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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3907—Organic compounds
  • C11D3/3917—Nitrogen-containing compounds
  • C11D3/3925—Nitriles; Isocyanates or quarternary ammonium nitriles
• • 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
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/22—Carbohydrates or derivatives thereof
  • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
• • 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
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
  • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
  • C11D3/38645—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
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3932—Inorganic compounds or complexes

Definitions

• the present invention relates to the enhancement of the cleaning performance of enzyme-containing detergents or cleaners, the in addition to usual ingredients a specific bleach activator from the group of contain cationic nitriles.
• Detergents contain in addition to the ingredients indispensable for the washing process As surfactants and builders are usually other ingredients that you see below the term washing aids can summarize and the so different groups of active ingredients such as foam regulators, grayness inhibitors, bleaches and Color transfer inhibitors. Such excipients also include substances which the surfactant performance by the enzymatic degradation of on the textile support stains present. The same applies mutatis mutandis to cleaning agents for hard surfaces. It comes next to the protein removal supporting Proteases and the lipolytic lipases the amylases, which is the task have the removal of starchy soils by the catalytic hydrolysis of starch polysaccharide, and cellulases are of particular importance.
• Cellulases have long been used as softening agents for cotton fabrics because of their Ability to break down cellulose is known. For this effect mechanism takes it is believed that laundry softening cellulases prefer microfibrous cellulose, so-called fibrils, hydrolytically attack and remove from the surface of the Cotton fiber protrudes and the free sliding of cotton fibers on top of each other with special needs. A side effect of this degradation of fibrils is also the deepening of the optical color impression.
• the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators, for the numerous proposals, especially from the classes of N- or O-acyl compounds, for example, polyacylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N- acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfururamides and cyanurates, in addition carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxy-benzenesulfonate and acylated sugar derivatives, such as pentaacetylglucose, have become known in the literature , By adding these substances,
• acetonitrile derivatives as bleach activators in washing or Cleaning agents are also known from the documents EP 0 897 974 A1, DE 197 40 171 A1, EP 0 464 880 A1, EP 0 303 520 A2, WO 98/23533 A1, WO 96/40661 A1, WO 98/23718 and EP 0 790 244 A1.
• the invention relates to the use of a combination of an acetonitrile derivative of the general formula I in which X is an anion, and a protease for increasing the cleaning performance of detergents and cleaners against proteinaceous soils when used in particular aqueous washing and cleaning solutions containing peroxygen compound.
• the anions X - include in particular the halides such as chloride, fluoride, iodide and bromide, nitrate, hydroxide, hexafluorophosphate, sulfate, hydrogen sulfate, metho and ethosulfate, chlorate, perchlorate, and the anions of carboxylic acids such as formate, acetate, benzoate or citrate , Preference is given to the use of compounds of the formula I in which X is chloride, sulfate, hydrogen sulfate or methosulfate.
• An acetonitrile derivative according to formula I is in funds in the context of the use according to the invention, preferably in amounts of from 1% by weight to 10% by weight, in particular from 2% by weight to 7% by weight contain.
• a washing or cleaning agent preferably contains 0.001 mg to 0.5 mg, in particular 0.02 mg to 0.3 mg, of enzymatically active protein per gram of the total composition.
• the protein concentration can be determined by known methods, for example the bicinchonic acid method (BCA method, Pierce Chemical Co., Rockford, IL) or the biuret method (AG Gornall, CS Bardawill and MM David, J. Biol. Chem. 177 , 751-766, 1948).
• proteases include those from microorganisms, especially bacteria or fungi, recoverable enzymes with a pH optimum in the alkaline range, for example, those described in international patent applications WO 92/07067, WO 91/02792, WO 88/03947 or WO 88/03946 or European Patent applications EP 471 265, EP 416 967 or EP 394 352 known proteases.
• Protease is in an agent in the context of the use according to the invention preferably used in such amounts.
• the finished agent is 100 PE / g to 7 500 PE / g (protease units per gram) according to the method described in Tenside 7, 125 (1970)), in particular 125 PE / g to 5,000 PE / g and more preferably 150 PE / g to 4 500 PE / g.
• Useful proteases are commercially available, for example under the name BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym®, Everlase®, Maxapem® or Purafect® OxP.
• amylases preferably in Combination with at least one other enzyme are used include the enzymes which can be obtained from bacteria or fungi, which preferably have a pH optimum in the alkaline range to about pH 10 have.
• Usable commercial products are for example Termamyl®, Maxamyl®, Duramyl® or Purafect® OxAm.
• amylase is used in the agent according to the invention preferably in such amounts that the finished means 0.01 KNU / g to 2 KNU / g ("Kilo-Novo-Units" per gram according to the Standard method of the company Novo, where 1 KNU is the amount of enzyme, the 5.26 g of starch at pH 5.6 and 37 ° C, based on that of P. Bernfeld in S.P. Colowick and N.D. Kaplan, Methods in Enzymology, Vol. 1, 1955, page 149), in particular from 0.015 KNU / g to 1.8 KNU / g and more preferably from 0.03 KNU / g to 1.6 KNU / g.
• the agent contains an amylase, it will preferably selected from genetically modified amylases. Genetically Modified amylases are known, for example, from the international patent applications WO 94/18314 or WO 95/21247.
• lipase is an enzyme obtainable from microorganisms, especially bacteria or fungi.
• microorganisms especially bacteria or fungi.
• EP 0 204 208 EP 0 214 761, EP 0 258 068, EP 0 385 401, EP 0 407 225, EP 0 571 982 or the international Patent applications WO 87/00859 or WO 90/10695 known.
• Lipase is in the Agent preferably used in amounts such that the finished Means a lipolytic activity ranging from 10 LU / g to 10,000 LU / g ("Lipase activity Units "per gram, determined by the enzymatic hydrolysis of tributyrin 30 ° C and pH 7 according to the method mentioned in EP 258 068), in particular 80 LU / g to 5,000 LU / g, and more preferably 100 LU / g to 1000 LU / g.
• commercial Lipases are for example Lipolase®, Lipomax®, Lumafast® and Lipozym®.
• the useful cellulase belongs to the enzymes obtainable from bacteria or fungi, which have a pH optimum preferably in the almost neutral to slightly alkaline pH range of 6 to 9.5.
• Such cellulases are known, for example, from German laid-open applications DE 31 17 250, DE 32 07 825, DE 32 07 847, DE 33 22 950, European patent applications EP 265 832, EP 269 977, EP 270 974, EP 273 125 and EP 339 550 or International Patent Applications WO 96/34108 and WO 97/34005.
• 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 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® from the manufacturer Novo Nordisk or KAC® from Kao.
• suitable peroxygen compounds in particular hydrogen peroxide and hydrogen peroxide under the washing conditions donating inorganic salts.
• alkali perborates, percarbonates. -persilicates and / or persulfates such as caroate, but also organic peracids, respectively pers acid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, into consideration.
• solid peroxygen compounds can be used in the form of powders or Granules are used, which can also be wrapped in a manner known in principle.
• Peroxygen compounds are in amounts of preferably up to 50% by weight, in particular from 5 wt% to 30 wt%, and more preferably from 8 wt% to 25 wt .-% present.
• bleach stabilizers such as phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.
• the use of the invention consists essentially in the presence of a contaminated with proteinaceous soils To create surface conditions under which a peroxidic oxidizer and the invention essential combination of acetonitrile derivative and enzyme with each other can react. Such conditions exist in particular if all Reactants in aqueous solution meet. This can be done by separate Addition of the peroxygen compound and the drug combination to a detergent-containing solution done. This is particularly advantageous using a detergent or cleaning agent containing the Combination of acetonitrile derivative and enzyme and a peroxygen-containing Contains oxidant carried out.
• the detergents and cleaners in particular powdered solids, in densified particle form, as homogeneous solutions or Suspensions may be present except those used in the invention Active ingredient combination in principle all known and customary in such agents ingredients contain.
• the agents may in particular be builders, Surface-active surfactants, additional bleaching agents based on organic and / or inorganic peroxygen compounds, additional bleach activators, water miscible organic solvents, additional enzymes, sequestering agents, Electrolytes, pH regulators and other auxiliaries, such as optical brighteners, grayness inhibitors, Color transfer inhibitors, foam regulators, silver corrosion inhibitors as well as colors and fragrances.
• the agents may contain one or more surfactants, wherein in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants come into question.
• Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or Propoxylation products of alkyl glycosides or linear or branched Alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups. Furthermore, corresponding ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides, which correspond to said long-chain alcohol derivatives with regard to the alkyl part, and of alkylphenols having 5 to 12 C atoms in the alkyl radical.
• nonionic surfactants are preferably alkoxylated, advantageously ethoxylated, especially primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol used in which the alcohol radical linear or preferably methyl branched in the 2-position may be or contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
• EO ethylene oxide
• alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
• the preferred ethoxylated alcohols include, for example, C 12 -C 14 -alcohols with 3 EO or 4 EO, C 9 -C 11 -alcohols with 7 EO, C 13 -C 15 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 -C 14 -alcohol with 3 EO and C 12 -C 18 -alcohol with 7 EO.
• the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
• Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
• fatty alcohols with more than 12 EO can also be used. Examples include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
• detergents for use in automatic dishwashing processes usually extremely low-foam compounds are used. These include preferably C 12 -C 18 -alkylpolyethylenglykol-polypropylene glycol ethers with in each case at to 8 mol ethylene oxide and propylene oxide units in the molecule.
• low-foam nonionic surfactants such as, for example, C 12 -C 18 -alkyl polyethylene glycol-polybutylene glycol ethers having in each case up to 8 mol of ethylene oxide and butylene oxide units in the molecule and end-capped alkylpolyalkylene glycol mixed ethers.
• C 12 -C 18 -alkyl polyethylene glycol-polybutylene glycol ethers having in each case up to 8 mol of ethylene oxide and butylene oxide units in the molecule and end-capped alkylpolyalkylene glycol mixed ethers.
• hydroxyl-containing alkoxylated alcohols as described in European Patent Application EP 0 300 305, so-called hydroxy mixed ethers.
• the nonionic surfactants also include alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G represents a glycose unit having 5 or 6 C atoms, preferably glucose.
• the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number-the size of which can be determined to be analytically determined-which may also be broken values-between 1 and 10; preferably x is 1.2 to 1.4.
• polyhydroxy fatty acid amides of the formula (II) in which R 1 is CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 2 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups:
• the polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
• the group of polyhydroxy fatty acid amides also includes compounds of the formula (III) in the R 3 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 4 is a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R 5 is a linear, branched or cyclic alkyl radical or a Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C 1 -C 4 alkyl or phenyl radicals are preferred, and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this group.
• [Z] is also obtained here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides according to the teaching of international patent application WO 95/07331 by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
• nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably from 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described for example in Japanese Patent Application JP 58/217598 or which are preferably prepared according to the method described in International Patent Application WO 90/13533.
• Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
• the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
• Other suitable surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups per molecule. These groups are usually separated by a so-called "spacer". This spacer is usually a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other.
• Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water.
• gemini surfactants not only such "dimer”, but also corresponding to "trimeric” surfactants understood.
• Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE 43 21 022 or dimer alcohol bis- and trimer alcohol tris sulfates and ether sulfates according to German patent application DE 195 03 061.
• End group-capped dimeric and trimeric mixed ethers according to German patent application DE 195 13 391 are characterized by their bi- and multi-functionality.
• the end-capped surfactants mentioned have good wetting properties and are low foaming, so that they are particularly suitable for use in machine washing or cleaning processes.
• gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides as described in international patent applications WO 95/19953, WO 95/19954 and WO 95/19955.
• Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups.
• surfactants of the sulfonate type are preferably C 9 -C 13 alkylbenzenesulfonates, Olefinsulfonate, that is, mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as they are, for example, from C 12 -C 18 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.
• alkanesulfonates which are obtained from C 12 -C 18 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
• esters of ⁇ -sulfo fatty acids esters of ⁇ -sulfo fatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids obtained by ⁇ -sulfonation of the methyl esters of fatty acids of plant and / or animal origin with 8 to 20 C -Atomen in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts are prepared, into consideration.
• ⁇ -sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids although sulfonated products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3 wt. %, can be present.
• ⁇ -sulfofatty acid alkyl esters are preferred which have an alkyl chain with not more than 4 C atoms in the ester group, for example, methyl ester, ethyl ester, propyl ester and butyl ester.
• the methyl esters of ⁇ -sulfo fatty acids (MES), but also their saponified disalts are used.
• Suitable anionic surfactants are sulfated fatty acid glycerol esters, which are mono-, di- and triesters and mixtures thereof, as in the preparation by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol to be obtained.
• alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
• alk (en) ylsulfates of said chain length which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
• C 12 -C 16 -alkyl sulfates and C 12 -C 15 -alkyl sulfates and C 14 -C 15 -alkyl sulfates are particularly preferred.
• 2,3-Alkyl sulfates which are prepared, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products of the Shell Oil Company under the name DAN®, are suitable anionic surfactants.
• sulfuric acid monoesters of straight-chain or branched C 7 -C 21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9 -C 11 -alcohols having on average 3.5 mol of ethylene oxide (EO) or C 12 - C 18 -fatty alcohols with 1 to 4 EO.
• EO ethylene oxide
• the preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or sulfosuccinic acid esters, and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
• alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
• Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures of these.
• Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which by themselves are nonionic surfactants.
• Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
• alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
• Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosides).
• sarcosides or the sarcosinates and here especially sarcosinates of higher and optionally monounsaturated or polyunsaturated fatty acids such as oleyl sarcosinate.
• anionic surfactants are particularly soaps into consideration.
• Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. Together with these soaps or as a substitute for soaps, it is also possible to use the known alkenylsuccinic acid salts.
• the anionic surfactants may be in the form of their sodium, Potassium or ammonium salts and as soluble salts of organic bases, such as mono-, Di- or triethanolamine.
• the anionic surfactants are in Form of their sodium or potassium salts, in particular in the form of the sodium salts.
• surfactants are present in detergents in proportions of preferably 5 wt .-% to 50 wt .-%, in particular from 8 wt .-% to 30 wt .-%, whereas Agent for cleaning hard surfaces, in particular for machine cleaning of dishes, lower surfactant contents of up to 10 wt .-%, in particular up to 5 wt .-%, and preferably in the range of 0.5 wt .-% to 3 wt .-% have.
• an agent preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.
• the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular the accessible by oxidation of polysaccharides or dextrins polycarboxylates of European Patent EP 0 625 992 or the international patent application WO 92/18542 or European Patent EP 0 232 202
• the molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 3,000 and 200,000, of the copolymers between 2,000 and 200,000, preferably 30,000 to 120,000, each based on the free acid.
• a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of from 30,000 to 100,000.
• Commercially available products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF.
• Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight.
• 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 may be a derivative of a C 4 -C 8 -dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical.
• Such polymers can be prepared in particular by methods which are described in German Patent DE 42 21 381 and German Patent Application DE 43 00 772, and generally have a molecular weight between 1,000 and 200,000. Further preferred copolymers are those which are described in the German patent applications DE 43 03 320 and DE 44 17 734 and preferably have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate.
• the organic builder substances can be used, in particular for the preparation 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 acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
• organic builders may be used in amounts up to 40 wt .-%, in particular up to 25 wt .-% and preferably from 1 wt .-% to 8 wt .-% be included. Quantities near the upper limit mentioned are preferably used in pasty or liquid, in particular hydrous, agents used.
• water-soluble inorganic builder materials are in particular alkali metal silicates, Alkaline carbonates and alkali phosphates, in the form of their alkaline, neutral or acidic Sodium or potassium salts may be present, into consideration.
• examples for this are Trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric Trisodium phosphate with degrees of oligomerization of 5 to 1000, in particular 5 to 50, and the corresponding potassium salts or mixtures of sodium and Potassium salts.
• water-insoluble, water-dispersible inorganic builder materials in particular crystalline or amorphous alkali metal aluminosilicates, in quantities of up to 50% by weight, preferably not more than 40% by weight and in particular in liquid agents from 1% by weight to 5% by weight.
• crystalline ones Detergent grade sodium aluminosilicates, in particular zeolite A, P and optionally X, alone or in mixtures, for example in the form of a co-crystallizate from the Zeolites A and X (Vegobond® AX, a commercial product of Condea Augusta S.p.A.), prefers.
• Quantities near the upper limit mentioned are preferably in solid, particulate Funds used.
• Suitable aluminosilicates have no particular Particles having a particle size greater than 30 microns and are preferably at least 80 wt .-% of particles with a size less than 10 microns.
• Your calcium binding capacity the can be determined according to the specifications of German Patent DE 24 12 837 is usually in the range of 100 to 200 mg CaO per gram.
• Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates.
• the alkali metal silicates useful as builders in the compositions 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 may be present in amorphous or crystalline form.
• Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of 1: 2 to 1: 2.8.
• crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na 2 Si x O 2x + 1 ⁇ y H are used 2 O, in which x, known as the modulus, an integer from 1 9 to 22, especially 1.9 to 4, and y is a number from 0 to 33 and preferred values for x are 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 phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
• both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O
• ⁇ -sodium disilicate can be obtained, for example, by the process described in international patent application WO 91/08171.
• ⁇ -Sodium silicates with a modulus between 1.9 and 3.2 can be prepared according to Japanese patent applications JP 04/238 809 or JP 04/260 610.
• Crystalline sodium silicates with a modulus in the range of 1.9 to 3.5, as obtainable by the processes of European patents EP 0 164 552 and / or EP 0 294 753, are used in a further preferred embodiment of such agents.
• Crystalline layer-form silicates of formula (I) given above are sold by Clariant GmbH under the trade name Na-SKS, eg Na-SKS-1 (Na 2 Si 22 O 45 .xH 2 O, Kenyaite), Na-SKS 2 (Na 2 Si 14 O 29 .xH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 .xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 .xH 2 O , Makatit).
• Na-SKS eg Na-SKS-1 (Na 2 Si 22 O 45 .xH 2 O, Kenyaite)
• Na-SKS 2 Na 2 Si 14 O 29 .xH 2 O, magadiite
• Na-SKS-5 ⁇ -Na 2 Si 2 O 5
• Na-SKS-7 ⁇ -Na 2 Si 2 O 5 , natrosilite
• Na-SKS-9 NaHSi 2 O 5 ⁇ 3H 2 O
• Na-SKS-10 NaHSi 2 O 5 ⁇ 3H 2 O, kanemite
• Na-SKS-11 t-Na 2 Si 2 O 5
• Na-SKS-13 NaHSi 2 O 5
• Na-SKS-6 ⁇ -Na 2 Si 2 O 5
• compositions within the scope of the inventive use a granular compound of crystalline phyllosilicate and citrate, of crystalline phyllosilicate and of the abovementioned (co) polymeric polycarboxylic acid, as described, for example, in German patent application DE 198 19 187, or from alkali metal silicate and alkali metal carbonate, as described, for example, in International Patent Application WO 95/22592 or as it is commercially available, for example, under the name Nabion® 15.
• Builders may be used in the compositions in the context of the use according to the invention optionally in quantities be contained up to 90 wt .-%. They are preferably in amounts of up to 75% by weight. contain.
• Detergents have in the context of the inventive use builder contents of particular 5 wt .-% to 50 wt .-% on. In means for cleaning hard Surfaces, especially for machine cleaning of dishes, the content is to builders, in particular 5 wt .-% to 88 wt .-%, wherein in such agents preferably no water-insoluble builder materials are used.
• means for particular mechanical Cleaning dishes are in the context of the use according to the invention 20 wt .-% to 40 wt .-% of water-soluble organic Builder, in particular alkali citrate, 5 wt .-% to 15 wt .-% alkali carbonate and 20 wt .-% contain up to 40 wt .-% Alkalidisilikat.
• bleach activators in particular Compounds which, under perhydrolysis conditions, are aliphatic peroxycarboxylic acids preferably 1 to 10 C-atoms, in particular 2 to 4 C-atoms, and / or optionally substituted perbenzoic acid, can be used.
• suitable Substances which contain O- and / or N-acyl groups of said C atom number and / or optionally bear substituted benzoyl groups.
• acylated Alkylenediamines especially tetraacetylethylenediamine (TAED), acylated Triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), Carboxylic anhydrides, especially phthalic anhydride, acylated polyvalent Alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and from German patent applications DE 196 16 693
• bleach activators in their place can also from sulfonimines known from European patents EP 0 446 982 and EP 0 453 003 and / or bleach-enhancing transition metal salts or Transition metal complexes may be included as so-called bleach catalysts.
• transition metal compounds include in particular those from the German patent application DE 195 29 905 known manganese, iron, cobalt, Ruthenium or molybdenum-salene complexes and their from the German Patent Application DE 196 20 267 known N-analogues, from the German Patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or Molybdenum-carbonyl complexes described in German Patent Application DE 196 05 688 described manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and Copper complexes with nitrogen-containing tripod ligands derived from the German Patent Application DE 196 20 411 discloses known cobalt, iron, copper and ruthenium-ammine complexes, those described in the German patent application DE 44 16 438 Manganese, copper and cobalt complexes described in the European patent application EP 0 272 030 described cobalt complexes described in the European patent application EP 0 693
• Bleach-enhancing active ingredient combination can be used in agents in the context of the use according to the invention used become.
• Combinations of bleach activators and transition metal bleach catalysts are for example from the German patent application DE 196 13 103 and the international patent application WO 95/27775.
• bleach-boosting Transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, in usual amounts, preferably in an amount up to 1 wt .-%, in particular from 0.0025% by weight to 0.25% by weight and more preferably from 0.01 wt .-% to 0.1 wt .-%, each based on the total agent used.
• agents additionally usable enzymes come from the class of Cutinases, pullulanases, hemicellulases, oxidases, laccases and peroxidases as well their mixtures in question.
• Particularly suitable are from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, Pseudomonas cepacia or Coprinus cinereus derived enzymatic agents.
• the enzymes can, as for example in the European patent EP 0 564 476 or in the International Patent Application WO 94/23005, adsorbed on carriers and / or embedded in encapsulating substances to prevent premature inactivation protect. They are in detergents or cleaners in the context of the use according to the invention preferably in amounts of up to 5% by weight, in particular from 0.2% by weight to 4% by weight, contain.
• water usable organic solvents include alcohols having 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 carbon atoms, in particular ethylene glycol and propylene glycol, as well as their mixtures and the derivable from the mentioned classes of compounds Ether.
• Such water-miscible solvents are in the compositions preferably in amounts not exceeding 30% by weight, in particular from 6% by weight to 20 wt .-%, present.
• the agents may be more common in detergents and cleaners Contain ingredients.
• These optional ingredients include in particular Enzyme stabilizers, grayness inhibitors, dye transfer inhibitors, foam inhibitors, and optical brighteners, as well as dyes and fragrances.
• Silver corrosion protection can be used in cleaning agents for dishes in the context of the use according to the invention Silver corrosion inhibitors are used.
• One Cleaning agent for hard surfaces can in the context of the inventive use beyond abrasive acting Ingredients, in particular from the group comprising quartz flours, wood flours, Plastic flours, chalks and glass microspheres and mixtures thereof.
• Abrasives are in the detergents in the context of the use according to the invention preferably not over 20 wt .-%, in particular from 5 wt .-% to 15 wt .-%, contain.
• non-self-evolving pH can be the means in the context of the inventive use system and environmentally friendly acids, in particular citric acid, acetic acid, tartaric acid, malic acid, Lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali hydroxides.
• Such pH regulators are in the funds in the context of the inventive use in amounts of preferably not more than 20 wt .-%, in particular of 1.2 wt .-% to 17 wt .-%, contained.
• color transfer inhibitors include polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-exide) and copolymers of Vinylpyrrolidone with vinylimidazole.
• Graying inhibitors have the task of removing the dirt removed from the textile fiber to keep suspended in the fleet.
• water-soluble colloids are usually more organic Naturally suitable, for example, starch, 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, acidic groups containing polyamides are suitable for this purpose.
• starch derivatives for example aldehyde starches.
• cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, Hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, Methylcarboxymethylcellulose and mixtures thereof, for example in amounts of 0.1 to 5 wt .-%, based on the means used.
• the detergents in the context of the use according to the invention may contain soil release polymers, which are generally composed of carboxylic acid units and optionally polymeric diol units and contain, for example, ethylene terephthalate and polyoxyethylene terephthalate groups.
• Other monomer units for example, propylene glycol, polypropylene glycol, alkylene or alkenylene dicarboxylic acids, isophthalic acid, carboxy- or sulfo-substituted phthalic acid isomers may be included in the soil release polymer.
• End-capped derivatives ie polymers which have neither free hydroxyl groups nor free carboxyl groups, but for example carry C 1-4 -alkyl groups or are terminally esterified with monobasic carboxylic acids, for example benzoic acid or sulfobenzoic acid, can be used.
• polyesters disclosed in European Patent Application EP 0 241 985 which in addition to oxyethylene groups and terephthalic acid units contain 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene groups and also glycerol units and end-capped with C 1 to C 4 alkyl groups, the soil release polymers of ethylene terephthalate and polyethylene oxide terephthalate having a molecular weight of 900 to 9000 used in the agents of European patent application EP 0 253 567, wherein the polyethylene glycol units are molecular weights from 300 to 3000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 0.6 to 0.95, from polyesters known from European Patent Application EP 0 272 033, at least partially end-capped by C 1-4 alkyl or acyl radicals propylene terephthalate and polyoxyethylene terephthalate units, the sulfoethyl end mentioned in European Patent Application EP
• polymers of ethylene terephthalate and Polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights of 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate 50:50 to 90:10 and their use in detergents in the German patent DE 28 57 292 is described, and Molecular weight polymers of from 15,000 to 50,000 ethylene terephthalate and polyethylene oxide terephthalate, wherein the polyethylene glycol units have molecular weights of 1000 to 10,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate 2: 1 to 6: 1, which can be used according to the German patent application DE 33 24 258 in detergents ,
• Textile detergents can in the context of the use according to the invention as optical brightener derivatives of Diaminostilbendisulfonklare or their alkali metal salts.
• salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid are suitable or similar compounds, instead of the morpholino group is a diethanolamino group, a methylamino group, a Anilino group or a 2-Methoxyethylaminoè wear.
• Brighteners of the type of substituted Diphenylstyryle be present, for example, the Alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) -diphenyls. Also mixtures of the aforementioned optical brighteners can be used.
• foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
• Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silicic acid or bis-fatty acid alkylenediamides. It is also advantageous to use mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes.
• the foam inhibitors in particular silicone and / or paraffin-containing foam inhibitors, are bound to a granular, water-soluble or dispersible carrier substance.
• a granular, water-soluble or dispersible carrier substance In particular, mixtures of paraffins and bistearylethylenediamide are preferred.
• suitable solid means no difficulties and can in a known manner, for example by spray-drying or granulation, where the enzymes and any other thermally sensitive ingredients such as Example bleach may be added separately later, if appropriate.
• agents of increased bulk density in particular in the range of 650 g / l to 950 g / l, is one known from the European patent EP 0 486 592, preferred method comprising an extrusion step.
• Another preferred Production by means of a granulation process is described in the European patent specification EP 0 642 576.
• compositions in tablet form single phase or multiphase, monochrome or multicolor and in particular of a layer or of can consist of several, in particular of two layers, one goes in the context of the use according to the invention preferably in such a way that all components - if necessary, each one layer - in a mixer mixed together and the mixture by means of conventional tablet presses, For example, eccentric presses or rotary presses, pressed.
• a tablet produced in this way has a weight of 10 g to 50 g, in particular from 15 g to 40 g.
• the room shape of the tablets is arbitrary and can be round, oval or angular, whereby intermediate forms are possible.
• Point round tablets preferably a diameter of 30 mm to 40 mm.
• the size of square or cuboid shaped tablets, which predominantly over the Dosing be introduced, for example, the dishwasher, is depending on the geometry and the volume of this metering device.
• exemplary preferred embodiments have a footprint of (20 to 30 mm) x (34 to 40 mm), in particular 26x36 mm or 24x38 mm.
• Liquid or pasty detergents or cleaners in Form of common solvent-containing solutions in the context of the use according to the invention usually by simple Mix the ingredients in bulk or as a solution in an automatic Mixer can be given, manufactured.

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• 1999
  • 1999-03-31 DE DE19914811A patent/DE19914811A1/de not_active Withdrawn
• 2000
  • 2000-03-22 KR KR1020017012470A patent/KR20010110474A/ko not_active Application Discontinuation
  • 2000-03-22 EP EP00920537A patent/EP1165737B1/de not_active Expired - Lifetime
  • 2000-03-22 AU AU41077/00A patent/AU4107700A/en not_active Abandoned
  • 2000-03-22 DE DE50010289T patent/DE50010289D1/de not_active Expired - Lifetime
  • 2000-03-22 JP JP2000609528A patent/JP2002541303A/ja active Pending
  • 2000-03-22 ES ES00920537T patent/ES2242613T3/es not_active Expired - Lifetime
  • 2000-03-22 WO PCT/EP2000/002534 patent/WO2000060036A2/de not_active Application Discontinuation
  • 2000-03-31 CA CA002304311A patent/CA2304311A1/en not_active Abandoned
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