EP0753046B1 - Detergent a base de lipases - Google Patents

Detergent a base de lipases Download PDF

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Publication number
EP0753046B1
EP0753046B1 EP95914299A EP95914299A EP0753046B1 EP 0753046 B1 EP0753046 B1 EP 0753046B1 EP 95914299 A EP95914299 A EP 95914299A EP 95914299 A EP95914299 A EP 95914299A EP 0753046 B1 EP0753046 B1 EP 0753046B1
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EP
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Prior art keywords
weight
detergent
alkyl
lipase
dlu
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EP95914299A
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German (de)
English (en)
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EP0753046A1 (fr
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Beatrix Kottwitz
Jörg Poethkow
Horst Upadek
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • 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

Definitions

  • the invention relates to detergents which, in addition to conventional components, comprise a certain lipase Contain Pseudomonas alcaligenes or Pseudomonas pseudoalcaligenes.
  • lipases with better efficacy and / or better compatibility with the other ingredients of detergents and cleaning agents.
  • efforts have recently been made to optimize the lipases occurring in nature, in particular in microorganisms, by genetic engineering or by protein engineering with regard to their performance and stability.
  • Lipolase ® a lipase from the fungus Humicola lanuginosa, lipases which can be isolated from bacterial sources, in particular from pseudomomas bacteria, have also been described.
  • the Applicant aim to develop a lipase-containing detergent, which has a performance at the lowest possible lipase to that of an agent which conventional lipases, in particular as it were the standard performing Lipolase contains ®, at least not inferior.
  • the invention accordingly relates to a textile detergent containing, in addition to conventional components a lipolytically effective amount of a genetically modified lipase from Pseudomonas alcaligenes or Pseudomonas pseudoalcaligenes, which have a molecular weight of 30 kD to 32 kD, an isoelectric point in the range of 4.5 to 6 and a specific one Has activity of 900 DLU / mg to 1000 DLU / mg and which is characterized in that it is a synthetic anionic surfactant of the sulfate and / or sulfonate type which is not an alkylbenzenesulfonate is contains.
  • the genetically modified lipases mentioned above include in particular those in which genetic engineering, that is, by cloning the for the gene encoding the lipase from the wild-type microorganism, mutating this Gene in vitro or in vivo and expression of the enzyme by recloning of the mutated gene in a suitable guest cell, usually fungi (e.g. Aspergillus) or bacteria (e.g. Bacillus, E. coli or Pseudomonas) are used, amino acids of the wild-type enzyme have been replaced so that more active under washing conditions and / or more stable enzymes result.
  • fungi e.g. Aspergillus
  • bacteria e.g. Bacillus, E. coli or Pseudomonas
  • the exchange of amino acids susceptible to oxidation such as Methionine
  • amino acids which are more stable to oxidation such as in particular asparagine, Aspartic acid, leucine, alanine, phenylalanine, valine or serine.
  • the genetically modified lipases are one Enzyme in which the methionine at position 21 of the wild type from Pseudomonas pseudoalcaligenes due to the aforementioned oxidation-stable amino acid, in particular leucine or alanine.
  • Such enzymes and their manufacture are described, for example, in the international patent application WO 94/25578.
  • the unit DLU for the lipolytic activity is based on the enzymatic cleavage of 1,2-0-dilauryl-rac-glycero-3-glutaric acid resorufin ester, whereby glutaric acid and resorufin are released.
  • the optical density of the resulting red resorufin which can be determined photometrically, is a measure of the enzyme activity.
  • the method using an Abbott (R) analyzer is described in analysis method No. 61722 from Gist-Brocades.
  • ILU International Lipase Unit
  • Lipases which can be used according to the invention normally have activities of about 5000 ILU to 10,000 ILU, in particular 6000 ILU to 8000 ILU, each per mg protein.
  • the lipase used in the agents according to the invention preferably has a specific activity in the range from 910 DLU / mg to 990 DLU / mg, in particular 925 DLU / mg to 965 DLU / mg. It is particularly preferred to use the enzyme Lipomax (R) from Gist-Brocades, which has a specific activity of 940 DLU / mg, an isoelectric point of 5.1 and a molecular weight of 30,323.
  • Lipase is preferably used in such amounts in the agent according to the invention used that the finished agent has a lipolytic activity in the range from 5,000 DLU / 100 g to 25,000 DLU / 100 g, in particular from 6 500 DLU / 100 g up to 17,500 DLU / 100 g.
  • lipases with the above Features the effect of certain other detergent ingredients synergistically influence and that conversely the lipolytic effect of Lipase is synergistically enhanced by certain other detergent ingredients becomes.
  • non-ionic surfactants in the case of copolyesters capable of removing dirt, in particular those with Terephthalic acid units, in water-insoluble inorganic builders, in water-soluble inorganic and organic builders, in particular Based on oxidized carbohydrates, for bleaching agents based on peroxygen, especially with alkali percarbonate, with proteolytic enzymes and with synthetic anionic surfactants of the sulfate and sulfonate type, however not or only slightly pronounced in alkylbenzenesulfonates, which is why the invention Agents preferably contain such ingredients.
  • a preferred embodiment of agents according to the invention comprises the presence of Fatty alkyl sulfate, fatty alkyl ether sulfate, sulfofatty acid esters and / or sulfofatty acid disalts, especially in an amount in the range from 2% to 25% by weight.
  • the anionic surfactant is preferred from the Alkyl or alkenyl sulfates and / or the alkyl or alkenyl ether sulfates selected in which the alkyl or alkenyl group 8 to 22, in particular Has 12 to 18 carbon atoms.
  • an agent according to the invention contains nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkyl amines, vicinal diols, fatty acid alkyl esters and / or fatty acid amides and mixtures thereof, especially in an amount in the range from 2% by weight to 25% by weight.
  • nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkyl amines, vicinal diols, fatty acid alkyl esters and / or fatty acid amides and mixtures thereof,
  • one contains Medium water-soluble and / or water-insoluble builder, in particular selected from alkali alumosilicate, crystalline alkali silicate with module about 1, monomeric polycarboxylate, polymeric polycarboxylate and their Mixtures, in particular in amounts in the range from 2.5% by weight to 60% by weight.
  • Medium water-soluble and / or water-insoluble builder in particular selected from alkali alumosilicate, crystalline alkali silicate with module about 1, monomeric polycarboxylate, polymeric polycarboxylate and their Mixtures, in particular in amounts in the range from 2.5% by weight to 60% by weight.
  • an agent according to the invention contains peroxygen-based bleach, especially hydrogen peroxide, Alkali perborate tetrahydrate, alkali perborate monohydrate and / or alkali percarbonate, especially in amounts in the range from 5% by weight to 70 wt .-%, and optionally bleach activator, especially in amounts in Range from 2 wt% to 10 wt%.
  • peroxygen-based bleach especially hydrogen peroxide, Alkali perborate tetrahydrate, alkali perborate monohydrate and / or alkali percarbonate, especially in amounts in the range from 5% by weight to 70 wt .-%
  • bleach activator especially in amounts in Range from 2 wt% to 10 wt%.
  • a further embodiment according to the invention comprises a means according to the invention the presence of dirt-releasing Substances based on copolyesters from dicarboxylic acids and glycols, the can be contained in particular in quantities of 0.01% by weight to 5% by weight.
  • Dirt-releasing substances often referred to as "soil-release" substances, which because of their chemical similarity to polyester fibers are effective, but also the desired for fabrics made of other material Can have an effect are copolyesters, the dicarboxylic acid units, Contain alkylene glycol units and polyalkylene glycol units.
  • Dirt-removing properties Copolyester of the type mentioned as well as their use in Detergents have been known for a long time. For example, the German Offenlegungsschrift DT 16 17 141 using a washing process of polyethylene terephthalate-polyoxyethylene glycol copolymers.
  • the German German Offenlegungsschrift DT 22 00 911 relates to detergents, nonionic surfactants and contain a copolymer of polyoxyethylene glycol and polyethylene terephthalate.
  • acidic textile finishing agents called a copolymer of a dibasic carboxylic acid and an alkylene or cycloalkylene polyglycol and optionally contain an alkylene or cycloalkylene glycol.
  • the European Patent EP 066 944 relates to textile treatment agents containing a copolyester from ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid contained in certain molar ratios.
  • the agents according to the invention contain the synthetic anionic surfactants of the sulfate or sulfonate type in amounts of preferably not more than 20% by weight, in particular of 0.1% by weight to 18% by weight, in each case based on the total average.
  • synthetic anionic surfactants are the alkyl and / or alkenyl sulfates with 8 to 22 carbon atoms, which are an alkali, ammonium or alkyl respectively Carry hydroxyalkyl-substituted ammonium ion as a counter cation.
  • the derivatives of the fatty alcohols, in particular 12 to 18, are preferred C atoms and their branched chain analogs, the so-called oxo alcohols.
  • the alkyl and alkenyl sulfates can in a known manner by reaction of the corresponding alcohol component with a conventional sulfating reagent, especially sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali, ammonium or alkyl or hydroxyalkyl substituted Ammonium bases are made.
  • a conventional sulfating reagent especially sulfur trioxide or chlorosulfonic acid
  • alkali, ammonium or alkyl or hydroxyalkyl substituted Ammonium bases are made.
  • Such alkyl and / or Alkenyl sulfates are preferred in the agents according to the invention in amounts from 0.1% by weight to 20% by weight, in particular from 0.5% by weight to Contain 18 wt .-%.
  • the sulfate-type surfactants that can be used also include the sulfated ones 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 from Sulfonate type include those by reacting fatty acid esters with sulfur trioxide and subsequent neutralization obtainable ⁇ -sulfoesters, in particular which are derived from fatty acids with 8 to 22 carbon atoms, preferably 12 to 18 C atoms, and linear alcohols with 1 to 6 C atoms, preferably 1 to 4 carbon atoms, derivative sulfonation products, as well as those by formal Saponification from these emerging sulfo fatty acids.
  • the nonionic surfactants in question 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.
  • Corresponding alkoxylation products of alkylamines, vicinal diols and carboxamides which correspond to the alcohols mentioned with regard to the alkyl part can also be used.
  • there are the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters as can be prepared in accordance with the process specified in international patent application WO 90/13533, and fatty acid polyhydroxyamides, as in accordance with the processes of US Pat.
  • alkyl polyglycosides suitable for incorporation into the agents according to the invention are compounds of the general formula (G) n -OR 1 , in which R 1 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.
  • R 1 is an alkyl or alkenyl radical having 8 to 22 C atoms
  • G is a glycose unit
  • n is a number between 1 and 10 mean.
  • 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 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 to.
  • 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 generally takes on 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 part R 1 of the glycosides 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 produce usable glycosides. Accordingly, the primary alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful.
  • Nonionic surfactant is preferably in the agents according to the invention in Amounts from 1% by weight to 30% by weight, in particular from 1% by weight to 25% by weight contain.
  • Soaps are further optional surfactant ingredients, 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, being 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.
  • 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 the polymeric (poly) carboxylic acids, in particular the polycarboxylates of the international patent application WO 93/16110 accessible by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which may also contain small amounts of polymerizable substances in copolymerized form without carboxylic acid functionality.
  • the relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200000, 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 are an ester of short-chain carboxylic acids, for example of C 1 -C 4 -carboxylic acids, with vinyl alcohol are particularly preferred.
  • 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 prepared in particular by processes which are described in German patent DE 42 21 381 and German patent application 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 in amounts up to 40% by weight, in particular up to 25% by weight and particularly preferably of Contain 1 wt .-% to 5 wt .-%. Quantities will be close to the upper limit preferably in pasty or liquid, especially water-containing, agents according to the invention used.
  • water-insoluble, water-dispersible inorganic builder materials are particularly crystalline or amorphous alkali alumosilicates, in quantities up to 50% by weight, preferably not more than 40% by weight and in liquid Agents used in particular from 1 wt .-% to 5 wt .-%. Under these are the crystalline aluminosilicates in detergent quality, in particular Zeolite NaA and optionally NaX, preferred. Amounts close to the above Upper limits are preferably in solid, particulate form used. Suitable aluminosilicates in particular have no particles a grain size over 30 microns and preferably exist at least 80 wt .-% of particles with a size below 10 microns. Your calcium binding capacity, determined according to the information in German patent DE 24 12 837 can be in the range of 100 to 200 mg CaO per gram.
  • Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates.
  • the alkali silicates which can be used as builders in the agents according to the invention preferably have a molar ratio of alkali oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na 2 O: SiO 2 molar ratio of 1: 2 to 1: 2.8.
  • Such amorphous alkali silicates are commercially available, for example, under the name Portil (R) .
  • Crystalline sheet silicates of the general formula Na 2 Si x O 2x + 1 .yH 2 O, in which x, the so-called modulus, is a number of 1.9, are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates to 4 and y is a number from 0 to 20 and are preferred values for x 2, 3 or 4.
  • Crystalline layered silicates which fall under this general formula are described, for example, in European patent application EP 0 164 514.
  • Preferred crystalline layered silicates are those in which x assumes the values 2 or 3 in the general formula mentioned.
  • both ⁇ - and ⁇ -sodium (Na 2 Si 2 O 5. YH 2 O) are preferred, with ⁇ -sodium disilicate being obtainable, for example, by the method described in International Patent Application WO 91/08171.
  • ⁇ -sodium silicates with a modulus between 1.9 and 3.2 can be produced according to Japanese patent applications JP 04/238 809 or JP 04/260 610.
  • Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of agents according to the invention.
  • the content of alkali silicates in the agents according to the invention is preferably 1% by weight to 50% by weight and in particular 5% by weight to 35% by weight, based on the anhydrous active substance. If alkali alumosilicate, in particular zeolite, is also present as an additional builder substance, the alkali silicate content is preferably 1% by weight to 15% by weight and in particular 2% by weight to 8% by weight, based on anhydrous active substance.
  • the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is then preferably 4: 1 to 10: 1.
  • the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
  • the Alkali carbonates, alkali hydrogen carbonates and alkali sulfates and their Mixtures are used.
  • additional inorganic material can be used in quantities up to 70% by weight is present, but is preferably absent entirely.
  • the agents according to the invention can be used to adjust a desired case acidic or weakly alkaline pH of in particular about 8.0 to 9.5 inorganic and / or organic solid in 1% by weight aqueous solution
  • Acids or acidic salts for example alkali hydrogen sulfates, Succinic acid, adipic acid or glutaric acid and mixtures thereof, contain.
  • Such acidic substances are in the invention Agents preferably in amounts not exceeding 5% by weight, especially of 0.1% to 3% by weight.
  • the agents according to the invention can be used in detergents and cleaning agents Contain common ingredients.
  • these optional components include in particular bleaches, bleach activators, complexing agents for heavy metals, for example aminopolycarboxylic acids, amino-hydroxypolycarboxylic acids, Polyphosphonic acids and / or aminopolyphosphonic acids, Graying inhibitors, for example cellulose ethers, color transfer inhibitors, for example polyvinylpyrrolidone, foam inhibitors, for example organopolysiloxanes or paraffins, solvents and optical brighteners, for example stilbene disulfonic acid derivatives.
  • bleaches bleach activators
  • complexing agents for heavy metals for example aminopolycarboxylic acids, amino-hydroxypolycarboxylic acids, Polyphosphonic acids and / or aminopolyphosphonic acids
  • Graying inhibitors for example cellulose ethers
  • color transfer inhibitors for example polyvinylpyrrolidone
  • foam inhibitors for example organopolysiloxanes or paraffin
  • 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 wt .-% complexing agent for heavy metals, especially 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 Contain 0.1 wt .-% to 1 wt .-% foam inhibitors, the said Percentages by weight refer to the entire average.
  • Solvents particularly in liquid agents according to the invention are used, in addition to water, preferably those that are water-miscible are. These include the lower alcohols, for example ethanol, Propanol, isopropanol, and the isomeric butanols, glycerin, lower glycols, for example ethylene and propylene glycol, and those from the above Classes of derivable ether.
  • Existing conventional enzyme stabilizers include amino alcohols, for example Mono-, di-, triethanol and propanolamine and mixtures thereof, lower carboxylic acids, such as from European patent applications EP 376 705 and EP 378 261 known, boric acid or alkali borates, Boric acid-carboxylic acid combinations, such as from the European Patent application EP 451 921 known, boric acid esters, such as from international patent application WO 93/11215 or European Patent application EP 511 456 known, boronic acid derivatives, such as known from European patent application EP 583 536, calcium salts, for example that known from European patent EP 28 865 Ca-formic acid combination, magnesium salts, such as from the European patent application EP 378 262 known, and / or sulfur-containing Reducing agents, such as from European patent applications EP 080 748 or EP 080 223 are known.
  • amino alcohols for example Mono-, di-, triethanol and propanolamine and mixtures thereof
  • lower carboxylic acids such as from European patent applications
  • Suitable foam inhibitors include long chain soaps, in particular Mild soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, Organopolysiloxanes and their mixtures, which are also microfine, if appropriate contain silanized or otherwise hydrophobized silica can.
  • foam inhibitors are preferably granular, water-soluble Carrier substances bound, such as in the German patent application DE 34 36 194, European patent applications EP 262 588, EP 301 414, EP 309 931 or the 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 so the graying of the fibers to prevent.
  • water-soluble colloids are usually more organic Suitable in nature, for example the water-soluble salts of polymeric carboxylic acids, Glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids the starch or the cellulose or salts of acidic sulfuric acid esters cellulose or starch.
  • water-soluble containing acidic groups Polyamides are suitable for this purpose.
  • soluble ones Use starch preparations and other starch products than those mentioned above, for example partially hydrolyzed starch. Na carboxymethyl cellulose, Methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof preferably used.
  • Bleaching agents are the per-compounds usually used in detergents such as perborate, which can be present as a tetra or monohydrate, Percarbonate, perpyrophosphate and persilicate, which are usually used as alkali salts, in particular as sodium salts.
  • Such bleaches are preferably in amounts up to in detergents according to the invention 25% by weight, in particular up to 15% by weight and particularly preferably of 5 wt .-% to 15 wt .-%, based in each case on total.
  • the optional component of the bleach activators usually includes used N- or O-acyl compounds, for example several times acylated alkylenediamines, especially tetraacetylethylenediamine, acylated Glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, Hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides and Cyanurates, also carboxylic anhydrides, in particular phthalic anhydride, Carboxylic acid esters, in particular sodium isononanoyl phenol sulfonate, and acylated sugar derivatives, especially pentaacetyl glucose.
  • N- or O-acyl compounds for example several times acylated alkylenediamines, especially tetraacetylethylenediamine, acylated Glycolurils, in particular tetraacetylglycoluril, N-acy
  • the bleach activators can avoid interaction with the per compounds when coated in a known manner with coating substances or have been granulated, with the help of carboxymethyl cellulose Granulated tetraacetylethylenediamine with medium grain sizes from 0.01 mm to 0.8 mm, as is the case, for example, in European
  • the method described in patent EP 037 026 can be produced, and / or granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, such as it according to the method described in German patent specification DD 255 884 can be produced, is particularly preferred.
  • Such bleach activators are preferably in amounts up to 8% by weight, in particular from 2% by weight to 6% by weight, in each case based on total means included.
  • enzymes which may be present in addition to lipase come in particular those from the class of proteases, amylases and cellulases as well their mixtures in question.
  • Mushrooms or bacterial strains are preferably such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus and Streptomyces griseus used enzymatic active ingredients.
  • 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 5000 PE / g and particularly preferably 150 PE / g to 4 500 PE / g.
  • Usable proteases are commercially available, for example under the names BLAP (R) , Savinase (R) , Esperase (R) , Maxatase (R) , Optimase (R) , Alcalase (R) , Durazym (R) or Maxapem (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 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. Ito et al.), in particular 0.07 IU / g to 1.4 IU / g and particularly preferably 0.1 IU / g to 1.3 IU / g.
  • Suitable commercial products include Celluzyme (R) from Novo Nordisk or KAC (R) from Kao.
  • the enzymes can be adsorbed on carriers in a known manner, in coating substances embedded and / or granulated with the aid of carrier substances to make them easier to use and to prevent inactivation protect when incorporated into particulate laundry detergent should be.
  • the possibly included in addition to lipase Enzymes, especially protease, are in washing or cleaning agents according to the invention preferably in amounts of up to 2% by weight, in particular of 0.01 wt .-% to 1.5 wt .-%, based in each case on total.
  • an agent according to the invention is particulate and contains 20 wt% to 55 wt% inorganic builder, bis 15% by weight, in particular 2% by weight to 12% by weight, of water-soluble organic Builder, 2.5% to 20% synthetic anionic surfactant, 1% to 20% by weight of nonionic surfactant, up to 25% by weight, in particular 1% by weight to 15% by weight of bleach, up to 8% by weight, in particular 0.5 wt% to 6 wt% bleach activator and up to 20 wt%, in particular 0.1% to 15% by weight of inorganic salts, in particular alkali carbonate and / or sulfate, and up to 2 wt .-%, in particular 0.4 wt .-% to 1.2% by weight of another enzyme, in particular in the form of particles Protease, amylase and / or cellulase.
  • another enzyme in particular in the form of particles Protease, amylase and / or cellulase.
  • powdery detergent especially for use as a mild detergent, 20% by weight to 55% by weight of inorganic builder, up to 15% by weight, in particular 2% by weight to 12% by weight of water-soluble organic builder, 4% by weight to 24% by weight of nonionic surfactant, up to 15% by weight, in particular 1% to 10% by weight synthetic anionic surfactant, up to 65% by weight, in particular 1% by weight to 30% by weight of inorganic
  • Another preferred embodiment comprises a liquid agent containing 5 wt% to 35 wt% 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 synthetic anionic surfactant, 1% by weight to 25% by weight 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 Solvents and up to 10% by weight, in particular 0.01% by weight up to 7.5% by weight enzyme stabilization system.
  • the preparation of particulate agents according to the invention can be done in the simplest way Way by mixing the individual particles in a conventional mixer, in particular a drum, roller, belt or free fall mixer, optional other powdered components and, if desired also liquid or liquefied components, in particular non-ionic surfactants, but also colors and fragrances, can be added by spraying.
  • a conventional mixer in particular a drum, roller, belt or free fall mixer
  • the thermal resilient components in a known manner by spray drying convert an aqueous slurry into a powder product and this with lipase and optionally other enzymatic active ingredients and other thermally sensitive components, in particular Bleach are to be expected to mix.
  • the familiarization of individuals Ingredients by admixing a granulate containing them Extrudate is possible and especially for production of agents according to the invention with a high apparent density of preferably
  • Flowable and liquid agents according to the invention can be easily Mixing the ingredients or their premixes that are liquid or in Water or an intended solvent can be dissolved will.
  • Detergent prepared in the conventional manner of the formulation (V1) given in Table 1 below was used according to the invention (M1) with Lipomax (R) CXT granules (activity 31,333 DLU / g, manufacturer Gist-Brocades) and for comparison (V3) with Lipolase (R) 100 T (manufacturer Novo) mixed.
  • V1 M1 V3 Nonionic surfactant 6 6 5 SECTION 5 5 5 Alkyl sulfate 5 5 5 Soap 1 1 1 sodium 10th 10th 10th Zeolite Na-A 25th 25th 25th Sodium silicate 2nd 2nd 2nd Sodium sulfate 1 1 1 1 Polycarboxylate 5 5 5 Sodium perborate 20th 20th 20th TAED 6 6 6 Protease 1 1 1 1 Foam inhibitor 5 5 5 Lipomax (R) - 0.5 - Lipolase (R) - - 0.5 Water to 100
  • agent M1 according to the invention has a significantly better cleaning performance than the directly comparable agent V1 without lipase or as the agent V3.

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  • Chemical & Material Sciences (AREA)
  • 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)
  • Detergent Compositions (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Claims (15)

  1. Agent de lavage pour les textiles ou détergent, renfermant outre les constituants usuels, également une quantité possédant une action lypolytique d'une lipase issue de Pseudomonas alcaligenes ou de Pseudomonas pseudoalcaligenes, modifiée par le génie génétique, qui présente un poids moléculaire de 30 à 32 kD, un point isoélectrique situé dans l'intervalle de 4,5 à 6 et une activité spécifique de 900 à 1000 DLU/mg, caractérisé en ce qu'il contient un surfactif anionique synthétique du type sulfate et/ou sulfonate, qui n'est pas un alkylbenzènesulfonate.
  2. Agent selon la revendications 1, caractérisé en ce qu'il présente une activité lipolytique dans la plage de 5000 à 25 000 DLU/100 g, en particulier de 6 500 à 17 500 DLU/100 g.
  3. Agent selon la revendication 1 ou 2, caractérisé en ce qu'il renferme une lipase modifiée par le génie génétique, dans laquelle des acides aminés de l'enzyme du phénotype sauvage ont été échangés de manière telle que l'on a obtenu une enzyme plus active et/ou plus stable dans les conditions de lavage.
  4. Agent selon la revendication 3, caractérisé en que des acides aminés sensibles à l'oxydation, tels la méthionine, ont été échangés contre des acides aminés plus résistants à l'oxydation, comme en particulier l'asparagine, l'acide asparagique, la leucine, l'alanine, la phénylalanine, la valine ou la sérine.
  5. Agent selon la revendication 3 ou 4, caractérisé en ce que la lipase est une enzyme dans laquelle la méthionine en position 21 du phénotype sauvage de Pseudomonas pseudoalcaligenes a été échangée contre l'asparagine, l'acide asparagique, la leucine, l'alanine, la phénylalanine, la valine ou la sérine, en particulier contre la leucine ou l'alanine.
  6. Agent selon une des revendications 1 à 5, caractérisé en ce qu'il renferme un tensioactif non ionique, sélectionné parmi les alkylpolyglycosides gras, les alkylpolyalcoxylates gras, en particulier les éthoxylates et/ou les propoxylates. les polyhydroxyamides d'acides gras et/ou les produits d'éthoxylation et/ou de propoxylation d'alkylamines grasses. de diols vicinaux, d'alkylesters et/ou d'amides d'acides gras ainsi que les mélanges de ceux-ci, en particulier dans une proportion située dans l'intervalle de 2 à 25 % en poids.
  7. Agent selon une des revendications 1 à 6, caractérisé en ce qu'il renferme comme surfactif anionique synthétique du type sulfate et/ou sulfonate, un alkylsulfate gras, un alkyléthersulfate gras, un ester d'acide sulfonique gras et/ou des sels dimétalliques d'acides sulfoniques gras, en particulier dans une proportion située dans l'intervalle de 2 à 25 % en poids.
  8. Agent selon la revendication 7, caractérisé en ce que le surfactif anionique est sélectionné parmi les alkyl- ou les alcénylsulfates et/ou les alkyl- ou les alcényléthersulfates, dans lesquels le groupe alkyle ou alcényle possède 8 à 22, en particulier 12 à 18 atomes de C.
  9. Agent selon une des revendications 1 à 8, caractérisé en ce qu'il renferme des adjuvants solubles et/ou insolubles dans l'eau, sélectionnés en particulier parmi l'aluminosilicate de métal alcalin, le silicate de métal alcalin cristallin avec un module supérieure à 1, le polycarboxylate monomère, le polycarboxylate polymère et les mélanges de ceux-ci, en particulier en proportions comprises dans l'intervalle de 2,5 à 60 % en poids.
  10. Agent selon une des revendications 1 à 9, caractérisé en ce qu'il renferme une enzyme protéolytique, en particulier dans une proportion telle que l'activité atteint 100 à 7500 UP/g, et/ou une enzyme cellulolytique, en particulier en quantité telle que l'activité atteint 0,05 à 1,5 Ul/g.
  11. Agent selon une des revendications 1 à 10, caractérisé en ce qu'il renferme des agents de blanchiment à base de peroxygène, en particulier d'eau oxygénée, de perborate de métal alcalin tétrahydraté, de perborate de métal alcalin monohydraté et/ou de percarbonate de métal alcalin, en particulier en proportions situées dans la plage de 5 à 70 % en poids, ainsi que le cas échéant, des activateurs de blanchiment, en particulier en quantités comprises dans l'intervalle de 2 à 10 % en poids.
  12. Agent selon une des revendications 1 à 11, caractérisé en ce qu'il renferme une substance capable de décoller la salissure à base de copolyesters d'acides dicarboxyliques et de glycols, qui peut être contenue, en particulier, en proportions de 0,01 à 5 % en poids.
  13. Agent selon une des revendications 1 à 12, caractérisé en ce qu'il est sous forme de particules et renferme 20 à 55 % en poids d'adjuvant inorganique, jusqu'à 15 % en poids, en particulier 2 à 12 % en poids d'adjuvant organique soluble dans l'eau, 2,5 à 20 % en poids de surfactif anionique synthétique, 1 à 20 % en poids de tensioactif non ionique, jusqu'à 25 % en poids, en particulier 1 à 15 % en poids d'agent de blanchiment, jusqu'à 8 % en poids, en particulier 0,5 à 6 % en poids d'activateur de blanchiment, jusqu'à 20 % en poids, en particulier 0,1 à 15 % en poids de sels inorganiques, en particulier du carbonate et/ou du sulfate de métal alcalin, ainsi que jusqu'à 2 % en poids, en particulier 0,4 à 1,2 % en poids d'une autre enzyme formulée sous forme de particules, en particulier la protéase, l'amylase et/ou la cellulase.
  14. Agent pulvérulent selon une des revendications 1 à 12, caractérisé en ce qu'il renferme 20 à 55 % en poids d'adjuvant inorganique, jusqu'à 15 % en poids, en particulier 2 à 12 % en poids d'adjuvant organique soluble dans l'eau, 4 à 24 % en poids de tensioactif non ionique, jusqu'à 15 % en poids, en particulier 1 à 10 % en poids de surfactif anionique synthétique, jusqu'à 65 % en poids, en particulier 1 à 30 % en poids de sels inorganiques, en particulier du carbonate et/ou du sulfate de métal alcalin, et ni agent de blanchiment ni activateur de blanchiment.
  15. Agent selon une des revendications 1 à 12, caractérisé en ce qu'il est liquide et renferme 5 à 35 % en poids d'adjuvant organique soluble dans l'eau, jusqu'à 15 % en poids, en particulier 0,1 à 5 % en poids d'adjuvant inorganique insoluble dans l'eau, jusqu'à 15 % en poids, en particulier 0,5 à 10 % en poids de surfactif anionique synthétique, 1 à 25 % en poids de tensioactif non ionique, jusqu'à 15 % en poids, en particulier 4 à 12 % en poids de savon, jusqu'à 30 % en poids, en particulier 1 à 25 % en poids d'eau et/ou de solvant miscible avec l'eau, ainsi que jusqu'à 10 % en poids, en particulier 0,01 à 7,5 % en poids de système stabilisateur d'enzyme.
EP95914299A 1994-03-31 1995-03-23 Detergent a base de lipases Expired - Lifetime EP0753046B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4411349A DE4411349A1 (de) 1994-03-31 1994-03-31 Lipasehaltiges Textilwaschmittel
DE4411349 1994-03-31
PCT/EP1995/001094 WO1995027029A1 (fr) 1994-03-31 1995-03-23 Detergent a base de lipases

Publications (2)

Publication Number Publication Date
EP0753046A1 EP0753046A1 (fr) 1997-01-15
EP0753046B1 true EP0753046B1 (fr) 1998-09-09

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AT (1) ATE170914T1 (fr)
DE (2) DE4411349A1 (fr)
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JP2859520B2 (ja) * 1993-08-30 1999-02-17 ノボ ノルディスク アクティーゼルスカブ リパーゼ及びそれを生産する微生物及びリパーゼ製造方法及びリパーゼ含有洗剤組成物
KR20140024365A (ko) * 2011-04-08 2014-02-28 다니스코 유에스 인크. 조성물

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0218272A1 (fr) * 1985-08-09 1987-04-15 Gist-Brocades N.V. Enzymes lipolytiques et leur usage dans des compositions détergentes
EP0334462A1 (fr) * 1988-03-25 1989-09-27 Genencor International, Inc. Clonage et expression moléculaire de gènes codant pour enzymes lipolytiques

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8826110D0 (en) * 1988-11-08 1988-12-14 Unilever Plc Enzyme-containing detergent compositions
US5063160A (en) * 1989-03-16 1991-11-05 Olin Corporation Identification, characterization, and method of production of a novel microbial lipase
GB8915658D0 (en) * 1989-07-07 1989-08-23 Unilever Plc Enzymes,their production and use
DK97190D0 (da) * 1990-04-19 1990-04-19 Novo Nordisk As Oxidationsstabile detergentenzymer
SK133194A3 (en) * 1992-05-08 1995-04-12 Procter & Gamble Pelletized detergent compositions and method of matters cleaning by these compositions
CA2097000A1 (fr) * 1992-05-27 1993-11-28 Norio Moriya Lipase alcaline, methode de production correspondante, microorganisme produisant cette lipase alcaline et composition detergente la contenant
CA2138519C (fr) * 1993-04-27 2007-06-12 Jan Metske Van Der Laan Nouveaux composes de type lipase pour detergents
DE4315854A1 (de) * 1993-05-12 1994-11-17 Henkel Kgaa Lipasehaltige Wasch- und Reinigungsmittel

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0218272A1 (fr) * 1985-08-09 1987-04-15 Gist-Brocades N.V. Enzymes lipolytiques et leur usage dans des compositions détergentes
US4933287A (en) * 1985-08-09 1990-06-12 Gist-Brocades N.V. Novel lipolytic enzymes and their use in detergent compositions
EP0334462A1 (fr) * 1988-03-25 1989-09-27 Genencor International, Inc. Clonage et expression moléculaire de gènes codant pour enzymes lipolytiques

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WO1995027029A1 (fr) 1995-10-12
DE59503525D1 (de) 1998-10-15
ES2123971T3 (es) 1999-01-16
DE4411349A1 (de) 1995-10-05
ATE170914T1 (de) 1998-09-15
EP0753046A1 (fr) 1997-01-15

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