EP2045317A1 - Liquid washing and cleaning agent - Google Patents

Abstract

Material mixture comprises a combination of at least one complexing agent with a complex forming constant to calcium of 3-6 with at least a calcium-binding enzyme with a calcium binding capability of at least 1 molar equivalent calcium per molar equivalent enzyme. An independent claim is included for use of the material mixture in liquid detergent or liquid cleaning agent at 10-65[deg] C.

Description

The present invention relates to compositions based on at least one complexing agent and at least one enzyme and their use in liquid detergents and liquid cleaning agents, wherein the complexing agent a complexing constant to calcium of 3 to 6 and the calcium-binding enzyme has a calcium binding capacity of at least 1 molar equivalent of calcium per molar equivalent Having enzyme.

In washing and cleaning agents, various complexing agents are used to bind the hardness of the water, especially of calcium and magnesium ions to prevent the formation of insoluble salts (deposits) and soaps (lime soaps). Known representatives of so-called organic builder substances are ethylenediamine-N, N'-disuccinate (EDDS), iminodisuccinate (IDS), hydroxyiminodisuccinate (HIDS), glycerol disuccinates, glycerol trisuccinates, ethylenediaminetetraacetic acid (EDTA) or methylglycinediacetic acid (MGDA), their derivatives or their salts with alkali metals, preferably with sodium and / or potassium. With the hardness of water, these complexing agents form so-called chelates and prevent in this way the unwanted formation of deposits and soaps.

For example, the combination of complexing agents, preferably IDS, with enzymes in liquid detergents US 2002/0004475 A1 known. WO 2005 052 108 A1 discloses a mixture of tetrasodiumiminodisuccinate and enzyme in a non-aqueous carrier component, an oil or a gel. Also US 2007/0129277 A1 discloses a dishwashing detergent formulation based on IDS, enzyme and a non-aqueous carrier component, a mineral oil.

A disadvantage of the liquid detergents based on IDS and enzyme described in the prior art is their lack of storage stability when they are formulated as liquid detergents or liquid cleaners. However, the effects of temperature and protolysis or autolysis make it difficult to use IDS and enzymes in liquid detergents and liquid cleaners.

The object of the present invention was therefore to provide complexing agent based, enzyme-containing liquid detergent or liquid detergent on the one hand withstand temperature effects, protolysis or autolysis even with prolonged storage, on the other hand, the requirements of modern detergents and cleaners, namely the unfolding of their full wash or Active cleaning effectiveness at low washing or cleaning temperatures meet.

The solution and thus the subject of the present invention is a mixture of substances which is a combination of at least one complexing agent with a complexing constant to calcium from 3 to 6, preferably from 3.1 to 5.9, more preferably from 3.5 to 5.2 with at least one calcium-binding enzyme having a calcium binding capacity of at least 1 molar equivalent of calcium per molar equivalent of enzyme, preferably from 1 to Contains 5 molar equivalent of calcium per molar equivalent of enzyme, more preferably from 1 to 3 molar equivalent of calcium per molar equivalent of enzyme. In a preferred embodiment, the substance mixture consists of the two components complexing agent and calcium-binding enzyme having a calcium binding capacity of at least 1 molar equivalent of calcium per molar equivalent of enzyme.

For clarification, it should be noted that the scope of the invention encompasses all of the following listed general or preferred definitions and parameters in any combination.

Preferred complexing agents according to the invention are IDS, HEIDA (N- (2-hydroxyethylimino-diacetic acid) -di-sodium salt) and / or EDDS, their derivatives and / or their salts with alkali metals. Particularly preferred according to the invention is IDS, its derivatives or its salts with alkali metals, in particular potassium or sodium. However, HEIDA is also particularly preferably used according to the invention.

According to the invention, the substance mixture comprising complexing agent and calcium-binding enzyme is preferably used in liquid detergents or liquid cleaners, in cleaning solutions or wash liquors at temperatures of 10 to 65 ° C., particularly preferably 15 to 40 ° C., particularly preferably 20 to 30 ° C. The aqueous cleaning solutions or wash liquors preferably have a pH of from 6 to 14, particularly preferably a pH of from 7 to 13, particularly preferably a pH of from 8 to 10.

Preferred calcium-binding enzymes in the context of the present invention having the above-defined calcium binding capacity are lipases, cellulases, proteases or alpha-amylases.

Lipases which are particularly preferred according to the invention are derived from Humicola or Pseudomonas, in particular preferably from Humicola lanuginosa ( EP-A 0 258 068 ), Humicola insolens ( WO 96/13580 ), Pseudomonas alcaligenes, Pseudomonas pseudoalcaligens ( EP-A 0 218 272 ), Pseudomonas cepacia ( EP-A 0 331 376 ), Pseudomonas stutzeri ( GB 1,372,034 ), Pseudomonas fluorescens, Pseudomonas sp strain SD 705 ( WO 95/06720 and WO 96/27002 ) or Pseudomonas wisconsinensis ( WO 96/12012 ). Especially preferred according to the invention are in particular lipases obtainable from Humicola lanuginosa or further developed with amino acid substitution D 96 h, in particular those under the trade name Lipex® (here Lipex®100) or Lumafast®.

Particularly preferred proteases according to the invention are alkaline, microbial proteases or trypsin-like proteases, very particularly preferably Bacillus subtilisin Novo, Bacillus subtilisin Carlsberg, Bacillus subtilisin 309, Bacillus. subtilisin 147, Bacillus. subtilisin 168 ( WO 89/06279 ), Fusarium proteases ( WO89 / 06270 and WO 94/25583 ), more preferably variants WO 92/19729 . WO 98/20115 . WO 98/20116 or WO 98/34946 , particularly preferably with substitutions in positions 27, 36, 57, 68, 76, 87, 97, 101, 104, 106, 120, 123, 167, 170, 194, 206, 218, 222, 224, 235, 245, 252 and 274, in particular very particularly preferably those under the trade name Polarzyme® (here Polarzyme®12), Purafect® or Properase®.

Particularly preferred alpha-amylases according to the invention are derived from Bacillus licheniformis ( GB 1,296,839 ), more preferably variants with substitutions in one or more of the positions 15, 23, 105, 106, 124, 128, 133, 154, 156, 181, 188, 190, 197, 202, 208, 209, 243, 264 , 304, 305, 391, 408 and 444. Particularly preferred are those under the trade name Stainzyme® (here Stainzyme®12) or Purastar® used.

Particularly preferred cellulases according to the invention are those of Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, very particularly preferably Humicola insolens, Myceliophthora thermophila, Fusarium oxysporum ( US 4,435,307 ; US 5,648,263 ; US 5,691,178 ; US 5,776,757 ; WO 89/09259 ). Especially preferred are variants EP 0 495 257 . EP 0 531 372 . WO 96/11262 . WO 96/29397 . WO 98/08940 . WO 94/07998 . EP 0 531 315 . US 5,457,046 . US 5,686,593 . US 5,763,254 . WO 95/24471 . WO 98/12307 and PCT / DK98 / 00299 , in particular very particularly preferably those under the trade name Celluzyme® (here Celluzyme®0.7), Genencor detergent cellulase L or IndiAge® Neutra are used.

Surprisingly, a mixture containing at least one complexing agent having a complexing constant to calcium of 3 to 6 and at least one calcium-binding enzyme having a calcium binding capacity of at least 1 molar equivalent of calcium per molar equivalent of enzyme shows excellent cleaning performance when used in cleaners or detergents, even at low washing temperatures , and allows storage of appropriate cleaning formulations in liquid form over a longer period of time without loss of activity of the enzymes brought about by temperature effects, protolysis or autolysis. Low temperatures in the sense of the present invention are the temperatures defined above, which are usually used during washing and cleaning operations.

The object of the storage stability to be solved in accordance with the invention relates to liquid washing or liquid cleaning agents which are dried under normal pressure in a temperature range from 0 to 50 ° C., preferably 10 to 35 ° C over a period of up to 90 days, preferably 70 to 90 days, stored and even have a pH of 7.5 to 10, preferably 8-9.

However, the invention also relates to liquid washing or liquid cleaning formulations containing such a mixture containing at least one complexing agent with a complexing constants to calcium of 3 to 6 with at least one calcium-binding enzyme having a calcium binding capacity of at least 1 molar equivalent of calcium per molar equivalent of enzyme from one of contain above-mentioned enzyme classes.

Particular preference is given according to the invention to liquid washing or cleaning formulations containing at least one complexing agent having a complexing constant to calcium of from 3 to 6 with at least three calcium-binding enzymes each having a calcium binding capacity of at least 1 molar equivalent of calcium per molar equivalent of enzyme from one of each contain above-mentioned enzyme classes.

Washing preparations and cleaning formulations containing at least one complexing agent with a complexing constant to calcium of 3 to 6 and four calcium-binding enzymes each having a calcium binding capacity of at least 1 molar equivalent of calcium per molar equivalent of enzyme from one of each are particularly preferred according to the invention contain four above-mentioned enzyme classes.

Particular preference is given to mixtures of substances comprising the combination of at least one complexing agent of the IDS, HEIDA or EDDS series with the calcium-binding enzymes Lipex® 100, Stainzyme® 12, Polarzyme® 12 and Celluzyme® 0.7 or those available from Novozymes A / S mentioned enzymes of the company Genencor. Especially particularly preferred according to the invention are mixtures of substances containing the combination of IDS with one or more of the abovementioned calcium-binding enzymes. Especially particularly preferred according to the invention are also mixtures of substances comprising the combination of HEIDA with one or more of the abovementioned calcium-binding enzymes or the above-mentioned enzymes from Genencor. Correspondingly preferred according to the invention are liquid detergents or cleaners containing the compositions of the invention based on the L variants of the abovementioned calcium-binding enzymes obtainable from Novozymes A / S.

In the liquid washing or liquid cleaning agents, the complexing agent with a complexing constant to calcium of 3 to 6 are preferably 0.01 to 25 wt .-%, particularly preferably 1 to 10 wt .-%. In addition to this complexing agent with a complexing constant to calcium of 3 to 6, however, other complexing agents can certainly also be used in liquid washing or liquid cleaning agents.

In the liquid washing or liquid cleaning agents, the proportion of enzymes to be used having a calcium binding capacity of at least 1 molar equivalent of calcium per molar equivalent of enzyme is preferably 0.1 to 5% by weight, particularly preferably 0.11 to 2.5% by weight. ,

In a preferred embodiment, liquid washing or liquid cleaning agents according to the invention comprise, in addition to the substance mixture, at least one complexing agent having a complexing constant to calcium of from 3 to 6 and calcium-binding enzyme having a calcium binding capacity of at least 1 molar equivalent of calcium per molar equivalent of water in quantities total agent - from preferably up to about 85 wt .-% and in particular from 40 wt .-% to 75 wt .-%, which if desired, this can also be partially exchanged for a water-soluble solvent component. Non-aqueous solvents that can be used in the liquid agents, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the specified concentration range. The solvents are preferably selected from ethanol, n- or i-propanol, the butanols, ethylene glycol, butanediol, glycerol, diethylene glycol, butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol monobutyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, -ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, diisopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures thereof. The amount of the non-aqueous water-soluble solvent component based on the total amount of the detergent and cleaner is preferably up to 15% by weight, especially 0.5% by weight to 10% by weight.

In a further preferred embodiment, the liquid washing and liquid cleaning agents may also contain surfactant, wherein anionic, nonionic, cationic and / or amphoteric surfactants can be used. Preference is given to the presence of anionic surfactants, mixtures of anionic and nonionic surfactants being particularly advantageous from an application point of view. The total surfactant content of the liquid agent is preferably in the range from 10% by weight to 60% by weight, in particular from 15% by weight to 50% by weight, in each case based on the total liquid agent.

Alcohol alkoxylates, that is to say alkoxylated alcohols, advantageously ethoxylated alcohols, in particular primary alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol are preferably used as nonionic surfactants, in which the alcohol radical is linear or preferably 2-position may be methyl-branched or may contain linear and methyl-branched radicals in the mixture, as they usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native 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, C12-14 alcohols with 3 EO, 4 EO or 7 EO, C9-11 alcohol with 7 EO, C13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C12 -18-alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-14-alcohol with 3 EO and C12-C18-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). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO units can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention. Here, block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers. It is also possible to use mixed alkoxylated nonionic surfactants in which EO and PO units are not distributed in blocks, but statistically distributed. Such products are available by the simultaneous action of ethylene and propylene oxide on fatty alcohols.

In addition, as nonionic surfactants and alkyl glycosides in particular of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which 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 between 1 and 10; preferably x is 1.2 to 1.4.

Another class of preferred nonionic surfactants to be used, either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.

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 alcohol alkoxylates, especially not more than half thereof.

Further suitable nonionic surfactants are polyhydroxy fatty acid amides of the formula (I)

R-CO-NR1- [Z] (I)

in which RCO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 1 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 known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

R-CO-N (-R 1 -O-R 2) - [Z] (II)

R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or a Oxy-alkyl radical having 1 to 8 carbon atoms, wherein C1-C4-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 radical , [Z] is preferably obtained by reductive amination of a sugar, for example 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 by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

The content of nonionic surfactants in the liquid detergents and cleaners is preferably 5 wt .-% to 30 wt .-%, in particular 7 wt .-% to 20 wt .-% and particularly preferably 9 wt .-% to 15 wt. %, in each case based on the total mean. In a preferred embodiment, the nonionic surfactant is selected from alcohol alkoxylate and alkyl polyglycoside and mixtures thereof.

As anionic surfactants, for example, those of the sulfonate type and sulfates can be used. As surfactants of the sulfonate type are preferably C9-C13-alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those of C12-C18 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.

Also suitable are alkanesulfonates which are obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also suitable are the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C12-C18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C10-C20 oxo alcohols and those half esters secondary Alcohols of these chain lengths are preferred. Also preferred are 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. From a technical point of view, C12-C16 alkyl sulfates and C12-C15 alkyl sulfates and C14-C15 alkyl sulfates are preferred. 2,3-Alkyl sulfates, which can be obtained, for example, as commercial products of the Shell Oil Company under the name DAN®, are suitable anionic surfactants.

Also the sulfuric acid monoesters of the above-mentioned alcohol alkoxylates, for example the straight-chain or branched C ₇ -C ₂₁ -alcohols ethoxylated with 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 C12-C18 fatty alcohols containing 1 to 4 EO are suitable. These are often referred to as ether sulfates.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C8-C18 fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). Again, sulfosuccinates whose fatty alcohol residues are of ethoxylated fatty alcohols with narrow homolog distribution derive, more preferably. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Preferred anionic surfactants are soaps. Suitable are saturated and unsaturated 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, olive oil or tallow fatty acids. In a preferred embodiment, the detergent contains 2 wt .-% to 20 wt .-%, in particular 3 wt .-% to 15 wt .-% and particularly preferably 5 wt .-% to 10 wt .-% fatty acid soap. Fatty acid soaps are an important ingredient for the detergency of a liquid, especially aqueous, detergent and cleaning agent. Surprisingly, it has been shown that clear and stable liquid detergents are obtained when using the low-methylated carboxymethyl cellulose ether even in the presence of high amounts of fatty acid soap. Typically, the use of high levels (≥2% by weight) of fatty acid soap in such systems results in cloudy and / or unstable products.

The anionic surfactants, including soaps, 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 preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

The content of preferred liquid detergents or cleaning agents on anionic surfactants is 5% by weight to 35% by weight, in particular 8% by weight to 30% by weight and particularly preferably 10% by weight to 25% by weight. , in each case based on the total mean. It is particularly preferred that the amount of fatty acid soap is at least 2% by weight, more preferably at least 3% by weight and in particular from 4% by weight to 10% by weight. In a further preferred embodiment, the compositions contain at least 2, in particular 3, different anionic surfactants selected from alkylbenzenesulfonate, ether sulfate and fatty acid soap.

In a further preferred embodiment, a liquid washing or liquid cleaning agent according to the invention may contain a polyacrylate acting as a co-builder or a polyaspartic acid and, if appropriate, also a thickener acting polyacrylate. The polyacrylates include polyacrylate or polymethacrylate thickeners, such as, for example, the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI name according to "International Dictionary of Cosmetic Ingredients", The Cosmetic, Toiletry and Fragrance Association (CTFA) ": carbomer), also referred to as carboxyvinyl polymers. Such polyacrylic acids are available, inter alia, from 3V Sigma under the trade name Polygel®, for example Polygel DA, and from Noveon under the trade name Carbopol®, for example Carbopol 940 4,000,000), Carbopol 941 (molecular weight about 1,250,000) or Carbopol 934 (molecular weight about 3,000,000). Furthermore, the following acrylic acid copolymers are included: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple ester, preferably formed with C ₁ -C ₄ -alkanols (INCI acrylates copolymer), to which such as the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS designation according to Chemical Abstracts Service: 25035-69-2 ) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) and which are available, for example, from Rohm & Haas under the trade names Aculyn® and Acusol® and from Degussa (Goldschmidt) under the trade name Tego® Polymer, for example, the anionic non-associative polymers Aculyn 22, Aculyn 28, Aculyn 33 (crosslinked), Acusol 810, Acusol 823 and Acusol 830 (CAS 25852-37-3); (ii) crosslinked high molecular weight acrylic acid copolymers, such as those crosslinked with an allyl ether of sucrose or pentaerythritol copolymers of C ₁₀ -C ₃₀ alkyl acrylates with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with C ₁ -C ₄ -alkanols formed esters (INCI acrylates / C ₁₀ -C ₃₀ alkyl acrylate crosspolymer) include and which are available, for example, from Noveon under the trade name Carbopol®, for example, the hydrophobized Carbopol ETD 2623 and Carbopol 1382 (INCI Acrylates / C ₁₀ -C ₃₀ alkyl acrylate crosspolymer) and Carbopol Aqua 30 (formerly Carbopol EX 473). Preferred liquid detergents contain the polyacrylate or polyaspartic acid in an amount of up to 5% by weight, in particular from 0.1% by weight to 2.5% by weight. It is advantageous if the polyacrylate is a copolymer of an unsaturated mono- or dicarboxylic acids and one or more C1-C30-alkyl esters of (meth) acrylic acid.

The viscosity of the liquid detergents and cleaning agents according to the invention can be measured by customary standard methods (for example Brookfield LVT-II viscosimeter at 20 rpm and 20 ° C., spindle 3) and is preferably in the range from 150 mPas to 5000 mPas. Preferred agents have viscosities from 500 mPas to 4000 mPas, with values from 1000 mPas to 3500 mPas being particularly preferred.

In addition, the liquid detergents and cleaners according to the invention may contain, in a further preferred embodiment, further ingredients which further improve their performance and / or aesthetic properties. In the context of the present invention, preferred agents comprise one or more substances from the group of builders, bleaches, bleach activators, enzymes, electrolytes, pH adjusters, perfumes, perfume carriers, fluorescers, dyes, hydrotropes, foam inhibitors, additional antiredeposition agents or grayness inhibitors, optical brighteners, Run-in inhibitors, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, Fungicides, antioxidants, corrosion inhibitors, antistatics, ironing aids, repellents and impregnating agents, swelling and anti-slip agents and UV absorbers.

As builders which may be contained in the liquid agents, in particular silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances may be mentioned.

Suitable crystalline layered sodium silicates have the general formula NaMSixO2x + 1 .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2.3 or 4 are. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ yH ₂ O are preferred.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays which have a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of up to a maximum of 50 nm and in particular up to a maximum of 20 nm being preferred. Such so-called X-ray amorphous silicates also have a dissolution delay compared to the conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ) sold by the company SASOL under the brand name VEGOBOND AX® · and is represented by the formula Na ₂ O. (1-n) K ₂ O · Al ₂ O ₃ · (2-2.5) SiO ₂ · (3.5-5.5) · H ₂ O with n = 0 , 90-1.0 can be described. The zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of its preparation. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C12-C18 fatty alcohols having 2 to 5 ethylene oxide groups, C12 C14-fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It is also possible to use the generally known phosphates as builders, if such use is not to be avoided for ecological reasons. Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates.

Among the compounds serving as bleaches in water H ₂ O ₂ , sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthalimino peracid or diperdodecanedioic acid. If present, they are preferably used in encased form to protect against disintegration upon storage.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below, bleach activators can be incorporated into the detergents and cleaners. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular 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, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5- diacetoxy-2,5-dihydrofuran.

In addition to or in place of the conventional bleach activators, so-called bleach catalysts can also be incorporated into the liquid laundry and liquid cleaners. These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.

Optionally in addition to the calcium-binding enzyme (s) used according to the invention having a calcium binding capacity of at least 1 molar equivalent of calcium per molar equivalent of enzyme are in particular those from the classes of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, amylases , Cellulasen or other Glykosylhydrolasen and mixtures of the mentioned enzymes in question. In contrast to the enzymes to be used according to the invention having the special calcium binding capacity, these optionally additionally employed hydrolases in the laundry contribute to the removal of stains such as protein-, fat- or starch-containing stains and graying. In addition, cellulases and other glycosyl hydrolases can contribute to color retention and to enhancing the softness of a textile by removing pilling and microfibrils. Oxide reductases can also be used for bleaching or inhibiting color transfer. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens derived enzymatic agents. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. In this case, enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferably cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof used. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

The bleach activators, catalysts and / or enzymes may be adsorbed and / or coated on carriers to protect them from premature decomposition. The proportion of these enzymes to be used in addition to the calcium-binding enzymes, enzyme liquid formulations, Enzyme mixtures or enzyme granules may be, for example, about 0.1% by weight to 5% by weight, preferably 0.12% by weight to about 2.5% by weight, based in each case on the entire liquid washing or liquid cleaning agent.

As electrolytes from the group of inorganic salts, a wide number of different salts can be used. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing point of view, the use of NaCl or MgCl ₂ in the compositions is preferred. The proportion of electrolytes in the compositions is usually not more than 8% by weight, in particular from 0.5% by weight to 5% by weight.

To bring the pH of the liquid agents within the desired range, the use of pH adjusters may be indicated. Can be used here are all known acids or alkalis, unless their use is not for technical application or environmental reasons or for reasons of consumer protection prohibited. Usually, the amount of these adjusting agents does not exceed 10% by weight of the total formulation.

A further component which may optionally also be present according to the invention in the liquid washing or liquid cleaning agents according to the invention is a hydrotrope. Preferred hydrotropes include the sulfonated hydrotropes such as the alkylarylsulfonates or alkylarylsulfonic acids. Preferred hydrotropes are selected from xylene, toluene, cumene, naphthalenesulfonate or naphthalenesulfonic acid and mixtures thereof. Counterions are preferably selected from sodium, calcium and ammonium. Optionally, the liquid agents may comprise up to 20% by weight of a hydrotrope, in particular from 0.05% to 10% by weight.

In order to improve the aesthetic impression of the liquid agents, they can be dyed in a further preferred embodiment with suitable dyes. Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to textile fibers so as not to stain them.

Suitable foam inhibitors which can be used in the liquid detergents and cleaners in a further preferred embodiment are, for example, soaps, paraffins or silicone oils which, if appropriate, may have been applied to support materials.

Suitable antiredeposition agents to be used in a further preferred embodiment of the liquid agents, which are also referred to as "soil repellents", are, for example, the polymers of phthalic acid and / or terephthalic acid known from the prior art. of their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives of these. Especially preferred of these are the sulfonated derivatives of the phthalic and terephthalic acid polymers.

Optical brighteners can be added to the liquid detergents and cleaning agents in a further preferred embodiment in order to eliminate yellowing of the treated textile fabrics. These fabrics attract and cause lightening by converting ultraviolet radiation invisible to the human eye into visible longer wavelength light, emitting the ultraviolet light absorbed from the sunlight as faint bluish fluorescence and turning the yellowish yellowed laundry to pure white. Suitable compounds are derived, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole , Benzisoxazole and benzimidazole systems as well as heterocyclic substituted pyrene derivatives. Optical brighteners are normally used in amounts of up to 0.5% by weight, in particular from 0.03% by weight to 0.3% by weight, based on the finished composition.

Since textile fabrics, in particular those made of rayon, rayon, cotton and mixtures thereof, can tend to wrinkle because the individual fibers are sensitive to bending, buckling, pressing and crushing transversely to the fiber direction, the compositions according to the invention can contain synthetic anti-crease agents in a further preferred embodiment , These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, fatty acid alkylol esters, fatty acid alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.

In order to combat microorganisms, the liquid detergents and cleaners in another preferred embodiment may contain antimicrobial agents. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate, and the compounds according to the invention can be completely dispensed with.

In order to prevent undesirable changes to the liquid detergents and cleaning agents and / or the treated textile fabrics caused by the action of oxygen and other oxidative processes, the compositions can be used in a further preferred embodiment Contains antioxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates. When using such antioxidants, the agents according to the invention are naturally free of oxidizing bleaches.

An increased wearing comfort can result from the additional use of antistatic agents, which are additionally added to the liquid detergents and cleaning agents in a further preferred embodiment. Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges. External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. External antistatic agents are, for example, lauryl (or stearyl) dimethylbenzylammonium chlorides, which are suitable as antistatic agents for textile fabrics or as an additive to detergents, in which case additionally a softening effect is achieved.

To improve the water absorbency, the rewettability of the treated fabrics and to facilitate the ironing of the treated fabrics, for example, silicone derivatives may be used in the liquid detergents and cleaners in another preferred embodiment. These additionally improve the rinsing behavior of the agents by their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. The viscosities of the preferred silicones are in the range between 100 and 100,000 mPas at 25 ° C, wherein the silicones in amounts between 0.2 and 5 wt .-%, based on the total agent can be used.

Finally, in a further preferred embodiment, the liquid detergents and cleaners may also contain UV absorbers which are applied to the treated textile fabrics and improve the light fastness of the fibers. Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. Also suitable are substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, salicylates optionally substituted by cyano groups in the 2-position, organic Ni complexes and natural substances such as umbelliferone and urocanic acid.

The liquid detergents and cleaning agents are preferably clear, that is they have no sediment and are transparent or at least translucent. The liquid detergents and cleaners without addition of a dye preferably have a transmission of the visible light (410 to 800 nm) of at least 30%, preferably at least 50% and especially preferably at least 75%.

In addition to the constituents mentioned, however, a liquid washing and cleaning agent may also contain particles dispersed therein whose diameter along their greatest spatial extent is, for example, 0.01 μm to 10,000 μm. Such particles may be microcapsules or speckles as well as granules, compounds and fragrance beads, with microcapsules or speckles being preferred.

The term "microcapsule" is understood to mean aggregates which contain at least one solid or liquid core which is enclosed by at least one continuous shell, in particular a shell of polymer (s). These are usually finely dispersed liquid or solid phases coated with film-forming polymers, during the production of which the polymers precipitate on the material to be enveloped after emulsification and coacervation or interfacial polymerization. The microscopic capsules can be dried like powder. Besides mononuclear microcapsules, multinuclear aggregates, also called microspheres, are known, which contain two or more cores distributed in the continuous shell material. Mono- or polynuclear microcapsules can also be enclosed by an additional second, third, etc., sheath. Preferred are mononuclear microcapsules with a continuous shell. The shell may be made of natural, semi-synthetic or synthetic materials. Natural shell materials are, for example, gum arabic, agar agar, agarose, maltodextrins, alginic acid or its salts, e.g. Sodium or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, lecithins, gelatin, albumin, shellac, polysaccharides such as starch or dextran, sucrose and waxes. Semisynthetic shell materials include chemically modified celluloses, especially cellulose esters and ethers, e.g. Cellulose acetate, ethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose and carboxymethylcellulose, as well as starch derivatives, in particular starch ethers and esters. Synthetic envelope materials are, for example, polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinylpyrrolidone.

Inside the microcapsule sensitive, chemically or physically incompatible as well as volatile components (= active ingredients) of the liquid agent can be trapped stable storage and transport. In the microcapsules, for example, optical brighteners, surfactants, complexing agents, bleaching agents, bleach activators, dyes and fragrances, antioxidants, builders, enzymes, enzyme stabilizers, antimicrobial agents, antiredeposition agents, pH adjusting agents, electrolytes, foam inhibitors and / or UV absorbers. In addition to the ingredients mentioned above as ingredients of the aqueous liquid compositions according to the invention, the microcapsules may contain, for example, vitamins, proteins, preservatives, detergency boosters or pearlescing agents. The fillings of the microcapsules may be solids or liquids in the form of solutions or emulsions or suspensions.

The microcapsules may have any shape in the production-related framework, but they are preferably approximately spherical. Their diameter along their largest spatial extent, depending on the components contained in their interior and the application between 0.01 microns (not visually recognizable as a capsule) and 10,000 microns. Preference is given to visible microcapsules having a diameter in the range from 100 μm to 7000 μm, in particular from 400 μm to 5000 μm. The microcapsules are accessible by methods known in the art, with coacervation and interfacial polymerization being the most important. As microcapsules, all surfactant-stable microcapsules available on the market can be used, for example the commercial products (the shell material is indicated in parentheses) Hallcrest microcapsules (gelatin, gum arabic), Coletica thalaspheres (marine collagen), Lipotec millicapsules (alginic acid, agar-agar) , Also unispheres (lactose, microcrystalline cellulose, hydroxypropyl methylcellulose); Unicerin C30 (lactose, microcrystalline cellulose, hydroxypropyl methylcellulose), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids), Softspheres (modified Agar Agar) and Kuhs Probiol Nanospheres (phospholipids).

Alternatively, it is also possible to use particles which have no core-shell structure but in which the active substance is distributed in a matrix of a matrix-forming material. Such particles are also referred to as "speckles". A preferred matrix-forming material is alginate. To produce alginate-based speckles, an aqueous alginate solution, which also contains the active substance to be enclosed or the active ingredients to be enclosed, is dripped off and then cured in a precipitation bath containing Ca 2+ ions or Al 3+ ions. It may be advantageous that the alginate-based speckles are then washed with water and then washed in an aqueous solution with a complexing agent to free Ca 2+ ions or free Al 3+ ions, which undesirable interactions with ingredients of the liquid detergent and cleaning agent, eg Fatty acid soaps, can enter, wash out. Subsequently, the alginate-based speckles are washed with water to remove excess complexing agent. Alternatively, other, matrix-forming materials can be used instead of alginate. Examples of matrix-forming materials include polyethylene glycol, polyvinylpyrrolidone, polymethacrylate, polylysine, poloxamer, polyvinyl alcohol, polyacrylic acid, polyethylene oxide, polyethoxyoxazoline, albumin, gelatin, acacia, chitosan, cellulose, dextran, ficoll®, starch, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, Hyaluronic acid, carboxymethylcellulose, deacetylated chitosan, dextran sulfate and derivatives of these materials. The matrix formation in these materials takes place for example via gelation, polyanion-polycation interactions or polyelectrolyte-metal ion interactions and is well known in the art as well as the production of particles with these matrix-forming materials. The particles can be stably dispersed in the aqueous liquid detergent and cleaner. Stable means that the compositions are stable at room temperature and at 40 ° C for a period of at least 4 weeks, and preferably at least 6 weeks, without the medium creaming or sedimenting.

The release of the active ingredients from the microcapsules or speckles is usually carried out during the application of the agents containing them by destruction of the shell or the matrix due to mechanical, thermal, chemical or enzymatic action. In a preferred embodiment of the invention, the liquid detergents contain identical or different particles in amounts of 0.01 to 10 wt .-%, in particular 0.2 to 8 wt .-% and most preferably 0.5 to 5 wt .-%.

The liquid detergents and cleaners according to the invention can be produced inexpensively and simply in customary mixing and bottling plants. For the preparation of the liquid agents, if present, the acidic components, such as, for example, the linear alkyl sulfonates, citric acid, boric acid, phosphonic acid, the fatty alcohol ether sulfates, and the nonionic surfactants are preferably initially introduced. The solvent component is preferably also added at this time, but the addition may also be made at a later time. To these components, the complexing agent to be used according to the invention and one or more of the abovementioned calcium-binding enzymes to be used according to the invention are added. Subsequently, a base such as NaOH, KOH, triethanolamine or monoethanolamine followed by a fatty acid, if present, is added. Subsequently, the remaining ingredients and optionally the remaining solvents of the aqueous liquid agent are added to the mixture and the pH is adjusted to the desired value. Finally, if desired, the particles to be dispersed can be added and distributed homogeneously in the aqueous liquid agent by mixing. This is preferably done without supplying heat energy, more preferably at temperatures in the range of 18 to 23 ° C.

However, the present invention also relates to the use of liquid detergents and cleaners according to the invention in apparatuses for the cleaning of laundry, fibers, textiles, dishes, glass and metal containers or plastic containers for the storage of Food or drinks. Suitable apparatuses are, for example, washing machines or dishwashers.

Examples

Table 1 shows the composition (ingredients in percent by weight, in each case based on the total agent) for a liquid detergent according to the invention: <b><u> Table 1 </ u></b> C ₁₁ -C ₁₂ LAS 9.5% C ₁₂ -C ₁₅ alcohol 9 EO ethoxylate 16% Fatty acid (oleic acid coconut 6: 4) 9.5% IDS-sodium salt 1-4% Polyaspartic acid Na salt 0-3% citric acid 0-6% caustic soda 0-6% Lipex® 100 L 0.25% Stainzyme® 12 L 0.25% Celluzyme® 0.7 L 0.25% Polarzyme® 12 L 0.25% pH 8-9 Water and residual components (eg salt) Rest to 100%

LAS means linear alkyl sulfonate, EO means Ethylenoxid_Einheiten in a polyglycol or an ethoxylate (reaction product of an alcohol or amine with ethylene oxide)

Table 2 shows four different non-inventive liquid formulations stabilized with subtilisin A (Subtilisin Carlsberg) without complexing agents for determining the factors which determine the stability. <b><u> Table 2 </ u></b> composition A B C D Water in% by weight 9.0 19.1 18.8 18.8 Formate (mol / kg) - - 0.48 0.52 Calcium (wt%) 0.01 0.059 0,068 0.1 Activity AU * / g 2.81 2.93 2.78 2.85 RA in% after 1 wk 89 96 97 99 RA in% after 2 weeks 87 95 97 98 RA in% after 3 weeks 79 94 95 97 RA in% after 4 weeks 76 91 94 95 RA in% after 6 weeks 67 85 92 93 RA in% after 8 weeks 64 82 90 94 RA in% after 10 weeks 61 80 89 93

As shown in Table 2, calcium plays a crucial role; Formate can still support the effect. Formulation D without formate served as the basis for the experiments with the corresponding complexing agents (see Table 3).

Table 3 shows, as a consequence of Tebelle 2, the combination of various complexing agents according to the invention as a substance mixture with a calcium-binding protease according to the invention, in this case subtilisin, from which the complexing agents to be used according to the invention are distinguished by their particular stability. <b><u> Table 3 </ u></b> composition IDS EDDS EDTA MGDA Water in% by weight 18.8 18.8 18.8 18.8 Complexing agent in% by weight 1 1 1 1 Calcium in% by weight 0.1 0.1 0.1 0.1 buffer 0.5 0.5 0.5 0.5 pH 6.4 6.4 6.4 6.4 Activity, AU * / g 2.85 2.85 2.85 2.85 RA in% after 1 wk 97 97 70 90 RA in% after 2 weeks 97 95 49 82 RA in% after 3 weeks 95 93 37 77 RA in% after 4 weeks 94 93 30 73 RA in% after 6 weeks 92 89 18 70 RA in% after 8 weeks 90 87 10 68 RA in% after 10 weeks 86 85 2 65

In Tables 2 and 3, AU stands for Anson Unit, RA for residual activity and Wo for week (s). An Anson Unit is defined as the amount of enzyme that degrades urea-denatured hemoglobin under standardized conditions to give an amount of TCA-soluble product per minute that gives the same color with folin-ciocalteu-phenol as 1 milliequivalent of tyrosine at 25 ° C and pH 7.5. (TCA = trichloroacetic acid).

Claims (13)

A mixture of substances, characterized in that it contains a combination of at least one complexing agent with a complexing constant to calcium of 3 to 6 with at least one calcium-binding enzyme having a calcium binding capacity of at least 1 molar equivalent of calcium per molar equivalent of enzyme. Mixture of substances according to Claim 1, characterized in that the complexing agents used are IDS, EDDS or HEIDA, their derivatives and / or their salts with alkali metals. Mixture of substances according to one of claims 1 or 2, characterized in that as complexing agent IDS, its derivatives or its salts with alkali metals, in particular potassium and sodium is used. Mixture of substances according to one of claims 1 or 2, characterized in that is used as a complexing agent HEIDA. Mixtures of substances according to one of claims 1 to 4, characterized in that as calcium-binding enzyme lipases, cellulases, proteases or alpha-amylases are used. Substance mixtures according to Claim 5, characterized in that lipases from Humicola or Pseudomonas, preferably from Humicola lanuginosa, Humicola insolens, Pseudomonas alcaligenes, Pseudomonas pseudoalcaligens, Pseudomonas cepacia, Pseudomonas stutzeri, Pseudomonas fluorescens, Pseudomonas sp strain SD 705 or Pseudomonas wisconsinensis are used. Substance mixtures according to claim 5, characterized in that as proteases alkaline, microbial proteases or trypsin-like proteases, preferably from Bacillus subtilisin Novo, Bacillus subtilisin Carlsberg, Bacillus subtilisin 309, B. subtilisin 147, B. subtilisin 168, Fusarium proteases are used. Substance mixtures according to claim 5, characterized in that Bacillus licheniformis alpha-amylases preferably of variants with substitutions in one or more of the positions 15, 23, 105, 106, 124, 128, 133, 154, 156, 181, 188, 190, 197, 202, 208, 209, 243, 264, 304, 305, 391, 408 and 444 are used. Substance mixtures according to Claim 5, characterized in that cellulases from Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, preferably from Humicola insolens, Myceliophthora thermophila, Fusarium oxysporum are used. Use of the mixtures according to Claims 1 to 9 in liquid detergents or liquid cleaners, preferably at temperatures of 10 to 65 ° C. Use of the mixtures according to claim 10, characterized in that the aqueous cleaning solutions or wash liquors, in which the liquid detergents or liquid cleaning agents are used, have a pH of 6 to 14. Agent, preferably liquid detergent or liquid cleaning agent, containing a mixture of substances containing a combination of a complexing agent with a complexing constant to calcium of 3 to 6 with at least one calcium-binding enzyme having a calcium binding capacity of at least 1 molar equivalent of calcium per molar equivalent of enzyme. Use of the liquid detergents or liquid cleaners according to claim 12 in apparatuses for the cleaning of laundry, fibers, textiles, dishes, glass and metal containers or plastic containers for the storage of food or drinks.