EP0975729A1

EP0975729A1 - Activators for peroxide compounds in detergents and cleaning agents

Info

Publication number: EP0975729A1
Application number: EP98917093A
Authority: EP
Inventors: Marita Grothus; Albrecht Weiss; Beatrix Kottwitz; Ulrich Pegelow; Günter Uphues; Inken PRÜSER
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1997-04-04
Filing date: 1998-03-26
Publication date: 2000-02-02
Anticipated expiration: 2018-03-26
Also published as: ATE276347T1; DE19713852A1; DE59811949D1; JP2001518956A; US6417151B1; WO1998045398A1; ES2229488T3; EP0975729B1

Abstract

A detergent or disinfectant composition comprising is presented having 0.5 to 10 percent by weight of an activator compound which under perhydrolysis conditions forms a percarboxylic acid, and releases a leaving group capable of being used as a substrate for enzymes, and up to 50 percent by weight of a peroxygen compound. The composition increases the oxidation of peroxide compounds in oxidation, bleaching, detergent, cleaning and disinfecting solutions, especially at low temperatures.

Description

Activators for peroxygen compounds in detergents and cleaning agents

The present invention relates to the use of activators which, in the case of perhydrolysis, release a percarboxylic acid by splitting off a leaving group, which is suitable as a substrate for enzymes, in particular redox-active enzymes, for increasing the bleaching action, in particular of inorganic peroxygen compounds and detergents, cleaning agents and disinfectants contain such activators and a peroxygen compound.

Inorganic peroxygen compounds, in particular hydrogen peroxide and solid peroxygen compounds which dissolve in water with the liberation of hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfection and bleaching purposes. The oxidizing effect of these substances in dilute solutions depends strongly on the temperature; For example, with H ₂ O ₂ or perborate in alkaline bleaching liquors, sufficiently quick bleaching of soiled textiles can only be achieved at temperatures above about 80 ° C. At lower temperatures, the oxidation effect of the inorganic peroxygen compounds can be improved by the addition of so-called activators, for which numerous suggestions, especially from the classes of the N- or O-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N- acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, also carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, especially sodium nonanoyloxy-benzene sulfonate, sodium isononanoyloxy-benzenesulfonate and acyl acylate, such as Literature has become known. By adding these substances, the bleaching effect of aqueous peroxide liquors can be increased to such an extent that even at temperatures around 60 ° C essentially the same effects occur as with the peroxide liquor alone at 95 ° C. The bleach-enhancing effectiveness of such substances is essentially based on the fact that they are present in the presence of peroxygen compounds means under perhydrolysis conditions, with elimination of the residual molecule, the so-called leaving group, to form percarboxylic acids which generally have a stronger oxidation or bleaching action than the peroxygen compound used.

In the effort to save energy in washing and bleaching, application temperatures significantly below 60 ° C, in particular below 45 ° C, down to the cold water temperature have become increasingly important in recent years.

At these low temperatures, the effect of the activator compounds known hitherto generally decreases significantly. There has been no shortage of efforts to develop more effective activators for this temperature range without convincing success to date. The present invention also aims to improve the oxidation and bleaching effect of inorganic peroxygen compounds at low temperatures below 80 ° C., in particular in the temperature range from approximately 15 ° C. to 45 ° C.

It has now been found that when compounds of the above-mentioned type which release percarboxylic acids under perhydrolysis conditions are used as activators, especially in this temperature range, there is an extraordinary increase in the oxidation and bleaching action, in particular of inorganic peroxygen compounds, in oxidation, bleaching, washing, cleaning or disinfecting solutions is achieved when this releases a leaving group during perhydrolysis, which can serve as a substrate for enzymes, in particular redox-active enzymes.

The preferred bleach activators which release such an enzyme substrate leaving group under perhydrolysis conditions include quaternized carboxylic acid alkanolamine esters, so-called ester quats. Esterquats are a known group of cationic surfactants which are usually obtained by esterification of alkanolamines such as triethanolamine or triethanolamine polyglycol ethers with carboxylic acids and subsequent quaternization in organic solvents. So far they have been used mainly because of their fabric softening effect in detergents and especially laundry aftertreatment. agents used. The preparation and properties of the ester quats are described, for example, in international patent application WO 91/01295 and the review articles by O. Ponsati in CR CED Congress, Barcelona, 167 (1992) and R. Puchta in CR CED Congress, Sitges, 59 ( 1993).

For the purposes of the invention, ester quats are to be understood as meaning quaternized carboxylic acid mono-, di- or triesters of the general formula (I)

R ²

R'CO-OXN -R ^J Z ^" (I)

R ⁴

in which R'CO- is a saturated and / or unsaturated acyl radical having 2 to 22 C atoms, in particular 2 to 12 C atoms and preferably 8 to 10 C atoms, R ^{2 is} an optionally substituted straight-chain or branched alkyl , Alkenyl or aryl radical having 1 to 22 carbon atoms, in particular 1 to 3 carbon atoms, or for the radical -X-OH, R ³ and R ⁴ independently of one another are R ² or R'CO-OX-, X represents a straight-chain or branched alkylene radical having 2 to 22 C atoms which is optionally interrupted by 1 to 10 oxygen atoms, and Z ^"represents a charge-balancing anion, in particular halide, methosulfate or ethosulfate.

The preferred compounds of the formula (I) include those in which at least one of the substituents on the quaternized nitrogen atom has an alkylene group (X in formula I) which is interrupted by oxygen atoms. The group OX is preferably an optionally oligomeric ethyleneoxy and / or propyleneoxy group, the degrees of oligomerization in these groups preferably being 2 to 5. The number of R'CO radicals in the compounds of the formula (I) is 1 to 3. Quaternization products of technical mono- / di- / triester mixtures are preferably used in which the degree of esterification, ie the average number of radicals R 'CO per molecule, in the range from 1.2 to 2.2, preferably 1.5 to 1.9. It is also possible to use derivatives of esters which are derived from technical C _2/18 or C _16/18 fatty acids, such as palm fatty acid, coconut fatty acid or tallow fatty acid, and which can have an iodine number in the range between 0 and 40. Such esterquats are perhydrolyzed in the presence of hydrogen peroxide with cleavage of the ester bonds and release of the percarboxylic acid R'COOOH. A compound of the general formula II arises from the leaving group,

R ²

HO-XN ⁺ -R ³ Z ^" (II)

R ⁴

in which X, R ² , R ³ , R ⁴ and Z have the meaning given for formula (I).

The above-mentioned substituents in the radical R ² can be, for example, halogens such as chlorine, fluorine and iodine, but also ionic groups such as sulfate, sulfonate, carboxylate, phosphate or phosphonate or the acid groups on which they are based. In the latter cases, the anion (Z ^" in formula I) can also be absent.

The bleach activator with an enzyme substrate leaving group, preferably an ester quat according to formula (I), is preferably used for bleaching color stains when washing textiles, in particular in an aqueous, surfactant-containing liquor. The formulation "bleaching of color stains" 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 inhibition of color transfer, that is to say that oxidative destruction of textile dyes in the wash liquor, which detach from textiles under the washing conditions before they can be drawn onto differently colored textiles. As part of this use, Use of ester quats as a further advantage of the invention also brings the textile-softening properties of the ester quat to bear if all of the ester quat is not decomposed perhydrolytically.

Another, albeit less preferred, use form according to the invention is the use of the bleach activator with an enzyme substrate leaving group, in particular an ester quat according to formula (I), in cleaning solutions for hard surfaces, in particular for dishes, for bleaching colored stains. Here too, the term bleaching is understood to mean 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.

The invention further relates to a process for activating peroxygen compounds using bleach activators with an enzyme substrate leaving group, in particular esterquats according to formula (I), as well as detergents, cleaning agents and disinfectants, the bleaching agents based on peroxygen and for enhancing the bleaching action with a bleach activator Enzyme substrate leaving group, in particular an ester quat according to formula (I).

Suitable peroxygen compounds are in particular organic peracids which do not correspond to the R'COOOH mentioned above, or peracidic salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperoxydodecanedioic acid, hydrogen peroxide and inorganic salts which give off hydrogen peroxide under the washing or cleaning conditions, such as perborate , Percarbonate, perphosphate and / or persilicate, alone or in mixtures. 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. The peroxygen compounds can be added to the washing or cleaning liquor as such or in the form of agents containing them, which can in principle contain all the usual washing, cleaning or disinfectant components. Alkali percarbonate, alkali perborate monohydrate, alkali perborate tetrahydrate or is particularly preferred Hydrogen peroxide in the form of aqueous solutions containing 3% by weight to 10% by weight of hydrogen peroxide. Peroxygen compounds are present in detergents or cleaning agents according to the invention in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight, while in the disinfectants according to the invention preferably from 0.5% by weight to 40% % By weight, in particular from 5% by weight to 20% by weight, of peroxygen compounds are contained.

In the process according to the invention and in the context of a use according to the invention, the compound with an enzyme substrate leaving group, in particular the esterquat according to formula (I), can be used in the sense of an activator wherever a particular increase in the oxidation effect of the peroxygen compounds at low temperatures is important, for example in the bleaching of textiles or hair, in the oxidation of organic or inorganic intermediates and in disinfection. Agents according to the invention preferably contain 0.5% by weight to 10% by weight, in particular 1% by weight to 8% by weight, of such bleach-boosting compounds having an enzyme substrate leaving group.

The perhydrolytic release of the percarboxylic acid mentioned, such as the cleavage of the ester function in the ester quat, can be further increased by the catalysis of a hydrolase enzyme. It was by no means to be expected that such enzymes would be able to do this, since they normally cannot bind charged fatty acid derivatives. Hydrolases are understood to mean enzymes which are able to cleave the corresponding bond comparatively quickly with the formation of peracid. The activity of enzymes is usually expressed in U / g, the unit corresponding to 1 U of the amount of enzyme which converts 1 μmol of its substrate at an optimal pH and 25 ° C. in 1 minute. 1 U corresponds to 1/60 μcatal. Hydrolases which are particularly useful according to the invention preferably have the highest possible hydrolysis activities. For perhydrolytic cleavage of the ester bond in the ester quat, not only ester-cleaving esterases can be defined, but also some representatives of the proteases his. Enzymes from the group of lipases or cutinases, which can be referred to as subgroups of esterases, can also be used according to the invention.

In such an activating system of hydrolase and actuator with enzyme substrate leaving group, in particular ester quat, the weight ratio of activator to hydrolase enzyme is preferably in the range from 1,000,000: 1 to 50: 1, in particular from 1,000: 1 to 100 :1.

The use according to the invention essentially consists in creating conditions under which the peroxygen compound and the activating compound with enzyme substrate leaving group according to the invention can react with one another with the aim of obtaining secondary products which have a stronger oxidizing action. Such conditions exist in particular when the reactants meet in aqueous solution. This can be done by separately adding the peroxygen compound and the activating compound with an enzyme substrate leaving group, for example the ester quat, to a solution which may contain detergents or cleaning agents. However, the method according to the invention is particularly advantageously carried out using a washing, cleaning or disinfecting agent according to the invention which contains a peroxidic oxidizing agent. The peroxygen compound can also be added separately, in bulk or as a preferably aqueous solution or suspension, to the washing, cleaning or disinfecting solution if a peroxygen-free agent is used.

The conditions can be varied widely depending on the intended use. In addition to purely aqueous solutions, mixtures of water and suitable organic solvents are also suitable as the reaction medium. The amounts of peroxygen compounds are generally chosen so that the solutions contain between 10 ppm and 10% active oxygen, preferably between 50 and 5000 ppm active oxygen. The amount of esterquat used also depends on the application. It is preferably used in amounts such that the aqueous liquor contains a concentration in the range from 25 ppm to 1% by weight, but in special cases these ranges can also be left. In a particular embodiment of the invention, the peroxygen compound to be activated is hydrogen peroxide and is supplied by an enzymatic system which is capable of producing hydrogen peroxide from oxygen, for example from atmospheric oxygen. Such enzymes are usually referred to as oxidases and are classified in more detail depending on their substrate. Oxidases are redox enzymes with the classification EC 1 (according to the classification of the Enzyme Commission), which are usually flavin-dependent and whose oxidized form is able to oxidize a substrate. The resulting reduced form of the enzyme is reoxidized by molecular oxygen in aqueous systems, whereby hydrogen peroxide forms as a further product. Examples of such enzymes and their substrates, which emerge from the name of the enzyme, are phenol oxidase, amino acid oxidase, xanthine oxidase, urate oxidase, alcohol oxidase, cholesterol oxidase and glucose oxidase. The use of oxidases in detergents has already been proposed on various occasions. For example, washing and cleaning agents are known from German published patent application DT 19 18 729, which, in addition to surfactants, contain 0.5% by weight to 10% by weight of glucose oxidase and 5% by weight to 30% by weight of glucose or starch. In the latter case, 0.5% to 10% by weight of amyloglucosidase should also be present. German laid-open specification DT 20 64 146 discloses washing and cleaning agents which contain 1% by weight to 50% by weight of water-soluble surfactant and 0.01% by weight to 2% by weight of lipoxidase. Polyunsaturated fatty acids are preferably additionally present as substrates for the lipoxidase. From the German patent application DT 25 57 623, detergents and cleaning agents are known which, in addition to surfactants and builder substances, 0.3% by weight to 10% by weight of urate oxidase, galactose oxidase or C]. ₃ alcohol oxidase and 3 wt .-% to 30 wt .-% uric acid, galactose or C ,. ₃ alcohols and / or corresponding keto alcohols contain. European patent EP 0 072 098 relates to liquid bleaching agents which contain a C _M alcohol oxidase and a C ₁ . ₄ -Alcohol included. In European patent application EP 0 603 931 it is proposed to stabilize the glucose oxidase / glucose system in liquid detergents by adding Cu ²⁺ and / or Ag ⁺ ions and by the presence of bleaching catalysts, in particular metal porphins, Metal porphyrins, metal phthalocyanines and / or hemin to increase the bleaching effect of the enzymatically generated hydrogen peroxide. It also aims in the same direction international patent application WO 95/07972, from which bleaching agents are known which contain an enzymatic system for producing hydrogen peroxide and a bleach-catalyzing coordination complex of Mn or Fe. International patent application WO 94/25574 discloses an L-amino acid oxidase from a particular strain of the microorganism Trichoderma harzianum and detergents which contain such an oxidase. The enzymatic systems mentioned can be used to generate hydrogen peroxide to be activated according to the invention; However, a bleaching system known from German patent application DE 195 45 729 and comprising an amino alcohol or D-amino acid oxidase and a substrate for this oxidase is preferably used, the term amino alcohol substrate also including compounds having a quaternized amine function, in particular one having a hydrolytic or perhydrolytic function Cleavage of at least one ester function from the molecule resulting from the compound of the formula I, for example one of the formula II. The use of choline oxidase, as is produced, for example, by Alcaligenes species or Arthrobacter globiformis, is particularly preferred. D-amino acid oxidase of standardized activity, for example obtained from pig kidneys, is commercially available and, like choline oxidase, is offered, for example, by Sigma. An oxidase is preferably used in agents according to the invention in amounts such that the entire agent has an oxidase activity of 30 U / g to 20,000 U / g, in particular of 60 U / g to 15,000 U / g. Agents with oxidase activities in the areas mentioned have a rapid hydrogen peroxide release, in particular for conventional European machine washing processes.

The detergents, cleaning agents and disinfectants according to the invention, which may be present in particular as powdery solids, in post-compacted particle form, as homogeneous solutions or suspensions, can, in addition to the activator to be used according to the invention with an enzyme substrate leaving group and the bleaching agent based on peroxygen, in principle all known and contain common ingredients in such agents. The washing and cleaning agents according to the invention can in particular builder substances, surface-active surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, graying agents. ungsinhibitors, color transfer inhibitors, foam regulators, additional peroxygen activators, dyes and fragrances contain. A disinfectant according to the invention can contain conventional antimicrobial active ingredients in addition to the previously mentioned ingredients in order to enhance the disinfectant action against special germs. Such anti-microbial additives are contained in the disinfectants according to the invention preferably in amounts of up to 10% by weight, in particular from 0.1% by weight to 5% by weight.

The agents according to the invention can contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof. 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-alkylamines, 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 of alkylphenols having 5 to 12 carbon atoms in the alkyl radical are also useful.

Suitable anionic surfactants are, in particular, soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations. Usable soaps are preferably the alkali salts of saturated or unsaturated fatty acids with 12 to 18 carbon atoms. Such fatty acids can also be used in a form that is not completely neutralized. The surfactants of the sulfate type which can be used include the salts of the sulfuric acid semiesters of fatty alcohols having 12 to 18 carbon atoms and the sulfation products of the nonionic surfactants mentioned with a low degree of ethoxylation. The surfactants of the sulfonate type that can be used include linear alkylbenzenesulfonates with 9 to 14 carbon atoms in the alkyl part, alkanesulfonates with 12 to 18 carbon atoms, and olefin sulfonates with 12 to 18 carbon atoms, which are formed in the reaction of corresponding mono-olefins with sulfur trioxide, as well as alpha-sulfofatty acid esters, which are formed in the sulfonation of fatty acid methyl or ethyl esters. It is extremely surprising in this context that the pale reinforcing effect of ester quats according to general formula (I) also occurs in the presence of such anionic surfactants.

Such surfactants are present in the cleaning or washing agents according to the invention in proportions of preferably 5% by weight to 50% by weight, in particular 8% by weight to 30% by weight, while the disinfectants according to the invention and agents according to the invention for cleaning dishes preferably contain 0.1% by weight to 20% by weight, in particular 0.2% by weight to 5% by weight of surfactants.

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 (methylenephosphine-methylene-ethylenediophosphonic acid), ethylenedi-ethylenedisonic acid (ethylenedisodium) -phosphonic acid (ethylenedi) ethylenediophosphonic acid (ethylenediophene) l, l-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular the polycarboxylates of international patent application WO 93/16110 accessible by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which can also be used in small amounts May contain substances without carboxylic acid functionality in copolymerized form. The relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, in each case based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight. Terpolymers 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 a mixed monomer as the third monomer. contain estered vinyl alcohol or a carbohydrate. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ -carboxylic acid and preferably from a C ₃ -C ₄ -monocarboxylic acid, in particular from (Mefh) acrylic acid. The second acidic monomer or its salt can be a derivative of a C ₄ -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.

Particularly suitable water-soluble inorganic builder materials are polyphosphates, preferably sodium triphosphate. The water-insoluble, water-dispersible inorganic builder materials used are, in particular, crystalline or amorphous alkali aluminum silicates, 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 these, the detergent grade crystalline sodium aluminosilicates, particularly zeolite A, P and optionally X, are preferred. Amounts close to the above upper limit are preferably used in solid, particulate compositions. Suitable aluminosilicates have in particular 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 ₂ 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 phyllosilicates of the general formula Na ₂ Si _x O _{2x + 1} y H ₂ O, in which x, the so-called modulus, is a number of 1.9, are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates to 4 and y is a number from 0 to 20 and are preferred values for x 2, 3 or 4. Crystalline layered silicates which fall under this general formula are described, for example, in European patent application EP 0 164 514. Preferred crystalline 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 produced 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 incorporated. sets how it can be produced from sand and soda according to 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 0 293 753, are used in a further preferred embodiment of agents according to the invention. If alkali aluminosilicate, in particular zeolite, is also present as an additional builder substance, the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is preferably 1:10 to 10: 1. In compositions which contain both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.

Builder substances are contained in the washing or cleaning agents according to the invention preferably in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight, while the disinfectants according to the invention are preferably free of the components which only complex the components of the water hardness Builder substances are and preferably not more than 20% by weight, in particular from 0.1% by weight to 5% by weight, of heavy metal complexing substances, preferably from the group comprising aminopolycarboxylic acids, aminopolyphosphonic acids and hydroxypolyphosphonic acids and their water-soluble salts and mixtures thereof.

In addition to conventional bleach activators which do not release any enzyme substrate leaving group under perhydrolysis conditions, the additional bleach-boosting active ingredients optionally contained in agents according to the invention include, in particular, bleach-catalytically active transition metal salts and / or complexes, which are preferably among the cobalt, iron, copper, titanium, Vanadium, manganese and ruthenium complexes can be selected. Suitable ligands in the transition metal complexes which can be used according to the invention are customary substances of both inorganic and organic nature. The organic ligands in such complexes include, in addition to carboxylates, in particular compounds having primary, secondary and / or tertiary amine and / or alcohol functions, such as pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, triazole, 2,2'-bispyridylamine , Tris (2-pyridylmethyl) amine, 1, 4,7-triazacyclononane, 1, 4,7-trimethyl-l, 4,7-triazacyclononane, 1,5,9-trimethyl-l, 5,9-triazacyclododecane, (bis- ((l-methylimidazol-2-yl) methyl)) - (2-pyridylmethyl) amine, N, N '- (bis (l-methylimidazol-2-yl) methyl) ethylenediamine, N- Bis (2-benzimidazolylmethyl) aminoethanol, 2,6-bis (bis (2-benzimidazolylmethyl) aminomethyl) -4-methylphenol, N, N, N ^' , N ^' -tetrakis (2-benzimidazolylmethyl) -2-hydroxy-1,3-diaminopropane, 2,6-bis (bis- (2-pyridylmethyl) aminomethyl) -4-methylphenol, 1,3-bis (bis- (2-benzimidazolylmethyl) aminomethyl) -benzene, sorbitol, mannitol, erythritol, adonitol, inositol, lactose, and optionally substituted salenes, porphins and porphyrins. The inorganic neutral ligands include, in particular, ammonia and water. In the case of the Co (III) complexes in particular, in which the central atom is normally present with the coordination number 6, the presence of at least 1 ammonia ligand is preferred. If not all of the coordination sites of the transition metal central atom are occupied by neutral ligands, a complex which may be present in agents according to the invention contains further, preferably anionic and, in particular, monodentate or bidentate ligands. These include in particular the halides such as fluoride, chloride, bromide and iodide, and the (NO ₂ ) ^" group. In the present case, a (NO ₂ ) ^" group should include a nitro ligand which is attached to the transition metal via the nitrogen atom is bound, or a nitrito ligand, which is bound to the transition metal via an oxygen atom, can be understood. The (NO ₂ ) ^" group can also be chelated to a transition metal or it can bridge two transition metal atoms asymmetrically or η'-O. In addition to the ligands mentioned, the transition metal complexes to be used, if appropriate, can also contain other ligands which are generally of simpler structure , in particular mono- or polyvalent anion ligands, such as nitrate, acetate, trifluoroacetate, formate, carbonate, citrate, perchlorate and complex anions such as hexafluorophosphate. The anion ligands are intended to balance the charge between the transition metal central atom and the ligand system The presence of oxo ligands, peroxo ligands and imino ligands is possible. In particular, such ligands can also act as bridges, so that multinuclear complexes are formed. In the case of bridged, dinuclear complexes, the two metal atoms in the complex do not have to be the same. Also the use of dinuclear complexes in which the two n transition metal central atoms have different oxidation numbers, is possible. If anion ligands are missing or the presence of anion ligands does not lead to charge balance in the complex, anionic counterions are present in the transition metal complex compounds, which neutralize the cationic transition metal complex. These anionic counterions include in particular nitrate, hydroxide, hexafluorophosphate, sulfate, chlorate, perchlorate, the halides such as chloride or the anions of carboxylic acids such as formate, acetate, benzoate or citrate. Examples of transition metal complex compounds which can be used according to the invention are Mn (IV) ₂ (μ- O) ₃ (1,4,7-triazacyclononane) ₂ -di-hexafluorophosphate, Mn (IV) ₂ (μ-O) ₃ (1,4, 7-trimethyl-1,4,7-triazacyclononane) ₂ -di-hexafluorophosphate, Mn (IV) ₄ (μ-O) ₆ (1, 4,7-triazacyclononane) ₄ -tetra-perchlorate, Mn (IV) ₄ ( µ-O) ₆ (l, 4,7-trimethyl-l, 4,7-triazacyclononane) _4- tetra-perchlorate, [N, N'- bis [(2-hydroxy-5-vinylphenyl) methylene] -l , 2-diaminocyclohexane] manganese (III) chloride, [N, N'-bis [(2-hydroxy-5-nitrophenyl) methylene] -1, 2-diaminocyclohexane] manganese (III) acetate, [N, N'-bis [(2-hydroxyphenyl) methylene] - 1, 2-phenylenediamine] manganese (III) acetate, [N, N'-bis [(2-hydroxyphenyl) methylene] - 1 , 2-diaminocyclohexane] manganese (III) chloride, [N, N '~

Bis [(2-hydroxyphenyl) methylene] - 1, 2-diaminoethane] manganese (III) chloride, [N, N'-bis [(2-hydroxy-5-sulfonatophenyl) methylene] -l, 2 -diaminoethane] -manganese (III) chloride, nitropentammine cobalt (III) chloride, nitritopentammine cobalt (III) chloride, hexamine cobalt (III) chloride, chloropentammine cobalt (III) chloride and peroxo -Complex [(NH ₃ ) ₅ Co-OO-Co (NH ₃ ) ₅ ] Cl ₄ . Further examples of bleaching catalysts which can be used according to the invention are ammonium and alkali molybdates and tungstates, which can also be used in the form of polymolybdates or poly tungstates.

In addition to the hydrolases and, if appropriate, oxidases mentioned, enzymes which can also be used in the compositions are those from the class of the proteases, lipases, cutinases, amylases, isoamylases, pullulanases, hemicellulases, cellulases and peroxidases and mixtures thereof, which are to be understood as meaning such enzymes which have no perhydrolysis activity in the sense of the invention. Enzymes obtained from fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia are particularly suitable. The enzymes that may be used can NEN, as described for example in international patent applications WO 92/11347 or WO 94/23005, adsorbed on carriers and / or embedded in coating substances in order to protect them against premature inactivation. They are contained in the washing, cleaning and disinfecting agents according to the invention preferably in amounts of up to 5% by weight, in particular from 0.2% by weight to 2% by weight. Particularly preferred is the use of peroxidases because of their additional bleaching power or dye transfer-inhibiting effect, which can optionally be used in combination with so-called mediators, which are known, for example, from international patent applications WO 94/12619, WO 94/12620 or WO 94/12621 .

The organic solvents which can be used in the agents according to the invention, in particular if they are in liquid or pasty form, include alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms , in particular ethylene glycol and propylene glycol, as well as their mixtures and the ethers derivable from the compound classes mentioned. Such water-miscible solvents are preferably present in the washing, cleaning and disinfecting agents according to the invention in amounts of not more than 30% by weight, in particular from 6% by weight to 20% 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, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are preferably not contained in the agents according to the invention in excess of 20% by weight, in particular from 1.2% by weight to 17% by weight.

In addition, the agents can contain further constituents customary in washing and cleaning agents. These optional components include, in particular, enzyme stabilizers, soil release active ingredients such as copolymers of dicarboxylic acids and diols and / or polyether diols, graying inhibitors such as carboxymethyl cellulose, color transfer inhibitors, for example polyvinylpyrrolidone or polyvinylpyridine-N-oxide, foam inhibitors, for example organopolysiloxanes or paraffins, and optical brighteners, for example stilbene disulfonic acid derivatives.

The preparation of solid agents according to the invention is not difficult and can be carried out in a manner known in principle, for example by spray drying or granulation, the peroxygen compound and bleach-activating system and any enzymes which may be present being added later, if appropriate. For the preparation 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 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. Detergents, cleaning agents or disinfectants according to the invention in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer. In a preferred embodiment of agents for the in particular machine cleaning of dishes, these are tablet-shaped and can be produced on the basis of the processes disclosed in European patent specifications EP 0 579 659 and EP 0 591 282.

Examples

example 1

Aqueous solutions which contain a bleach activator (counterion methosulfate) to be used according to the invention according to the formula R-CO-OCH ₂ CH ₂ -N ⁺ (CH ₃ ) ₃ with R given in Table 1 in a concentration also given in Table 1 and a pH So much aqueous hydrogen peroxide was added to the buffer system that they had the active oxygen concentration of H ₂ O ₂ (ppm AO) given in Table 1. After exposure times (t) of 20 minutes to 60 minutes, the amount of percarboxylic acid formed (expressed likewise in ppm of active oxygen) was determined iodometrically.

Table 1

Example 2

Example 1 was repeated, except that the pH buffer system was dispensed with and instead an anionic surfactant-containing, bleach and bleach activator-free detergent was used in a concentration relevant to the application. The peracid concentrations listed in Table 2 resulted. Table 2

Example 3

Example 1 was repeated, but using bleach activators (counterion methosulfate) according to the formula (R-CO-OCH ₂ CH ₂ ) ₂ N ⁺ (CH ₃ ) ₂ . The amounts of peracid formed are given in Table 3.

Table 3

Example 4

Example 3 was repeated, except that the pH buffer system was dispensed with and instead a detergent containing anionic surfactant, bleach and bleach activator-free was used in a concentration relevant to the application. The peracid concentrations listed in Table 4 resulted. Table 4

Example 5

Example 1 was repeated, but using bleach activators (counterion methosulfate) according to the formula (R-CO-OCH ₂ CH ₂ ) ₃ N ⁺ CH ₃ . The amounts of peracid formed are given in Table 5.

Table 5

Example 6

Example 5 was repeated, except that the pH buffer system was dispensed with and instead a detergent containing anionic surfactant, bleach and bleach activator-free was used in a concentration relevant to the application. The peracid concentration shown in Table 6 resulted. Table 6

Claims

claims

1. Use of compounds which release percarboxylic acids under perhydrolysis conditions and which release a leaving group during perhydrolysis, which can serve as a substrate for enzymes, in particular redox-active enzymes, as activators for, in particular, inorganic peroxygen compounds in oxidation, bleaching, washing, cleaning or disinfecting solutions.

2. Use of compounds which split off percarboxylic acids under perhydrolysis conditions and which release a leaving group during perhydrolysis, which can serve as a substrate for enzymes, in particular redox-active enzymes, for bleaching color stains when washing textiles, in particular in aqueous, surfactant-containing liquor.

3. Use according to claim 1 or 2, characterized in that the compound releasing an enzyme substrate leaving group in the perhydrolysis is a quaternized carboxylic acid alkanolamine ester of the general formula (I),

R ²

R'CO-OXN ⁺ -R ³ Z ^" (I)

R ⁴ in the R'CO- represents a saturated and / or unsaturated acyl radical having 2 to 22 C atoms, R ^{2 represents} an optionally substituted straight-chain or branched alkyl, alkenyl or aryl radical having 1 to 22 C atoms or the radical -X-OH, R ³ and R ⁴ independently of one another are R ² or R'CO-OX-, X is optionally a

1 to 10 oxygen atoms interrupted straight-chain or branched alkylene radical with

2 to 22 carbon atoms, and Z ^"stands for a charge-balancing anion.

4. Use according to claim 3, characterized in that in the compound of general formula (I) R'CO- for a saturated and / or unsaturated acyl radical with 2 to 12 carbon atoms, in particular 8 to 10 carbon atoms, R ^{2 stands} for an optionally substituted alkyl or alkenyl radical with 1 to 3 carbon atoms and / or Z ^"stands for halide, methosulfate or ethosulfate.

5. Use according to claim 3 or 4, characterized in that in the compound according to general formula (I) at least one of the substituents of the quaternized nitrogen atom has an alkylene group interrupted by oxygen atoms.

6. Use according to one of claims 3 to 5, characterized in that in the compound according to general formula (I) the group OX is an optionally oligomeric ethyleneoxy and / or propyleneoxy group, the degrees of oligomerization in these groups in particular 2 to 5 be.

7. Use according to one of claims 3 to 6, characterized in that quaternization products of technical mono- / di- / triester mixtures are used as compounds according to general formula (I), in which the degree of esterification is in the range from 1.2 to 2, 2, in particular 1.5 to 1.9.

8. Use according to one of claims 1 to 7, characterized in that the peroxygen compound to be activated is an organic peracid or a peracidic salt of an organic acid, hydrogen peroxide or an inorganic salt emitting hydrogen peroxide under the washing or cleaning conditions or a mixture of these.

9. Use according to one of claims 1 to 8, characterized in that the peroxygen compound to be activated is hydrogen peroxide, which is supplied by an enzymatic system.

10. Use according to claim 9, characterized in that an enzymatic system of an amino alcohol or D-amino acid oxidase and a substrate for this oxidase is used, the amino alcohol substrate in particular being after cleavage serves at least one ester function from the compound of formula I resulting molecule.

11. Use according to one of claims 1 to 10, characterized in that the perhydrolytic release of the percarboxylic acid is increased by the catalysis of a hydrolase enzyme.

12. Detergent, cleaning agent and disinfectant, characterized in that it contains a compound which releases percarboxylic acid under perhydrolysis conditions and which releases a leaving group during perhydrolysis, which can serve as a substrate for enzymes, in particular redox-active enzymes, to enhance the bleaching action.

13. Composition according to claim 12, characterized in that it is up to 50 wt .-%, in particular 5 wt .-% to 30 wt .-%, peroxygen compound and / or 0.5 wt .-% to 10 wt .-% contains, in particular, 1% by weight to 8% by weight of a bleach activator which releases an enzyme substrate leaving group under perhydrolysis conditions.

14. Composition according to claim 12 or 13, characterized in that it additionally contains bleach-catalytically active transition metal salts and / or complexes.

15. Agent according to one of claims 12 to 14, characterized in that it additionally contains a peroxidase, optionally in combination with a mediator.

16. A process for activating peroxygen compounds using a compound which releases percarboxylic acid under perhydrolysis conditions and which releases a leaving group during perhydrolysis, which can serve as a substrate for enzymes, in particular redox-active enzymes.