EP3068859B1 - Dishwashing composition and use - Google Patents

Description

The present invention relates to dishwashing detergents, as well as the use of these detergents, in particular in automatic dishwashing.

Modern machine dishwashing detergents are subject to a large number of requirements. They are intended to show improved cleaning and rinsing performance, even in low-temperature cleaning operations or in cleaning operations with reduced water consumption. Particular attention is paid to the drying properties of the automatic dishwashing detergents used. The need for additional manual drying of the cleaned dishes is undesirable, dripping and residue on the treated dishes should be avoided.

In addition, machine dishwashing detergents should be environmentally compatible and, if possible, should not contain any phosphate-containing constituents, in particular phosphate builders.

However, the sodium aluminum silicates (zeolites) used in laundry detergents as phosphate substitutes or substitutes are not suitable for use in automatic dishwashing detergents. As alternatives to the alkali metal phosphates in automatic dishwashing detergents, therefore, a number of substitutes are discussed in the literature, of which the citrates are particularly noteworthy.

Another alternative to the alkali metal phosphates used as sole builder but preferably in combination with citrates is methylglycine diacetic acid (MGDA). Machine dishwashing detergents containing MGDA are described, for example, in the European patent EP 906 407 B1 (Reckitt Benckiser) or in the European patent application with the disclosure number EP 1 113 070 A2 (Reckitt Benckiser).

Automatic dishwashing detergents with high citrate contents have the disadvantage that, in particular after several rinses, deposits become visible through the formation of calcium carbonate deposits, in particular on glasses.

This application was therefore based on the object to provide automatic dishwashing detergent with improved cleaning and rinsing performance and good deposit-inhibiting effect.

1. a) 10 bis 90 Gew.-% eines oder mehrerer Builder, wobei mindestens 10 Gew-%, bezogen auf die Gesamtmenge des oder der Builder, aus kristallinem Natriumschichtsilikat der Formel (1) bestehen
   
           Na₂Si_xO_2x+1 · y H₂O     Formel (1)
   
   wobei x eine Zahl von 1.9 bis 4 und y eine Zahl von 0 bis 20 ist,
2. b) 0,0025 bis 2,0000 Gew.-%, vorzugsweise 0,0025 bis 1,0000 Gew. % eines oder mehrerer Bleichkatalysatoren enthaltend Formel (2)
   
   wobei a 1 oder 2 ist, b eine Zahl von 0 bis 4 ist, X für ein beliebiges ein- bis zweiwertiges Anion steht,0,1 bis 20 Gew.-% eines oder mehrerer sauerstoffhaltiger Bleichmittel,
   • c) 0 bis 10 Gew.-% eines oder mehrerer Bleichaktivatoren,
   • d) 1 bis 85 Gew.-%, vorzugsweise 1 bis 60 Gew. % eines oder mehrerer pH-Regulatoren,
   • e) 0 bis 10 Gew.-% eines oder mehrerer oberflächenaktiver Substanzen
   • f) 0 bis 5 Gew.-% eines oder mehrerer Enzyme,

wobei die Mengenangaben der Komponenten a) bis g) sich auf die Gesamtmenge der Zusammensetzung beziehen.This object has been achieved in a first embodiment by dishwashing detergents, which are characterized in that they contain the following components

1. a) 10 to 90 wt .-% of one or more builders, wherein at least 10% by weight, based on the total amount of the builder or, of crystalline sodium layer of the formula (1) consist
   
   Na ₂ Si _x O _{2x + 1} · y H ₂ O Formula (1)
   
   where x is a number from 1.9 to 4 and y is a number from 0 to 20,
2. b) 0.0025 to 2.0000% by weight, preferably 0.0025 to 1.0000% by weight of one or more bleach catalysts comprising formula (2)
   
   where a is 1 or 2, b is an integer from 0 to 4, X is any monovalent to divalent anion, 0.1 to 20% by weight of one or more oxygen-containing bleaching agents,
   • c) 0 to 10% by weight of one or more bleach activators,
   • d) 1 to 85% by weight, preferably 1 to 60% by weight, of one or more pH regulators,
   • e) 0 to 10 wt .-% of one or more surface-active substances
   • f) 0 to 5% by weight of one or more enzymes,

wherein the amounts of components a) to g) refer to the total amount of the composition.

1. a) 10 bis 90 Gew.-% eines oder mehrerer Builder, wobei mindestens 10 Gew-%, bezogen auf die Gesamtmenge des oder der Builder, aus kristallinem Natriumschichtsilikat der Formel (1) bestehen
   
           Na₂Si_xO_2x+1 · y H₂O     Formel (1)
   
   wobei x eine Zahl von 1.9 bis 4 und y eine Zahl von 0 bis 20 ist,
2. b) 0,0025 bis 2,0000 Gew.-%, vorzugsweise 0,0025 bis 1,0000 Gew. % eines oder mehrerer Bleichkatalysatoren enthaltend α-Manganoxalatdihydrat,
3. c) 0,1 bis 20 Gew.-% eines oder mehrerer sauerstoffhaltiger Bleichmittel,
4. d) 0 bis 10 Gew.-% eines oder mehrerer Bleichaktivatoren,
5. e) 1 bis 85 Gew.-%, vorzugsweise 1 bis 60 Gew. % eines oder mehrerer pH-Regulatoren,
6. f) 0 bis 10 Gew.-% eines oder mehrerer oberflächenaktiver Substanzen
7. g) 0 bis 5 Gew.-% eines oder mehrerer Enzyme,

wobei die Mengenangaben der Komponenten a) bis g) sich auf die Gesamtmenge der Zusammensetzung beziehen, und wobei die Zusammensetzung phosphatfrei ist.In a second embodiment, this object has been achieved by dishwashing agents, which are characterized in that they contain the following components

1. a) 10 to 90 wt .-% of one or more builders, wherein at least 10% by weight, based on the total amount of the builder or, of crystalline sodium layer of the formula (1) consist
   
   Na ₂ Si _x O _{2x + 1} · y H ₂ O Formula (1)
   
   where x is a number from 1.9 to 4 and y is a number from 0 to 20,
2. b) 0.0025 to 2.0000% by weight, preferably 0.0025 to 1.0000% by weight of one or more bleach catalysts comprising α-manganese oxalate dihydrate,
3. c) 0.1 to 20% by weight of one or more oxygen-containing bleaching agents,
4. d) 0 to 10% by weight of one or more bleach activators,
5. e) from 1 to 85% by weight, preferably from 1 to 60% by weight, of one or more pH regulators,
6. f) 0 to 10 wt .-% of one or more surface-active substances
7. g) 0 to 5% by weight of one or more enzymes,

wherein the amounts of components a) to g) refer to the total amount of the composition, and wherein the composition is phosphate-free.

Crystalline layered silicates according to formula (1) are described, for example, in European patent application with the disclosure number EP 0 164 514 A1 described.

Preferred crystalline layered silicates are those in which x in the abovementioned general formula assumes the values 1.9 to 3.5.

In particular, both delta and beta disodium disilicates (Na ₂ Si ₂ O ₅ .yH ₂ O) are preferred, wherein beta disodium disilicate can be obtained, for example, by the process described in US Pat WO 91/08171 A1 is described. Beta-disodium silicates having a molar ratio of SiO ₂ / Na ₂ O between 1, 9 and 3.2 can be prepared according to Japanese Patent Application Laid-Open Nos JP 04/238 809 A or JP 04/260 610 A getting produced. Also prepared from amorphous silicates, practically anhydrous crystalline alkali silicates of the abovementioned general formula (1), in which x is a number from 1.9 to 2.1, can be used.

In a further preferred embodiment of such agents, a crystalline sodium layer silicate with a molar ratio of SiO ₂ / Na ₂ O of 1.8 to 3 is used.

In a preferred form, the crystalline layered disodium disilicate of the builder a) is composed of varying percentages of the polymorphic phases alpha, beta and delta. In commercially produced products, amorphous portions may also be present. By the latter, x can also be odd in commercial products. Preferably, 1.9 ≤ x ≥ 2.2.

The definitions of alpha, beta and delta disodium disilicate are known and may be, for example, the EP 0 164 514 A1 are removed, as has been explained below.

The disodium disilicate is preferably a layered crystalline disodium disilicate which consists of at least one of the polymorphic phases of disodium disilicate and of sodium silicates of non-layered silicate nature.

Particular preference is given to using crystalline sodium layer silicates having a content of from 80 to 100% by weight of delta-disodium disilicate.

In a further preferred variant, it is also possible to use crystalline sodium layer silicates having a content of 70 to 100% by weight of beta disodium disilicate.

Crystalline sodium layer silicates used with particular preference contain 1 to 40% by weight of alpha disodium disilicate, 0 to 50% by weight, in particular 0 to 45% by weight, of beta disodium disilicate, 50 to 98% by weight of delta disodium disilicate and 0 to 40 wt .-% of non-layered silicate sodium silicates (amorphous portions).

Very particularly preferably used crystalline layered sodium silicates contain 7 to 21 wt .-% alpha disodium disilicate, 0 to 12 wt .-% beta disodium disilicate, 65 to 95 wt .-% delta disodium disilicate and 0 to 20 wt .-% amorphous shares.

The aforementioned alpha disodium disilicate corresponds to that in the EP 0 164 514 A1 described Na-SKS-5, characterized by the reproduced there X-ray diffraction data, which are assigned to the alpha-Na ₂ Si ₂ O ₅ . The X-ray diffraction patterns are registered with the Joint Committee of Powder Diffraction Standards under the numbers 18-1241, 22-1397, 22-1397A, 19-1233, 19-1234 and 19-1237.

The aforementioned beta-disodium disilicate corresponds to that in the EP 0 164 514 A1 described Na-SKS-7, characterized by the reproduced there X-ray diffraction data, which are assigned to the beta-Na ₂ Si2O ₅ . The X-ray diffraction patterns are registered with the Joint Committee of Powder Diffraction Standards under numbers 24-1123 and 29-1261.

The aforementioned delta-disodium disilicate corresponds to that in the EP 0 164 514 A1 described Na-SKS-6, characterized by the reproduced there X-ray diffraction data, which are assigned to the delta-Na ₂ Si ₂ O ₅ . The X-ray diffraction diagrams are registered with the Joint Committee of Powder Diffraction Standards under the number 22-1396.

In a further preferred embodiment of the invention, the compositions according to the invention contain crystalline sodium layer silicate of the formula (1) in granulated form, and also cogranulates containing crystalline sodium layer silicate and sparingly soluble metal carbonate, such as, for example, in US Pat WO2007 / 101622 A1 described.

In a further preferred embodiment of the invention, the compositions according to the invention contain crystalline sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O with y being 0 to 2.

In a preferred form, the crystalline layered sodium silicates additionally contain cationic and / or anionic constituents. The cationic constituents are preferably combinations of alkali metal and / or alkaline earth metal cations and / or Fe, W, Mo, Ta, Pb, Al, Zn, Ti, V, Cr, Mn, Co and / or Ni.

The anionic constituents are preferably aluminates, sulfates, fluorides, chlorides, bromides, iodides, carbonates, bicarbonates, nitrates, hydrated oxides, phosphates and / or borates.

In an alternative preferred form, the crystalline layered sodium silicates, based on the total content of SiO ₂ , contain up to 10 mol% of boron.

In another alternative preferred form, the crystalline layered sodium silicates, based on the total content of SiO ₂ , contain up to 20 mol% of phosphorus.

Sodium disilicates of the formula beta-Na ₂ Si ₂ O ₅ prepared by hydrothermal methods are also particularly preferred, as described in the patent documents WO 92/09526 A1 . US-A-5,417,951 . DE 41 02 743 A1 and WO 92/13935 A1 to be discribed.

As sodium layer silicates are those according to WO 00/09444 A1 especially prefers.

As sodium layer silicates are also those according to EP 0 550 048 A1 and EP 0 630 855 A1 prefers

The compositions according to the invention may contain, in addition to crystalline sodium layer silicate according to the formula (1), further water-soluble organic and / or inorganic builders.

Suitable water-soluble inorganic builder materials are, in particular, alkali metal silicates and polymeric alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts.

Likewise, amorphous sodium silicates having a molar ratio of Na ₂ O: SiO _{2 of} from 1: 1 to 1: 3.5 can be used.

The water-soluble organic builder substances include polycarboxylic acids or their salts, in particular citric acid and sugar acids, aminopolycarboxylic acids, in particular methylglycinediacetic acid or its salt (MGDA), glutamic diacetic acid or its salt (GLDA) and ethylenediamine disuccinic acid or its salt (EDDS), nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid. Polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1, 1-diphosphonic acid, may also be used. Preferred builders or co-builders are also polycarboxylic acids, in particular the polycarboxylates obtainable by oxidation of polysaccharides or dextrins, as in US Pat WO 93/16110 A1 . WO 92/18542 A1 or EP 0 232 202 A2 described, as well as polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which einpoly-polymerized even small amounts of polymerizable substances without carboxylic acid functionality can contain. According to the manufacturer, the average molecular weight of the homopolymers of unsaturated carboxylic acids, expressed as M _w , is generally between 5000 and 200 000, that of the copolymers between 2000 and 200 000, preferably between 50 000 to 120 000, in each case based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has an average molecular weight of 50,000 to 100,000. Commercially available products are, for example, Sokalan® CP 5, Sokalan® CP 10 and PA 30 from BASF. Also suitable 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 acid is at least 50% by weight. It is also possible to use terpolymers which contain two unsaturated acids and / or salts thereof as monomers and also vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ -carboxylic acid, preferably from a C ₃ -C ₄ -monocarboxylic acid, in particular of (meth) acrylic acid, where the second acidic monomer or its Salt may be a derivative of a C ₂ -C ₆ dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid substituted in the 2-position with an alkyl or aryl radical. Such polymers can be prepared in particular by methods described in the German patent documents DE 42 21 381 and DE 43 00 772 are generally described, and generally have a molecular weight between 1000 and 200,000. Further preferred copolymers are those described in German patent applications with the disclosure number DE 43 03 320 A1 and DE 44 17 734 A1 be described and as monomers preferably acrolein and acrylic acid / acrylic acid salts or vinyl acetate.

The organic builder substances can, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 wt .-% aqueous solutions are used. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

Other possible water-soluble builder components, in addition to polyphosphonates and phosphonate alkyl carboxylates, are, for example, organic polymers of the above-mentioned type of polycarboxylates, which act as co-builders in hard water regions, and naturally occurring hydroxycarboxylic acids, such as mono-, dihydroxysuccinic acid, alpha- Hydroxypropionic acid and gluconic acid.

Likewise, the salts of citric acid, especially sodium citrate, both anhydrous trisodium citrate, and trisodium citrate dihydrate can be used.

When used as dishwashing agents, the compositions according to the invention exhibit pronounced detergency when, in addition to crystalline sheet silicate of formula (1), they additionally contain builders selected from methylglycinediacetic acid or its salts, sodium polyphosphate (NTP) and / or sodium citrate.

wobei a 1 oder 2 ist, b eine Zahl von 0 bis 4 ist, X für ein beliebiges ein- bis zweiwertiges Anion, bevorzugt für PF₆ ^-, CH₃COO^-, Cl^-, SO₄ ^2-, und insbesondere für PF₆ ^- steht.In one embodiment of the invention, the compositions according to the invention contain bleach catalysts according to the formula (2)

wherein a is 1 or 2, b is a number from 0 to 4, X is any monovalent to divalent anion, preferably PF ₆ ^- , CH ₃ COO ^- , Cl ^- , SO ₄ ^2- , and in particular PF ₆ ^- stands.

In an extremely preferred embodiment of the invention, the compositions according to the invention contain the bleach catalyst bis (N, N ', N "-trimethyl-1,4,7-triazacyclononane) -trioxo-dimangane (IV) di (hexafluorophosphate) monohydrate, which is known as Peractive® MnTACN is available.

In a further embodiment of the invention, the compositions according to the invention comprise the bleach catalyst α-manganese oxalate dihydrate according to the formula (3) as in J. Soleimannejad et al., Acta Cryst. (2007) E63, m 2389 - m 2390 described and available as Peractive® MnOx.

Formula (3) corresponds to (OOC-COO) Mn (2H ₂ O) (OOC-COO) Mn (2H ₂ O) (OOC-COO).

Bleaching agents are, on the one hand, compounds which react with bleach activators to form peroxyacids which bleach much more effectively at low temperatures (e.g., <70 ° C) than the bleaches alone.

Suitable bleaching agents are hydrogen peroxide and inorganic persalts, preferably percarbonates, perborates, persulfates and persilicates, in particular in the form of alkali metal salts. Particularly preferred such bleaching agents are hydrogen peroxide, sodium perborate (monohydrate and tetrahydrate) and / or sodium percarbonate, particularly preferably sodium perborate (monohydrate and tetrahydrate) and / or sodium percarbonate.

In a particularly preferred embodiment of the invention, therefore, the one or more bleaching agents are selected from the group consisting of sodium perborate (monohydrate and tetrahydrate) and sodium percarbonate.

Bleaching agents are, on the other hand, compounds which act without a bleach activator. Suitable such bleaching agents are peracids or their salts.

wobei R für eine Alkylgruppe, Aralkylgruppe, Cycloalkylgruppe, Arylgruppe oder heterocyclische Gruppe, bevorzugt für eine lineare oder verzweigte, substituierte oder unsubstituierte Alkylgruppe, insbesondere bevorzugt für eine Alkylgruppe mit 6 bis 9 Kohlenstoffatomen, steht und X⁺ ein geeignetes Gegenion, bevorzugt ein H⁺, Kalium- oder Natriumion bedeutet. Bevorzugt sind Peroxyhexanoylsäure, Peroxyheptanoylsäure, Peroxyoctanoylsäure, Peroxynonanoylsäure, Peroxydecanoylsäure und deren Salze.Particularly preferred peracids or peracid salts are peroxycarboxylic acids and their salts according to the formula

wherein R is an alkyl group, aralkyl group, cycloalkyl group, aryl group or heterocyclic group, preferably a linear or branched, substituted or unsubstituted alkyl group, particularly preferably an alkyl group having 6 to 9 carbon atoms, and X ^{+ is} a suitable counterion, preferably an H ⁺ , Potassium or sodium ion. Preference is given to peroxyhexanoic acid, peroxyheptanoic acid, peroxyoctanoic acid, peroxynonanoic acid, peroxydecanoic acid and salts thereof.

wobei R für eine Alkylgruppe, Aralkylgruppe, Cycloalkylgruppe, Arylgruppe oder heterocyclische Gruppe, bevorzugt für eine lineare oder verzweigte, substituierte oder unsubstituierte Alkylgruppe, insbesondere bevorzugt für eine Alkylgruppe mit 6 bis 9 Kohlenstoffatomen, steht und X⁺ ein geeignetes Gegenion, bevorzugt H⁺, ein Kalium- oder Natriumion bedeutet.Further particularly preferred peracids or peracid salts are peroxysulfonic acids and their salts according to the formula

wherein R is an alkyl group, aralkyl group, cycloalkyl group, aryl group or heterocyclic group, preferably a linear or branched, substituted or unsubstituted alkyl group, particularly preferably an alkyl group having 6 to 9 carbon atoms, and X ^{+ is} a suitable counterion, preferably H ⁺ , a potassium or sodium ion.

Further particularly preferred peracids or peracid salts are peroxophthalic acids and their salts, phthalimino peracids and their salts, diperoxycarboxylic acids and their salts or peroxy-sulfuric acids and their salts.

Among the bleaching agents which have no bleach activator, particular preference is given to the peracids or salts thereof selected from the group consisting of monoperoxyphthalic acid and its salts, N, N-phthaloylaminoperoxycaproic acid (PAP) and its salts, diperazelaic acid and its salts, diperdodecanedioic acid and their salts and monoperoxy-sulfuric acid and their salts, the salts preferably being selected from the sodium and / or potassium salts. Among monoperoxy sulfuric acid and its salts, in particular, the potassium peroxymonosulfate (available under the trade name Caroat) is preferred.

The quantities of bleach used are generally chosen so that in the solutions of the compositions when used as automatic dishwashing detergent during the rinsing process between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5000 ppm of active oxygen are present.

In a preferred embodiment of the invention, the amount of the one or more bleach catalysts in the compositions of the invention is from 0.01 mmol to 25 mmol, preferably 0.1 mmol to 2 mmol bleach catalyst per mole of bleach.

In a preferred embodiment, the compositions of the invention contain one or more bleach activators. Bleach activators are compounds which release peroxycarboxylic acids under perhydrolysis conditions.

Suitable bleach activators containing O- and / or N-acyl groups. The compositions according to the invention preferably contain acylated alkylenediamines, in particular tetraacetylethylenedianim (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated phenylsulfonates, in particular Nonanoyl, isononanoyl or lauroylbenzene sulfonate (NOBS, ISONOBS or LOBS) or their amido derivatives (eg NACAOBS), acylated hydroxycarboxylic acids, such as acetylsalicylic acid or nonanoyloxybenzoic acid (NOBA) and decanoyloxybenzoic acid (DOBA), acetyltriethycitrate, acylated polyhydric alcohols, in particular triacetin, Ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran as well as acetylated sorbitol and mannitol, and acylated sugar derivatives, especially pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and N-acetylcaprolactam, N-benzoyl caprolactam and 4-morpholinecarbonitrole. Likewise, in the dishwashing detergent according to the invention, open-chain or cyclic nitrile quats, as well as those of US Pat DE-A 44 43 177 be known combinations of bleach activators.

In a preferred embodiment of the invention, the compositions contain acylated alkylenediamines, in particular tetraacetylethylenedianim (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT ), acylated phenylsulfonates, especially nonanoyl, isononanoyl or lauroylbenzenesulfonate (NOBS, ISONOBS or LOBS) or their amido derivatives (eg NACAOBS), acylated hydroxycarboxylic acids such as acetylsalicylic acid or nonanoyloxybenzoic acid (NOBA) and decanoyloxybenzoic acid (DOBA)

In a particularly preferred embodiment of the invention, the compositions contain acylated alkylenediamines, in particular tetraacetylethylenedianim (TAED).

In an extremely preferred embodiment of the invention, the compositions according to the invention contain TAED and one of the bleach catalysts according to the above-mentioned formula (2) and preferably in a mixing ratio of 20: 1 to 1: 1, more preferably 15: 1 to 2: 1, and most preferably 10: 1 to 3: 1.

The compositions of the invention contain one or more bleach activators in an amount of 0.1 to 10 wt .-%, preferably 0.5 to 8 wt .-%, particularly preferably 1 to 6 wt .-%, each based on the total weight of the inventive compositions.

In order to adjust the application pH of the compositions according to the invention to between 9 and 11, the compositions according to the invention comprise one or more pH regulators. The compositions according to the invention preferably contain alkali metal carbonates, in particular sodium carbonate, alkali hydrogen carbonates, alkali metal hydroxides, in particular potassium hydroxide and sodium hydroxide, disilicates and amino acids.

Likewise, inorganic acids, such as the mineral acids, eg. Hydrochloric acid, and organic acids, for example saturated or unsaturated mono-, di- and tricarboxylic acids and hydroxycarboxylic acids having one or more hydroxy groups, e.g. As citric acid, glycolic acid, lactic acid, maleic acid, formic acid and acetic acid, amidosulfuric, C ₆ -C ₂₂ fatty acids and anionic sulfonic acids, and mixtures thereof are used.

In a preferred embodiment of the invention, the compositions contain one or more pH regulators in amounts of from 1 to 40% by weight, in particular from 2 to 30% by weight, based on the total weight of the compositions according to the invention.

The compositions of the invention may contain one or more surfactants, in particular anionic surfactants and nonionic surfactants and mixtures thereof, but also zwitterionic and amphoteric surfactants in question.

Advantageously, the compositions according to the invention may contain alkyl ether carboxylates R- (OCH ₂ CH ₂ ) _x OCH ₂ COOM, where R is an alk (en) yl radical having 12 to 18 carbon atoms and x is a number from 2 to 5.

The anionic surfactants can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. Anionic surfactants are preferably present in the compositions according to the invention in amounts of from 0 to 10% by weight and in particular in amounts of from 0.5 to 5% by weight.

Preferred nonionic surfactants in the compositions according to the invention are alkoxylated, advantageously ethoxylated and / or propoxylated, in particular primary, alcohols having preferably 8 to 18 C atoms and on average 1 to 12 moles of ethylene oxide (EO) and 2 to 17 moles of ethylene oxide (EO) / propylene oxide (PO) are used per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, alcohol ethoxylates having linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol used, more preferably C ₁₂ -C ₁₄ alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ alcohols with 7 EO , C ₁₃ -C ₁₅ -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₁₂ -C ₁₄ Alcohol with 3 EO and C ₁₂ -C ₁₈ -alcohol with 7 EO, lauryl alcohol with 7 EO and 10 PO, lauryl alcohol with 2 EO and 4 PO, lauryl alcohol with 4 EO and 5 PO, lauryl alcohol with 5 EO and 4 PO, lauryl alcohol with 6 EO and 4 PO, lauro alcohol with 8 EO and 4 PO, C ₁₀ -C ₁₂ alcohol with 4 EO and 4 PO, isodecyl alcohol with 2 PO and 12 EO, isodecyl alcohol with 2 PO and 4 EO, undecyl alcohol with 8 EO and 2PO, C ₁₂ -C ₁₅ oxo alcohol with 2EO and 5PO, C ₁₂ -C ₁₅ oxo alcohol with 4EO and 4PO, C ₁₂ -C ₁₅ oxo alcohol with 5PO and 2EO, C ₁₂ -C ₁₅ oxo alcohol with 6EO and 4PO, C ₁₂ -C ₁₅ oxo alcohol with 8EO and 4PO, C ₆ -C ₁₂ alcohol with 6EO and 8PO.

The degrees of ethoxylation and degrees of propoxylation given above represent statistical averages which may be an integer or a fractional number for a particular product.

The compositions of the invention may advantageously Alkylglykoside of the general formula RO (G) _x , in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms, and G is a glycose unit having 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number which, as the size to be determined analytically, can also be fractions, between 1 and 10; preferably x is 1.2 to 1.4.

in der Rest R¹ CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und Z für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Vorzugsweise leiten sich die Polyhydroxyfettsäureamide von reduzierenden Zuckern mit 5 oder 6 Kohlenstoffatomen, insbesondere von der Glucose ab.It is likewise possible for polyhydroxy fatty acid amides of the formula (VIII) to be present,

in the radical R ¹ CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and Z is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups , The polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.

in der R³ einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 21 Kohlenstoffatomen, R⁴ einen linearen, verzweigten oder cyclischen Alkylenrest oder einen Arylenrest mit 6 bis 8 Kohlenstoffatomen und R⁵ einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen bedeutet, wobei C₁-C₄-Alkyl- oder Phenylreste bevorzugt sind, und Z für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes. Z wird auch hier vorzugsweise durch reduktive Aminierung eines Zuckers wie Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose erhalten. Die N-Alkoxy- oder N-Alyloxy-substituierten Verbindungen können dann beispielsweise durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden.The group of polyhydroxy fatty acid amides also includes compounds of the formula (IX)

in R ^{3 is} a linear or branched alkyl or alkenyl radical having 7 to 21 carbon atoms, R ^{4 is} a linear, branched or cyclic alkylene radical or an arylene radical having 6 to 8 carbon atoms and R ^{5 is} a linear, branched or cyclic alkyl radical or an aryl radical or a Oxy-alkyl radical having 1 to 8 carbon atoms, wherein C ₁ -C ₄ alkyl or phenyl radicals are preferred, and Z is a linear polyhydroxyalkyl radical whose alkyl chain having at least two Is substituted hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical. Z is also obtained here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-allyloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides, for example, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Another class in the context of the present invention of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters , preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide and of the fatty acid alkanolamide type may also be suitable according to the invention.

The proportion by weight of the one or more nonionic surfactants in the total weight of the compositions according to the invention is preferably 0.1 to 10 wt .-%, preferably 0.5 to 8 wt .-%, particularly preferably 1 to 6 wt .-%.

In a preferred embodiment, the compositions according to the invention comprise one or more enzymes selected from proteases, amylases, mannases, lipases, endolases, pectinases, cellulases, pullinases, cutinases or peroxidases.

Examples of proteases available are Liquanase® Ultra 2.0 XL, BLAP®, Opticlean®, Maxacal®, Maxapem®, Esperase®, Savinase®, Purafect®, OxP and / or Duraxym®.
on amylases for example Stainzyme® Plus 12L, Termamyl®, Amylase® LT, Maxamyl®, Duramyl® and / or Pruafect® Ox,
Mannasen, for example, Mannaway 4.0 L,
lipases, for example Lipex® 100 L, Lipolase®, Lipomax®, Lumafast® and / or Lipozym®,
on endolases, for example Endolase® 5000L,
at pectinases for example Pectinex 3X L and / or Pectinex Ultra SPL and
on cellulases, for example Carezyme 1000 L and / or Celluclast 1.5 L.

The proportion by weight of the one or more enzymes in the total weight of the compositions according to the invention is preferably from 0.001 to 8% by weight, more preferably from 0.001 to 4.5% by weight and most preferably from 0.01 to 3.5% by weight. %.

In a further preferred embodiment of the invention, the compositions according to the invention contain crystalline sodium layer silicate of the formula (1) in the form of a compound containing crystalline sodium layer silicate of the formula (1) and an acidic component.

The acidic component is preferably polycarboxylates, in particular a not or only partially neutralized homo- and / or copolymer of acrylic acid, methacrylic acid, maleic acid, polyaspartic acid, sugar carboxylic acid and / or further monomers. The molecular weight of the homopolymers and the copolymers is preferably in the range of 1000 to 100,000 g / mol, more preferably 2,000 to 50,000 g / mol. Particularly preferred are acrylic acid / maleic acid copolymers having a molecular weight of 4,000 to 50,000 g / mol. Prefers are also copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ether, vinyl ester, ethylene, propylene and styrene.

Commercially available products are z. Sokalan ™ CP 5 and PA 30 from BASF, Alcosperse ™ 175 or 177 from Alco, and LMW 45 N and SP02 N from Norsohaas.

Preferably, the weight ratio of alkaline silicate to acidic polycarboxylate is 40 to 1 to 1, preferably 20 to 2 to 1.

In an extraordinarily preferred embodiment of the invention, the compositions according to the invention contain crystalline layered sodium disilicate / copolymer compound based on acrylic acid / maleic acid, which is obtainable, for example, as SKS®-6 HD from Clariant GmbH.

The compositions according to the invention may contain further components, such as electrolytes, silver corrosion inhibitors, foam regulators, for example chlorine-stable phosphoric acid esters, such as triisobutyl phosphate (defoamer TIP from Clariant GmbH), or known silicones such as SP types from Wacker Chemie GmbH, disintegrants, and colorants Contain fragrances.

In the first embodiment of the compositions according to the invention, these may both contain phosphate as well as be phosphate-free.

In a preferred embodiment of the invention, the compositions according to the invention are phosphate-free.

When used as automatic dishwashing agents, the compositions according to the invention have a very good cleaning performance and are distinguished by a reduced deposit formation, in particular by reduced staining and film formation. Significant is the synergistically enhanced detergency of the combination of crystalline layered silicate and bleach catalyst over oatmeal / chocolate soils.

The compositions according to the invention are preferably in the form of pulverulent, granular or tablet-form preparations which can be prepared in a conventional manner, for example by mixing, granulating, roll compacting and / or spray-drying.

Furthermore, the invention relates to a method for cleaning surfaces, in particular dishes and glasses. The method comprises contacting the composition according to the invention with water and with the surface to be cleaned, in particular with dishes and glasses, and the action of the aqueous cleaning liquid formed on the surface to be cleaned.

The invention moreover relates to the use of the compositions according to the invention as dishwashing agents, in particular as automatic dishwasher detergent.

The following examples are intended to illustrate the invention without limiting it thereto. All percentages are, unless explicitly stated otherwise, to be understood as percent by weight (% by weight).

Experiments were carried out with the following formulations.

Example 1 (automatic dishwashing detergent according to the invention)

composition % By weight (tel quel) SKS® 6 granules 12 Peractive® FDO AN C 2 Trilon® M 12 sodium 19 Sokalan® PA30CL 6 sodium 15 Genapol EP 2544 1.5 Blaze evity® 100T 1.7 Stainzyme® 12T 0.6 sodium sulphate 30.2

Example 2 (automatic dishwashing detergent without bleach catalyst)

composition % By weight (tel quel) SKS® 6 granules 12 TAED granules 4 Trilon® M 12 sodium 19 Sokalan® PA3OCL 6 sodium 15 Genapol EP 2544 1.5 Blaze evity® 100T 1.7 Stainzyme® 12T 0.6 sodium sulphate 28.2

Example 3 (automatic dishwashing detergent without crystalline layered silicate)

composition % By weight (tel quel) Peractive® FDO AN C 2 Trilon® M 12 sodium 31 Sokalan® PA3OCL 6 sodium 15 Genapol EP 2544 1.5 Blaze evity® 100T 1.7 Stainzyme® 12T 0.6 sodium sulphate 30.2

Example 4 (automatic dishwashing detergent with sodium disilicate, amorphous)

composition % By weight (tel quel) Sodium disilicate, amorphous 12 Peractive® FDO AN C 2 Trilon® M 12 sodium 19 Sokalan® PA3OCL 6 sodium 15 Genapol EP 2544 1.5 Blaze evity® 100T 1.7 Stainzyme® 12T 0.6 sodium sulphate 30.2

Example 5 (automatic dishwashing detergent according to the invention, sodium citrate)

composition % By weight (tel quel) SKS® 6 granules 12 Peractive® FDO AN C 2 sodium citrate 20 sodium 25.5 Sokalan® PA30CL 6 sodium 15 Genapol EP 2544 1.5 Blaze evity® 100T 1.7 Stainzyme® 12T 0.6 sodium sulphate 15.7

Example 6 (automatic dishwashing detergent according to the invention, sodium citrate)

composition % By weight (tel quel) SKS® 6 HD 17 Peractive® FDO AN C 2 sodium citrate 20 sodium 25.5 Sokalan® PA30CL 3 sodium 15 Genapol EP 2544 1.5 Blaze evity® 100T 1.7 Stainzyme® 12T 0.6 sodium sulphate 13.7

Example 7 (automatic dishwashing detergent according to the invention, sodium triphosphate)

composition % By weight (tel quel) SKS® 6 granules 15 Peractive® FDO AN C 2 sodium triphosphate 35 sodium 15 Sokalan® PA3OCL 3 sodium 15 Genapol EP 2544 1.5 Blaze evity® 100T 0.8 Stainzyme® 12T 0.4 sodium sulphate 12.3

Example 8 (automatic dishwashing detergent according to the invention)

composition % By weight (tel quel) SKS® 6 granules 12 Peractive® MnTACN 0,015 sodium citrate 20 sodium 25.5 Sokalan® PA3OCL 6 sodium 15 Genapol EP 2544 1.5 Blaze evity® 100T 0.7 Stainzyme® 12T 0.6 sodium sulphate 17.685

Used commercial products

• SKS® 6, Na layered silicate Na ₂ Si ₂ O ₅ , manufacturer WeylChem
• SKS® 6 HD, compound of SKS-6 with acidic polycarboxylate, manufacturer WeylChem
• Peractive® FDO AN C, Compound of Compound of TAED and Mn-Oxalate, manufacturer WeylChem
• Peractive® MnTACN, Mn bleach catalyst, manufacturer WeylChem
• Trilon® M, MGDA (Alanine, N, N-bis (carboxymethyl) -, trisodium salt), manufacturer BASF AG
• Sokalan® PA3OCL, polycarboxylate, manufacturer BASF AG
• Genapol EP 2544, C12 / C15 oxo-alcohol EO-PO adduct, manufacturer Clariant
• Blaze evity® 100 T, enzyme blend, manufacturer Novozymes
• Stainzyme® 12T, enzyme, manufacturer Novozymes

Method of preparation: The components SKS® 6, sodium carbonate, sodium citrate or sodium triphosphate and sodium sulfate were initially charged and homogeneously mixed in a Lödige mixer at room temperature over a period of 15 minutes and transferred to a Turbula mixer. Genapol® EP2544 was slowly added with mixing in the Turbula mixer and mixed homogeneously over a period of 10 minutes. Peractive® FDO AN C or Peractive® MnTACN, sodium percarbonate, Blaze evity® 100 T, Stainzyme® 12T, optionally Sokalan® PA30CL and possibly Trilon® M were added in succession and mixed homogeneously in the period of 10 minutes.

Cleaning performance of the formulations for automatic dishwashing compositions according to Example 1, 2 and 3

• Programm Fein,
• natürliche Wasserhärte 21°dH,
• Reinigungstemperatur 45°C

Dishwashers were placed in a Miele 688SC dishwasher with 4 different test soils (tea on teacups, egg yolk on one-side brushed sheet steel, oatmeal / chocolate and starch mixed on prefabricated melamine plates from CFT). With in each case 20 g of the abovementioned formulations according to Examples 1, 2 and 3, purification tests were carried out:

• Program fine,
• natural water hardness 21 ° dH,
• Cleaning temperature 45 ° C

Then, the cleaning performance was evaluated. This was done visually on the teacups and on egg yolk soiling by weighing the plates before and after cleaning. The degree of purification of the melamine plates (prefabricated dishwasher monitors) was determined by differential whiteness measurement at 457nm.

The results obtained are summarized in Table 1. Table 1: Cleaning performance of the formulations according to Example 1, 2 and 3 Formulation Example No. 1 2 3 Cleaning performance in% tea 94 65 73 egg yolk 80 77 63 Starch mixed 44 40 37 Oatmeal / chocolate 10 6 1

The results show a synergistic increase in the detergency of the inventive automatic dishwashing detergent, according to Example 1, which is characterized in that it contains bleach catalyst and crystalline layered silicate.

Automatic dishwashing detergent of the same composition, but without bleach catalyst (Example 2) and automatic dishwashing detergent of the same composition, but without crystalline layered silicate (Example 3) show a significantly lower cleaning power, in particular over oatmeal / chocolate stains. Table 2: Cleaning performance of the formulations according to Example 5, 6, 7 and 8 Formulation Example No. 5 6 7 8th Cleaning performance in% tea 92 95 94 97 egg yolk 85 86 88 80 Starch mixed 42 43 47 45 Oatmeal / Chocolate 9 11 9 13

The experiments were carried out as above and evaluated.

Glass effects of the formulations for automatic dishwashing compositions according to Example 1, 2, 3 and 4

There were new glasses with 20g of the o.g. Formulations according to Example 1, 2, 3 and 4 and each 50 g of liquid soiling (IKW Schmutz 2012) at 55 ° C, 21 ° dH rinsed in the program Eco in the dishwasher type Miele 688SC.

After 3 cleaning cycles, the glasses were visually patterned and with the notes 1 - 5 (1 = very good, 5 = very bad). In spotting the drop frequency is evaluated, while filming the surface turbidity. Table 3: Glass effects due to superficial deposits Formulation Example No. 1 4 2 3 Spotting Note 2.2 2.6 2.2 3.5 Filming Note 2.8 3.2 2.8 3.7

Glass care effects of automatic dishwashing formulations according to Example 1, and 4

There were each 14 new glasses, consisting of 2 cups "Salute" (Leonardo), 2 long drinks glasses "Ciao", 2 beer glasses "Ciao" (Leonardo), 2 white wine glasses "Vino" (Leonardo), 2 red wine glasses "Vino" (Leonardo) , 1 apple spritzer (flirt), 1 Bitburger (rastal), 1 Jim Beam (rastal), 1 latte macchiato (flirt), 1 Ramazzotti (rastal) at 65 ° C with demineralized water in 30 rinsing cycles without dirt loading in the Miele 688SC dishwasher rinsed, 20g of the formulation of Example 1 or Example 4 were added before each rinse.

After completion of the two series of tests, the glasses were visually assessed in a box lined with black felt and illuminated from the inside ("black box").

It turns out that the glasses rinsed with the formulation 1 according to the invention have an undamaged, high-gloss surface, while those washed with the dishwashing detergent of the formulation according to Example 4, which is characterized in that crystalline sodium disilicate was replaced by amorphous sodium disilicate, rinsed glasses Gloss turbidity and partly Have line corrosion effects.

Claims (21)

1. Dishwashing agent comprising the components

   a) 10 to 90% by weight of one or more builders, wherein at least 10 % by weight, referring to the total amount of that or of the builders consist of crystalline sodium layered silicate of formula (1)
   
           Na₂Si_xO_2x+1 · y H₂O     formula (1)
   
   wherein x is a number from 1.9 to 4 and y is a number from 0 to 20,

   b) 0.0025 to 2.0000 % by weight of one or more bleaching catalysts comprising formula (2)

   

   whererin a is 1 or 2, b is a number from 0 to 4, X stands for any mono- to divalent anion,

   c) 0.1 to 20 % by weight or one or more oxygen-containing bleaching agents,

   d) 0 to 10 % by weight of one ore more bleaching activators,

   e) 1 to 85% by weight of one or more pH-regulators,

   f) 0 to 10 % by weight of one or more surface-active substances,

   g) 0 to 5 % by weight of one or more enzymes,

   wherein the amounts of components a) to g) refer to the total amount of the composition.
2. A dishwashing agent comprising the components

   a) 10 to 90% by weight of one or more builders, wherein at least 10 % by weight, referring to the total amount of that or the builders consist of crystalline sodium layered silicate of formula (1)
   
           Na₂Si_xO_2x+1 · y H₂O     formula (1)
   
   wherein x is a number from 1.9 to 4 and y is a number from 0 to 20,

   b) 0.0025 to 2,0000 % by weight of one or more bleaching catalysts comprising α-manganese-oxalate-dihydrate,

   c) 0.1 to 20 % by weight of one or more oxygen-containing bleaching agents,

   d) 0 to 10 % by weight of one ore more bleaching activators,

   e) 1 to 85% by weight of one or more pH-regulators,

   f) 0 to 10 % by weight of one or more surface-active substances,

   g) 0 to 5 % by weight of one or more enzymes,

   wherein the amounts of components a) to g) refer to the total amount of the composition and wherein the composition is phosphate-free.
3. A dishwashing agent according to one of claims 1 or 2, wherein the crystalline sodium layerd silicate of formula (1) is composed of changing precentages of polymorphous phases alpha, beta and delta.
4. A dishwashing agent according to one of claims 1 to 3, wherein 1,9 ≤ x ≥ 2,2.
5. A dishwashing agent according to one of claims 1 to 4, wherein this contains crystalline sodium layered silicate of formula (1) in the form of granules as well as co-granules comprising crystalline sodium layered silicate of formula (1) and sparingly soluble metal carbonate.
6. A dishwashing agent according to one of claims 1 to 5, wherein this contains crystalline disodium-disilicates Na₂Si₂O₅ · y H₂O with y being from 0 to 2.
7. A dishwashing agent according to one of claims 1 to 6, wherein this contains crystalline sodium layered silicates having a content of beta-disodium-disilicate between 70 and 100 % by weight.
8. A dishwashing agent according to one of claims 1 to 7, wherein this contains crystalline sodium layered silicates having a content of delta-disodium-disilicate between 80 and 100 % by weight.
9. A dishwashing agent according to one of claims 1 to 5, wherein this contains crystalline sodium layered silicates, which comprise 1 to 40 % by weight of an alpha-disodium-disilicate, 0 to 50 % by weight of a beta-disodium-disilicate, 50 to 98 % by weight of a delta-disodium-disilicate and 0 to 40 by weight of amorphous fractions, preferably 7 to 21 % by weight of alpha-disodium-disilicate, 0 to 12 % by weight of beta-disodium-disilicate, 65 to 95 % by weight of delta-disodium-disilicate and 0 to 20 % by weight of amorphous fractions.
10. A dishwashing agent according to one of claims 1 or 3 to 9, wherein component a) besides the crystalline sodium layered silicate of formula (1) in addition contains builders selected from methylglycine-diacetic acid or its salts, sodium polyphosphate and/or sodium citrate.
11. A dishwashing agent according to one of claims 1 or 3 to 10, wherein X stands for PF₆ ^-, CH₃COO^-, Cl^-, SO₄ ^2-, and preferably for PF₆ ^-.
12. A dishwashing agent according to one of claims 1 to 11, wherein this contains the bleaching catalyst bis (N,N',N"-trimethyl-1,4,7-triazacyclononane)-trioxo-dimanganese (IV) di(hexafluorophosphate) monohydrate.
13. Composition according to claim 1, wherein this is phosphate-free.
14. A dishwashing agent according to one of claims 1 to 13, wherein this contains one or more bleaching agents selected from the group consisting of sodium perborate (monohydrate and tetrahydrate) and sodiuim percarbonate.
15. A dishwashing agent according to one of claims 1 to 14, wherein this contains acylated alkylene diamines, preferably tetraacetylethylenediamine (TAED), acylated glykoluriles, preferably tetraacetylglykolurile (TAGU), acylated triazine derivatives, preferably 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated phenylsulfonates, preferably nonanoyl-, isononanoyl- or lauroyloxybenzene-sulfonate (NOBS, ISONOBS or LOBS) or amido-derivatives thereof, preferably NACAOBS), acylated hydroxycarboxylic acids, preferably acetyl salicylic acid or nonanoyloxy benzoic acid (NOBA) and decanoyloxy benzoic acid (DOBA).
16. A dishwashing agent according to claim 15, wherein this contains acylated alkylene diamines, preferably tetraacetyl ethylene diamine (TAED).
17. A dishwashing agent according to one of claims 1 to 16, wherein this contains TAED and one of the bleaching catalysts according to formula (2)

    

    wherein a is 1 or 2, b is a number from 0 to 4, X stands for any mono- to divalent anion, preferably for PF₆ ^-, CH3COO^-, Cl^-, SO₄ ^2-, and especially for PF₆ ^-, and x stands for a number from 1 to 4, preferably for 1, wherein TAED and bleaching catalysts according to formula (2) are preferably utilised in a mixing ratio between 20 to 1 and 1 to 1.
18. A dishwashing agent according to one of claims 1 to 17, wherein this contains one or more enzymes selected from proteases, amylases, mannases, lipases, endolases, pectinases, cellulases, pullinases, cutinases or peroxidases.
19. A dishwashing agent according to one of claims 1 to 18, wherein this contains a compound comprising crystalline sodium layered silicate of formula (1) and an acid component, preferably a compound comprising crystalline sodium layered silicate of formula (1) and polycarboxylates as acid component, preferably preferred a compound comprising crystalline sodium layered silicate of formula (1) and a non- or only partially-neutralized homo- or copolymer from acrylic acid, methacrylic acid, maleic acid, polyaspartic acid and/or sugar carboxylic acid as acid component, and most preferably a crystalline layered sodium disilicate-/copolymer compound based on acrylic acid/maleic acid.
20. Method for cleaning surfaces comprising the contacting of the dishwashing agent according to one of the claims 1 to 19 with water and with the surface to be cleaned, in particular with dishes and glasses, and the interaction of the formed aqueous cleaning liquid with the surface to be cleaned.
21. Use of the composition according to one of claims 1 to 19 as a dishwashing agent, in particular as a machine dishwashing agent.