EP2052066A1

EP2052066A1 - Cleaning formulation for a dish washer

Info

Publication number: EP2052066A1
Application number: EP07788080A
Authority: EP
Inventors: Guido Vandermeulen; Lidcay Herrera Taboada; Tanja Seebeck
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2006-08-10
Filing date: 2007-07-31
Publication date: 2009-04-29
Also published as: CN101528907A; US8101027B2; KR20090048455A; BRPI0715378A2; US20100167975A1; WO2008017620A1; CA2660193A1; JP2010500431A; MX2009001409A

Abstract

A cleaning formulation for machine dishwashing, comprising: a) 1 to 20 % by weight of one or more copolymers, obtainable by polymerization of aa) 5 to 80 % by weight of one or more monoethylenic unsaturated monocarbon acids or the salts thereof, bb) 5 to 60 % by weight of one or several monoethylecic unsaturated dicarbon acids or the salts or anhydrides thereof, cc) 1 to 50% by weight of one or more sulfon acid containing monomers or the salts thereof and dd) 0 to 50 % by weight of further ionic or non-ionic monomers: b) 1 to 50 % by weight of one or more complexing agents from the group consisting of nitrilotriacetic acid, ethylenediaminetetraacetic acid, glycine-N,N-diacetic acid, glutamic acid-N,N-diacetic acid, minodisuccinate, hydroxyiminodisuccinate, S,S-ethylenediamine-disuccinate aspartic acid-diacetic acid, and the salts thereof: c) 1 to 15 % by weight nonionic surfectants; d) 0 to 30 % by weight of bleaches and optionally bleach activators: e) 0 to 60 % by weight of one or more further additives, such as anionic or zwitterionic surfactants, bleach catalysts, alkali carriers, corrosion inhibitors, antifoams, dyes, fragrances, fillers, organic solvents and water.

Description

Cleaning formulation for dishwashers

description

The invention relates to cleaning formulations for machine dishwashing, which contain copolymers with sulfonic and carboxylic acid functions, as well as the use of such copolymers in machine dishwashing.

During the cleaning of dishes in the dishwasher, the dishes are cleaned during the cleaning cycle of dirt that comes from different food residues, which also contain greasy and oily components. The detached ones

Dirt particles and components are circulated during further cleaning in the rinse water of the machine. It must be ensured that the detached

Dirt particles are well dispersed and emulsified, so they do not settle back on the dishes.

Many of the formulations on the market are phosphate-based. The phosphate used is technically ideal for this application because it combines many useful properties that are needed in machine dishwashing. On the one hand, phosphate is able to disperse water hardness (i.e., insoluble salts of ions such as calcium and magnesium ions). Although this is also achieved via the ion exchanger of the machines, a large proportion of the products for automatic dishwashing is currently offered in the form of so-called 3-in-1 formulations, in which the function of the separate ion exchanger is no longer necessary. In such formulations, the phosphate, usually combined with phosphonates, takes over the softening of the water. Furthermore, the phosphate disperses the detached dirt and thus prevents re-deposition of the dirt on the dishes.

For detergents, many countries have switched to completely phosphate-free systems for environmental reasons. Also for the products for machine dishwashing it is discussed whether a conversion to phosphate-free products makes sense. However, the phosphate-free products that were still on the market in the mid-nineties no longer meet today's demands on the washing result. Today, consumers expect flawless, streak-free, non-stick and drip-free dishes, preferably without the use of additional rinse aid or regenerating salt for the ion exchanger.

In DE-A 43 21 429 dishwashing agents are described, which are preferably phosphate-free and copolymers containing at least the monomers of a monoethylenically unsaturated C 3 -C 8 -carboxylic acid, a 2-alkylallylsulfonic acid or 2-arylallylsulfonic acid and a carbohydrate.

In DE-A 37 43 739, phosphate-free dishwashing detergents are preferably described which contain copolymers based on (meth) acrylic acid, sulfonic acids and optionally (meth) acrylamide.

WO-A 02/04583 describes automatic dishwasher detergents which contain copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and, if appropriate, further ionic or nonionic monomers and which optionally contain, as further ingredients, chelate complexing agents such as ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA ) exhibit. Phosphates are proposed as builders unless their use should be avoided for environmental reasons.

Although good results have already been achieved with the known formulations, there is nevertheless a broad scope for improvements, in particular with regard to phosphate-free formulations with high cleaning performance.

The object of the invention is therefore to provide phosphate-free cleaning formulations for machine dishwashing, in particular those that without the use of additional rinse aid and Regeneriersalz a strip, covering and drip-free dishes.

It has now been found that the replacement of phosphate can be achieved by the use of certain sulfonic acid group-containing polycarboxylates in combination with certain complexing agents.

The invention relates to a cleaning formulation for machine dishwashing, containing

a) from 1 to 20% by weight of one or more copolymers obtainable by polymerization of aa) from 5 to 80% by weight of one or more monoethylenically unsaturated monocarboxylic acids or their salts, bb) from 5 to 60% by weight on one or more monoethylenically unsaturated dicarboxylic acids or their salts or anhydrides,

cc) 1 to 50 wt .-% of one or more sulfonic acid-containing, ethylenically unsaturated monomers or their salts and dd) O to 50% by weight of other ionic or nonionic monomers;

b) 1 to 50 wt .-% of one or more complexing agents selected from the group consisting of nitrilotriacetic acid, ethylenediaminetetraacetic acid and glycine-N, N-diacetic acid derivatives, glutamic acid-N, N-diacetic acid, iminodisuccinate, Hydroxyiminodisuccinat, S, S Ethylenediamine disuccinate, aspartic acid diacetic acid and their salts; c) from 1 to 15% by weight of nonionic surfactants; d) 0 to 30% by weight of bleaching agent and optionally bleach activators; e) 0 to 60% by weight of further builders; f) 0 to 8 wt .-% enzymes and g) 0 to 50 wt .-% of one or more other additives, such as anionic see or zwitterionic surfactants, bleach catalysts, alkali carriers, corrosion inhibitors, defoamers, dyes, fragrances, fillers, organic Solvent and water.

The invention furthermore relates to the use of a combination of copolymers (a) and complexing agents (b) in cleaning formulations for dishwashers, in particular as builders (builders).

Another object of the invention is the use of a combination of the copolymers (a) and complexing agents (b) as a deposit-inhibiting additive in cleaning formulations for machine dishwashing.

Likewise subject of the invention is a method for machine cleaning of dishes, wherein the dishes are brought into contact with the cleaning formulation described above.

The cleaning formulation according to the invention has a very good rinsing performance and in particular prevents the formation of deposits, which makes it possible to dispense with the addition of phosphate. The complexing agent takes over the task of complexing the water hardness-causing ions (calcium and magnesium ions) contained in the rinse water or in the food residues. Sulfone group-containing polycarboxylates are in particular capable of effectively dispersing salts which form from the water of hardness, sparingly soluble and, in addition, of dispersing the dirt present in the wash liquor. The combination of the two substance classes thus leads to a particularly good deposit prevention during the automatic dishwashing process. The formulations according to the invention are preferably phosphate-free.

The copolymer used according to the invention is obtainable by polymerization of the monomers (aa), (bb), (cc) and optionally (dd). The monomer (aa) is at least one monoethylenically unsaturated monocarboxylic acid. It is of course also possible to use mixtures of a plurality of different ethylenically unsaturated monocarboxylic acids.

Preferred monomers (aa) are monocarboxylic acids of the formula (I)

R ¹ (R ² ) C = C (R ³ ) COOH (I)

in which R ¹ , R ² , R ³ independently of one another are H, a straight-chain or branched alkyl radical having 1 to 12 C atoms or a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 C atoms, where both last-mentioned radicals are unsubstituted or, preferably, substituted by NH ₂ and / or OH, and their water-soluble salts, in particular alkali metal salts, such as potassium and, more preferably, sodium salts, and ammonium salts.

Particularly preferred are C ₃ -C ₆ monocarboxylic acids and the corresponding salts.

Particularly preferred monoethylenically unsaturated monocarboxylic acids (aa) are acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid. Very particularly preferred monomers are acrylic acid and methacrylic acid, particularly preferred is acrylic acid. The preferences also apply accordingly to the salts. Of course, mixtures of these acids can also be used.

The monomer (bb) is preferably one or more monoethylenically unsaturated dicarboxylic acids of the general formula (II) or (III)

(HOOC) R ⁴ C = CR 1 COOH) (II)

R ⁴ R ⁵ C = C (- (CH ₂ ) _n -COOH) (COOH) (III)

in which

R ⁴ and R ⁵ independently of one another denote H or a straight-chain or branched alkyl radical having 1 to 20 C atoms which is unsubstituted or substituted, and in which in the formula (II) or (III) two radicals R ⁴ , R ⁵ together can also form an alkylene radical having 3 to 20 C atoms, and n is an integer from 0 to 5,

and their anhydrides and water-soluble salts, in particular alkali metal salts, such as potassium and, particularly preferably, sodium salts and ammonium salts.

It is also possible to use mixtures of different monomers (bb). In the case of (I), it may be the ice and / or the trans form of the monomer. The monomers can also be used in the form of the corresponding carboxylic anhydrides or other hydrolyzable carboxylic acid derivatives. If the COOH groups are arranged in cis form, cyclic anhydrides can be used with particular advantage.

R ⁴ and R ^{5 are} preferably H or an alkyl radical having 1 to 4 C atoms. R ⁴ and R ⁵ are particularly preferably H or a methyl group. Further preferred are monoethylenically unsaturated C ₄ -C ₈ -dicarboxylic acids and their corresponding salts and anhydrides.

In the case of the formula (III), R ⁴ and R ^{5 may} further together be an alkylene radical having 3 to 20 C atoms, which is unsubstituted or substituted. Preferably, the ring formed from the double bond and the alkylene radical contains 5 or 6 carbon atoms. Examples of alkylene radicals are the 1, 3-propylene or 1, 4-butylene radical, which may also have other alkyl groups as substituents. N is an integer from 0 to 5, preferably 0 to 3 and most preferably 0 or 1.

Preferably, the radicals R ⁴ , R ^{5 are} unsubstituted. Examples of suitable monomers (bb) of the formula (II) include maleic acid, fumaric acid, methyl fumaric acid, methylmaleic acid, dimethylmaleic acid and the corresponding cyclic anhydrides. Examples of monomers of formula (III) include methylenemalonic acid and itaconic acid. Preference is given to using maleic acid, maleic anhydride and itaconic acid. Of course, mixtures of these acids can also be used.

The sulfonic acid group-containing monomers (cc) are preferably those of the formula (IV)

R ⁶ (R ⁷ ) C = C (R ⁸ ) -X-SO ₃ H (IV) wherein R ⁶ , R ⁷ and R ⁸ independently of one another are -H, a straight-chain or branched alkyl radical having 1 to 12 C atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 C atoms, the two last-mentioned Radicals are unsubstituted or substituted by one or more groups -NH ₂ , -OH or -COOH,

-COOH or -COOR ⁹ , or

R ⁶ also XSO ₃ H;

R ^{9 is} a saturated or unsaturated, straight-chain or branched

Hydrocarbon radical having 1 to 12 carbon atoms; X is a single bond, - (CH ₂ ) _n - where n = 1 to 4, phenylene, preferably

1, 4-phenylene, -CH ₂ -O-phenylene (preferably 1, 4), -CH ₂ -O-CH ₂ - CH (OH) -CH ₂ -, -COO- (CH ₂ ) _k with k = 1 to 6, -CO-NH-, -CO-NH-CR'R "- (CH ₂ ) _m with m = 0 to 3 OdOr -CO-NH-CH ₂ -CH (OH) -CH ₂ -;

R 'is -H, -CH ₃ or -C ₂ H ₅ and R "is -H or -CH ₃ ,

and their water-soluble salts, in particular alkali metal salts, such as potassium and, particularly preferably, sodium salts, and ammonium salts.

Of the monomers (cc), particular preference is given to those of the formulas (IVa), (IVb) and / or (IVc),

H ₂ C = CH-X-SO ₃ H (IVa)

H ₂ C = C (CH ₃ ) -X-SO ₃ H (IVb)

HO ₃ SX- (R ¹⁰ ) C = C (R ¹¹ ) -X-SO ₃ H (IVc) where

R ¹⁰ and R ^{11 are} independently -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , or

-CH (CH ₃ ), and

X is a single bond, - (CH ₂ ) _n - where n = 1 to 4, phenylene, preferably

1, 4-phenylene, -CH ₂ -O-phenylene (preferably 1, 4), -CH ₂ -O-CH ₂ - CH (OH) -CH ₂ -, -COO- (CH ₂ ) _k - with k = 1 to 6, -CO-NH-, -CO-NH-CR'R "-

(CH ₂ ) _m - with m = 0 to 3 OdOr -CO-NH-CH ₂ -CH (OH) -CH ₂ -; R 'is -H, -CH ₃ or -C ₂ H ₅ and

R "-H or -CH ₃ mean.

Very particularly preferred sulfonic acid group-containing monomers are 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 (2-methyl-2-propene-1-sulfonic acid), allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts and esters of said acids, wherein the alkali and alkaline earth metal salts, in particular the Na and K salts are preferred.

Particularly preferred monomers (cc) are 2-acrylamido-2-methyl-1-propanesulfonic acid, vinylsulfonic acid, methallylsulfonic acid and styrenesulfonic acid.

Suitable further ionic or nonionic monomers (dd) are, in particular, ethylenically unsaturated compounds. The content of the copolymers of monomers (dd) used according to the invention is preferably less than 20% by weight, based on the copolymer. Preferably used copolymers (a) consist only of monomers of groups (aa), (bb) and (cc).

The copolymers used according to the invention generally have a low pH. For mixing with components (a) and (c) and optionally (d), (e) and (f), the copolymer solution may either be used directly or the pH adjusted by base or acid addition.

A preferred pH range for mixing is as a rule from 5 to 11, preferably from 6 to 10 and more preferably from 6.5 to 9, very particularly preferably from 7 to 8.9.

If the pH of the copolymer solution is lower after the polymerization, it can be increased by adding base. Suitable bases for this are e.g. Hydroxides and amines.

The copolymers used according to the invention generally have a K value of from 10 to 150, preferably from 10 to 80 and particularly preferably from 10 to 50 (determined by H. Fikentscher, Cellulose-Chemie, Vol. 13, pp. 58 to 64 and 71 to 74 (1932); K value measured at pH 7 in 1% strength by weight aqueous solution at 25 ^° C.).

The copolymers used according to the invention preferably contain 10 to 80% by weight, more preferably 20 to 70% by weight of component (aa), 10 to 60% by weight, particularly preferably 10 to 55% by weight of component (bb ), 1 to 50 wt .-%, particularly preferably 5 to 30 wt .-% of component (cc) and 0 to 10 wt .-%, particularly preferably 0 to 5 wt .-% of component (dd).

The copolymers (a) can be prepared by known methods known to the person skilled in the art. The copolymers (a) are preferably prepared by free-radical polymerization of the monomers described. In addition to the polymerization in substance, particular mention should be made of solution and emulsion polymerization, the solution polymerization being preferred.

The polymerization is preferably carried out in water as a solvent. However, it can also be carried out in alcoholic solvents, in particular in C ₄ -alcohols, such as methanol, ethanol and isopropanol, or in mixtures of these solvents with water.

Suitable polymerization initiators are both thermally and photochemically (photoinitiators) decomposing and thereby radical-forming compounds.

Among the thermally activatable polymerization initiators, preference is given to initiators having a decomposition temperature in the range from 20 to 180 ^° C., in particular from 50 to 120 ^° C. Examples of suitable thermal initiators are inorganic peroxo compounds and azo compounds. These initiators can be used in combination with reducing compounds as starter / regulator systems. Examples of suitable photoinitiators are benzophenone, acetophenone, benzoin ethers, Benzildial- kylketale and derivatives thereof.

Preferably, thermal initiators are used, with inorganic peroxo compounds, in particular hydrogen peroxide and especially sodium peroxodisulfate (sodium persulfate) being preferred.

If desired, polymerization regulators can also be used. Suitable compounds known to those skilled in the art, e.g. Sulfur compounds such as mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid and dodecylmercaptan.

When polymerization regulators are used, their amount used is usually 0.1 to 15 wt .-%, preferably 0.1 to 5 wt .-% and particularly preferably 0.1 to 2.5 wt .-%, based on the total the monomers.

The polymerization temperature is generally from 30 to 200 ⁰ C, preferably at 50 to 150 ° C and particularly preferably at 80 to 130 ° C.

The polymerization is preferably carried out under protective gas, such as nitrogen or argon, and may be carried out under atmospheric pressure, preferably However, it is made in a closed system under the evolving self-pressure.

The copolymers used according to the invention are usually obtained in the form of a polymer solution which has a solids content of from 10 to 70% by weight, preferably from 25 to 60% by weight.

As component (b), the cleaning formulations according to the invention contain one or more chelate complexing agents. Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination site on a central atom, i. H. In this case, usually stretched compounds are formed by complex formation via an ion into rings, and the number of bound ligands depends on the coordination number of the central ion.

According to the invention, complexing agents (b) are used which are selected from the group consisting of nitrilotriacetic acid, ethylenediaminetetraacetic acid, glycine-N, diacetic acid derivatives, glutamic acid-N, N-diacetic acid, iminodisuccinate, hydroxyimidisuccinate, S, S-ethylenediamine disuccinate, Aspartic acid and its salts. Preferred complexing agents (b) are methylglycinediacetic acid and its salts.

Preferred glycine-N, N-diacetic acid derivatives are compounds of the general formula (V),

R ¹²

, _{^ /} CH ₇ COOM MOOC N ²

CH ₂ COOM _(V) wherein

R ¹² Ci to Ci ₂ alkyl and

M alkali metal or ammonium mean.

In the compounds of the general formula (V), M is preferably sodium or potassium, more preferably sodium.

R ¹² is preferably a Ci _-6 alkyl group, more preferably a methyl or ethyl radical. Particular preference is given to using as component (b) an alkali metal salt of methylglycinediacetic acid (MGDA). Very particular preference is given to using the trisodium salt of methylglycinediacetic acid.

The preparation of glycine-N, N-diacetic acid derivatives (V) is known, see e.g. EP-A-0 845 456 and the literature cited therein.

The cleaning formulations according to the invention preferably contain from 5 to 45% by weight, particularly preferably from 10 to 40% by weight (based on the total formulation) of complexing agent (b).

As component (c), the cleaning formulations according to the invention comprise nonionic surfactants, preferably low or low foaming. These are preferably present in proportions of from 0.1 to 15% by weight, more preferably from 0.25 to 10% by weight.

Preferred nonionic surfactants include the surfactants of general formula (VI),

R ¹³ - (OCH ₂ CHR ¹⁴ ) _p - (OCH ₂ CHR ¹⁵ ) _m -OR ¹⁶ (VI) wherein

R ^{13 is} a linear or branched alkyl radical having 6 to 24 C atoms,

R ¹⁴ and R ^{15 are} different from each other hydrogen or a linear or branched alkyl radical having 1-16 C atoms,

R ^{4 is} a linear or branched alkyl radical having 1 to 8 C atoms and p and m are independently of one another integers 0 to 300.

Preferably, p is 1-50 and m is 0-30.

The surfactants of formula (VI) may be both random copolymers and block copolymers having one or more blocks.

Further, di- and multiblock copolymers composed of ethylene oxide and product are pylenoxid used, for example, under the name Pluronic ^® (BASF Aktiengesellschaft) or Tetronic ^® (BASF Corporation) are commercially available. Likewise, reaction products of sorbitan esters with ethylene oxide and / or propylene oxide can be used. Also suitable are amine oxides or alkyl glycosides. An overview of suitable nonionic surfactants are, for example, EP-A 851 023 and DE-A 198 19 187. As component (d), the cleaning formulations of the invention may contain bleaches and optionally bleach activators.

Bleaching agents are subdivided into oxygen bleaching agents and chlorine-containing bleaching agents. For example, alkali metal perborates and their hydrates and alkali metal percarbonates are used as oxygen bleaching agents. Preferred bleaching agents here are sodium perborate in the form of the mono- or tetrahydrate, sodium percarbonate or the hydrates of sodium percarbonate.

Also usable as oxygen bleaching agents are persulfates and hydrogen peroxide.

Typical oxygen bleaches are also organic peracids, such as perbenzoic acid, peroxy-alpha-naphthoic acid, peroxylauric acid, peroxystearic acid, phthalimidope roxycaproic acid, 1,12-diperoxydodecanedioic acid, 1,9-diperoxyazelaic acid, diperoxoisophthalic acid or 2-decyldiperoxybutan-1,4-diacid.

In addition, for example, the following oxygen bleaches can also be used in the detergent formulation:

Cationic peroxyacids described, for example, in US Pat. Nos. 5,422,028, 5,294,362 and 5,292,447;

Sulfonyl peroxyacids described, for example, in US Pat. Nos. 5,039,447.

Oxygen bleaching agents are used in amounts of generally from 0 to 30% by weight, preferably from 1 to 20% by weight, particularly preferably from 3 to 15% by weight, based on the total cleaning formulation.

Chlorine-containing bleaches as well as the combination of chlorine-containing bleach with peroxide-containing bleaches may also be used. Known chlorine-containing bleaching agents are for example 1, 3-dichloro-5,5-dimethylhydantoin, N-Chlorosulfamid, chloramine T, dichloramine T, chloramine B, N, N ^{'-Dichlorbenzoylharnstoff,} p-toluene- or sulfondichloramid Trichlorethylamin. Preferred chlorine-containing bleaching agents are sodium hypochlorite, calcium hypochlorite, potassium hypochlorite, magnesium hypochlorite, potassium dichloroisocyanurate or sodium dichloroisocyanurate.

Chlorine-containing bleaching agents are used in amounts of generally from 0 to 20% by weight, preferably from 0.2 to 10% by weight, particularly preferably from 0.3 to 8% by weight, based on the total detergent formulation. Furthermore, bleach stabilizers, such as phosphonates, borates, metaborates, metasilicates or magnesium salts, may be added in small amounts.

Bleach activators are compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or substituted perbenzoic acid. Suitable compounds are those which contain one or more N- or O-acyl groups and / or optionally substituted benzoyl groups, for example substances from the class of the anhydrides, esters, imides, acylated imidazoles or oximes. Examples are tetraacetylethylenediamine (TAED), tetraacetylmethylenediamine (TAMD), tetraacetylglycoluril (TAGU), tetraacetylhexylenediamine (TAHD), N-acylimides such as N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates such as n-nonanoyl or isononanoyloxybenzenesulfonates (n or iso-NOBS), pentaacetylglucose (PAG), 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine (DADHT) or isatoic anhydride (ISA). Likewise suitable as bleach activators are nitrile quats, such as, for example, N-methyl-morpholinium-acetonitrile salts (MMA salts) or trimethylammonium acetonitrile salts (TMAQ salts).

Bleach activators are preferably suitable from the group consisting of polyacylated alkylenediamines, particularly preferably TAED, N-acylimides, particularly preferably NOSI, acylated phenolsulfonates, more preferably n- or iso-NOBS, MMA and TMAQ.

Furthermore, for example, the following substances can be used as bleach activators in the cleaning formulation:

Carboxylic acid anhydrides, such as phthalic anhydride; acylated polyhydric alcohols, such as triacetin, ethylene glycol diacetate or 2,5-diacetoxy-2,5-dihydrofuran; the enol esters known from DE-A 196 16 693 and DE-A 196 16 767 and acetylated sorbitol and mannitol or their mixtures described in EP-A 525 239; acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose, as well as acetylated, optionally N-alkylated, glucamine and gluconolactone, N-acylated lactams, for example N-benzoylcaprolactam, which are described in WO 94/27970, WO 94/28102 , WO 94/28103, WO 95/00626, WO 95/14759 and WO 95/17498.

The hydrophilically substituted acylacetals listed in DE-A 196 16 769 and the acyl lactams described in DE-A 196 16 770 and WO 95/14075 can, as well as the known from DE-A 44 43 177 combinations of conventional bleach activators are used.

Bleach activators are used in amounts of generally 0.1 to 10 wt .-%, preferably from 1 to 9 wt .-%, particularly preferably from 1, 5 to 8 wt .-%, based on the total detergent formulation.

As component (e), the cleaning formulations according to the invention may contain further builders. It can be used water-soluble and water-insoluble BuN- der whose main task in the binding of calcium and magnesium.

As additional builders can be used, for example:

low molecular weight carboxylic acids and their salts, such as alkali citrates, in particular anhydrous trisodium citrate or trisodium citrate dihydrate, alkali metal succinates, alkali metalates, fatty acid sulfonates, oxydisuccinate, alkyl or alkenyl disuccinates, gluconic acids, oxadiacetates, carboxymethyloxysuccinates, tartrate monosuccinate, tartrate disuccinate, tartrate monoacetate, tartrate diacetate, .alpha.-hydroxypropionic acid;

oxidized starches, oxidized polysaccharides;

homo- and copolymeric polycarboxylic acids and their salts, such as polyacrylic acid, polymethacrylic acid, copolymers of maleic acid and acrylic acid;

Graft polymers of monoethylenically unsaturated mono- and / or dicarboxylic acids on monosaccharides, oligosaccharides, polysaccharides, aminopolycarboxylates and polyaspartic acid;

Phosphonates, such as 2-phosphono-1, 2,4-butanetricarboxylic acid, aminotri (methylenephosphonic acid), 1-hydroxyethylene (1,1-diphosphonic acid), ethylenediamine tetramethylene phosphonic acid, hexamethylene diamine tetramethylene phosphonic acid or diethylene triamine pentamethylene phosphonic acid;

Silicates such as sodium disilicate and sodium metasilicate;

water-insoluble builders, such as zeolites and crystalline sheet silicates.

As component (f), the cleaning formulations according to the invention optionally contain one or more enzymes. The cleaning agent can be between 0 and 8 wt .-%, preferably between 0 and 5 wt .-%, enzymes, based on the total preparation, are added to increase the performance of the detergent or to ensure the cleaning performance of the same quality under milder conditions. Among the most commonly used enzymes are lipases, amylases, cellulases and proteases. Furthermore, for example, esterases, pectinases, lactases and peroxidases can be used.

The enzymes may be adsorbed to carriers or embedded in encapsulants to protect against premature degradation.

In addition, the cleaning agents according to the invention optionally contain further additives as component (g), for example further surfactants, bleach catalysts, alkali carriers, corrosion inhibitors, defoamers, dyes, fragrances, fillers, organic solvents and water.

The cleaning formulations of the invention may further contain anionic, cationic, amphoteric or zwitterionic surfactants, preferably in admixture with nonionic surfactants. Suitable anionic and zwitterionic surfactants are also mentioned in EP-A 851 023 and DE-A 198 19 187. Suitable cationic surfactants are, for example, Cs-C16-dialkyldimethylammonium halides, dialkoxydimethylammonium halides or imidazolinium salts with a long-chain alkyl radical. Suitable amphoteric surfactants are, for example, derivatives of secondary or tertiary amines, such as Cβ-Cis-alkylbetaines, Cβ-C-is-alkylsulfobetaines or amine oxides, such as alkyl dimethylamine oxides. In addition to the conventional bleach activators listed above or in their place, the sulfone imines and / or bleach-enhancing transition metal salts or transition metal complexes known from EP-A 446 982 and EP-A 453 003 can also be present as so-called bleach catalysts in the inventive cleaning formulations.

Suitable transition metal compounds include, for example, the manganese, iron, cobalt, ruthenium or molybdenum salt complexes known from DE-A 195 29 905 and their N-analog compounds known from DE-A 196 20 267, US Pat. the manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes known from DE-A 195 36 082, the manganese, iron, cobalt, ruthenium, molybdenum, compounds described in DE-A 196 05 688, Titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium-amine complexes known from DE-A 196 20 411, the manganese, copper described in DE-A 44 16 438 and cobalt complexes, the cobalt complexes described in EP-A 272 030, the manganese complexes known from EP-A 693 550, which are known from EP-A 392 592 known manganese, iron, cobalt and copper complexes and / or in EP-A 443 651, EP-A 458 397, EP-A 458 398, EP-A 549 271, EP-A 549 272, EP-A A 544 490 and EP-A 544 519 described manganese complexes. Combinations of bleach activators and transition metal bleach catalysts are known, for example, from DE-A 196 13 103 and WO 95/27775.

Dinuclear manganese complexes containing 1, 4,7-trimethyl-1,4,7-triazacyclononane (TMTACN), such as [(TMTACN) ₂ Mn ^lv Mn ^lv (μ-O) ₃ ] ²⁺ (PF ₆ ^~ ) ₂ , are also useful as effective bleach catalysts. These manganese complexes are also described in the aforementioned publications.

Suitable bleach catalysts are preferably bleach-enhancing transition metal complexes or salts from the group consisting of the manganese salts and complexes and the cobalt salts and complexes. Particularly suitable are the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate or [(TMTACN) ₂ Mn ^lv Mn ^lv (μ-)

Bleaching catalysts, if used, may be used in amounts of from 0.0001 to 5% by weight, preferably from 0.0025 to 1% by weight, more preferably from 0.01 to 0.25% by weight, based on the entire cleaner formulation can be used.

As further constituents (f) of the cleaning formulation, alkali carriers may be present. Suitable alkali carriers are ammonium and / or alkali metal hydroxides, ammonium and / or alkali metal carbonates, ammonium and / or alkali metal hydrogencarbonates, ammonium and / or alkali metal sesquicarbonates, ammonium and / or alkali metal silicates, ammonium and / or alkali disilicates, ammonium and / or alkali metal metasilicates and mixtures of the aforementioned substances, preferably ammonium and / or carbonates Alkalicar- and ammonium and / or alkali metal disilicates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate and SS and δ-sodium Na ₂ Si ₂ O _O are used yH ₂ O.

Examples of corrosion inhibitors which can be used are silver protectants from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. In addition, active chlorine-containing agents are often used in cleaner formulations, which can significantly reduce the corrosion of the silver surface. In chlorine-free cleaners, preference is given to oxygen-containing and nitrogen-containing organic redox-active compounds, such as dihydric and trihydric phenols, for example hydroquinone, pyrocatechol, hydroxyl hydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds used. Salts and complex inorganic compounds such as salts of the metals Mn, Ti, Zr Hf, V, Co and Ce are often used. Preferred here are the transition metal salts, which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably from the group of cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl ) Complexes, the chlorides of cobalt or manganese and of manganese sulfate. Also, zinc compounds or bismuth compounds can be used to prevent corrosion of the items to be washed, in particular glass.

Paraffin oils and silicone oils may optionally be used as defoamers and for the protection of plastic and metal surfaces. Defoamers are generally used in proportions of 0.001 wt .-% to 5 wt .-%. In addition, dyes such as patent blue, preservatives such as Kathon CG, perfumes and other perfumes may be added to the cleansing formulation of the present invention.

A suitable filler is, for example, sodium sulfate.

The cleaning formulations according to the invention can be formulated in any desired form. Depending on the choice of other ingredients both liquid and solid means are readily produced. In the case of the liquid agents, liquid dishwashing detergents with viscosities from a few pas to gel-like or even paste-proof pastes can be prepared. In the case of the solid compositions, both particulate agents such as powders, granules, extrudates, flakes, pellets and flakes can be produced, as well as compact shaped articles, such as blocks or tablets, the latter being clearly preferred due to their high consumer acceptance.

Detergent tablets for machine dishwashing can be pressed from a single premix and thus provided in the form of a single-phase tablet. However, it is also possible to press several differently composed premixes in succession, with tablets resulting in the simplest case with a layer structure. Depending on the number of premixes, two-layered, three-layered or four-layered tablets are obtained. The different layers thereby open up the possibility of separating active ingredients from one another, in which case both the ingredients necessarily contained according to the invention can be separated from one another, as well as other optional ingredients, such as, for example, bleaching agents and bleach activators. The cleaning formulations according to the invention can be used both for the household and for the commercial sector. Commercial cleaner types contain, for example, complexing agents, such as nitrilotriacetate. Frequently, in contrast to household cleaners with caustic soda or potassium hydroxide solution is used as alkali carrier. Furthermore, chlorine compounds, such as sodium diisocyanate, are frequently used as bleaching agents.

The invention is explained in more detail by the examples.

Examples

used abbreviations

AS: acrylic acid

MS: maleic acid

IS: itaconic acid

VS: vinylsulfonic acid

AMPS: 2-acrylamido-2-methyl-1-sulfonic acid

FG: solids content

Demineralised water

K-value: see above

TABLE 1 Copolymers used according to the invention (a)

Examples Example 1:

In a 2 l pilot stirrer with anchor stirrer and internal thermometer, 91.2 g of maleic anhydride and 142.5 g of demineralized water are sparged with nitrogen and stirred at 99.degree. C. for 1 h. Then 527.3 mg of iron (II) sulfate • 7H ₂ O and 15 g of water are added and then in 5 minutes feed (1) consisting of 37.5 g of deionized water and 64.9 g Triethanolamine. Then within 5 h feed (2) consisting of 322.5 g of acrylic acid and 100 g of deionized water and feed (3) consisting of 108 g of 2-acrylamido-2-methyl-1-sulfonic acid and 241, 3 g of VE Water was added, and within 6 h feed (4) consisting of 35.9 g of hydrogen peroxide (30% strength) in 120 g of deionized water. The reaction mixture is stirred for a further 2 hours at 99.degree. A brown solution is obtained. Solids content: 47%. K value: 20.2 (1% in water).

Example 2:

In a 2 l pilot-scale with anchor stirrer and internal thermometer 2 g ma- (25%) Golpanol ^® VS () 91 leinsäureanhydrid and 306.1 g of vinyl sulfonic acid sodium salt gassed with nitrogen and stirred for 1 h at 99 ° C. Then 527.3 mg of iron (II) sulfate • 7H ₂ O and 15 g of water are added and then in 5 minutes feed (1) consisting of 37.5 g of deionized water and 64.9 g of triethanolamine. Then within 5 h feed (2) consisting of 324 g of acrylic acid and 246.4 g of demineralized water and within 6 h feed (3) consisting of 30.6 g of sodium persulfate in 120 g of deionized water was added. The reaction mixture is stirred for a further 2 h at 99.degree. A yellow solution is obtained. Solids content: 51.5%. K value: 20.2 (1% in water).

Example 3: In a 2 l pilot-scale with anchor stirrer and internal thermometer 91, 2 g of maleic anhydride and 153.8 g of vinyl sulfonic acid sodium salt (VS Golpanol ^® (25%)) and 28 g of deionized water and sparged with nitrogen for 1 hour at 99 ° C stirred. Then 527.3 mg of iron (II) sulfate • 7H ₂ O and 15 g of water are added and then in 5 minutes feed (1) consisting of 37.5 g of deionized water and 64.9 g of triethanolamine. Subsequently, feed (2) consisting of 324 g of acrylic acid and 289.1 g of deionized water are added over the course of 5 hours and feed (3) consisting of 28.3 g of sodium persulfate in 120 g of demineralized water is added over the course of 6 hours. The reaction mixture is stirred for a further 2 h at 99.degree. A yellow solution is obtained. Solids content: 50.1%. K value: 19.5 (1% in water).

Example 4:

In a 2 l pilot-scale with anchor stirrer and internal thermometer, 121 g itaconic acid and 510.2 g are vinyl sulfonic acid sodium salt (VS Golpanol ^® (25.5% in deionized water)), gassed with nitrogen and heated to 99 ° C. Then 527.3 mg of iron (II) sulfate • 7H ₂ O and 15 g of water are added. Then within 5 h feed (1) consisting of 324 g of acrylic acid and 79.4 g of deionized water and within 6 h feed (2) consisting of 34.5 g of sodium persulfate in 160 g of deionized water was added. The reaction mixture is stirred for a further 2 h at 99.degree. A yellow solution is obtained. Solids content: 54.1%. K value: 22.4 (1% in water). Example 5:

In a 2 l pilot-scale with anchor stirrer and internal thermometer, 121 g itaconic acid and 164.3 g are vinyl sulfonic acid sodium salt (VS Golpanol ^® (25%)) and 29.8 g of deionized water gassed with nitrogen and heated to 99 ° C , Then 527.3 mg of iron (II) sulfate • 7H ₂ O and 15 g of water are added. Then within 5 h feed (1) consisting of 324 g of acrylic acid and 210 g of deionized water and within 6 hours feed (2) consisting of 29.2 g of sodium persulfate in 160 g of deionized water was added. The reaction mixture is stirred for a further 2 h at 99.degree. A yellow solution is obtained. Solids content: 51.4%. K value: 22.7 (1% in water).

Example 6:

In a 2 l pilot-scale with anchor stirrer and internal thermometer, 148.1 g of maleic anhydride and 306.1 g of vinyl sulfonic acid sodium salt (VS Golpanol ^® (25.5% in deionized water)), gassed with nitrogen, and 1 h at 99 ° C for , Then 24.9 mg of iron (II) sulfate • 7H ₂ O and 15 g of water are added and then in 5 minutes feed (1) consisting of 60 g of deionized water and 105.3 g of triethanolamine. Then within 5 h feed (2) consisting of 324 g of acrylic acid and 221, 4 g of deionized water and within 6 h feed (3) consisting of 17.3 g of sodium persulfate and 57.7 g of hydrogen peroxide (30%) in 162.3 g of demineralized water. The reaction mixture is stirred for a further 2 h at 99.degree. After cooling, the pH is adjusted to 7.2 with sodium hydroxide solution. A brown solution is obtained. Solids content: 45.9%. K value: 24.5 (1% in water).

EXAMPLE 7 179.9 g of maleic anhydride, 2.1 g of phosphorous acid (50%) and 323.3 g of deionised water are sparged with nitrogen in a 2 l pilot stirrer with anchor stirrer and internal thermometer, then with feed (1) consisting of 293.6 g of NaOH (50%) were neutralized and heated to 95 ° C. Then within 4 h feed (2) consisting of 132.1 g of acrylic acid and 136.4 g of vinylsulfonic acid sodium salt (Golpanol ^® VS (25% strength)) and feed (3) consisting of 259.6 g of sodium bisulfite and subsequently within of 4.25 h feed (4) consisting of 17.3 g of sodium persulfate and 155.7 g of demineralized water added. Subsequently, the reaction mixture is stirred at 95 ° C for 1 h. After cooling, the reaction mixture is then adjusted to pH 7.2 with sodium hydroxide solution. A pale brown solution is obtained. Solids content: 41, 3%. K value: 15.9 (1% in water).

Example 8:

In a 2I pilot stirrer with anchor stirrer and internal thermometer, 174.6 g of maleic anhydride, 2.1 g of phosphorous acid (50%) and 159.7 g of demineralized water are sparged with nitrogen, then with feed (1) consisting of 285.1 g NaOH (50%) neutral and heated to 101-104 ⁰ C. Then within 5 h feed (2) consisting of 128.3 g of acrylic acid and 128.3 g of demineralized water and feed (3) consisting of 261, 9 g sodium bisulfite added within 3 h feed (4) consisting of 185, 4 g of vinyl sulfonic acid sodium salt (Golpanol ^® VS (25%)) and within 5.24 h feed (5) consisting of 17.5 g of sodium persulfate and 157.2 g of deionized water was added. The reaction mixture stirred for 1 hour at 101-104 ⁰ C. After cooling, the reaction mixture is then adjusted to pH 7.2 with sodium hydroxide solution. A pale brown solution is obtained. Solids content: 40.1%. K value: 14.3 (1% in water).

Application examples

The following formulations were used to test the combinations of copolymers and complexing agents according to the invention (Table 2):

Table 2

^* The indication in% by weight refers in each case to the stated formulation. The copolymer is calculated in each case with an active content of 100%.

The test was carried out under the following test conditions:

Dishwasher: Miele G 1 140 SC

Rinses: 2 rinses 55 ⁰ C Normal (without pre-rinse)

Washware: Knife (WMF table knife Berlin, Monoblock) and

Barrel shaped glass beaker (Matador, Ruhr Kristall);

Ballast dishes: 6 dessert plates black, plastic plates (SAN-

Plate Kayser)

Rinsing temperature: 65 ° C water hardness: 25 ° dH (corresponding to 445 mg CaCO ₃ / kg) In one part of the experiments in each case 50 g of IKW ballast dirt, according to SÖFW journal, 124th year, 14/98, p 1029, added to the beginning of the experiment in the dishwasher.

The washware was evaluated 18 hours after cleaning by visual inspection in a black painted light box with halogen spot and pinhole using a grading scale from 10 (very good) to 1 (very bad). The highest grade of 10 corresponds to surface and drip-free surfaces, from grades <3 on, coverings and drops are already recognizable under normal room lighting, so they are perceived as disturbing.

The results of the rinsing tests are summarized in Table 3 below.

Table 3:

Claims

claims

1. Cleaning formulation for machine dishwashing, containing

a. 1 to 20 wt .-% of one or more copolymers, obtainable by polymerization of

aa) 5 to 80 wt .-% of one or more monoethylenically unsaturated monocarboxylic acids or their salts, and

bb) 5 to 60% by weight of one or more monoethylenically unsaturated dicarboxylic acids or their salts or anhydrides,

cc) 1 to 50 wt .-% of one or more sulfonic acid group-containing monomers or their salts and

dd) 0 to 50 wt .-% of further ionic or nonionic monomers;

b. 1 to 50% by weight of one or more complexing agents from the group consisting of nitrilotriacetic acid, ethylenediaminetetraacetic acid, and glycine-N, N-diacetic acid derivatives, glutamic acid-N, N-diacetic acid, iminodisuccinate, hydroxyiminodisuccinate, S, S-ethylenediamine disuccinate, aspartic acid and their salts; c. 1 to 15% by weight of nonionic surfactants; d. 0 to 30% by weight of bleaching agent and optionally bleach activators; e. From 0% to 60% by weight of further builders; f. 0 to 8 wt .-% of enzymes and g) 0 to 50 wt .-% of one or more other additives, such as anionic or zwitterionic surfactants, bleach catalysts, alkali carriers, corrosion inhibitors, defoamers, dyes, fragrances, fillers, organic solvents and water.

2. Cleaning formulation according to claim 1, wherein as monomers (aa) monocarboxylic acids of the formula (I)

R ⁴ (R ² ) C = C (R ³ ) COOH (I), in which R ¹ 'R ² , R ³ are each independently H, a straight-chain or branched alkyl radical having 1 to 12 C atoms or a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 C atoms, wherein the both latter radicals are unsubstituted or substituted and their water-soluble salts are used.

3. Cleaning formulation according to claim 2, wherein the monoethylenically unsaturated monocarboxylic acids (AA) are selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid.

4. Cleaning formulation according to one of claims 1 to 3, wherein as monomer (bb) one or more monoethylenically unsaturated dicarboxylic acids of the general formula (II) or (III)

(HOOC) R ⁴ C = CR 1 COOH) (II)

R ⁴ R ⁵ C = C (- (CH ₂ ) _n -COOH) (COOH) (III),

where R ⁴ and R ⁵ independently of one another are H or a straight-chain or branched alkyl radical having 1 to 20 C atoms which is unsubstituted or substituted, and where in the formula (II) or (III) two radicals R ⁴ , R ⁵ together can also form an alkylene radical having 3 to 20 C atoms, and n is an integer from 0 to 5, or their anhydrides and water-soluble salts are used.

5. Cleaning formulation according to claim 4, wherein the monomers (bb) from the group of maleic acid, fumaric acid, methyl fumaric acid, methylmaleic acid, dimethylmaleic acid and their cyclic anhydrides methylenmalonic acid and itaconic acid are selected.

6. Cleaning formulation according to one of claims 1 to 5, wherein as the sulfonic acid group-containing monomers (cc) those of the formula (IV),

R ⁶ (R ⁷ ) C = C (R ⁸ ) -X-SO ₃ H (IV) wherein

R ⁶ , R ⁷ and R ⁸ independently of one another are -H, a straight-chain or branched alkyl radical having 1 to 12 C atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, the latter two radicals being unsubstituted or substituted by one or more groups -NH ₂ , -OH or -COOH, -COOH or -COOR ⁹ , or R ⁶ also being XSO ₃ H;

R ^{9 is} a saturated or unsaturated straight-chain or branched hydrocarbon radical having 1 to 12 C atoms;

X is a single bond, - (CH ₂ ) _n - where n = 1 to 4, phenylene, -CH ₂ -

O-phenylene, -CH ₂ -O-CH ₂ -CH (OH) -CH ₂ -, -COO- (CH ₂ ) _k - where k = 1 to 6, -CO-NH-, -CO-NH-CR 'R' - (CH ₂ ) _m - with m = 0 to 3 or

-CO-NH-CH ₂ -CH (OH) -CH ₂ -;

R 'is -H, -CH ₃ or -C ₂ H ₅ and

R "-H or -CH ₃ , or their water-soluble salts are used.

7. Cleaning formulation according to claim 6, wherein sulfonic acid group-containing monomers from the group 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, styrenesulfonic acid, vinylsulfonic acid, Sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts and esters of said acids can be selected.

8. Use of a combination of copolymers (a) and complexing agents (b) according to any one of claims 1 to 7 in cleaning formulations for machine dishwashing.

9. Use of a combination of the copolymers (a) and complexing agents (b) according to any one of claims 1 to 7 as a deposit-inhibiting additive in cleaning formulations for machine dishwashing.

10. A method of machine cleaning dishes, wherein the dishes are brought into contact with a cleaning formulation according to any one of claims 1 to 7.