WO2014075799A1 - Detergent composition containing manganese oxalate and carboxymethyloxysuccinic acid (cmos) and/or the salts thereof - Google Patents

Abstract

The invention relates to a detergent formulation containing a) carboxymethyloxysuccinic acid (CMOS), and the alkaline or ammonia salts thereof; b) a manganese oxalate, and c) an inorganic persalt. The invention further relates to a detergent for dishwashers having said detergent formulation, and containing further additives such as builders, tensides, enzymes etc. in the form of a compressed tablet.

Description

 A detergent composition containing manganese oxalate and

Carboxymethyloxy succinic acid (CMOS) and / or salts thereof

The invention relates to a composition for washing and

Detergent agent which is particularly suitable for use in dishwashers.

Dishwashing detergent for dishwashing (ADW) included

so-called builders as important components. Typically, inorganic phosphates, for example sodium tripolyphosphate (STPP), are used for this purpose.

Current environmental considerations on the impact of phosphates in the

Wastewater, however, makes it desirable to completely dispense with phosphates in detergents and cleaners, because they are associated with eutrophication problems. For this reason, regulatory changes are expected that could lead to a ban on phosphates in ADW in the foreseeable future or at least reduce the amount of

Prescribe phosphorus compounds.

For several years, therefore, for alternative environmentally friendly,

sought phosphate-free complexing agents. Of particular interest in this connection are methylglycinediacetic acid (MGDA) and its salts, which are frequently used in phosphate-free ADCs. Preferred are further

Tetranamine immunosuccinates or imidodisuccinic acid (IDS) and (hydroxy) iminodibemic acid (HIDS) and alkali metal salts or ammonium salts thereof. Iminodibernsteirisäurederivate are z. In US Pat. No. 5,977,053.

Further described are aspartic acid-N-monoacetic acid (ASMA),

Aspartic acid-M, N-diacetic acid (ASDA), aspartic acid-N-monopropionic acid (AS P), iminodisuccinic acid (IDA), N - (2-sulfomethyl) aspartic acid (SMAS), N- (2-sulfoethyl) aspartic acid (SEE) , N- (2-sulfomethyl) glutamic acid (SGML), N- (2-sulfoethyl) glutamic acid (Segl), N-methyliminodiacetic acid

CONFIRMATION COPY (MIDA), a-alanine-N, N-diacetic acid (a-ALDA), - alanine-N, N-diacetic acid ([beta] -ALDA), serine-N, N-diacetic acid (SEDA), isoserine-N, N-diacetic acid (ISDA), phenylalanine-N, N-diacetic acid (PHDA), anthranilic acid N, N-diacetic acid (ANDA), sulphanilic acid N, N-diacetic acid (SLDA), taurine N, N-diacetic acid (TUDA) and sulfomethyl-N, N-diacetic acid (SMDA) and alkali metal salts or ammonium salts thereof.

All of these substitutes contain one or more nitrogen atoms. The introduction of large quantities of such substances into the environment could in the long term lead to similar effects as the use of phosphates. alternative to

Nitrogen-containing builders and complexing agents are therefore of particular interest in nitrogen-free systems.

Many of the alternative phosphate-free builders have problems with the

Cleaning performance, especially when it comes to the removal of tea stains in dishwashers. There is therefore a need for nitrogen-free builders, co-builders or complexing agents that are available in ADW

Formulations can be used without sacrificing

Cleaning performance occur.

The bleaching performance, especially of tea stains, depends on the type and amount of the bleaching system used and the pH of the washing liquor. The bleaching systems today typically comprise an oxygen source such as e.g. For example, hydrogen peroxide or persalt, such as. For example, sodium percarbonate, a bleach activator and / or an oxidation catalyst.

The object of the present invention was to provide a phosphate-free ADW formulation with a superior cleaning performance on tea soiling, wherein the use of nitrogen-containing builders or co-builders can be dispensed with.

Surprisingly, it has now been found that phosphate-free

Detergent formulations containing a combination of the nitrogen-free Builder Carboxymethyloxybersteinsäure (CMOS) or their alkali or

Ammonium salts, a manganese oxalate as a bleach catalyst and a

inorganic persalt, has increased bleaching performance. The

Detergent formulations of the present invention are particularly effective in automatic dishwashing machines.

The invention therefore detergent formulations containing a) carboxymethyloxy succinic acid (CMOS) or their alkali metal or

 Ammonium salts,

b) a manganese oxalate, preferably in the form of the di- or trihydrate, and c) an inorganic persalt, e.g. sodium

The excellent effectiveness of this formulation results from the

Combination of CMOS or its salts with manganese oxalates. It is not observed when using the structural isomeric citric acid instead of CMOS. It is believed that manganese oxalate and CMOS form an active, complex species that is the most potent bleaching-active agent. The combination of CMOS with a persalt, without the addition of a Manganoxalates, surprisingly shows no positive effect in

Removing tea stains.

The amount of CMOS or salts thereof in the invention

Detergent formulations are between 2 and 95% by weight, preferably between 10 and 75% by weight, more preferably between 15 and 60% by weight, and most preferably between 20 and 50% by weight.

For the preparation and isolation of CMOS and their salts, a number of methods are described, for. In US 3,914,297, DE-OS 27 38 825 and

DE-OS 28 2 194. The preparation is normally carried out by addition of a hydroxyl-containing component (glycolic acid) to the double bond of maleic acid or its salts in the sense of a Michael addition. The catalysts used are usually alkaline earth, zinc or lanthanide salts, oxides, hydroxides or carbonates used. The amount of manganese oxalate in the inventive

Detergent formulations are 0.005 to 5% by weight, preferably 0.01 to 2.5% by weight, more preferably between 0.05 and 1% by weight, and most preferably between 0.1 and 0.5% by weight. , Manganese oxalates can be used in the form of their dihydrates or trihydrates, but also in anhydrous form. According to the invention, the di- and trihydrates are preferred. They can be prepared in a manner known per se by reacting manganese salts with oxalic acid in water. Examples of such syntheses are u. a. by A. Huizing et al. in Mat. Res. Bull. Vol. 12, pp. 605-616, (1977) and by B. Donkova et al., In Thermochimica Acta, Vol. 421, pp. 141-149, (2004). For the detergent formulations according to the invention, both the white manganese (II) oxalate dihydrate and the pink manganese (II) oxalate trihydrate are suitable. Particularly preferred is the use of alpha manganese oxalate dihydrate. To increase the storage stability of the detergent formulations, the manganese oxalate is preferably used in granulated form. In a preferred embodiment of the invention are co-granules consisting of

Manganese oxalate, TAED and binders used particularly advantageously. As inorganic persalts, alkali perborate mono- or tetrahydrate and / or alkali percarbonates are primarily suitable, with sodium being the preferred alkali metal. The use of sodium percarbonate has particular advantages in dishwashing detergents, since it has a particularly favorable effect on the corrosion behavior of glasses. The oxygen-based bleaching agent is therefore preferably an alkali percarbonate, preferably sodium percarbonate. To increase the storage stability of the detergent formulations, the persalt used is preferably used in granulated form.

The amounts of inorganic persalts used in the detergent formulations according to the invention are from 1 to 25% by weight, preferably from 5 to 20% by weight, particularly preferably from 8 to 16% by weight. In addition, the detergent formulations according to the invention may also contain conventional bleach activators, ie

Perhydrolysis conditions optionally substituted perbenzoic acid and / or

Peroxycarboxylic acids having 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms result. Suitable for this purpose are the customary bleach activators which carry O- and / or N-acyl groups 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 Tnazinderivate, in particular 1, 5-diacetyl-2,4-dioxohexahydro-1, 3,5-triazine (DADHT), acylated Phenylsulfonate, in particular nonanoyl or Isononanoyloxybenzolsulfonat acylated

polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and

2,5-diacetoxy-2,5-dihydrofuran and also acetylated sorbitol and mannitol, and acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose and acetylated, optionally N-alkylated glucamine and gluconolactone. The combinations of conventional bleach activators known from DE 44 43 177 can also be used to advantage. In a preferred embodiment of the detergent formulations according to the invention is simultaneously with the manganese oxalate and the hydrogen peroxide-generating compound and such, under

Perhydrolysis conditions Peroxocarboxylic acid releasing compound

used. In a preferred embodiment, inventive

Detergent formulations are present at from 0.5% to 10%, preferably from 2% to 6%, by weight of such compound releasing under perhydrolysis conditions of peroxycarboxylic acid.

Furthermore, detergent formulations according to the invention may be organic

Peracids include, for example, perbenzoic acid or peroxycarboxylic acids such as mono- or diperoxyphthalic acid, diperoxydodecanedicarboxylic acid and imidoperoxycarboxylic acids. Particularly preferred is phthalimidoperhexanoic acid (PAP).

It is also possible to use bleaching agents from the group of organic bleaching agents be used. Typical organic bleaching agents are the diacyl peroxides, such as. B. dibenzoyl peroxide. Other typical organic bleaches are

Peroxyacids, examples of which are the alkyl peroxyacids and the aryl peroxyacids.

The pH of the detergent formulations according to the invention may be between 6 and 14, preferably between 8 and 12 and more preferably between 9 and 11. Further optional ingredients:

 In addition to the above ingredients, the

Detergent formulations according to the invention contain one or more of the following optional ingredients. Builder

The detergent formulations according to the invention additionally contain further builders, but no phosphate. In addition to CMOS and salts thereof, in particular one or more inorganic or organic phosphate and nitrogen-free builders may be present. Suitable inorganic builders are, in particular, sodium carbonates, bicarbonates or silicates. The sodium silicates may be present in amorphous or crystalline form. Particularly preferred crystalline layered silicates of the general formula NaMSi _x O2x ₊ i yH ₂ O are used, wherein M represents sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1, 9 to 4, with particularly preferred values for x 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. The invention

Detergent formulations preferably contain a weight fraction of the crystalline layered silicate of the formula NaMSi _x O _{2x +} 1yH ₂ O of from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular from 0.4 to 10 wt .-%, each based on the total weight of

Detergent formulations. With regard to the formation of deposits, it has proven to be advantageous to use the

To limit the weight fraction of silicate in the total weight of the detergent formulations. Preference is therefore less than 8.0 wt .-% silicate, more preferably less than 6.0 wt .-% silicate and in particular less than

4.0 wt .-% silicate, so for example between 0.1 and 4.0 wt .-% silicate.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8, and in particular from 1: 2 to 1: 2.6. In addition to the known organic builders such as citric acid, itaconic acid or tartaric acid in monomolecular or polymeric form (for example polyitaconic acid), in particular ether carboxylic acids or ether polycarboxylic acids of

Interest. The best known representatives of these classes of compounds are

Oxidisuccinic acid (ODS), 1-hydroxy-3-oxapentane-1, 2,4,5-tetracarboxylic acid (TMS) and 3,6-dioxaoctane-1, 2,4,5,7,8-hexacarboxylic acid (TDS), next to it but also sugar acids, such as. B. gluconic acid. It is preferred to avoid phosphorus-containing builders.

Preferably, the total amount of builder in the formulation is in the range of from 5 to 95 wt%, preferably from 15 to 75 wt%, more preferably from 25 to 65 wt%, most preferably from 30 to 60 wt% ,

In addition to the builders, the formulations according to the invention may also contain complexing phosphonates. This group includes in addition to the 1-hydroxyethane-1, 1-diphosphonic acid, a number of different compounds such as diethylene triamine penta (methylenephosphonic acid) (DTPMP). In this application, in particular hydroxyalkane or

Aminoalkanephosphonates. Among the hydroxyalkane phosphonates is the

1-hydroxyethane-1, 1-diphosphonate (HEDP) of particular importance as

Co-builders. It is preferably used as the sodium salt, the

Disodium salt neutral and the tetrasodium salt alkaline (pH 9). Ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and also their higher homologues in question. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity.

Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

Particular preference is given to automatic dishwasher detergents which are used as

Phosphonates 1-hydroxyethane-1, 1-diphosphonic acid (HEDP) or

Diethylenetriaminepenta (methylenephosphonic acid) (DTPMP).

Of course, the machine according to the invention can

Dishwashing detergents contain two or more different phosphonates. The proportion by weight of the phosphonates in the total weight of automatic dishwashing agents according to the invention is preferably from 1 to 8% by weight,

preferably 1, 2 to 6 wt .-% and in particular 1, 5 to 4 wt .-%.

The addition of phosphonate allowed the coating properties

Dishwashing detergent according to the invention can be further improved.

Another group of organic builders for use in

Detergent formulations according to the invention can be used are polymeric sulfonates. Preferred polysulfonates contain in addition

sulfonic acid group-containing monomer (s) at least one monomer from the group of unsaturated carboxylic acids.

As unsaturated carboxylic acid (s), it is particularly advantageous to use unsaturated carboxylic acids of the formula R ¹ (R ² ) C =C (R ³ ) COOH in which R to R ³ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to

12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched

Hydrocarbon radical having 1 to 12 carbon atoms.

Particularly preferred unsaturated carboxylic acids are acrylic acid,

Methacrylic acid, ethacrylic acid, chloroacrylic acid, cyanoacrylic acid, crotonic acid, phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or their

Mixtures. Of course, it is also possible to use the unsaturated dicarboxylic acids.

In the case of the monomers containing sulfonic acid groups, preference is given to those of the following formulas: R ⁵ (R ⁶ ) C =C (R ⁷ ) -X-SO ₃ H j _n of R ⁵ to R ⁷ independently

each represents -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl substituted with -NH ₂ , -OH or -COOH or alkenyl radicals or -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ -, -C (O) -NH-C (CH ₃ ) ₂ - CH ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the following formulas:

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH ₃ ) -X-SO ₃ H

HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H, in which R ⁶ and R ^{7 are} independent of one another and -H, -CH ₃ , -CH ₂ CH ₃ ,

-CH2CH2CH3, -CH (CH ₃₎ 2 and X is an optionally present

Spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) k- with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ -, -C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are included

 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid,

 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid,

 Allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid,

Methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid,

2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid,

 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide,

Sulfomethylmethacrylamid and mixtures of said acids or their water-soluble salts.

In the polymers, the sulfonic acid groups may be wholly or partially in neutralized form, d. H. that the acidic hydrogen atom of the

Sulfonic acid group in some or all sulfonic acid groups against metal ions, preferably alkali metal ions and in particular against sodium ions,

can be exchanged. The use of partially or fully neutralized

Sulfonsäuregruppenhaltigen copolymers is inventively preferred. The monomer distribution of the invention preferably used

polymeric sulfonates in copolymers containing only monomers from the

Groups of unsaturated carboxylic acids i) and unsaturated sulfonic acids ii), preferably each 5 to 95 wt .-% of i) or ii), more preferably 50 to 90 wt .-% of monomer from the group ii) and 10 bis 50 wt .-% of monomer from group i), each based on the weight of the polymeric sulfonates.

The molecular weight of the sulfo copolymers preferably used according to the invention can be varied to match the properties of the polymers to the desired use. It has proved to be advantageous for automatic dishwasher detergents if the copolymers have a molecular weight in the range from 2000 to 200,000 g / mol, preferably from 4000 to 25,000 g / mol, and

in particular from 5000 to 15,000 g / mol.

In a further preferred embodiment, the polymeric

Sulfonates in addition to carboxyl-containing monomer and

Also contains at least one nonionic, preferably hydrophobic monomer monomer containing sulfonic acid. The use of these hydrophobically modified polymers enabled, in particular, the rinse-aid performance

Detergent formulations according to the invention can be improved.

The nonionic monomers used are preferably monomers of the general formula R ¹ (R ² ) C =C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another are -H, -CH ₃ or -C ₂ H ₅ , X is an optional spacer group selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a

straight-chain or branched saturated alkyl radical having 2 to

22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.

Particularly preferred nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene,

Methylcyclohexene, 2,4,4-trimethylpentene-1, 2,4,4-trimethylpentene-2, 2,3-

Dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1, 3,5-dimethylhexene

1, 4,4-dimehtylhexene-1, ethylcyclohexene, 1-octene, 1-olefins having 10 or more carbon atoms, such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22-olefin, 2-methylstyrene, 3-methylstyrene, 4-propylstryol,

4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, -vinylnaphthalene,

2, vinylnaphthalene, methyl acrylate, ethyl acrylate,

Acrylic acid propyl ester, butyl acrylate, acrylic acid pentyl ester,

Hexyl acrylate, methyl methacrylate, N- (methyl) acrylamide, acrylic acid 2-ethylhexyl ester, 2-ethylhexyl methacrylate, N- (2-ethylhexyl) acrylamide, octyl acrylate, octyl methacrylate, N- (octyl) acrylamide,

Acrylic acid lauryl ester, methacrylic acid lauryl ester, N- (lauryl) acrylamide,

Acrylic acid stearyl ester, methacrylic acid stearyl ester, N- (stearyl) acrylamide,

Acrylic behenyl ester, methacrylic acid behenyl ester and N- (behenyl) acrylamide or mixtures thereof.

Automatic dishwashing detergent containing at least one anionic copolymer, comprising i) mono- or polyunsaturated monomers from the group of the carboxylic acids

ii) one or more polyunsaturated monomers from the group of

sulfonic acids

iii) optionally contain other nonionic monomers

preferred according to the invention. The proportion by weight of these polymers on

Total weight of the automatic dishwashing agent is preferably 2.0 to 20 wt .-%, preferably 2.5 to 15 wt .-% and in particular 2.5 to

10% by weight.

surfactants

Surfactants form key components of detergents. Of the four classes of surfactants (anionic, cationic, amphoteric and nonionic), nonionic surfactants are preferred for automatic dishwashing (ADW), especially low foaming surfactants. The basis of such surfactants are usually fatty alcohols with a C8-C20 chain which are ethoxylated or propoxylated. The degree of ethoxylation is described by the number of ethylene oxide units (EO) and the degree of propoxylation is by number

Propylene oxide units (PO) described.

The length of the fatty alcohol and the degree of ethoxylation and / or

Propoxylation determines whether the surfactant structure has a melting point above or below room temperature or, in other words, whether it is a liquid or a solid at room temperature. Surfactants may also contain butylene oxide units (BO) prepared by Butoxylation of fatty alcohol. Preferably, these are used in admixture with PO and EO units.

Examples of particularly preferred nonionic surfactants are the Plurafac ^®, Lutensol ^® and Pluronic ^® series from BASF and the Genapol ^® series from Clariant.

The total amount of surfactants that are typically in the

Detergent formulations is in the range of up to 15 wt .-%, preferably from 0.1 to 10 wt .-% and particularly preferably from 0.5 to

5% by weight.

Preferably, nonionic surfactants are included in the detergent formulations of the invention in an amount of from 0.1% to 5%, more preferably from 0.25% to 3%, and most preferably from 0.5% to 2.5% .-% used.

enzymes

 As a further component, detergent formulations according to the invention may comprise enzyme (s). These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically natural

origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly. Detergents or detergents contain enzymes preferably in total amounts of 1 × 10 ^-6 to 5% by weight, based on active protein The protein concentration can be determined by known methods, for example the BCA method or the biuret method Enzymes are contained in the detergent formulations according to the invention, then preferably protease and / or amylase, in particular amylase.

Among the proteases, those of the subtilisin type are preferable. Examples are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY, and the enzymes thermitase, proteinase K and the subtilisins, but not the subtilisins in the narrower sense

Proteases TW3 and TW7. Examples of amylases which can be used according to the invention are the [alpha] -amylases from Bacillus licheniformis, B. amyloliquefaciens, B. stearothermophilus, Aspergillus niger and Aspergillus oryzae and the further developments of the aforementioned amylases which are improved for use in detergents and cleaners. Furthermore, the [alpha] -amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodext n-glucanotransferase

(CGTase) from B. agaradherens (DSM 9948).

Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. Furthermore, enzymes can be used which are under the term

 Hemicellulases are summarized. These include, for example

Mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and [beta] - glucanases.

To increase the bleaching effect can according to the invention

Oxidoreductases, for example oxidases, oxygenases, catalases,

Peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases,

Polyphenoloxidasen) can be used. Advantageously, it is additionally preferable to add organic, particularly preferably aromatic, compounds which interact with the enzymes, in order to enhance the activity of the relevant oxidoreductases (enhancers) or in the case of strongly different ones Redox potentials between the oxidizing enzymes and the soiling to ensure the flow of electrons (mediators).

A preferred detergent formulation according to the invention is characterized in that it contains, based on its total weight, enzyme

Preparation (s) in amounts of 0.1 to 12 wt .-%, preferably from 0.2 to 10 wt .-% and in particular from 0.5 to 8 wt .-%, contains.

A protein and / or enzyme may be especially useful during storage

Damage such as inactivation, denaturation or decomposition may be protected by, for example, physical influences, oxidation or proteolytic cleavage. In microbial recovery of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.

Washing or cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storable and transportable preparations. Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.

As can be seen from the above, the enzyme protein forms only a small fraction of the total weight of conventional enzyme preparations. Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10 wt .-%, of the enzyme protein. Anticorrosive

 Preferred silver / copper corrosion inhibitors are benzotriazole (BTA) or bis-benzotriazole and the substituted derivatives thereof. Other suitable agents are organic and / or inorganic, redox-active substances and paraffin oil.

Glass retardants

 Zinc or bismuth salts may be used in the detergent formulations as

Glaskorrosioninhibitoren in a total amount of 0.01 to 5 wt .-%, preferably from 0.05 to 3 wt .-%, particularly preferably from 0.1 to

2.5 wt .-%, or from 0.1 to 1 wt .-%, based on the total weight of the detergent formulations, be contained.

application forms

 The detergent formulations according to the invention can be used in the

Known skilled in confectionery forms, so for example in solid or liquid form but also as a combination of solid and liquid supply forms.

Powder, granules, extrudates or compactates, in particular tablets, are particularly suitable as firm supply forms. The liquid supply forms

Base of water and / or organic solvents may be thickened, in the form of gels.

If they are formulated in liquid form, contain preferred

Laundry detergent formulations of the invention based on their total weight, a water content of preferably 20 to 70 wt .-%, particularly preferably from 30 to 60 wt .-% and in particular from 35 and 55 wt .-%.

Depending on the invention, detergent formulations may be formulated as single-phase or multi-phase products. In particular, automatic dishwashing detergents with one, two, three or four phases are preferred.

Detergent formulations which are in the form of a preformed dosing unit having two or more phases are particularly preferred. The individual phases of multiphase agents may have the same or different states of matter. Machine dishwashing detergents which have at least two different solid phases and / or at least two liquid phases and / or at least one solid and at least one liquid phase are preferred. Particularly preferred are in particular two- or multi-phase tablets, for example two-layer tablets, in particular two-layer tablets having a centrally arranged trough and a mold body located in the trough.

Automatic dishwashing agents preferred according to the invention are in the form of a tablet, preferably in the form of a multilayer tablet.

Automatic dishwasher detergents according to the invention are preferably prefabricated to form metering units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or

cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g.

The volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher. The volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml and in particular between 15 and 25 ml.

The automatic dishwasher detergents according to the invention, in particular the prefabricated metering units, have a water-soluble coating, with particular preference.

In order to facilitate the disintegration of prefabricated moldings, it is also possible Disintegrationshilfsmittel, so-called tablet disintegrants in this

To incorporate detergent formulations to reduce disintegration times. These substances, which are also referred to as "explosives" due to their effect, increase their volume upon ingress of water, whereby on the one hand the intrinsic volume increases (swelling), on the other hand a pressure can also be generated by the release of gases which reduces the tablet into smaller volumes Particles decay. Well-known disintegration aids are, for example

Carbonate / citric acid systems, although other organic acids can be used. Swelling disintegration aids are

For example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural products such as cellulose and starch and their derivatives, alginates or casein derivatives.

Disintegration aids are preferably used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the automatic dishwashing detergent.

Disintegrating agents are preferred disintegrating agents

Cellulose base used, so that preferred washing or cleaning agent such a disintegration agent based on cellulose in amounts of 0.5 to

10 wt .-%, preferably 3 to 7 wt .-% and in particular 4 to 6 wt .-%. The cellulose used as a disintegration aid

preferably not used in finely divided form, but converted into a coarser form before admixing with the premixes to be compressed,

for example, granulated or compacted. The particle sizes of such

Disintegrating agents are usually above 200 μιη, preferably at least 90 wt .-% between 300 and 1600 μιτι and in particular at least 90 wt .-% between 400 and 1200 μιτι.

Preferred disintegration aids, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, are present in the disintegrating agent-containing agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6 wt .-%, each based on the total weight of disintegrant-containing agent.

Furthermore, according to the invention, gas-evolving effervescent systems can furthermore be used as tablet disintegration auxiliaries.

However, preferred effervescent systems consist of at least two components which react with one another to form gas, for example alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution. An acidifying agent which releases carbon dioxide from the alkali salts in aqueous solution is, for example, citric acid.

The detergent formulations described above are particularly suitable for use in the cleaning of dishes in machine

Dishwashing.

Another object of the present application is a method for cleaning dishes in a dishwasher, using detergent formulations according to the invention, wherein the machine

Dishwashing agent preferably during the passage of a

Dishwashing program, before the start of the main wash cycle or during the course of the

Hauptpülgangs be metered into the interior of a dishwasher. The metering or the entry of the invention

Detergent formulations in the interior of the dishwasher can be done manually, but preferably the detergent formulation is metered into the interior of the dishwasher with the aid of the metering chamber of the dishwasher. In the course of the cleaning process preferably no additional water softener and no additional rinse aid is dosed into the interior of the dishwasher.

A kit for a dishwasher, comprising

a) a machine dishwashing detergent according to the invention;

(b) instructions informing the consumer that the automatic dishwashing detergent should not be added without the addition of a rinse aid and / or a rinse aid Softener salt is to be used,

is another subject of this application.

embodiments

Comparative Examples V1 to V3:

 Powdered detergent formulations V1, V2 and V3 were prepared by mixing the components. With 20 g of the respective powder bleaching tests were carried out on each of 6 tea cups (soiled according to IKW test protocol) in an automatic dishwasher (Miele G 688 SC) according to the IKW test protocol (IKW test method: SOFW, 132 (8), 2006, 35-49 ) in the rinse program 45 ° C fine. The evaluation was done optically. The experiments were repeated three times (3 times) and the average was formed. The pH was measured in the dishwasher during the cleaning cycle. The exact

 Composition of the detergent formulations is summarized in the following Table 1, the figures correspond to wt .-%.

Table 1

 Formulation V1 V2 V3

CMOS-Na3 45

MDGA 45

Na citrate 45

Sodium carbonate 10 10 10

Sodium percarbonate 15 15 15

Genapol EP 2544 2 2 2

Co-polymer (Reckitt) 8 8 8

Sodium sulfate 20 20 20 pH 10.0 10.3 10.0 Bleaching result:

In the comparative experiments V1 to V3, the combination according to the invention of sodium percarbonate, CMOS and manganese oxalate was not used. It was found that the formulation V2 with the nitrogen-containing phosphate substitute MDGA (= methylglycinediacetic acid) already ensures a relatively good removal of the tea soil. The effectiveness of the two formulations with the nitrogen-free substitutes CMOS or Na citrate showed only insufficient effectiveness in Teeschmutz.

Example WF1 (Inventive) and Comparative Examples V4 and V5:

Experiments V1 to V3 were repeated, but now in the presence of

0.2% by weight. Manganese oxalate dihydrate. The inventive

Detergent formulation WF1 containing a combination of

Sodium percarbonate, CMOS sodium salt and manganese oxalate showed a significant increase in performance, which significantly exceeded the bleaching performance of Formulation V5 (with citrate as the nitrogen-free builder). The use of manganese oxalate under these conditions had no effect on the bleaching performance of V4. The exact composition of those used in this series

Detergent formulations are summarized in the following Table 2, the figures correspond to wt .-%.

Table 2

 Formulation WF1 V4 V5

CMOS-Na3 45

MDGA 45

Na citrate 45

Manganese Oxalate Dihydrate 0.2 0.2 0.2 Sodium carbonate 10 10 10

Sodium percarbonate 14.8 14.8 14.8

Nonionic surfactant

 (Genapol EP 2544) 2 2 2

Co-polymer (sulfonate) 8 8 8

Sodium sulfate 20 20 20 pH 10.1 10.3 10.1

Bleaching result:

 Formulation WF1 V4 V5

Tea removal [%] 68 67 50

The results show that the inventive combination of manganese oxalate, CMOS and persalt (Example WF1) has a better bleaching action than the combination manganese oxalate / citrate according to Example V5, while the

Purification effect of methylglycinediacetic acid (MDGA) in combination with manganese oxalate according to Example V4 proved to be almost equivalent.

Examples WF2 to WF4 (according to the invention):

 Additional examples WF2, WF3 and WF4 for even more optimized

formulations according to the invention are summarized in Table 3 below. The numbers correspond again wt .-%.

Table 3

 Formulation WF2 WF3 WF4

CMOS - Na3 45 30 30

Na citrate - ~ 15 Manganese oxalate dihydrate 0.4 0.2 0.5

Sodium carbonate 15 30 15

Sodium percarbonate 14.6 14.8 14.5

Nonionic surfactant

 (Genapol EP 2544) 2 2 2

Co-polymer (sulfonate) 8 8 8

Other: (enzymes,

 HEDP,

 polyethylene glycol,

 Silver protectant BTA) 3 4 5

Sodium sulfate 12 11 10

Bleaching result:

 Formulation WF2 WF3 WF4

Tea removal [%] 71 73 85

The results show that the combination of manganese oxalate, CMOS and persalt according to the invention consistently shows a good cleaning effect on tea soil.

Claims

claims 1. containing detergent formulation a) Carboxymethyloxybernsteinsäure (CMOS) or their alkali or  Ammonium salts, b) a manganese oxalate and c) an inorganic persalt. 2. Detergent formulation according to claim 1, characterized in that it contains the manganese oxalate in the form of a di- or trihydrate. 3. A detergent formulation according to claim 1 or 2, characterized in that it contains as organic persalt Aikaliperboratmono- or tetrahydrate and / or alkali metal percarbonate, wherein the preferred alkali metal is sodium, preferably sodium percarbonate. 4. Detergent formulation according to one or more of claims 1 to 3, characterized in that it contains CMOS or salts thereof in an amount in the range of 2 to 95 wt .-%, preferably from 10 to 75 wt .-%, particularly preferably of 15 to 60 wt .-% and most preferably from 20 to Contains 50 wt .-%, each based on the total weight of Detergent formulation. 5. Detergent formulation according to one or more of claims 1 to 4, characterized in that it manganese oxalate in an amount in the range of 0.005 to 5% by weight, preferably from 0.01 to 2.5 wt .-%, particularly preferably from 0.05 to 1 wt .-% and most preferably from 0.1 to 0.5 wt.%, In each case based on the total weight of Detergent formulation. Detergent formulation according to one or more of claims 1 to 5, characterized in that it contains the inorganic persalt in an amount in the range from 1 to 25% by weight, preferably from 5 to 20% by weight, especially preferably from 8 to 16 wt .-%, in each case based on the total weight of the detergent formulation. 7. A detergent formulation according to one or more of claims 1 to 6, characterized in that it comprises the inorganic persalt in granulated Contains form. 8. A machine dishwashing detergent containing a detergent formulation according to one or more of claims 1 to 7, characterized in that it additionally contains further additives such as builders, surfactants, enzymes, Contains anticorrosive agents and glass preservatives. 9. Machine dishwashing detergent according to claim 8, characterized in that it is in the form of a pressed tablet, preferably in the form of a single or multilayer tablet. 10. Machine dishwashing detergent according to claim 8 or 9, characterized in that it is prefabricated into a dosing unit which contains a quantity of washing or cleaning-active substances necessary for a cleaning cycle and has a weight between 12 and 30 g, preferably between 14 and 26 g and particularly preferably between 15 and 22 g. 11. Machine dishwashing detergent according to one or more of claims 8 to 10, characterized in that the volume of Dosing unit and the spatial form are chosen so that the prefabricated unit can be dosed via the dosing of a dishwasher, wherein its volume is in the range between 10 and 35 ml, preferably between 12 and 30 ml and more preferably between 15 and 25 ml. 12. Machine dishwashing detergent according to one or more of claims 8 to 11, characterized in that it is designed as a two-layer tablet, preferably as a two-layer tablet with a center arranged trough and a mold located in the trough. 13. Machine dishwashing detergent according to one or more of claims 8 to 12, characterized in that the prefabricated metering unit has a water-soluble sheath on. 14. Machine dishwashing detergent according to one or more of claims 8 to 13, characterized in that it additionally Disintegration aids in an amount in the range of 0.5 to 10 wt .-%, preferably from 3 to 7 wt .-% and particularly preferably from 4 to 6 wt .-%, each based on the total weight of the automatic dishwashing detergent contains.