EP0902832A1

EP0902832A1 - Anol esters as bleach activators for detergents and cleaners

Info

Publication number: EP0902832A1
Application number: EP97918144A
Authority: EP
Inventors: Andreas Wilde
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1996-04-26
Filing date: 1997-04-17
Publication date: 1999-03-24
Also published as: JP2000509416A; DE19616693A1; US6075001A; WO1997041201A1; KR20000064998A

Abstract

Peroxy compounds, particularly for use in bleaching colored stains when washing textiles or cleaning hard surfaces, are activated very effectively using compounds of the general formula (I), wherein R is hydrogen, an aryl, alkyl, alkenyl or cycloalkyl radical with 1 to 17 C atoms, n stands for a number from 1 to 8, and A, B and Y independently of one another are hydrogen, an aryl, alkyl, alkenyl or cycloalkyl group with 1 to 17 C atoms or a hydrophilic group selected from -SO3H, -OSO3H, -PO(OH)2-CO2H and their anions as well as -N?+R1R2R3X-¿, wherein R?1, R2 and R3¿ independently of one another are hydrogen, an aryl, alkyl, alkenyl or cycloalkyl radical with 1 to 17 C atoms and X- is a charge-balancing anion, provided that at least one of the A, B or Y substituents in the molecule is a specified hydrophilic group.

Description

Enol esters as bleach activators for detergents and cleaning agents

The present invention relates to the use of hydrophilically substituted enol esters as bleach activators for activating peroxygen compounds, in particular for bleaching color stains when washing textiles, and detergents, cleaning agents and disinfectants which contain such bleach activators.

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 strongly depends on the temperature in dilute solutions; 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 bleach activators, which are able to deliver peroxocarboxylic acids under the perhydrolysis conditions mentioned and for which numerous suggestions, especially from the substance classes of the N- or O-acyl compounds, for example polyacylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulphurylamides and cyanurates, also carboxylic acid anhydride acid, especially phthaloyl anoyl acid, particularly phthalide benzenesulfonate, sodium isononanoyloxy-benzenesulfonate, O-acylated sugar derivatives, such as pentaacetyl glucose, and N-acylated lactams, such as N-benzoylcaprolactam, have become known in the literature. 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. 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 noticeably. There has been no shortage of efforts to develop more effective activators for this temperature range without convincing success to date.

In European patent applications EP 0 092 932 AI and EP 0 122 763 A2, the use of enol esters which carry C, _.5 -alkyl or C ₂ ^ -alkenyl groups on the enolic double bond has been recommended as bleach activators. Surprisingly, it has now been found that enol esters which carry at least one hydrophilic group have a significantly higher bleach-activating effect.

The invention accordingly relates to the use of compounds of the general formula I

in which R is hydrogen, an aryl, alkyl, alkenyl or cycloalkyl radical having 1 to 17 carbon atoms, n is a number of 1 to 8, A, B and Y independently of one another for hydrogen, an aryl, Alkyl, alkenyl or cycloalkyl group with 1 to 17 carbon atoms or a hydrophilic group selected from -SO ₃ H, -OSO ₃ H, -PO (OH) ₂ , -OPO (OH) ₂ , -CO ₂ H and their anions and -N R'Rt ^J X ^" , in which R, R and R independently of one another are hydrogen, an aryl, alkyl, alkenyl or cycloalkyl radical having 1 to 17 C atoms and X ^{" are} a charge-balancing anion , with the proviso that at least one of the substituents A, B or Y in the molecule has a hydrophilic Group is as activators for in particular inorganic peroxygen compounds in oxidation, washing, cleaning or disinfection solutions.

The compounds of formula (I) with R = phenyl, C _r to C _n -alkyl, 9-decenyl and mixtures thereof are preferred, it being possible for the alkyl radicals to be linear or branched-chain. Among the compounds of the formula (I) with linear alkyl radicals R, those having 1 to 9 carbon atoms in the alkyl radical R are particularly preferred.

Mixtures of compounds of the formula I which split off different peroxocarboxylic acids, in particular those which, under perhydrolysis conditions, give substituted perbenzoic acid and / or peroxocarboxylic acids having 1 to 5 carbon atoms, in particular 2 to 4 carbon atoms, with those which come under perhydrolysis conditions linear or branched chain peroxocarboxylic acids having 6 to 18 carbon atoms, in particular 7 to 12 carbon atoms, are used in a preferred embodiment of the invention. For use in particulate detergents, cleaning agents and disinfectants, the substances of the formula I to be used according to the invention are preferably solid at room temperature.

The hydrophilic groups, of which at least 1 is present in the enol esters to be used according to the invention, are selected from the sulfonate, sulfate, phosphonate, phosphate and carboxylate groups, which may also be in protonated form, and the ammonium groups. If the anionic groups mentioned are present, counter cations, preferably alkali metal ions such as sodium, potassium and / or lithium ions are present. If there is an ammonium group, charge-balancing anions X ^" , preferably halides such as chloride. Bromide, iodide and / or fluoride, are present.

Preferred representatives of the compounds according to general formula I include the enol esters according to general formula II derived from the enol form of glutaconic acid monoaldehyde

and the enol esters derived from the enol form of phenylpyruvic acid according to general formula III,

in which in each case R has the meaning given above and whose carboxyl group can also be present in salt form.

The compounds to be used according to the invention can be prepared according to or analogously to those from the publications by R. Schmidt and A. Wagner in Synthesis 1982. page 958 ff. And Y. Chigata, M. Masaki and M.Ohta in Bull. Chem. Soc. Jpn. 42 (1969), page 224ff. known methods can be produced.

The compounds of the formula I are 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 washing liquor, detached from the textile, and the oxidative destruction of itself in the washing liquor textile dyes that detach from textiles under the washing conditions before they can be drawn onto textiles of a different color.

Another preferred application form according to the invention is the use of compounds according to formula I in cleaning solutions for hard surfaces, in particular for dishes, for bleaching colored stains. Here too The term bleaching both the bleaching of on the hard surface befind¬ writeln dirt, especially tea ^~ and bleaching in the dishwashing, detached from the hard surface dirt understood.

The invention further relates to detergents, cleaning agents and disinfectants which contain a compound of the formula I as a bleach activator and a process for activating peroxygen compounds using such a compound according to the formula I.

In the process according to the invention and in the context of a use according to the invention, the compounds of the formula I can be used as activators wherever a particular increase in the oxidation activity of inorganic peroxygen compounds at low temperatures is important, for example in the bleaching of textiles and hair or hard surfaces, in the oxidation of organic or inorganic intermediates and in disinfection.

The use according to the invention essentially consists in creating conditions under which a peroxygen compound and a compound according to formula I 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 reaction partners meet in aqueous solution. This can be done by adding the peroxygen compound and the bleach activator separately in a separate form to an optionally detergent-containing solution. However, the process according to the invention is particularly advantageously carried out using a washing, cleaning or disinfectant according to the invention which contains the bleach activator according to formula I and optionally 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, there are also mixtures of water and suitable organic solutions Solvents as a reaction medium in question. The amounts of peroxygen compounds used 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 bleach activator according to formula I used also depends on the application. Depending on the desired degree of activation, so much of the bleach activator according to formula I to be used according to the invention is used that 0.03 mol to 1 mol, preferably 0.1 mol to 0.5 mol, of bleach activator are used per mol of peroxygen compound, but these limits can be met in special cases can also be exceeded or fallen below.

A detergent, cleaning agent or disinfectant according to the invention preferably contains 0.2% by weight to 30% by weight, in particular 1% by weight to 20% by weight, of bleach activator according to formula I, in addition to conventional ones which are compatible with the bleach activator Ingredients. The activating substances to be used according to the invention can be adsorbed onto carriers in a manner known in principle and / or embedded in enveloping substances.

The detergents, cleaning agents and disinfectants according to the invention, which can be present in particular as powdery solids, in post-compacted particle form, as homogeneous solutions or suspensions, can, in addition to the bleach activator according to formula I to be used according to the invention, in principle all known and such agents contain usual ingredients. The washing and cleaning agents according to the invention can in particular builder substances, surface-active surfactants, organic and / or in particular inorganic peroxygen compounds, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and further auxiliaries, such as optical brighteners, graying inhibitors, color transfer inhibitors. Foam regulators, additional peroxygen activators, dyes and fragrances contain.

A disinfectant according to the invention can be used to strengthen the disinfectant effect against special germs in addition to those previously mentioned Contain ingredients common antimicrobial agents. Such antimicrobial additives are preferably contained in the disinfectants according to the invention in amounts of up to 10% by weight, in particular from 0.1% by weight to 5% by weight.

In addition to the bleach activators according to formula I to be used according to the invention, customary substances mentioned at the outset which form peroxocarboxylic acids under perhydrolysis conditions and / or customary transition metal complexes activating the bleach can be used.

Suitable peroxygen compounds are in particular organic peracids or peracidic salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which give off hydrogen peroxide under the washing or cleaning conditions, such as perborate, percarbonate and / or persilicate, into consideration. 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 disinfecting agent components. Alkali percarbonate, alkali perborate monohydrate or hydrogen peroxide is particularly preferably used in the form of aqueous solutions which contain 3% by weight to 10% by weight of hydrogen peroxide. If a washing or cleaning agent according to the invention contains peroxygen compounds, these are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight, while in the disinfectants according to the invention preferably 0.5 % By weight to 40% by weight, in particular from 5% by weight to 20% by weight, of peroxygen compounds are present.

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 especially alkyl glycosides and ethoxy Lation 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, can also be used.

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 half-esters 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 alkyl benzenesulfonates 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 used in the reaction of corresponding monoolefins with sulfur trioxide arise, as well as alpha-sulfo fatty acid esters, which arise in the sulfonation of fatty acid methyl or ethyl esters.

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 and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1, 1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and also polymeric (poly-) carboxylic acids polycarboxylates of international patent application WO 93/16110 or international patent application WO 92/18542 or European patent specification EP 0 232 202 accessible from polysaccharides or dextrins, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which also contain small amounts of polymerizable substances without Polymerized carboxylic acid functionality can contain. 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 the third monomer. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ carboxylic acid and preferably from a C 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 . 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. Other preferred copolymers are such, the written in the German patent applications DE 43 03 320 and DE 44 17 734 be¬ and ^"preferably as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate have. The organic builders NEN kön¬, liquid in particular for producing agent, in 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 tripolyphosphate. In particular, crystalline or amorphous alkali alumosilicates are used as water-insoluble, water-dispersible inorganic builder materials, in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid compositions in particular from 1% by weight to 5% by weight. %, used. Among 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 in particular have no particles with a grain size above 30 μm and preferably consist of at least 80% by weight of particles with a size below 10 μm. Their calcium binding capacity, which can be determined according to the information in German patent DE 24 12 837, is generally in the range from 100 to 200 mg CaO per gram.

Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates. The alkali metal compounds which can be used as builders in the agents according to the invention Likates 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 layered silicates of the general formula Na ₂ Si _x O _{2x +} | are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates y H ₂ O is used, in which x, the so-called module, is a number from 1, 9 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, wherein β-sodium disilicate can be obtained, for example, by the method described in the international patent application WO 91/08171 is. 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 oil alkali silicates of the above general formula, in which x is 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 0436 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. In a preferred embodiment of agents according to the invention, a granular compound of alkali silicate and alkali carbonate is used, as described, for example, in international patent application WO 95/22592 or how it is commercially available, for example, under the name Nabion® 15. If alkali aluminosilicate, in particular zeolite, is also present as an additional builder substance, the weight ratio of aluminosilicate to silicate, in each case based 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 only the components of the Water hardness-complexing 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 amino polycarboxylic acids, aminopolyphosphonic acids and hydroxypolyphosphonic acids and their water-soluble salts and mixtures thereof.

Enzymes which can be used in the agents are those from the class of proteases, lipases, cutinases, amylases, pullulanases, cellulases, hemicellulases, xylanases, oxidases and peroxidases and mixtures thereof. 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 optionally used enzymes can, as described for example in European patent EP 0 564 476 or in international patent applications WO 94/23005, be 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. The organic solvents which can be used in the agents according to the invention, especially 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 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 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.

Color transfer inhibitors which are suitable for use in agents according to the invention, in particular those for washing textiles, include in particular polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole.

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

The agents can contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly structured compounds which are used instead of morpholino Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned optical brighteners can also be used.

In particular when used in machine washing and cleaning processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin that have a high proportion of C _| Have ₈ -C ₂₄ fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bisfatty acid alkylene diamides. Mixtures of different foam inhibitors are also used with advantages, for example those made of silicone, paraffins or waxes. The foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamide are particularly preferred. In addition, agents for preventing tarnishing of silver objects, so-called silver corrosion inhibitors, can be used in cleaning agents for dishes according to the invention. Preferred silver corrosion inhibitors are organic disulfides, dihydric phenols, trihydric phenols, optionally alkyl- or aminoalkyl-substituted triazoles such as benzotriazole and cobalt, manganese, titanium, zirconium, hafnium, vanadium or cerium salts and / or complexes, in which the metals mentioned are in one of the oxidation states II, III, IV, V or VI.

The preparation of solid compositions 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 activator optionally being added later. 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. 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

Phenylpyruvic acid acetate (Bl; see general formula III, R = CH ₃ ) according to the invention and for comparison N, N for the preparation of phenylpyruvic acid acetate prepared from phenylpyruvic acid and acetic anhydride by the process of R. Schmidt and A. Wagner in Synthesis 1982 , N ', N'-tetraacetylethylenediamine (VI; TAED), sodium n-nonanoyloxybenzenesulfonate (V2; n-NOBS) and the non-inventive enol ester isopropenyl nonanoate (V3) were examined for their bleaching effect at 30 ° C. and pH 10. 100 ml of a wash liquor, containing 5 l (residual distilled water), 2.5 g sodium alkylbenzenesulfonate, 2 g fatty alkyl ethoxylate, 10 g sodium tripolyphosphate, 1.5 g sodium silicate, 7.5 g sodium sulfate, 1.75 g CaCl _{2 were added} Dihydrate, 0.48 g MgCl ₂ hexahydrate, 12.5 g sodium diphosphate decahydrate and 20 ml isopropanol, with 2 ml red wine, 138 mg sodium perborate monohydrate and the amount of activator given in the table below (equal to active oxygen based on the peroxocarboxylic acid formed ) added and held at the temperature mentioned for 30 minutes. Table 1 below shows the decolorization performance determined under these conditions, expressed in relation to the extinction value for the wash liquor only mixed with red wine (corresponding to 0% decolorization), the extinction value of the pure wash liquor being used as the zero value (corresponding to 100% decolorization), specified. It can be seen that the bleach activators used according to the invention have decolorization performances which are higher than those of known activators.

Table 1: Bleaching performance

100 ml of a solution were also added to 100 ml of a solution which contained 20 mg of morin per liter of fully demineralized water and the pH of which was adjusted to 9.5 and maintained at this value with the aid of a pH-stat device during the entire subsequent measurement period 1 g of sodium perborate monohydrate and 0.3 g of the bleach activator to be tested were added to the temperature, which was kept constant at 20 ° C., over the entire measuring period. The absorbance E of the solution at 400 nm was measured every minute over a period of 30 minutes. Table 2 below shows the values for the percent decolorization D (t), calculated according to D (t) = [E (0) - E (t)] / E (0) * 100.

The were tested according to the method of Y. Chigata, M. Masaki and M.Ohta, published in Bull. Chem. Soc. Jpn. 42 (1969), page 224ff, 5-benzoyloxy-2,4-pentadienoic acid (B2; see general formula II, R = phenyl) produced from 5-benzoyloxy-2,4-pentadienal and for comparison N, N, N ' , N'-tetraacetylethylenediamine (VI; TAED) and sodium n-nonanoyloxybenzenesulfonate (V2; n-NOBS). The superiority of the bleach activator used according to the invention can be seen from the values given in Table 2 below.

Table 2: Decolorization as a function of time

Claims

claims

1. Use of compounds of the general formula I,

A

in which R represents hydrogen, an aryl, alkyl, alkenyl or cycloalkyl radical having 1 to 17 C atoms, n represents a number from 1 to 8, A, B and C independently of one another represent hydrogen, an aryl, alkyl , Alkenyl or cycloalkyl group with 1 to 17 carbon atoms or a hydrophilic group selected from -SO ₃ H, -OSO ₃ H, -PO (OH) ₂ , - OPO (OH) ₂ , -CO ₂ H and their anions and -N ⁺ R ¹ R ² R ³ X ^" , where R ¹ , R ² and R independently of one another are hydrogen, an aryl, alkyl, alkenyl or cycloalkyl radical having 1 to 17 C atoms and X ^{" is} a With the proviso that at least one of the substituents A, B or Y in the molecule is a hydrophilic group, charge-compensating anions are available as activators for in particular organic peroxygen compounds in oxidation, washing, cleaning or disinfecting solutions.

2. Use of compounds of the general formula I,

A

in which R represents hydrogen, an aryl, alkyl, alkenyl or cycloalkyl radical having 1 to 17 carbon atoms, n represents a number from 1 to 8, A, B and Y independently of one another represent hydrogen, an aryl, alkyl , Alkenyl or cycloalkyl group with 1 to 17 carbon atoms or a hydrophilic group selected from -SO ₃ H, -OSO ₃ H, -PO (OH) ₂ , - OPO (OH) ₂ , -CO ₂ H and their anions as well as -N ⁺ R ^! R ² R ³ X ^" , in which R ¹ , R ² and R ³ independently of one another are hydrogen, an aryl, alkyl, alkenyl or cycloalkyl radical having 1 to 17 C atoms and X ^{" is} a charge-balancing anion with the proviso that at least one of the substituents A, B or Y in the molecule is a hydrophilic group mentioned, for bleaching color stains when washing textiles, in particular in an aqueous, surfactant-containing liquor.

3. Use of compounds of the general formula I,

A

in which R represents hydrogen, an aryl, alkyl, alkenyl or cycloalkyl radical having 1 to 17 carbon atoms, n represents a number from 1 to 8, A, B and Y independently of one another represent hydrogen, an aryl, alkyl , Alkenyl or cycloalkyl group with 1 to 17 carbon atoms or a hydrophilic group selected from -SO ₃ H, -OSO ₃ H, -PO (OH) ₂ , - OPO (OH) ₂ , -CO ₂ H and their anions and -N ⁺ R'R ² R ³ X ^" , where R ¹ , R ² and R ^" independently of one another are hydrogen, an aryl, alkyl, alkenyl or cycloalkyl radical having 1 to 17 C atoms and X ^" for a charge-balancing anion, with the proviso that at least one of the substituents A, B or Y in the molecule is a hydrophilic group mentioned, in cleaning solutions for hard surfaces, in particular for dishes, for bleaching colored stains.

4. Use according to one of claims 1 to 3, characterized in that the compounds according to general formula I from the enol esters according to general formula II

to be selected.

5. Use according to one of claims 1 to 3, characterized in that the compounds according to general formula I from the enol esters according to general Formula III

to be selected.

6. Use according to one of claims 1 to 5, characterized in that the radical R is phenyl, C, - to C _π- alkyl or 9-decenyl.

7. Use according to one of claims 1 to 6, characterized in that the peroxygen compound to be activated is selected from the group comprising organic peracids, hydrogen peroxide, perborate and percarbonate and mixtures thereof.

8. washing, cleaning or disinfectant, characterized in that it is an enol ester selected from the compounds of formula (I),

A

^{/ l}

in which R represents hydrogen, an aryl, alkyl, alkenyl or cycloalkyl radical having 1 to 17 carbon atoms, n represents a number from 1 to 8, A, B and Y independently of one another represent hydrogen, an aryl, alkyl , Alkenyl or cycloalkyl group with 1 to 17 carbon atoms or a hydrophilic group selected from -SO ₃ H, -OSO ₃ H, -PO (OH) ₂ , - OPO (OH) ₂ , -CO ₂ H and their anions and -N "R ¹ R ² R ³ X ^" , where R ¹ , R ² and R ^" independently of one another represent hydrogen, an aryl, alkyl, alkenyl or cycloalkyl radical having 1 to 17 C atoms and X ^" for are a charge-balancing anion with the proviso that at least one of the substituents A, B or Y in the molecule is a hydrophilic group mentioned, and mixtures thereof.

9. Composition according to claim 8, characterized in that it contains 0.2 wt .-% to 30 wt .-%, in particular 1 wt .-% to 20 wt .-% bleach activator according to formula I.

10. Composition according to claim 8 or 9, characterized in that it is 5 to 50 wt .-%, in particular 8 to 30 wt .-% anionic and / or nonionic surfactant, up to 60 wt .-%, in particular 5 to 40% by weight of builder substance, up to 5% by weight, in particular 0.2 to 2% by weight, enzyme, up to 30% by weight, in particular 6 to 20% by weight, of organic solvent the group comprising alcohols with 1 to 4 carbon atoms, diols with 2 to 4 carbon atoms and mixtures thereof and the ethers derived from these classes of compounds and up to 20% by weight, in particular 1.2 to 17% by weight .-% pH regulator contains.

11. Composition according to claim 8 or 9 for in particular machine cleaning of dishes, characterized in that it contains 0.1 wt .-% to 20 wt .-%, in particular 0.2 wt .-% to 5 wt .-% surfactant .

12. Disinfectant according to claim 8 or 9, characterized in that it contains 0.1 wt .-% to 20 wt .-%, in particular 0.2 wt .-% to 5 wt .-% surfactant and / or antimicrobial additives contains up to 10 wt .-%, in particular from 0.1 wt .-% to 5 wt .-%.

13. Disinfectant according to claim 12, characterized in that it comprises, in addition to the constituents mentioned, 0.5% by weight to 40% by weight, in particular 5% by weight to 20% by weight, of a peroxygen compound selected from the group Hydrogen peroxide, perborate and percarbonate and mixtures thereof contains.

14. Composition according to one of claims 8 to 11, characterized in that it contains up to 50 wt .-%, in particular from 5 wt .-% to 30 wt .-% peroxygen compound in addition to the ingredients mentioned.

15. Process for activating peroxygen compounds using a compound of the general formula I, A

in which R represents hydrogen, an aryl, alkyl, alkenyl or cycloalkyl radical having 1 to 17 carbon atoms, n represents a number from 1 to 8, A, B and Y independently of one another represent hydrogen, an aryl, alkyl , Alkenyl or cycloalkyl group with 1 to 17 carbon atoms or a hydrophilic group selected from -SO ₃ H, -OSO ₃ H, -PO (OH) ₂ , - OPO (OH) ₂ , -CO ₂ H and their anions and -N ⁺ R ^] R ² R ³ X ^' , where R ¹ , R ² and R independently of one another are hydrogen, an aryl, alkyl, alkenyl or cycloalkyl radical having 1 to 17 C atoms and X ^"is a Charge-balancing anions are provided that at least one of the substituents A, B or Y in the molecule is a hydrophilic group.