EP0729502B1 - Detergent et nettoyant liquide contenant des combinaisons d'enzymes - Google Patents

Detergent et nettoyant liquide contenant des combinaisons d'enzymes Download PDF

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Publication number
EP0729502B1
EP0729502B1 EP95900124A EP95900124A EP0729502B1 EP 0729502 B1 EP0729502 B1 EP 0729502B1 EP 95900124 A EP95900124 A EP 95900124A EP 95900124 A EP95900124 A EP 95900124A EP 0729502 B1 EP0729502 B1 EP 0729502B1
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EP
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Prior art keywords
weight
detergent
alkyl
nonionic surfactant
glycoside
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EP95900124A
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German (de)
English (en)
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EP0729502A1 (fr
Inventor
Georg Meine
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/835—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 washing and cleaning agents, the protease, amylase and cellulase and water-soluble and optionally water-insoluble builders and a nonionic Contain surfactant component consisting essentially of alkyl or alkenyl glycoside consists.
  • enzymes or enzyme combinations to improve the cleaning effect of detergents and cleaning agents is in the field of detergents and Commonly known cleaning agents.
  • the most commonly used enzymes include protease. Amylase, cellulase and lipase. These enzymes can be different from each other Have properties and come from different sources.
  • European patent application EP 0 365 103 discloses a detergent which is an organic. non-ionic surfactant and builder for this surfactant and an enzyme combination, consisting of protease, amylase and cellulase.
  • European patent application EP 0 425 214 describes an enzyme-containing washing and Described detergent, which anionic and / or nonionic surfactants, preferably one Builder and an enzyme combination of three enzymes, namely protease, amylase and either Contains lipase or cellulase.
  • liquid detergent which in addition to anionic and nonionic surfactants, an enzyme combination of protease and one contains second enzyme such as cellulase, which stabilizes with the help of an aromatic borate ester becomes.
  • liquid compositions known which contain 1-70% by weight alkyl glycoside and 0.005-5% by weight enzyme.
  • useful enzymes are proteases, lipases and amylases.
  • the one for the present Invention essential cellulase is not mentioned in this document.
  • Surfactants based on glucose and other sugars that contain alkyl glycosides long-chain alkyl groups belong to the non-ionic surfactants.
  • Laundry detergent, the alkyl glycosides in combination with at least one conventional anionic Surfactant are included in the European patent application EP 070 074.
  • Detergents containing alkyl glycosides and anionic surfactants are also known from European patent application EP 092 877.
  • European patent application EP 105 556 are liquid Detergents are known, the alkyl glycosides, certain other nonionic surfactants and contain anionic surfactants.
  • From the international patent application WO 86/2943 alkyl detergent-containing liquid detergents are known which additionally Contain common anionic surfactants.
  • the object of the present invention is a washing and cleaning agent to provide, which has sufficient stability of the containing Enzymes guaranteed and has an 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, of a glycoside of the formula (I) R 1 -O (G) n in which R 1 is an alkyl or alkenyl radical having 8 to 22 carbon atoms, G is a glycose unit and n is a number from 1 to 10, consists.
  • a nonionic surfactant component which comprises at least 50% by weight, in particular at least 80% by weight, of a glycoside of the formula (I) R 1 -O (G) n in which R 1 is an alkyl or alkenyl radical having 8 to 22 carbon atoms, G is a glycose unit and n is a number from 1 to 10, consists.
  • the agent according to the invention was compared a similar and with the prior art at a lower dosage sometimes even has better washing properties and that the contained Enzymes still show 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 1 is an alkyl or alkenyl radical having 8 to 22 carbon atoms, G is a glycose unit and n is a number between 1 and 10.
  • R 1 is an alkyl or alkenyl radical having 8 to 22 carbon atoms
  • G is a glycose unit
  • n is a number between 1 and 10.
  • Such compounds and their preparation are described, for example, in European patent applications EP 092 355, EP 301 298, EP 357 969 and EP 362 671 or US Pat. No. 3,547,828.
  • the glycoside component ((G) n in formula I) is an oligomer or polymer from naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose , Ribose, arabinose, xylose and lyxose.
  • the oligomers consisting of such glycosidically linked monomers are characterized not only by the type of sugar they contain, but also by their number, the so-called degree of oligomerization.
  • the degree of oligomerization (n in formula I) generally 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 portion (R 1 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 to prepare usable glycosides can. Accordingly, the primary alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly suitable.
  • 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, but is even advantageous in the case of liquid products.
  • Fatty alcohols can also be used as additional skin-protecting components in shampoos, hand-washing pastes, etc.
  • the proportion of further nonionic surfactant contained in addition to the glycoside is up to up to 50% by weight, preferably at most 25% by weight, in particular 0.5% by weight 20% by weight, based on the total nonionic surfactant component.
  • nonionic surfactants in question include the alkoxylates, in particular the ethoxylates and / or propoxylates of saturated or one to polyunsaturated linear or branched chain alcohols with 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms.
  • the degree of alkoxylation of the alcohols is usually between 1 and 20, preferably between 3 and 10. You can in a known manner by reacting the corresponding alcohols be prepared with the corresponding alkylene oxides.
  • Alkoxylates can be used.
  • the alkoxylates can be used, especially the ethoxylates, primary alcohols with linear, in particular Dodecyl, tetradecyl, hexadecyl or octadecyl residues and mixtures thereof.
  • Corresponding alkoxylation products of alkylamines, vicinal diols and carboxamides, which with regard to the alkyl part correspond to the alcohols mentioned, can be used.
  • ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters as specified in the international patent application WO 90/13533 Processes can be produced, as well as fatty acid polyhydroxyamides, as they do according to the procedures of the U.S. patents US 1 985 424, US 2 016 962 and US 2 703 798 and the international patent application WO 92/06984 can be considered.
  • nonionic surfactant system consisting of glycoside according to the formula (I) and optionally further nonionic surfactant is in the invention Agents preferably in amounts of 1% by weight to 50% by weight, in particular from 1% to 40% by weight. If it is with the invention Means around a cleaning agent, for example a manual or machine Dishwashing detergent or a cleaning agent for hard surfaces acts, the content of nonionic surfactant can also be lower and lies then preferably at 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, preferably, further surfactants synthetic anionic surfactants of the sulfate or sulfonate type, in amounts of preferably not more than 20% by weight, in particular from 0.1% by weight to 18% by weight, in each case based on the total mean.
  • synthetic anionic surfactants the alkyl and / or alkenyl sulfates with 8 to 22 carbon atoms, which are an alkali, Ammonium or alkyl or hydroxyalkyl substituted ammonium ion wear as a counter cation.
  • the derivatives of fatty alcohols are preferred with in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols.
  • the alkyl and alkenyl sulfates can be known Way by reaction of the corresponding alcohol component with a conventional one Sulfating reagent, especially sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali, ammonium or alkyl or Hydroxyalkyl-substituted ammonium bases can be produced.
  • Such alkyl and / or alkenyl sulfates are in the agents according to the invention preferably in amounts of 0.1% by weight to 20% by weight, in particular of Contain 0.1 wt .-% to 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 such ether sulfates 2 to 30, in particular 4 to 10, Ethylene glycol groups per molecule.
  • Suitable sulfonate-type anionic surfactants belong to the reaction of fatty acid esters with sulfur trioxide and subsequent neutralization obtainable a-sulfoesters, especially the 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, deriving sulfonation products, as well as by formal saponification these emerging sulfo fatty acids.
  • the weight ratio is from glycoside to alkyl or alkenyl or ether sulfate preferably 5: 1 to 1: 4, in particular 1: 1 to 1: 3.5, with anionic surfactant a linear, primary alkyl or alkenyl radical with 14 to 18 C atoms is particularly preferred.
  • soaps with saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and from natural fatty acid mixtures, for example coconut, palm kernel or tallow 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 12 -C 18 fatty acid soaps and up to 50% by weight of oleic acid soap.
  • Soap is preferably contained in amounts of 0.1% by weight to 5% by weight. In particular, however, higher amounts of soap of up to 20% by weight can also be contained in liquid agents.
  • the washing and cleaning agent contains enzymes from the class of proteases, amylases and cellulases.
  • enzymes from the class of proteases, amylases and cellulases Preferably mushrooms or Strains of bacteria such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus and Streptomyces griseus used enzymatic active ingredients.
  • 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 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 15000 PE / g (protease units per gram, determined by the method described in surfactants 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 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 3 KNU / g ("Kilo-Novo-Units" per gram according to the Novo standard method, where 1 KNU is the amount of enzyme which breaks down 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 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 269 077, EP 270 974, EP 273 125 and EP 339 550 known.
  • the agent according to the invention preferably in amounts such that the finished agent has a cellulolytic activity of 0.05 IU / g to 1.5 IU / g ("International Units" per gram, based on the enzymatic hydrolysis of Na-carboxymethylcellulose) pH 9.0 and 40 ° C, as described in Agric. Biol. Chem. 53, 1275 (1989) by S. Ito et al.), in particular 0.07 IU / g to 1.4 IU / g and particularly preferred 0.1 IU / g to 1.3 IU / g.
  • Suitable commercial products include Celluzyme (R) from Novo Industri or KAC (R) from Kao.
  • the agent according to the invention preferably contains 5% by weight to 55% by weight, in particular 5 to 35 wt .-%, water-soluble, organic and / or inorganic Builder.
  • the water-soluble, organic builder substances include especially those from the class of polycarboxylic acids, especially citric acid and sugar acids and polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which also contain small amounts of polymerisable Polymerized substances without carboxylic acid functionality can.
  • 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 one Acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000.
  • Suitable, albeit less preferred, compounds this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50 wt .-%.
  • 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 nonocarboxylic 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 as well 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 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 a 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.
  • Substances are used in the agents according to the invention. Are suitable in this Relationship between the alkali carbonates, alkali hydrogen carbonates and alkali sulfates and their Mixtures. Such additional inorganic material can be used in amounts of up to 20% by weight. be present, but is preferably missing entirely.
  • the agents according to the invention can also contain up to 15% by weight, in particular 0.1% by weight to 5 Contain wt .-% water-insoluble inorganic builder.
  • a suitable water-insoluble Inorganic builders are especially the known crystalline or amorphous Alkaline alumosilicates in detergent quality, in particular zeolite NaA and optionally NaX, as well as crystalline layered silicates described in European patent application EP 0 164 514 be used.
  • the agents according to the invention can be acidic or weak alkaline pH of about 8.0 to 9.5 in particular 1% by weight aqueous solution solid inorganic and / or organic Acids or acidic salts, for example alkali hydrogen sulfates, Succinic acid, adipic acid or glutaric acid and mixtures thereof.
  • acidic substances are preferred in the agents according to the invention in quantities not exceeding 5% by weight, in particular from 0.1% by weight to 3% by weight, where quantities close to the above limit, especially for detergents are interesting.
  • the agents according to the invention can be used in detergents and cleaning agents Contain common ingredients.
  • these optional components include in particular abrasives, for example quartz flour, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydrodoxypolycarboxylic 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.
  • abrasives for example quartz flour
  • complexing agents for heavy metals for example aminopolycarboxylic acids, aminohydrodoxypolycarboxylic acids, Polyphosphonic acids and / or aminopolyphosphonic acids
  • Graying inhibitors for example cellulose ethers
  • foam inhibitors for example organopolysiloxanes or paraffins
  • optical brighteners for example stilbene disulfonic acid derivatives.
  • optical brighteners in particular compounds from the class of 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 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 0.1% by weight to 1% by weight, of foam inhibitors included, with the stated weight fractions in each case to the total Obtain funds.
  • Solvents used in liquid agents according to the invention can, in addition to water, are preferably those which are water-miscible. 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 classes of compounds mentioned derivable ether.
  • 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 Agents preferably contain 2 to 12% by weight and in particular 3 to 10% by weight 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, such as from the European Patent applications EP 376 705 and EP 378 261 known, boric acid respectively Alkaliborate, boric acid-carboxylic acid combinations, such as those from the European patent application EP 451 921 are known, calcium salts, for example the Ca-formic acid combination known from European patent EP 028 865, 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 their Mixtures
  • lower carboxylic acids such as from the European Patent applications EP 376 705 and EP 378 261 known
  • boric acid respectively Alkaliborate boric acid-carboxylic acid combinations
  • calcium salts for example
  • Suitable foam inhibitors include long chain soaps, in particular Beenic acid, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and their mixtures, which are also microfine, if appropriate may contain silanized or otherwise hydrophobized silica.
  • Foam inhibitors preferably on 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 151 386.
  • the agent according to the invention can furthermore contain graying inhibitors.
  • Graying inhibitors have the task of removing the dirt detached from the fiber keep suspended in the liquor and thus prevent 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 of cellulose or salts of acidic sulfuric acid esters of cellulose or of strength.
  • Water-soluble polyamides containing acidic groups are also suitable for suitable for this purpose. Soluble starch preparations and use starch products other than those mentioned above, for example partially hydrolyzed Strength. Na carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof and polyvinylpyrrolidone are preferred used.
  • 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 204 208, EP 214 761, EP 258 068, EP 407 225 or international patent application WO 87/00859. Examples of useful commercially available lipases are Lipolase (R) and Lipozym (R) .
  • Lipase is preferably used in the agent according to the invention in amounts such that the finished agent 10 LU / g to 10,000 LU / g ("lipase activity units" per gram, determined by the enzymatic hydrolysis of tributyrin at 30 ° C. and pH 7 after the method mentioned in EP 258 068), in particular 80 LU / g to 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 0.1% 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 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 to 10% by weight, in particular 0.01 to 7.5% by weight, of enzyme stabilizer system.
  • the liquid agents of the present invention can be easily mixed of the constituents or their premixes, which are liquid or in water respectively can be present dissolved in an intended solvent become.

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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)

Claims (8)

  1. Détergent et nettoyant liquide contenant du tensioactif, de la protéase, de l'amylase, de la cellulase et de l'adjuvant, qui renferme un composant surfactif non ionique, qui est constitué à au moins 50 % en poids, en particulier à au moins 80 % en poids, d'un glycoside de la formule (I) R1-O(G)n dans laquelle R1 représente un radical alkyle ou alcényle comportant 8 à 22 atomes de C, G correspond à une unité d'ose et n est un nombre compris entre 1 et 10.
  2. Produit selon la revendication 1, caractérisé en ce que le composant surfactif non ionique est constitué à au moins 80 % en poids d'un glycoside de la formule (I), et renferme en plus de celui-ci, comme autre surfactif non ionique, un polyalcoxylate d'alkyle gras, en particulier un éthoxylate et/ou un propoxylate, un polyhydroxyamide d'acide gras et/ou un produit d'éthoxylation et/ou de propoxylation d'alkylamines grasses, de diols vicinaux, d'alkylesters d'acides gras et/ou d'amides d'acides gras.
  3. Produit selon la revendication 1, caractérisé en ce que la proportion de l'autre surfactif non ionique contenu en plus du glycoside atteint au maximum 25 % en poids, en particulier 0,5 à 20 % en poids, par rapport à la totalité du composant surfactif non ionique.
  4. Produit selon une des revendications 1 à 3, caractérisé en ce qu'il contient 5 à 55 % en poids d'adjuvants solubles dans l'eau, de la protéase en proportion telle que l'activité est comprise entre 100 et 15 000 UP/g, en particulier entre 125 et 7500 UP/g, par rapport à la totalité du produit, de l'amylase en quantité telle, que l'activité est comprise entre 0,01 et 3 KNU/g, en particulier entre 0,01 et 1,8 KNU/g, par rapport à la totalité du produit, et de la cellulase en proportion telle que l'activité est comprise entre 0,05 et 1,5 Ul/g, en particulier entre 0,07 et 1,4 Ul, par rapport à la totalité du produit, jusqu'à 20 % en poids, en particulier entre 0,1 et 18 % en poids de surfactif anionique et 1 à 50 % en poids de composant tensioactif non ionique.
  5. Produit selon la revendication 4, caractérisé en ce que le surfactif anionique est sélectionné parmi les alkyl- ou les alcénylsulfates et/ou parmi les alkyl- ou les alcényléthersulfates, dans lesquels le groupe alkyle ou alcényle comporte 8 à 22, de préférence 12 à 18 atomes de C.
  6. Produit selon une des revendications 1 à 5, caractérisé en ce qu'il renferme 5 à 35 % en poids d'adjuvants organiques solubles dans l'eau, jusqu'à 15 % en poids, en particulier 0,1 à 5 % en poids d'adjuvants inorganiques insolubles dans l'eau. jusqu'à 15 % en poids, en particulier 0,5 à 10 % en poids de surfactif anionique synthétique, 1 à 40 % en poids de tensioactif non ionique, jusqu'à 15 % en poids, en particulier 4 à 12 % en poids de savon, et 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 de stabilisant d'enzymes.
  7. Produit selon une des revendications 1 à 6, caractérisé en ce que le glycoside de la formule (I) est un alkyl- ou un alcénylglucoside et qu'il possède un degré d'oligomérisation n inférieur à 1,5, en particulier compris entre 1,2 et 1,4.
  8. Produit selon une des revendications 1 à 7, caractérisé en ce qu'il renferme un glycoside selon la formule (I) et un alkyl-, alcényl- ou éthersulfate avec un radical alkyle ou alcényle primaire linéaire, comportant 14 à 18 atomes de C, dans un rapport pondéral de 5:1 à 1:4, en particulier de 1:1 à 1:3,5.
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 EP0729502A1 (fr) 1996-09-04
EP0729502B1 true EP0729502B1 (fr) 1999-07-28

Family

ID=6502894

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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

Also Published As

Publication number Publication date
EP0729502A1 (fr) 1996-09-04
WO1995014074A1 (fr) 1995-05-26
ES2136270T3 (es) 1999-11-16
DE59408552D1 (de) 1999-09-02
ATE182616T1 (de) 1999-08-15
DE4339382A1 (de) 1995-05-24

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