EP0729502A1 - Detergent et nettoyant liquide contenant des combinaisons d'enzymes - Google Patents

Detergent et nettoyant liquide contenant des combinaisons d'enzymes

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Publication number
EP0729502A1
EP0729502A1 EP95900124A EP95900124A EP0729502A1 EP 0729502 A1 EP0729502 A1 EP 0729502A1 EP 95900124 A EP95900124 A EP 95900124A EP 95900124 A EP95900124 A EP 95900124A EP 0729502 A1 EP0729502 A1 EP 0729502A1
Authority
EP
European Patent Office
Prior art keywords
weight
alkyl
composition according
water
nonionic surfactant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP95900124A
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German (de)
English (en)
Other versions
EP0729502B1 (fr
Inventor
Georg Meine
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Filing date
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Publication of EP0729502A1 publication Critical patent/EP0729502A1/fr
Application granted granted Critical
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Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/835—Mixtures of non-ionic with cationic 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
    • 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
    • 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
    • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/42—Amino alcohols or amino ethers
    • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/526—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 are polyalkoxylated
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols

Definitions

  • the invention relates to liquid detergents and cleaning agents which contain protease, amylase and cellulase and water-soluble and optionally water-insoluble builders and a nonionic surfactant component which consists essentially of alkyl or alkenyl glycoside.
  • enzymes or enzyme combinations to improve the cleaning action of detergents and cleaning agents is generally known in the field of detergents and cleaning agents.
  • the most commonly used enzymes include protease, amylase, cellulase and lipase. These enzymes can each have different properties from one another and can come from different sources.
  • the prior art also describes enzyme combinations which are intended to improve the cleaning action of the detergents and cleaning agents in the case of a wide variety of enzymatically degradable soils.
  • European patent application EP 0365103 discloses a detergent which contains an organic, nonionic surfactant and builder for this surfactant and an enzyme combination consisting of protease, amylase and cellulase.
  • European patent application EP 0425214 describes an enzyme-containing washing and cleaning agent which contains anionic and / or nonionic surfactants, preferably a builder and an enzyme combination of three enzymes, namely protease, amylase and either lipase or cellulase.
  • liquid detergent which, in addition to anionic and nonionic surfactants, contains an enzyme combination of protease and a second enzyme such as cellulase, which is stabilized with the aid of an aromatic borate ester.
  • Surfactants based on glucose and other sugars, the alkyl glycosides with long-chain alkyl groups, are non-ionic surfactants.
  • Detergents which contain alkyl glycosides in combination with at least one conventional anionic surfactant are described in European patent application EP 070074.
  • Detergents which contain alkyl glycosides and anionic surfactants are also known from European patent application EP 092877.
  • liquid detergents are known from European patent application EP 105556, which contain alkyl glycosides, certain other nonionic surfactants and anionic surfactants. From international patent application WO 86/2943, alkyl glycoside-containing liquid detergents are known which additionally contain conventional anionic surfactants.
  • the object of the present invention is to provide a washing and cleaning agent which ensures sufficient stability of the enzymes contained and has improved washing activity.
  • the invention relates to a detergent and cleaning agent containing surfactant, protease, amylase, cellulase and builder, which contains a nonionic surfactant component which comprises at least 50% by weight, in particular at least 80% by weight 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
  • n is a number from 1 to 10.
  • the agent according to the invention compared to the prior art, has similar and sometimes even better washing properties at lower doses and that the enzymes contained also have good activity even after prolonged storage.
  • 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 092355, EP 301 298, EP 357969 and EP 362671 or US Pat. No. 3547828.
  • 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, or alelose , Idose, ribose, arabinose, xylose and lyxose.
  • the oligomers consisting of such glycosidically linked monomers are characterized not only by the type of sugar they contain, but also by their number, the so-called degree of oligomerization.
  • the degree of oligo erization (n in formula I) generally assumes fractional numerical values as the quantity to be determined analytically; it is between 1 and 10, for the glycosides preferably used below 1.5, in particular between 1.2 and 1.4.
  • the preferred monomer building block is glucose because of its good availability.
  • the alkyl or alkenyl moiety (R 1 in formula I) of the glycosides contained in the agents according to the invention preferably also originates from easily accessible derivatives of renewable raw materials, in particular from fatty alcohols, although also their branched chain isomers, in particular so-called oxo alcohols. can 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 suitable.
  • the proportion of further nonionic surfactant present in addition to the glycoside is up to 50% by weight, preferably at most 25% by weight, in particular 0.5% by weight to 20% by weight, based on the total nonionic surfactant component.
  • the further nonionic surfactants that come into 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 usable alkoxylates.
  • 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.
  • Such a nonionic surfactant system consisting of glycoside of the formula (I) and optionally further nonionic surfactant, is preferably used in the agents according to the invention in amounts of 1% by weight to 50% by weight, in particular contain from 1 wt .-% to 40 wt .-%.
  • the agent according to the invention is a cleaning agent, for example a manual or machine dishwashing agent or a cleaning agent for hard surfaces, the nonionic surfactant content can also be lower and is then preferably 0.5% by weight. up 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 metal, ammonium or alkyl or hydroxyalkyl substituted ammonium ion as countercation.
  • the alkyl and alkenyl sulfates may be prepared be ⁇ by reacting the corresponding alcohol component with a Usually, for chen sulfating agent, 'particularly sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali metal, ammonium or alkyl relationship as hydroxyalkyl-substituted ammonium bases in bekann ⁇ ter manner .
  • Such alkyl and / or alkenyl sulfates are contained in the agents according to the invention preferably in amounts from 0.1% by weight to 20% by weight, in particular from 0.1% by weight to 18% by weight.
  • the sulfate-type surfactants that can be used also include the sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates.
  • ether sulfates preferably contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule.
  • Suitable anionic surfactants of the sulfonate type include the a-sulfoesters obtainable by reacting fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those derived from fatty acids having 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 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, where Anionic surfactant with a linear, primary alkyl or alkenyl radical having 14 to 18 carbon atoms is particularly preferred.
  • soaps with saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, pal itic acid or stearic acid, and from natural fatty acid mixtures, for example coconut and palm kernels -, or Taig fatty acids, derived soaps are suitable.
  • those soap mixtures are preferred which are composed of 50% by weight to 100% by weight of saturated C 1 -C 6 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 washing and cleaning agent contains enzymes from the class of proteases, amylases and cellulases. 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 in the agents according to the invention 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 to 15000 PE / g (protease units per gram, determined by the method described in Tenside 7, 125 (1970)), in particular 125 PE / g to 7500 PE / g and particularly preferably 150 PE / g to 4500 PE / g.
  • Suitable proteases are commercially available, for example under the names BLAP ( R ), Savinase ( R ), Esperase ( R ), Maxatase ( R ), 0ptimase ( R ) or Alcalase ( R ).
  • amylases which can be used in agents according to the invention include the enzymes which can be obtained from bacteria or fungi and which have a pH optimum, preferably in the alkaline range up to about pH 10.
  • Useful commercial products include TermamyH) and Maxamyl ( R ).
  • Amylase is preferably used in the agent according to the invention in such amounts that the finished agent 0.01 KNU / g to 3 KNU / g ("Kilo-Novo-Units" per gram according to the Novo standard method, where 1 KNU is the amount of enzyme that degrades 5.26 g of starch at pH 5.6 and 37 ° C, based on the method described by P.
  • the cellulase used according to the invention also 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 3322950 or European patent applications EP 265832, EP 269077, EP 270974, EP 273 125 and EP 339550.
  • 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 are, for example, Celluzyme ( R ) from Novo Industri or KAC ( R ) from Kao.
  • the agent according to the invention preferably contains 5% by weight to 55% by weight, in particular 5 to 35% by weight, of water-soluble, organic and / or inorganic builders.
  • the water-soluble, organic builder substances include, in particular, those from the class of the polycarboxylic acids, in particular citric acid and sugar acids, and also polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which can also contain small amounts of polymerizable substances without carboxylic acid functionality in copolymerized form .
  • the relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000. preferably 50,000 to 120,000, based on free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000.
  • Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight.
  • Terpolymers which contain two carboxylic acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer can also be used as water-soluble organic builder substances.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C3-Cs-carboxylic acid and preferably from a Cj-Ctj-monocarboxylic acid, in particular from (meth) acrylic acid.
  • the second acidic monomer or its salt may be a derivative of a Cj-C ⁇ -dicarboxylic acid, preferably a C j -Cs-dicarboxylic be, 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 C1-C4 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. 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% by weight %, preferably 15% by weight up to 25% by weight of methyl sulfonic acid or methyl sulfonate and as the third monomer 15% by weight to 40% by weight, preferably 20% by weight to 40% by weight of a carbohydrate.
  • This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred.
  • the use of the third monomer presumably creates predetermined breaking points in the polymer, which are responsible for the good biodegradability of the polymer.
  • These terpolymers can be produced in particular by processes which are described in German patent applications P 42 21 381.9 and P 43 00 772.4, and generally have a relative molecular weight between 1000 and 200000, preferably between 200 and 50,000 and in particular between 3000 and 10,000 . They can be used in particular for the production of liquid agents, 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 salts.
  • the finished agent preferably contains these organic builder substances 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.
  • alkali metal carbonates A. potassium hydrogen carbonates and alkali metal 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 also contain up to 15% by weight, in particular 0.1% by weight to 5% by weight, of water-insoluble inorganic builders.
  • Suitable known water-insoluble inorganic builders are, in particular, the known crystalline or amorphous alkali alumosilicate in detergent quality, in particular zeolite NaA and optionally NaX, and crystalline layered silicates which are described in European patent application EP 0164514.
  • the agents according to the invention can, if desired, set an acidic or weakly alkaline pH of in particular about 8.0 to 9.5 inches 1% by weight aqueous solution containing solid inorganic and / or organic acids or acidic salts, for example alkali hydrogen sulfates, succinic acid, adipic acid or glutaric acid and mixtures thereof.
  • Such acidic substances are preferably contained in the agents according to the invention in amounts of not more than 5% by weight, in particular from 0.1% by weight to 3% by weight, with amounts close to the above-mentioned upper limit especially for cleaning agents are interesting.
  • the agents according to the invention can contain further constituents customary in washing and cleaning agents.
  • These optional constituents include, in particular, abrasive substances, for example quartz powder, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, graying inhibitors, for example cellulose ethers, foam inhibitors, for example organopolysiloxane siloxanesiloxane and optical derivatives, paraffin sulfonic acid and derivatives .
  • abrasive substances for example quartz powder
  • complexing agents for heavy metals for example aminopolycarboxylic acids, aminohydroxypypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids
  • graying inhibitors for example cellulose ethers
  • foam inhibitors for example organopolysiloxane siloxanesiloxane and optical derivatives, paraffin sulfonic acid and 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 Contain foam inhibitors, the weight percentages each referring to the entire composition.
  • solvents which can be used in 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 compound classes mentioned.
  • the water content of the compositions is preferably 10% by weight to 50% by weight and in particular 20% by weight to 40% by weight.
  • the compositions preferably contain 2 to 12% by weight and in particular 3 to 10% by weight of ethanol or any mixture of ethanol and glycerin.
  • the customary enzyme stabilizers which may be present include amino alcohols, for example mono-, di-, triethanol and propanolamine and their mixtures, lower carboxylic acids, as known, for example, from European patent applications EP 376705 and EP 378261, boric acid or alkali borates, boric acid Carboxylic acid combinations, as are known, for example, from European patent application EP 451 921, calcium salts, for example the calcium formic acid combination known from European patent EP 028865, magnesium salts, as known, for example, from European patent application EP 378262 , and / or sulfur-containing reducing agents, as known for example from European patent applications EP 080748 or EP 080223.
  • amino alcohols for example mono-, di-, triethanol and propanolamine and their mixtures
  • lower carboxylic acids as known, for example, from European patent applications EP 376705 and EP 378261
  • boric acid or alkali borates boric acid Carboxylic acid combinations
  • boric acid Carboxylic acid combinations
  • Suitable foam inhibitors include long-chain soaps, in particular behenic acid, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which may also contain microfine, optionally silanized or otherwise hydrophobized silica.
  • foam inhibitors are preferably bound to granular, water-soluble carrier substances, as described, for example, in German patent application DE 3436 194, European patent applications EP 262588, EP 301 414, EP 309931 or European patent EP 151 386.
  • the agent according to the invention can furthermore contain graying inhibitors.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the graying of the fibers.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example partially hydrolyzed starch.
  • the agent according to the invention can also contain further enzymes, for example oxidase, peroxidase and / or lipase.
  • the lipase is an enzyme that can be obtained from microorganisms, in particular bacteria or fungi. Such is known for example from European patent applications EP 204208, EP 214761, EP 258068, EP 407225 or international patent application WO 87/00859.
  • Useful commercially available lipases include Lipolase ' R ) and Lipozym ( R ).
  • Lipase is preferably used in the agent according to the invention in amounts such that the finished agent 10 LU / g to 10000 LU / g ("lipase activity units" per gram, determined via the enzymatic hydrolysis of tri-butyrin at 30 ° C. and pH 7 according to 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.
  • a 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% 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 40% 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 to 7.5 wt .-% enzyme stabilizer system.
  • liquid compositions of the present invention can be prepared by simply mixing the constituents or their premixes, which can be liquid or dissolved in water or in a solvent provided.
  • Table 1 lists the components of a liquid detergent according to the invention and a detergent from the prior art.
  • the detergents were prepared by thoroughly mixing the components listed in Table 1.
  • To check the cleaning performance washing tests were carried out with artificial soiling under conditions of use (drum washing machine Miele W 918, 2.0 kg of normally soiled laundry, water hardness) 16 ° d; Evaluation carried out by remission measurement at 460 nm, without UV).
  • the reflectance values given in Table 2 were determined as a double determination.
  • Amylase ⁇ 0.05 0.5
  • the enzyme stability in an agent according to the invention which had the composition described in Table 1, was determined.
  • the agent was stored for 3 months at room temperature.
  • the residual activities of the various enzymes in% of the starting activity are listed in Table 3.

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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)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Detergent Compositions (AREA)
EP95900124A 1993-11-18 1994-11-09 Detergent et nettoyant liquide contenant des combinaisons d'enzymes Expired - Lifetime EP0729502B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4339382A DE4339382A1 (de) 1993-11-18 1993-11-18 Enzymkombinationhaltige flüssige Wasch- und Reinigungsmittel
DE4339382 1993-11-18
PCT/EP1994/003691 WO1995014074A1 (fr) 1993-11-18 1994-11-09 Detergent et nettoyant liquide contenant des combinaisons d'enzymes

Publications (2)

Publication Number Publication Date
EP0729502A1 true EP0729502A1 (fr) 1996-09-04
EP0729502B1 EP0729502B1 (fr) 1999-07-28

Family

ID=6502894

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95900124A Expired - Lifetime EP0729502B1 (fr) 1993-11-18 1994-11-09 Detergent et nettoyant liquide contenant des combinaisons d'enzymes

Country Status (5)

Country Link
EP (1) EP0729502B1 (fr)
AT (1) ATE182616T1 (fr)
DE (2) DE4339382A1 (fr)
ES (1) ES2136270T3 (fr)
WO (1) WO1995014074A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0798371A1 (fr) * 1996-03-29 1997-10-01 The Procter & Gamble Company Compositions détergentes comprenant une amylase spécifique et des alkyl-polyglucosides tensioactifs
WO1999002634A1 (fr) * 1997-07-11 1999-01-21 The Procter & Gamble Company Compositions detergentes comprenant une cellulase specifique et un tensio-actif d'alkylpolyglucoside
BE1027322B1 (fr) * 2019-05-29 2021-01-12 Realco Composition nettoyante et dégraissante pour le traitement de surfaces dures

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0214278A1 (fr) * 1985-03-07 1987-03-18 A.E. Staley Manufacturing Company Composition detergente contenant un enzyme et un agent tensio-actif glucoside
US4959179A (en) * 1989-01-30 1990-09-25 Lever Brothers Company Stabilized enzymes liquid detergent composition containing lipase and protease
GB8923788D0 (en) * 1989-10-23 1989-12-13 Unilever Plc Enzymatic detergent compositions and their use

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9514074A1 *

Also Published As

Publication number Publication date
WO1995014074A1 (fr) 1995-05-26
ES2136270T3 (es) 1999-11-16
DE59408552D1 (de) 1999-09-02
EP0729502B1 (fr) 1999-07-28
ATE182616T1 (de) 1999-08-15
DE4339382A1 (de) 1995-05-24

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