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EP0264615A1 - Laundry agent having a reduced phosphate content containing N-alkoxylated fatty acid amides - Google Patents

Laundry agent having a reduced phosphate content containing N-alkoxylated fatty acid amides Download PDF

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Publication number
EP0264615A1
EP0264615A1 EP87113376A EP87113376A EP0264615A1 EP 0264615 A1 EP0264615 A1 EP 0264615A1 EP 87113376 A EP87113376 A EP 87113376A EP 87113376 A EP87113376 A EP 87113376A EP 0264615 A1 EP0264615 A1 EP 0264615A1
Authority
EP
European Patent Office
Prior art keywords
fatty acid
weight
alkoxylated fatty
acid
reduced
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP87113376A
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German (de)
French (fr)
Inventor
Horst Dr. Upadek
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication date
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Publication of EP0264615A1 publication Critical patent/EP0264615A1/en
Withdrawn legal-status Critical Current

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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid 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
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic compounds
    • C11D1/652—Mixtures of anionic compounds with carboxylic amides or alkylol amides
    • 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
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/526—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 are polyalkoxylated
    • 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 present invention relates to a phosphate-reduced detergent containing phyllosilicate with improved washing power through the use of N-alkoxylated fatty acid amides, in addition to a conventional surfactant mixture.
  • Phosphate-reduced detergents which contain layered silicates as textile softeners or cobuilders are known.
  • EP-A-26 529 describes a detergent which, in addition to layered silicates, contains anionic surfactants and cationic salts of primary, secondary or tertiary alkylamines or water-soluble, quaternary ammonium compounds.
  • anionic surfactants and cationic salts of primary, secondary or tertiary alkylamines or water-soluble, quaternary ammonium compounds can worsen the washing result, since the cationic and anionic surfactants react with one another in an undesired manner. It was therefore investigated to use nonionic surfactants instead of the anionic ones in detergents.
  • EP-A-26 529 refers among other things to this GB-A-1 079 388 and other literature which has been found that the amounts of nonionic surfactant required for good detergency reduce the effectiveness of the cationic fabric softener.
  • the object of the present invention is to improve the washing power of detergents containing layered silicate, particularly in the case of cosmetic soiling, without impairing the textile-softening properties of the layered silicates.
  • Another object of the present invention is to produce reduced phosphate detergents by combining them with small amounts of N-alkoxylated fatty acid amides with a conventional mixed surfactant base of anionic and nonionic surfactant.
  • an improved phosphate-reduced, layered silicate-containing detergent comprising 2 to 20% by weight of layered silicates, 4 to 15% by weight of anionic surfactants, 0 to 10% by weight of nonionic surfactants, 0 to 6.5% by weight of inorganically bound phosphorus, characterized in that it 0.5 to 10% by weight of at least one N-alkoxylated fatty acid amide or mixtures thereof of the general formula contains, where R1C stands for the aliphatic residue of a fatty acid with 8 to 22 carbon atoms, at least half of which consist of saturated C 12-14 carbon atoms and / or of mono- or polyunsaturated fatty acids with 18 to 22 carbon atoms, R2 and R3 each represent hydrogen or an ethanol radical and their ethylene oxide and / or propylene oxide adducts each having 1 to 10 ethylene oxide and / or propylene oxide groups with the proviso that at least one of the radicals R2 and R3 is derived from
  • a phosphate-reduced detergent which contains in particular 5 to 15% by weight of layered silicate.
  • Another embodiment of the present invention contains inorganic bound phosphorus in an amount of 0 to 4.5 wt .-%.
  • Further preferred embodiments of the invention are characterized in that they contain 1.0 to 4% by weight contain at least one or mixtures of the N-alkoxylated fatty acid amides.
  • phosphate-reduced detergents can be obtained by adjusting the ratio of the sum of anionic surfactant and nonionic surfactant to the N-alkoxylated fatty acid amide in a ratio of 15: 1 to 1: 1.
  • Particular embodiments are detergents which contain at least one N-alkoxylated fatty acid amide selected from the group consisting of oleic acid diethanolamide, soy fatty acid diethanolamide, coconut fatty acid diethanolamide, lauric myristic acid diethanolamide and coconut fatty acid monoethanolamide.
  • rapeseed oil or fish oil can be used as the starting material for the production of the N-alkoxylated fatty acid amides according to the invention.
  • the N-alkoxylated fatty acid amides contain 1 to 5 ethylene oxide and / or propylene oxide groups, 1 to 2 ethylene oxide and / or propylene oxide groups being particularly preferred.
  • DE-PS-23 34 899 describes in column 4 under the heading "clay compounds” phyllosilicates which are the basis of the basic formulations of the detergent formulations according to the invention. This list of phyllosilicates is expressly referred to, as is the list of bentonites (smectites) in EP-A-26 529.
  • layered silicates within the meaning of the present invention includes synthetic, finely divided, water-insoluble layered silicates with a smectite-like crystal phase, but increased contents of bound alkali and silicate and a swelling capacity in aqueous suspension with the total oxide formula which is significantly reduced compared to pure layered silicates of this type MgO. aM2O. bAl2O3. cSiO2.
  • synthetic phyllosilicates which are characterized in that after suspension in water (16 ° dH, room temperature) they have a swelling capacity - determined as the quotient of the sediment volume (V s ) / total volume (V) after previous treatment with excess Soda solution, careful washing and 20 hours after slurrying in 9 parts by weight of water / one part by weight of layered silicate - of V s / V less than 0.6, in particular less than 0.4, as well synthetic phyllosilicates, which are mixed-crystalline and have structure-determining saponite and / or hectorite-like crystal phases, which are interspersed in an irregular arrangement with crystalline alkali polysilicate, the mixed crystal systems of the structural formula Na x + y (Mg 3-x Li x ) (Si 4-y Al y ) O10 (OH) 2 .m Na2Si z O 2z + 1 .
  • Such synthetic phyllosilicates are further characterized in that they contain excess alkali which is not incorporated into the crystal structure, in particular sodium hydroxide or sodium carbonate, and / or in intimate admixture with in particular water-soluble salts, preferably alkali sulfates and / or carbonates.
  • Suitable organic and inorganic builder substances are weakly acidic, neutral or alkaline-reacting salts, in particular alkali salts, which are able to precipitate or bind calcium ions in a complex manner.
  • alkali salts which are able to precipitate or bind calcium ions in a complex manner.
  • the water-soluble alkali metal or alkali polyphosphates in particular pentasodium triphosphate, in addition to the alkali ortho- and alkali pyrophosphates, are of particular importance. All or part of these phosphates can be replaced by organic complexing agents for calcium ions.
  • organic complexing agents for calcium ions include compounds of the aminopolycarboxylic acid type, e.g.
  • Nitrilotriacetic acid NTA
  • ethylenediaminetetraacetic acid diethylenetriaminepentaacetic acid and higher homologues.
  • Suitable phosphorus-containing organic complexing agents are the water-soluble salts of alkane polyphosphonic acids, amino and hydroxyalkane polyphosphonic acids and phosphonopolycarboxylic acids such as e.g. Methane diphosphonic acid, dimethylaminomethane-1,1-diphosphonic acids, aminotrimethylene triphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 1-phosphonoethane-1,2-dicarboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid.
  • the nitrogen-free and phosphorus-free polycarboxylic acids which form complex salts with calcium ions which also include polymers containing carboxyl groups, are of particular importance.
  • citric acid wine are suitable acid, benzene hexacarboxylic acid and tetrahydrofuran tetracarboxylic acid.
  • Polycarboxylic acids containing ether groups are also suitable, such as 2,2′-oxydisuccinic acid and polyhydric alcohols or hydroxycarboxylic acids partially or completely etherified with glycolic acid, for example biscarboxymethylethylene glycol, carboxymethyloxy succinic acid, carboxymethyl tartronic acid and carboxymethylated or oxidized polysaccharides.
  • Polymeric carboxylic acids with a molecular weight between 350 and about 1,500,000 in the form of water-soluble salts are also suitable.
  • Particularly preferred polymeric polycarboxylates have a molecular weight in the range from 500 to 175,000 and in particular in the range from 10,000 to 100,000.
  • These compounds include, for example, polyacrylic acid, polyhydroxyacrylic acid, polymaleic acid and the copolymers of the corresponding monomeric carboxylic acids with one another or with ethylenically unsaturated Compounds such as vinyl methyl ether.
  • the water-soluble salts of polyglyoxylic acid are also suitable.
  • Suitable water-insoluble inorganic builders are the finely divided, synthetic, bound water-containing sodium aluminosilicates of the zeolite A type described in DE-OS 24 12 837 as phosphate substitutes for detergents and cleaning agents.
  • the cation-exchanging sodium aluminosilicates are used in the usual hydrated, finely crystalline form, that is to say that they have practically no particles larger than 30 ⁇ m and preferably consist of at least 80% of particles smaller than 10 ⁇ m.
  • Your calcium binding capacity is in the range of 100 to 200 mg CaO / g.
  • Zeolite NaA is particularly suitable, as is zeolite NaX and mixtures of NaA and NaX.
  • Suitable inorganic, non-complexing salts are the alkali salts of bicarbonates, carbonates, borates, sulfates and silicates - also referred to as "washing alkalis".
  • alkali silicates the sodium silicates in which the ratio Na2O: SiO2 is between 1: 1 and 1: 3.5 are particularly preferred.
  • builder substances that are mostly used in liquid agents because of their hydrotropic properties are the salts of the non-capillary active sulfonic acids containing 2 to 9 carbon atoms, carboxylic acids and sulfocarboxylic acids, for example the alkali salts of alkanoic, benzene, toluene, xylene or cumene sulfonic acids, of sulfobenzoic acids, sulfophthalic acid, sulfoacetic acid, sulfosuccinic acid and the salts of acetic acid or lactic acid.
  • Acetamide and ureas are also suitable as solubilizers.
  • Surfactants which are contained as a further essential component in detergents and cleaning agents, have at least one hydrophobic organic residue and one water-solubilizing anionic, zwitterionic or nonionic group in the molecule.
  • the hydrophobic radical is usually an aliphatic hydrocarbon radical with 8 to 26, preferably 10 to 22 and in particular 12 to 18 C atoms or an alkyl aromatic radical with 6 to 18, preferably 8 to 16 aliphatic C atoms.
  • anionic surfactants e.g. Soaps from natural or synthetic, preferably saturated fatty acids, optionally also from resin or naphthenic acids, can be used.
  • Suitable synthetic anionic surfactants are those of the sulfate, sulfonate and synthetic carboxylate type.
  • the surfactants of the sulfonate type are alkylbenzenesulfonates (C 9-15- alkyl), olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from C 12-18 monoolefins with a terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
  • alkylbenzenesulfonates C 9-15- alkyl
  • olefin sulfonates ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates
  • alkanesulfonates which are obtainable from C 12-18 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and the esters of alpha-sulfo fatty acids, for example the alpha-sulfonated methyl or ethyl esters of hydrogenated coconut palm kernel or tallow fatty acids.
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, ie from fatty alcohols, such as, for example, coconut oil alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the C 10-20 oxo alcohols, and those secondary Alcohols of this chain length.
  • the sulfuric acid monoesters of the aliphatic primary alcohols or ethoxylated secondary alcohols or alkylphenols ethoxylated with 1 to 6 mol of ethylene oxide are also suitable.
  • Sulfated fatty acid alcoholamides and sulfated fatty acid monoglycerides are also suitable.
  • anionic surfactants are the fatty acid esters or amides of hydroxy or aminocarboxylic acids or sulfonic acids, e.g. the fatty acid sarcosides, glycolates, lactates, taurides or isethionates.
  • the anionic surfactants can be in the form of their sodium, potassium and ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • Addition products of 1 to 40, preferably 2 to 20 moles of ethylene oxide with 1 mole of a compound having essentially 10 to 20 carbon atoms from the group of alcohols, alkylphenols and fatty acids can be used as nonionic surfactants.
  • water-soluble polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants.
  • Nonionic surfactants of the amine oxide or sulfoxide type can also be used, for example the compounds N-cocoalkyl-N, N-dimethylamine oxide, N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) amine oxide, N-tallow alkyl-N, n-dihydroxyethylamine oxide.
  • N-alkoxylated fatty acid amides are not to be understood as nonionic surfactants.
  • the optionally used zwitterionic surfactants are preferably derivatives of aliphatic quaternary ammonium compounds in which one of the aliphatic radicals consists of a C8-C18 radical and another contains an anionic, water-solubilizing carboxy, sulfo or sulfato group.
  • Typical representatives of such surface-active betaines are, for example, the compounds 3- (N-hexadecyl-N, N-dimethylammonio) propane sulfonate; 3- (N-tallow alkyl-N, N-dimethylammonio) -2-hydroxypropanesulfonate; 3- (N-hexadecyl-N, N-bis (2-hydroxyethyl) ammonium) -2-hydroxypropyl sulfate; 3- (N-cocoalkyl-N, N-bis (2,3-dihydroxypropyl) ammonium) propane sulfonate; N-tetradecyl-N, N-dimethyl-ammonioacetate; N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) ammonioacetate.
  • a reduced foaming power which is desirable when working in machines, can be achieved, for example, by using soaps.
  • soaps foam attenuation increases with the degree of saturation and the C number of the fatty acid ester; Soaps of saturated C 20-24 fatty acids are therefore particularly suitable as foam suppressants.
  • the non-surfactant-like foam inhibitors are generally water-insoluble, mostly aliphatic C8-C22-carbon-containing compounds.
  • Suitable non-surfactant foam inhibitors are e.g. the N-alkylaminotriazines, i.e. Reaction products of 1 mol of cyanuric chloride with 2 to 3 mol of a mono- or dialkylamine with essentially 8 to 18 carbon atoms in the alkyl radical.
  • Propoxylated and / or butoxylated aminotriazines e.g. the reaction products of 1 mole of melamine with 5 to 10 moles of propylene oxide and additionally 10 to 50 moles of butylene oxide and the aliphatic C18-C40 ketones, e.g.
  • the washing and cleaning agents can contain dirt carriers, which keep the dirt detached from the fibers suspended in the liquor and thus prevent graying.
  • water-soluble colloids of mostly organic nature are suitable, such as, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose.
  • they can be solved Use starch preparations and starch products other than those mentioned above, such as degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
  • NaBO2. H2O2. 3 H2O sodium perborate tetrahydrate
  • NaBO2. H2O2 monohydrate
  • These compounds can be partially or completely replaced by other active acid carriers, in particular by peroxy hydrates, such as peroxycarbonates (Na2CO3. 1.5 H2O2), oxypyrophosphates, citrate perhydrates, urea-H2O2- or melamine-H2O2-compounds as well as by H2O2-delivering peracid salts, e.g. Caroate (KHSO5), perbenzoate or peroxyphthalate can be replaced.
  • peroxycarbonates Na2CO3. 1.5 H2O2
  • oxypyrophosphates citrate perhydrates
  • urea-H2O2- or melamine-H2O2-compounds as well as by H2O2-delivering peracid salts, e.g. Caroate (KHSO5), perbenzoate or peroxyphthalate can be replaced.
  • Suitable water-insoluble stabilizers which preferably make up 0.5 to 8% by weight, based on the overall detergent formulation, are the magnesium silicates which are usually obtained by precipitation from aqueous solutions.
  • Suitable water-soluble stabilizers which are preferably present together with water-insoluble ones, are organic heavy metal complexing agents, in particular those of the type of the aminopolycarboxylic acids and polyphosphonic acids described above.
  • activator-containing bleaching components are preferably incorporated into the preparations.
  • N-acyl or O-acyl compounds which form organic peracids and which form H2O2, in particular acetyl, propionyl or benzoyl compounds, and carbonic acid or pyrocarbonic acid esters are used as activators for per compounds which supply H2O2 in water.
  • Useful compounds include: N-diacylated and N, N'-tetraacylated amines such as N, N, N ⁇ , N'-tetraacetyl-methylenediamine or -ethylenediamine, N, N-diacetylaniline and N, N-diacetyl-p- toluidine or 1,3-diacylated hydantoins, alkyl-N-sulfonylcarbonamides, for example N-methyl-N-mesyl-acetamide, N-methyl-N-mesyl-benzamide, N-methyl-N-mesyl-p-nitrobenzamide, and N-methyl-N-mesyl-p-methoxybenzamide, N-acylated cyclic hydrazides, acylated triazoles or urazoles such as the monoacetyl maleic hydrazide, O, N, N-trisubstituted hydroxylamines such as O-benzoyl-
  • carboxylic anhydrides e.g. benzoic anhydride, m- Chlorobenzoic anhydride, phthalic acid reanhydride, 4-chlorophthalic anhydride
  • sugar esters such as, for example, glucose pentaacetate, 1,3-diacyl-4,5-diacyloxy-imidazolidine, for example the compounds 1,3-diformyl-4,5-diacetoxyimidazolidine, 1,3-diacetyl-4,5 -diacetoxyimidazolidine, 1,3-diacetyl-4,5-dipropionyloxy-imidazo lidin
  • acylated glycolurils such as, for example, tetrapropionylglycoluril or diacetyl-dibenzoyl-glycoluril
  • diacylated 2,5-diketopiperazines such as, for example, 1,4-di
  • the detergents can contain, as optical brighteners for cotton, in particular derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2 2 ⁇ -disulfonic acid or compounds of the same structure which replace the morpholino group carry a diethanolamino group, a methylamino group or a 2-methoxyethylamino group.
  • Possible brighteners for polyamide fibers are those of the 1,3-diaryl-2-pyrazoline type, for example the compound 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline and compounds of the same structure which instead of the sulfamoyl group, for example the methoxycarbonyl, 2-methoxyethoxycarbonyl, the acetylamino or the vinylsulfonyl group.
  • Useful polyamide brighteners are also the substituted aminocoumarins, for example 4-methyl-7-dimethylamino or 4-methyl-7-diethylaminocoumarin.
  • the compounds 1- (2-benzimidazolyl) -2- (1-hydroxyethyl-2-benzimidazolyl) ethylene and 1-ethyl-3-phenyl-7-diethylamino-carbostyril are also useful as polyamide brighteners.
  • polyester and polyamide fibers are the compounds 2,5-di- (2-benzoxyzolyl) -thiophene, 2- (2-benzoxylolyl-naphto [2,3-b] -thiophene and 1,2-di- (5-methyl -2-benzoxazolyl) ethylene and brighteners of the substituted 4,4'-distyryl-diphenyl type may also be present, for example the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl Mixtures of the aforementioned brighteners can be used.
  • the lower alcohols, ether alcohols, glycols or ketones with 1 to 6 carbon atoms such as e.g. Methanol, ethanol, propanol, isopropanol, ethylene glycol, propylene glycol, diethylene glycol, methyl glycol, ethyl glycol, butyl glycol or acetone and methyl ethyl ketone.
  • EO attached ethylene oxide
  • the incorporation of the N-alkoxylated fatty acid amides into the detergent formulations can be carried out according to conventional techniques for the production of detergents, e.g. B. by hot atomization together with others Detergent components, by granulation together with solid and / or liquid detergent components (including layered silicate) or by subsequent application to solid detergent parts (e.g. spray powder, granulate, perborate, zeolite, layered silicate) according to the single or multi-powder strategy.
  • conventional techniques for the production of detergents e.g. B. by hot atomization together with others Detergent components, by granulation together with solid and / or liquid detergent components (including layered silicate) or by subsequent application to solid detergent parts (e.g. spray powder, granulate, perborate, zeolite, layered silicate) according to the single or multi-powder strategy.
  • a copolymer of acrylic acid and maleic acid with an average molecular weight of 70,000 (Sokalan CP5 R ) in the form of the sodium salt was used as the polycarboxylic acid.
  • a basic recipe was prepared according to Comparative Example 1, which contained 1.5% coconut fatty acid diethanolamide, the coconut fatty acid containing more than 50% C 12-14 carbon atoms and the precursor fatty acids with less than 10 C atoms being separated off.
  • a basic recipe was prepared according to Comparative Example 1, which contained 1.5% coconut fatty acid monoethanolamide, the coconut fatty acid containing more than 50% C 12-14 carbon atoms and the precursor fatty acids with less than 10 C atoms being separated off.
  • a basic formulation was prepared according to Comparative Example 2, which contained 1.5% of a hydroxyamine (reaction product of 9,10-epoxystearyl alcohol with monoethanolamine).
  • the washing tests with the above-mentioned recipes were carried out in a commercial household washing machine in a 60 ° C soak program with a water hardness of 16 ° dH, corresponding to 160 mg CaO per liter, 3.5 kg load and 252 g (Table 1), 285 g (Table 2) and 225 g (Table 3) detergent.
  • Make-up, lipstick and mascara on a refined polyester / cotton fabric were used as stains.
  • the maximum score is 15, which is the product of the number of evaluators (five) times the number of determinations (three).
  • the last columns of the tables contain the totals of the scores from the evaluation of the removal of stains from make-up, lipstick and mascara.
  • Tables 1, 2 and 3 show the superiority of the additives according to the invention not only compared to the basic formulations (comparative examples 1, 2 and 6), but also compared to other non-surfactant additives.

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Abstract

The agent has textile-softening properties and contains 2 to 20% by weight of sheet silicates, 4 to 15% by weight of anionic surfactants, 0 to 10% by weight of non-ionic surfactants, 0 to 6.5% by weight of inorganically bound phosphorus and 0.5 to 10% by weight of at least one N-alkoxylated fatty acid amide of the formula <IMAGE> in which R1C is the aliphatic radical of a fatty acid with 8 to 22 C atoms, at least half of which consist of saturated C12-14 carbon atoms and/or of mono- or polyunsaturated fatty acids with 18 to 22 C atoms, R2 and R3 are each hydrogen or an ethanol radical and the ethylene oxide and/or propylene oxide adducts thereof, in each case with 1 to 10 ethylene oxide and/or propylene oxide groups, with the proviso that at least one of the radicals R2 and R3 is derived from an alkanol, where the total content of anionic surfactant, non-ionic surfactant and N-alkoxylated fatty acid amide is 8 to 20% by weight.

Description

Die vorliegende Erfindung betrifft ein phosphatreduziertes schichtsilicathaltiges Waschmittel mit verbesserter Waschkraft durch die Verwendung von N-alkoxylierten Fettsäureamiden, neben einem üblichen Tensidgemisch.The present invention relates to a phosphate-reduced detergent containing phyllosilicate with improved washing power through the use of N-alkoxylated fatty acid amides, in addition to a conventional surfactant mixture.

Phosphatreduzierte Waschmittel, die Schichtsilicate als Textilweichmacher bzw. Cobuilder enthalten sind bekannt.Phosphate-reduced detergents which contain layered silicates as textile softeners or cobuilders are known.

EP-A-26 529 beschreibt ein Waschmittel, das neben Schichtsilicaten anionische Tenside sowie kationische Salze von primären, sekundären oder tertiären Alkylaminen oder wasserlösliche, quartäre Ammoniumverbindungen enthält. Die Verwendung derartiger Tensidgemische in Waschmittelrezepturen kann das Waschergebnis verschlechtern, da sich die kationischen und anionischen Tenside in ungewünschter Weise miteinander umsetzen. Es wurde daher untersucht, nichtionische Tenside anstelle der anionischen in Waschmitteln zu verwenden. EP-A-26 529 verweist dazu unter anderem auf GB-A-1 079 388 und weitere Literatur, dergemäß gefunden wurde, daß die erforderlichen Mengen an nichtionischem Tensid, die für eine gute Waschkraft erforderlich sind, die Wirksamkeit der kationischen Weichspüler herabsetzen.EP-A-26 529 describes a detergent which, in addition to layered silicates, contains anionic surfactants and cationic salts of primary, secondary or tertiary alkylamines or water-soluble, quaternary ammonium compounds. The use of such surfactant mixtures in detergent formulations can worsen the washing result, since the cationic and anionic surfactants react with one another in an undesired manner. It was therefore investigated to use nonionic surfactants instead of the anionic ones in detergents. EP-A-26 529 refers among other things to this GB-A-1 079 388 and other literature which has been found that the amounts of nonionic surfactant required for good detergency reduce the effectiveness of the cationic fabric softener.

H. Schott, Journal of American Oil Chemist's Society, Vol. 45, 1968, S. 414 beschreibt, daß Waschmittel auf der Basis von Nonionics und Schichtsilicat auf Cellulosefasern (Baumwolle) nicht die erwartete Ablagerung des Schichtsilicates zum Zwecke des Weichmachens hervorrufen.H. Schott, Journal of American Oil Chemist's Society, Vol. 45, 1968, p. 414 describes that detergents based on nonionics and layered silicate on cellulose fibers (cotton) do not cause the expected deposition of the layered silicate for the purpose of softening.

Die vorliegende Erfindung hat sich zur Aufgabe gestellt, die Waschkraft schichtsilicathaltiger Waschmittel insbesondere bei kosmetischen Anschmutzungen zu verbessern, ohne die textilweichmachenden Eigenschaften der Schichtsilicate zu verschlechtern.The object of the present invention is to improve the washing power of detergents containing layered silicate, particularly in the case of cosmetic soiling, without impairing the textile-softening properties of the layered silicates.

Eine weitere Aufgabe der vorliegenden Erfindung besteht darin, phosphatreduzierte Waschmittel durch Kombination mit kleinen Mengen N-alkoxylierter Fettsäureamide mit einer herkömmlichen gemischten Tensidbasis aus anionischem und nichtionischem Tensid herzustellen.Another object of the present invention is to produce reduced phosphate detergents by combining them with small amounts of N-alkoxylated fatty acid amides with a conventional mixed surfactant base of anionic and nonionic surfactant.

Gemäß der vorliegenden Erfindung wird ein verbessertes phosphatreduziertes, schichtsilicathaltiges Waschmittel zur Verfügung gestellt, enthaltend
2 bis 20 Gew.-% Schichtsilicate,
4 bis 15 Gew.-% anionische Tenside,
0 bis 10 Gew.-% nichtionische Tenside,
0 bis 6,5 Gew.-% an anorganisch gebundenem Phosphor,
dadurch gekennzeichnet, daß es
0,5 bis 10 Gew.-% wenigstens eines N-alkoxylierten Fettsäureamides oder Gemische davon der allgemeinen Formel

Figure imgb0001
enthält, wobei
    R₁C für den aliphatischen Rest einer Fettsäure mit 8 bis 22 C-Atomen steht, die mindestens zur Hälfte aus gesättigten C 12-14 Kohlenstoffatomen und/oder aus einfach oder mehrfach ungesättigten Fettsäuren mit 18 bis 22 C-Atomen bestehen,
    R₂ und R₃ jeweils für Wasserstoff oder einen Ethanolrest sowie deren Ethylenoxid- und/oder Propylenoxidaddukte mit jeweils 1 bis 10 Ethylenoxid- und/oder Propylenoxidgruppen mit der Maßgabe stehen, daß wenigstens einer der Reste R₂ und R₃ sich von einem Alkanol ableitet,
wobei die Waschmittelzusammensetzung 8 bis 20 Gew.-% anionsiche Tenside, nichtionische Tenside und N-alkoxylierte Fettsäureamide aufweist.According to the present invention there is provided an improved phosphate-reduced, layered silicate-containing detergent comprising
2 to 20% by weight of layered silicates,
4 to 15% by weight of anionic surfactants,
0 to 10% by weight of nonionic surfactants,
0 to 6.5% by weight of inorganically bound phosphorus,
characterized in that it
0.5 to 10% by weight of at least one N-alkoxylated fatty acid amide or mixtures thereof of the general formula
Figure imgb0001
 contains, where
R₁C stands for the aliphatic residue of a fatty acid with 8 to 22 carbon atoms, at least half of which consist of saturated C 12-14 carbon atoms and / or of mono- or polyunsaturated fatty acids with 18 to 22 carbon atoms,
R₂ and R₃ each represent hydrogen or an ethanol radical and their ethylene oxide and / or propylene oxide adducts each having 1 to 10 ethylene oxide and / or propylene oxide groups with the proviso that at least one of the radicals R₂ and R₃ is derived from an alkanol,
the detergent composition comprising 8 to 20% by weight of anionic surfactants, nonionic surfactants and N-alkoxylated fatty acid amides.

Gemäß einer Ausführungsform der vorliegenden Erfindung wird ein phosphatreduziertes Waschmittel zur Verfügung gestellt, das insbesondere 5 bis 15 Gew.-% an Schichtsilicat enthält.According to one embodiment of the present invention, a phosphate-reduced detergent is provided which contains in particular 5 to 15% by weight of layered silicate.

Eine weitere Ausführungsform der vorliegenden Erfindung enthält anorganisch gebundenen Phosphor in einer Menge von 0 bis 4,5 Gew.-%.Another embodiment of the present invention contains inorganic bound phosphorus in an amount of 0 to 4.5 wt .-%.

Weitere bevorzugte Ausführungsformen der Erfindung sind dadurch gekennzeichnet, daß sie 1,0 bis 4 Gew.-% wenigstens eines oder Gemische der N-alkoxylierten Fettsäureamide enthalten.Further preferred embodiments of the invention are characterized in that they contain 1.0 to 4% by weight contain at least one or mixtures of the N-alkoxylated fatty acid amides.

Phosphatreduzierte Waschmittel können in einer bevorzugten Ausführungsfor m dadurch erhalten werden, daß das Verhältnis der Summe aus anionischem Tensid und nichtionischem Tensid zu dem N-alkoxylierten Fettsäureamid im Verhältnis 15:1 bis 1:1 eingestellt wird.In a preferred embodiment, phosphate-reduced detergents can be obtained by adjusting the ratio of the sum of anionic surfactant and nonionic surfactant to the N-alkoxylated fatty acid amide in a ratio of 15: 1 to 1: 1.

Besondere Ausführungsformen stellen Waschmittel dar, die wenigstens ein N-alkoxyliertes Fettsäureamid, ausgewählt aus der aus Ölsäurediethanolamid, Sojafettsäurediethanolamid, Kokosfettsäurediethanolamid, Laurin-Myristinsäurediethanolamid und Kokosfettsäuremonoethanolamid bestehenden Gruppe enthalten. Weiterhin können als Ausgangsmaterial zur Herstellung der erfindungsgemäßen N-alkoxylierten Fettsäureamide beispielsweise Rapsöl oder Fischöl verwendet werden.Particular embodiments are detergents which contain at least one N-alkoxylated fatty acid amide selected from the group consisting of oleic acid diethanolamide, soy fatty acid diethanolamide, coconut fatty acid diethanolamide, lauric myristic acid diethanolamide and coconut fatty acid monoethanolamide. Furthermore, rapeseed oil or fish oil can be used as the starting material for the production of the N-alkoxylated fatty acid amides according to the invention.

In einer bevorzugten Ausführungsform der vorliegenden Erfindung enthalten die N-alkoxylierten Fettsäureamide 1 bis 5 Ethylenoxid- und/oder Propylenoxidgruppen, wobei 1 bis 2 Ethylenoxid- und/oder Propylenoxidgruppen besonders bevorzugt werden.In a preferred embodiment of the present invention, the N-alkoxylated fatty acid amides contain 1 to 5 ethylene oxide and / or propylene oxide groups, 1 to 2 ethylene oxide and / or propylene oxide groups being particularly preferred.

DE-PS-23 34 899 beschreibt in Spalte 4 unter der Überschrift "Tonverbindungen" Schichtsilicate, die den Grundrezepturen der erfindungsgemäßen Waschmittelrezepturen zugrundegelegt werden. Auf diese Aufzählung der Schichtsilicate wird ebenso ausdrücklich Bezug genommen, wie auf die Aufzählung der Bentonite (Smectite) der EP-A-26 529.DE-PS-23 34 899 describes in column 4 under the heading "clay compounds" phyllosilicates which are the basis of the basic formulations of the detergent formulations according to the invention. This list of phyllosilicates is expressly referred to, as is the list of bentonites (smectites) in EP-A-26 529.

Weiterhin werden vom Begriff der Schichtsilicate im Sinne der vorliegenden Erfindung synthetische, feinteilige, wasserunlösliche Schichtsilicate mit smectitähnlicher Kristallphase, jedoch erhöhten Gehalten an gebundenem Alkali und Silicat und einem im Vergleich zu reinen Schichtsilicaten dieses Typs deutlich verringerten Quellvermögen in wäßriger Suspension mit der Oxidsummenformel

    MgO . aM₂O . bAl₂O₃ . cSiO₂ . nH₂O

eingeschlossen, worin
    M für Natrium, gegebenenfalls zusammen mit Lithium mit der Maßgabe steht, daß das Molverhältnis Na/Li wenigstens 2 beträgt und worin weiterhin
    a, b, c und n jeweils eine Zahl in den Bereichen

a = 0,05 bis 0,4;
b = 0 bis 0,3;
c = 1,2 bis 2,0;
n = 0,3 bis 3,0

bedeuten und dabei n für das in der Kristallphase gebundene Wasser steht, sowie
synthetische Schichtsilicate, die dadurch gekennzeichnet sind, daß die Parameter a, b und c in den folgenden Bereichen liegen:

a = 0,15 bis 0,30;
b = 0 bis 0,10;
c = 1,3 bis 1,5

wobei bevorzugterweise das Verhältnis a/b gleich oder größer 3 ist.Furthermore, the term layered silicates within the meaning of the present invention includes synthetic, finely divided, water-insoluble layered silicates with a smectite-like crystal phase, but increased contents of bound alkali and silicate and a swelling capacity in aqueous suspension with the total oxide formula which is significantly reduced compared to pure layered silicates of this type

MgO. aM₂O. bAl₂O₃. cSiO₂. nH₂O

included in what
M stands for sodium, optionally together with lithium, with the proviso that the molar ratio Na / Li is at least 2 and in which further
a, b, c and n each have a number in the ranges

a = 0.05 to 0.4;
b = 0 to 0.3;
c = 1.2 to 2.0;
n = 0.3 to 3.0

mean and n stands for the water bound in the crystal phase, and
synthetic layered silicates, which are characterized in that the parameters a, b and c are in the following ranges:

a = 0.15 to 0.30;
b = 0 to 0.10;
c = 1.3 to 1.5

wherein the ratio a / b is preferably equal to or greater than 3.

Weiterhin eingeschlossen im Sinne der Erfindung sind synthetische Schichtsilicate, die dadurch gekennzeichnet sind, daß sie nach Suspension in Wasser (16°dH, Raumtemperatur) ein Quellvermögen - bestimmt als Quotient des Sedimentvolumens (V s) / Gesamtvolumen (V) nach vorheriger Behandlung mit überschüssiger Sodalösung, sorgfältigem Waschen und 20 Stunden nach Aufschlämmung in 9 Gewichtsteilen Wasser / ein Gewichtsteil Schichtsilicat - von V s/V kleiner als 0,6, insbesondere kleiner als 0,4 besitzen, sowie
synthetische Schichtsilicate, die mischkristallin ausgebildet sind und dabei strukturbestimmende saponit- und/oder hectoritähnliche Kristallphasen aufweisen, welche in unregelmäßiger Anordnung mit kristallinem Alkalipolysilicat durchsetzt sind, wobei die Mischkristallsysteme der Strukturformel

Na x+y (Mg 3-xLi x) (Si 4-yAl y)O₁₀(OH)₂ .m Na₂Si zO 2z+1 . nH₂O

entsprechen, worin gilt

x = 0 - 0.3      bevorzugt: 0 - 0.4
y = 0 - 0.5      bevorzugt: 0 - 0.4
x+y = 0.1 - 0.5      bevorzugt: 0.2 - 0.4
z = 1 - 22      bevorzugt: 1 - 14
m = 0.1 - 0.5      bevorzugt: 0.1 - 0.3
n = 0 - 8      bevorzugt: 2 - 6Also included in the sense of the invention are synthetic phyllosilicates which are characterized in that after suspension in water (16 ° dH, room temperature) they have a swelling capacity - determined as the quotient of the sediment volume (V s ) / total volume (V) after previous treatment with excess Soda solution, careful washing and 20 hours after slurrying in 9 parts by weight of water / one part by weight of layered silicate - of V s / V less than 0.6, in particular less than 0.4, as well
synthetic phyllosilicates, which are mixed-crystalline and have structure-determining saponite and / or hectorite-like crystal phases, which are interspersed in an irregular arrangement with crystalline alkali polysilicate, the mixed crystal systems of the structural formula

Na x + y (Mg 3-x Li x ) (Si 4-y Al y ) O₁₀ (OH) ₂ .m Na₂Si z O 2z + 1 . nH₂O

correspond to what applies

x = 0 - 0.3 preferred: 0 - 0.4
y = 0 - 0.5 preferred: 0 - 0.4
x + y = 0.1 - 0.5 preferred: 0.2 - 0.4
z = 1 - 22 preferred: 1 - 14
m = 0.1 - 0.5 preferred: 0.1 - 0.3
n = 0-8 preferred: 2-6

Derartige synthetische Schichtsilicate sind weiterhin dadurch gekennzeichnet, daß sie überschüssiges, nicht in die Kristallstruktur eingebundenes Alkali, insbesondere Natriumhydroxid oder Soda, enthal ten und/oder in inniger Abmischung mit insbesondere wasserlöslichen Salzen, vorzugsweise Alkalisulfaten und/oder -carbonaten, vorliegen.Such synthetic phyllosilicates are further characterized in that they contain excess alkali which is not incorporated into the crystal structure, in particular sodium hydroxide or sodium carbonate, and / or in intimate admixture with in particular water-soluble salts, preferably alkali sulfates and / or carbonates.

Auf die in der DE-A 35 26 405 beschriebenen Schichtsilicate wird hiermit ausdrücklich Bezug genommen.Reference is hereby expressly made to the layer silicates described in DE-A 35 26 405.

Die Builderbestandteile, die in den erfindungsgemäßen Waschmitteln enthalten sein können, werden im folgenden näher beschrieben:The builder constituents which may be present in the detergents according to the invention are described in more detail below:

Als organische und anorganische Buildersubstanzen eignen sich schwachsauer, neutral oder alkalisch reagierende Salze, insbesondere Alkalisalze, die in der Lage sind, Calciumionen auszufällen oder komplex zu binden. Von den anorganischen Salzen sind die wasserlöslichen Alkalimeta- oder Alkalipolyphosphate, insbesondere das Pentanatriumtriphosphat, neben den Alkaliortho- und Alkalipyrophosphaten, von besonderer Bedeutung. Diese Phosphate können ganz oder teilweise durch organische Komplexbildner für Calciumionen ersetzt werden. Dazu gehören Verbindungen vom Typ der Aminopolycarbonsäuren wie z.B. Nitrilotriessigsäure (NTA), Ethylendiamintetraessigsäure, Diethylentriaminpentaessigsäure sowie höhere Homologe. Geeignete phosphorhaltige organische Komplexbildner sind die wasserlöslichen Salze der Alkanpolyphosphonsäuren, Amino- und Hydroxyalkanpolyphosphonsäuren und Phosphonopolycarbonsäuren wie z.B. Methandiphosphonsäure, Dimethylaminomethan-1,1-diphosphonsäuren, Aminotrimethylentriphosphonsäure, 1-Hydroxyethan-1,1-diphosphonsäure, 1-Phosphonoethan-1,2-dicarbonsäure, 2-Phosphonobutan-1,2,4-tricarbonsäure.Suitable organic and inorganic builder substances are weakly acidic, neutral or alkaline-reacting salts, in particular alkali salts, which are able to precipitate or bind calcium ions in a complex manner. Of the inorganic salts, the water-soluble alkali metal or alkali polyphosphates, in particular pentasodium triphosphate, in addition to the alkali ortho- and alkali pyrophosphates, are of particular importance. All or part of these phosphates can be replaced by organic complexing agents for calcium ions. These include compounds of the aminopolycarboxylic acid type, e.g. Nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and higher homologues. Suitable phosphorus-containing organic complexing agents are the water-soluble salts of alkane polyphosphonic acids, amino and hydroxyalkane polyphosphonic acids and phosphonopolycarboxylic acids such as e.g. Methane diphosphonic acid, dimethylaminomethane-1,1-diphosphonic acids, aminotrimethylene triphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 1-phosphonoethane-1,2-dicarboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid.

Unter den organischen Gerüstsubstanzen sind die Stickstoff- und Phosphor-freien, mit Calciumionen Komplexsalze bildenden Polycarbonsäuren, wozu auch Carboxylgruppen enthaltende Polymerisate zählen, von besonderer Bedeutung. Geeignet sind z.B. Citronensäure, Wein säure, Benzolhexacarbonsäure und Tetrahydrofurantetracarbonsäure. Auch Ethergruppen enthaltende Polycarbonsäuren sind geeignet, wie 2,2′-Oxydibernsteinsäure sowie mit Glykolsäure teilweise oder vollständig veretherte mehrwertige Alkohole oder Hydroxycarbonsäuren, z.B. Biscarboxymethylethylengylkol, Carboxymethyloxybernsteinsäure, Carboxymethyltartronsäure und carboxymethylierte bzw. oxydierte Polysaccharide. Weiterhin eignen sich polymere Carbonsäuren mit einem Molekulargewicht zwischen 350 und etwa 1 500 000 in Form wasserlöslicher Salze. Besonders bevorzugte polymere Polycarboxylate haben ein Molekulargewicht im Bereich von 500 bis 175 000 und insbesondere im Bereich von 10 000 bis 100 000. Zu diesen Verbindungen gehören beispielsweise Polyacrylsäure, Poly- -Hydroxyacrylsäure, Polymaleinsäure sowie die Copolymerisate der entsprechenden monomeren Carbonsäuren untereinander oder mit ethylenisch ungesättigten Verbindungen wie Vinylmethylether. Geeignet sind weiterhin die wasserlöslichen Salze der Polyglyoxylsäure.Of the organic framework substances, the nitrogen-free and phosphorus-free polycarboxylic acids which form complex salts with calcium ions, which also include polymers containing carboxyl groups, are of particular importance. For example, citric acid, wine are suitable acid, benzene hexacarboxylic acid and tetrahydrofuran tetracarboxylic acid. Polycarboxylic acids containing ether groups are also suitable, such as 2,2′-oxydisuccinic acid and polyhydric alcohols or hydroxycarboxylic acids partially or completely etherified with glycolic acid, for example biscarboxymethylethylene glycol, carboxymethyloxy succinic acid, carboxymethyl tartronic acid and carboxymethylated or oxidized polysaccharides. Polymeric carboxylic acids with a molecular weight between 350 and about 1,500,000 in the form of water-soluble salts are also suitable. Particularly preferred polymeric polycarboxylates have a molecular weight in the range from 500 to 175,000 and in particular in the range from 10,000 to 100,000. These compounds include, for example, polyacrylic acid, polyhydroxyacrylic acid, polymaleic acid and the copolymers of the corresponding monomeric carboxylic acids with one another or with ethylenically unsaturated Compounds such as vinyl methyl ether. The water-soluble salts of polyglyoxylic acid are also suitable.

Als wasserunlösliche anorganische Gerüstsubstanzen eignen sich die in der DE-OS 24 12 837 als Phosphatsubstitute für Wasch- und Reinigungsmittel näher beschriebenen feinteiligen, synthetischen, gebundenes Wasser enthaltenden Natriumalumosilicate vom Zeolith-A-Typ.Suitable water-insoluble inorganic builders are the finely divided, synthetic, bound water-containing sodium aluminosilicates of the zeolite A type described in DE-OS 24 12 837 as phosphate substitutes for detergents and cleaning agents.

Die kationen-austauschenden Natriumalumosilicate kommen in der üblichen hydratisierten, feinkristallinen Form zum Einsatz, das heißt, sie weisen praktisch keine Teilchen größer als 30 µm auf und bestehen vorzugsweise zu wenigstens 80 % aus Teilchen einer Größe kleiner als 10 µm. Ihr Calciumbindevermögen, das nach den Angaben der DE-OS 24 12 837 bestimmt wird, liegt im Bereich von 100 bis 200 mg CaO/g. Geeignet ist insbesondere der Zeolith NaA, ferner auch der Zeolith NaX und Mischungen aus NaA und NaX.The cation-exchanging sodium aluminosilicates are used in the usual hydrated, finely crystalline form, that is to say that they have practically no particles larger than 30 μm and preferably consist of at least 80% of particles smaller than 10 μm. Your calcium binding capacity, according to the details of DE-OS 24 12 837 is determined, is in the range of 100 to 200 mg CaO / g. Zeolite NaA is particularly suitable, as is zeolite NaX and mixtures of NaA and NaX.

Geeignete anorganischen, nicht komplexbildende Salze sind die - auch als "Waschalkalien" bezeichneten - Alkalisalze der Bicarbonate, Carbonate, Borate, Sulfate und Silicate. Von den Alkalisilicaten sind die Natriumsilicate, in denen das Verhältnis Na₂O : SiO₂ zwischen 1 : 1 und 1 : 3,5 liegt, besonders bevorzugt.Suitable inorganic, non-complexing salts are the alkali salts of bicarbonates, carbonates, borates, sulfates and silicates - also referred to as "washing alkalis". Of the alkali silicates, the sodium silicates in which the ratio Na₂O: SiO₂ is between 1: 1 and 1: 3.5 are particularly preferred.

Weitere Gerüstsubstanzen, die wegen ihrer hydrotropen Eigenschaften m eist in flüssigen Mitteln eingesetzt werden, sind die Salze der nichtkapilaraktiven 2 bis 9 Kohlenstoffatome enthaltenden Sulfonsäuren, Carbonsäuren und Sulfocarbonsäuren, beispielsweise die Alkalisalze der Alkan-, Benzol-, Toluol-, Xylol- oder Cumolsulfonsäuren, der Sulfobenzoesäuren, Sulfophthalsäure, Sulfoessigsäure, Sulfobernsteinsäure sowie die Salze der Essigsäure oder der Milchsäure. Als Lösungsvermittler sind auch Acetamid und Harnstoffe geeignet.Other builder substances that are mostly used in liquid agents because of their hydrotropic properties are the salts of the non-capillary active sulfonic acids containing 2 to 9 carbon atoms, carboxylic acids and sulfocarboxylic acids, for example the alkali salts of alkanoic, benzene, toluene, xylene or cumene sulfonic acids, of sulfobenzoic acids, sulfophthalic acid, sulfoacetic acid, sulfosuccinic acid and the salts of acetic acid or lactic acid. Acetamide and ureas are also suitable as solubilizers.

Tenside, die als weitere essentielle Komponente in Wasch- und Reinigungsmitteln enthalten sind, besitzen im Molekül wenigstens einen hydrophoben organischen Rest und eine wasserlöslich machende anionische, zwitterionische oder nichtionische Gruppe. Bei dem hydrophoben Rest handelt es sich meist um einen aliphatischen Kohlenwasserstoffrest mit 8 bis 26, vorzugsweise 10 bis 22 und insbesondere 12 bis 18 C-Atomen oder um einen alkylaromatischen Rest mit 6 bis 18, vorzugsweise 8 bis 16 aliphatischen C-Atomen.Surfactants, which are contained as a further essential component in detergents and cleaning agents, have at least one hydrophobic organic residue and one water-solubilizing anionic, zwitterionic or nonionic group in the molecule. The hydrophobic radical is usually an aliphatic hydrocarbon radical with 8 to 26, preferably 10 to 22 and in particular 12 to 18 C atoms or an alkyl aromatic radical with 6 to 18, preferably 8 to 16 aliphatic C atoms.

Als anionische Tenside sind z.B. Seifen aus natürlichen oder synthetischen, vorzugsweise gesättigten Fettsäuren, gegebenenfalls auch aus Harz- oder Naphthensäuren, brauchbar. Geeignete synthetische anionische Tenside sind solche vom Typ der Sulfate, Sulfonate und der synthetischen Carboxylate.As anionic surfactants e.g. Soaps from natural or synthetic, preferably saturated fatty acids, optionally also from resin or naphthenic acids, can be used. Suitable synthetic anionic surfactants are those of the sulfate, sulfonate and synthetic carboxylate type.

Als Tenside vom Sulfonattyp kommen Alkylbenzolsulfonate (C 9-15-Alkyl), Olefinsulfonate, d.h. Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie beispielsweise aus C 12-18-Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält, in Betracht.The surfactants of the sulfonate type are alkylbenzenesulfonates (C 9-15- alkyl), olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from C 12-18 monoolefins with a terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.

Geeignet sind auch die Alkansulfonate, die aus C 12-18Alkanen durch Sulfochlorierung oder Sulfoxydation und anschließende Hydrolyse bzw. Neutralisation bzw. durch Bisulfitaddition an Olefine erhältlich sind, sowie die Ester von alpha-Sulfofettsäuren, z.B. die alpha-sulfonierten Methyl- oder Ethylester der hydrierten Kokos-Palmkern- oder Talgfettsäuren.Also suitable are the alkanesulfonates which are obtainable from C 12-18 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and the esters of alpha-sulfo fatty acids, for example the alpha-sulfonated methyl or ethyl esters of hydrogenated coconut palm kernel or tallow fatty acids.

Geeignete Tenside vom Sulfattyp sind die Schwefelsäuremonoester aus primären Alkoholen natürlichen und synthetischen Ursprungs, d.h. aus Fettalkoholen, wie z.B. Kokosfettalkoholen, Talgfettalkoholen, Oleylalkohol, Lauryl-, Myristyl-, Palmityl- oder Stearylalkohol, oder den C 10-20-Oxoalkoholen, und diejenigen sekundären Alkohole dieser Kettenlänge. Auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten aliphatischen primären Alkohole bzw. ethoxylierten sekundären Alkohole bzw. Alkylphenole sind geeignet. Ferner eignen sich sulfatierte Fettsäurealkoholamide und sulfatierte Fettsäuremonoglyceride.Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, ie from fatty alcohols, such as, for example, coconut oil alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the C 10-20 oxo alcohols, and those secondary Alcohols of this chain length. The sulfuric acid monoesters of the aliphatic primary alcohols or ethoxylated secondary alcohols or alkylphenols ethoxylated with 1 to 6 mol of ethylene oxide are also suitable. Sulfated fatty acid alcoholamides and sulfated fatty acid monoglycerides are also suitable.

Weitere geeignete anionische Tenside sind die Fettsäureester bzw. -amide von Hydroxy- oder Aminocarbonsäuren bzw. -sulfonsäuren, wie z.B. die Fettsäuresarcoside, -glycolate, -lactate, -tauride oder -isethionate.Other suitable anionic surfactants are the fatty acid esters or amides of hydroxy or aminocarboxylic acids or sulfonic acids, e.g. the fatty acid sarcosides, glycolates, lactates, taurides or isethionates.

Die anionischen Tenside können in Form ihrer Natrium-, Kalium- und Ammoniumsalze sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder Triethanolamin, vorliegen.The anionic surfactants can be in the form of their sodium, potassium and ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.

Als nichtionische Tenside sind Anlagerungsprodukte von 1 bis 40, vorzugsweise 2 bis 20 Mol Ethylenoxid an 1 Mol einer Verbindung mit im wesentlichen 10 bis 20 Kohlenstoffatomen aus der Gruppe der Alkohole, Alkylphenole und Fettsäuren verwendbar. Besonders wichtig sind die Anlagerungsprodukte von 8 bis 20 Mol Ethylenoxid an primäre Alkohole, wie z.B. an Kokos- oder Talgfettalkohole, an Oleylalkohol, an Oxoalkohole, oder an sekundäre Alkohole mit 8 bis 18, vorzugsweise 12 bis 18 C-Atomen, sowie an Mono- oder Dialkylphenole mit 6 bis 14 C-Atomen in den Alkylresten. Neben diesen wasserlöslichen Nonionics sind aber auch nicht bzw. nicht vollständig wasserlösliche Polyglykolether mit 2 bis 7 Ethylenglykoletherresten im Molekül von Interesse, insbesondere, wenn sie zusammen mit wasserlöslichen nichtionischen oder anionischen Tensiden eingesetzt werden.& <PAR>Weiterhin sind als nichtionische Tenside die wasserlöslichen, 20 bis 250 Ethylenglykolethergruppen und 10 bis 100 Propylenglykolethergruppen enthaltenden Anlagerungsprodukte von Ethylenoxid an Polypropylenglykol, Alkylendiamin-polypropylenglykol und an Alkylpolypropylenglykole mit 1 bis 10 Kohlenstoffatomen in der Alkylkette brauchbar, in denen die Polypropylenglykolkette als hydrophober Rest fungiert. Auch nichtionische Tenside vom Typ der Aminoxide oder Sulfoxide sind verwendbar, beispielsweise die Verbindungen N-Kokosalkyl-N, N-dimethylaminoxid, N-Hexadecyl-N, N-bis (2,3-dihydroxypropyl)-aminoxid, N-Talgalkyl-N, n-dihydroxyethylaminoxid. N-alkoxylierte Fettsäureamide werden im Sinne der vorliegenden Erfindung nicht unter dem Begriff der nichtionischen Tenside verstanden.Addition products of 1 to 40, preferably 2 to 20 moles of ethylene oxide with 1 mole of a compound having essentially 10 to 20 carbon atoms from the group of alcohols, alkylphenols and fatty acids can be used as nonionic surfactants. The addition products of 8 to 20 mol of ethylene oxide with primary alcohols, such as, for example, with coconut oil or tallow fatty alcohols, with oleyl alcohol, with oxo alcohols, or with secondary alcohols with 8 to 18, preferably 12 to 18, carbon atoms, and with mono- or dialkylphenols with 6 to 14 carbon atoms in the alkyl radicals. In addition to these water-soluble nonionics, non-fully or not completely water-soluble polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants. &<PAR> Furthermore, the water-soluble, 20 to 250 ethylene glycol ether groups and 10 up to 100 propylene glycol ether group-containing adducts of ethylene oxide with polypropylene glycol, alkylenediamine-polypropylene glycol and with alkylpolypropylene glycols with 1 to 10 carbon atoms in the alkyl chain, in which the polypropylene glycol chain acts as a hydrophobic radical. Nonionic surfactants of the amine oxide or sulfoxide type can also be used, for example the compounds N-cocoalkyl-N, N-dimethylamine oxide, N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) amine oxide, N-tallow alkyl-N, n-dihydroxyethylamine oxide. For the purposes of the present invention, N-alkoxylated fatty acid amides are not to be understood as nonionic surfactants.

Bei den gegebenenfalls verwendeten zwitterionischen Tensiden handelt es sich bevorzugt um Derivate aliphatischer quartärer Ammoniumverbindungen, in denen einer der aliphatischen Reste aus einem C₈-C₁₈-Rest besteht und ein weiterer eine anionische, wasserlöslich machende Carboxy-, Sulfo- oder Sulfato-Gruppe enthält. Typische Vertreter derartiger oberflächenaktiver Betaine sind beispielsweise die Verbindungen 3-(N-Hexadecyl-N,N-dimethylammonio)-propansulfonat; 3-(N-Talgalkyl-N,N-dimethylammonio)-2-hydroxypropansulfonat; 3-(N-Hexadecyl-N,N-bis (2-hydroxyethyl)-ammonio)-2-hydroxypropylsulfat; 3-(N-Kokosalkyl-N,N-bis(2,3-dihydroxypropyl)-ammonio)-propansulfonat; N-Tetradecyl-N,N-dimethyl-ammonioacetat; N-Hexadecyl-N,N-bis(2,3-dihydroxypropyl)-ammonioacetat.The optionally used zwitterionic surfactants are preferably derivatives of aliphatic quaternary ammonium compounds in which one of the aliphatic radicals consists of a C₈-C₁₈ radical and another contains an anionic, water-solubilizing carboxy, sulfo or sulfato group. Typical representatives of such surface-active betaines are, for example, the compounds 3- (N-hexadecyl-N, N-dimethylammonio) propane sulfonate; 3- (N-tallow alkyl-N, N-dimethylammonio) -2-hydroxypropanesulfonate; 3- (N-hexadecyl-N, N-bis (2-hydroxyethyl) ammonium) -2-hydroxypropyl sulfate; 3- (N-cocoalkyl-N, N-bis (2,3-dihydroxypropyl) ammonium) propane sulfonate; N-tetradecyl-N, N-dimethyl-ammonioacetate; N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) ammonioacetate.

Ein verringertes Schäumvermögen, das beim Arbeiten in Maschinen erwünscht ist, erreicht man beispielsweise durch Mitverwendung von Seifen. Bei Seifen steigt die Schaumdämpfung mit dem Sättigungsgrad und der C-Zahl des Fettsäureesters an; Seifen der gesättigten C 20-24-Fettsäuren eignen sich deshalb besonders als Schaumdämpfer.A reduced foaming power, which is desirable when working in machines, can be achieved, for example, by using soaps. With soaps, foam attenuation increases with the degree of saturation and the C number of the fatty acid ester; Soaps of saturated C 20-24 fatty acids are therefore particularly suitable as foam suppressants.

Bei den nichttensidartigen Schauminhibitoren handelt es sich im allgemeinen um wasserunlösliche, meist aliphatische C₈-C₂₂-Kohlenstoffreste enthaltende Verbindungen. Geeignete nichttensidartige Schauminhibitoren sind z.B. die N-Alkylaminotriazine, d.h. Umsetzungsprodukte von 1 Mol Cyanurchlorid mit 2 bis 3 Mol eines Mono- oder Dialkylamins mit im wesentlichen 8 bis 18 C-Atomen im Alkylrest. Geeignet sind auch propoxylierte und/oder butoxylierte Aminotriazine, z.B. die Umsetzungsprodukte von 1 Mol Melamin mit 5 bis 10 Mol Proplyenoxid und zusätzlich 10 bis 50 Mol Butylenoxid sowie die aliphatischen C₁₈-C₄₀-Ketone, wie z.B. Stearon, die Fettketone aus gehärteter Tranfettsäure oder Talgfettsäure, sowie ferner die Paraffine und Halogenparaffine mit Schmelzpunkten unterhalb 100°C und Silikonölemulsionen auf Basis polymerer siliciumorganischer Verbindungen.The non-surfactant-like foam inhibitors are generally water-insoluble, mostly aliphatic C₈-C₂₂-carbon-containing compounds. Suitable non-surfactant foam inhibitors are e.g. the N-alkylaminotriazines, i.e. Reaction products of 1 mol of cyanuric chloride with 2 to 3 mol of a mono- or dialkylamine with essentially 8 to 18 carbon atoms in the alkyl radical. Propoxylated and / or butoxylated aminotriazines, e.g. the reaction products of 1 mole of melamine with 5 to 10 moles of propylene oxide and additionally 10 to 50 moles of butylene oxide and the aliphatic C₁₈-C₄₀ ketones, e.g. Stearon, the fatty ketones from hardened trans-fatty acid or tallow fatty acid, as well as the paraffins and halogen paraffins with melting points below 100 ° C and silicone oil emulsions based on polymeric organosilicon compounds.

Als weitere Komponente können die Wasch- und Reinigungsmittel Schmutzträger enthalten, die den von der Faser abgelösten Schmutz in der Flotte suspendiert halten und so das Vergrauen verhindern. Hierzu sind wasserlösliche Kolloide meist organischer Natur geeignet, wie beispielsweise die wasserlöslichen Salze polymerer Carbonsäuren, Leim, Gelantine, Salze von Ethercarbonsäuren oder Ethersulfonsäuren der Stärke oder der Cellulose oder Salze von sauren Schwefelsäureestern der Cellulose oder der Stärke. Auch wasserlösliche, saure Gruppen enthaltende Polyamide sind für diesen Zweck geeignet. Weiterhin lassen sich lös liche Stärkepräparate und andere als die oben genannten Stärkeprodukte verwenden, wie z.B. abgebaute Stärke, Aldehydstärken usw. Auch Polyvinylpyrrolidon ist brauchbar.As a further component, the washing and cleaning agents can contain dirt carriers, which keep the dirt detached from the fibers suspended in the liquor and thus prevent graying. For this purpose, water-soluble colloids of mostly organic nature are suitable, such as, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Furthermore, they can be solved Use starch preparations and starch products other than those mentioned above, such as degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.

Unter den als Bleichmittel dienenden, in Wasser H₂O₂ liefernden Verbindungen haben das Natriumperborattetrahydrat (NaBO₂ . H₂O₂ . 3 H₂O) und das -monohydrat (NaBO₂ . H₂O₂) besondere Bedeutung. Diese Verbindungen können teilweise oder vollständig durch andere Aktivsäurestoffträger, insbesondere durch Peroxyhydrate, wie Peroxycarbonate (Na₂CO₃ . 1,5 H₂O₂), oxypyrophosphate, Citratperhydrate, Harnstoff-H₂O₂- oder Melamin-H₂O₂-Verbindungen sowie durch H₂O₂ liefernde persaure Salze, wie z.B. Caroate (KHSO₅), Perbenzoate oder Peroxyphthalate ersetzt werden.Of the compounds used as bleaching agents which supply H₂O₂ in water, sodium perborate tetrahydrate (NaBO₂. H₂O₂. 3 H₂O) and monohydrate (NaBO₂. H₂O₂) are of particular importance. These compounds can be partially or completely replaced by other active acid carriers, in particular by peroxy hydrates, such as peroxycarbonates (Na₂CO₃. 1.5 H₂O₂), oxypyrophosphates, citrate perhydrates, urea-H₂O₂- or melamine-H₂O₂-compounds as well as by H₂O₂-delivering peracid salts, e.g. Caroate (KHSO₅), perbenzoate or peroxyphthalate can be replaced.

Es empfiehlt sich, übliche wasserlösliche und/oder wasserunlösliche Stabilisatoren für die Peroxyverbindungen zusammen mit diesen in Mengen von 0,25 bis 10 Gew.-% einzuarbeiten. Als wasserunlösliche Stabilisatoren, die vorzugsweise 0,5 bis 8 Gew.-% - bezogen auf die gesamte Waschmittelrezeptur - ausmachen, eignen sich die meist durch Fällung aus wäßrigen Lösungen erhaltenen Magnesiumsilicate. Als wasserlösliche Stabilisatoren, die vorzugsweise zusammen mit wasserunlöslichen vorhanden sind, eignen sich organische Schwermetallkomplexbildner, insbesondere solche vom Typ der oben beschriebenen Aminopolycarbonsäuren und Polyphosphonsäuren.It is advisable to incorporate conventional water-soluble and / or water-insoluble stabilizers for the peroxy compounds together with them in amounts of 0.25 to 10% by weight. Suitable water-insoluble stabilizers, which preferably make up 0.5 to 8% by weight, based on the overall detergent formulation, are the magnesium silicates which are usually obtained by precipitation from aqueous solutions. Suitable water-soluble stabilizers, which are preferably present together with water-insoluble ones, are organic heavy metal complexing agents, in particular those of the type of the aminopolycarboxylic acids and polyphosphonic acids described above.

Um beim Waschen bei Temperaturen unterhalb 80°C, insbesondere im Bereich von 40 bis 60°C, eine befriedi gende Bleichwirkung zu erreichen, werden bevorzugt aktivatorhaltige Bleichkomponenten in die Präparate eingearbeitet.To be a satisfactory when washing at temperatures below 80 ° C, especially in the range of 40 to 60 ° C to achieve sufficient bleaching effect, activator-containing bleaching components are preferably incorporated into the preparations.

Als Aktivatoren für in Wasser H₂O₂ liefernde Perverbindungen dienen bestimmte, mit diesem H₂O₂ organische Persäuren bildende N-Acyl- bzw. O-Acyl-Verbindungen, insbesondere Acetyl-, Propionyl- oder Benzoylverbindungen, sowie Kohlensäure- bzw. Pyrokohlensäureester. Brauchbare Verbindungen sind unter anderen: N-diacylierte und N,N′-tetraacylierte Amine wie z.B. N,N,Nʹ,N′-Tetraacetyl-methylendiamin bzw. -ethylendiamin, N,N-Diacetylanilin und N,N-Diacetyl-p-toluidin bzw. 1,3-diacylierte Hydantoine, Alkyl-N-sulfonylcarbonamide, z.B. N-Methyl-N-mesyl-acetamid, N-Methyl-N-mesyl-benzamid, N-Methyl-N-mesyl-p-nitrobenzamid, und N-Methyl-N-mesyl-p-methoxybenzamid, N-acylierte cyclische Hydrazide, acylierte Triazole oder Urazole wie z.B. das Monoacetylmaleinsäurehydrazid, O,N,N-trisubstituierte Hydroxylamine wie z.B. O-Benzoyl-N,N-succinyl-hydroxylamin, O-Acetyl-N,N-succinylhydroxylamin, O-p-Methoxybenzoyl-N,N-succinyl-hydroxylamin, O-p-Nitrobenzoyl-N,N-succinylhydroxylamin und O,N,N-Triacetyl-hydroxylamin, N,N′-Diacyl-sulfurylamide, wie z.B. N,N′-Dimethyl-N,N′-diacetyl-sulfurylamid, und N,N′-Diethyl-N,N′-dipropionyl-sulfurylamid, Triacylcyanurate, z.B. Triacetyl- oder Tribenzoylcyanurat, Carbonsäureanhydride, z.B. Benzoesäureanhydrid, m-Chlorbenzoesäureanhydrid, Phthalsäureanhydrid, 4-Chlorphthalsäureanhydrid, Zuckerester, wie z.B. Glucosepentaacetat, 1,3-Diacyl-4,5-diacyloxy-imidazolidine, beispielsweise die Verbindungen 1,3-Diformyl-4,5-diacetoxyimidazolidin, 1,3-Diacetyl-4,5-diacetoxyimidazolidin, 1,3-Diacetyl-4,5-dipropionyloxy-imidazo lidin, acylierte Glykolurile, wie z.B. Tetrapropionylglykoluril oder Diacetyl-dibenzoyl-glykoluril, diacylierte 2,5-Diketopiperazine, wie z.B. 1,4-Diacetyl-2,5-diketopiperazin, 1,4-Dipropionyl-2,5-diketopiperazin, 1,4-Dipropionyl-3,6-dimethyl-2,5-diketopiperazin, Acetylierungs- bzw. Benzoylierungsprodukte von Propylendiharnstoff bzw. 2,2-Dimethyl-propylendiharnstoff (2,4,6,8-Tetraaza-bicyclo-(3,3,1)-nonan-3,7-dion bzw. dessen 9,9-Dimethylderivat), Natriumsalze der p-(Ethoxycarbonyloxy)-benzoesäure und p-(Propoxycarbonyloxy)-benzolsulfonsäure.Certain N-acyl or O-acyl compounds which form organic peracids and which form H₂O₂, in particular acetyl, propionyl or benzoyl compounds, and carbonic acid or pyrocarbonic acid esters are used as activators for per compounds which supply H₂O₂ in water. Useful compounds include: N-diacylated and N, N'-tetraacylated amines such as N, N, Nʹ, N'-tetraacetyl-methylenediamine or -ethylenediamine, N, N-diacetylaniline and N, N-diacetyl-p- toluidine or 1,3-diacylated hydantoins, alkyl-N-sulfonylcarbonamides, for example N-methyl-N-mesyl-acetamide, N-methyl-N-mesyl-benzamide, N-methyl-N-mesyl-p-nitrobenzamide, and N-methyl-N-mesyl-p-methoxybenzamide, N-acylated cyclic hydrazides, acylated triazoles or urazoles such as the monoacetyl maleic hydrazide, O, N, N-trisubstituted hydroxylamines such as O-benzoyl-N, N-succinyl-hydroxylamine, O Acetyl-N, N-succinylhydroxylamine, Op-methoxybenzoyl-N, N-succinyl-hydroxylamine, Op-nitrobenzoyl-N, N-succinylhydroxylamine and O, N, N-triacetyl-hydroxylamine, N, N'-diacylsulfurylamide, such as N, N'-dimethyl-N, N'-diacetyl-sulfurylamide, and N, N'-diethyl-N, N'-dipropionyl-sulfurylamide, triacylcyanurates, e.g. triacetyl- or tribenzoylcyanurate, carboxylic anhydrides, e.g. benzoic anhydride, m- Chlorobenzoic anhydride, phthalic acid reanhydride, 4-chlorophthalic anhydride, sugar esters, such as, for example, glucose pentaacetate, 1,3-diacyl-4,5-diacyloxy-imidazolidine, for example the compounds 1,3-diformyl-4,5-diacetoxyimidazolidine, 1,3-diacetyl-4,5 -diacetoxyimidazolidine, 1,3-diacetyl-4,5-dipropionyloxy-imidazo lidin, acylated glycolurils, such as, for example, tetrapropionylglycoluril or diacetyl-dibenzoyl-glycoluril, diacylated 2,5-diketopiperazines, such as, for example, 1,4-diacetyl-2,5-diketopiperazine, 1,4-dipropionyl-2,5-diketopiperazine, 1, 4-dipropionyl-3,6-dimethyl-2,5-diketopiperazine, acetylation or benzoylation products of propylene diurea or 2,2-dimethyl-propylene diurea (2,4,6,8-tetraaza-bicyclo- (3,3, 1) -nonane-3,7-dione or its 9,9-dimethyl derivative), sodium salts of p- (ethoxycarbonyloxy) -benzoic acid and p- (propoxycarbonyloxy) -benzenesulfonic acid.

Die Waschmittel können als optische Aufheller für Baumwolle insbesondere Derivate der Diaminostilbendisulfonsäure bzw. deren Alkalimetallsalze enthalten. Geeignet sind z.B. Salze der 4,4′-Bis(2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino)-stilben-2 2ʹ-disulfonsäure oder gleichartig aufgebaute Verbindungen, die anstelle der Morpholinogruppe eine Diethanolaminogruppe, eine Methylaminogruppe oder eine 2-Methoxyethylaminogruppe tragen. Als Aufheller für Polyamidfasern kommen solche vom Typ der 1,3-Diaryl-2-pyrazoline in Frage, beispielsweise die Verbindung 1-(p-Sulfamoylphenyl)-3-(p-chlorphenyl)-2-pyrazolin sowie gleichartig aufgebaute Verbindungen, die anstelle der Sulfamoylgruppe z.B. die Methoxycarbonyl-, 2-Methoxyethoxycarbonyl-, die Acetylamino- od er die Vinylsulfonylgruppe tragen. Brauchbare Polyamidaufheller sind ferner die substituierten Aminocumarine, z.B. das 4-Methyl-7-dimethylamino- oder das 4-Methyl-7-diethylaminocumarin. Weiterhin sind als Polyamidaufheller die Verbindungen 1-(2-Benzimidazolyl)-2-(1-hydroxyethyl-2-benzinimidazolyl)-ethylen und 1-Ethyl-3-phenyl-7-diethylamino-carbostyril brauchbar. Als Aufheller für Polyester- und Polyamidfasern sind die Verbindungen 2,5-Di-(2-benzoxyzolyl)-thiophen,2-(2-Benzoxylolyl-naphto[2,3-b]-thioph n und 1,2-Di-(5-methyl-2-benzoxazolyl)-ethylen geeignet. Weiterhin können Aufheller vom Typ des substituierten 4,4′-Distyryl-diphenyls anwesend sein; z.B. die Verbindung 4,4′-Bis-(4-chlor-3-sulfostyryl)-diphenyl. Auch Gemische der vorgenannten Aufheller können verwendet werden.The detergents can contain, as optical brighteners for cotton, in particular derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2 2ʹ-disulfonic acid or compounds of the same structure which replace the morpholino group carry a diethanolamino group, a methylamino group or a 2-methoxyethylamino group. Possible brighteners for polyamide fibers are those of the 1,3-diaryl-2-pyrazoline type, for example the compound 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline and compounds of the same structure which instead of the sulfamoyl group, for example the methoxycarbonyl, 2-methoxyethoxycarbonyl, the acetylamino or the vinylsulfonyl group. Useful polyamide brighteners are also the substituted aminocoumarins, for example 4-methyl-7-dimethylamino or 4-methyl-7-diethylaminocoumarin. The compounds 1- (2-benzimidazolyl) -2- (1-hydroxyethyl-2-benzimidazolyl) ethylene and 1-ethyl-3-phenyl-7-diethylamino-carbostyril are also useful as polyamide brighteners. As a brightener for Polyester and polyamide fibers are the compounds 2,5-di- (2-benzoxyzolyl) -thiophene, 2- (2-benzoxylolyl-naphto [2,3-b] -thiophene and 1,2-di- (5-methyl -2-benzoxazolyl) ethylene and brighteners of the substituted 4,4'-distyryl-diphenyl type may also be present, for example the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl Mixtures of the aforementioned brighteners can be used.

Als wasserlösliche organische Lösungsmittel eignen sich die niederen Alkohole, Etheralkohole, Glykole oder Ketone mit 1 bis 6 Kohlenstoffatomen, wie z.B. Methanol, Ethanol, Propanol, Isopropanol, Ethylenglykol, Proplenglykol, Diethylenglykol, Methylglykol, Ethylglykol, Butylglykol oder Aceton und Methylethylketon.The lower alcohols, ether alcohols, glycols or ketones with 1 to 6 carbon atoms, such as e.g. Methanol, ethanol, propanol, isopropanol, ethylene glycol, propylene glycol, diethylene glycol, methyl glycol, ethyl glycol, butyl glycol or acetone and methyl ethyl ketone.

Die an kosmetischen Anschmutzungen (wie Make-up, Lippenstift und Wimperntusche) deutlich sichtbare Waschkraftverbesserung durch die Verwendung von N-alkoxylierten Fettsäureamiden war angesichts der gleichzeitigen Verwendung von Schichtsilicaten und der damit möglicherweise verbundenen Wechselwirkung nicht vorhersehbar.The clearly visible improvement in washing power due to the use of N-alkoxylated fatty acid amides on cosmetic stains (such as make-up, lipstick and mascara) was not foreseeable in view of the simultaneous use of layered silicates and the associated interaction.

In den folgenden Grundrezepturen und Beispielen steht "EO" für angelagertes Ethylenoxid. Die Prozentangaben bedeuten Gew.-%, bezogen auf die Gesamtzusammensetzung des Waschmittels.In the following basic formulations and examples, "EO" stands for attached ethylene oxide. The percentages are% by weight, based on the total composition of the detergent.

Die Einarbeitung der N-alkoxylierten Fettsäureamide in die Waschmittelrezepturen kann nach herkömmlichen Techniken zur Herstellung von Waschmitteln erfolgen, z. B. durch Heißzerstäubung zusammen mit anderen Waschmittelkomponenten, durch Granulierung zusammen mit festen und/oder flüssigen Waschmittelbestandteilen (u. a. mit Schichtsilicat) bzw. durch nachträgliches Aufbringen auf feste Waschmittelteile (z. B. Sprühpulver, Granulat, Perborat, Zeolith, Schichtsilicat) gemäß der Ein- oder Mehrpulverstrategie.The incorporation of the N-alkoxylated fatty acid amides into the detergent formulations can be carried out according to conventional techniques for the production of detergents, e.g. B. by hot atomization together with others Detergent components, by granulation together with solid and / or liquid detergent components (including layered silicate) or by subsequent application to solid detergent parts (e.g. spray powder, granulate, perborate, zeolite, layered silicate) according to the single or multi-powder strategy.

Beispiele:Examples: Vergleichsbeispiel 1Comparative Example 1

Es wurde ein Gemisch folgender Zusammensetzung hergestellt:A mixture of the following composition was produced:

Grundrezeptur 1:Basic recipe 1:

8,0 % Alkylbenzolsulfonat
4,0 % C 16-18-Fettalkohol-5 EO
0,5 % Talgalkohol-14 EO
0,8 % C 16-22-Fettsäure-Na-Salz
20,0 % Zeolith Na A
12,0 % Bentonit (Schichtsilikat)
4,0 % Acrylsäure-Maleinsäure-Copolymer, MG=70 000
0,1 % EDTA
5,0 % Soda
3,0 % Wasserglas, Verhältnis Na₂O zu SiO₂ = 3,35
0,8 % Celluloseethermischung
22,5 % Natriumperborat-tetrahydrat
0,2 % optischer Aufheller
0,1 % Siliconöl
0,3 % Protease
7,0 % Natriumsulfat
Rest      Wasser, Salze
8.0% alkyl benzene sulfonate
4.0% C 16-18 fatty alcohol-5 EO
0.5% tallow alcohol-14 EO
0.8% C 16-22 fatty acid Na salt
20.0% zeolite Na A
12.0% bentonite (layered silicate)
4.0% acrylic acid-maleic acid copolymer, MW = 70,000
0.1% EDTA
5.0% soda
3.0% water glass, ratio Na₂O to SiO₂ = 3.35
0.8% cellulose ether mixture
22.5% sodium perborate tetrahydrate
0.2% optical brightener
0.1% silicone oil
0.3% protease
7.0% sodium sulfate
Balance water, salts

Als Polycarbonsäure wurde ein Copolymerisat aus Acrylsäure und Maleinsäure mit einem mittleren Molekulargewicht von 70 000 (Sokalan CP5 R) in Form des Natriumsalzes zum Einsatz gebracht.A copolymer of acrylic acid and maleic acid with an average molecular weight of 70,000 (Sokalan CP5 R ) in the form of the sodium salt was used as the polycarboxylic acid.

Beispiel 1:Example 1:

Bei Verminderung des Gehalts an Natriumsulfat wurde gemäß Vergleichsbeispiel 1 eine Grundrezeptur hergestellt, die 1,5 % Ölsäurediethanolamid enthielt.When the sodium sulfate content was reduced, a basic formulation was prepared according to Comparative Example 1, which contained 1.5% oleic acid diethanolamide.

Beispiel 2:Example 2:

Bei Verminderung des Gehalts an Natriumsulfat wurde gemäß Vergleichsbeispiel 1 eine Grundrezeptur hergestellt, die 1,5 % Sojafettsäurediethanolamid enthielt.When the sodium sulfate content was reduced, a basic formulation was prepared according to Comparative Example 1, which contained 1.5% soy fatty acid diethanolamide.

Beispiel 3:Example 3:

Bei Verminderung des Gehalts an Natriumsulfat wurde gemäß Vergleichsbeispiel 1 eine Grundrezeptur hergestellt, die 1,5 % Kokosfettsäurediethanolamid enthielt, wobei die Kokosfettsäure mehr als 50 % C 12-14-Kohlenstoffatome enthält und die Vorläuferfettsäuren mit weniger als 10 C-Atomen abgetrennt wurden.When the content of sodium sulfate was reduced, a basic recipe was prepared according to Comparative Example 1, which contained 1.5% coconut fatty acid diethanolamide, the coconut fatty acid containing more than 50% C 12-14 carbon atoms and the precursor fatty acids with less than 10 C atoms being separated off.

Beispiel 4:Example 4:

Bei Verminderung des Ge halts an Natriumsulfat wurde gemäß Vergleichsbeispiel 1 eine Grundrezeptur hergestellt, die 1,5 % Laurin-Myristinsäurediethanolamid enthielt, wobei das Verhältnis von Laurinsäure zu Myristinsäure etwa 60 : 40 beträgt.When the Ge content of sodium sulfate was reduced, a basic recipe was prepared according to Comparative Example 1, which contained 1.5% lauric myristic acid diethanolamide, the ratio of lauric acid to myristic acid being about 60:40.

Beispiel 5:Example 5:

Bei Verminderung des Gehalts an Natriumsulfat wurde gemäß Vergleichsbeispiel 1 eine Grundrezeptur hergestellt, die 1,5 % Laurinsäurediethanolamid enthielt.When the sodium sulfate content was reduced, a basic formulation was prepared according to Comparative Example 1, which contained 1.5% lauric acid diethanolamide.

Beispiel 6:Example 6:

Bei Verminderung des Gehalts an Natriumsulfat wurde gemäß Vergleichsbeispiel 1 eine Grundrezeptur hergestellt, die 1,5 % Kokosfettsäuremonoethanolamid enthielt, wobei die Kokosfettsäure mehr als 50 % C 12-14-Kohlenstoffatome enthält und die Vorläuferfettsäuren mit weniger als 10 C-Atomen abgetrennt wurden.When the content of sodium sulfate was reduced, a basic recipe was prepared according to Comparative Example 1, which contained 1.5% coconut fatty acid monoethanolamide, the coconut fatty acid containing more than 50% C 12-14 carbon atoms and the precursor fatty acids with less than 10 C atoms being separated off.

Vergleichsbeispiel 2:Comparative Example 2:

Es wurde ein Gemisch folgender Zusammensetzung hergestellt:A mixture of the following composition was produced:

Grundrezeptur 2:Basic recipe 2:

8,0 % Alkylbenzolsulfonat
4,5 % C 12-18 Fettalkohol-5EO
0,8 % C 16-22-Fettsäure-Na-Salz
25,0 % Zeolith Na A
12,0 % Bentonit (Schichtsilikat)
2,0 % Acrylsäure-Maleinsäure-Copolymer, MG=70 000
0,4 % Ethylendiamin-tetramethylen-phosphonat-Na-Salz
0,1 % EDTA
5,0 % Soda
3,0 % Wasserglas, Verhältnis Na₂O zu SiO₂ = 3,35
0,8 % Celluloseethermischung
13,0 % Natriumberborat-monohydrat
1,5 % TAED
0,1 % Siliconöl
0,3 % Protease
13,5 % Natriumsulfat
Rest      Wasser, Salze

8.0% alkyl benzene sulfonate
4.5% C 12-18 fatty alcohol-5EO
0.8% C 16-22 fatty acid Na salt
25.0% zeolite Na A
12.0% bentonite (layered silicate)
2.0% acrylic acid-maleic acid copolymer, MW = 70,000
0.4% ethylenediamine tetramethylene phosphonate Na salt
0.1% EDTA
5.0% soda
3.0% water glass, ratio Na₂O to SiO₂ = 3.35
0.8% cellulose ether mixture
13.0% sodium berborate monohydrate
1.5% TAED
0.1% silicone oil
0.3% protease
13.5% sodium sulfate
Balance water, salts

Vergleichsbeispiel 3:Comparative Example 3:

Bei Verminderung des Gehalts an Natriumsulfat wurde gemäß Vergleichsbeispiel 2 eine Grundrezeptur hergestellt, die 1,5 % eines Hydroxyamins (Umsetzungsprodukt von 9,10-Epoxystearylalkohol mit Monoethanolamin) enthielt.When the sodium sulfate content was reduced, a basic formulation was prepared according to Comparative Example 2, which contained 1.5% of a hydroxyamine (reaction product of 9,10-epoxystearyl alcohol with monoethanolamine).

Vergleichsbeispiel 4:Comparative Example 4:

Bei Verminderung des Gehalts an Natriumsulfat wurde gemäß Vergleichsbeispiel 2 eine Grundrezeptur hergestellt, die 1,5 % eines C 12-14-Fettsäure-dimethylaminopropylamides enthielt.When the sodium sulfate content was reduced, a basic formulation was prepared according to Comparative Example 2, which contained 1.5% of a C 12-14 fatty acid dimethylaminopropylamide.

Vergleichsbeispiel 5:Comparative Example 5:

Bei Verminderung des Gehalts an Natriumsulfat wurde gemäß Vergleichsbeispiel 2 eine Grundrezeptur hergestellt, die 1,5 % eines Etheramins (C 12-14-Alkyl-(OCH₂CH₂)₅- N(CH₂CH₂OH)₂) enthielt.When reducing the sodium sulfate content, a basic recipe was prepared according to Comparative Example 2, which contained 1.5% of an etheramine (C 12-14 -alkyl- (OCH₂CH₂) ₅- N (CH₂CH₂OH) ₂).

Beispiel 7:Example 7:

Bei Verminderung des Gehalts an Natriumsulfat wurde gemäß Vergleichsbeispiel 2 eine Grundrezeptur hergestellt, die 1,5 % Ölsäurediethanolamid enthielt.When the sodium sulfate content was reduced, a basic formulation was prepared according to Comparative Example 2, which contained 1.5% oleic acid diethanolamide.

Vergleichsbeispiel 6:Comparative Example 6:

Es wurde ein Gemisch folgender Zusammensetzung hergestellt:

5,0 % Alkylbenzolsulfonat
3,0 % Talgalkoholsulfat
4,0 % C 16-18Fettalkohol-5EO
0,5 % Talgalkohol-14EO
0,8 % C 16-22 Fettsäure-Na-Salz
20,0 % Zeolith Na A
12,0 % Bentonit (Schichtsilikat)
4,0 % Acrylsäure-Maleinsäure-Copolymer, MG=70 000
0,3 % Ethylendiamin-tetramethylen-phosphonat-Na-Salz
0,1 % EDTA
5,0 % Soda
3,0 % Wasserglas, Verhältnis Na₂O zu SiO₂ = 3,35
0,8 % Celluloseethermischung
20,0 % Natriumperborat-tetrahydrat
1,5 % TAED
0,2 % Siliconöl
0,3 % Protease
10,0 % Natriumsulfat
Rest      WasserA mixture of the following composition was produced:

5.0% alkyl benzene sulfonate
3.0% tallow alcohol sulfate
4.0% C 16-18 fatty alcohol-5EO
0.5% tallow alcohol-14EO
0.8% C 16-22 fatty acid Na salt
20.0% zeolite Na A
12.0% bentonite (layered silicate)
4.0% acrylic acid-maleic acid copolymer, MW = 70,000
0.3% ethylenediamine tetramethylene phosphonate Na salt
0.1% EDTA
5.0% soda
3.0% water glass, ratio Na₂O to SiO₂ = 3.35
0.8% cellulose ether mixture
20.0% sodium perborate tetrahydrate
1.5% TAED
0.2% silicone oil
0.3% protease
10.0% sodium sulfate
Rest of water

Beispiel 8:Example 8:

Bei Verminderung des Gehaltes an Natriumsulfat wurde gemäß Vergleichsbeispiel 6 eine Grundrezeptur hergestellt, die 2,0 % Ölsäurediethanolamid enthielt.When the content of sodium sulfate was reduced, a basic formulation was prepared according to Comparative Example 6, which contained 2.0% oleic acid diethanolamide.

Die Waschversuche mit oben genannten Rezepturen erfolgten in einer handelsüblichen Haushaltswaschmaschine in einem 60°C-Einlaugenprogramm bei einer Wasserhärte von 16°dH, entsprechend 160 mg CaO pro Liter, 3,5 kg Beladung und 252 g (Tabelle 1), 285 g (Tabelle 2) bzw. 225 g (Tabelle 3) Waschmittel. Als Fleckanschmutzung wurde Make-up, Lippenstift und Wimperntusche auf einem veredelten Polyester/Baumwollgewebe verw endet.The washing tests with the above-mentioned recipes were carried out in a commercial household washing machine in a 60 ° C soak program with a water hardness of 16 ° dH, corresponding to 160 mg CaO per liter, 3.5 kg load and 252 g (Table 1), 285 g (Table 2) and 225 g (Table 3) detergent. Make-up, lipstick and mascara on a refined polyester / cotton fabric were used as stains.

Die nachfolgenden Tabellen geben die Resultate der Waschversuche wieder. In der paarweise durchgeführten visuellen Bewertung entspricht:
1 Punkt = Produkt besser
0 Punkte = Produkt schlechter
0,5 Punkte = Produkt gleichThe following tables show the results of the washing tests. In the visual evaluation carried out in pairs, the following corresponds:
1 point = product better
0 points = product worse
0.5 points = product equal

Die maximale Punktzahl beträgt 15, entsprechend dem Produkt der Zahl der Bewerter (fünf) mal der Zahl der Bestimmungen (drei). Die letzten Spalten der Tabellen enthalten die Summen der Punktzahlen aus der Bewertung der Entfernung von Fleckanschmutzungen von Make-up, Lippenstift und Wimperntusche.

Figure imgb0002
Figure imgb0003
 The maximum score is 15, which is the product of the number of evaluators (five) times the number of determinations (three). The last columns of the tables contain the totals of the scores from the evaluation of the removal of stains from make-up, lipstick and mascara.
Figure imgb0002
Figure imgb0003

Die Tabellen 1, 2 und 3 zeigen die Überlegenheit der erfindungsgemäßen Zusätze nicht nur gegenüber den Grundrezepturen (Vergleichsbeispiele 1, 2 und 6), sondern auch gegenüber anderen niotensidischen Zusätzen. Tables 1, 2 and 3 show the superiority of the additives according to the invention not only compared to the basic formulations (comparative examples 1, 2 and 6), but also compared to other non-surfactant additives.

Claims (9)

1. Phosphatreduziertes Waschmittel, enthaltend
2 bis 20      Gew.-% Schichtsilicate,
4 bis 15      Gew.-% anionische Tenside,
0 bis 10      Gew.-% nichtionische Tenside,
0 bis 6,5      Gew.-% an anorganisch gebundenem Phosphor,
dadurch gekennzeichnet, daß es
0,5 bis 10      Gew.-% wenigstens eines N-alkoxylierten Fettsäureamides oder Gemische davon der allgemeinen Formel
Figure imgb0004
enthält, wobei
      R₁C für den aliphatischen Rest einer Fettsäure mit 8 bis 22 C-Atomen steht, die mindestens zur Hälfte aus gesättigten C 12-14 Kohlenstoffatomen und/oder aus einfach oder mehrfach ungesättigten Fettsäuren mit 18 bis 22 C-Atomen bestehen,
      R₂ und R₃ jeweils für Wasserstoff oder einen Ethanolrest sowie deren Ethylenoxid- und/oder Propylenoxidaddukte mit jeweils 1 bis 10 Ethylenoxid- und/oder Propylenoxidgruppen mit der Maßgabe stehen, daß wenigstens einer der Reste R₂ und R₃ sich von einem Alkanol ableitet,
wobei die Waschmittelzusammensetzung 8 bis 20 Gew.-% anionsiche Tenside, nichtionische Tenside und N-alkoxylierte Fettsäureamide aufweist.1. Phosphate-reduced detergent containing
2 to 20% by weight of layered silicates,
4 to 15% by weight of anionic surfactants,
0 to 10% by weight of nonionic surfactants,
0 to 6.5% by weight of inorganically bound phosphorus,
characterized in that it
0.5 to 10% by weight of at least one N-alkoxylated fatty acid amide or mixtures thereof of the general formula
Figure imgb0004
 contains, where
R₁C stands for the aliphatic residue of a fatty acid with 8 to 22 carbon atoms, at least half of which consist of saturated C 12-14 carbon atoms and / or of mono- or polyunsaturated fatty acids with 18 to 22 carbon atoms,
R₂ and R₃ each represent hydrogen or an ethanol radical and their ethylene oxide and / or propylene oxide adducts each having 1 to 10 ethylene oxide and / or propylene oxide groups with the proviso that at least one of the radicals R₂ and R₃ is derived from an alkanol,
the detergent composition comprising 8 to 20% by weight of anionic surfactants, nonionic surfactants and N-alkoxylated fatty acid amides. 2. Phosphatreduziertes Waschmittel nach Anspruch 1,
dadurch gekennzeichnet, daß es 5 bis 15 Gew.-% Schichtsilicate enthält.2. Reduced phosphate detergent according to claim 1,
characterized in that it contains 5 to 15 wt .-% layered silicates. 3. Phosphatreduziertes Waschmittel nach Anspruch 1, dadurch gekennzeichnet, daß es 0 bis 4,5 Gew.-% an anorganisch gebundenem Phosphor enthält.3. Reduced phosphate detergent according to claim 1, characterized in that it contains 0 to 4.5 wt .-% of inorganic phosphorus. 4. Phosphatreduziertes Waschmittel nach Anspruch 1, dadurch gekennzeichnet, daß es 1,0 bis 4 Gew.-% wenigstens eines N-alkoxylierten Fettsäureamides oder Gemische davon enthält.4. Reduced phosphate detergent according to claim 1, characterized in that it contains 1.0 to 4 wt .-% of at least one N-alkoxylated fatty acid amide or mixtures thereof. 5. Phosphatreduziertes Waschmittel nach Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß das Gewichtsverhältnis von anionischen Tensiden und nichtionischen Tensiden zu N-alkoxylierten Fettsäureamiden im Bereich von 15 : 1 bis 1 : 1 eingestellt wird.5. Reduced phosphate detergent according to claims 1 to 4, characterized in that the weight ratio of anionic surfactants and nonionic surfactants to N-alkoxylated fatty acid amides is set in the range from 15: 1 to 1: 1. 6. Phosphatreduziertes Waschmittel nach Ansprüchen 1 bis 5, dadurch gekennzeichnet, daß die N-alkoxylierten Fettsäureamide 1 bis 5 Ethylenoxid- und/oder Propylenoxidgruppen enthalten.6. Reduced phosphate detergent according to claims 1 to 5, characterized in that the N-alkoxylated fatty acid amides contain 1 to 5 ethylene oxide and / or propylene oxide groups. 7. Phosphatreduziertes Waschmittel nach Ansprüchen 1 bis 5, dadurch gekennzeichnet, daß die N-alkoxylierten Fettsäureamide 1 bis 2 Ethylenoxid- und/oder Propylenoxidgruppen enthalten.7. Reduced phosphate detergent according to claims 1 to 5, characterized in that the N-alkoxylated fatty acid amides contain 1 to 2 ethylene oxide and / or propylene oxide groups. 8. Phosphatreduziertes Waschmittel nach Ansprüchen 1 bis 7, dadurch gekennzeichnet, daß das N-alkoxylierte Fettsäureamid ausgewählt ist aus der aus Ölsäurediethanolamid, Sojafettsäurediethanolamid, Kokosfettsäurediethanolamid, Laurin-Myristinsäurediethanolamid und Kokosfettsäuremonoethanolamid bestehenden Gruppe.8. Reduced phosphate detergent according to claims 1 to 7, characterized in that the N-alkoxylated fatty acid amide is selected from the group consisting of oleic acid diethanolamide, soy fatty acid diethanolamide, coconut fatty acid diethanolamide, lauric myristic acid diethanolamide and coconut fatty acid monoethanolamide. 9. Phosphatreduziertes Waschmittel nach Ansprüchen 1 bis 8, dadurch gekennzeichnet, daß es phosphatfrei ist.9. Reduced phosphate detergent according to claims 1 to 8, characterized in that it is phosphate-free.
EP87113376A 1986-09-22 1987-09-14 Laundry agent having a reduced phosphate content containing N-alkoxylated fatty acid amides Withdrawn EP0264615A1 (en)

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DE19863632107 DE3632107A1 (en) 1986-09-22 1986-09-22 REDUCED PHOSPHATE DETERGENT CONTAINING N-ALKOXYLATED FATTY ACID AMIDES
DE3632107 1986-09-22

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0285050A2 (en) * 1987-04-03 1988-10-05 Henkel Kommanditgesellschaft auf Aktien Phosphate-free softening detergent
WO1992006153A1 (en) * 1990-09-28 1992-04-16 The Procter & Gamble Company Detergent compositions with polyhydroxy fatty acid amide surfactant and polymeric dispersing agent
WO1992006160A1 (en) * 1990-09-28 1992-04-16 The Procter & Gamble Company Nonionic surfactant systems containing polyhydroxy fatty acid amides and one or more additional nonionic surfactants
WO1992006151A1 (en) * 1990-09-28 1992-04-16 The Procter & Gamble Company Polyhydroxy fatty acid amides in zeolite/layered silicate built detergents
TR27539A (en) * 1990-09-28 1995-06-07 Procter & Gamble Non-ionic surfactant systems containing polyhydroxy fatty acid amides and one or more additional non-ionic surfactants.
GB2315766A (en) * 1996-08-01 1998-02-11 Procter & Gamble Detergent compositions for laundering clothes with sulphate, suds suppressor and fatty soap
WO2000039274A1 (en) * 1998-12-24 2000-07-06 The Procter & Gamble Company Cleaning compositions

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GB1047771A (en) * 1962-04-24 1966-11-09 Stepan Chemical Co Improvements in or relating to synthetic detergent compositions
EP0026529A1 (en) * 1979-09-29 1981-04-08 THE PROCTER &amp; GAMBLE COMPANY Detergent compositions
EP0160873A2 (en) * 1984-05-05 1985-11-13 Hoechst Aktiengesellschaft Softening washing agent
EP0163910A1 (en) * 1984-05-04 1985-12-11 Hoechst Aktiengesellschaft Washing materials containing softening agent
GB2170236A (en) * 1985-01-28 1986-07-30 Colgate Palmolive Co Particulate fabric softening and antistatic built detergent composition and particulate agglomerate for use in manufacture thereof
DE3526405A1 (en) * 1985-07-24 1987-02-05 Henkel Kgaa LAYERED SILICATES WITH RESTRICTED SOURCE, PROCESS FOR THEIR PRODUCTION AND THEIR USE IN DETERGENT AND CLEANING AGENTS

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1047771A (en) * 1962-04-24 1966-11-09 Stepan Chemical Co Improvements in or relating to synthetic detergent compositions
EP0026529A1 (en) * 1979-09-29 1981-04-08 THE PROCTER &amp; GAMBLE COMPANY Detergent compositions
EP0163910A1 (en) * 1984-05-04 1985-12-11 Hoechst Aktiengesellschaft Washing materials containing softening agent
EP0160873A2 (en) * 1984-05-05 1985-11-13 Hoechst Aktiengesellschaft Softening washing agent
GB2170236A (en) * 1985-01-28 1986-07-30 Colgate Palmolive Co Particulate fabric softening and antistatic built detergent composition and particulate agglomerate for use in manufacture thereof
DE3526405A1 (en) * 1985-07-24 1987-02-05 Henkel Kgaa LAYERED SILICATES WITH RESTRICTED SOURCE, PROCESS FOR THEIR PRODUCTION AND THEIR USE IN DETERGENT AND CLEANING AGENTS

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0285050A2 (en) * 1987-04-03 1988-10-05 Henkel Kommanditgesellschaft auf Aktien Phosphate-free softening detergent
EP0285050A3 (en) * 1987-04-03 1990-04-04 Henkel Kommanditgesellschaft auf Aktien Phosphate-free softening detergent
WO1992006153A1 (en) * 1990-09-28 1992-04-16 The Procter & Gamble Company Detergent compositions with polyhydroxy fatty acid amide surfactant and polymeric dispersing agent
WO1992006160A1 (en) * 1990-09-28 1992-04-16 The Procter & Gamble Company Nonionic surfactant systems containing polyhydroxy fatty acid amides and one or more additional nonionic surfactants
WO1992006151A1 (en) * 1990-09-28 1992-04-16 The Procter & Gamble Company Polyhydroxy fatty acid amides in zeolite/layered silicate built detergents
TR25764A (en) * 1990-09-28 1993-09-01 Procter & Gamble POLYHIDROXY OIL ACID AMIDES IN DETERGENTS FORCE WITH ZEOLITE / LAYERED SILICATE
TR27539A (en) * 1990-09-28 1995-06-07 Procter & Gamble Non-ionic surfactant systems containing polyhydroxy fatty acid amides and one or more additional non-ionic surfactants.
GB2315766A (en) * 1996-08-01 1998-02-11 Procter & Gamble Detergent compositions for laundering clothes with sulphate, suds suppressor and fatty soap
WO2000039274A1 (en) * 1998-12-24 2000-07-06 The Procter & Gamble Company Cleaning compositions

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