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WO1994026861A1 - 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
WO1994026861A1
WO1994026861A1 PCT/EP1994/001400 EP9401400W WO9426861A1 WO 1994026861 A1 WO1994026861 A1 WO 1994026861A1 EP 9401400 W EP9401400 W EP 9401400W WO 9426861 A1 WO9426861 A1 WO 9426861A1
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WO
WIPO (PCT)
Prior art keywords
weight
alkyl
water
nonionic surfactant
glycoside
Prior art date
Application number
PCT/EP1994/001400
Other languages
German (de)
English (en)
Inventor
Georg Meine
Eric Sung
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to EP94916185A priority Critical patent/EP0698079B1/fr
Priority to JP6523604A priority patent/JPH08510268A/ja
Priority to DE59403971T priority patent/DE59403971D1/de
Publication of WO1994026861A1 publication Critical patent/WO1994026861A1/fr

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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 cleaners which contain lipase and water-soluble and / or insoluble builders and a nonionic surfactant component which consists essentially of alkyl or alkenyglycoside.
  • 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, where the The content of nonionic surfactants of this type, in which at most 5 alkoxylate groups per molecule are 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 70074.
  • 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 105556, which contain alkyl glycosides, certain other nonionic surfactants and anionic surfactants. From the international patent application WO 86/2943, alkyl detergent-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, contains 2 to 60% by weight of surfactants, which are 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 lower viscosity.
  • Preferred surfactants are anionic surfactants, especially those of the alkylbenzenesulfonate type, and nonionic surfactants, especially ethoxylated fatty alcohols.
  • the invention relates to a detergent or cleaning agent containing surfactant, lipase and builder, which contains a nonionic surfactant component which consists of at least 50% by weight, in particular at least 80% by weight, of a glycoside of the formula (I),
  • 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 * 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 * 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 92355, 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 belong.
  • 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 broken 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 portion (R * in formula I) of the glycosides contained in the agents according to the invention preferably also comes from easily accessible derivatives of renewable raw materials, in particular from fatty alcohols, although their branched chain isomers, in particular so-called oxo alcohols, are also used Production of usable glycosides can be used. 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 does not have a disadvantageous effect on the properties of the products produced therewith.
  • the proportion of further nonionic surfactant present 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 are suitable 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. Accordingly, the alkoxylates, especially the ethoxylates, of primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals, and mixtures thereof, can be used. In addition, speaking alkoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the alcohols mentioned with regard to the alkyl part, can be used.
  • ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters such as can be prepared in accordance with the process specified in international patent application WO 90/13533, and fatty acid polyhydroxyamides, as are used in accordance with the processes of US Pat. No. 1,984,524 , US 2016962 and US 2703798 and international patent application WO 92/6984 can be considered.
  • nonionic surfactant system consisting of glycoside according to formula (I) and optionally further nonionic surfactant, is preferably in the inventive compositions in amounts of 1% by weight to 30% by weight, in particular 1% by weight contain up to 25 wt .-%.
  • 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 from 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 based on total mean.
  • synthetic anionic surfactants which are particularly suitable for use in the agents according to the invention are the alkyl and / or alkenyl sulfates with 8 to 22 carbon atoms, which carry an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as countercation call.
  • 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 may in a known manner by reaction of the entspre ⁇ sponding alcohol component with a 'typical sulfating agent, more particularly sulfur trioxide or chlorosulfonic acid sondere, and subsequent organization Neutrali ⁇ with alkali metal, ammonium or alkyl- or hydroxyalkyl-substituted ammonium bases .
  • Such alkyl and / or alkenyl sulfates are preferably present in the agents according to the invention in quantities gen from 0.1 wt .-% to 20 wt .-%, in particular from 0.5 wt .-% to 18 wt.
  • 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 oc 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 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derived sulfonation products, and also 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, anion anionic surfactant having a linear, primary alkyl or alkenyl radical having 14 to 18 C atoms being particularly preferred.
  • Soaps are further optional surfactant ingredients, with 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, suitable are.
  • 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, suitable are.
  • preference is given to those soap mixtures which are composed of 50% by weight to 100% by weight of saturated Ci2-Ci8 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 the European patent applications EP 204208, EP 214761, EP 258068, EP 407225 or the international patent application WO 87/859. Usable commercially available- Examples of lipases are lipolase ( R ) and lipozyme ( R ).
  • Lipase is preferably used in the agent according to the invention in amounts such that the finished agent 10 LU / g to 10000 LU / g ("lipase activity units" per gram, determined via the enzymatic hydrolysis of tributyrin at 30 ° C. and pH 7 after the method mentioned in EP 258068), in particular 80 LU / g to 5000 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 builder.
  • 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 can also contain small amounts of polymerizable substances without carboxylic acid functionality in a polymerized 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 ethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the 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 an onoethylenically unsaturated C3 ⁇ C8 carboxylic acid and preferably from a C3 ⁇ C4 monocarboxylic acid, in particular from (meth) acrylic acid.
  • the second acidic monomer or its salt can be a derivative of a C4-Cs-dicarboxylic acid, preferably a C4-C8-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 are preferred which contain an ester of short-chain carbon acids, for example of -C-C4 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% by weight to 40% by weight, preferably 10% by weight to 30% by weight, of vinyl alcohol and / or vinyl acetate.
  • the second acidic monomer or its salt can also be a derivative of an alkylsulfonic 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 benzene or benzene. Derives 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% .-%, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid or methyl sulfonate and as a third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% 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 prepared 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 10000.
  • 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 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 in quantities 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, are used as water-insoluble, water-dispersible inorganic builder materials. , used.
  • the crystalline aluminosilicates in detergent quality in particular zeolite NaA and optionally NaX, are preferred. Amounts close to the upper limit mentioned 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 alumosilicate 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 02 ⁇ + ⁇ + yH2 ⁇ , in which M represents 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 represents sodium and x assumes the values 2 or 3.
  • 'sodium disilicates Na2Si2 ⁇ 5 * yH2 ⁇ are both .beta.- and ⁇ preferred, with beta-sodium disilicate being obtainable, for example, by the method described in the intermetallic national 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, in each case based on water-free Active substance, at least 5: 1.
  • the Weight ratio of 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 of 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 are included.
  • Such acidic substances are preferably present in the agents according to the invention in amounts not exceeding 5% by weight, in particular from 0.1% by weight to 3% by weight. quantities close to the upper limit mentioned are of particular interest for cleaning agents.
  • the agents according to the invention can contain further constituents customary in washing and cleaning agents.
  • These optional components include, in particular, solvents, bleaching agents, bleach activators, abrasives, for example quartz powder, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, graying inhibitors, for example cellulose ethers, foam inhibitors, for example Organopolysiloxanes or paraffins, and optical brighteners, 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 1% by weight of foam inhibitors, the proportions by weight referred to in each case 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, isopropanol, 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 may be present, in particular in liquid agents according to the invention, include amino alcohols, for example mono-, di-, triethanol- and -propanolamine and their mixtures, and lower carboxylic acids, for example from European patent applications EP 376705 and EP 378261, 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 calcium formic acid combination known from European patent EP 28865, magnesium salts, such as known for example from European patent application EP 378262, and / or sulfur-containing reducing agents, such as known from European patent applications EP 080748 or EP 080223.
  • amino alcohols for example mono-, di-, triethanol- and -propanolamine and their mixtures
  • lower carboxylic acids for example from European patent applications EP 376705 and EP 378261
  • boric acid or alkali borates boric acid-carboxylic acid combinations
  • Suitable foam inhibitors include long-chain soaps, in particular beef soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which can also contain microfine, optionally silanized or otherwise hydrophobized silica.
  • foam inhibitors are preferably bound to granular, water-soluble carrier substances, such as, for example, in German Offenlegungsschrift DE 34 36 194, European patent applications EP 262588, EP 301 414, EP 309 931 or European patent EP 150 386 described.
  • the agent according to the invention can furthermore contain graying inhibitors.
  • Graying inhibitors have the task of removing the fiber To keep dirt suspended in the liquor and thus prevent the fibers from turning gray.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, 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 mixtures thereof, and polyvinyl pyrrolidone are preferably used.
  • the bleaching agents which are suitable as further constituents of agents according to the invention are the perver compounds generally used in detergents, such as perborate, which can be present as tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally used as alkali 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 Means included.
  • the optional component of the bleach activators comprises the N- or O-acyl compounds normally used, for example multiple acylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N-acylated hydantines, hydrazides, triazoles, urazoles Diketopiperazines, sulfurylamides and cyanurates, also carboxylic anhydrides, especially phthalic anhydride, carboxylic acid esters, especially sodium isononanoyl-phenolsulfonate, and acylated sugar derivatives, especially pentaacetyl glucose.
  • N- or O-acyl compounds normally used for example multiple acylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N-acylated hydantines,
  • the bleach activators can be coated or granulated with coating substances in a known manner in order to avoid the interaction with the perverbin ⁇ compounds during storage, with the aid of carboxymethyl cellulose granulated tetraacetyl ethylenediamine with average grain sizes of 0.01 mm to 0.8 m as can be produced, for example, by the method described in European patent EP 037 026, and / or granulated l, 5-diacetyl-2,4-dioxohexahydro-l, 3,5-triazine, as can be prepared by the process described in German Patent DD 255 884, is particularly preferred.
  • such bleach activators are preferably in amounts of up to 8% by weight, in particular from 2% by weight to
  • 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 416967 or EP 394352 known proteases.
  • Protease is preferably used in the agent according to the invention in amounts such that the finished agent 100 PE / g bis
  • PE / g protease units per gram, determined by the method described in Tenside 7, 125 (1970)
  • 125 PE / g to 5000 PE / g and particularly preferably 150 PE / g to 4500 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 are, for example, 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, 1 KNU the enzyme quantity that 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 patent applications DE 31 17250, DE 3207825, DE 3207847, DE 33 22950 or European patent applications EP 265832, EP 269977, EP 270974, EP 273 125 and EP 339550. They are preferably used in the agent according to the invention 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 Carboxymethyl cellulose at pH 9.0 and 40 ° C., as described in Agric. Biol. Chem. 53_, 1275 (1989) by S.
  • Suitable commercial products are, for example, 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 them against premature inactivation when they are in particulate washing or cleaning means to be incorporated.
  • the enzymes, in particular protease, which are optionally present in addition to lipase are preferably in amounts of up to 2% by weight, in particular from 0.01% by weight to 1.5% by weight, in detergents or cleaning agents according to the invention. , each based on the total mean.
  • an agent according to the invention is particulate and contains 30% by weight to 55% by weight of water-insoluble inorganic builders, up to 15% by weight, in particular 2% by weight to 12% by weight of water-soluble organic builders Builder, 2.5 wt% to 20 wt% synthetic anionic surfactant, 1 wt% to 20 wt% nonionic surfactant component, up to 25 wt%, in particular 1 wt% to 15 wt.
  • % Bleach 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 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.
  • 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 up to 1% by weight 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 wt .-% 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 a very simple manner by mixing the individual particles in a conventional mixer, in particular a drum, roller, belt or free-fall mixer, optional other powdery components and, if desired, also liquid or liquefied components, in particular ⁇ special non-ionic surfactants, but also colorants 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 an intended solvent.
  • 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 shown in Table 1 in the amounts indicated were the detergents M1 to M3 according to the invention and, for comparison, the lipase-free agents VI and V2 and the glycoside-free agent V3.
  • Ci2 / i8 fatty alcohol, 5-fold ethoxylated b) Ci2 / i4 alkyl glucoside, degree of polymerization 1.4 c) Linear Ci6 / i8 ⁇ alkyl sulfate (sulfopone ( R ) T, manufacturer Henkel) d) ratio SiO2 to Na2O: 3 , 0 e) acrylic acid / maleic acid copoly er, Na salt (Sokalan ( R ) CP 5, manufacturer BASF) f) adipic acid / glutaric acid / succinic acid mixture (Sokalan ( R ) DCS, manufacturer BASF) g) monohydrate h) Tetraacetylethylenediamine granules, produced in accordance with European patent specification EP 037026 i) Protease granules (BLAP ( R ) 140, manufacturer Biozym) k) Lipase granules (Lipolase ( R )
  • Foam inhibitor concentrate containing 10% by weight of paraffin, remainder Na sulfate, Na silicate and Na carboxymethyl cellulose, produced according to European patent application EP 309931
  • the agents M1 and M2 according to the invention have a significantly better cleaning performance than the directly comparable agents VI and V2 without lipase and the agents according to the invention generally have a higher cleaning performance than the agent containing a surfactant system not according to the invention Own V3.

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  • Life Sciences & Earth Sciences (AREA)
  • 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)
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Abstract

Le but de l'invention est d'accroître le pouvoir nettoyant de produits de lavage et de nettoyage contenant un tensio-actif, une lipase et des adjuvants et d'améliorer la stabilité au stockage de l'enzyme dans le produit fini, sans avoir à employer d'ingrédients présentant des inconvénients d'ordre écologique ou difficiles à employer. Cet objectif a été atteint essentiellement par une optimisation du système tensio-actif pour obtenir des produits contenant un composant tensio-actif non ionique comprenant au moins 50 % en poids d'un glucoside de formule R1-O(G)n, dans laquelle R1 désigne un reste alkyle ou alcényle ayant 8 à 22 atomes de C, G désigne une unité glucose et n est un nombre de 1 à 10.
PCT/EP1994/001400 1993-05-12 1994-05-03 Produits de lavage et de nettoyage contenant une lipase WO1994026861A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP94916185A EP0698079B1 (fr) 1993-05-12 1994-05-03 Produits de lavage et de nettoyage contenant une lipase
JP6523604A JPH08510268A (ja) 1993-05-12 1994-05-03 リパーゼを含有する洗浄および清浄製剤
DE59403971T DE59403971D1 (de) 1993-05-12 1994-05-03 Lipasehaltige wasch- und reinigungsmittel

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4315854.4 1993-05-12
DE4315854A DE4315854A1 (de) 1993-05-12 1993-05-12 Lipasehaltige Wasch- und Reinigungsmittel

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WO1994026861A1 true WO1994026861A1 (fr) 1994-11-24

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JP (1) JPH08510268A (fr)
AT (1) ATE157698T1 (fr)
DE (2) DE4315854A1 (fr)
ES (1) ES2108456T3 (fr)
WO (1) WO1994026861A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995027029A1 (fr) * 1994-03-31 1995-10-12 Henkel Kommanditgesellschaft Auf Aktien Detergent a base de lipases
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
RU2811470C2 (ru) * 2021-11-24 2024-01-12 Общество С Ограниченной Ответственностью "Сплат Глобал" Биоразлагаемая моющая композиция на основе липазы для расщепления низкоплавких ацилглицеридов различной пространственной конфигурации и регуляции пенной устойчивости и гидрофилизации поверхностей

Families Citing this family (7)

* 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
CA2254781A1 (fr) * 1996-05-15 1997-11-20 The Procter & Gamble Company Compositions detergentes comprenant une enzyme lipolytique et un systeme tensio-actif specifique
WO1997043377A1 (fr) * 1996-05-15 1997-11-20 The Procter & Gamble Company Compositions de detergence comprenant une enzyme lipolytique specifique ainsi qu'un tensioactif a base de polyglucoside d'alkyle
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
KR102228443B1 (ko) * 2013-09-30 2021-03-16 엔자 바이오테크 에이비 계면활성제 조성물
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

Citations (3)

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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
EP0381262A2 (fr) * 1989-01-30 1990-08-08 Unilever N.V. Composition détergente liquide enzymatique
WO1992007930A1 (fr) * 1990-11-02 1992-05-14 Henkel Kommanditgesellschaft Auf Aktien Detergent enzymatique liquide

Patent Citations (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
EP0381262A2 (fr) * 1989-01-30 1990-08-08 Unilever N.V. Composition détergente liquide enzymatique
WO1992007930A1 (fr) * 1990-11-02 1992-05-14 Henkel Kommanditgesellschaft Auf Aktien Detergent enzymatique liquide

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995027029A1 (fr) * 1994-03-31 1995-10-12 Henkel Kommanditgesellschaft Auf Aktien Detergent a base de lipases
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
US20210139817A1 (en) * 2017-12-20 2021-05-13 Basf Se Laundry formulation for removing fatty compounds having a melting temperature > 30°c deposited on textiles
WO2023096523A1 (fr) * 2021-11-24 2023-06-01 "Скайлаб Аг" Composition détergente biodégradable à base de lipase
RU2811470C2 (ru) * 2021-11-24 2024-01-12 Общество С Ограниченной Ответственностью "Сплат Глобал" Биоразлагаемая моющая композиция на основе липазы для расщепления низкоплавких ацилглицеридов различной пространственной конфигурации и регуляции пенной устойчивости и гидрофилизации поверхностей

Also Published As

Publication number Publication date
ES2108456T3 (es) 1997-12-16
EP0698079A1 (fr) 1996-02-28
DE4315854A1 (de) 1994-11-17
ATE157698T1 (de) 1997-09-15
JPH08510268A (ja) 1996-10-29
DE59403971D1 (de) 1997-10-09
EP0698079B1 (fr) 1997-09-03

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