EP0698079B1 - Produits de lavage et de nettoyage contenant une lipase - Google Patents

Produits de lavage et de nettoyage contenant une lipase Download PDF

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Publication number
EP0698079B1
EP0698079B1 EP94916185A EP94916185A EP0698079B1 EP 0698079 B1 EP0698079 B1 EP 0698079B1 EP 94916185 A EP94916185 A EP 94916185A EP 94916185 A EP94916185 A EP 94916185A EP 0698079 B1 EP0698079 B1 EP 0698079B1
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EP
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Prior art keywords
weight
alkyl
detergent
cleaning composition
water
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EP94916185A
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German (de)
English (en)
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EP0698079A1 (fr
Inventor
Georg Meine
Eric Sung
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38663—Stabilised liquid enzyme compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the invention relates to detergents and cleaning agents which contain lipase and water-soluble and / or insoluble builders and a nonionic surfactant component which consists essentially of alkyl or alkenyglycoside.
  • the international patent application WO 86/05187 relates to detergents which contain 1 to 70% by weight of glycosidic surfactant, 0.005 to 5% by weight of enzyme, in particular protease, and 5 to 80% by weight of water, lower alcohols, glycols, builders and / or their mixtures and optionally further surfactants.
  • European patent application EP 341 999 describes lipase-containing agents with a surfactant composition which contains anionic surfactants and nonionic surfactants which are selected from alkylene oxide adducts with fatty alcohols, fatty acids, fatty acid esters, fatty acid amides and fatty amines with at least 10 carbon atoms in the molecule, the content such nonionic surfactants, in which a maximum of 5 alkoxylate groups are contained per molecule, is at least 30% and in which the total content of surfactant is 1 to 30% by weight.
  • the fat-dissolving power of the agents is increased by the content of such low alkoxylated nonionic surfactants.
  • the stability of the enzyme used during storage is not always satisfactory when using low-ethoxylated nonionic surfactants.
  • alkyl glycosides with long-chain alkyl groups belong to the nonionic surfactants.
  • Detergents which contain alkyl glycosides in combination with at least one customary anionic surfactant are described in European patent application EP 70 074.
  • Detergents containing alkyl glycosides and anionic surfactants are also known from European patent application EP 92 877.
  • liquid detergents are known from European patent application EP 105 556, which contain alkyl glycosides, certain other nonionic surfactants and anionic surfactants. From the international patent application W0 86/2943 alkylglycoside-containing liquid detergents are known which additionally contain conventional anionic surfactants.
  • a process for the production of particulate detergents by drying a 40 to 80 percent aqueous slurry which, based on the resulting solid, 2 to 60% by weight of surfactants, which is at least 0.1 % By weight consist of alkyl glycosides, the total amount of alkyl glycosides being at most 2% by weight, containing 5 to 70% by weight builder substances and up to 40% by weight water-soluble fillers. Act in such slurries the alkyl glycosides as viscosity reducers.
  • Preferred surfactants are anionic surfactants, especially those of the alkylbenzenesulfonate type, and nonionic surfactants, especially ethoxylated fatty alcohols.
  • the invention relates to an enzyme- and builder-containing detergent or cleaning agent which contains a glycoside-containing nonionic surfactant component, characterized in that it contains 0.1% by weight to 20% by weight of soap and lipase and the nonionic surfactant component is at least 50% by weight.
  • % in particular at least 80% by weight, consists of a glycoside of the formula (I), R 1 -O (G) n (I) in which R 1 is an alkyl or alkenyl radical having 8 to 22 carbon atoms, G is a glycose unit and n is a number from 1 to 10.
  • glycosides suitable for incorporation into the surfactant mixtures according to the invention are compounds of the general formula I in which R 1 is an alkyl or alkenyl radical having 8 to 22 carbon atoms, G is a glycose unit and n is a number between 1 and 10.
  • R 1 is an alkyl or alkenyl radical having 8 to 22 carbon atoms
  • G is a glycose unit
  • n is a number between 1 and 10.
  • Such compounds and their preparation are described, for example, in European patent applications EP 92 355, EP 301 298, EP 357 969 and EP 362 671 or US Pat. No. 3,547,828.
  • the glycoside component ((G) n in formula I) is an oligomer or polymer from naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose , Ribose, arabinose, xylose and lyxose.
  • the oligomers consisting of such glycosidically linked monomers are characterized not only by the type of sugar they contain, but also by their number, the so-called degree of oligomerization.
  • the degree of oligomerization (n in Formula I) generally takes fractional numerical values as the quantity to be determined analytically; it is between 1 and 10, for the glycosides preferably used below 1.5, in particular between 1.2 and 1.4.
  • the preferred monomer building block is glucose because of its good availability.
  • the alkyl or alkenyl part (R 1 in formula I) of the glycosides contained in the agents according to the invention preferably also originates from easily accessible derivatives of renewable raw materials, in particular from fatty alcohols, although their branched chain isomers, in particular so-called oxo alcohols, can also be used to prepare usable glycosides . Accordingly, the primary alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful.
  • the glycosides can contain small amounts, for example 1 to 2%, of unreacted free fatty alcohol, which has no adverse effect on the properties of the products produced therewith.
  • the proportion of further nonionic surfactant contained in addition to the glycoside is up to 50% by weight, preferably at most 15% by weight and in particular 0.5% by weight to 10% by weight, based on the total nonionic surfactant component.
  • Other nonionic surfactants that may be used 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.
  • the degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides.
  • the derivatives of fatty alcohols are particularly suitable, although their branched chain isomers, in particular so-called oxo alcohols, can also be used to prepare alkoxylates which can be used.
  • the alkoxylates in particular the ethoxylates, of primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals, and mixtures thereof, can be used.
  • They are also appropriate Alkoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the alcohols mentioned with regard to the alkyl part, can be used.
  • Such a nonionic surfactant system consisting of glycoside according to formula (I) and optionally further nonionic surfactant, is preferably present in the agents according to the invention in amounts of 1% by weight to 30% by weight, in particular 1% by weight to 25% by weight. -% contain.
  • the agent according to the invention is a cleaning agent, for example a manual or machine dishwashing agent or a cleaning agent for hard surfaces, the content of nonionic surfactant can also be lower and is then preferably 0.5% by weight to 20% by weight. -%, in particular 0.9% by weight to 10% by weight.
  • the agents according to the invention can contain further surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type, in amounts of preferably not more than 20% by weight, in particular from 0.1% by weight to 18% by weight, in each case based on total means included.
  • synthetic anionic surfactants which are particularly suitable for use in the agents according to the invention are the alkyl and / or alkenyl sulfates having 8 to 22 carbon atoms and carrying an alkali metal, ammonium or alkyl or hydroxyalkyl substituted ammonium ion as countercation.
  • the derivatives of fatty alcohols with in particular 12 to 18 carbon atoms and their branched chain analogs, the so-called oxo alcohols, are preferred.
  • the alkyl and alkenyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and then neutralizing with alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases.
  • a conventional sulfating reagent in particular sulfur trioxide or chlorosulfonic acid
  • Such alkyl and / or alkenyl sulfates are preferably in amounts in the agents according to the invention from 0.1% by weight to 20% by weight, in particular from 0.5% by weight to 18% by weight.
  • the sulfate-type surfactants that can be used also include the sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates.
  • ether sulfates preferably contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule.
  • Suitable anionic surfactants of the sulfonate type include the .alpha.-sulfoesters obtainable by reacting fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those derived from fatty acids with 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and linear alcohols with 1 up to 6 carbon atoms, preferably 1 to 4 carbon atoms, derived sulfonation products, as well as the sulfofatty acids resulting from these by formal saponification.
  • the weight ratio of glycoside to alkyl or alkenyl or ether sulfate is preferably 5: 1 to 1: 4, in particular 1: 1 to 1: 3.5 , with anionic surfactant having a linear, primary alkyl or alkenyl radical having 14 to 18 carbon atoms being particularly preferred.
  • Soaps are included as further surfactant ingredients, whereby saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, as well as soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids, are suitable.
  • Soap mixtures are particularly preferred which are composed of 50% by weight 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 preferably contained in amounts of 0.1% by weight to 5% by weight. In particular, however, higher amounts of soap of up to 20% by weight can also be contained in liquid agents.
  • the lipase contained in the agent according to the invention is an enzyme that can be obtained from microorganisms, in particular bacteria or fungi. Such is known for example from European patent applications EP 204 208, EP 214 761, EP 258 068, EP 407 225 or international patent application WO 87/859.
  • Useful commercially available Examples of lipases are Lipolase (R) and Lipozym (R) .
  • Lipase is preferably used in the agent according to the invention in amounts such that the finished agent 10 LU / g to 10,000 LU / g ("lipase activity units" per gram, determined by the enzymatic hydrolysis of tributyrin at 30 ° C. and pH 7 after the method mentioned in EP 258 068), in particular 80 LU / g to 5,000 LU / g and particularly preferably 100 LU / g to 1000 LU / g.
  • An agent according to the invention preferably contains 20% by weight 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 the polycarboxylic acids, in particular citric acid and sugar acids, and also polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain small amounts of polymerizable substances without carboxylic acid functionality in copolymerized form.
  • the relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably 50,000 to 120,000, based on free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000.
  • Suitable, albeit 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% by weight.
  • Terpolymers which contain two carboxylic acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer can 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 can be a derivative of a C 4 -C 8 dicarboxylic acid, preferably a C 4 -C 8 dicarboxylic acid, maleic acid being particularly preferred.
  • the third monomeric unit is formed from vinyl alcohol and / or preferably an esterified vinyl alcohol.
  • Vinyl alcohol derivatives which contain an ester of short-chain carboxylic acids, for example of C 1 -C 4 carboxylic acids, with vinyl alcohol.
  • Preferred terpolymers contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% vinyl alcohol and / or vinyl acetate.
  • the second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which, in the 2-position, has an alkyl radical, preferably 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 40% by weight to 60% by weight, in particular 45 to 55% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10% by weight to 30% by weight. %, preferably 15% by weight to 25% by weight of methallylsulfonic acid or methallylsulfonate and as the third monomer 15% by weight to 40% by weight, preferably 20% by weight to 40% by weight, of a carbohydrate.
  • This carbohydrate can 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 creates predetermined breaking points in the polymer, which are responsible for the good biodegradability of the polymer.
  • These terpolymers can be produced in particular by processes which are described in German patent applications P 42 21 381.9 and P 43 00 772.4 and generally have a relative molecular weight between 1000 and 200000, preferably between 200 and 50,000 and in particular between 3000 and 10,000 . They can be used, in particular for the preparation of liquid compositions, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of 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 water-containing, agents according to the invention.
  • crystalline or amorphous alkali alumosilicates are used as water-insoluble, water-dispersible inorganic builder materials, in amounts of not more than 40% by weight, preferably not more than 20% by weight and in particular from 1% by weight to 5% by weight.
  • the crystalline aluminosilicates in detergent quality in particular zeolite NaA and optionally NaX, are preferred. Amounts close to the above upper limit are preferably used in solid, particulate compositions.
  • Suitable aluminosilicates in particular have no particles with a grain size above 30 ⁇ m and preferably consist of at least 80% by weight of particles with a size below 10 ⁇ m.
  • Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline, layered alkali silicates, which can be present alone or in a mixture with amorphous silicates. These include crystalline layered silicates of the formula NaMSi x O 2x + 1 + yH 2 O, in which M stands for sodium, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application 164 514.
  • Preferred crystalline layered silicates are those in which M is sodium and x is 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 .yH 2 O are preferred, it being possible, for example, to obtain ⁇ -sodium disilicate by the process described in international patent application WO 91/08171.
  • the crystalline layered silicates are preferably used in amounts of 1% by weight to 15% by weight and in particular 2% by weight to 7% by weight, the weight ratio of zeolite to crystalline layered silicate, based in each case on anhydrous active substance, at least 5 : 1 is.
  • the weight ratio is amorphous alkali silicate: crystalline alkali silicate preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
  • alkali carbonates alkali hydrogen carbonates and alkali sulfates and mixtures thereof are suitable.
  • additional inorganic material can be present in amounts up to 20% by weight, but is preferably absent entirely.
  • the agents according to the invention can be used to set a desired acidic or weakly alkaline pH of in particular about 8.0 to 9.5 in 1% by weight aqueous solution, solid inorganic and / or organic acids or acidic salts, for example alkali metal bisulfates, succinic acid, adipic acid or Glutaric acid and mixtures thereof.
  • Such acidic substances are contained in the agents according to the invention preferably in amounts not exceeding 5% by weight, in particular from 0.1% by weight to 3% by weight, amounts close to the above-mentioned upper limit being of particular interest for cleaning agents.
  • the agents according to the invention can contain further constituents customary in washing and cleaning agents.
  • These optional constituents in particular solvents, bleaching agents, bleach activators, abrasives, such as quartz powder, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic, polyphosphonic acids and / or aminopolyphosphonic acids, redeposition inhibitors, for example cellulose ethers, foam inhibitors, for example organopolysiloxanes or paraffins, and optical brighteners include, for example stilbene disulfonic acid derivatives .
  • 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% by weight, in particular 0.1% by weight to 2% by weight, of complexing agents for heavy metals, in particular aminoalkylenephosphonic acids and their Salts, up to 3% by weight, in particular 0.5% by weight to 2% by weight, of graying inhibitors and up to 2% by weight, in particular 0.1% by weight to Contain 1% by weight of foam inhibitors, the weight percentages based on the total average.
  • solvents which are used in particular in the case of liquid compositions according to the invention are preferably those which are water-miscible. These include the lower alcohols, for example ethanol, propanol, iso-propanol, and the isomeric butanols, glycerol, lower glycols, for example ethylene and propylene glycol, and the ethers which can be derived from the classes of compounds mentioned.
  • the customary enzyme stabilizers which are optionally present, in particular in liquid agents according to the invention, include amino alcohols, for example mono-, di-, triethanol- and propanolamine and mixtures thereof, lower carboxylic acids, as known, for example, from European patent applications EP 376 705 and EP 378 261, Boric acid or alkali borates, boric acid-carboxylic acid combinations, as known, for example, from European patent application EP 451 921, calcium salts, for example the Ca-formic acid combination known from European patent EP 28 865, magnesium salts, such as from European patent application EP 378 262, and / or sulfur-containing reducing agents, as known, for example, from European patent applications EP 080 748 or EP 080 223.
  • amino alcohols for example mono-, di-, triethanol- and propanolamine and mixtures thereof
  • lower carboxylic acids as known, for example, from European patent applications EP 376 705 and EP 378 261
  • Boric acid or alkali borates Boric acid or
  • Suitable foam inhibitors include long-chain soaps, in particular beech soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which may also contain microfine, optionally silanized or otherwise hydrophobized silica.
  • foam inhibitors are preferably bound to granular, water-soluble carrier substances, as described, for example, in German patent application DE 34 36 194, European patent applications EP 262 588, EP 301 414, EP 309 931 or European patent EP 150 386 .
  • the agent according to the invention can furthermore contain graying inhibitors.
  • Graying inhibitors have the task of removing the fiber Keep dirt suspended in the liquor and prevent the fibers from graying.
  • Water-soluble colloids of mostly organic nature are suitable for this, 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.
  • Soluble starch preparations and starch products other than those mentioned above can also be used, for example partially hydrolyzed starch. Na-carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose and their mixtures and polyvinyl pyrrolidone are preferably used.
  • the bleaching agents which can be considered as further constituents of agents according to the invention are the per compounds generally used in detergents, such as perborate, which can be present as a tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally present as alkali metal salts, in particular as sodium salts.
  • Such bleaching agents are preferably present in washing or cleaning agents according to the invention in amounts of up to 25% by weight, in particular up to 15% by weight and particularly preferably from 5% by weight to 15% by weight, in each case based on the total agent, contain.
  • the optional component of the bleach activators includes the commonly used N- or O-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines and sulfuryl amides, sulfuryl amides , in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl-phenolsulfonate, and acylated sugar derivatives, in particular pentaacetyl glucose.
  • N- or O-acyl compounds for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hy
  • the bleach activators can be coated or granulated with coating substances in a known manner in order to avoid the interaction with the per-compounds during storage, with tetraacetylethylenediamine granulated with carboxymethyl cellulose with average grain sizes of 0.01 mm to 0.8 mm, as described, for example, by can be produced in the method described in the European patent EP 037 026, and / or granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, as can be prepared by the process described in German Patent DD 255 884, is particularly preferred.
  • Bleach activators of this type are preferably present in washing or cleaning agents according to the invention in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, in each case based on the total agent.
  • Enzymes which may be present in addition to lipase are in particular those from the class of proteases, amylases and cellulases and mixtures thereof. Enzymes obtained from fungi or bacterial strains such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus and Streptomyces griseus are preferably used.
  • proteases which can be used include the enzymes which can be obtained from microorganisms, in particular bacteria or fungi, with a pH optimum in the alkaline range, for example those from the international patent applications WO 92/07067, WO 91/02792, WO 88/03947 or WO 88/03946 or the European patent applications EP 471 265, EP 416 967 or EP 394 352 known proteases.
  • Protease is preferably used in the agent according to the invention in amounts such that the finished agent 100 PE / g to 7 500 PE / g (protease units per gram, determined by the method described in Tenside 7, 125 (1970)), in particular 125 PE / g to 5,000 PE / g and particularly preferably 150 PE / g to 4,500 PE / g.
  • Useful proteases are commercially available, for example under the names BLAP (R) , Savinase (R) , Esperase (R) , Maxatase (R) , 0ptimase (R) or Alcalase (R) .
  • amylases which can be used in agents according to the invention include the enzymes which can be obtained from bacteria or fungi and which have a pH optimum, preferably in the alkaline range up to about pH 10.
  • Useful commercial products include Termamyl (R) and Maxamyl (R) .
  • Amylase is preferably used in the agent according to the invention in amounts such that the finished agent 0.01 KNU / g to 2 KNU / g ("Kilo-Novo-Units" per gram according to the Novo standard method, where 1 KNU is the amount of enzyme which degrades 5.26 g of starch at pH 5.6 and 37 ° C., based on the method described by P.
  • the cellulase which can be used according to the invention belongs to the enzymes which can be obtained from bacteria or fungi and which have a pH optimum, preferably in the almost neutral to weakly alkaline pH range from 6 to 9.5.
  • Such cellulases are known, for example, from German published applications DE 31 17 250, DE 32 07 825, DE 32 07 847, DE 33 22 950 or European patent applications EP 265 832, EP 269 977, EP 270 974, EP 273 125 and EP 339 550 known.
  • the agent according to the invention preferably in amounts such that the finished agent has a cellulolytic activity of 0.05 IU / g to 1.5 IU / g ("International Units" per gram, based on the enzymatic hydrolysis of Na-carboxymethylcellulose) pH 9.0 and 40 ° C, as described in Agric. Biol. Chem. 53 , 1275 (1989) by S. Ito et al.), in particular 0.07 IU / g to 1.4 IU / g and particularly preferred 0.1 IU / g to 1.3 IU / g.
  • Suitable commercial products include Celluzyme (R) from Novo Industri or KAC (R) from Kao.
  • the enzymes can be adsorbed onto carrier substances in a known manner, embedded in coating substances and / or granulated with the aid of carrier substances in order to make them easier to handle and to protect against premature inactivation if they are to be incorporated into particulate washing or cleaning agents.
  • the enzymes, in particular protease, optionally present in addition to lipase are preferably present in detergents or cleaning agents according to the invention in amounts of up to 2% by weight, in particular from 0.01% by weight to 1.5% by weight, in each case based on total means included.
  • an agent according to the invention is particulate and contains 30% by weight to 55% by weight of water-insoluble inorganic builder, up to 15% by weight, in particular 2% by weight to 12% by weight of water-soluble organic builder, 2.5% by weight to 20% by weight of synthetic anionic surfactant, 1% by weight to 20% by weight of nonionic surfactant component, up to 25% by weight, in particular 1% by weight to 15% by weight Bleaching agent, up to 8% by weight, in particular 0.5% by weight to 6% by weight, of bleach activator and up to 20% by weight, in particular 0.1% by weight to 15% by weight, of inorganic salts , in particular alkali carbonate, sulfate and / or silicate, and up to 2% by weight, in particular 0.4% by weight to 1.2% by weight of further enzyme, in particular in the form of particles, in particular protease, amylase and / or cellulase.
  • further enzyme in particular in the form of particles, in particular protease, amylase and /
  • a further preferred embodiment comprises a liquid agent containing 5% by weight to 35% by weight of water-soluble organic builder, up to 15% by weight, in particular 0.1% by weight to 5% by weight of water-insoluble inorganic builder , up to 15% by weight, in particular 0.5% by weight to 10% by weight of synthetic anionic surfactant, 1% by weight to 25% by weight of nonionic surfactant, up to 15% by weight, in particular 4 %
  • By weight to 12% by weight of soap and up to 30% by weight in particular 1% by weight to 25% by weight of water and / or water-miscible solvent and up to 10% by weight, in particular 0, 01 wt% to 7.5 wt% enzyme stabilization system.
  • a preferred cleaning agent according to the invention contains 0.5% by weight to 20% by weight, in particular 0.9% by weight to 10% by weight of nonionic surfactant, up to 25% by weight, in particular 12% by weight. % to 20% by weight of bleach, up to 10% by weight, in particular 2% by weight to 8% by weight of bleach activator, up to 2% by weight, in particular 0.1% by weight to 1 %
  • foam inhibitor up to 2% by weight, in particular 0.1% by weight to 1.2% by weight of additional enzyme, up to 50% by weight, in particular 25% by weight to 35% by weight .-% abrasive, and up to 5 wt .-%, in particular 0.5 wt .-% to 2 wt .-% anionic surfactant.
  • Particulate compositions according to the invention can be produced in the simplest manner by mixing the individual particles in a conventional mixer, in particular a drum, roller, belt or free-fall mixer, optional other powdery constituents and, if desired, also liquid or liquefied constituents, in particular nonionic surfactants , but also colors and fragrances belong, can be mixed by spraying. It is preferred to convert the thermally resilient components into a powder product in a manner known in principle by spray drying an aqueous slurry and to mix this with lipase and optionally other enzymatic active ingredients and other thermally sensitive constituents, which in particular include bleaching agents.
  • Flowable and liquid agents according to the invention can be prepared by simply mixing the constituents or their premixes, which can be liquid or dissolved in water or a solvent provided.
  • aqueous slurries containing alkyl sulfate, the nonionic surfactants, soap, sodium carbonate, sodium silicate, zeolite and Na polycarboxylate By spray drying aqueous slurries containing alkyl sulfate, the nonionic surfactants, soap, sodium carbonate, sodium silicate, zeolite and Na polycarboxylate, the zeolite in the form of an approximately 50% by weight aqueous slurry containing the alkyl glycoside as an approximately 50% by weight aqueous solution and the sodium silicate was used in the form of an approximately 35% by weight water glass solution, and subsequent mixing with the other ingredients indicated in Table 1 in the amounts indicated were the detergents M1 to M3 according to the invention and, for comparison, the lipase-free agents V1 and V2 and the produces glycoside-free agent V3 .
  • compositions M1 and M2 according to the invention have a significantly better cleaning performance than the directly comparable compositions V1 and V2 without lipase and the compositions according to the invention generally have a higher cleaning performance than the composition V3 containing a surfactant system not according to the invention .

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Detergent Compositions (AREA)
  • Enzymes And Modification Thereof (AREA)

Claims (10)

  1. Produit de lavage ou de nettoyage contenant un enzyme et des adjuvants, qui renferme un composant tensioactif non ionique contenant un glycoside,
    caractérisé en ce qu'
    il renferme de 0,1 à 20 % en poids de savon et de lipase et que le composant tensioactif non ionique consiste pour au moins 50 % en poids en un glycoside de formule (I),

            R1-O(G)n

    dans laquelle R1 signifie un radical alkyle ou alkényle ayant de 8 à 22 atomes de carbone, G signifie une unité de glycose et n un nombre allant de 1 à 10.
  2. Produit selon la revendication 1,
    caractérisé en ce que
    le composant tensioactif non ionique consiste pour au moins 80 % en poids dun glycoside de formule (I) et à côté du glycoside selon la formule (I), contient comme agent tensioactif non ionique supplémentaire, des alcoxylates en particulier des éthoxylates et/ou propoxylates d'alcools saturés ou non saturés une fois ou plusieurs fois, linéaires ou ramifiés, ayant de 10 à 22 atomes de carbone, en particulier de 12 à 18 atomes de carbone ; des polyhydroxyamides d'acide gras, des produits d'alcoxylation d'alkylamines, de diols vicinaux et d'amides d'acide carboxylique, qui en ce qui concerne la partie alkyle correspond aux alcools cités et/ou contient des produits d'insertion d'oxyde d'éthylène et/ou d'oxyde de propylène d'esters d'alcoyle d'acide gras.
  3. Produit selon la revendication 1 ou la revendication 2,
    caractérisé en ce que
    la quantité d'agent tensioactif non ionique supplémentaire contenu à côté du glycoside, s'élève au maximum à 15 % en poids, en particulier de 0,5 % en poids à 10 % en poids, rapporté aux composants tensioactifs non ioniques totaux.
  4. Produit selon l'une des revendications 1 à 3,
    caractérisé en ce qu'
    il contient de 20 % en poids à 55 % en poids d'adjuvants solubles dans l'eau ou insolubles dans l'eau, de la lipase en une quantité telle que l'activité s'élève à 10 LU/g à 10.000 LU/g, en particulier de 80 LU/g a 5000 LU/g rapporté au produit total ; jusqu'à 20 % en poids, en particulier de 0,1 % en poids à 18 % en poids d'agent tensioactif anionique synthétique et de 1 % en poids à 30 % en poids de composant tensioactif non ionique.
  5. Produit selon la revendication 4,
    caractérisé en ce que
    l'agent tensioactif anionique est choisi parmi les sulfates d'alkyle ou d'alkényle et/ou les alkyl- ou alkényléthersulfates, dans lesquels le groupe alkyle ou alkényle possède de 8 à 22, de préférence de 12 à la atomes de carbone.
  6. Produit selon l'une des revendications 1 à 5,
    caractérisé en ce qu'
    il est sous forme de particules et qu'il renferme de 30 % en poids à 55 % en poids d'adjuvant minéral insoluble dans l'eau ; jusqu'à 15 % en poids, en particulier de 2 % en poids à 12 % en poids d'adjuvant organique soluble dans l'eau, de 2,5 % en poids à 20 % en poids d'agent tensioactif anionique synthétique, de 1% en poids à 20 % en poids de composant tensioactif non ionique, jusqu'à 25 % en poids, en particulier de 1% en poids à 15 % en poids, d'agent de blanchiment, jusqu'à 8 % en poids, en particulier de 0,5 % en poids à 6 % en poids d'activateur de blanchiment, et jusqu'à 20 % en poids, en particulier de 0,1 % en poids à 15 % en poids de sels minéraux ainsi que jusqu'à 2 % en poids, en particulier de 0,4 % en poids à 1,2 % en poids d'un autre enzyme conditionné sous forme de particules, en particulier une protéase, une amylase et/ou une cellulase.
  7. Produit selon l'une des revendications 1 à 5,
    caractérisé en ce qu'
    il est liquidé et qu'il contient de 5 % en poids à 35 % en poids d'adjuvant organique soluble dans l'eau, jusqu'à 15 % en poids, en particulier de 0,1 % en poids à S % en poids, d'adjuvant organique insoluble dans l'eau, jusqu'à 10 % en poids d'agent tensioactif anionique synthétique, de 1% en poids à 25 % en poids d'agent tensioactif non ionique, jusqu'à 15 % en poids en particulier de 4 % en poids à 12 % en poids de savons, et jusqu'à 30 % en poids, en particulier de 1% en poids à 25 % en poids, d'eau et/ou de solvant miscible à l'eau ainsi que jusqu'à 10 % en poids, en particulier de 0,01% en poids à 7,5 % en poids de système de stabilisation d'enzyme.
  8. Produit de nettoyage selon l'une des revendications 1 à 3,
    caractérisé en ce qu'
    il renferme de 0,5 % en poids à 20 % en poids en particulier de 0,9 % en poids à 10 % en poids d'agent tensioactif non ionique, jusqu'à 25 % en poids en particulier de 12 % en poids à 20 % en poids, d'agent de blanchiment, jusqu'à 10 % en poids, en particulier de 2 % en poids à 8 % en poids d'activateur de blanchiment, jusqu'à 2 % en poids, en particulier de 0,1 % en poids à 1 % en poids d'inhibiteur de mousse, de 2 % en particulier de 0,1 % en poids à 1,2 % en poids d'enzyme supplémentaire, jusqu'à 50 % en poids en particulier de 25 % en poids à 35 % en poids de substance abrasive et jusqu'à 5 % en poids, en particulier de 0,5 % en poids à 2 % en poids d'agent tensioactif anionique.
  9. Prcduit selon l'une des revendication 1 à 8,
    caractérisé en ce que
    le glycoside de formule (I), est un alkyle ou un alkényle glucoside et qu'il possède un degré d'oligomérisation en dessous de 1,5, en particulier de 1,2 à 1,4.
  10. Produit selon l'une des revendications 1 à 9,
    caractérisé en ce qu'
    il renferme un glycoside selon la formule (I) et un alkyle ou alkenyl- ou éthersulfate avec un radical alkyle ou alkényle linéaire, primaire, ayant de 14 à 18 atomes de carbone, dans un rapport pondéral de 5:1 à 1:4 en particulier de 1:1 à 1:3,5.
EP94916185A 1993-05-12 1994-05-03 Produits de lavage et de nettoyage contenant une lipase Expired - Lifetime EP0698079B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4315854 1993-05-12
DE4315854A DE4315854A1 (de) 1993-05-12 1993-05-12 Lipasehaltige Wasch- und Reinigungsmittel
PCT/EP1994/001400 WO1994026861A1 (fr) 1993-05-12 1994-05-03 Produits de lavage et de nettoyage contenant une lipase

Publications (2)

Publication Number Publication Date
EP0698079A1 EP0698079A1 (fr) 1996-02-28
EP0698079B1 true EP0698079B1 (fr) 1997-09-03

Family

ID=6487905

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Application Number Title Priority Date Filing Date
EP94916185A Expired - Lifetime EP0698079B1 (fr) 1993-05-12 1994-05-03 Produits de lavage et de nettoyage contenant une lipase

Country Status (6)

Country Link
EP (1) EP0698079B1 (fr)
JP (1) JPH08510268A (fr)
AT (1) ATE157698T1 (fr)
DE (2) DE4315854A1 (fr)
ES (1) ES2108456T3 (fr)
WO (1) WO1994026861A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015047188A1 (fr) * 2013-09-30 2015-04-02 Enza Biotech Ab Composition tensioactive

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4344154A1 (de) * 1993-12-23 1995-06-29 Henkel Kgaa Enzymhaltiges Flüssigwaschmittel
DE4411349A1 (de) * 1994-03-31 1995-10-05 Henkel Kgaa Lipasehaltiges Textilwaschmittel
CA2254781A1 (fr) * 1996-05-15 1997-11-20 The Procter & Gamble Company Compositions detergentes comprenant une enzyme lipolytique et un systeme tensio-actif specifique
AU5861896A (en) * 1996-05-15 1997-12-05 Procter & Gamble Company, The Detergent compositions comprising specific lipolytic enzyme and alkyl poly glucoside surfactant
DE19928922A1 (de) * 1999-06-24 2000-12-28 Cognis Deutschland Gmbh Schaumkontrollierte feste Waschmittel
WO2011078949A1 (fr) * 2009-12-21 2011-06-30 Danisco Us Inc. Agents tensio-actifs qui améliorent le nettoyage de taches à base de lipides traitées par des lipases
JP6732424B2 (ja) * 2015-10-05 2020-07-29 花王株式会社 衣料用液体洗浄剤組成物
CN111566195A (zh) * 2017-12-20 2020-08-21 巴斯夫欧洲公司 用于除去沉积在纺织品上的熔融温度>30°c的脂肪族化合物的洗衣配制剂
WO2023096523A1 (fr) * 2021-11-24 2023-06-01 "Скайлаб Аг" Composition détergente biodégradable à base de lipase

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1986005187A1 (fr) * 1985-03-07 1986-09-12 A.E. Staley Manufacturing Company Composition detergente contenant un enzyme et un agent tensio-actif glucoside
US4959179A (en) * 1989-01-30 1990-09-25 Lever Brothers Company Stabilized enzymes liquid detergent composition containing lipase and protease
DE4034840A1 (de) * 1990-11-02 1992-05-07 Henkel Kgaa Enzymatisches fluessigwaschmittel

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015047188A1 (fr) * 2013-09-30 2015-04-02 Enza Biotech Ab Composition tensioactive
US10188736B2 (en) 2013-09-30 2019-01-29 Enza Biotech Ab Surfactant composition
US10857232B2 (en) 2013-09-30 2020-12-08 Enza Biotech Ab Surfactant composition

Also Published As

Publication number Publication date
ES2108456T3 (es) 1997-12-16
EP0698079A1 (fr) 1996-02-28
JPH08510268A (ja) 1996-10-29
DE59403971D1 (de) 1997-10-09
DE4315854A1 (de) 1994-11-17
WO1994026861A1 (fr) 1994-11-24
ATE157698T1 (de) 1997-09-15

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