Seifen in Flüssigwaschmitteln kommt insbesondere die Kokosfettsäure zum Einsatz, welche hauptsächlich ein Gemisch von C12- und C14-Fettsäure darstellt. Es können aber auch längerkettige Fettsäuren wie Ölsäure, Sojafettsäure, Talgfettsäure, Stearinsäure, Behensäure oder deren Gemische verwendet werden. Eingesetzt werden können die Fettsäuren als Seifen in der Form ihrer Na-, K-, Ammonium-, Mono-, Di- oder Triethanolammoniumsalze.
    Besonders bevorzugt für Flüssigwaschmittel sind die K-, Ammonium-, Mono-, Di- oder Triethanolammoniumsalze der Kokosfettsäure, der Sojafettsäure, der Ölsäure und ihrer Mischungen untereinander oder ggf. mit andere n Fettsäuren.
    In den erfindungsgemäßen Flüssigwaschmitteln wird Seife zu 1 bis 30 Gew.-%, bevorzugt zu 5 bis 25 Gew.-% und besonders bevorzugt zu 10 bis 20 Gew.-% eingesetzt.
  • c) Als nichtionische Tenside kommen insbesondere die Ethoxylate langkettiger, aliphatischer, synthetischer oder nativer Alkohole mit einem C8- bis C22-Alkylrest in Betracht. Diese können ca. 1 bis ca. 25 mol Ethylenoxid enthalten. Die Alkylkette der aliphatischen Alkohole kann linear oder verzweigt, primär oder sekundär, gesättigt oder auch ungesättigt sein.
    Bevorzugt sind die Kondensationsprodukte von C10- bis C18-Alkoholen mit ca. 2 bis ca. 18 mol Ethylenoxid pro mol Alkohol. Die Alkoholethoxylate können eine enge ("Narrow Range Ethoxylates") oder eine breite Homologenverteilung des Ethylenoxides ("Broad Range Ethoxylates") aufweisen. Besonders bevorzugt sind der C9-C11 Oxoalkohol mit 6 bis 10 mol EO und der C12/C14-Fettalkohol mit 5 bis 9 mol EO. Ganz besonders bevorzugt sind das C11-Oxoalkohol-8EO-ethoxylat und das C12/14-Fettalkohol-7EO-ethoxylat. Die oxethylierten Alkohole weisen vorzugsweise einen HLB-Wert von 10 bis 15, vorzugsweise 11 bis 14 auf. Die Einsatzkonzentration liegt im allgemeinen bei 5 bis 35 Gew.-%, bevorzugt bei 10 bis 30 Gew.-%, besonders bevorzugt bei 15 bis 25 Gew.-% und ganz besonders bevorzugt bei 16 bis 23 Gew.-%.
The components a1, a2 and a3 are used individually or in combination in concentrations of from 3 to 30% by weight, preferably from 5 to 20% by weight, more preferably from 7 to 17% by weight and most preferably from 7 used to 15 wt .-%.
  • b) Soaps are the salts of long-chain, native fatty acids with 10 to 22 carbon atoms. Suitable fatty acid soaps for liquid detergents in particular coconut fatty acid, which constitutes mainly a mixture of C 12 -, and C 14 fatty acid. However, it is also possible to use longer-chain fatty acids such as oleic acid, soybean fatty acid, tallow fatty acid, stearic acid, behenic acid or mixtures thereof. The fatty acids can be used as soaps in the form of their sodium, potassium, ammonium, mono-, di- or triethanolammonium salts.
    Particularly preferred for liquid detergents are the K, ammonium, mono-, di- or triethanolammonium salts of coconut fatty acid, soybean fatty acid, oleic acid and their mixtures with each other or optionally with other fatty acids.
    In the liquid detergents according to the invention, soap is used at 1 to 30% by weight, preferably at 5 to 25% by weight and particularly preferably at 10 to 20% by weight.
  • c) Suitable nonionic surfactants are, in particular, the ethoxylates of long-chain, aliphatic, synthetic or native alcohols having a C 8 - to C 22 -alkyl radical. These may contain about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohols may be linear or branched, primary or secondary, saturated or unsaturated.
    Preference is given to the condensation products of C 10 - to C 18 -alcohols with about 2 to about 18 moles of ethylene oxide per mole of alcohol. The alcohol ethoxylates may have a narrow range ("narrow range ethoxylates") or a broad homolog distribution of the ethylene oxide ("Broad Range Ethoxylates"). Particularly preferred the C 9 -C 11 oxoalcohol with 6 to 10 mol EO and the C 12 / C14 fatty alcohol with 5 to 9 mol EO. Very particular preference is given to the C 11 -oxoalcohol-8EO-ethoxylate and the C 12/14 -fatty alcohol 7EO-ethoxylate. The ethoxylated alcohols preferably have an HLB value of 10 to 15, preferably 11 to 14. The use concentration is generally from 5 to 35% by weight, preferably from 10 to 30% by weight, more preferably from 15 to 25% by weight and most preferably from 16 to 23% by weight.

Das Massenverhältnis Aniontenside zu Nichtionischen Tensiden beträgt im allgemeinen 1:4 bis 4:1, bevorzugt 1:2 bis 2:1, insbesondere 0,8 zu 1 bis 1,5 zu 1.The mass ratio of anionic surfactants to nonionic surfactants is generally from 1: 4 to 4: 1, preferably from 1: 2 to 2: 1, in particular from 0.8 to 1 to 1.5: 1.

Die Farbfixiermittel, die in erfindungsgemäßen Flüssigwaschmitteln eingearbeitet werden können, sind nichtionisch oder kationisch und werden im Folgenden beschrieben:The color fixing agents which can be incorporated in liquid detergents according to the invention are nonionic or cationic and are described below:

Polykondensate, die als Farbfixiermittel eingesetzt werden können, werden durch die Umsetzung von Cyanamiden mit Aldehyden und Ammoniumsalzen und/oder Monoaminen (z.B. Farbfixiermittel FFM 3), durch die Umsetzung von Monoaminen und/oder Polyaminen mit Epichlorhydrin (z.B. Farbfixiermittel FFM 2 und FFM 4), oder durch die Umsetzung von Polyaminen mit Cyanamiden und Amidoschwefelsäure (z.B. Farbfixiermittel FFM 1), erhalten.Polycondensates which can be used as dye fixing agents are prepared by the reaction of cyanamides with aldehydes and ammonium salts and / or monoamines (eg dye fixing agent FFM 3), by the reaction of monoamines and / or polyamines with epichlorohydrin (eg dye fixing agents FFM 2 and FFM 4). , or by the reaction of polyamines with cyanamides and amidosulfuric (eg color fixing FFM 1) obtained.

Die eingesetzten Monoamine können primäre, sekundäre und tertiäre Amine sein. Dabei kann es sich um aliphatische Amine wie z.B. Dialkylamine, insbesondere Dimethylamin, alicyclische Amine wie z.B. Cyclohexylamin und aromatische Amine wie z.B. Anilin handeln. Die verwendeten Amine können aber auch gleichzeitig aliphatische, alicyclische und aromatische Substituenten besitzen. Ferner können auch heterocyclische Verbindungen wie z.B. Pyridin eingesetzt werden.The monoamines used may be primary, secondary and tertiary amines. These may be aliphatic amines, e.g. Dialkylamines, especially dimethylamine, alicyclic amines, e.g. Cyclohexylamine and aromatic amines such as e.g. Aniline act. However, the amines used can also have aliphatic, alicyclic and aromatic substituents at the same time. Furthermore, heterocyclic compounds such as e.g. Pyridine can be used.

Der Begriff Polyamine umfasst hierbei z.B. Diamine, Triamine, Tetraamine, u.s.w., sowie die analogen N-Alkyl-polyamine bzw. die N,N-Dialkyl-polyamine.The term polyamines here includes, for example, diamines, triamines, tetraamines, etc, as well as the analogous N-alkyl-polyamines or the N, N-dialkyl-polyamines.

Beispiele hierfür sind Ethylendiamin, Propylendiamin, Butylendiamin, Pentylendiamin, Hexylendiamin, Diethylentriamin, Triethylentetraamin und höhere Polyamine.
Besonders bevorzugte Polyamine sind Ethylendiamin, Diethylentriamin und Dimethylaminopropylamin.
Bei den Ammoniumsalzen handelt es sich um Salze des Ammoniaks, insbesondere um Ammoniumchlorid oder der oben erwähnten Amine bzw. Polyamine mit verschiedenen anorganischen oder organischen Säuren oder auch um quartäre Ammoniumsalze.Examples of these are ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, diethylenetriamine, triethylenetetraamine and higher polyamines.
Particularly preferred polyamines are ethylenediamine, diethylenetriamine and dimethylaminopropylamine.
The ammonium salts are salts of ammonia, in particular ammonium chloride or the above-mentioned amines or polyamines with various inorganic or organic acids or quaternary ammonium salts.

Bei den Cyanamiden kann es sich um Cyanamid oder um Dicyandiamid handeln. Aldehyde, die zur Synthese der Farbfixiermittel eingesetzt werden können, sind zum Beispiel aliphatische Aldehyde wie z.B. Formaldehyd, Acetaldehyd, Propionaldehyd, Butyraldehyd; Dialdehyde wie z.B. Glyoxal; ungesättigte Aldehyde wie z.B. Acrolein, Crotonaldehyd und aromatische Aldehyde wie z.B. Benzaldehyd. Besonders bevorzugt sind die aliphatischen Aldehyde, insbesondere Formaldehyd.The cyanamides may be cyanamide or dicyandiamide. Aldehydes that can be used to synthesize the color fixing agents include, for example, aliphatic aldehydes, e.g. Formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde; Dialdehydes, e.g. glyoxal; unsaturated aldehydes, e.g. Acrolein, crotonaldehyde and aromatic aldehydes, e.g. Benzaldehyde. Particularly preferred are the aliphatic aldehydes, in particular formaldehyde.

Als Farbfixiermittel können weiterhin Homo- und Co-Polymere auf Basis von Diallyl-dimethyl-ammonium-chlorid (DADMAC) eingesetzt werden (z.B. Farbfixiermittel FFM 5, FFM 6 und FFM 7).
Copolymere auf Basis DADMAC enthalten als weitere Komponenten andere vinylische Monomere wie z.B. Vinylimidazol, Vinylpyrrolidon, Vinylalkohol, Vinylacetat, (Meth-)-Acrylsäure(-ester), Acrylamid, Styrol, Styrolsulfonsäure, Acrylamidomethylpropan-sulfonsäure (AMPS) u.s.w. Homopolymere auf Basis DADMAC sind auch erhältlich unter den Handelsnamen Dodigen® 3954, Dodigen 4033 und Genamin® PDAC (Fa. Clariant).It is also possible to use homo- and co-polymers based on diallyl-dimethylammonium chloride (DADMAC) as dye-fixing agents (eg dye-fixing agents FFM 5, FFM 6 and FFM 7).
Copolymers based on DADMAC contain as other components other vinylic monomers such as vinylimidazole, vinylpyrrolidone, vinyl alcohol, vinyl acetate, (meth) acrylic acid (ester), acrylamide, styrene, styrenesulfonic acid, acrylamidomethylpropane-sulfonic acid (AMPS), etc. homopolymers based on DADMAC also available under the trade names Dodigen ® 3954, Dodigen 4033 and Genamin ® PDAC (Fa. Clariant).

Die Farbfixiermittel werden in den Flüssigwaschmitteln im Allgemeinen in Mengen von 0,25 bis 5 Gew.-%, bevorzugt zu 0,5 bis 3 Gew.-% und besonders bevorzugt zu 0,5 bis 1 Gew.-% eingesetzt.The dye fixing agents are generally used in the liquid detergents in amounts of from 0.25 to 5% by weight, preferably from 0.5 to 3% by weight and more preferably from 0.5 to 1% by weight.

Die erfindungsgemäßen Flüssigwaschmittel sind bevorzugt flüssig und haben eine Viskosität von max. 500 mPas. Sie können aber auch höherviskose, noch fließfähige Gele oder streichfähige Pasten sein.The liquid detergents according to the invention are preferably liquid and have a viscosity of max. 500 mPas. But they can also be higher viscosity, still flowable gels or spreadable pastes.

In einer besonders bevorzugten Ausführungsform enthalten die erfindungsgemäßen Wasch- und Reinigungsmittel als Lösungsmittel Propandiol, Glyzerin oder Ethanol in eine Konzentration von 1 bis 10 Gew.-%, bevorzugt zu 1 bis 5 Gew.-%.In a particularly preferred embodiment, the detergents and cleaners according to the invention contain as solvent propanediol, glycerol or ethanol in a concentration of 1 to 10% by weight, preferably 1 to 5% by weight.

In einer weiteren besonders bevorzugten Ausführungsform wird der pH-Wert der Formulierungen durch die Zugabe saurer oder alkalischer Stoffe auf einen Wert zwischen 5 und 12 eingestellt. Saure Stoffe können z.B. anorganische oder organische Säuren sein, wie z.B. Schwefelsäure, Phosphonsäuren, Zitronensäure. Alkalische Stoffe sind z.B. Natronlauge, Kalilauge und Soda. Saure bis neutrale Flüssigwaschmittel sind z.B. Wollwaschmittel, neutrale bis schwach alkalische Flüssigwaschmittel sind z.B. Feinwaschmittel und alkalische Waschmittel sind so genannte Vollwaschmittel.In a further particularly preferred embodiment, the pH of the formulations is adjusted to a value between 5 and 12 by the addition of acidic or alkaline substances. Acidic substances may e.g. inorganic or organic acids, e.g. Sulfuric acid, phosphonic acids, citric acid. Alkaline substances are e.g. Caustic soda, caustic soda and soda. Acid to neutral liquid detergents are e.g. Wool detergents, neutral to weak alkaline liquid detergents are e.g. Detergents and alkaline detergents are so-called heavy-duty detergents.

Flüssige Wasch- und Reinigungsmittel, welche die erfindungsgemäße Tensid-Farbfixiermittel-Kombination enthalten, können darüber hinaus weitere Bestandteile enthalten, wie sie in derartigen Mitteln üblich sind. Diese werden im Folgenden beschrieben.
Der Gesamttensidanteil der erfindungsgemäßen Waschmittelformulierungen kann dabei von 10 bis 70 Gew.-%, bevorzugt von 10 bis 55 Gew.-% und ganz besonders bevorzugt von 20 bis 50 Gew.-% sein.Liquid detergents and cleaners containing the surfactant-dye fixative combination of the present invention may further contain other ingredients conventional in such compositions. These are described below.
The total surfactant content of the detergent formulations according to the invention may be from 10 to 70% by weight, preferably from 10 to 55% by weight and very particularly preferably from 20 to 50% by weight.

Weitere anionische TensideOther anionic surfactants

Als weitere anionische Tenside Alkylestersulfonate und Alkylethersulfonate, in Betracht, Geeignete Kationen sind hierbei Alkalimetalle, wie z.B. Natrium oder Kalium oder Erdalkalimetalle, wie z.B. Calcium oder Magnesium, sowie Ammonium, substituierte Ammoniumverbindungen, einschließlich Mono-, Di- oder Triethanolammoniumkationen, und Mischungen daraus.Suitable further anionic surfactants are alkyl ester sulfonates and alkyl ether sulfonates, suitable cations being alkali metals, for example sodium or potassium or alkaline earth metals, for example calcium or magnesium, and also ammonium, substituted Ammonium compounds, including mono-, di- or Triethanolammoniumkationen, and mixtures thereof.

Alkylestersulfonate sind unter anderem lineare Ester von C8-C20-Carbonsäuren (d.h. Fettsäuren), welche mittels gasförmigem SO3 sulfoniert werden. Geeignete Ausgangsmaterialien sind natürliche Fette wie z.B. Talg, Kokosöl und Palmöl, können aber auch synthetischer Natur sein.Alkyl ester sulfonates include linear esters of C 8 -C 20 carboxylic acids (ie, fatty acids) which are sulfonated by means of gaseous SO 3 . Suitable starting materials are natural fats such as tallow, coconut oil and palm oil, but may also be synthetic in nature.

Bevorzugte Alkylestersulfonate, speziell für Waschmittelanwendungen, sind Verbindungen der Formel

Figure imgb0001
worin R1 einen C8-C20-Kohlenwasserstoffrest, bevorzugt Alkyl, und R einen C1-C6 Kohlenwasserstoffrest, bevorzugt Alkyl, darstellt. M steht für ein Kation, das ein wasserlösliches Salz mit dem Alkylestersulfonat bildet. Geeignete Kationen sind Natrium, Kalium, Lithium oder Ammoniumkationen, wie Monoethanolamin, Diethanolamin und Triethanolamin. Bevorzugt bedeuten R1 C10-C16-Alkyl und R Methyl, Ethyl oder Isopropyl. Besonders bevorzugt sind Methylestersulfonate, in denen R1 C10-C16-Alkyl bedeutet.Preferred alkyl ester sulfonates, especially for detergent applications, are compounds of the formula
Figure imgb0001
 wherein R 1 is a C 8 -C 20 hydrocarbon radical, preferably alkyl, and R is a C 1 -C 6 hydrocarbon radical, preferably alkyl. M is a cation which forms a water-soluble salt with the alkyl ester sulfonate. Suitable cations are sodium, potassium, lithium or ammonium cations, such as monoethanolamine, diethanolamine and triethanolamine. Preferably, R 1 is C 10 -C 16 -alkyl and R is methyl, ethyl or isopropyl. Particularly preferred are methyl ester sulfonates in which R 1 is C 10 -C 16 alkyl.

Alkylethersulfate sind wasserlösliche Salze oder Säuren der Formel RO(A)m SO3M, worin R einen unsubstituierten C10-C24-Alkyl- oder Hydroxyalkylrest, bevorzugt einen C12-C20 Alkyl- oder Hydroxyalkylrest, besonders bevorzugt C12-C18-Alkyl- oder Hydroxyalkylrest darstellt.
A ist eine Ethoxy- oder Propoxyeinheit, m ist eine Zahl größer als 0, vorzugsweise zwischen ca. 0,5 und ca. 6, besonders bevorzugt zwischen ca. 0,5 und ca. 3 und M ist ein Wasserstoffatom oder ein Kation wie z.B. Natrium, Kalium, Lithium, Calcium, Magnesium, Ammonium oder ein substituiertes Ammoniumkation. Spezifische Beispiele von substituierten Ammoniumkationen sind Methyl-, Dimethyl-, Trimethylammonium- und quarternäre Ammoniumkationen wie Tetramethylammonium und Dimethylpiperidiniumkationen sowie solche, die von Alkylaminen, wie Ethylamin, Diethylamin, Triethylamin oder Mischungen davon abgeleitet sind. Als Beispiele seien C12- bis C18-Fettalkoholethersulfate genannt wobei der Gehalt an EO 1, 2, 2.5, 3 oder 4 mol pro mol des Fettalkoholethersulfats beträgt, und in denen M Natrium oder Kalium ist. Aufgrund ihrer starken Schaumentwicklung ist die Einsatzkonzentration der Alkylethersulfate von dem Einsatzzweck abhängig. In Waschmitteln für die maschinelle Wäsche kommen geringere Konzentrationen zur Anwendung als in Waschmitteln für die manuelle Wäsche. Die in der Praxis anzutreffenden Konzentrationen liegen zwischen 1 bis 20 Gew.-%. Für die vorliegende Erfindung bevorzugt sind Konzentrationen von 1 bis 10 Gew.-% und bevorzugt von 1 bis 5 Gew.-%.Alkyl ether sulfates are water-soluble salts or acids of the formula RO (A) m SO 3 M, where R is an unsubstituted C 10 -C 24 -alkyl or hydroxyalkyl radical, preferably a C 12 -C 20 -alkyl or hydroxyalkyl radical, more preferably C 12 -C 18 represents alkyl or hydroxyalkyl.
A is an ethoxy or propoxy moiety, m is a number greater than 0, preferably between about 0.5 and about 6, more preferably between about 0.5 and about 3 and M is a hydrogen atom or a cation such as Sodium, potassium, lithium, calcium, magnesium, ammonium or a substituted ammonium cation. Specific examples of substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine or mixtures thereof. Examples C 12 were - to C 18 called fatty alcohol ether sulfates wherein the content of EO is 1, 2, 2.5, 3, or 4 mol per mol of fatty alcohol ether sulfate, and in which M is sodium or potassium. Due to their strong foam development, the use concentration of the alkyl ether sulfates depends on the intended use. Detergent laundry detergents use lower concentrations than laundry detergents. The ones encountered in practice Concentrations are between 1 to 20 wt .-%. Concentrations of from 1 to 10% by weight and preferably from 1 to 5% by weight are preferred for the present invention.

Nichtionische Tenside, die zusätzlich zu den eingangs erwähnten eingesetzt werden können.Nonionic surfactants, which can be used in addition to those mentioned above.

Kondensationsprodukte von Ethylenoxid mit einer hydrophoben Basis, gebildet durch Kondensation von Propylenoxid mit Propylenglykol.Condensation products of ethylene oxide having a hydrophobic base formed by condensation of propylene oxide with propylene glycol.

Der hydrophobe Teil dieser Verbindungen weist bevorzugt ein Molekulargewicht zwischen ca. 1500 und ca. 1800 auf. Die Anlagerung von Ethylenoxid an diesen hydrophoben Teil führt zu einer Verbesserung der Wasserlöslichkeit. Das Produkt ist flüssig bis zu einem Polyoxyethylengehalt von ca. 50 % des Gesamtgewichtes des Kondensationsproduktes, was einer Kondensation mit bis zu ca. 40 mol Ethylenoxid entspricht. Kommerziell erhältliche Beispiele dieser Produktklasse sind die Pluronic®-Marken der BASF und die ®Genapol PF-Marken der Clariant GmbH.The hydrophobic part of these compounds preferably has a molecular weight between about 1500 and about 1800. The addition of ethylene oxide to this hydrophobic part leads to an improvement in water solubility. The product is liquid up to a polyoxyethylene content of about 50% of the total weight of the condensation product, which corresponds to a condensation with up to about 40 moles of ethylene oxide. Commercially available examples of this product class are the Pluronic ® brands from BASF and the ® Genapol PF brands from Clariant GmbH.

Kondensationsprodukte von Ethylenoxid mit einem Reaktionsprodukt von Propylenoxid und Ethylendiamin.Condensation products of ethylene oxide with a reaction product of propylene oxide and ethylenediamine.

Die hydrophobe Einheit dieser Verbindungen besteht aus dem Reaktionsprodukt von Ethylendiamin mit überschüssigem Propylenoxid und weist im Allgemeinen ein Molekulargewicht von ca. 2500 bis 3000 auf. An diese hydrophobe Einheit wird Ethylenoxid bis zu einem Gehalt von ca. 40 bis ca. 80 Gew.-% Polyoxyethylen und einem Molekulargewicht von ca. 5000 bis 11000 addiert. Kommerziell erhältliche Beispiele dieser Verbindungsklasse sind die ®Tetronic-Marken der BASF und die ®Genapol PN-Marken der Clariant GmbH. Polyethylen-, Polypropylen- und Polybutylenoxidkondensate von Alkylphenolen.The hydrophobic moiety of these compounds consists of the reaction product of ethylenediamine with excess propylene oxide and generally has a molecular weight of about 2500 to 3000. Ethylene oxide is added to this hydrophobic unit to a content of about 40 to about 80 wt .-% polyoxyethylene and a molecular weight of about 5000 to 11000. Commercially available examples of this class of compounds are the ® Tetronic brands of BASF and the ® Genapol PN brands of Clariant GmbH. Polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols.

Diese Verbindungen umfassen die Kondensationsprodukte von Alkylphenolen mit einer C6- bis C20-Alkylgruppe, die entweder linear oder verzweigt sein kann, mit Alkenoxiden. Bevorzugt sind Verbindungen mit ca. 5 bis 25 mol Alkenoxid pro mol Alkylphenol. Kommerziell erhältliche Tenside diesen Typs sind z.B. Igepal® CO-630, Triton® X-45, X-114, X-100 und X102, und die ®Arkopal-N-Marken der Clariant GmbH. Diese Tenside werden als Alkylphenolalkoxilate, z.B. Alkylphenolethoxilate, bezeichnet.These compounds include the condensation products of alkylphenols having a C 6 to C 20 alkyl group, which may be either linear or branched, with alkene oxides. Preference is given to compounds having about 5 to 25 mol of alkene oxide per mole of alkylphenol. Commercially available surfactants of this type include Igepal ® CO-630, Triton ® X-45, X-114, X-100 and X102, and the Arkopal N ® brands from Clariant GmbH. These surfactants are referred to as Alkylphenolalkoxilate, eg Alkylphenolethoxilate.

Semipolare nichtionische TensideSemipolar nonionic surfactants

Diese Kategorie von nichtionischen Verbindungen umfasst wasserlösliche Aminoxide, wasserlösliche Phosphinoxide und wasserlösliche Sulfoxide, jeweils mit einem Alkylrest von ca. 8 bis ca. 18 Kohlenstoffatomen. Semipolare nichtionische Tenside sind auch Aminoxide der Formel

Figure imgb0002
This category of nonionic compounds includes water-soluble amine oxides, water-soluble phosphine oxides, and water-soluble sulfoxides each having an alkyl group of from about 8 to about 18 carbon atoms. Semi-polar nonionic surfactants are also amine oxides of the formula
Figure imgb0002

R ist hierbei eine Alkyl-, Hydroxyalkyl- oder Alkylphenolgruppe mit einer Kettenlänge von ca. 8 bis ca. 22 Kohlenstoffatomen, R2 ist eine Alkylen- oder Hydroxyalkylengruppe mit ca. 2 bis 3 Kohlenstoffatomen oder Mischungen hiervon, jeder Rest R1 ist eine Alkyl- oder Hydroxy-alkylgruppe mit ca. 1 bis ca. 3 Kohlenstoffatomen oder eine Polyethylenoxidgruppe mit ca. 1 bis ca- 3 Ethylenoxideinheiten und x bedeutet eine Zahl von 0 bis etwa 10. Die R1-Gruppen können miteinander über ein Sauerstoff- oder Stickstoffatom verbunden sein und somit einen Ring bilden.
Besonders bevorzugte Aminoxide sind C8-C18-Alkyl-dimethyl-aminoxide und C8-C12-Alkoxiethyl-dihydroxyethyl-aminoxide und C8-C18-Fettsäureamidoalkyldimethyl-aminoxide. Aminoxide können in Einsatzkonzentrationen von 0,5 bis 10 Gew.-% und bevorzugt zwischen 1 und 5 Gew.-% eingesetzt werden.R here is an alkyl, hydroxyalkyl or alkylphenol group having a chain length of about 8 to about 22 carbon atoms, R 2 is an alkylene or hydroxyalkylene group having about 2 to 3 carbon atoms or mixtures thereof, each R 1 is an alkyl or hydroxy alkyl group having from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about - 3 ethylene oxide units, and x denotes a number from 0 to about 10. The R 1 - Groups may be linked to each other via an oxygen or nitrogen atom and thus form a ring.
Particularly preferred amine oxides are C 8 -C 18 -alkyl-dimethyl-amine oxides and C 8 -C 12 -alkoxy-diethyl-dihydroxyethyl-amine oxides and C 8 -C 18 fatty acid-amidoalkyl-dimethyl-amine oxides. Amine oxides can be used in use concentrations of 0.5 to 10 wt .-%, and preferably between 1 and 5 wt .-%.

Fettsäureamidefatty acid amides Fettsäureamide besitzen die FormelFatty acid amides have the formula

Figure imgb0003
worin R eine Alkylgruppe mit ca. 7 bis ca. 21, bevorzugt ca. 9 bis ca. 17 Kohlenstoffatomen ist und jeder Rest R1 Wasserstoff, C1-C4-Alkyl, C1-C4-Hydroxyalkyl oder (C2H4O)xH bedeutet, wobei x von ca. 1 bis ca. 3 variiert. Bevorzugt sind die C8-C20-Fettsäureamide, insbesondere die entsprechenden Monoethanolamide, Diethanolamide und Isopropanolamide. Diese können in Konzentrationen zwischen 0,5 bis 5 Gew.-% und insbesondere von 0,5 bis 3 Gew.-% eingesetzt werden.
Figure imgb0003
 wherein R is an alkyl group having from about 7 to about 21, preferably about 9 to about 17 carbon atoms and each R 1 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl or (C 2 H 4 O) x H, where x varies from about 1 to about 3. Preference is given to the C 8 -C 20 -fatty acid amides, in particular the corresponding monoethanolamides, diethanolamides and isopropanolamides. These can be used in concentrations between 0.5 to 5 wt .-% and in particular from 0.5 to 3 wt .-%.

Weitere geeignete nichtionische Tenside sind Alkyl- und Alkenyloligoglycoside sowie Fettsäurepolyglykolester oder Fettaminpolyglykolester mit jeweils 8 bis 20, vorzugsweise 12 bis 18 C-Atomen im Fettalkylrest, alkoxylierte Triglycamide, Mischether oder Mischformyle, Alkyloligoglycoside, Alkenyloligoglycoside, Fettsäure-N-alkylglucamide, Phosphinoxide, Dialkylsulfoxide und Proteinhydrolysate.Further suitable nonionic surfactants are alkyl and Alkenyloligoglycoside and Fettsäurepolyglykolester or Fettaminpolyglykolester having in each case 8 to 20, preferably 12 to 18 carbon atoms in the fatty alkyl, alkoxylated triglycamides, mixed ethers or Mischformyle, Alkyloligoglycoside, Alkenyloligoglycoside, fatty acid N-alkylglucamides, phosphine oxides, dialkyl sulfoxides and protein.

Weitere Waschmittelinhaltsstoffe, die in der vorliegenden Erfindung enthalten sein können, umfassen anorganische und/oder organische Gerüststoffe, um den Härtegrad des Wassers zu mindern.Other detergent ingredients that may be included in the present invention include inorganic and / or organic builders to reduce the degree of hardness of the water.

Anorganische Gerüststoffe umfassen beispielsweise Alkali-, Ammonium- und Alkanolammoniumsalze von Polyphosphaten wie etwa Tripolyphosphate, Pyrophosphate und glasartige polymere Metaphosphate, Phosphonate, Silikate, Carbonate einschließlich Bicarbonate und Sesquicarbonate und Aluminosilikate, wie folgend beschrieben:Inorganic builders include, for example, alkali, ammonium and alkanolammonium salts of polyphosphates such as tripolyphosphates, pyrophosphates and glassy polymeric metaphosphates, phosphonates, silicates, carbonates including bicarbonates, and sesquicarbonates and aluminosilicates, as described below:

Aluminosilikatgerüststoffe, insbesondere Zeolithe mit der Formel Naz[(AlO2)z(SiO2)y]·xH2O, worin z und y ganze Zahlen von mindestens 6 bedeuten, dass Verhältnis von z zu y zwischen 1,0 bis etwa 0,5 liegt, und x eine ganze Zahl von etwa 15 bis etwa 264 bedeutet.
Geeignete Ionentauscher auf Aluminosilikatbasis sind im Hand el erhältlich. Diese Aluminosilikate können von kristalliner oder amorpher Struktur sein und können natürlich vorkommend oder auch synthetisch hergestellt sein. Bevorzugte Ionentauscher auf der Basis synthetischer kristalliner Aluminos ilikate sind erhältlich unter der Bezeichnung Zeolith A, Zeolith P(B) und Zeolith X. Bevorzugt sind Aluminosilikate mit einem Partikeldurchmesser zwischen 0,1 und 10 µm.Aluminosilicate builders, particularly zeolites having the formula Na z [(AlO 2 ) z (SiO 2 ) y ] .xH 2 O, where z and y are integers of at least 6, the ratio of z to y is between 1.0 and about 0 , 5, and x is an integer from about 15 to about 264.
Suitable aluminosilicate-based ion exchangers are readily available. These aluminosilicates may be of crystalline or amorphous structure and may be naturally occurring or synthetically produced. Preferred ion exchangers based on synthetic crystalline aluminosilicates are obtainable under the name of zeolite A, zeolite P (B) and zeolite X. Preference is given to aluminosilicates having a particle diameter of between 0.1 and 10 μm.

Geeignete organische Gerüststoffe umfassen Polycarboxylverbindungen, wie beispielsweise Etherpolycarboxylate und Oxydisuccinate. Ebenfalls soll auf "TMS/TDS"-Gerüststoffe aus US-4,663,071 verwiesen werden.Suitable organic builders include polycarboxylic compounds such as ether polycarboxylates and oxydisuccinates. Likewise on "TMS / TDS" equipment from US 4,663,071 to get expelled.

Andere geeignete Gerüststoffe umfassen die Etherhydroxypolycarboxylate, Copolymere von Maleinsäureanhydrid mit Ethylen oder Vinylmethylether, 1,3,5-Trihydroxybenzol-2,4,6-trisulfonsäure und Carboxymethyloxybernsteinsäure, die Alkali-, Ammonium- und substituierten Ammoniumsalze von Polyessigsäuren wie z.B. Ethylendiamin-tetraessigsäure und Nitrilotriessigsäure, sowie Polycarbonsäuren, wie Mellithsäure, Bernsteinsäure, Oxydibernsteinsäure, Polymaleinsäure, Benzol-1,3,5-tricarbonsäure, Carboxymethyloxybernsteinsäure, sowie deren lösliche Salze.Other suitable builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, the alkali, ammonium and substituted ammonium salts of polyacetic acids such as e.g. Ethylenediamine-tetraacetic acid and nitrilotriacetic acid, and polycarboxylic acids, such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and their soluble salts.

Bevorzugte organische Gerüststoffe sind die Polycarboxylate auf Basis von Acrylsäure und/oder Maleinsäure, wie z.B. die Sokalan CP-Marken (BASF) oder die Acusol-Marken (Rhom and Haas), sowie Gerüststoffe auf Citratbasis, z.B. die Zitronensäure und ihre löslichen Salze, insbesondere das Natriumsalz.Preferred organic builders are the polycarboxylates based on acrylic acid and / or maleic acid, e.g. the Sokalan CP brands (BASF) or the Acusol brands (Rhom and Haas), as well as citrate-based builders, e.g. the citric acid and its soluble salts, in particular the sodium salt.

Weitere geeignete Gerüststoffe sind die 3,3-Dicarboxy-4-oxa-1 ,6-hexandioate und die verwandten Verbindungen.Other suitable builders are the 3,3-dicarboxy-4-oxa-1, 6-hexanedioates and the related compounds.

Gerüststoffe auf Phosphorbasis sind Alkalimetallphosphate, wie etwa Natriumtripolyphosphat, Natriumpyrophosphat und Natriumorthophosphat. Bevorzugt kommen für die vorliegende Erfindung Phosphonate, wie Ethan-1-hydroxy-1,1-diphosphonat (HEDP) und andere bekannte Phosphonate in Frage.Phosphorus-based builders are alkali metal phosphates such as sodium tripolyphosphate, sodium pyrophosphate, and sodium orthophosphate. Phosphonates, such as ethane 1-hydroxy-1,1-diphosphonate (HEDP) and other known phosphonates are preferably suitable for the present invention.

Die erfindungsgemäßen Flüssigwaschmittel, welche das Tensidsystem und ein Farbfixiermittel enthalten, können ferner die üblichen Hilfsstoffe enthalten, die die Reinigungswirkung verstärken, zur Pflege des zu waschenden Textils dienen oder die Gebrauchseigenschaften der Waschmittelzusammensetzung ändern.The liquid detergents according to the invention, which contain the surfactant system and a color fixing agent, may further contain the usual auxiliaries which enhance the cleaning action, serve to care for the textile to be washed or change the performance properties of the detergent composition.

Geeignete Hilfsmittel umfassen beispielsweise Enzyme, insbesondere Proteasen, Lipasen, Cellulasen, Amylasen und Mannanasen; Enzymstabilisatoren; Schaumverstärker; Schauminhibitoren, wie Silikonöle oder Paraffine; Korrosionsschutzmittel; Farbübertragungsinhibitoren; optische Aufheller; UV-Absorber; Bleichmittel; Konservierungsmittel; Alkalien; hydrotrope Verbindungen; Antioxidantien; Lösungsmittel bzw. Lösungsvermittler, wie Ethanol, Glycerin, Propandiol; Dispergiermittel; Anti-Redepositionsmittel; Vergrauungsinhibitoren; Weichmacher; Antistatika; Farbstoffe und Parfüme.Suitable adjuvants include, for example, enzymes, in particular proteases, lipases, cellulases, amylases and mannanases; Enzyme stabilizers; Foam boosters; Foam inhibitors, such as silicone oils or paraffins; Corrosion inhibitors; Color transfer inhibitors; optical brighteners; UV absorbers; Bleach; Preservatives; alkalis; hydrotrope compounds; antioxidants; Solvents or solubilizers, such as ethanol, glycerol, propanediol; dispersant; Anti-redeposition agents; graying; plasticizers; antistatic agents; Dyes and perfumes.

Farbstoffedyes

Der Begriff Farbstoffe umfasst hier sowohl wasserlösliche Farbstoffe als auch unlösliche Farbpigmente. Wasserlösliche Farbstoffe werden aber bevorzugt in Flüssigwaschmitteln verwendet. Hierzu gehören die Gruppen der Säurefarbstoffe, Direktfarbstoffe und Reaktivfarbstoffe. Diesen Gruppen lassen sich z.B. Vertreter der Azofarbstoffe, Metallkomplexfarbstoffe und der polycyclischen Farbstoffe zuordnen.The term dyes here includes both water-soluble dyes and insoluble color pigments. However, water-soluble dyes are preferably used in liquid detergents. These include the groups of acid dyes, direct dyes and reactive dyes. These groups can be e.g. Represent representatives of azo dyes, metal complex dyes and polycyclic dyes.

Parfümöle und RiechstoffePerfume oils and fragrances

Als Duft- bzw. Parfümöle können einzelne Riechstoffverbindungen, z.B. die synthetischen Produkte vom Typ der Ester, Ether, Aldehyde, Ketone, Alkohole und Kohlenwasserstoffe verwendet werden. Bevorzugt werden Mischungen verschiedener Riechstoffe verwendet, die gemeinsam eine ansprechende Duftnote erzeugen.As fragrance or perfume oils, individual perfume compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Preferably, mixtures of different fragrances are used, which together produce an attractive fragrance.

Parfümöle können auch natürliche Riechstoffgemische und ätherische Öle geringerer Flüchtigkeit enthalten.Perfume oils may also contain natural fragrance mixtures and lower-volatility essential oils.

Optische AufhellerOptical brighteners

Hierzu gehören insbesondere die Aufheller von Typ Diaminostilbene und Distyryl-Biphenyle.These include in particular the brighteners of the type diaminostilbene and distyryl biphenyls.

FarbübertragungsinhibitorenColor transfer inhibitors

Hierzu gehören Polyamin-N-oxide wie etwa Poly-(4-vinylpyridin-N-oxid), Poly-(4-vinylpyridin-betain), Polyvinylpyrrolidon und Copolymere von N-Vinylpyrrolidon mit N-Vinylimidazol und gegebenenfalls anderen Monomeren, Polyvinylimidazol, außerdem Cyclodextrine und Cyclodextrinderivate.These include polyamine N-oxides such as poly (4-vinylpyridine-N-oxide), poly (4-vinylpyridine-betaine), polyvinylpyrrolidone, and copolymers of N-vinylpyrrolidone with N-vinylimidazole and optionally other monomers, polyvinylimidazole, as well Cyclodextrins and cyclodextrin derivatives.

Die erfindungsgemäßen Wasch- und Reinigungsmittel zeichnen sich dadurch aus, dass sie klar oder zumindest opak durchscheinend bis schwach trüb sind. Wesentlich ist, dass diese Formulierungen stabil sind und nicht ausflocken. Sie bewirken eine farberhaltende und farbübertragungsinhibierende Wirkung, einen weich machenden Effekt, einen Antiknittereffekt und einen Schutz von mechanischem Verschleiß.The detergents and cleaning agents according to the invention are characterized in that they are clear or at least opaque translucent to slightly cloudy. It is essential that these formulations are stable and do not flocculate. They provide a color-retaining and color transfer inhibiting effect, a softening effect, an anti-wrinkle effect and protection of mechanical wear.

BeispieleExamples

Die Vergleichsbeispiele 1 bis 4 belegen die Unverträglichkeit von Aniontensiden mit den Farbfixiermitteln (FFM) und die Problematik der Herstellung stabiler anionischer Flüssigwaschmittel.
Die Beispiele 1 und 2 beschreiben erfindungsgemäße stabile, flüssige Waschmittelformulierungen auf Basis des Aniontensids Alkylbenzolsulfonat und polymeren Farbfixiermitteln (FFM).Comparative Examples 1 to 4 demonstrate the incompatibility of anionic surfactants with the color fixing agents (FFM) and the problem of preparing stable anionic liquid detergents.
Examples 1 and 2 describe stable, liquid detergent formulations based on the anionic surfactant alkylbenzenesulfonate and polymeric color fixing agents (FFM) according to the invention.

Folgende Aniontenside wurden für die Versuche verwendet:

Alkylbenzolsulfonat:
Marlon® A 365 = C10-C13-Alkylbenzolsulfonat, Na-Salz, 65 %ig
Olefinsulfonat:
Hostapur® fl. = C14/16 - Alphaolefinsulfonat, Na-Salz, ca. 40 %ig
Alkylsulfat:
Sulfopon® 101 spez. = Na-Laurylsulfat, 30 %ig.
Sek. Alkansulfonat:
Hostapur® SAS 60 = Sek. C13-17-Alkansulfonat, Na-Salz, 60 %ig
Ethersulfat:
Genapol® LRO Paste = C12/14-Alkylethersulfat, Na-Salz, 70 %ig
The following anionic surfactants were used for the experiments:
alkylbenzenesulfonate:
Marlon ® A 365 = C 10 -C 13 alkyl benzene sulfonate, Na salt, 65% strength
olefin:
HostapurTM ® fl = C 14/16 -. Alpha olefin sulfonate, sodium salt, 40% strength
alkyl sulfate:
Sulfopon ® 101 spec. = Na lauryl sulfate, 30%.
Sec. Alkanesulfonate:
Hostapur SAS ® 60 = sec. C 13-17 alkane sulfonate, Na salt, 60%
ether sulfate:
Genapol ® LRO paste = C 12/14 alkyl ether sulfate, Na salt, 70% strength

Vergleichsbeispiel 1:Comparative Example 1 Inkompatibilität von Aniontensiden mit Farbfixiermitteln.Incompatibility of anionic surfactants with dye fixatives.

Es wurden wässrige Lösungen mit einem Aniontensidgehalt von 5 % bzw. 15 % (Wirkstoff) und einem Gehalt von 1 % (Wirkstoff) der Farbfixiermittel hergestellt und visuell beurteilt (s. Tabellen 1 und 2). Der pH-Wert wurde nicht reguliert. Als Referenz dienten die Tensidlösungen ohne Farbfixiermittel. Tabelle 1: Inkompatibilität von Aniontensiden, 5 %ig, pH tq. mit Farbfixiermitteln 5 %ige Tensidlösungen mit Zusatz von 1 % FFM... Tenside ohne FFM FFM 1 FFM 2 FFM 3 FFM 4 Sek. Alkansulfonat Klar Flockung Flockung Flockung Flockung Alkylethersulfat Klar Flockung Flockung Flockung Flockung Alkylsulfat Trübe Flockung Flockung Flockung Flockung Alkylbenzolsulfonat Klar Flockung Flockung Flockung Flockung Olefinsulfonat Klar Flockung Flockung Flockung Flockung Tabelle 2: Inkompatibilität von Aniontensiden, 15 %ig, pH tq. mit Farbfixiermitteln 15 %ige Tensidlösungen mit Zusatz von 1 % FFM... Tenside ohne FFM FFM 1 FFM 2 FFM 3 FFM 4 Sek. Alkansulfonat Klar Flockung Flockung Flockung Flockung Alkylethersulfat Klar Flockung Flockung Flockung Flockung Alkylsulfat Trübe Flockung Flockung Flockung Flockung Alkylbenzolsulfonat Klar Flockung Flockung Flockung Flockung Olefinsulfonat Klar Flockung Flockung Flockung Flockung Aqueous solutions having an anionic surfactant content of 5% and 15% (active ingredient) and containing 1% (active ingredient) of the color fixing agents were prepared and visually evaluated (see Tables 1 and 2). The pH was not regulated. The surfactant solutions without color fixing agents served as reference. Table 1: Incompatibility of anionic surfactants, 5%, pH tq. with color fixatives 5% surfactant solutions with 1% FFM added ... surfactants without FFM FFM 1 FFM 2 FFM 3 FFM 4 Sec. Alkanesulfonate Clear flocculation flocculation flocculation flocculation Alkylethersulfat Clear flocculation flocculation flocculation flocculation alkyl sulfate cloudy flocculation flocculation flocculation flocculation alkylbenzenesulfonate Clear flocculation flocculation flocculation flocculation olefin sulfonate Clear flocculation flocculation flocculation flocculation 15% surfactant solutions with the addition of 1% FFM ... surfactants without FFM FFM 1 FFM 2 FFM 3 FFM 4 Sec. Alkanesulfonate Clear flocculation flocculation flocculation flocculation Alkylethersulfat Clear flocculation flocculation flocculation flocculation alkyl sulfate cloudy flocculation flocculation flocculation flocculation alkylbenzenesulfonate Clear flocculation flocculation flocculation flocculation olefin sulfonate Clear flocculation flocculation flocculation flocculation

Vergleichsbeispiel 2:Comparative Example 2: Inkompatibilität von Aniontensiden mit Farbfixiermitteln.Incompatibility of anionic surfactants with dye fixatives.

Es wurden wässrige Lösungen mit einem Anio ntensidgehalt von 5 % bzw. 15 % (Wirkstoff) und einem Gehalt von 1 % (Wirkstoff) der Farbfixiermittel hergestellt. Der pH-Wert wurde auf 9 eingestellt, da Waschmittel in der Regel einen alkalischen pH besitzen. Die Lösungen wurden visuell beurteilt (s. Tabellen 3 und 4). Als Referenz dienten die Tensidlösungen ohne Farbfixiermittel, die ebenfalls auf einen pH-Wert = 9 eingestellt wurden. Tabelle 3: Inkompatibilität von Aniontensiden, 5 %ig, pH = 9, mit Farbfixiermitteln 5 %ige Tensidlösungen mit Zusatz von 1 % FFM... Tenside ohne FFM FFM 1 FFM 2 FFM 3 FFM 4 Sek. Alkansulfonat Klar Flockung Flockung Flockung Flockung Alkylethersulfat Klar Flockung Flockung Flockung Flockung Alkylsulfat Trübe Flockung Flockung Flockung Flockung Alkylbenzolsulfonat Klar Flockung Flockung Flockung Flockung Olefinsulfonat Klar Flockung Flockung Flockung Flockung Tabelle 4: Inkompatibilität von Aniontensiden, 15 %ig, pH = 9, mit Farbfixiermitteln 15 %ige Tensidlösungen mit Zusatz von 1 % FFM... Tenside ohne FFM FFM 1 FFM 2 FFM 3 FFM 4 Sek. Alkansulfonat Klar Flockung Flockung Flockung Flockung Alkylethersulfat Klar Flockung Flockung Flockung Flockung Alkylsulfat Trübe Flockung Flockung Flockung Flockung Alkylbenzolsulfonat Klar Flockung Flockung Flockung Flockung Olefinsulfonat Klar Flockung Flockung Flockung Flockung There were prepared aqueous solutions having a Anio ntensidgehalt of 5% or 15% (active ingredient) and a content of 1% (active ingredient) of the dye fixing. The pH was adjusted to 9 because detergents usually have an alkaline pH. The solutions were assessed visually (see Tables 3 and 4). The surfactant solutions without color fixing agents, which were likewise adjusted to a pH value of 9, served as reference. Table 3: Incompatibility of anionic surfactants, 5%, pH = 9, with dye fixatives 5% surfactant solutions with 1% FFM added ... surfactants without FFM FFM 1 FFM 2 FFM 3 FFM 4 Sec. Alkanesulfonate Clear flocculation flocculation flocculation flocculation Alkylethersulfat Clear flocculation flocculation flocculation flocculation alkyl sulfate cloudy flocculation flocculation flocculation flocculation alkylbenzenesulfonate Clear flocculation flocculation flocculation flocculation olefin sulfonate Clear flocculation flocculation flocculation flocculation 15% surfactant solutions with the addition of 1% FFM ... surfactants without FFM FFM 1 FFM 2 FFM 3 FFM 4 Sec. Alkanesulfonate Clear flocculation flocculation flocculation flocculation Alkylethersulfat Clear flocculation flocculation flocculation flocculation alkyl sulfate cloudy flocculation flocculation flocculation flocculation alkylbenzenesulfonate Clear flocculation flocculation flocculation flocculation olefin sulfonate Clear flocculation flocculation flocculation flocculation

Vergleichsbeispiel 3:Comparative Example 3

Inkompatibilität von linearem Alkylbenzolsulfonat mit FFM 5 und FFM 7.
Es wurde eine wässrige, 6,3 %ige Lösung (Wirkstoff) von linearem Alkylbenzolsulfonat hergestellt. Der Wirkstoffgehalt entspricht dem stabiler Tensidmischungen mit Farbfixiermitteln (s. Beispiel 1 und 2).
Zu der Lösung wurde 1 % (Wirkstoff) FFM 5 bzw. FFM 7 gegeben. Tabelle 5: Inkompatibilität von linearem Alkylbenzolsulfonat, 6,3 %ig mit FFM 5 bzw. FFM 7 Visuelle Beurteilung Lin. Alkylbenzolsulfonat, 6,3 %ig ohne FFM mit FFM 5 mit FFM 7 klare Lösung Flockung Flockung Incompatibility of Linear Alkylbenzenesulfonate with FFM 5 and FFM 7.
An aqueous, 6.3% solution (active ingredient) of linear alkylbenzenesulfonate was prepared. The active ingredient content corresponds to the stable surfactant mixtures with dye fixing agents (see Examples 1 and 2).
To the solution was added 1% (drug) FFM 5 and FFM 7, respectively. Table 5: Incompatibility of Linear Alkylbenzenesulfonate, 6.3% with FFM 5 and FFM 7, respectively Visual assessment Lin. Alkylbenzenesulfonate, 6.3% pure without FFM with FFM 5 with FFM 7 clear solution flocculation flocculation

Beispiele für stabile anionische Flüssigwaschmittel, enthaltend Farbfixiermittel, auf Basis des Tensidsystems lineares Alkylbenzolsulfonat /Seife/nichtionisches Tensid:Examples of stable anionic liquid detergents containing dye fixing agents based on the surfactant system linear alkylbenzenesulfonate / soap / nonionic surfactant:

Beispiel 1:Example 1:

Es wurde eine anionische Flüssigwaschmittelformulierung mit einem Gesamttensidgehalt von 26 % (Wirkstoff) hergestellt.
Als Aniontenside wurden lineares Alkylbenzolsulfonat und Seife, als nichtionisches Tensid C12/14-Alkyl-7EO-ethoxylat und als Farbfixiermittel FFM 5 verwendet. Tabelle 6: Anionisches, 26%iges Flüssigwaschmittel enthaltend FFM 5 Zusammensetzung: Formulierung: A Lin. Alkylbenzolsulfonat 6,3% Kali-Kokos-Seife 3,3% C12/14-Alkyl-7EO-ethoxylat 16,3% 1,2-Propandiol 5% FFM 5 1 % Wasser ad 100% Beurteilung: Trüb, homogen An anionic liquid detergent formulation having a total surfactant content of 26% (active ingredient) was prepared.
As anionic surfactants, linear alkyl benzene sulfonate and soap, nonionic surfactant C 12/14 alkyl 7EO ethoxylate, and color dye FFM 5 were used. Table 6: Anionic, 26% liquid detergent containing FFM 5 Composition: Formulation: A Lin. alkylbenzenesulfonate 6.3% Kali and coconut soap 3.3% C12 / 14-alkyl-7EO ethoxylate 16.3% 1,2-propanediol 5% FFM 5 1 % water ad 100% Evaluation: Dim, homogeneous

Beispiel 2:Example 2:

Es wurde eine anionische Flüssigwaschmittelformulierung mit einem Gesamttensidgehalt von 26 % (Wirkstoff) hergestellt.
Als Aniontenside wurden lineares Alkylbenzolsulfonat und Seife, als nichtionisches Tensid C12/14-Alkyl-7EO-ethoxylat und als Farbfixiermittel FFM 7 verwendet. Tabelle 7: Anionisches, 26 %iges Flüssigwaschmittel enthaltend FFM 7 Zusammensetzung: Formulierung: A Lin. Alkylbenzolsulfonat 6,3% Kali-Kokos-Seife 3,3% C12/14-Alkyl-7EO-ethoxylat 16,3% 1,2-Propandiol 5% FFM 7 1 % Wasser ad 100% Beurteilung: Trüb, homogen An anionic liquid detergent formulation having a total surfactant content of 26% (active ingredient) was prepared.
As the anionic surfactants, linear alkyl benzene sulfonate and soap, nonionic surfactant C 12/14 alkyl 7EO ethoxylate and color fixing agent FFM 7 were used. Table 7: Anionic, 26% liquid detergent containing FFM 7 Composition: Formulation: A Lin. alkylbenzenesulfonate 6.3% Kali and coconut soap 3.3% C12 / 14-alkyl-7EO ethoxylate 16.3% 1,2-propanediol 5% FFM 7 1 % water ad 100% Evaluation: Dim, homogeneous

Beispiel 3:Example 3:

Es wurde eine anionische Flüssigwaschmittelformulierung mit einem Gesamttensidgehalt von 26 % (Wirkstoff) hergestellt.
Als Aniontenside wurde Olefinsulfonat und Seife, als nichtionisches Tensid C12/14-Alkyl-7EO-ethoxylat und als Farbfixiermittel FFM 2 verwendet. Tabelle 8: Anionisches, 26 %iges Flüssigwaschmittel enthaltend FFM 2 Zusammensetzung: Formulierung: A Olefinsulfonat 6,3% Kali-Kokos-Seife 3,3% C12/14-Alkyl-7EO-ethoxylat 16,3% 1,2-Propandiol 5% FFM 2 1 % Wasser ad 100% Beurteilung: Klare Lösung erwendete Abkürzungen:

FM =
Farbfixiermittel
FM 1 =
Umsetzungsprodukt aus Diethylendiamin, Dicyandiamid und Sulfaminsäure.
FM 2 =
Umsetzungsprodukt aus Dimethylamin und Epichlorhydrin.
FM 3 =
Umsetzungsprodukt aus Dicyandiamid, Ammoniumchlorid und Formaldehyd.
FM 4 =
Umsetzungsprodukt aus Dimethylaminopropylamin und Epichlorhydrin.
FM 5 =
Poly-diallyl-dimethyl-ammoniumchlorid, MM = 40.000
FM 7 =
Poly-diallyl-dimethyl-ammoniumchlorid, MM = 115.000
An anionic liquid detergent formulation having a total surfactant content of 26% (active ingredient) was prepared.
As anionic surfactants, olefin sulfonate and soap, nonionic surfactant C 12/14 alkyl 7EO ethoxylate and color fixing agent FFM 2 were used. Table 8: Anionic, 26% liquid detergent containing FFM 2 Composition: Formulation: A olefin sulfonate 6.3% Kali and coconut soap 3.3% C12 / 14-alkyl-7EO ethoxylate 16.3% 1,2-propanediol 5% FFM 2 1 % water ad 100% Evaluation: Clear solution used abbreviations:
FM =
dye fixative
FM 1 =
Reaction product of diethylenediamine, dicyandiamide and sulfamic acid.
FM 2 =
Reaction product of dimethylamine and epichlorohydrin.
FM 3 =
Reaction product of dicyandiamide, ammonium chloride and formaldehyde.
FM 4 =
Reaction product of dimethylaminopropylamine and epichlorohydrin.
FM 5 =
Poly-diallyldimethylammonium chloride, MM = 40,000
FM 7 =
Poly-diallyldimethylammonium chloride, MM = 115,000

Claims (12)

  1. A liquid washing and cleaning composition comprising a surfactant system consisting of
    a) alkylbenzenesulfonate, and/or olefinsulfonate and/or alkylsulfate
    b) soap
    c) a nonionic surfactant
    and optionally
    d) alkyl ester sulfonates, alkyl ether sulfonates and/or condensation products of ethylene oxide with a hydrophobic base formed by condensation of propylene oxide with propylene glycol, condensation products of ethylene oxide with a reaction product of propylene oxide and ethylenediamine, condensation products of C6-C20-alkylphenols with alkene oxides
    and
    e) a dye fixative from the group of the
    homo- and copolymers of diallyldimethylammonium chloride or
    the reaction products of cyanamides with aldehydes and ammonium salts
    or cyanamides with aldehydes and monoamines
    or monoamines and/or polyamines with epichlorohydrin
    or polyamines with cyanamides and amidosulfuric acid.
  2. The washing and cleaning composition as claimed in claim 1, comprising from 3 to 30% by weight, preferably from 5 to 20% by weight, more preferably from 7 to 17% by weight and most preferably from 7 to 15% by weight of one or more of components a.
  3. The washing and cleaning composition as claimed in claim 1, comprising from 1 to 30% by weight, preferably from 5 to 25% by weight and more preferably from 10 to 20% by weight of soap.
  4. The washing and cleaning composition as claimed in claim 1, comprising from 5 to 35% by weight, preferably from 10 to 30% by weight, more preferably from 15 to 25% by weight and most preferably from 16 to 23% by weight of a nonionic surfactant.
  5. The washing and cleaning composition as claimed in claim 1, comprising, as a nonionic surfactant, an ethoxylate of a synthetic or native alcohol having an HLB value of from 10 to 15, preferably from 11 to 14.
  6. The washing and cleaning composition as claimed in claim 1, in which the mass ratio of anionic surfactants:nonionic surfactants is from 1:4 to 4:1, preferably from 1:2 to 2:1 and most preferably from 0.8:1 to 1.5:1.
  7. The washing and cleaning composition as claimed in claim 1, in which the total surfactant content of the surfactant system consisting of components a, soap and nonionic surfactant is between 10 and 70% by weight, preferably from 10 to 55% by weight and more preferably from 20 to 45% by weight.
  8. The washing and cleaning composition as claimed in claim 1, which is opaquely translucent to slightly cloudy.
  9. The washing and cleaning composition as claimed in claim 1, which is clear.
  10. The washing and cleaning composition as claimed in claim 1, wherein the dye fixative is a cationic polymer.
  11. The washing and cleaning composition as claimed in claim 1, characterized in that it comprises, as solvents, propanediol, glycerol or ethanol to an extent of from 1 to 10% by weight, preferably to an extent of from 1 to 5% by weight.
  12. The washing and cleaning composition as claimed in claim 1, characterized in that it is adjusted to a pH between 5 and 12.
EP05798081A 2004-10-23 2005-10-18 Liquid detergent comprising a dye fixing agent Revoked EP1805289B1 (en)

Applications Claiming Priority (2)

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DE102004051715A DE102004051715A1 (en) 2004-10-23 2004-10-23 Stable liquid detergent or cleansing compositions, especially for washing textiles, containing anionic and nonionic surfactants, soap and dye fixing agent, e.g. diallyl dimethylammonium chloride (co)polymer
PCT/EP2005/011181 WO2006045482A1 (en) 2004-10-23 2005-10-18 Liquid detergent comprising a dye fixing agent

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Families Citing this family (12)

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DE102005039168A1 (en) * 2005-08-17 2007-02-22 Cognis Ip Management Gmbh Solid agents containing cationic polymers
WO2010025116A1 (en) 2008-08-28 2010-03-04 The Procter & Gamble Company Fabric care compositions, process of making, and method of use
US20100050346A1 (en) 2008-08-28 2010-03-04 Corona Iii Alessandro Compositions and methods for providing a benefit
CA2769162C (en) 2009-07-31 2017-12-05 Ascendis Pharma As Biodegradable polyethylene glycol based water-insoluble hydrogels
SG178195A1 (en) 2009-07-31 2012-03-29 Sanofi Aventis Deutschland Long acting insulin composition
CA2769340C (en) 2009-07-31 2018-09-11 Harald Rau Prodrugs comprising an insulin linker conjugate
EP2438930A1 (en) 2010-09-17 2012-04-11 Sanofi-Aventis Deutschland GmbH Prodrugs comprising an exendin linker conjugate
WO2017102402A1 (en) 2015-12-14 2017-06-22 Unilever N.V. Isotropic detergent composition comprising weight-efficient polymers
WO2018124989A1 (en) * 2016-12-29 2018-07-05 Hayat Kimya San. A. Ş. Liquid laundry detergent
EP3421583A1 (en) 2017-06-26 2019-01-02 Basf Se Use of cationic vinylcarboxamide/vinylamine copolymers as a color care agent for laundering formulations
US11788031B2 (en) * 2020-10-29 2023-10-17 Henkel Ag & Co. Kgaa Opacified liquid detergent composition comprising a fatty acid/Mg cation/Ca cation mixture and having improved structural stability
CN114317142A (en) * 2021-11-03 2022-04-12 广州立白企业集团有限公司 Low-foam easy-rinsing liquid detergent

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006042716A1 (en) * 2004-10-20 2006-04-27 Clariant Produkte (Deutschland) Gmbh Liquid detergent comprising anionic surfactants and colour fixing agent

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3332880A (en) 1965-01-04 1967-07-25 Procter & Gamble Detergent composition
GB1082179A (en) 1965-07-19 1967-09-06 Citrique Belge Nv Unsaturated carboxylic salt materials and derivatives thereof
US4663071A (en) 1986-01-30 1987-05-05 The Procter & Gamble Company Ether carboxylate detergent builders and process for their preparation
DE3814208A1 (en) 1988-04-27 1989-11-09 Sandoz Ag USE OF UNCOLORED AND / OR COLORED SUBSTRATES
CA2001927C (en) 1988-11-03 1999-12-21 Graham Thomas Brown Aluminosilicates and detergent compositions
DE4116807A1 (en) 1991-05-23 1992-11-26 Henkel Kgaa CONCENTRATED AQUEOUS LIQUID DETERGENT
US5783548A (en) 1992-11-06 1998-07-21 The Procter & Gamble Company Stable liquid detergent compositions inhibiting dye transfer
EP0704523A1 (en) 1994-09-30 1996-04-03 The Procter & Gamble Company Dye transfer inhibiting compositions containing betaines
CA2377017C (en) * 1999-06-29 2006-05-30 The Procter & Gamble Company Fabric enhancement compositions having improved color fidelity
EP1239025A3 (en) * 2001-03-03 2003-09-03 Clariant GmbH Detergent composition and laundry treatment compositon comprising dye transfer inhibiting and dye fixing agent
DE10150724A1 (en) * 2001-03-03 2003-04-17 Clariant Gmbh Washing agents such as detergents contain dye transfer inhibitors which are polyamine/cyanamide/amidosulfuric acid, cyanamide/aldehyde/ammonium salt or amine/epichlorhydrin reaction products
GB0126280D0 (en) 2001-11-01 2002-01-02 Unilever Plc Liquid detergent compositions
DE102004018051A1 (en) 2004-04-08 2005-11-10 Clariant Gmbh Detergents and cleaning agents containing dye fixing agents and soil release polymers
DE102004043728A1 (en) 2004-09-10 2005-06-30 Clariant Gmbh Stable liquid detergent or cleansing compositions, especially for washing textiles, containing anionic and nonionic surfactants, soap and dye fixing agent, e.g. diallyl dimethylammonium chloride (co)polymer

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006042716A1 (en) * 2004-10-20 2006-04-27 Clariant Produkte (Deutschland) Gmbh Liquid detergent comprising anionic surfactants and colour fixing agent

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EP1805289A1 (en) 2007-07-11
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