EP3409756A1 - Bleaching detergent composition - Google Patents

Abstract

The oxidation and bleaching action of peroxygen compounds at low temperatures should be improved. This was achieved mainly by the use of certain Peroxopolyoxometallate.

Description

The present invention relates to the use of certain peroxo-polyoxometalates for the activation of peroxygen compounds in connection with the bleaching of soils when washing textiles, as well as detergents and cleaners containing such peroxo-polyoxometallate.

Inorganic peroxygen compounds, particularly 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 disinfecting and bleaching purposes. The oxidation effect of these substances in dilute solutions depends strongly on the temperature; Thus, for example, with H ₂ O ₂ or alkali perborate in alkaline bleaching liquors only at temperatures above about 80 ° C, a sufficiently fast bleaching of soiled textiles. At lower temperatures, the oxidation effect of the inorganic peroxygen compounds can be improved by addition of so-called bleach activators which are able to provide peroxycarboxylic under the abovementioned perhydrolysis and for the numerous proposals, especially from the classes of N- or O-acyl compounds, for example several times acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulphurylamides and cyanurates, and also carboxylic anhydrides, in particular phthalic anhydride and alkylsuccinic anhydrides, carboxylic esters, in particular sodium nonanoyloxybenzenesulphonate, sodium isononanoyloxy Benzenesulfonate, O-acylated sugar derivatives, such as pentaacetyl glucose, and N-acylated lactams, such as N-benzoyl-caprolactam, have become known in the literature. By adding these substances, the bleaching action of aqueous peroxide liquors can be increased so much that even at temperatures around 60 ° C substantially the same effects as with the peroxide solution alone at 95 ° C occur.

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

At low temperatures, the effect of the previously known activator compounds usually decreases noticeably.

From the European patent application EP 0 761 809 A1 bleaching agents are known which contain peroxygen compounds and polyoxometalates as bleach catalysts, wherein in the polyoxometalates Mo, W, Nn, Ta and / or V must be present and in addition transition metals of the 2nd and 8th subgroup may be included. Specifically disclosed are (Na / N (CH ₃ ) ₄ ) ₈ [MnMo ₆ O ₂₄ ], K ₄ [MnMo ₆ O ₈ (OH) ₆ ], (NH ₄ ) ₁₀ [Mn ₃ Sb ₂ W ₁₉ O ₆₈ ], Na ₁₇ [Mn ₂ Se ₆ W ₂₄ O ₉₄ Cl], Na ₂ (N (CH ₃ ) ₄ ) ₂ [Mn ₂ W ₁₂ O ₄₀ (OH) ₁₂ ] .12H ₂ O, (Na / K) ₁₀ [Mn ₃ Se ₂ W ₁₈ O ₆₆ ], Na ₈ [MnW ₁₂ O ₄₀ (OH) ₂ ] .6H ₂ O, Na ₆ [MnW ₁₂ O ₄₀ (OH) ₂ ] .6H ₂ O, Na ₇ [MnMo ₉ O ₃₂ ], and K ₇ [MnMo ₉ O ₃₂ ].

From the international patent application WO 97/07886 A1 peroxide compounds and / or oxygen are activated manganese catalysts of formula (Q) is known _q (Mn _p A _a X _x Y _y M _m O _d Z _z (H ₂ O) _b) c H ₂ O, wherein Q is H, Li, K, Na, Rb, Cs, Ca, Mg, Sr, Ba, Al, PR ¹ R ² R ³ R ⁴ and / or NR ¹ R ² R ³ R ⁴ with R ¹ , R ² , R ³ and R ^{4 is} H or C ₁ -C ₂₀ alkyl, C ₅ -C ₈ cycloalkyl or aryl; q is in the range of 1 to 60; p is in the range of 0.1 to 10; A is one or more transition metals of the 2nd to 8th subgroup except Zn; X is Ga, B, P, Si, Ge, As, F, Cl, Br and / or J; Y stands for Sb, S, Se, Te or Bi; y is in the range of 0.1 to 10; M is Mo, W, Nb, Ta and / or V; m is in the range of 0.5 to 60; Z is one or more anions; a, x and z are each in the range of 0 to 10; d represents the number of oxygen atoms necessary for charge balancing; and b and c are numbers in the range of 0 to 50.

The international patent application WO 99/28426 A1 relates to compositions which contain a bleaching agent and as a bleach catalyst a Keggin, Dawson or Finke polyoxocobaltate.

The international patent application WO 00/39264 A1 relates to a bleaching process using a bleaching composition containing a polyoxometalate and air as the primary source of oxygen atoms. Specifically disclosed are the polyoxometalates NaWO ₄ , H ₄ SiW ₁₂ O ₄₀ , H ₃ PW ₁₂ O ₄₀ , α- and γ-K ₈ SiW ₁₁ O ₃₉ , β-Na ₁₀ SiW ₉ O ₃₄ , α-K ₇ PW ₁₁ O ₃₉ , K ₇ SiVMnW ₁₀ O ₃₉ , K ₈ [P ₂ CuW ₁₇ O ₆₂ H ₂ ], K ₈ [P ₂ CuW ₁₇ O ₆₂ H ₂ ], K ₁₀ [α-2-P ₂ W ₁₇ O ₆₁ ], Cs ₅ NbSiW ₁₁ O ₄₀ , K ₅ (NbO ₂ ) SiW ₁₁ O ₃₉ , ((CH ₃ ) ₃ NH) ₄ (NbO ₂ ) PW ₁₁ O ₃₉ , K ₇ Mo ₂ VSiW ₉ O ₄₀ , K ₇ VMnSiW ₁₀ O ₃₉ and K ₇ VCoSiW ₁₀ O ₃₉ .

From the European patent application EP 2 703 553 A1 discloses a two-stage bleaching process for textile materials, in its first step, an aqueous suspension of 0.01-0.03 g / l peroxo-polyoxometalat selected from (NH ₄ ) ₈ [Mo ₁₀ O ₂₂ (O ₂ ) ₁₂ ], Na ₂ [MoO (O ₂ ) ₂ (C ₂ O ₄ )], MoO (O ₂ ) ₂ , WO (O ₂ ) ₂ , 0.001-0.003% ionic surfactant, and up to 5% H ₂ O ₂ for 60-90 minutes is used at a temperature of 70-90 ° C.

Peroxomolybdates and peroxotungstates, including K ₂ [W ₂ O ₃ (O ₂ ) ₄ (H ₂ O) ₂ ] .2H ₂ O, and their preparation are described in US Pat WP Griffith et al., J. Chem. Soc. Dalton Trans. 1989, 1203-1208 described.

The present invention aims to improve the oxidation and bleaching performance of inorganic peroxygen compounds, especially at low temperatures in the range of about 10 ° C to 45 ° C.

The invention relates to the use of H ₂ [W ₂ O ₃ (O ₂ ) ₄ (H ₂ O) ₂ ] and / or its alkali metal or ammonium salts to enhance the cleaning performance of peroxygen-containing detergents or cleaners in aqueous, especially surfactant-containing liquor , Said peroxo-polyoxometalate may be anhydrous or containing water of crystallization, in particular as a dihydrate, and be used according to the invention.

Essentially, the use of the present invention is to provide conditions under which the peroxygen compound and said peroxo-polyoxometalate can react with each other with the aim of obtaining more strongly oxidizing secondary products. Such conditions are particularly present when the reactants meet in an aqueous system. This can be done by separately adding the peroxygen compound and the peroxo-polyoxometalate to a possibly washing or cleaning agent-containing liquor. However, it is particularly advantageous using a washing or cleaning agent containing the peroxo polyoxometallate and a peroxidic oxidizing agent, performed. The peroxygen compound may also be added to the aqueous system separately, in bulk or as a preferably aqueous solution or suspension, if a peroxygen-free detergent or cleaner is used. Depending on the purpose, the conditions can be varied widely. Thus, in addition to purely aqueous solutions and mixtures of water and suitable organic solvents as the reaction medium in question.

Further objects of the invention are a process for washing laundry and a process for cleaning hard surfaces, comprising the process steps of (a) providing an aqueous liquor containing H ₂ O ₂ or a water H ₂ O ₂ supplying, in particular inorganic peroxygen compound and said peroxo-polyoxometalate, and (b) contacting said liquor with textiles to be washed or hard surfaces to be cleaned. Further objects of the invention are a method for washing laundry and a method for cleaning hard surfaces, wherein to be washed textiles or hard surfaces to be cleaned with an aqueous liquor containing H ₂ O ₂ or in water H ₂ O ₂ supplying, in particular inorganic peroxygen compound and said peroxo polyoxometalate. Preferably, the contact between the aqueous Fleet and the object to be washed or cleaned at temperatures in the range of 20 ° C to 80 ° C, in particular from 40 ° C to 60 ° C ago. Preferably, the object to be washed or cleaned remains in contact with the aqueous liquor over a period of from 20 minutes to 120 minutes, in particular from 30 minutes to 90 minutes. The methods according to the invention can be carried out manually or with the aid of conventional devices, for example washing machines or dishwashers. In the context of a use according to the invention and of a process according to the invention, the amounts of peroxygen compounds used are generally selected such that between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5000 ppm active oxygen are present in the liquor; Preferably, the concentration of the peroxo-polyoxometallate in the aqueous liquor is from 0.0009 mg / l to 90 mg / l, in particular from 0.9 mg / l to 9 mg / l.

A combination of peroxygen compound and said peroxo-polyoxometalate is preferably used for bleaching stains, especially tea, in the washing of textiles, especially in aqueous, surfactant-containing liquor. The phrase "bleaching stains" is to be understood in its broadest sense and includes both the bleaching of colored stains on the textile, the bleaching of stained fabric removed from the wash liquor, and the oxidative destruction of itself textile dyes in the wash liquor, which under the washing conditions of textiles come off before they can be put on differently colored textiles.

Another preferred embodiment of the invention is the use of a combination of peroxygen compound and said peroxo-polyoxometalate in particular aqueous surfactant-containing cleaning solutions for hard surfaces, in particular for dishes, for bleaching colored stains, for example tea. Here too, the term bleaching is understood as meaning both the bleaching of dirt on the hard surface, in particular tea, and the bleaching of dirt removed from the hard surface in the dishwashing liquor.

The uses according to the invention for enhancing the cleaning performance of detergents and cleaning agents and for bleaching dyed soiling can be realized in a particularly simple manner by introducing the peroxo-polyoxometalate into a preferably surfactant-containing aqueous liquor which also contains peroxygen compound and the textile or textile to be cleaned Contains the order of introduction of peroxo-polyoxometallat, peroxygen compound and textile or hard-surface article is arbitrary, or a preferably surfactant-containing aqueous liquor containing the peroxo-polyoxometallat and peroxygen compound on the textile to be cleaned or apply the hard surface to be cleaned. Preferably, the peroxo polyoxometalate is as Component of a washing or cleaning agent used, which particularly preferably also contains the peroxygen compound.

Further objects of the invention are therefore detergents and cleaners which contain the abovementioned peroxo-polyoxometalate. Solid agents according to the invention preferably contain from 1.91 × 10 ^-6 % by weight to 1.53% by weight, in particular from 1.9 × 10 ^-4 % by weight to 0.153% by weight, of such polyoxometalate. Preferably, liquid agents of the invention contain from 1.53 × 10 ^-6 % by weight to 0.765% by weight, in particular from 1.53 × 10 ^-4 % by weight to 0.0765% by weight, of such polyoxometalate.

The detergents and cleaners according to the invention, which may be present as particularly pulverulent solids, in densified particle form, as homogeneous solutions or as suspensions or dispersions, may contain, in principle, all known ingredients customary in such agents besides the bleach-enhancing compound used according to the invention and preferably peroxygen compound. The detergents and cleaners according to the invention may contain, in particular, builder substances, surface-active surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, grayness inhibitors, dye transfer inhibitors, foam regulators, additional peroxygen activators and dyes and fragrances ,

Suitable organic or inorganic peroxygen compounds are organic peracids or peracid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, but especially inorganic peroxygen compounds such as hydrogen peroxide and inorganic salts releasing hydrogen peroxide under the conditions of purification, such as perborate, percarbonate and / or persilicate, and hydrogen peroxide Inclusion compounds, such as H ₂ O ₂ -urea adducts. Hydrogen peroxide can also be produced by means of an enzymatic system, ie an oxidase and its substrate. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped 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 these containing agents, which may in principle contain all conventional detergent or cleaner ingredients. Particular preference is given to using alkali metal percarbonate, alkali metal perborate monohydrate or hydrogen peroxide in the form of aqueous solutions which contain from 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 preferably used in amounts of from 0.1% by weight to 50% by weight, in particular of 5 wt% to 20 wt%, and more preferably from 7 wt% to 17 wt%, and most preferably 8 wt% to 15 wt%.

If desired, in the context of the invention, in addition to the peroxo-polyoxometallat peroxycarbonic acid-supplying compounds can also be used under perhydrolysis conditions, although the bleach-improving effect of the peroxo-polyoxometallats also occurs in their absence. Compounds which give peroxocarboxylic acid under perhydrolysis conditions can in particular be compounds which give perbenzoic acid which is optionally substituted under perhydrolysis conditions and / or aliphatic peroxycarboxylic acids having 1 to 12 C atoms, in particular 2 to 4 C atoms, alone or in mixtures. Suitable are the bleach activators cited at the beginning, which carry O- and / or N-acyl groups, in particular of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates or carboxylates or the sulfonic or carboxylic acids of these, in particular nonanoyl or isononanoyl or lauroyl oxybenzenesulfonate (NOBS or iso-NOBS or LOBS), 4- (2-decanoyloxyethoxycarbonyloxy) - benzenesulfonate (DECOBS) or decanoyloxybenzoate (DOBA), acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran, and also acetylated sorbitol and mannitol and mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG) , Pentaacetylfruktose, Tetraacetylxylose and Octaacetyllactose, acetylated, optionally N-alkylated glucamine and G luconolactone, and / or N-acylated lactams, for example N-benzoyl-caprolactam. A washing or cleaning agent according to the invention preferably contains up to 10% by weight, in particular 1% by weight to 8% by weight, of peroxycarboxylic acid-yielding compound under perhydrolysis conditions, and in another preferred embodiment is free of such compounds.

in der R¹ für -H, -CH₃, einen C_2-24-Alkyl- oder -Alkenylrest, einen substituierten C_1-24-Alkyl- oder C_2-24-Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN und -N⁽⁺⁾-CH₂-CN, einen Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit mindestens einer, vorzugsweise zwei, gegebenenfalls substituierten C_1-24-Alkylgruppe(n) und gegebenenfalls weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -CH₂-CN, -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃,-CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, -(CH₂CH₂-O)_nH mit n = 1, 2, 3, 4, 5 oder 6, R⁴ und R⁵ unabhängig voneinander eine voranstehend für R¹, R² oder R³ angegebene Bedeutung haben, wobei mindestens 2 der genannten Reste, insbesondere R² und R³, auch unter Einschluß des Stickstoffatoms und gegebenenfalls weiterer Heteroatome ringschließend miteinander verknüpft sein können und dann vorzugsweise einen Morpholino-Ring ausbilden, und X ein ladungsausgleichendes Anion, vorzugsweise ausgewählt aus Benzolsulfonat, Toluolsulfonat, Cumolsulfonat, den C_9-15-Alkylbenzolsulfonaten, den C_1-20-Alkylsulfaten, den C_8-22-Carbonsäuremethylestersulfonaten, Sulfat, Hydrogensulfat und deren Gemischen, ist, können eingesetzt werden.In addition to, or in place of, compounds which form peroxycarboxylic acids under perhydrolysis conditions, other bleach activating compounds, such as nitriles, from which perimic acids are formed may be present. These include in particular aminoacetonitrile derivatives with quaternized nitrogen atom according to the formula

in the R ^{1 is} -H, -CH ₃ , a C _2-24 -alkyl or alkenyl radical, a substituted C _1-24 -alkyl or C _2-24 -alkenyl radical having at least one substituent from the group -Cl, -Br, -OH, -NH ₂ , -CN and -N ⁽⁺⁾ -CH ₂ -CN, an alkyl or alkenylaryl radical having a C _1-24 -alkyl group, or a substituted alkyl- or alkenylaryl radical having at least one, preferably two, optionally substituted C _1-24 alkyl group (s) and optionally further substituents on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H where n = 1, 2, 3, 4, 5 or 6, R ⁴ and R ⁵ independently of one another have the meaning given above for R ¹ , R ² or R ³ , where at least 2 of the radicals mentioned, in particular R ² and R ³ , also include the Nitrogen atom and optionally further heteroatoms may be linked ring-wise and then preferably form a morpholino ring, and X is a charge-balancing anion, preferably selected from benzenesulfonate, toluenesulfonate, cumene sulfonate, the C _9-15 -alkylbenzenesulfonates, the C _1-20 -alkyl sulfates, C _8-22 carboxylic _acid methyl _ester sulfonates, sulfate, hydrogen sulfate and mixtures thereof can be used.

Oxygen-carrying sulfonimines and / or acylhydrazones can also be used. The presence of further bleach-catalyzing transition metal complexes is also possible. These are preferably selected from the cobalt, iron, copper, titanium, vanadium, manganese and ruthenium complexes. Suitable ligands in the transition metal complexes are both inorganic and organic compounds, in addition to carboxylates in particular compounds having primary, secondary and / or tertiary amine and / or alcohol functions, such as pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole , Triazole, 2,2'-bispyridylamine, tris (2-pyridylmethyl) amine, 1,4,7-triazacyclononane, 1,4,7-trimethyl-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-methylimidazole-2-yl) 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 (bis) 2-benzimidazolylmethyl) aminomethyl) benzene, sorbitol, mannitol, erythritol, adonitol, inositol, lactose, and optionally substituted salene , Porphins and porphyrins belong. The inorganic neutral ligands include in particular ammonia and water. If not all coordination sites of the transition metal central atom are occupied by neutral ligands, the complex contains further, preferably anionic and among these in particular mono- or bidentate ligands. These include in particular the halides such as fluoride, chloride, bromide and iodide, and the (NO ₂ ) ^- group, that is a nitro ligand or a nitrito ligand. The (NO ₂ ) ^- group may also be chelated to a transition metal or it may be asymmetric or two transition metal atoms η ¹ -O-bridge. Apart from the ligands mentioned, the transition metal complexes to be used in the activator system according to the invention may also contain further, generally simpler ligands, in particular mono- or polyvalent anion ligands. In question, for example, nitrate, actetate, trifluoroacetate, formate, carbonate, citrate, perchlorate and complex anions such as hexafluorophosphate. The anion ligands should provide charge balance between the transition metal central atom and the ligand system. The presence of oxo ligands, peroxo ligands and imino ligands is also possible. In particular, such ligands can also act bridging, so that polynuclear complexes arise. In the case of bridged, dinuclear complexes, both metal atoms in the complex need not be the same. The use of binuclear 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 anionic ligands does not result in charge balance in the complex, anionic counterions which neutralize the cationic transition metal complex are present in the transition metal complex compounds. 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, citrate or oxalate. Examples of such additional transition metal complex compounds are Mn (IV) ₂ (μ-O) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) di-hexafluorophosphate, [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, manganese oxalate, nitropentammine cobalt (III) chloride, nitritopentammine cobalt (III) chloride, hexammine cobalt (III) chloride, chloropentammine cobalt (III) chloride and the peroxo complex [(NH ₃ ) ₅ Co-OO-Co (NH ₃ ) ₅ ] Cl ₄ .

The compositions of the invention may contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof come into question. Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups. Also suitable are ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which correspond to said long-chain alcohol derivatives with respect to the alkyl moiety and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical.

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 the saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in incompletely neutralized form. Useful surfactants of the sulfate type include the salts of the sulfuric acid half-esters of fatty alcohols having 12 to 18 carbon atoms and the sulfation products of said nonionic surfactants having a low degree of ethoxylation. Suitable surfactants of the sulfonate type include linear alkylbenzenesulfonates having 9 to 14 carbon atoms in the alkyl moiety, alkane sulfonates having 12 to 18 carbon atoms, and olefin sulfonates having 12 to 18 carbon atoms, which are formed in the reaction of corresponding monoolefins with sulfur trioxide, and alpha-sulfofatty acid esters resulting from the sulfonation of fatty acid methyl or ethyl esters.

Such surfactants are in the detergents or detergents according to the invention in proportions of preferably 5 wt .-% to 50 wt .-%, in particular from 8 wt .-% to 30 wt .-%, while the inventive compositions for the purification of hard Surfaces, especially of tableware, preferably 0.1 wt .-% to 20 wt .-%, 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, sugar acids and carboxymethylinulines, monomeric and polymeric aminopolycarboxylic acids, in particular glycinediacetic acid, methylglycinediacetic acid, nitrilotriacetic acid, iminodisuccinates such as ethylenediamine-N, N'-disuccinic acid and hydroxyiminodisuccinates, ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid ), Ethylenediaminetetrakis (methylenephosphonic acid), lysine tetra (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular by the oxidation of polysaccharides accessible polycarboxylates, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers from these, which may also contain copolymerized small amounts of polymerizable substances without carboxylic acid functionality. The relative average molecular weight (here and hereinafter: weight average) of the homopolymers of unsaturated carboxylic acids is generally between 5,000 g / mol and 200,000 g / mol, that of the copolymers between 2,000 g / mol and 200,000 g / mol, preferably 50 000 g / mol to 120 000 g / mol, in each case based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative average molecular weight of 50,000 g / mol to 100,000 g / mol. Suitable, though less preferred compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene in which the proportion of the acid is at least 50 wt .-% is. As water-soluble organic builders, it is also possible to use terpolymers which contain two unsaturated 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 polymers contain from 60% by weight to 95% by weight, in particular from 70% by weight to 90% by weight, 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 polymers 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, particularly preferably acrylic acid or acrylate, from 10% by weight to 30% by weight. %, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid or Methallylsulfonat and as the 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. Particularly preferred is sucrose. The use of the third monomer presumably incorporates predetermined breaking points into the polymer which are responsible for the good biodegradability of the polymer. These terpolymers generally have a relative average molecular weight between 1,000 g / mol and 200,000 g / mol, preferably between 200 g / mol and 50,000 g / mol. Further preferred copolymers are those which have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate. The organic builder substances 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 of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

If desired, such organic builder substances may 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. Quantities close to the stated upper limit are preferably used in paste-form or liquid, in particular water-containing, agents according to the invention.

Suitable water-soluble inorganic builder materials are, in particular, polyphosphates, preferably sodium triphosphate. As water-insoluble inorganic builder materials are in particular crystalline or amorphous, water-dispersible alkali metal aluminosilicates, in amounts not exceeding 25 wt .-%, preferably from 3 wt .-% to 20 wt .-% and in particular in amounts of 5 wt .-% to 15 wt. -% used. Among these, the detergent-grade crystalline sodium aluminosilicates, particularly zeolite A, zeolite P, and zeolite MAP, and optionally zeolite X, 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 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m. Their calcium binding capacity is generally in the range of 100 to 200 mg CaO per gram.

In addition to or as an alternative to said water-insoluble aluminosilicate and alkali carbonate, further water-soluble inorganic builder materials may be included. In addition to the polyphosphates, such as sodium triphosphate, these include in particular the water-soluble crystalline and / or amorphous alkali metal silicate builders. Such water-soluble inorganic builder materials are preferably present in agents according to the invention in amounts of from 1% by weight to 20% by weight, in particular from 5% by weight to 15% by weight. The alkali silicates useful as builder materials preferably have a molar ratio of alkali oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and may be amorphous or crystalline. 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. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula of Na ₂ Si _x O used _{2x + 1} · y H ₂ O in which x, known as the modulus, an integer of 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both .beta.- and δ-Natriumdisitikate (Na ₂ Si ₂ O ₅ · y H ₂ O) is preferred. Also prepared from amorphous alkali silicates, practically anhydrous crystalline alkali silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1, can be used in inventive compositions. In a further preferred embodiment of the composition according to the invention, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Sodium silicates with a modulus in the range of 1.9 to 3.5 are used in another embodiment of the invention used. In a preferred embodiment of compositions according to the invention, a granular compound of alkali silicate and alkali carbonate is used, as is commercially available, for example, under the name Nabion® 15.

Machine dishwashing detergents according to the invention are preferably of low alkalinity and contain the customary alkali carriers, for example alkali metal silicates, alkali metal carbonates and / or alkali hydrogen carbonates. The alkali carriers used conventionally include carbonates, bicarbonates and alkali silicates having a molar ratio of SiO ₂ / M ₂ O (M = alkali atom) of from 1.5: 1 to 2.5: 1. Alkali silicates may be used in amounts of up to 30% by weight. %, based on the total mean. The use of the highly alkaline metasilicates as alkali carriers is preferably completely dispensed with. The alkali carrier system preferably used in the inventive compositions is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, which is present in an amount of up to 60 wt .-%, preferably 10 wt .-% to 40 wt .-% , Depending on which pH is ultimately desired, the ratio of carbonate used and bicarbonate used varies, but usually an excess of sodium bicarbonate is used, so that the weight ratio of bicarbonate to carbonate is generally from 1: 1 to 15: 1.

In a further embodiment of dishwashing detergent compositions according to the invention, these contain from 20% by weight to 40% by weight of water-soluble organic builders, in particular alkali citrate, from 5% by weight to 15% by weight of alkali metal carbonate and from 20% by weight to 40 wt .-% Alkalidisilikat included.

Suitable enzymes in the compositions according to the invention are, in particular, those from the class of proteases, lipases, cutinases, amylases, pullulanases, xylanases, hemicellulases, cellulases, peroxidases and oxidases or mixtures thereof, the use of protease, amylase, lipase and / or cellulase is particularly preferred. The proportion is preferably 0.2 wt .-% to 1.5 wt .-%, in particular 0.5 wt .-% to 1 wt .-%. The enzymes can be adsorbed in a customary manner on carriers and / or embedded in coating substances or incorporated as concentrated, as anhydrous liquid formulations.

Suitable gravel inhibitors or soil release agents are cellulose ethers, such as carboxymethylcellulose, methylcellulose, hydroxyalkylcelluloses and cellulose mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose and methylcarboxymethylcellulose. Preferably, sodium carboxymethylcellulose and mixtures thereof with methylcellulose are used. Commonly used soil release agents include copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. The proportion of grayness inhibitors and / or soil release agents in agents according to the invention is generally not more than 2 wt .-% and is preferably 0.5 wt .-% to 1.5 wt .-%.

Examples of optical brighteners for textiles made of cellulose fibers (for example cotton) include derivatives of diaminostilbenedisulfonic acid or alkali metal salts thereof. For example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulphonic acid or similarly constructed compounds which are suitable instead of the morpholino group, carry a diethanolamino group, a methylamino group or a 2-methoxyethylamino group. Further, brighteners of the substituted 4,4'-distyryl-diphenyl type may be present, for example, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl. Also, mixtures of brighteners can be used. For polyamide fibers, brighteners of the 1,3-diaryl-2-pyrazolines type, for example 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline, and compounds of similar construction are particularly suitable. The content of the composition in optical brighteners or brightener mixtures is generally not more than 1 wt .-%, preferably 0.05 wt .-% to 0.5 wt .-%. In a preferred embodiment of the invention, the agent is free of such agents.

The usual foam regulators which can be used in the compositions according to the invention include, for example, polysiloxane-silica mixtures, the finely divided silica contained therein preferably being silanated or otherwise rendered hydrophobic. The polysiloxanes can consist of both linear compounds as well as crosslinked polysiloxane resins and mixtures thereof. Further antifoams are paraffin hydrocarbons, in particular microparaffins and paraffin waxes whose melting point is above 40 ° C., saturated fatty acids or soaps having in particular 20 to 22 carbon atoms, for example sodium behenate, and alkali metal salts of phosphoric mono- and / or dialkyl esters in which the alkyl chains each having 12 to 22 carbon atoms. Among these, preference is given to using sodium monoalkyl phosphate and / or dialkyl phosphate having C ₁₆ - to C ₁₈ -alkyl groups. The proportion of foam regulators may preferably be from 0.2% by weight to 2% by weight.

Among the organic solvents which can be used in the compositions according to the invention, especially if they are in liquid or pasty form, are alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C atoms , in particular ethylene glycol and propylene glycol, and mixtures thereof and the derivable from said classes of compound ethers. Such water-miscible solvents are present in compositions according to the invention in amounts of preferably not more than 20% by weight, in particular from 1% by weight to 15% by weight.

In order to establish a desired pH, which does not result from the mixture of the other components, the compositions 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 alkali hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are preferably not more than 10 wt .-%, in particular from 0.5 wt .-% to 6 wt .-%, contained in the inventive compositions.

The preparation of the solid compositions according to the invention presents no difficulties and can be carried out in a manner known in the art, for example by spray-drying or granulation, wherein peroxygen compound and bleach catalyst are optionally added separately later.

Compositions according to the invention in the form of solutions containing aqueous or other conventional solvents are produced particularly advantageously by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.

The compositions according to the invention are preferably in the form of pulverulent, granular or tablet-like preparations which are prepared in a manner known per se, for example by mixing, granulating, roll compacting and / or spray-drying the thermally stable components and admixing the more sensitive components, in particular enzymes, bleaches and the bleach-activating system can be expected to be prepared. For the preparation of inventive compositions having an increased bulk density, in particular in the range from 650 g / l to 950 g / l, a process comprising an extrusion step is preferred.

For the preparation of compositions in tablet form, the procedure is preferably such that all components are mixed together in a mixer and the mixture by means of conventional tablet presses, such as eccentric or rotary presses, with pressing pressures in the range of 200 · 10 ⁵ Pa to 1 500 · 10 ⁵ Pa pressed. This gives unbreakable, yet sufficiently rapidly soluble tablets under application conditions with flexural strength of usually over 150 N. Preferably, a tablet thus produced has a weight of 15 g to 40 g, in particular from 20 g to 30 g, with a diameter of 35 mm to 40 mm.

The preparation of compositions according to the invention in the form of non-dusting, storage-stable free-flowing powders and / or granules with high bulk densities in the range from 800 g / l to 1000 g / l can also be effected by using at least one of the builder components in a first process step Mixing proportion of liquid mixture components to increase the bulk density of this premix and subsequently - if desired, after an intermediate drying - the other ingredients of the agent, including the performance enhancing agent or the performance enhancing agent combination combined with the thus obtained premix.

Examples Example 1: Preparation of K ₂ [W ₂ O ₃ (O ₂ ) ₄ (H ₂ O) ₂ ] .2H ₂ O.

To a solution of 2.0 g of K ₂ WO ₄ (6.1 mmol) in 15 ml of distilled water was added 10 ml of 30% H ₂ O ₂ solution and the resulting yellow solution was carefully washed with as much aqueous HCl solution (3 M) until it became colorless (at about pH 2.5). The solution was then held at about 8 ° C (refrigerator) for 24 hours. The precipitated colorless crystals were filtered off, washed with ethanol and the product dried in air for one day. 0.8 g of K ₂ [W ₂ O ₃ (O ₂ ) ₄ (H ₂ O) ₂ ] .2H ₂ O was obtained.

Example 2: bleaching experiments

Washing tests were carried out at 60 ° C. with the standardized stains on cotton indicated in the table below using a wash liquor of a bleach-activator-free and bleach-containing detergent V1 (resulting in a concentration of 0.075 g / l H ₂ O ₂ in the wash liquor) and 0.009 g / l K ₂ [W ₂ O ₃ (O ₂ ) ₄ (H ₂ O) ₂ ] .2H ₂ O. For comparison, an otherwise identical wash liquor was used, which contained only the detergent V1. The evaluation was carried out by color distance measurement according to the L * a * b * values and the Y values calculated therefrom as a measure of the brightness. The following table shows the Y values that resulted after washing. soiling V1 V1 + K ₂ [W ₂ O ₃ (O ₂ ) ₄ (H ₂ O) ₂ ] .2H ₂ O tea 54.6 57.1 olive oil 55.2 57.1

The Y values when using the active substance according to the invention are greater than those which result when using only the detergent, which corresponds to a higher degree of whiteness and thus improved stain removal.

Claims (10)

Use of H ₂ [W ₂ O ₃ (O ₂ ) ₄ (H ₂ O) ₂ ] and / or its alkali metal or ammonium salts to enhance the cleaning performance of peroxygen-containing detergents or cleaners in aqueous, in particular surfactant-containing liquor. Use of a combination of peroxygen compound and H ₂ [W ₂ O ₃ (O ₂ ) ₄ (H ₂ O) ₂ ] and / or its alkali metal or ammonium salts for bleaching paint stains during the washing of textiles, in particular in aqueous, surfactant-containing liquor, or in particular aqueous, surfactant-containing cleaning solutions for hard surfaces, especially for crockery, for bleaching dyed stains, especially tea. Washing or cleaning agent, characterized in that it contains H ₂ [W ₂ O ₃ (O ₂ ) ₄ (H ₂ O) ₂ ] and / or its alkali metal or ammonium salts. Composition according to claim 3, characterized in that it contains peroxygen compound. Composition according to claim 4, characterized in that it contains 0.1 wt .-% to 50 wt .-%, in particular from 5 wt .-% to 20 wt .-% peroxygen compound. Use according to claim 1 or 2 or agent according to claim 4 or 5, characterized in that it is an inorganic peroxygen compound. A process for laundering laundry comprising the process steps of (a) providing an aqueous liquor containing H ₂ O ₂ or an H ₂ O ₂ yielding, especially inorganic, peroxygen compound and H ₂ [W ₂ O ₃ (O ₂ ) ₄ (H ₂ O) ₂ ] and / or its alkali metal or ammonium salts, and (b) contacting this liquor with textiles to be washed. A process for cleaning hard surfaces, comprising the process steps of (a) providing an aqueous liquor containing H ₂ O ₂ or a water-H ₂ O ₂ supplying, in particular inorganic peroxygen compound and H ₂ [W ₂ O ₃ (O ₂ ) ₄ (H ₂ O) ₂ ] and / or its alkali metal or ammonium salts, and (b) contacting this liquor with hard surfaces to be cleaned. Process according to Claim 7 or 8, characterized in that the concentration of H ₂ [W ₂ O ₃ (O ₂ ) ₄ (H ₂ O) ₂ ] and / or its alkali metal or ammonium salts in the aqueous liquor is 0.00009 mg / 1 to 9 mg / l, in particular 0.009 mg / l to 0.9 mg / l. Method according to one of claims 7 to 9, characterized in that the contact between the aqueous liquor and the object to be washed or cleaned at temperatures ranging from 20 ° C to 80 ° C, in particular from 40 ° C to 60 ° C. , and / or that the object to be washed or cleaned remains in contact with the aqueous liquor for a period of from 20 minutes to 120 minutes, in particular from 30 minutes to 90 minutes.