EP1694806B1 - Bleaching detergent or cleaning agent - Google Patents

Abstract

A detergent or cleaning agent that exhibits high bleaching properties without attacking the textiles to be cleaned or hard surfaces in an unreasonably harsh manner. Said aim is achieved by using a combination consisting of a percarbonate-based bleaching agent and a persulfate-based bleaching agent.

Description

The present patent application relates to a bleaching detergent or cleaning agent containing two different types of bleaching agents.

For a long time detergents and cleaners contain so-called bleaching agents, which attack redox reactions on the surface to be cleaned or destroy surface contaminants that have already been removed, so that they do not deposit again recognizable on the surface. In addition to the playing a minor role reductive bleaching agents come in particular oxidizing agents are used. Although chlorine, for example, accessible from hypochlorite, because of its high oxidation potential is a generally well-suited bleaching agent, usually oxidizing agents are used, which exploit the oxidizing power of oxygen, as these represent a lower risk of damage to the surface to be cleaned.

Peroxygen compounds suitable for use as bleaches in both detergents for cleaning textiles and in hard surface cleaners are both inorganic and in particular organic peracids or persalts of organic acids, for example phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, but also hydrogen peroxide and under the washing or cleaning conditions, hydrogen peroxide-releasing inorganic salts such as perborate, percarbonate and / or persilicate have been described. On various occasions, for example in international patent applications WO 00/3604 and WO 00/3605 , it has been proposed to use atmospheric oxygen with the aid of these activating substances such as aldehydes and transition metal salts as bleaching agents. It is also known that hydrogen peroxide can be produced in the course of washing or purification processes by means of an enzymatic system, that is to say an oxidase and its substrate. One is However, always strives to find even more effective bleaches or to optimize the known bleaches so that the highest possible bleaching performance results without the textile or hard surface to be cleaned is unreasonably attacked. The US-A-5 599 781 discloses detergent feedstocks containing persulfate and percarbonate as the leading agent.

Surprisingly, it has now been found that the bleaching result of detergents and cleaners over that of those agents which contain only one of the two active ingredients, when using both a percarbonate-based bleach and a bleach on persulfate basis, where it Percarbonate-based bleach and persulfate bleach in the active oxygen ratio of 4: 1 to 1: 4 contains.

An object of the invention is therefore a washing or cleaning agent containing percarbonate based bleaching agent and persulfate bleaching agent.

The content of the combination of percarbonate-based bleaching agent and persulfate-bleaching agent in the compositions of the present invention is preferably 10% by weight to 70% by weight, especially 15% by weight to 30% by weight, particularly preferably from 20% to 40% by weight. In one embodiment of the invention, the agent contains at least 5% by weight, preferably 7.5% to 50% by weight and especially 9% to 35% by weight of persulfate-based bleach.

In addition to the combination of percarbonate-based bleaching agent and persulfate bleaching agent, detergents or cleaners according to the present invention may have all of the ingredients usually present in them, as long as they do not interact in unduly negative ways with the bleaching agents or bleaches. In a preferred embodiment, the compositions according to the invention are solid, wherein they may be present in powder form or as larger shaped bodies, for example as granules, extrudates or tablets.

The percarbonate-based bleach contained in the compositions of the present invention is an adduct of hydrogen peroxide to an alkali carbonate, a so-called alkali percarbonate. In this case, sodium percarbonate (theoretical composition 2Na ₂ CO ₃ .3H ₂ O ₂ ) is particularly preferred. It can be prepared by known methods and, if desired, compounded or stabilized in granular form and optionally enveloped, as for example from the international patent applications WO 91/15423 . WO 92/17400 . WO 92/17404 . WO 93/04159 . WO 93/04982 . WO 93/20007 . WO 94/03553 . WO 94/05594 . WO 94/14701 . WO 94/14702 . WO 94/24044 . WO 95/02555 . WO 95/02672 . WO 95/06615 . WO 95/15291 . WO 95/15292 . WO 95/18064 . WO 95/18065 . WO 95/23208 . WO 95/23210 . WO 96/11252 . WO 96/11253 . WO 96/14389 . WO 96/19408 . WO 96/23354 . WO 97/19890 . WO 97/35951 or WO 97/45524 or the European patent applications EP 0 745 664 . EP 0 748 764 . EP 0 791642 . EP 0 796 817 . EP 0 873 971 . EP 0 922 575 . EP 0 962 424 . EP 0 970 917 . EP 1 127 840 or EP 1 149 800 is known. In a preferred embodiment, it is possible to use an alkali metal percarbonate stabilized with specific borates, as disclosed in the European patent applications EP 459 625 . EP 487 256 or EP 567,140 or an alkali metal percarbonate coated with a combination of alkali metal salts, as disclosed in European patent applications EP 0 623 553 or EP 0 592 969 known. As is clear from the above theoretical formula, about 104.675 g of sodium percarbonate can release 1 mole of active oxygen; however, the actual active oxygen content of commercially available sodium percarbonates may also be below this theoretical maximum value. This need not be attributed to decomposition of the percarbonate at all or not exclusively, but may result from the presence of granulation or formulation aids or coating materials in the commercial products.

The bleaches based on persulfate present in the compositions according to the invention are preferably peroxomono- and disulphuric acid and mixtures thereof which are also present in the form of their alkali metal salts and / or their acidic alkali metal salts, that is to say alkali hydrogen peroxomono- and disulphates can. Peroxomonosulfuric acid and / or their alkali salts or acidic alkali metal salts are particularly preferred, among these in particular potassium hydrogen peroxomonosulfate. They can be used as pure substances or, if appropriate, in commercial form in admixture with one another and / or in admixture with the corresponding alkali metal sulphates or alkali hydrogen sulphates. Particularly preferred is the use of potassium hydrogen peroxomonosulfate in the form of the triple salt Potassium hydrogen peroxomonosulfate, potassium hydrogen sulfate and potassium sulfate as commercially available under the names Curox®, Oxone® or Caroat® and which approximately corresponds to the gross formula 2KHSO ₅ · KHSO ₄ · K ₂ SO ₄ . Its active oxygen content can thus be up to about 1 mole per 307.365 g. Agents containing such persulfate bleaches are known, for example, from the European patent applications EP 0 135 226 . EP 0 271 189 and EP 0 726 309 and the US patents US 3 556 711 and US 5 559 089 known.

Further objects of the invention are the use of a combination of a percarbonate-based bleaching agent with a persulf bleach-based bleaching agent to enhance the cleaning performance of detergents, as well as a laundry washing process and a hard-surface cleaning process using each Combination of a percarbonate-based bleaching agent with a persulf bleach-based bleach. In the context of the process according to the invention preferably a washing or cleaning agent according to the invention is used, but the washing process according to the invention can also be carried out by mixing the percarbonate-based bleaching agent and the bleaching agent based on persulfate, premixed or as individual components, in a washing machine or a container intended for hand washing is metered in and previously, simultaneously or thereafter a conventional detergent, which may be free of bleach components, in the washing machine or the hand washing vessel brings. The same applies mutatis mutandis to the inventive method for cleaning hard surfaces. If it is desired to use the percarbonate-based bleaching agent and the bleaching agent based on persulfate in premixed form, it is also possible to use it in the form of an aqueous solution containing both bleaching agents. It is also possible to dissolve them separately in water and to introduce the two resulting solutions separately into the washing or cleaning process. The same applies mutatis mutandis to the use according to the invention.

An agent according to the invention contains the two bleaching agents, namely the percarbonate-based bleaching agent and the persulfur bleaching agent, in the ratio of the molar amounts of active oxygen (active oxygen ratio) present in both of 4: 1 to 1: 4. Relationships in the area from 3: 1 to 1: 3, especially from 2.5: 1 to 1: 2.5, are particularly preferred, with those of about 1: 1, for example 2: 1 to 1: 2, being most preferred.

Detergents or cleaning agents according to the invention may contain, in addition to the bleaching agent combination mentioned, all customary other constituents of such agents which do not interact in an undesired manner with the bleaching agents. In the context of the use according to the invention or the process according to the invention, this interaction is of no importance if the compounding agents with otherwise undesirably interacting ingredients are allowed to come into contact with the bleach combination only shortly before the time of application, so that in these cases they are in addition to the bleach combination are not subject to any special restrictions on their ingredients.

If desired, an agent according to the invention may comprise bleach activator, in particular in amounts ranging from 2% by weight to 10% by weight. The group of eligible bleach activators includes the commonly used N- or O-acyl compounds, for example, polyacylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides, and cyanurates Carboxylic anhydrides, especially phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl-phenolsulfonat, and acylated sugar derivatives, in particular pentaacetylglucose, and cationic nitrile derivatives such as trialkylammoniumacetonitrile salts. The bleach activators may have been coated or granulated in a known manner with coating substances in order to avoid the interaction with the per compounds, with the aid of carboxymethylcellulose granulated tetraacetylethylenediamine having average particle sizes of 0.01 mm to 0.8 mm, as for example according to the in the European patent specification EP 37 026 granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, as described in the German Patent DD 255 884 can be prepared, and / or according to those in the international patent applications WO 00/50553 . WO 00/50556 . WO 02/12425 . WO 02/12426 or WO 02/26927 in Particulate preformed Trialkylammoniumacetonitrile is particularly preferred. Detergents or cleaning agents contain such bleach activators, if present, preferably in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the total agent. It is particularly advantageous, however, that agents according to the invention also have a very good bleaching performance even without the presence of customary peracid peracid-forming bleach activators or bleach catalysts, for example redox-active metal complexes, so that in a preferred embodiment they are free of bleach activators and bleach catalysts.

In a further preferred embodiment, an agent according to the invention contains nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkylamines, vicinal diols, fatty acid alkyl esters and / or fatty acid amides and their derivatives Mixtures, in particular in an amount in the range of 1 wt .-% to 20 wt .-%, preferably from 1 wt .-% to 20 wt .-%.

Suitable nonionic surfactants include the alkoxylates, in particular the ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched-chain alcohols having 10 to 22 C atoms, preferably 12 to 18 C atoms. The degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides. Particularly suitable are the derivatives of fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can be used for the preparation of usable alkoxylates. Useful are accordingly the alkoxylates, in particular the ethoxylates, primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof. In addition, suitable alkoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the said alcohols with respect to the alkyl part, usable. In addition, the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters, as described in the international Patent application WO 90/13533 as well as fatty acid polyhydroxyamides, as prepared according to the methods of US Pat US 1,985,424 . US 2 016 962 and US 2,703,798 as well as the international patent application WO 92/06984 can be prepared. So-called alkylpolyglycosides which are suitable for incorporation in the compositions according to the invention are compounds of the general formula (G) _n -OR ¹² , in which R ^{12 is} an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and n is a number between 1 and 10 mean. Such compounds and their preparation are described, for example, in the European patent applications EP 92 355 . EP 301 298 . EP 357 969 and EP 362,671 or the US patent US 3,547,828 described. The glycoside component (G) _n are oligomers or polymers of naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, Include xylose and lyxose. The oligomers consisting of such glycosidically linked monomers are characterized not only by the nature of the sugars contained in them by their number, the so-called Oligomerisierungsgrad. The degree of oligomerization n assumes as the value to be determined analytically generally broken numerical values; it is between 1 and 10, with the glycosides preferably used below a value of 1.5, in particular between 1.2 and 1.4. Preferred monomer building block is glucose because of its good availability. The alkyl or alkenyl moiety R ^{12 of} the glycosides preferably also originates from readily available derivatives of renewable raw materials, in particular from fatty alcohols, although their branched-chain isomers, in particular so-called oxoalcohols, can also be used for the preparation of useful glycosides. Accordingly, the primary alcohols having linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly suitable. Particularly preferred alkyl glycosides contain a Kokosfettalkylrest, that is, mixtures having substantially R ¹² = dodecyl and R ¹² = tetradecyl. Particularly preferred are agents which have a content of alkyl polyglycosides in the range of 0.1 wt .-% to 7 wt .-%.

Another embodiment of such agents comprises the presence of sulfate and / or sulfonate synthetic anionic surfactant, in particular Fatty alkyl sulfate, fatty alkyl ether sulfate, sulfo fatty acid esters and / or sulfo fatty acid salts, in particular in an amount in the range from 0.01% by weight to 15% by weight, preferably 0.01% by weight to 5% by weight. The anionic surfactant is preferably selected from the alkyl or alkenyl sulfates and / or the alkyl or alkenyl ether sulfates in which the alkyl or alkenyl group has 8 to 22, in particular 12 to 18, carbon atoms.

Suitable synthetic anionic surfactants which are particularly suitable for use in compositions according to the invention are the alkyl and / or alkenyl sulfates having 8 to 22 C atoms which carry an alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as counter cation. Preference is given to the derivatives of the fatty alcohols having in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols. The alkyl and alkenyl sulfates can be prepared in a known manner by reaction of the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases. Sulfur-type surfactants which can be used also include the sulfated alkoxylation products of the alcohols mentioned, known as ether sulfates. Such ether sulfates preferably contain from 2 to 30, in particular from 4 to 10, ethylene glycol groups per molecule. Suitable anionic surfactants of the sulfonate type include the α-sulfoesters obtainable by reaction of fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those of fatty acids having 8 to 22 C atoms, preferably 12 to 18 C atoms, and linear alcohols having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derivative sulfonation, as well as the formal saponification resulting from these sulfo fatty acids.

Other optional surface-active ingredients are soaps, suitable being saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids. In particular, those soap mixtures are preferred which are composed of 50% to 100% by weight of saturated C ₁₂ -C ₁₈ fatty acid soaps and up to 50% by weight of oleic acid soap. Preferably soap is present in amounts of from 0.5% to 7% by weight but may be absent altogether. However, especially in liquid or gel-like compositions according to the invention, higher amounts of soap, generally up to 20% by weight, can also be present.

If desired, the compositions may also contain betaines and / or cationic surfactants, which, if present, are preferably used in amounts of from 0.5% by weight to 7% by weight. Among them, the so-called esterquats, that is, quaternized esters of carboxylic acid and aminoalcohol, are particularly preferred. These are known substances that can be obtained by the relevant methods of preparative organic chemistry. In this connection, please refer to the international patent application WO 91/01295 referenced, after which triethanolamine partially esterified with fatty acids in the presence of hypophosphorous acid, air passes and then quaternized with dimethyl sulfate or ethylene oxide. From the German patent DE 43 08 794 moreover, a process for the preparation of solid ester quats is known in which the quaternization of triethanolamine esters is carried out in the presence of suitable dispersants, preferably fatty alcohols. Reviews on this topic are, for example, by R. Puchta et al. in tens. Surf. Det., 30 , 186 (1993), M.Brock in Tens.Surf.Det. 30 , 394 (1993), R. Lagerman et al. in J.Am.Oil.Chem.Soc., 71, 97 (1994) and I.Shapiro in Cosm.Toil. 109 , 77 (1994).

In a further embodiment, an agent according to the invention may comprise water-soluble and / or water-insoluble builder, in particular selected from alkali metal aluminosilicate, crystalline alkali metal silicate with modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts of up to 60% by weight.

The water-soluble organic builder substances include, in particular, those from the class of the polycarboxylic acids, in particular citric acid and sugar acids, and also the polymeric (poly) carboxylic acids, in particular the polycarboxylates of the international patent application obtainable by oxidation of polysaccharides WO 93/16110 , polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which also small amounts of polymerizable substances without carboxylic acid functionality may contain polymerized. The molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200,000, and of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000. Suitable, though less preferred compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers such as vinyl ethyl ethers, vinyl esters, ethylene, propylene and styrene in which the proportion of acid is at least 50% by weight. It is also possible to use as water-soluble organic builder substances terpolymers which contain two carboxylic acids and / or salts thereof as monomers and vinyl alcohol and / or a vinyl alcohol derivative 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, with maleic acid being particularly preferred. The third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol. In particular, preferred are vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example C ₁ -C ₄ carboxylic acids, with vinyl alcohol. Preferred terpolymers contain 60 wt .-% to 95 wt .-%, in particular 70 wt .-% to 90 wt .-% of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleinate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% of vinyl alcohol and / or vinyl acetate. Very particular preference is given to terpolymers in which the weight ratio of (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2 , 5: 1 lies. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C ₁ -C ₄ -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives , is substituted. Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid or (meth) acrylate, more preferably acrylic acid or acrylate, 10 wt .-% to 30 wt .-%, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid or Methallylsulfonat and as a third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% of a carbohydrate. This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred. The use of the third monomer presumably incorporates predetermined breaking points in the polymer which are responsible for the good biodegradability of the polymer. These terpolymers can be prepared in particular by processes described in the German patent DE 42 21 381 and the German patent application DE 43 00 772 are generally described, and generally have a molecular weight between 1000 and 200,000, preferably between 200 and 50,000 and in particular between 3000 and 10,000. They can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All the polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts. An agent of the invention preferably contains from 0.1% to 15% by weight of water-soluble organic builder.

Crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials. used. Among these, the detergent-grade crystalline aluminosilicates, especially zeolite NaA and optionally NaX, are preferred. Amounts near the above upper limit are preferably used in solid, particulate agents. In particular, suitable aluminosilicates have no particles with a particle size greater than 30 mm and preferably consist of at least 80% by weight of particles having a size of less than 10 mm. Their calcium binding capacity, according to the information of the German Patent DE 24 12 837 can be determined ranges from 100 to 200 mg CaO per gram. Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates. Those in the funds as builders useful alkali metal silicates preferably have a molar ratio of alkali metal oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12 and may be present in amorphous or crystalline form. Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na ₂ O: SiO ₂ of 1: 2 to 1: 2.8. Such amorphous alkali silicates are commercially available, for example, under the name Portil®. Those with a molar ratio Na ₂ O: SiO ₂ of 1: 1.9 to 1: 2.8 can be prepared by the process of European patent application EP 0 425 427 getting produced. They are preferably added in the course of the production as a solid and not in the form of a solution. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na ₂ Si _x O _{2x + 1} · are used yH ₂ O, in which x, the so-called module, a number from 1.9 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 the European patent application EP 0 164 514 described. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates (Na ₂ Si ₂ O ₅ .yH ₂ O) are preferred, whereby β-sodium disilicate can be obtained, for example, by the process described in International Patent Application WO 91/08171 is described. δ-Sodium silicates with a modulus between 1.9 and 3.2 can according to Japanese Patent Applications JP 04/238 809 or JP 04/260 610 getting produced. Also prepared from amorphous alkali metal silicates, practically anhydrous crystalline alkali metal silicates of the above general formula in which x is a number from 1.9 to 2.1, preparable as in the European patent applications EP 0 548 599 . EP 0 502 325 and EP 0 425 428 can be used in agents according to the invention. In a further preferred embodiment of the compositions, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as it is by the process of European patent application EP 0 436 835 made from sand and soda. Crystalline sodium silicates with a modulus ranging from 1.9 to 3.5, as prepared by the methods of European patents EP 0 164 552 and / or the European patent application EP 0 294 753 are available are used in a further preferred embodiment of inventive detergents or cleaning agents. Their content Alkali silicates is preferably 1 wt .-% to 50 wt .-% and in particular 5 wt .-% to 35 wt .-%, based on anhydrous active substance. If alkali metal aluminosilicate, in particular zeolite, is present as an additional builder substance, the content of alkali silicate is preferably 1% by weight to 15% by weight and in particular 2% by weight to 8% by weight, based on anhydrous active substance. The weight ratio of aluminosilicate to silicate, in each case based on anhydrous active substances, is then preferably 4: 1 to 10: 1. In agents containing both amorphous and crystalline alkali metal silicates, the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and especially 1: 1 to 2: 1.

Suitable water-soluble inorganic builders are also the known alkali metal phosphates, in particular trisodium polyphosphate. Alkaliphosphat is the summary term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to high molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance. Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and pass on Madrell's salt. NaH ₂ PO _{4 is} acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (potassium phosphate primary or monobasic potassium, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt of density 2.33 gcm ^-3 , has a melting point of 253 ° (decomposition to form (KPO ₃ ) _x , potassium polyphosphate) and is slightly soluble in water. Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm ^-3 , loss of water at 95 °), 7 moles (density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 moles water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° C and goes on stronger heating in the diphosphate Na ₄ P ₂ O ₇ . Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is readily soluble in water. Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which have a density of 1.62 gcm ^-3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder of density 2.56 gcm ^-3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry. Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals. Na ₄ P ₂ O ₇ is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4. Condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ results in higher mol. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: melting or annealing phosphates, Graham's salt, Kurrol and Madrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates. The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or with 6 H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with soda solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakalium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is marketed, for example, in the form of a 50% strength by weight solution (> 23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

These are just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two applicable; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used.

In addition to the builders mentioned, other water-soluble or water-insoluble inorganic substances can be used in agents according to the invention. Suitable in this context are the alkali metal carbonates, alkali metal bicarbonates and alkali metal sulfates and mixtures thereof. Such additional inorganic material may be present in amounts up to 70% by weight.

In addition, the agents may contain other ingredients customary in detergents and cleaners. These optional ingredients include, in particular, enzymes, enzyme stabilizers, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, color fixing agents, color transfer inhibitors, for example polyvinylpyrrolidone or polyvinylpyrdine N-oxide, foam inhibitors, for example organopolysiloxanes or paraffins, solvents, thickeners, and optical brighteners, for example stilbene disulfonic acid derivatives. Preferably, in inventive compositions up to 1 wt .-%, in particular 0.01 wt .-% to 0.5 wt .-% optical brightener, in particular compounds from the class of substituted 4,4'-bis (2,4 , 6-triamino-s-triazinyl) -stilbene-2,2'-disulfonic acids, up to 5 wt .-%, in particular 0.1 wt .-% to 2 wt .-% complexing agent for heavy metals, especially Aminoalkylenphosphonsäuren and their salts , up to 3% by weight, in particular from 0.5% by weight to 2% by weight, of grayness inhibitors and up to 2% by weight, in particular from 0.1% by weight to 1% by weight, of foam inhibitors, wherein said parts by weight each refer to total means.

Solvents which are used in particular for liquid or gel-like agents are, in addition to water, preferably those which are water-miscible. These include the lower alcohols, for example, ethanol, propanol, isopropanol, and the isomeric butanols, glycerol, lower glycols, such as ethylene and propylene glycol, and the derivable from said classes of compounds ether. Liquid agents according to the invention are preferably anhydrous.

Optionally present enzymes are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase or mixtures thereof. First and foremost, proteases derived from microorganisms, such as bacteria or fungi, come into question. It can be obtained in a known manner by fermentation processes from suitable microorganisms, for example, in the German Offenlegungsschriften DE 19 40 488 . DE 20 44 161 . DE 21 01 803 and DE 21 21 397 , the US patents US Pat. No. 3,623,957 and US 4,264,738 , the European patent application EP 006 638 as well as the international patent application WO 91/02792 are described. Proteases are commercially available, for example available under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym® or Maxapem®. The lipase which can be used can be obtained from Humicola lanuginosa, as for example in European patent applications EP 258,068 . EP 305 216 and EP 341 947 described from Bacillus species, such as in the international patent application WO 91/16422 or the European patent application EP 384 717 described, from Pseudomonas species, such as in the European patent applications EP 468 102 . EP 385 401 . EP 375 102 . EP 334 462 . EP 331 376 . EP 330 641 . EP 214,761 . EP 218 272 or EP 204 284 or the international patent application WO 90/10695 described, from Fusarium species, such as in the European patent application EP 130 064 described from Rhizopus species, such as in the European patent application EP 117 553 described or from Aspergillus species, such as in the European patent application EP 167,309 be described. Suitable lipases are commercially available, for example, under the names Lipolase®, Lipozym®, Lipomax®, Amano®-Lipase, Toyo-Jozo®-Lipase, Meito®-Lipase and Diosynth®-Lipase. Suitable amylases are commercially available, for example, under the names Maxamyl®, Termamyl®, Duramyl® and Purafect® OxAm. The usable cellulase may be a recoverable from bacteria or fungi enzyme, which has a pH optimum, preferably in the weakly acidic to slightly alkaline range of 6 to 9.5. Cellulases of this type are known, for example, from German Offenlegungsschriften DE 31 17 250 . DE 32 07 825 . DE 32 07 847 . DE 33 22 950 or the European patent applications EP 265 832 . EP 269 977 . EP 270 974 . EP 273 125 such as EP 339,550 and international patent applications WO 95/02675 and WO 97/14804 known and commercially available under the names Celluzyme®, Carezyme® and Ecostone®.

The customary enzyme stabilizers present, if appropriate, in particular in liquid and / or gelled agents, include amino alcohols, for example mono-, di-, triethanol- and -propanolamine and mixtures thereof, lower carboxylic acids, for example from the European patent applications EP 376,705 and EP 378,261 Boric acid or alkali borates, boric acid-carboxylic acid combinations, such as from the European patent application EP 451 921 known, boric acid esters, such as from the international patent application WO 93/11215 or the European patent application EP 511 456 known boronic acid derivatives, such as from the European patent application EP 583 536 known, calcium salts, for example from the European patent EP 28,865 known Ca-formic acid combination, magnesium salts, such as from the European patent application EP 378 262 known, and / or sulfur-containing reducing agents, such as from the European patent applications EP 080 748 or EP 080 223 known.

Suitable foam inhibitors include long-chain soaps, especially behenic soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which moreover can contain microfine, optionally silanated or otherwise hydrophobicized silica. For use in particulate agents, such foam inhibitors are preferably bound to granular, water-soluble carrier substances, as for example in the German Offenlegungsschrift DE 34 36 194 , the European patent applications EP 262 588 . EP 301 414 . EP 309 931 or the European patent specification EP 150 386 described.

Examples Example 1:

Standardized soils (tea, red wine) on white cotton fabric were washed at 30 ° C with a particulate bleach-free detergent V0 (4 g / L). Further, a detergent V1 obtained from VO by adding sodium percarbonate and a detergent V2 obtained from VO by adding TAED (6.25% by weight to VO) and sodium percarbonate were used. Sodium percarbonate was added in each case in such an amount that at a concentration of the respective agent of 4 g / L in the washing solution mathematically 130 ppm of active oxygen are obtained from it. Alternatively, potassium monopersulfate (in an amount calculated to give 130 ppm at a 4 g / L concentration in the wash solution) was added to V0 (Agent V3). In order to obtain agents M1 to M3 according to the invention, V0 was admixed with mixtures (M1, 75:25, M2, 50:50, M3, 25:75) of the active oxygen sources sodium percarbonate and potassium monopersulfate. The bleach combinations mentioned were also added in amounts such that, when 4 g / l of the resulting agent were used, the active oxygen content in the wash solution was calculated at 130 ppm. The washed and rinsed cotton test fabrics were then dried, ironed and measured (determination of remission, Minolta CM 508d). There was a significant improvement in remission when using the compositions of the invention are detected, although the active oxygen contents were the same in the wash solution. Table 1 below shows the brightness value differences ΔL * for the test fabric washed with only V0. <u> Table 1 </ u> tea red wine V1 -0.01 -0.2 V2 1.6 1.6 V3 0.6 nb M1 2.1 nb M2 2.4 1.2 M3 0.8 2.4 nb: not determined

Example 2:

Example 1 was repeated, with the use of agents to which the bleaching agents or bleaching agent combinations had been added in amounts such that, when 4 g / l of the agent were used, the active oxygen content in the washing solution was calculated to be 300 ppm. In the following Table 2, in turn, the brightness value differences ΔL * are given for the test fabric washed with only V0. <u> Table 2 </ u> tea red wine V1 ' 0.9 0.8 V2 ' 2.8 2.0 V3 ' 2.1 4.4 M1 ' 4.3 nb M2 ' 4.2 5.3 M3 ' 2.9 4.9 nb: not determined

Example 3:

Example 1 was repeated, now using agents were used to which the bleach or bleach combinations were added in such amounts that when using 4 g / l of the agent, the active oxygen content in the Washing solution calculated 500 ppm. In the following Table 3, in turn, the brightness value differences ΔL * are given for the test fabric washed with only V0. <u> Table 3 </ u> tea red wine V1 " 1.4 0.2 V2 " 2.9 1.8 V3 " 0.8 3.7 M1 " 8.7 6.2 M2 " 7.4 7.7 M3 " 6.5 6.3

Claims (10)

1. Washing or cleaning composition comprising percarbonate-based bleach and persulphate-based bleach which is peroxomono- and -disulphuric acid, which may also be present in the form of their alkali metal salts and/or of their acidic alkali metal salts, or is a mixture thereof, said composition comprising percarbonate-based bleach and persulphate-based bleach in an active oxygen ratio of 4:1 to 1:4.
2. Composition according to Claim 1, characterized in that it comprises percarbonate-based bleach and persulphate-based bleach in an active oxygen ratio of 3:1 to 1:3, especially 2.5:1 to 1:2.5.
3. Composition according to Claim 1 or 2, characterized in that the percarbonate-based bleach is an alkali metal percarbonate, especially sodium percarbonate.
4. Composition according to any one of Claims 1 to 3, characterized in that the persulphate-based bleach is a mixture of peroxomono- and -disulphuric acid which may also be present in the form of their alkali metal salts and/or of their acidic alkali metal salts.
5. Composition according to Claim 4, characterized in that the persulphate-based bleach is potassium peroxodisulphate and/or potassium hydrogenperoxomonosulphate.
6. Composition according to any one of Claims 1 to 5, characterized in that the persulphate-based bleach is the triple salt of potassium hydrogenperoxomonosulphate, potassium hydrogensulphate and potassium sulphate, which corresponds approximately to the empirical formula 2KHSO₅·KHSO₄·K₂SO₄.
7. Composition according to any one of Claims 1 to 6, characterized in that the content of the combination of percarbonate-based bleach and persulphate-based bleach is 10% by weight to 70% by weight, especially 15% by weight to 30% by weight.
8. Use of a combination of a percarbonate-based bleach with a persulphate-based bleach which is peroxomono- and -disulphuric acid, which may also be present in the form of their alkali metal salts and/or of their acidic alkali metal salts, or is a mixture thereof, the percarbonate-based bleach and the persulphate-based bleach being present in an active oxygen ratio of 4:1 to 1:4, for boosting the cleaning power of washing or cleaning compositions.
9. Process for washing laundry using a combination of a percarbonate-based bleach with a persulphate-based bleach which is peroxomono- and -disulphuric acid, which may also be present in the form of their alkali metal salts and/or of their acidic alkali metal salts, or is a mixture thereof, the percarbonate-based bleach and the persulphate-based bleach being present in an active oxygen ratio of 4:1 to 1:4.
10. Process for cleaning hard surfaces using a combination of a percarbonate-based bleach with a persulphate-based bleach which is peroxomono- and -disulphuric acid, which may also be present in the form of their alkali metal salts and/or of their acidic alkali metal salts, or is a mixture thereof, the percarbonate-based bleach and the persulphate-based bleach being present in an active oxygen ratio of 4:1 to 1:4.