EP2931858B1 - Produits détergents et nettoyants contenant une polyamine polyalcoxylée et un tensioactif non ionique adapté - Google Patents

Produits détergents et nettoyants contenant une polyamine polyalcoxylée et un tensioactif non ionique adapté Download PDF

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Publication number
EP2931858B1
EP2931858B1 EP13805851.6A EP13805851A EP2931858B1 EP 2931858 B1 EP2931858 B1 EP 2931858B1 EP 13805851 A EP13805851 A EP 13805851A EP 2931858 B1 EP2931858 B1 EP 2931858B1
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Prior art keywords
acid
weight
range
washing
alcohol
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German (de)
English (en)
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EP2931858A1 (fr
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Inga Kerstin Vockenroth
Nicole PLATH
Eva-Maria Wikker
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL13805851T priority Critical patent/PL2931858T3/pl
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/42—Amino alcohols or amino ethers
    • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines

Definitions

  • the present invention relates to the use of alkoxylated polyamines in combination with low alkoxylated nonionic surfactants to enhance the primary detergency of laundry detergents or cleaners when washing textiles or cleaning hard surfaces against especially proteinaceous soils, and detergents and cleaners containing such a combination.
  • Detergents contain in addition to the indispensable for the washing process ingredients such as surfactants and builder materials usually further ingredients that can be summarized under the term washing aids and include as different drug groups such as foam regulators, grayness inhibitors, bleach, bleach activators and dye transfer inhibitors.
  • Such excipients also include substances whose presence enhances the detergency of surfactants, without them usually having to have a surfactant behavior itself. The same applies mutatis mutandis to cleaners for hard surfaces. Such substances are often referred to as Waschkraftverschreibr.
  • Alkoxylated polyamines and their use in detergents and cleaners are known, for example, from international patent applications WO 95/32272 A1 and WO 2006/108857 A1 known. From the international patent application WO 2006/108856 A1 For example, amphiphilic water-soluble alkoxylated polyamines having an inner polyoxyethylene block and an outer polyoxypropylene block are known
  • alkoxylated polyamines then have particularly good primary washing power enhancing properties when combined with certain nonionic surfactants.
  • the invention therefore provides the use of a combination of polyalkoxylated polyamines which are obtainable by reacting polyamines with alkylene oxide, in particular ethylene oxide and / or propylene oxide, with alkoxylated C 8 -C 18 -alcohols having an average degree of alkoxylation in the range from 1 to 5, in particular from 2 to 4, in detergents or cleaners to enhance the primary washing or cleaning power when washing textiles or when cleaning hard surfaces against soiling.
  • the weight ratio of polyalkoxylated polyamine to alkoxylated C 8 -C 18 -alcohol having an average degree of alkoxylation of 1 to 5 is in the range of 1: 3 to 3: 1, in particular 1: 2 to 2: 1.
  • Another object of the invention is the use of polyalkoxylated polyamines which are obtainable by reacting polyamines with alkylene oxide, in particular ethylene oxide and / or propylene oxide, to enhance the primary washing or cleaning power of detergents or cleaners containing alkoxylated C 8 -C 18 - Alcohol with average degree of alkoxylation in the range of 1 to 5, in particular from 2 to 4, when washing textiles or when cleaning hard surfaces.
  • alkylene oxide in particular ethylene oxide and / or propylene oxide
  • the primary washing power-boosting effect is particularly pronounced if the aim is to remove protein-containing soiling.
  • An embodiment of the invention is therefore the corresponding use for the removal of proteinaceous soils, such as blood, egg, milk, or stains proteinaceous preparations, such as chocolate, latte, pudding.
  • proteinaceous soils such as blood, egg, milk, or stains proteinaceous preparations, such as chocolate, latte, pudding.
  • Another object of the invention is a method for removing stains, especially proteinaceous stains or stains proteinaceous preparations, textiles or hard surfaces, in which a detergent or cleaning agent and a combination of polyalkoxylated polyamine and low alkoxylated alcohol are used.
  • This method can be carried out manually or mechanically, for example by means of a household washing machine or dishwasher. It is possible to apply the particular liquid agent and drug combination simultaneously or sequentially. The simultaneous application can be particularly advantageous by the use of an agent containing the drug combination perform.
  • the concentration of said polyalkoxylated polyamine in the especially aqueous washing or cleaning liquor is preferably 1 mg / l to 500 mg / l, in particular 5 mg / l to 200 mg / l; the concentration of said low alkoxylated alcohol in the particular aqueous washing or cleaning liquor is preferably 1 mg / l to 500 mg / l, in particular 5 mg / l to 200 mg / l.
  • the polyalkoxylated polyamine is a polymer having an N-atom-containing backbone which carries polyalkoxy groups on the N atoms.
  • the polyamine has primary amino functions at the ends and preferably both secondary and tertiary amino functions inside; if appropriate, it may also have only secondary amino functions on the inside, so that the result is not a branched-chain but a linear polyamine.
  • the ratio of primary to secondary amino groups in the polyamine is preferably in the range from 1: 0.5 to 1: 1.5, in particular in the range from 1: 0.7 to 1: 1.
  • the ratio of primary to tertiary amino groups in the polyamine is preferably in the range from 1: 0.2 to 1: 1, in particular in the range from 1: 0.5 to 1: 0.8.
  • the polyamine has an average molecular weight in the range of 500 g / mol to 50,000 g / mol, in particular from 550 g / mol to 5000 g / mol. If applicable here and later for others polymeric ingredients indicated average molecular weights are weight average molecular weights M w , which can be determined in principle by means of gel permeation chromatography using an RI detector, the measurement is advantageously carried out against an external standard.
  • the N atoms in the polyamine are separated from one another by alkylene, alkenylene, arylene and / or alkylarylene groups, preferably by alkylene groups having 2 to 12 C atoms, in particular 2 to 6 C atoms, where not all groups have the same C Must have atomic number. Particularly preferred are ethylene groups, 1,2-propylene groups, 1,3-propylene groups, and mixtures thereof.
  • the primary amino functions in the polyamine can carry 1 or 2 polyalkoxy groups and the secondary amino functions 1 polyalkoxy group, although not every amino function must be alkoxy group substituted.
  • the average number of alkoxy groups per primary and secondary amino function in the polyalkoxylated polyamine is preferably 1 to 100, in particular 5 to 70.
  • the alkoxy groups in the polyalkoxylated polyamine are alkoxy groups, preferably propoxy and / or ethoxy groups, which are directly attached to N atoms are bonded, and optionally to alkoxy groups, preferably propoxy and / or ethoxy groups which are bonded to alkoxy.
  • the polyalkoxylated polyamines are obtainable by reacting polyamines with alkylene oxide, preferably propylene oxide and / or ethylene oxide, together with a plurality of alkylene oxides, preferably propylene oxide and ethylene oxide, together or first one and then the other, preferably propylene oxide and then ethylene oxide or first ethylene oxide and then propylene oxide, can be used.
  • the terminal OH function of at least some of the polyalkoxy substituents can be replaced by an alkyl ether function having 1 to 10, in particular 1 to 3, C atoms.
  • Alkoxylated C 8 -C 18 -alcohols in the context of the present invention and their individual aspects are obtainable by reacting corresponding alcohols with alkylene oxide, preference being given to primary linear or branched-chain alcohols. Accordingly, the alkoxylates of primary alcohols having linear, in particular decyl, dodecyl, tridecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are useful.
  • the alcohol has a maximum of 16 C atoms, in particular 12 to 14 C atoms.
  • the degree of alkoxylation, that is the average number of alkoxy groups per alcohol function, of the lower alkoxylated alcohol can be integer or fractional and preferably in the range from 2 to 4, in particular from 2 to 3.5.
  • Preferred alkoxy groups are ethoxy, propoxy and butoxy groups, especially ethoxy groups and mixtures of ethoxy and propoxy groups.
  • the use according to the invention of said combination of polyalkoxylated polyamine and alkoxylated alcohol is carried out in detergents or cleaners, preferably by adding polyalkoxylated polyamine in an amount of 0.1% by weight to 10% by weight, in particular in an amount of 0, 2 wt .-% to 1.5 wt .-%, and said alkoxylated alcohol in an amount of 0.2 wt .-% to 10 wt .-%, in particular in an amount of 0.5 wt .-% to 5% by weight unless otherwise stated, in each case the statements of "% by weight" in each case relate to the weight of the entire washing or cleaning agent.
  • Another object of the invention is therefore a washing or cleaning agent containing a combination of polyalkoxylated polyamine, which is obtainable by reacting polyamines with alkylene oxide, with alkoxylated C 8 -C 18 alcohol having average degree of alkoxylation in the range of 1 to 5.
  • Detergents or cleaning agents containing the active ingredients to be used in combination according to the invention or used together with them or used in the process according to the invention may contain all other usual constituents of such agents which do not undesirably interact with an active ingredient essential to the invention.
  • the washing or cleaning agent contains an active substance combination as defined above in amounts of from 0.3% by weight to 20% by weight, in particular from 0.7% by weight to 6.5% by weight.
  • An agent which contains or is used together with an active ingredient combination to be used according to the invention or is used in the process according to the invention preferably contains synthetic anionic surfactants of the sulphate or sulphonate type, in amounts of preferably not more than 20% by weight, in particular of 0.1 wt .-% to 18 wt .-%, each based on the total agent.
  • Suitable synthetic anionic surfactants which are particularly suitable for use in such compositions are the alkyl and / or alkenyl sulfates having 8 to 22 C atoms which carry an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as counter cation.
  • the alkyl and alkenyl sulfates can be prepared in a known manner by reaction of the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases.
  • a conventional sulfating reagent in particular sulfur trioxide or chlorosulfonic acid
  • the sulfate-type surfactants which can be used with particular preference include the abovementioned sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates.
  • Such ether sulfates preferably contain from 2 to 30, in particular from 4 to 10, ethylene glycol groups per molecule.
  • Suitable anionic surfactants of the sulfonate type include those by reaction of fatty acid esters with sulfur trioxide followed by neutralization available ⁇ -sulfoesters, in particular those of fatty acids having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and linear alcohols having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derivative sulfonation, and the by formal saponification of these resulting sulfo fatty acids.
  • the anionic surfactants which can be used also include the salts of sulfosuccinic acid esters, which are also referred to as alkylsulfosuccinates or dialkylsulfosuccinates, and which are monoesters or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain an ethoxylated fatty alcohol radical, which in itself is a nonionic surfactant.
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • Another synthetic anionic surfactant is alkylbenzenesulfonate in question.
  • compositions comprises the presence of further nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates other than the above-mentioned alkoxylated C 8 -C 22 alcohols of average alkoxylation degree in the range of 1 to 5, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation of fatty alkylamines, vicinal diols, fatty acid alkyl esters and / or fatty acid amides and mixtures thereof, in particular in an amount in the range of 2 wt .-% to 25 wt .-%.
  • further nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates other than the above-mentioned alkoxylated C 8 -C 22 alcohols of average alkoxylation degree in the range of 1 to 5, fatty acid polyhydroxyamides and / or ethoxylation and / or
  • Suitable nonionic surfactants include the alkoxylates, in particular the ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched-chain alcohols having 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms, in which the degree of alkoxylation the alcohols are below 20, preferably below 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides. Particularly suitable are the derivatives of fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can be used for the preparation of usable alkoxylates.
  • alkylpolyglycosides which are suitable for incorporation in the compositions according to the invention are compounds of the general formula (G) n -OR 12 , in which R 12 is an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and n is a number between 1 and 10 mean.
  • the glycoside component (G) n are oligomers or polymers of naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, Include xylose and lyxose.
  • the oligomers consisting of such glycosidically linked monomers are, in addition to the Type of sugar contained in them by their number, the so-called Oligomermaschinesgrad characterized.
  • the degree of oligomerization n assumes as the value to be determined analytically generally broken numerical values; it is between 1 and 10, with the glycosides preferably used below a value of 1.5, in particular between 1.2 and 1.4.
  • Preferred monomer building block is glucose because of its good availability.
  • Nonionic surfactant is in agents which contain a combination of active substances used according to the invention or used in the context of the inventive use, including the amount of low alkoxylated C 8 -C 18 -alcohol from the active ingredient combination essential to the invention, preferably in amounts of 1 wt .-% to 30 Wt .-%, in particular from 1 wt .-% to 25 wt .-%, wherein amounts in the upper part of this range are more likely to be found in liquid detergents and particulate detergents preferably contain rather lower amounts of up to 5 wt .-%.
  • soaps suitable being saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids.
  • those soap mixtures are preferred which are composed of 50% to 100% by weight of saturated C 12 -C 18 fatty acid soaps and up to 50% by weight of oleic acid soap.
  • soap is included in amounts of from 0.1% to 5% by weight.
  • liquid agents which contain a combination of active ingredients used in the invention, but higher amounts of soap can be contained, usually up to 20 wt .-%.
  • compositions may also contain betaines and / or cationic surfactants, which, if present, are preferably used in amounts of from 0.5% by weight to 7% by weight.
  • betaines and / or cationic surfactants which, if present, are preferably used in amounts of from 0.5% by weight to 7% by weight.
  • esterquats are particularly preferred.
  • the compositions may contain peroxygen bleaching agents, in particular in amounts ranging from 5% to 70% by weight, and optionally bleach activators, especially in amounts ranging from 2% to 10% by weight.
  • the bleaches in question are preferably the peroxygen compounds usually used in detergents such as percarboxylic acids, for example dodecanedioic or Phthaloylaminoperoxicapronsäure, hydrogen peroxide, alkali metal perborate, which may be present as tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally present as alkali metal salts, especially as sodium salts.
  • Such bleaching agents are in detergents containing an active ingredient combination used in the invention, preferably in amounts of up to 25 wt .-%, in particular up to 15 wt .-% and particularly preferably from 5 wt .-% to 15 wt .-%, respectively on total agent, present, in particular percarbonate is used.
  • the optionally present component of the bleach activators comprises the commonly used N- or O-acyl compounds, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulphurylamides and cyanurates, and also carboxylic anhydrides , in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl-phenolsulfonate, and acylated sugar derivatives, in particular pentaacetylglucose, and also cationic nitrile derivatives such as trimethylammonium acetonitrile salts.
  • N- or O-acyl compounds for example polyacylated alkylenediamines, in particular tetraacetyl
  • the bleach activators may have been coated and / or granulated in a known manner with coating substances in order to avoid the interaction with the per compounds, granulated tetraacetylethylenediamine having mean particle sizes of from 0.01 mm to 0.8 mm, granulated 1, with the aid of carboxymethylcellulose. 5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and / or in particulate form, trialkylammonium acetonitrile is particularly preferred.
  • Such bleach activators are preferably contained in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the total agent.
  • the composition contains water-soluble and / or water-insoluble builder, in particular selected from alkali metal aluminosilicate, crystalline alkali metal silicate with modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts ranging from 2.5 wt .-% to 60 wt .-%.
  • water-soluble and / or water-insoluble builder in particular selected from alkali metal aluminosilicate, crystalline alkali metal silicate with modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts ranging from 2.5 wt .-% to 60 wt .-%.
  • the agent preferably contains from 20% to 55% by weight of water-soluble and / or water-insoluble, organic and / or inorganic builders.
  • the water-soluble organic builder substances include, in particular, those from the class of polycarboxylic acids, in particular citric acid and sugar acids, as well as the polymeric (poly) carboxylic acids, in particular the polycarboxylates obtainable by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers thereof, which also small amounts of polymerizable substances without carboxylic acid functionality may contain polymerized.
  • the relative molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5000 g / mol and 200,000 g / mol, of the copolymers between 2000 g / mol and 200,000 g / mol, preferably 50,000 g / mol to 120,000 g / mol, based on the free acid ,
  • a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 g / mol to 100,000 g / mol.
  • Suitable, although less preferred compounds of this class are Copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50 wt .-%.
  • vinyl ethers such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene
  • the proportion of acid is at least 50 wt .-%.
  • Terpolymers which contain two carboxylic acids and / or salts thereof as monomers and also vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer may also be used as water-soluble organic builder substances.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid and preferably from a C 3 -C 4 -monocarboxylic acid, in particular from (meth) acrylic acid.
  • the second acidic monomer or its salt may be a derivative of a C 4 -C 8 dicarboxylic acid, with maleic acid being particularly preferred.
  • the third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol.
  • Preferred terpolymers contain from 60% by weight to 95% by weight, in particular from 70% by weight to 90% by weight, of (meth) acrylic acid and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, and maleic acid and / or maleate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% of vinyl alcohol and / or vinyl acetate.
  • the second acidic monomer or its salt may also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C 1 -C 4 -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives , is substituted.
  • Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, 10% by weight to 30 wt .-%, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid and / or Methallylsulfonat and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt. % of a carbohydrate.
  • This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred.
  • the use of the third monomer presumably incorporates predetermined breaking points in the polymer which are responsible for the good biodegradability of the polymer.
  • These terpolymers generally have a molecular weight between 1000 g / mol and 200000 g / mol, preferably between 2000 g / mol and 50,000 g / mol and in particular between 3000 g / mol and 10,000 g / mol.
  • polycarboxylic acids can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions.
  • All the polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • Such organic builder substances are preferably present in amounts of up to 40% by weight, in particular up to 25% by weight and particularly preferably from 1% by weight to 5% by weight. amounts close to the upper limit mentioned are preferably used in paste-like or liquid, in particular hydrous, agents.
  • crystalline or amorphous alkali metal aluminosilicates in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are used as water-insoluble, water-dispersible inorganic builder materials.
  • the detergent-grade crystalline aluminosilicates especially zeolite NaA and optionally NaX, are preferred. Amounts near the above upper limit are preferably used in solid, particulate agents.
  • suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m.
  • Their calcium binding capacity according to the information of the German Patent DE 24 12 837 can be determined ranges from 100 to 200 mg CaO per gram.
  • Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali metal silicates which may be present alone or in a mixture with amorphous silicates.
  • the alkali metal silicates useful as builders in the compositions preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form.
  • Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of 1: 2 to 1: 2.8.
  • Such amorphous alkali silicates are commercially available, for example, under the name Portil®.
  • Those with a molar ratio of Na 2 O: SiO 2 of 1: 1.9 to 1: 2.8 are preferably added in the course of the production as a solid and not in the form of a solution.
  • the crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na 2 Si x O 2x + 1 ⁇ are used yH 2 O, in which x, the so-called module, a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Crystalline layered silicates which fall under this general formula are described, for example, in the European patent application EP 0 164 514 described.
  • Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates are preferred.
  • amorphous alkali metal silicates practically anhydrous crystalline alkali metal silicates of the above general formula in which x is a number from 1.9 to 2.1, can be used in agents which contain an active ingredient combination to be used according to the invention.
  • a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of detergents which contain an active ingredient combination used according to the invention.
  • alkali metal silicates Their content of alkali metal silicates is preferably 1 wt .-% to 50 wt .-% and in particular 5 wt .-% to 35 wt .-%, based on anhydrous active substance. If alkali metal silicate, in particular zeolite, is also present as an additional builder substance, the content of alkali metal silicate is preferably 1% by weight to 15% by weight. and in particular 2 wt .-% to 8 wt .-%, based on anhydrous active substance.
  • the weight ratio of aluminosilicate to silicate, in each case based on anhydrous active substances, is then preferably 4: 1 to 10: 1. In agents containing both amorphous and crystalline alkali metal silicates, the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and especially 1: 1 to 2: 1.
  • inorganic builder In addition to the said inorganic builder, other water-soluble or water-insoluble inorganic substances may be contained in the compositions which contain a combination of active ingredients to be used according to the invention, used together with the latter or used in methods according to the invention. Suitable in this context are the alkali metal carbonates, alkali metal bicarbonates and alkali metal sulfates and mixtures thereof. Such additional inorganic material may be present in amounts up to 70% by weight.
  • the water-soluble builder block contains at least 2 of components b), c), d) and e) in amounts greater than 0% by weight.
  • component a in a preferred embodiment of the composition according to the invention, 15% by weight to 25% by weight of alkali carbonate, which may at least partly be replaced by alkali metal hydrogencarbonate, and up to 5% by weight, in particular 0.5% by weight. % to 2.5% by weight of citric acid and / or alkali citrate.
  • inventive compositions are as component a) 5 wt .-% to 25 wt .-%, in particular 5 wt .-% to 15 wt .-% citric acid and / or alkali citrate and up to 5 wt .-%, in particular 1 wt .-% to 5 wt .-% alkali carbonate, which may be at least partially replaced by alkali metal bicarbonate included. If both alkali metal carbonate and alkali metal bicarbonate are present, the component a) alkali carbonate and alkali metal bicarbonate preferably in a weight ratio of 10: 1 to 1: 1.
  • component b) in a preferred embodiment of the composition according to the invention, 1% by weight to 5% by weight of alkali metal silicate with a modulus in the range from 1.8 to 2.5 are contained.
  • agents according to the invention contain from 0.05% by weight to 1% by weight of phosphonic acid and / or alkali metal phosphonate.
  • Phosphonic acids are also understood as meaning optionally substituted alkylphosphonic acids, which may also have a plurality of phosphonic acid groups (so-called polyphosphonic acids).
  • They are preferably selected from the hydroxy and / or aminoalkylphosphonic acids and / or their alkali salts, for example dimethylaminomethane diphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethane diphosphonic acid, 1-hydroxyethane 1,1-diphosphonic acid, amino-tris (methylenephosphonic acid), N, N, N ', N'-ethylenediamine tetrakis (methylenephosphonic acid) and acylated derivatives of phosphorous acid, which can also be used in any mixtures.
  • dimethylaminomethane diphosphonic acid 3-aminopropane-1-hydroxy-1,1-diphosphonic acid
  • 1-amino-1-phenylmethane diphosphonic acid 1-hydroxyethane 1,1-diphosphonic acid
  • amino-tris methylenephosphonic acid
  • component d in a preferred embodiment of the composition according to the invention, 15% by weight to 35% by weight of alkali metal phosphate, in particular trisodium polyphosphate, are contained.
  • agents according to the invention contain from 1.5% by weight to 5% by weight of polymeric polycarboxylate, in particular selected from the polymerization or copolymerization products of acrylic acid, methacrylic acid and / or maleic acid.
  • polymeric polycarboxylate in particular selected from the polymerization or copolymerization products of acrylic acid, methacrylic acid and / or maleic acid.
  • homopolymers of acrylic acid particularly preferred are those having an average molecular weight in the range of 5,000 g / mol to 15,000 g / mol (PA standard).
  • the agents may contain other ingredients customary in detergents or cleaners.
  • These optional ingredients include in particular enzymes, enzyme stabilizers, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, foam inhibitors, for example Organopolysiloxanes or paraffins, solvents and optical brighteners, for example stilbene disulfonic acid derivatives.
  • agents which contain a combination of active substances used according to the invention up to 1% by weight, in particular 0.01% by weight to 0.5% by weight, of optical brighteners, in particular compounds from the class of the substituted 4,4 ' -Bis (2,4,6-triamino-s-triazinyl) -stilbene-2,2'-disulfonic acids, up to 5 wt .-%, in particular 0.1 wt .-% to 2 wt .-% complexing agent for Heavy metals, in particular Aminoalkylenphosphonkla and their salts and up to 2 wt .-%, in particular 0.1 wt .-% to 1 wt .-% foam inhibitors, wherein said weight fractions refer to the total agent.
  • optical brighteners in particular compounds from the class of the substituted 4,4 ' -Bis (2,4,6-triamino-s-triazinyl) -stilbene-2,2'-disulfonic acids, up
  • Solvents that can be used in particular for liquid agents are, in addition to water, preferably those nonaqueous solvents which are water-miscible. These include the lower alcohols, for example, ethanol, propanol, isopropanol, and the isomeric butanols, glycerol, lower glycols, such as ethylene and propylene glycol, and the derivable from said classes of compounds ether.
  • the active compounds used in the invention are usually dissolved or in suspended form.
  • Optionally present enzymes are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase, pectinase and mixtures thereof.
  • proteases derived from microorganisms such as bacteria or fungi, come into question. It can be obtained in a known manner by fermentation processes from suitable microorganisms.
  • Proteases are commercially available, for example, under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym® or Maxapem®.
  • the lipase which can be used can be obtained, for example, from Humicola lanuginosa, from Bacillus species, from Pseudomonas species, from Fusarium species, from Rhizopus species or from Aspergillus species.
  • Suitable lipases are commercially available, for example, under the names Lipolase®, Lipozym®, Lipomax®, Lipex®, Amano®-Lipase, Toyo-Jozo®-Lipase, Meito®-Lipase and Dio-synth®-Lipase.
  • Suitable amylases are commercially available, for example, under the names Maxamyl®, Termamyl®, Duramyl® and Purafect® OxAm.
  • the usable cellulase may be a recoverable from bacteria or fungi enzyme, which has a pH optimum, preferably in the weakly acidic to slightly alkaline range of 6 to 9.5.
  • Such cellulases are commercially available under the names Celluzyme®, Carezyme® and Ecostone®.
  • Suitable pectinases are, for example, under the names Gamanase®, Pektinex AR®, X-Pect® or Pectaway® from Novozymes, under the name Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, Rohapect MA plus HC, Rohapect DA12L ®, Rohapect 10L®, Rohapect B1L® from AB Enzymes and available under the name Pyrolase® from Diversa Corp., San Diego, CA, USA.
  • enzyme stabilizers include amino alcohols, for example mono-, di-, triethanol- and -propanolamine and their mixtures, lower carboxylic acids, boric acid, alkali metal borates, boric acid-carboxylic acid combinations, boric acid esters, boronic acid derivatives, calcium salts, for example Ca-formic acid combination, magnesium salts, and / or sulfur-containing reducing agents.
  • Suitable foam inhibitors include long-chain soaps, especially behenic soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which moreover can contain microfine, optionally silanated or otherwise hydrophobicized silica.
  • foam inhibitors are preferably bound to granular, water-soluble carrier substances.
  • polyester-active soil release polymers which can be used in addition to the active substance combination of the invention include copolyesters of dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol.
  • dicarboxylic acids for example adipic acid, phthalic acid or terephthalic acid
  • diols for example ethylene glycol or propylene glycol
  • polydiols for example polyethylene glycol or polypropylene glycol.
  • Preferred soil release polymers include those compounds which are formally accessible by esterification of two monomeric moieties, wherein the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO- (CHR 11 -) a OH, also known as polymeric Diol H- (O- (CHR 11 -) a ) b OH may be present.
  • Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof
  • R 11 denotes hydrogen
  • a is a number from 2 to 6
  • b is a number from 1 to 300.
  • the molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10.
  • the degree of polymerization b is preferably in the range of 4 to 200, particularly 12 to 140.
  • the molecular weight or the average molecular weight or the maximum of the molecular weight distribution of preferred soil release polyester is in the range of 250 g / mol to 100,000 g / mol, in particular from 500 g / mol to 50,000 g / mol.
  • the acid underlying the radical Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferable.
  • acids having at least two carboxyl groups may be included in the soil release-capable polyester.
  • these include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and Sebacic acid.
  • the preferred diols HO- (CHR 11 -) a OH include those in which R 11 is hydrogen and a is a number from 2 to 6, and those in which a is 2 and R 11 is hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 C-atoms is selected.
  • R 11 is hydrogen and a is a number from 2 to 6
  • R 11 is hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 C-atoms is selected.
  • those of the formula HO-CH 2 -CHR 11 -OH in which R 11 has the abovementioned meaning are particularly preferred.
  • diol components are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-decanediol, 1, 2-dodecanediol and neopentyl glycol.
  • Particularly preferred among the polymeric diols is polyethylene glycol having an average molecular weight in the range from 1000 g / mol to 6000 g / mol.
  • the polyesters may also be end-capped, alkyl groups having from 1 to 22 carbon atoms and esters of monocarboxylic acids being suitable as end groups.
  • the ester groups bound by end groups alkyl, alkenyl and Arylmonocarbonklaren with 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms, based.
  • valeric acid caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleinic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, levostearic acid, arachidic acid , Gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, which may carry 1 to 5 substituents having a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms, for example tert-butyl
  • the hydroxymonocarboxylic acids may in turn be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group.
  • the number of hydroxymonocarboxylic acid units per end group is in the range from 1 to 50, in particular from 1 to 10.
  • polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights of 750 g / mol to 5000 g / mol and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate 50:50 to 90:10 used together with a combination of active substances essential to the invention.
  • the soil release polymers are preferably water-soluble, the term "water-soluble" being understood to mean a solubility of at least 0.01 g, preferably at least 0.1 g, of the polymer per liter of water at room temperature and pH 8.
  • preferred polymers have a solubility of at least 1 g per liter, in particular at least 10 g per liter, under these conditions.
  • compositions according to the invention presents no difficulties and can be carried out in a known manner, for example by spray-drying or granulation, enzymes and possibly other thermally sensitive ingredients, for example bleaching agents, if appropriate be added separately later.
  • a process comprising an extrusion step is preferred.
  • compositions according to the invention in tablet form, which may be monophasic or multiphase, monochromatic or multicolor and in particular consist of one or more layers, in particular two layers
  • the procedure is preferably such that all constituents - if appropriate one per layer - in one Mixer mixed together and the mixture by means of conventional tablet presses, such as eccentric or rotary presses, with compression forces in the range of about 50 to 100 kN, preferably compressed at 60 to 70 kN.
  • a tablet produced in this way has a weight of 10 g to 50 g, in particular 15 g up to 40 g.
  • the spatial form of the tablets is arbitrary and can be round, oval or angular, with intermediate forms are also possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm.
  • the size of rectangular or cuboid-shaped tablets, which are introduced predominantly via the metering device, for example the dishwasher, is dependent on the geometry and the volume of this metering device.
  • Exemplary preferred embodiments have a base area of (20 to 30 mm) x (34 to 40 mm), in particular of 26x36 mm or 24x38 mm.
  • Liquid or pasty compositions according to the invention in the form of customary solvents, in particular water, containing solutions are usually prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.
  • an agent into which the active ingredient combination to be used according to the invention is incorporated is liquid and contains 1% by weight to 15% by weight, in particular 2% by weight to 10% by weight, of nonionic surfactant, 2% by weight % to 30% by weight, in particular 5% by weight to 20% by weight of synthetic anionic surfactant, up to 15% by weight, in particular 2% by weight to 12.5% by weight, of soap, 0 , 5 wt .-% to 5 wt .-%, in particular 1 wt .-% to 4 wt .-% organic builder, especially polycarboxylate such as citrate, up to 1.5 wt .-%, in particular 0.1 wt. % to 1 wt .-% complexing agent for heavy metals, such as phosphonate, and in addition to optionally contained enzyme, enzyme stabilizer, color and / or fragrance water and / or water-miscible solvent.
  • soap 0 , 5 wt .-% to 5 wt
  • an agent into which the active substance combination to be used according to the invention is incorporated is particulate and contains up to 25% by weight, in particular 5% by weight to 20% by weight, of bleaching agent, in particular alkali percarbonate, up to 15 Wt .-%, in particular 1 wt .-% to 10 wt .-% bleach activator, 20 wt .-% to 55 wt .-% inorganic builder, up to 10 wt .-%, in particular 2 wt .-% to 8 wt % of water-soluble organic builder, 10% by weight to 25% by weight of synthetic anionic surfactant, 1% by weight to 5% by weight of nonionic surfactant and up to 25% by weight, in particular 0.1% by weight. % to 25 wt .-% of inorganic salts, in particular alkali carbonate and / or bicarbonate.
  • Table 1 Detergent compositions (in% by weight) A B C D e F G H C9-13-Alkylbenzenesulfonate, Na salt 9 10 6 6 5 15 15 9 C12-18 fatty alcohol, 7 EO 8th 9 6 6 5 6 6 10 C12-14 fatty alcohol sulfate with 2EO - - 8th 8th 10 2 2 5 C12-18 fatty acid, Na salt 4 3 3 - 4 2 - 7 citric acid 2 3 3 3 2 2 2 3 sodium hydroxide 3 3 2 2 3 3 3 4 boric acid 1 1 1 1 1 1 1 1 1 enzymes + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + +
  • Household washing machines (Miele® W 1514) were loaded with 3.5 kg of clean accompanying laundry as well as cotton test fabrics, which were provided with 108 different standardized stains, including the soiling chocolate milk / soot, and dirt ballast. 66 ml of the detergent C listed in Example 1 were metered in and washed at 40.degree. After hanging drying and mangling of the test textiles, their whiteness was determined spectrophotometrically (Minolta® CR400).
  • the detergent with an active ingredient combination to be used according to the invention showed a significantly better primary washing performance than the otherwise equal composition with only one component of the combination or without it.

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Claims (10)

  1. Utilisation d'une combinaison de polyamines polyalcoxylées que l'on peut obtenir par réaction de polyamines avec un oxyde d'alkylène, en particulier de l'oxyde d'éthylène et/ou de l'oxyde de propylène, avec des alcools de type C8C18 alcoxylés ayant un degré d'alcoxylation moyen dans la plage de 1 à 5, en particulier de 2 à 4, dans des détergents pour améliorer le pouvoir de lavage ou de nettoyage primaire lors du lavage de textiles ou lors du nettoyage de surfaces dures contre la saleté.
  2. Utilisation de polyamines polyalcoxylées que l'on peut obtenir par réaction de polyamines avec un oxyde d'alkylène, en particulier de l'oxyde d'éthylène et/ou de l'oxyde de propylène, pour améliorer le pouvoir de lavage ou de nettoyage primaire de détergents contenant un alcool de type C8C18 alcoxylé ayant un degré d'alcoxylation moyen dans la plage de 1 à 5, en particulier de 2 à 4, lors du lavage de textiles ou lors du nettoyage de surfaces dures.
  3. Utilisation selon la revendication 1 ou 2, caractérisée en ce que les taches contiennent des préparations protéiques.
  4. Procédé d'élimination de taches, en particulier de taches protéiniques ou de taches de préparations protéiques, textiles ou de surfaces dures, dans lequel un détergent nettoyage et une combinaison de polyamines polyalcoxylées, que l'on peut obtenir par réaction de polyamines avec un oxyde d'alkylène, en particulier de l'oxyde d'éthylène et/ou de l'oxyde de propylène, sont utilisés avec des alcools de type C8C18 alcoxylés ayant un degré d'alcoxylation moyen dans la plage de 1 à 5, en particulier de 2 à 4, le rapport en poids de la polyamine polyalcoxylée à l'alcool de type C8C18 alcoxylé ayant un degré d'alcoxylation moyen de 1 à 5 étant situé dans la plage de 1:3 à 3:1.
  5. Procédé selon la revendication 4, caractérisé en ce que la concentration de polyamine polyalcoxylée dans la solution de lavage ou de nettoyage, notamment aqueuse, va de 1 mg/l à 500 mg/l, en particulier de 5 mg/l à 200 mg/l, et/ou en ce que la concentration de l'alcool de type C8C18 alcoxylé ayant un degré d'alcoxylation moyen dans la plage de 1 à 5 mg/l va de 1 à 500 mg/l, en particulier de 5 mg/l à 200 mg/l.
  6. Agent de lavage ou de nettoyage contenant une combinaison de polyamine polyalcoxylée, que l'on peut obtenir par réaction de polyamines avec un oxyde d'alkylène, avec un alcool de type C8C18 alcoxylé ayant un degré d'alcoxylation moyen dans la gamme de 1 à 5, le rapport en poids de la polyamine polyalcoxylée à l'alcool de type C8C18 alcoxylé ayant un degré d'alcoxylation moyen de 1 à 5 étant situé dans la plage de 1:3 à 3:1, en particulier dans des quantités de 0,3 à 20 % en fonction de la masse.
  7. Utilisation selon l'une des revendications 1 à 3, procédé selon la revendication 4 ou 5, ou agent selon la revendication 6, caractérisés en ce que les atomes d'azote dans la polyamine sont séparés les uns des autres par des groupes alkylène ayant 2 à 12 atomes de carbone, en particulier 2 à 6 atomes de carbone, les groupes alkylènes ne comportant pas tous nécessairement le même nombre d'atomes de carbone.
  8. Utilisation, procédé ou agent selon l'une des revendications précédentes, caractérisés en ce que la polyamine a une masse molaire moyenne dans la plage de 500 g/mol à 50000 g/mol, en particulier de 550 g/mol à 5000 g/mol, et/ou en ce que le nombre moyen de groupes alcoxy par fonction amino primaire et secondaire dans la polyamine polyalcoxylée est de 1 à 100, en particulier de 5 à 70.
  9. Utilisation, procédé ou agent selon l'une des revendications précédentes, caractérisés en ce que l'alcool possède au maximum 16 atomes de carbone, en particulier 12 à 14 atomes de carbone.
  10. Utilisation, procédé ou agent selon l'une des revendications précédentes, caractérisés en ce que le degré d'alcoxylation de l'alcool est situé dans la gamme allant de 2 à 4, en particulier de 2 à 3,5.
EP13805851.6A 2012-12-17 2013-12-12 Produits détergents et nettoyants contenant une polyamine polyalcoxylée et un tensioactif non ionique adapté Active EP2931858B1 (fr)

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DE102012223336.9A DE102012223336A1 (de) 2012-12-17 2012-12-17 Wasch- und Reinigungsmittel mit polyalkoxyliertem Polyamin und angepasstem Niotensid
PCT/EP2013/076303 WO2014095540A1 (fr) 2012-12-17 2013-12-12 Produits détergents et nettoyants contenant une polyamine polyalcoxylée et un tensioactif non ionique adapté

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DE102013216776A1 (de) * 2013-08-23 2015-02-26 Henkel Ag & Co. Kgaa Wasch- und Reinigungsmittel mit verbesserter Leistung
DE102014225789A1 (de) * 2014-12-15 2016-06-16 Henkel Ag & Co. Kgaa Wasch- und Reinigungsmittel
DE102023200330A1 (de) 2023-01-17 2024-07-18 Henkel Ag & Co. Kgaa Waschmittel mit erhöhter Waschkraft gegenüber öligen und fettigen Anschmutzungen

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AT330930B (de) 1973-04-13 1976-07-26 Henkel & Cie Gmbh Verfahren zur herstellung von festen, schuttfahigen wasch- oder reinigungsmitteln mit einem gehalt an calcium bindenden substanzen
DE3413571A1 (de) 1984-04-11 1985-10-24 Hoechst Ag, 6230 Frankfurt Verwendung von kristallinen schichtfoermigen natriumsilikaten zur wasserenthaertung und verfahren zur wasserenthaertung
PE6995A1 (es) 1994-05-25 1995-03-20 Procter & Gamble Composicion que comprende un polimero de polialquilenoamina etoxilado propoxilado como agente de separacion de sucio
ZA978601B (en) * 1996-10-07 1998-03-26 Procter & Gamble Alkoxylated, quaternized polyamine detergent ingredients.
US6964943B1 (en) * 1997-08-14 2005-11-15 Jean-Luc Philippe Bettiol Detergent compositions comprising a mannanase and a soil release polymer
US20020160924A1 (en) * 1999-06-15 2002-10-31 The Procter & Gamble Company Cleaning compositions
WO2005080538A1 (fr) * 2004-02-25 2005-09-01 Unilever Plc Composition detergente amelioree et procede associe
US8669221B2 (en) 2005-04-15 2014-03-11 The Procter & Gamble Company Cleaning compositions with alkoxylated polyalkylenimines

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DE102012223336A1 (de) 2014-06-18
US20150275134A1 (en) 2015-10-01
US9587204B2 (en) 2017-03-07
EP2931858A1 (fr) 2015-10-21
ES2703329T3 (es) 2019-03-08

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