EP1084223A1

EP1084223A1 - Detergents containing amylase and transition metal compound activating bleaching

Info

Publication number: EP1084223A1
Application number: EP99927752A
Authority: EP
Inventors: Horst-Dieter Speckmann; Beatrix Kottwitz; Christian Nitsch; Karl-Heinz Maurer; Helmut Blum; Lars Züchner
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1998-06-03
Filing date: 1999-05-25
Publication date: 2001-03-21
Anticipated expiration: 2019-05-25
Also published as: EP1084223B1; JP2002517556A; ATE225393T1; DE19824704A1; HUP0102182A2; WO1999063041A1; PL344591A1; DE59902952D1

Abstract

The invention aims at improving the cleaning performance of detergents containing enzymes, especially in relation to starch-containing and dyed stains. This is substantially achieved in that the detergent contains α-amylase from Bacillus amyloliquefaciens and a transition metal compound activating bleaching, in addition to other usual ingredients compatible with said constituents.

Description

Amylase and bleach activating transition metal compound containing washing and

cleaning supplies

The present invention relates to enzyme-containing detergents and cleaning agents which, in addition to conventional constituents, contain an amylase from Bacillus amylollquefaciens and certain bleach-activating active ingredients.

In addition to the ingredients that are indispensable for the washing process, such as surfactants and builder materials, detergents generally contain further constituents, which can be summarized under the term washing aids and which comprise such different active ingredient groups as foam regulators, graying inhibitors, bleaching agents, bleach activators and color transfer inhibitors. Such auxiliaries also include substances which support the surfactant performance through the enzymatic degradation of soiling on the textile. The same applies analogously to cleaning agents for hard surfaces. In addition to the proteases that support protein removal and the fat-cleaving lipases, amylases are of particular importance. Amylases have the task of facilitating the removal of starchy soiling by the catalytic hydrolysis of the starch polysaccharide and for this purpose have been used for a long time in detergents for dishes, but also in detergents for use in textile washing. For the most part, it was previously a thermostable amylase from Bacillus licheniformis, which is commercially available, for example, under the name Termamyl®. More recently, such agents have increasingly used genetically modified amylases, that is to say with amino acid sequences modified in comparison to naturally occurring amylases with the aid of genetic engineering methods. In addition to increasing their performance, the genetic modification of amylases essentially aims to increase the stability of the enzyme, in particular against the attack of oxidizing agents. An approach to achieve this goal, which is proposed in international patent application WO 94/18314 suggests, the removal of amino acids particularly susceptible to oxidation, such as methionine, tryptophan, cysteine or tyrosine, consists of the amino acid sequence of the amylase, or its replacement by other amino acids which are more stable to oxidation. A similar procedure is also proposed in international patent application WO 95/21247, which recommends that at least one methionine in the amylase amino acid sequence be replaced by an amino acid which is neither methionine nor cysteine.

Although such genetic modifications can lead to improved amylase stability under certain application conditions, they do not contribute to increasing the contribution of the amylase to the washing or cleaning performance of corresponding agents in which the amylase is contained.

Surprisingly, it has now been found that the combination of a naturally occurring α-amylase with certain bleach-activating agents leads to unexpected synergistic performance improvements when used in detergents or cleaning agents.

The invention therefore relates to an amylase-containing washing or cleaning agent which contains .alpha.-amylase from Bacillus amylollquefaciens and a bleach-enhancing transition metal complex compound in addition to conventional ingredients which are compatible with such constituents.

Another object of the invention is the use of a corresponding combination to increase the cleaning performance of detergents and cleaning agents, in particular compared to starchy and / or colored, in particular tea-based soiling, when used in aqueous washing and cleaning solutions, in particular, which contain a peroxygen compound. The cleaning performance in relation to colored soiling is to be understood in its broadest meaning and includes both the bleaching of dirt on the textile, the bleaching of dirt in the wash liquor, detached from the textile, and the oxidative destruction of textile colors in the wash liquor that detach from textiles under the washing conditions before they can be drawn onto textiles of a different color. Also when used in cleaning solutions for hard surfaces this term means both the bleaching of dirt located on the hard surface, in particular tea, and the bleaching of dirt located in the dishwashing liquor and detached from the hard surface.

α-Amylase from Bacillus amylollquefaciens has long been known, for example from US Pat. No. 1,227,374. For example, it is commercially available under the name Amylase BAN®.

An agent according to the invention preferably contains 0.001 mg to 0.5 mg, in particular 0.02 mg to 0.3 mg, of amylolytic protein per gram of the total agent. The protein concentration can be determined using 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).

The bleach-enhancing transition metal complex is preferably made from the complex compounds of Mn. Fe, Co, Cu, Mo, V, Ti or Ru or their mixtures selected. The bleach-strengthening transition metal complex compounds which are possible include in particular the manganese, iron, cobalt, ruthenium or molybdenum-salt complexes known from international patent application WO 97/07192 and their N-analog compounds known from international patent application WO 97/44430 , the manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes known from German patent application DE 195 36 082, the manganese, iron, cobalt, ruthenium, molybdenum described in international patent application WO 97/30144 -, Titanium, Vanadium and copper complexes with nitrogenous tripod ligands, which from the international

Patent application WO 97/36988 known cobalt, iron, copper and ruthenium amine complexes, the complexes described in German patent applications DE 197 57 918 and DE 198 09 713 with dendrimer ligands, which are described in German patent application DE 44 16 438 Manganese, copper and cobalt complexes, the cobalt complexes described in European patent application EP 0 272 030, the manganese complexes known from European patent application EP 0 693 550, the manganese known from European patent EP 0 392 592 , Iron, cobalt and copper complexes, the cobalt complexes known from international patent applications WO 96/23859, WO 96/23860 and WO 96/23861 and / or those described in European patent specification EP 0 443 651 or European patent applications EP 0 458 397, EP 0 458 398, EP 0 549 271, EP 0 549 272, EP 0 544 490 and EP 0 544 519 described manganese complexes. Bleach-activating transition metal complex compounds are preferably used in an amount of up to 1% by weight, in particular from 0.001% by weight to 0.25% by weight and particularly preferably from 0.015% by weight to 0.1% by weight. each based on transition metal, used in agents according to the invention.

The bleach-enhancing transition metal complex compound is preferably composed of the compounds of the general formula I

[M (NH ₃ ) _6-x-2y Lχ (L ² ) _y ] A _n (I) in which M is a transition metal selected from cobalt, iron, copper and ruthenium, L is a bonded via a coordination point and L is a ligand bound via two coordination sites, x is a number from 0 to 5, y is a number from 0 to 2 with the proviso that x + 2y is at most 5, A is a salt-forming anion and n is a number of size. that the compound of the formula (I) has no charge, or from complex compounds of the general formula (II),

X

in the

UM stands for manganese, iron, cobalt, ruthenium or molybdenum,

R represents an alkylene, alkenylene, phenylene or cycloalkylene radical which, in addition to the substituent X, can optionally be alkyl and / or aryl-substituted, with a total of 1 to 12 carbon atoms, where within R the shortest distance between the N atoms complexing with UM is 1 to 5 C atoms,

X represents -H, -OR ³ , -NO ₂ , -F, -Cl, -Br or -J,

R ¹ , R ² and R ³ independently of one another represent hydrogen or an alkyl radical having 1 to 4 carbon atoms,

Y ¹ and Y ² independently of one another represent hydrogen or an electron-shifting substituent, where Y ¹ and Y ^{2 are} not simultaneously hydrogen if R is alkylene or cyclohexlyene,

Z ¹ and Z ² independently of one another represent hydrogen, -CO ₂ M, -SO M or -NO ₂ ,

M represents hydrogen or an alkali metal such as lithium, sodium or

Potassium stands and

A stands for a charge-balancing anion ligand, or complexes of the transition metals manganese, iron, cobalt, ruthenium, molybdenum,

Titanium, vanadium and / or copper, the one or more of the ligands III

- R

(HI)

in which R is a direct bond or an optionally amino-substituted alkylene group having 1 to 4 carbon atoms, A represents a condensed or uncondensed ring system which contains at least one nitrogen atom, and B is hydrogen, an OH group or A, or have the general formula IV

R "-"

I (IV)

S /

in which A and R have the meaning given for formula III and X is an optionally hydroxy- and / or C _-4 alkyl-substituted phenylene ring or an optionally hydroxy-substituted C _M alkylene group. In a preferred embodiment of agents according to the invention, the transition metal complex compound has O

at least one optionally N-alkylated triazacyclononane ligand. A further preferred embodiment of agents according to the invention contains the bleach-enhancing transition metal complex compound in the form of a combination of active ingredients, which by intimately mixing a water-soluble salt of a divalent transition metal selected from cobalt, iron, copper and ruthenium and their mixtures, a water-soluble ammonium salt and optionally an oxidizing agent based on peroxygen and inert carrier material is available and has been described in European patent application EP 0 832 969.

The detergents and cleaning agents according to the invention, which can be present in particular as powdery solids, in post-compacted particle form, as homogeneous solutions or suspensions, can, in addition to the active ingredient combination used according to the invention, in principle contain all known ingredients which are customary in such agents. The agents according to the invention can include, in particular, builder substances, surface-active surfactants, 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 further auxiliaries, such as optical brighteners, graying inhibitors, color transfer inhibitors , Foam regulators, silver corrosion inhibitors and dyes and fragrances.

The agents according to the invention can contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.

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 part and 3 to 20, preferably 4 to 10, alkyl ether groups. Corresponding ethoxylation and / or propoxylation products of N-alkyl amines, vicinal diols, fatty acid esters and fatty acid amides, which correspond to the long-chain alcohol derivatives mentioned with regard to the alkyl part, and also of alkyl phenols with 5 to 12 carbon atoms in the alkyl radical, can be used. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular 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 in which the alcohol radical has a methyl or linear branching in the 2-position may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, -C ₂ -C ₄ alcohols with 3 EO or 4 EO, C ₉ -C ₄ alcohols with 7 EO, C ₁₃ - C, ₅ alcohols with 3 EO. 5 EO, 7 EO or 8 EO, C ₁₂ -C1 »alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Cι ₂ -Cι ₄ - alcohol with 3 EO and C ₁₂ - Cι ₈ - Alcohol with 7 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. 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 can also be used. Examples of these are (tallow) fatty alcohols with 14 EO. 16 EO, 20 EO, 25 EO, 30 EO or 40 EO. Extremely low-foaming compounds are usually used in particular in cleaning agents for use in machine dishwashing processes. These preferably include Ci ₂ -C ₈ alkyl polyethylene glycol polypropylene glycol ethers, each with up to 8 moles of ethylene oxide and propylene oxide units in the molecule. However, it is also possible to use other known low-foam nonionic surfactants, such as, for example, C ₁₂ -C ₁₈ -alkylpolyethylene glycol-polybutylene glycol ether, each with up to 8 moles of ethylene oxide and butylene oxide units in the molecule, and also end-capped alkylpolyalkylene-glycol mixed ethers. Also particularly preferred are the 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 methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, and G stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The Degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which as an analytically determinable variable can also take fractional values - between 1 and 10; x is preferably 1.2 to 1.4. Also suitable are polyhydroxy fatty acid amides of the formula (V) in which R * CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R for hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical 3 to 10 carbon atoms and 3 to 10 hydroxyl groups:

R ^l

R'-CO-N- [Z] (V)

The polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose. The group of polyhydroxy fatty acid amides also includes compounds of the formula (VI)

R ⁴ -OR ⁵

! (VI)

R ³ -CO-N- [Z]

in which R ^{3 represents} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{4 represents} a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R ^{5 represents} a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -C ₄ -alkyl or phenyl radicals being preferred, and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this residue. [Z] is also preferably obtained here by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example, according to the teaching of international patent application WO 95/07331, by reaction with fatty acid methyl esters in counterparts. were an alkoxide as a catalyst in the desired polyhydroxy fatty acid amides. Another class of preferably used nonionic surfactants, which are 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 with 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 by the process described in international patent application WO 90/13533. Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them. So-called gemini surfactants can be considered as further surfactants. These are generally understood to mean those compounds which have two hydrophilic groups per molecule. These groups are generally separated from one another by a so-called “spacer”. This spacer is generally a carbon chain which should be long enough that the hydrophilic groups are sufficiently far apart that they can act independently of one another. Such surfactants are distinguished generally by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, the term gemini surfactants is understood not only to mean “dimeric” in this way, but also correspondingly “trimeric” surfactants. Surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE 43 21 022 or dimer alcohol bis- and trimeral alcohol tris-sulfates and ether sulfates according to German patent application DE 195 03 061. End group-blocked dimer and trimeric mixed ethers according to German patent application DE 195 13 391 itself i n especially by their bi- and multifunctionality. 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 can also be used. 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. Preferred surfactants of the sulfonate type are C ₁ -C ₁₃ -alkylbenzenesulfonates, olefin sulfonates. that is, mixtures of alkene and hydroxyalkanesulfonates and disulfonates as obtained, for example, from C ₂ -C ₁₈ monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C ₂ -C ₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also suitable are the esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, which have from 8 to by α-sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin 20 carbon atoms in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts are considered. These are preferably the α-sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids, with sulfonation products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3% by weight. %, can be present. In particular, α-sulfofatty acid alkyl esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters. The methyl esters of α-sulfofatty acids (MES), but also their saponified disalts, are used with particular advantage. Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters as well as their mixtures, such as those produced 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 be preserved. As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid half esters of the C ₂ -C ₁ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C ₁₀ -C ₂ o-oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. Cj ₂ -C ₁₆ alkyl sulfates and C ₁ d ₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are particularly preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN®, are also suitable anionic surfactants. Also suitable are the sulfuric acid monoesters of the straight-chain or branched C -C ₂ ι- alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C -Cn alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 1 -C 8 fatty alcohols with 1 to 4 EO. The preferred anionic surfactants also include 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 especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ -C ₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which are nonionic surfactants in themselves. Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof. Fatty acid derivatives of amino acids, for example of N-methyl taurine (taurides) and / or of N-methyl glycine (sarcosides) are suitable as further anionic surfactants. The sarcosides or sarcosinates, and in particular sarcosinates of higher and optionally mono- or polyunsaturated fatty acids such as oleyl sarcosinate, are particularly preferred. Soaps are particularly suitable as further anionic surfactants. Saturated fatty acid soaps are particularly suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, for example coconut, Palm kernel or tallow fatty acids, derived soap mixtures. The known alkenyl succinic acid salts can also be used together with these soaps or as a substitute for soaps.

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

Surfactants are present in detergents according to the invention in proportions of preferably 5% by weight to 50% by weight, in particular 8% by weight to 30% by weight, whereas agents for cleaning hard surfaces, in particular for machine cleaning of dishes , have lower surfactant contents of up to 10% by weight, in particular up to 5% by weight and preferably in the range from 0.5% by weight to 3% by weight.

An agent according to the invention 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 as well as polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonethoxyphosphonic acid) ethylenediaminethoxy (ethylenediamine) ethylenediaminethoxy (ethylenediamine) ethylenediaminethoxy (ethylenediamine) ethylenediaminethoxy (1) ethylenediamine (1) , 1 -diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular the polycarboxylates of European patent EP 0 625 992 or of international patent application WO 92/18542 or of European patent EP 0 232, which are accessible by oxidation of polysaccharides or dextrins 202, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which also copolymerize small amounts of polymerizable substances without carboxylic acid functionality can contain. The relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 3,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 30,000 to 120,000, in each case based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular measures from 30,000 to 100,000. Commercial products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight. Terpolymers can also be used as water-soluble organic builder substances which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ carboxylic acid and preferably from a C -C ₄ monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C -C ₈ dicarboxylic acid, 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. Polymers of this type can be produced in particular by processes which are described in German patent specification DE 42 21 381 and German patent application DE 43 00 772 and generally have a relative molecular weight of between 1,000 and 200,000. Further preferred copolymers are those which are described in German patent applications DE 43 03 320 and DE 44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers. The organic builder substances can be used, in particular for the production of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

Such organic builder substances can, if desired, be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Amounts close to the upper limit mentioned are preferably used in paste-like or liquid, in particular water-containing agents according to the invention.

In particular, alkali silicates, alkali carbonates and alkali phosphates come in the form of their alkaline, neutral or acidic as water-soluble inorganic builder materials Sodium or potassium salts can be considered. Examples of 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. In particular, crystalline or amorphous alkali alumosilicates are used as water-insoluble, water-dispersible inorganic builder materials, in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid compositions in particular from 1% by weight to 5% by weight. %, used. Among them, the crystalline sodium aluminosilicates in detergent quality, 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 SpA), are preferred . Quantities close to the upper limit mentioned are preferably used in solid, particulate compositions. Suitable aluminosilicates in particular have no particles with a grain size above 30 μm and preferably consist of at least 80% by weight of particles with a size below 10 μm. Their calcium binding capacity, which can be determined according to the information in German patent DE 24 12 837, is generally in the range from 100 to 200 mg CaO per gram.

Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates. The alkali silicates which can be used as builders in the agents according to the invention preferably have a molar ratio of alkali oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na ₂ O: SiO ₂ molar ratio of 1: 2 to 1: 2.8. Those with a Na ₂ O: SiO molar ratio of 1: 1.9 to 1: 2.8 can be produced by the process of European patent application EP 0 425 427. Crystalline sheet silicates of the general formula Na ₂ Si _x O _2x + ι y HO, in which x, the so-called modulus, is a number from 1.9 to 22, are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates , in particular 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 that fall under this general formula are described, for example, in European patent application EP 0 164 514. Preferred crystalline layered silicates are those in which x assumes the values 2 or 3 in the general formula mentioned. In particular, both β- and δ-sodium disilicate (Na ₂ Si ₂ O ₅ y H ₂ O) are preferred, with β-sodium disilicate being able to be obtained, for example, by the method described in international patent application WO 91/08171. δ- 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. Practically anhydrous crystalline alkali silicates of the above general formula, in which x denotes a number from 1.9 to 2.1, can also be prepared from amorphous alkali silicates, as in European patent applications EP 0 548 599, EP 0 502 325 and EP 0 452 428 described, can be used in agents according to the invention. In a further preferred embodiment of agents according to the invention, a crystalline layered sodium silicate with a modulus of 2 to 3 is used, as can be produced from sand and soda by the process of European patent application EP 0 436 835. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5, as can be obtained by the processes of European patent EP 0 164 552 and / or EP 0 294 753, are used in a further preferred embodiment of agents according to the invention. Crystalline layered silicates of the formula (I) given above are sold by Clariant GmbH under the trade name Na-SKS, for example Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ xH ₂ O, Kenyait), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ xH ₂ 0, magadiite), Na-SKS-3 (Na ₂ Si ₈ Oι ₇ xH ₂ O) or Na-SKS-4 (Na Si ₄ O ₉ xH ₂ O, makatite). Of these, Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O ₅ , natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ ) are particularly suitable 3H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ 3H ₂ O, Kanemit), Na-SKS-11 (t-Na ₂ Si ₂ O ₅ ) and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (δ-Na Si ₂ O ₅ ). An overview of crystalline layered silicates is given, for example, in "Hoechst High Chem Magazine 14/1993" on pages 33 - 38 and in "Soap-oil-fat-waxes, 116 year, No. 20/1990" on pages 805 - 808 published articles. In a preferred embodiment of agents according to the invention, a granular compound composed of crystalline layered silicate and citrate, of crystalline layered silicate and the (co) polymeric polycarboxylic acid mentioned above is used, as described, for example, in German patent application DE 198 19 187 or from alkali silicate and alkali 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.

Builder substances can optionally be present in the agents according to the invention in amounts of up to 90% by weight. They are preferably contained in amounts of up to 75% by weight. Detergents according to the invention have builder contents of in particular 5% by weight to 50% by weight. In agents according to the invention for cleaning hard surfaces, in particular for machine cleaning of dishes, the builder substance content is in particular 5% by weight to 88% by weight, with such agents preferably not using any water-insoluble builder materials. In a preferred embodiment, agents according to the invention for in particular machine cleaning of dishes are 20% by weight to 40% by weight of water-soluble organic builders, in particular alkali metal citrate. Contain 5 wt .-% to 15 wt .-% alkali carbonate and 20 wt .-% to 40 wt .-% alkali disilicate.

Suitable peroxygen compounds for use in agents according to the invention are, in particular, organic peracids or peracidic salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which give off hydrogen peroxide under the washing conditions, including perborate, percarbonate, persilicate and / or Persulfate such as caroate should be considered. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be coated in a manner known in principle. If an agent according to the invention contains peroxygen compounds, these are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight. The addition of small amounts of known bleach stabilizers such as, for example, phosphonates, borates or metaborates and metasilicates, and magnesium salts such as magnesium sulfate may be useful.

In addition to the bleach-activating transition metal complex compound, compounds which split off peroxocarboxylic acid, so-called bleach activators, can be used under perhydrolysis conditions. Combinations of bleach activators and Transition metal bleaching catalysts are known, for example, from international patent applications WO 97/36987 and WO 95/27775. Bleach activators which can be used are, in particular, compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic 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 number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are multiply acylated 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, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetyloxy, 2,5-acetiacetyl, ethylene glycol 2,5-dihydrofuran and the enol esters known from German patent applications DE 196 16 693 and DE 196 16 767 as well as acetylated sorbitol and mannitol or their mixtures described in European patent application EP 0 525 239 (SORMAN), acylated sugar derivatives, in particular pentaacetyl glucose (PAG ), Pentaacetylfruktose, Tetraacetylxylose and Octaacetyllactose as well as acetylated, optionally N-alkylie Red glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam. which are known from international patent applications WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95/14759 and WO 95/17498. The hydrophilically substituted acylacetals known from German patent application DE 196 16 769 and the acyl lactams described in German patent application DE 196 16 770 and international patent application WO 95/14075 are also preferably used. The combinations of conventional bleach activators known from German patent application DE 44 43 177 can also be used. Bleach activators of this type can be present in the customary quantitative range, preferably in amounts of 0.5% by weight to 10% by weight, in particular 1% by weight to 8% by weight, based on the total agent. In addition to the conventional bleach activators or in their place, those from the European patent specifications EP 0446 982 and EP 0 453 003 known sulfonimines may be included.

Enzymes which can be used in the compositions in addition to the amylase essential to the invention are those from the class of proteases, lipases, cutinases, pullulanases, hemicellulases, cellulases, oxidases, laccases and peroxidases and mixtures thereof. If appropriate, amylase other than the essential to the invention may also be present in addition to this. Enzymes obtained 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 are particularly suitable. The amylase essential to the invention and the optionally additionally used enzymes can, as described for example in European patent EP 0 564 476 or in international patent application WO 94/23005, be adsorbed on carriers and / or be embedded in coating substances in order to prevent them from being inactivated prematurely protect. They are contained in the washing or cleaning agents according to the invention preferably in amounts of up to 5% by weight, in particular from 0.2% by weight to 4% by weight. If the agent according to the invention contains protease, it preferably has a proteolytic activity in the range from about 100 PE / g to about 100 OOO PE / g, in particular 300 PE / g to 8000 PE / g. If several enzymes are to be used in the agent according to the invention, this can be done by incorporating the two or more separate or, in a known manner, separately assembled enzymes or by two or more enzymes assembled together in a granulate, as for example from international patent applications WO 96/00772 or WO 96/00773 known.

The organic solvents which can be used in the agents according to the invention, in particular if they are in liquid or pasty form, in addition to water include alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms -Atoms, especially ethylene glycol and propylene glycol, as well as their mixtures and the ethers derivable from the compound classes mentioned. Such water-miscible solvents are in the agents according to the invention preferably in amounts not exceeding 30% by weight, in particular from 6% by weight to 20% by weight.

In addition, the agents can contain further constituents customary in washing and cleaning agents. These optional components include, in particular, enzyme stabilizers, graying inhibitors, color transfer inhibitors, foam inhibitors, and optical brighteners, and colorants and fragrances. In order to provide silver corrosion protection, silver corrosion inhibitors can be used in dishwashing detergents according to the invention. A cleaning agent according to the invention for hard surfaces can also contain abrasive components, in particular from the group comprising quartz flours, wood flours, plastic flours, chalks and micro-glass balls and mixtures thereof. Abrasives are preferably not contained in the cleaning agents according to the invention in excess of 20% by weight, in particular from 5% by weight to 15% by weight.

To set a desired pH value which does not result from the mixture of the other components, the agents according to the invention can contain system and environmentally compatible 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 contain mineral acids, especially sulfuric acid, or bases, especially ammonium or alkali hydroxides. Such pH regulators are contained in the agents according to the invention in amounts of preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.

The color transfer inhibitors which are suitable for use in textile detergents according to the invention include, in particular, polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole.

Graying inhibitors have the task of keeping the dirt detached from the textile fibers suspended in the liquor. For this purpose, water-soluble colloids of mostly organic nature are suitable, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic ones Sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Starch derivatives other than those mentioned above can also be used, for example aldehyde starches. Cellulose ethers, such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, for example in amounts of 0.1 to 5% by weight, based on the agent, are preferably used .

Textile detergents according to the invention can contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-mo holino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which are used instead of Morpholino group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type can also 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) diphenyl. Mixtures of the aforementioned optical brighteners can also be used.

In particular when used in machine processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable 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-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and also paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bisfatty acid alkyl diamides. Mixtures of different foam inhibitors are also used with advantages, for example those made of silicone, paraffins or waxes. The foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamide are particularly preferred. The preparation of solid agents according to the invention is not difficult and can be carried out in a known manner, for example by spray drying or granulation, the enzymes and any further thermally sensitive ingredients, such as bleaching agents, optionally being added separately later. For the production of agents according to the invention with increased bulk density, in particular in the range from 650 g / 1 to 950 g / 1, a process known from European patent EP 0 486 592 and having an extrusion step is preferred. A further preferred production using a granulation process is described in European patent EP 0 642 576.

For the preparation of agents according to the invention in tablet form, which can consist of one or more phases, of one color or of more than one color and in particular of one layer or of more than one, in particular of two layers, the procedure is preferably such that all constituents - optionally one layer each - are combined in one Mixer mixed together and the mixture by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressing forces in the range from about 50 to 100 kN. preferably pressed at 60 to 70 kN. In the case of multi-layer tablets in particular, it can be advantageous if at least one layer is pre-compressed. This is preferably carried out at press forces between 5 and 20 kN, in particular at 10 to 15 kN. In this way, break-resistant tablets, which nevertheless dissolve sufficiently quickly under application conditions, are obtained with breaking and bending strengths of normally 100 to 200 N, but preferably over 150 N. A tablet produced in this way preferably has a weight of 10 g to 50 g, in particular 15 g up to 40 g. The shape of the tablets is arbitrary and can be round, oval or angular, intermediate forms are also possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm. In particular, the size of angular or cuboid tablets, which are mainly introduced via the metering device, for example the dishwasher, depends on the geometry and the volume of this metering device. Exemplary preferred embodiments have a base area of (20 to 30 mm) x (34 to 40 mm), in particular of 26x36 mm or of 24x38 mm. Liquid or pasty washing or cleaning agents according to the invention in the form of solutions containing customary solvents are generally produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.

Examples

example 1

A cleaning agent (VI) for the automatic cleaning of dishes, containing 55% by weight sodium tripolyphosphate (calculated as anhydrous), 4% by weight amorphous sodium disilicate (calculated as anhydrous), 22% by weight sodium carbonate, 9% by weight Sodium perborate, 2% by weight of TAED, 2% by weight of nonionic surfactant and 2% by weight of amylase granules (Termamyl® 60T) and 1.4% by weight of a protease granulate (activity 200,000 PU / g) with the Bacillus lentus protease (remainder to 100% by weight of water, perfume and dye), an agent V2 which was otherwise composed like VI, but additionally contained so much of a Co-containing active ingredient combination according to EP 0 832 969 that the Co Content was 100 ppm, and agents according to the invention (Ml or M2), which were otherwise composed as VI, but instead of Termamyl® protein-identical amounts of amylase from Bacillus amylollquefaciens and additionally as much of a Co-containing combination of active ingredients according to EP 0 832,969 contained that the Co content at 50 ppm or 100 ppm were tested as follows:

6 plates with standardized starch stains or bleachable stains were washed in a Miele® G 575 dishwasher (doses of 20 g each of the agent to be tested in the universal program, water hardness 14-16 ° dH, operating temperature 55 ° C) and the remaining residue of the stains determined gravimetrically and in relation to the initial value before rinsing (= 100%). The table below shows the percentage of soiling removed.

Table 1: Cleaning performance [% starch removal]

It can be seen that the agents according to the invention are significantly superior in cleaning performance to agents not according to the invention. Substantially the same results were obtained if the agents containing the Co were replaced in the agents according to the invention by chloropentammine-cobalt (III) chloride in amounts such that the Co concentration remained the same.

Claims

claims

1. Amylase-containing washing or cleaning agent, characterized in that it contains α-amylase from Bacillus amylollquefaciens and bleach-enhancing transition metal complex compound in addition to conventional ingredients compatible with such constituents.

2. Composition according to claim 1, characterized in that it contains amylase in amounts of 0.001 mg to 0.5 mg, in particular 0.02 mg to 0.3 mg, per gram of the total composition.

3. Composition according to claim 1 or 2, characterized in that the bleach-enhancing transition metal complex compound is selected from the complex compounds of Mn, Fe, Co, Cu, Mo, V, Ti or Ru or mixtures thereof.

4. Agent according to one of claims 1 to 3, characterized in that the bleach-enhancing transition metal complex compound from the compounds of general formula I,

[M (NH ₃ ) _6-x-2y Lχ (L ² ) _y ] A _n (I) in which M is a transition metal selected from cobalt, iron, copper and ruthenium, L a bonded via a coordination point and L ² a is a ligand bound via two coordination sites, x is a number from 0 to 5, y is a number from 0 to 2 with the proviso that x + 2y is at most 5, A is a salt-forming anion and n is a number of the size that the compound of formula (I) has no charge is selected.

5. Composition according to one of claims 1 to 3, characterized in that the bleach-enhancing transition metal complex compound is a combination of active ingredients, obtainable by intimately mixing a water-soluble salt of a divalent transition metal, selected from cobalt, iron, copper and ruthenium and mixtures thereof, a water-soluble ammonium salt and optionally an oxidizing agent based on peroxygen as well as inert carrier material.

6. Agent according to one of claims 1 to 3, characterized in that the transition metal complex compound has at least one optionally N-alkylated triazacyclononane ligand.

7. Composition according to one of claims 1 to 3, characterized in that the bleach-enhancing transition metal complex compound from the compounds of general formula (II),

X

in the

UM manganese, iron. Is cobalt, ruthenium or molybdenum,

R represents an alkylene, alkenylene, phenylene or cycloalkylene radical, which may optionally be alkyl and / or aryl substituted, with a total of 1 to 12 carbon atoms. where within R the shortest distance between the N atoms complexing with UM is 1 to 5 C atoms,

X for -H, -OR ³ . -NO ₂ , -F, -Cl, -Br or -J,

R ', R ² and R ³ independently of one another represent hydrogen or an alkyl radical having 1 to 4 carbon atoms,

Z ¹ and Z ² independently of one another represent hydrogen, -CO ₂ M, -SO ₃ M or - NO ₂ ,

M represents hydrogen or an alkali metal and A stands for a charge-balancing anion ligand is selected.

8. Agent according to one of claims 1 to 3, characterized in that the bleach-enhancing transition metal complex compound among the complexes of the transition metals manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and / or copper, the one or more of the ligands of the general formula III own

R (III) i B

A in which R is a direct bond or an alkylene group with 1 to 4 C atoms which is optionally substituted by amino groups, A represents a condensed or uncondensed ring system which contains at least one nitrogen atom, and B is hydrogen, an OH group or A, is selected.

9. Composition according to one of claims 1 to 3, characterized in that the bleach-enhancing transition metal complex compound among the complexes of the transition metals manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and / or copper, the one or more of the ligands of the general formula Own IV.

A ^ A y r (iv)

in which R is a direct bond or an optionally amino-substituted alkylene group having 1 to 4 carbon atoms, A is a condensed or uncondensed ring system which contains at least one nitrogen atom, and B is hydrogen, an OH group or A. becomes.

10. Composition according to one of claims 1 to 9, characterized in that it contains the transition metal complex compound, based on transition metal, in an amount up to 1 wt .-%, in particular from 0.001 wt .-% to 0.25 wt .-% . 2ö

11. Agent according to one of claims 1 to 10, characterized in that it contains up to 50 wt .-%, in particular 5 wt .-% to 30 wt .-% peroxygen compound.

12. Composition according to one of claims 1 to 11, characterized in that it contains 0.5% by weight to 10% by weight, in particular 1% by weight to 8% by weight, of compound releasing peroxocarboxylic acid under perhydrolysis conditions .

13. Use of a combination of α-amylase from Bacillus amylollquefaciens and transition metal complex compound to increase the cleaning performance of detergents and cleaning agents when they are used in particular aqueous washing and cleaning solutions which contain a peroxygen compound.

14. Use according to claim 13, characterized in that the cleaning performance compared to starchy and / or colored, in particular tea-based soiling is increased.