EP0975729B1 - Activators for peroxide compounds in detergents and cleaning agents - Google Patents

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

The present invention relates to the use of activators in perhydrolysis release a percarboxylic acid with elimination of a leaving group, which acts as a substrate for redox-active enzymes come into question to enhance the bleaching effect especially inorganic peroxygen compounds and washing, cleaning and Disinfectants containing such activators and a peroxygen compound.

Inorganic peroxygen compounds, especially hydrogen peroxide and solid peroxygen compounds, which dissolve in water to release 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 adding 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, as well as carboxylic acid anhydrides, especially phthalic anhydride, carboxylic acid esters, especially sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxy-benzenesulfonate, and known as pentacellated sugar, acylated aq , 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 form percarboxylic acids in the presence of peroxygen compounds, i.e. under perhydrolysis conditions, with elimination of the residual molecule, the so-called leaving group, which generally have a stronger oxidation or bleaching action than the one used peroxygen compound.

Patent application JP 01 198 700 A discloses such precursor molecules for percarboxylic acids with quaternary Ammonium groups, including such acetic acid esters, as activators for peroxide bleaching agents in phosphate-free detergents. At the same time, accordingly including a starch hydrolyzing enzyme to be present. The application EP 684 304 A2 discloses a detergent especially for machine cutting Many different quaternary substituted bleach activators as representative of gentle bleach ingredients; they are especially in with at the same time the amylases contained in the agents concerned. The application WO 27/03158 A1 mentions one above Series of quaternary substituted bleach activators, including fatty acid choline esters as components of Detergents and cleaning agents, also in combination with active enzymes; the latter in their state-of-the-art function. Activators of the same type also go out No. 5,399,746, in particular those with two quaternary ammonium groups. In summary one can say that in the state of the Technology Numerous examples of the formation of percarboxylic acids also from starting compounds with to find quaternary ammonium groups and that at the same time the use of enzymes in them Means is shown.

In the effort for energy-saving washing and bleaching processes have won in recent years Application temperatures well below 60 ° C, especially below 45 ° C to down to the cold water temperature in importance.

At these low temperatures, the effect of the activator compounds known hitherto usually significantly behind. There has been no shortage of efforts for him To develop more effective activators in the temperature range without being convincing to this day Success would have been recorded. The present invention also has the improvement the oxidation and bleaching effect of inorganic peroxygen compounds low temperatures below 80 ° C, especially in the temperature range of approx. 15 ° C to 45 ° C, to the goal.

It has now been found that using percarboxylic acids under perhydrolysis conditions releasing compounds of the above type as activators in particular then an extraordinary increase in the oxidation and Bleaching effect, especially of inorganic peroxygen compounds in oxidation, Bleaching, washing, cleaning or disinfection solutions are achieved if these are used in the Perhydrolysis release a leaving group that acts as a substrate for redox-active enzymes, and that from luffing oxygen, hydrogen peroxide supplying enzymatic system is included.

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

in der R¹CO- für einen gesättigten und/oder ungesättigten Acylrest mit 2 bis 22 C-Atomen, insbesondere 2 bis 12 C-Atomen und vorzugsweise 8 bis 10 C-Atomen steht, R² für einen gegebenenfalls substituierten geradkettigen oder verzweigten Alkyl-, Alkenyl- oder Arylrest mit 1 bis 22 C-Atomen, insbesondere 1 bis 3 C-Atomen, oder für den Rest -X-OH steht, R³ und R⁴ unabhängig voneinander für R² oder R¹CO-O-X- stehen, X für einen gegebenenfalls durch 1 bis 10 Sauerstoffatome unterbrochenen geradkettigen oder verzweigten Alkylenrest mit 2 bis 22 C-Atomen steht, und Z^- für ein ladungsausgleichendes Anion, insbesondere Halogenid, Metho- oder Ethosulfat steht.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)

in which R ¹ CO- represents 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 represents} 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 ¹ 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.

in der X, R², R³, R⁴ und Z die für Formel (I) angegebene Bedeutung haben.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, that is to say the average number of radicals R ¹ CO per molecule, is in the range of 1.2 to 2.2, preferably 1.5 to 1.9. Derivatives of esters can also be used, which are derived from technical C _12/18 or C _16/18 fatty acids, such as palm fatty acid, coconut fatty acid or tallow fatty acid, and 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,

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) may also be absent.

The enzyme substrate leaving group bleach activator, preferably an ester quat according to Formula (I) is preferably used for bleaching color stains when washing Textiles, especially in aqueous, surfactant-containing liquor, used. The wording "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 detached from the textile as well as the inhibition of the Color transfer, i.e. the oxidative destruction of those in the wash liquor Textile dyes that detach from textiles under the washing conditions before they open up different colored textiles. As part of this use, Use of esterquats as a further advantage of the invention also includes fabric softening agents Properties of the ester quat come into play if not all ester quat is decomposed perhydrolytically.

Another, albeit less preferred, use form according to claim 2 on the enzyme system described in accordance with the invention is Use of the bleach activator with an enzyme substrate leaving group, in particular one Esterquats according to formula (I), in cleaning solutions for hard surfaces, especially for Dishes, for bleaching colored stains. Here too the term bleaching and the bleaching of dirt on the hard surface, in particular tea, as well as the bleaching of those in the dishwashing liquor from the hard surface detached dirt understood.

The invention further relates to a method for activating peroxygen compounds according to claim 15 using bleach activators with an enzyme substrate leaving group, in particular of esterquats according to formula (I), as well as washing, cleaning and disinfecting agents according to claim 11, the bleaching agents based on peroxygen and to enhance the bleaching effect Bleach activator with an enzyme substrate leaving group, in particular an ester quat according to Formula (I) included.

Suitable peroxygen compounds are in particular organic peracids which do not correspond to the above-mentioned R ¹ COOOH, 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 and 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 which, in principle, can contain all the usual washing, cleaning or disinfectant components. Alkali percarbonate, alkali perborate monohydrate, alkali perborate tetrahydrate or hydrogen peroxide are particularly preferably used in the form of aqueous solutions which contain 3% by weight to 10% by weight of hydrogen peroxide. Peroxygen compounds are present in washing 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 method according to the invention and in the context of a use according to the invention may be the compound with the enzyme substrate leaving group, especially the ester quat according to formula (I) in the sense of an activator wherever there is a special increase in the oxidation effect of the peroxygen compounds at low Temperatures arrive, for example in the bleaching of textiles or hair, at Oxidation of organic or inorganic intermediates and during disinfection. In the invention Agents are preferably 0.5% to 10% by weight, in particular 1% to 8% by weight of such bleach-boosting compounds with an enzyme substrate leaving group contain.

The aforementioned perhydrolytic release of the percarboxylic acid, such as that Cleavage of the ester function in the ester quat can be done by catalysing a hydrolase enzyme to be reinforced. It was by no means to be expected that such enzymes would be able to do this, since they normally cannot bind loaded fatty acid derivatives. Under Hydrolases are to be understood as enzymes that are capable of binding to split comparatively quickly with the formation of peracid. The activity of Enzymes are usually expressed in U / g, with the unit being 1 U of activity corresponds to the amount of enzyme corresponding to 1 µmol of its substrate at an optimal pH and 25 ° C in 1 minute. 1 U thus corresponds to 1/60 µkatal. According to the invention particularly usable hydrolases preferably have the highest possible perhydrolysis activities. For perhydrolytic cleavage of the ester bond in the ester quat, not only per Definition of ester-cleaving esterases, but also some representatives of proteases able his. Also enzymes from the group of lipases or cutinases, which are called Sub-groups of the esterases can be used according to the invention.

In such an activating system of hydrolase and activator with an enzyme substrate leaving group, especially 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 up to 100: 1.

The use according to the invention essentially consists in creating conditions among which the peroxygen compound and the activating compound with enzyme substrate leaving group according to the invention can react with each other with the aim of being stronger to obtain oxidizing secondary products. Such conditions lie in particular then when the reactants meet in aqueous solution. This can be done by separate addition of the peroxygen compound and the activating compound with the enzyme substrate leaving group, for example of the ester quat, optionally to a wash or detergent solution happen. The invention is particularly advantageous However, method using a washing, cleaning or Disinfectant containing a peroxidic oxidizing agent. The peroxygen compound can also be separately, in bulk or as a preferably aqueous solution or suspension, added 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. So come along purely aqueous solutions also mixtures of water and suitable organic solvents as a reaction medium in question. The quantities of peroxygen compounds used are generally chosen so that in the solutions between 10 ppm and 10% Active oxygen, preferably between 50 and 5000 ppm active oxygen are present. The amount of esterquat used also depends on the application. Preferably it is used in such amounts that a concentration in the aqueous liquor Range of 25 ppm to 1 wt .-% is included, but in special cases this can Areas will also be left.

According to the invention, the enzymatic system is contained which is able to produce hydrogen peroxide from atmospheric oxygen. Such enzymes are usually referred to as oxidases and are classified according to 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, German published patent application DT 19 18 729 discloses washing and cleaning agents 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 Offenlegungsschrift 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. The German published patent application DT 25 57 623 discloses detergents and cleaning agents which, in addition to surfactants and builder substances, contain 0.3% by weight to 10% by weight of urate oxidase, galactose oxidase or C _1-3 alcohol oxidase and 3% by weight to Contain 30 wt .-% uric acid, galactose or C _1-3 alcohols and / or corresponding keto alcohols. European patent EP 0 072 098 relates to liquid bleaches which contain a C _1-4 alcohol oxidase and a C _1-4 alcohol. European patent application EP 0 603 931 proposes 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. The international patent application WO 95/07972, in which bleaching agents are known which contain an enzymatic system for producing hydrogen peroxide and a bleach-catalyzing coordination complex of Mn or Fe, also aims in the same direction. 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 consisting of 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 with quaternized amine function, in particular at least one after hydrolytic or perhydrolytic cleavage an ester function from the compound resulting from the formula I, for example one according to 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 as in particular powdery solids, in densified particle form, as homogeneous solutions or Suspensions can be present in addition to the activator to be used according to the invention with enzyme substrate leaving group, the hydrogen peroxide supplying from luff oxygen enzymatic system and the peroxygen-based bleach in Principle contain all known ingredients common in such agents. The invention Detergents and cleaning agents can in particular builder substances, surface-active Surfactants, water-miscible organic solvents, enzymes, sequestering agents, Electrolytes, pH regulators and other auxiliary substances such as optical brighteners, graying inhibitors, Color transfer inhibitors, foam regulators, additional peroxygen activators, Dyes and fragrances included. A disinfectant according to the invention can to strengthen the disinfectant effect against special germs in addition to previously mentioned ingredients contain common antimicrobial agents. Such antimicrobial Additives are preferred in the disinfectants according to the invention in amounts 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 their mixtures come into question. suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or Propoxylation products of alkyl glycosides or linear or branched Alcohols each with 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 are also of N-alkyl amines, vicinal diols, fatty acid esters and fatty acid amides, the correspond to the long-chain alcohol derivatives mentioned with respect to the alkyl part, and of alkylphenols with 5 to 12 carbon atoms in the alkyl radical.

Suitable anionic surfactants are in particular soaps and those containing sulfate or sulfonate groups preferably contain alkali ions as cations. Soaps that can be used are preferably the alkali metal 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 become. The sulfate-type surfactants that can be used include the salts of the sulfuric acid half-esters of fatty alcohols with 12 to 18 carbon atoms and the sulfation products of called nonionic surfactants with a low degree of ethoxylation. Among the usable ones Sulfonate-type surfactants include linear alkylbenzenesulfonates with 9 to 14 carbon atoms in the Alkyl part, alkane sulfonates with 12 to 18 carbon atoms, and olefin sulfonates with 12 to 18 carbon atoms, that result from the implementation of corresponding monoolefins with sulfur trioxide, as well as alpha-sulfofatty acid esters which are used in the sulfonation of fatty acid methyl or - ethylestem arise. It is extremely surprising in this connection that the bleach-enhancing Effect of esterquats according to general formula (I) even in the presence of such Anionic surfactant occurs.

Such surfactants are present in quantitative proportions in the cleaning or washing agents according to the invention from preferably 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight, while the disinfectants according to the invention as well as the invention Dishwashing detergent, preferably 0.1% to 20% by weight, in particular 0.2 wt .-% to 5 wt .-% 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 and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid and ethylenediaminephosphonic 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 may also contain small amounts of polymerizable 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 an esterified vinyl alcohol or a carbohydrate as 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 ₃ -C ₄ monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C ₄ -C ₈ dicarboxylic acid, maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical. Such polymers can be produced in particular by processes which are described in German patent DE 42 21 381 and German patent application DE 43 00 772, and generally have a relative molecular weight 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, in particular for the production of liquid agents, can be used 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 used in amounts of up to 40% by weight, contain in particular up to 25% by weight and preferably from 1% by weight to 8% by weight his. Amounts close to the above limit are preferably in paste or liquid, in particular water-containing agents according to the invention.

The water-soluble inorganic builder materials used are, in particular, polyphosphates, preferably sodium triphosphate. As water-insoluble, water-dispersible inorganic builder materials are in particular crystalline or amorphous alkali alumosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid agents used in particular from 1 wt .-% to 5 wt .-%. Among them are Crystalline detergent grade sodium aluminosilicates, especially zeolite A, P and optionally X, preferred. Amounts close to the above limit are preferred used in solid, particulate media. Suitable aluminosilicates have in particular no particles with a grain size over 30 microns and preferably exist at least 80 wt .-% of particles with a size below 10 microns. Your calcium binding capacity, according to the details of German patent specification DE 24 12 837 can be determined in the Usually in the range of 100 to 200 mg CaO per gram.

Suitable substitutes or partial substitutes for the alumosilicate 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, especially the amorphous sodium silicates, with a Na ₂ O: SiO ₂ molar ratio of 1: 2 to 1: 2.8. Those with a molar Na ₂ O: SiO ₂ 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} .yH ₂ O, in which x, the so-called modulus, a number of 1, are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates. 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Crystalline layered silicates which fall under this general formula are described, for example, in European patent application EP 0 164 514. Preferred crystalline layered silicates are those in which x in the general formula mentioned assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate (Na ₂ Si ₂ O ₅ .yH ₂ O) are preferred, wherein β-sodium disilicate can 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 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 specifications 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 preferred in the washing or cleaning agents according to the invention 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 only those Components of the water hardness complexing builder substances are and preferably not over 20 wt .-%, in particular from 0.1 wt .-% to 5 wt .-%, of heavy metal complexing Substances, preferably from the group comprising aminopolycarboxylic acids, aminopolyphosphonic acids and hydroxypolyphosphonic acids and their water-soluble salts and their mixtures.

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 with 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-1,4,7-triazacyclononane, 1,5,9-trimethyl-1,5,9-triazacyclododecane, (Bis - ((1-methylimidazol-2-yl) methyl)) - (2-pyridylmethyl) amine, N, N '- (bis (1-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 is understood to mean a nitro ligand which is bonded to the transition metal via the nitrogen atom, or a nitrito ligand which is bonded to the transition metal via an oxygen atom. The (NO ₂ ) ^- group can also be chelated to a transition metal or it can bridge two transition metal atoms asymmetrically or η ¹ -O. In addition to the ligands mentioned, the transition metal complexes which may be used can also carry other ligands, generally of a simpler structure, in particular mono- or polyvalent anion ligands. For example, nitrate, acetate, trifluoroacetate, formate, carbonate, citrate, perchlorate and complex anions such as hexafluorophosphate are suitable. The anion ligands are supposed 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 also possible. Such ligands in particular can also act as bridges, so that multinuclear complexes are formed. In the case of bridged dinuclear complexes, both metal atoms in the complex do not have to be the same. The use of dinuclear complexes in which the two transition metal central atoms have different oxidation numbers is also 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 -tetraperchlorate, Mn (IV) ₄ (µ- O) ₆ (1,4,7-trimethyl-1,4,7-triazacyclononane) _4- tetra-perchlorate, [N, N'-bis [(2-hydroxy-5-vinylphenyl) methylene] -1.2 -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] -1,2-diaminoethane] manganese (III) chloride, nitropentammine cobalt (III) chloride, nitritopentammine cobalt (III) chloride, hexamine cobalt ( III) chloride, Chl oropentammine cobalt (III) chloride and the 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 mentioned, the enzymes which can additionally be used in the compositions are and optionally oxidases from the class of proteases, lipases, cutinases, Amylases, isoamylases, pullulanases, hemicellulases, cellulases and peroxidases as well their mixtures in question, which should be understood to mean those enzymes that do not Have perhydrolysis activity in the sense of the invention. Are particularly suitable Fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia obtained enzymatic agents. The enzymes which may be used can as for example in international patent applications WO 92/11347 or WO 94/23005 described, adsorbed on carriers and / or embedded in coating substances to protect them against premature inactivation. They are in the invention Detergents, cleaning agents and disinfectants preferably in amounts up to 5 wt .-%, in particular from 0.2 wt .-% to 2 wt .-%, contain. Is particularly preferred because of their additional bleaching performance or color transfer inhibiting Effect of the use of peroxidases, possibly in combination with so-called Mediators which, for example, from international patent applications WO 94/12619, WO 94/12620 or WO 94/12621 are known can be used.

To those in the agents according to the invention, especially if they are in liquid or pasty Form, usable organic solvents include alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms, especially ethylene glycol and propylene glycol, as well as their mixtures and the the aforementioned classes of derivable ether. Such water-miscible solvents are preferred in the washing, cleaning and disinfecting agents according to the invention in amounts not exceeding 30% by weight, in particular from 6% by weight to 20% by weight, available.

To set a desired, not by mixing the other components the pH value of the agents according to the invention can be system and environmentally compatible Acids, especially citric acid, acetic acid, tartaric acid, malic acid, lactic acid, Glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, especially sulfuric acid, or bases, especially ammonium or alkali hydroxides, contain. Such pH regulators are preferred in the agents according to the invention not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.

In addition, the detergents can contain other constituents customary in washing and cleaning agents contain. These optional components include in particular enzyme stabilizers, Soil-release agents 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 offers no difficulties and can be in Principle of known manner, for example by spray drying or granulation, whereby peroxygen compound and bleach activating system as well as optionally contained Enzymes may be added later. For the production of the invention Medium with increased bulk density, in particular in the range from 650 g / l to 950 g / l, is a. known from the European patent EP 486 592, which has an extrusion step Process preferred. Another preferred production using a granulation process is described in European patent EP 0 642 576. invention Detergents, cleaning agents or disinfectants in the form of aqueous or other Solutions containing conventional solvents are particularly advantageous by simple Mix the ingredients in bulk or as a solution in an automatic mixer can be given. In a preferred embodiment of means for the in particular mechanical cleaning of dishes, these are tablet-shaped and can in Similar to those in European patent specifications EP 0 579 659 and EP 0 591 282 disclosed methods are produced.

Examples

The following examples illustrate perhydrolysis and fall therefore not under the claims.

example 1

Aqueous solutions which contain a bleach activator (counterion methosulfate) according to the formula R-CO-OCH ₂ CH ₂ -N ⁺ (CH ₃ ) ₃ to be used according to the invention with R given in Table 1 in a concentration likewise 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 (also expressed in ppm of active oxygen) was determined iodometrically. R Concentration [%] H ₂ O ₂ [ppm AO] t [minutes] pH Peracid [ppm AO] C ₃ H ₇ 1 94 30 9 8th C ₇ H ₁₅ 1 1000 30 9 24.7 C ₁₅ H ₃₁ 0.5 200 20 10 2 C ₁₅ H ₃₁ 1 200 30 10 2.5

Example 2

Example 1 was repeated, but without the pH buffer system and instead using an anionic surfactant-containing, bleach and bleach activator-free detergent in an application-relevant concentration. The peracid concentrations listed in Table 2 resulted. R Concentration [%] H ₂ O ₂ [ppm AO] t [minutes] Peracid [ppm AO] C ₇ H ₁₅ 1 1000 30 34.3 C ₇ H ₁₅ 0.5 1000 30 29.3

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. R Concentration [%] H ₂ O ₂ [ppm AO] t [minutes] pH Peracid [ppm AO] C ₇ H ₁₅ 1 1000 30 9 26.8 C ₈ H ₁₇ 1 1000 30 9 29

Example 4

Example 3 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 4 resulted. R Concentration [%] H ₂ O ₂ [ppm AO] t [minutes] Peracid [ppm AO] C ₇ H ₁₅ 1 1000 30 12.3 C ₇ H ₁₅ 0.5 1000 30 7.3 C ₈ H ₁₇ 1 1000 30 14.5 C ₈ H ₁₇ 0.5 1000 30 9.5

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. R Concentration [%] H ₂ O ₂ [ppm AO] t [minutes] pH Peracid [ppm AO] C ₇ H ₁₅ 1 1000 30 9 11.5

Example 6

Example 5 was repeated, but without the pH buffer system and instead using an anionic surfactant-containing, bleach and bleach activator-free detergent in an application-relevant concentration. The peracid concentration listed in Table 6 resulted. R Concentration [%] H ₂ O ₂ [ppm AO] t [minutes] Peracid [ppm AO] C ₇ H ₁₅ 0.5 1000 30 12.6

Claims (15)

1. Use of compounds which under perhydrolysis conditions give off percarboxylic acids and on perhydrolysis release a leaving group that serves as a substrate for redox-active enzymes as activators for peroxygen compounds, especially inorganic peroxygen compounds, in oxidizing, bleaching, washing, cleaning or disinfecting solutions, comprising the enzymatic system which forms hydrogen peroxide from atmospheric oxygen.
2. Use of compounds which under perhydrolysis conditions give off percarboxylic acids and on perhydrolysis release a leaving group that serves as a substrate for redox-active enzymes as activators for peroxygen compounds, especially inorganic peroxygen compounds, for bleaching colour stains when washing textiles, in particular in aqueous, surfactant-containing liquor, comprising the enzymatic system which forms hydrogen peroxide from atmospheric oxygen.
3. Use according to Claim 1 or 2, characterized in that the compound which on perhydrolysis releases an enzyme substrate leaving group is a quaternized carboxylic acid alkanolamine ester of the general formula (I)

   

   wherein R¹CO- is a saturated and/or unsaturated acyl radical containing 2 to 22 carbon atoms, R² is an optionally substituted, linear or branched alkyl, alkenyl or aryl radical containing 1 to 22 carbon atoms or is the radical -X-OH, R³ and R⁴ independently of one another are R² or R¹CO-O-X-, X is a linear or branched alkylene radical containing 2 to 22 carbon atoms and optionally interrupted by 1 to 10 oxygen atoms, and Z-is a charge-equalizing anion.
4. Use according to Claim 3, characterized in that in the compound of general formula (I) R¹CO- is a saturated and/or unsaturated acyl radical containing 2 to 12 carbon atoms, in particular 8 to 10 carbon atoms, R² is an optionally substituted alkyl or alkenyl radical containing 1 to 3 carbon atoms and/or Z^- is halide, methosulphate or ethosulphate.
5. Use according to Claim 3 or 4, characterized in that in the compound of general formula (I) at least one of the substituents of the quaternized nitrogen atom contains an alkylene group interrupted by oxygen atoms.
6. Use according to one of Claims 3 to 5, characterized in that in the compound of general formula (I) the group O-X is an optionally oligomeric ethyleneoxy and/or propyleneoxy group, the degrees of oligomerization in these groups being in particular 2 to 5.
7. Use according to one of Claims 3 to 6, characterized in that as compounds of general formula (I) quaternization products of technical mono-/di-/tri-ester mixtures are used in which the degree of esterification is in the range from 1.2 to 2.2, in particular from 1.5 to 1.9.
8. Use according to one of Claims 1 to 7, characterized in that the peroxygen compound for activation is an organic peracid or a peracidic salt of an organic acid, hydrogen peroxide or an inorganic salt that releases hydrogen peroxide under the washing or cleaning conditions, or is a mixture thereof.
9. Use according to one of Claims 1 to 8, characterized in that an enzymatic system comprising an amino alcohol oxidase or D-amino acid oxidase and a substrate for said oxidase is used, the amino alcohol substrate being in particular a molecule formed from the compound of formula I after cleavage of at least one ester function.
10. Use according to one of Claims 1 to 9, characterized in that the perhydrolytic release of the percarboxylic acid is promoted by the catalysis of a hydrolase enzyme.
11. Washing, cleaning or disinfecting composition characterized in that for boosting the bleaching effect it comprises a compound which under perhydrolysis conditions gives off percarboxylic acid and on perhydrolysis releases a leaving group that serves as a substrate for redox-active enzymes, and comprises the enzymatic system which produces hydrogen peroxide from atmospheric oxygen.
12. Composition according to Claim 11, characterized in that it comprises up to 50% by weight, in particular from 5% by weight to 30% by weight, of peroxygen compound and from 0.5% by weight to 10% by weight, in particular from 1% by weight to 8% by weight, of the bleach activator which under perhydrolysis conditions releases an enzyme substrate leaving group.
13. Composition according to Claim 11 or 12, characterized in that it further comprises transition metal salts and/or transition metal complexes which are catalytically active in bleaching.
14. Composition according to one of Claims 11 to 13, characterized in that it further comprises a peroxidase, optionally in combination with a peroxidase mediator.
15. Process for activating peroxygen compounds using a compound which under perhydrolysis conditions gives off percarboxylic acid and on perhydrolysis releases a leaving group that serves as a substrate for redox-active enzymes, the peroxygen compound for activation being hydrogen peroxide which is produced by the enzymatic system from atmospheric oxygen.