EP1924676A1 - Cleaning formulations for machine dishwashing comprising hyrdophilically modified polycarboxylates - Google Patents

Abstract

Phosphate-free cleaning formulation for dishwasher, comprises: (a) copolymers from monoethylenic unsaturated monocarboxylic acids; (b) a complexing agent from e.g. nitrilotriacetic acid; (C) weak foaming nonionic surfactant, (D) a bleaching agent and optionally a bleach activator; (e) a further builder; (f) enzyme; and (g) a further additives e.g. anionic or zwitterionic surfactant and bleaching catalyst. Phosphate-free cleaning formulation for dishwasher, comprises: (a) 1-20 wt.% of copolymers from (a1) 50-99.5 mol.% of a monoethylenic unsaturated monocarboxylic acid and/or its salt, (a2) 0.5-20 mol.% of an alkoxylated monoethylenic unsaturated monomer (I) of formula (CH 2=C(R1)-R2-[R3-O] n-R4), (a3) 0-50 mol.% of a monoethylenic unsaturated dicarboxylic acid, an anhydride and/or its salt and (a4) 0-20 mol.% of an another copolymerizable monoethylenic unsaturated monomer, where the copolymer exhibits an average molecular weight of 30000-500000 g/mol and a K-value of 40-150, measured at the pH of 7 in 1 wt.% aqueous solution at 25[deg]C; (b) 1-50 wt.% of complexing agent from nitrilotriacetic acid, ethyl diaminetetra acetic acid, diethyletriaminepentaacetic acid, hydroxyethylethyldiaminetriacetic acid and glycine-N, N-diacetic acid and its derivative, glutamic acid-N,N-diacetic acid, iminodisuccinate, hydroxyiminodisuccinate, S,S-ethyldiaminedisuccinate and asparaginic acid diacetic acid and the salts of the aforementioned substances; (C) 1-15 wt.% of weak foaming nonionic surfactant, (D) 0.1-30 wt.% of a bleaching agent and optionally a bleach activator; (e) 0-60 wt.% of a further builder; (f) 0-8 wt.% of enzyme; and (g) 0-50 wt.% of a further additives like anionic or zwitterionic surfactant, bleaching catalyst, alkali carrier, corrosion inhibitors, antifoaming agents, coloring materials, perfumes, fillers, organic solvents and water. An independent claim is included for a powder mixture or a granulate mixture for the cleaning formulations of the dishwasher, comprising: 30-95 wt.% of the copolymers from (a1), (a2) and optionally (a3) and (a4); (b) 5-70 wt.% of complexing agent; and (C) 0-20 wt.% of polyethylene glycol and/or nonionic surfactant. R1 : H or CH 3; R2 : -(CH 2) x-O-, -CH 2-NR5, -CH 2-O-CH 2-CR6R7-CH 2-O or -CONH; R3 : 2-4C-alkylene that can be arranged as block wise or static manner, where the portion of ethylene amounts to at least 50 mol.%; R4 : H, 1-4C-alkyl, -SO 3M or -PO 3M 2; R5 : H or -CH 2-CR1=CH 2; R6 : -O-[R3-O] n-R4, where the -[R3-O] n of the R6 is different compared to the [R3-O] n of (I); R7 : H or ethyl; M : alkali metal or H; n : 4-250; and x : 0 or 1.

Description

Cleaning formulations for machine dishwashing containing hydrophilically modified polycarboxylates

description

The invention relates to cleaning formulations for machine dishwashing.

When cleaning dishes in the dishwasher, the dishes during the cleaning cycle of the dirt, which consists of a variety of food residues, which also contain greasy and oily ingredients, free. The detached dirt particles and components are pumped 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 that they do not settle on the dishes again.

Many of the formulations on the market are phosphate-based. The phosphate used is ideal for use as it combines many of the useful properties required in machine dishwashing. For one thing, phosphate is able to disperse water hardness (i.e., insoluble salts of water hardness causing ions such as calcium and magnesium ions). This task is still achieved via the ion exchanger of the machines. However, a large proportion of dishwashing products today are offered in the form of so-called 3-in-1 formulations, in which the function of the ion exchanger is no longer necessary. The phosphate usually takes over the softening of the water in combination with phosphonates. 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 fully phosphate-free systems for environmental reasons. It is also being discussed for the products for machine dishwashing, whether a reversal to phosphate-free products makes sense. However, the phosphate-free products, which were still on the market in the mid-nineties, no longer meet today's demands on the washing results. Today the consumer expects a flawless, streak-free, covering and drip-free dishes. And that preferably without the use of additional rinse aid or regenerating salt for the ion exchanger.

The object of the invention is to provide phosphate-free cleaning formulations for machine dishwashing. The object of the invention is, in particular, to provide such formulations which, without the use of additional rinse aid, result in a dish-free, covering-free and drip-free dish. It has now been found that the replacement of phosphate can be achieved by the use of certain hydrophilic modified polycarboxylates in combination with certain complexing agents.

The complexing agent takes on the task of complexing the water hardness causing ions (calcium and magnesium ions) contained in the rinse water or in the food residues. Polycarboxylates also have a calcium binding capacity and are capable of dispersing the sparingly soluble salts which form from water hardness, and are also capable of dispersing the soil present in the wash liquor. The combination of complexing agents and polycarboxylates thus leads to a particularly good deposit prevention during the automatic dishwashing process.

Thus, the object is achieved by phosphate-free cleaning formulations for machine dishwashing containing as components:

a) 1 to 20 wt .-% copolymers of

a1) 50 to 99.5 mol% of a monoethylenically unsaturated monocarboxylic acid and / or a salt thereof,

a2) 0.5 to 20 mol% of an alkoxylated monoethylenically unsaturated monomer of the formula (I)

R '

H ₂ C = CR-R ^J -O- -R ^* (I)

in which the variables have the following meaning:

R ^{1 is} hydrogen or methyl; R ^{2 is} - (CH ₂ ) _X -O-, -CH ₂ -NR ⁵ -, -CH ₂ -O-CH ₂ -CR ⁶ R ⁷ -CH ₂ -O- or -CONH-;

R ^{3 are} identical or different C ₂ -C ₄ -alkylene radicals which may be arranged in blocks or randomly, the proportion of ethylene radicals being at least 50 mol%;

R ⁴ is hydrogen, C _r C ₄ alkyl, -SO ₃ M or -PO ₃ M _2; R ^{5 is} hydrogen or -CH ₂ -CR ¹ = CH ₂ ;

R ^{6 is} -O- [R ³ -O] _n -R ⁴ , where the radicals - [R ³ -O] _n - may be different from the other radicals contained in formula I - [R ³ -O] _n -; R ^{7 is} hydrogen or ethyl;

M alkali metal or hydrogen; n 4 to 250; x O or i,

a3) 0 to 50 mol% of a monoethylenically unsaturated dicarboxylic acid, an anhydride and / or a salt thereof,

a4) 0 to 20 mol% of a further copolymerizable monoethylenically unsaturated monomer,

the copolymer having an average molecular weight M _{w of} from 30,000 to 500,000 g / mol and a K value of from 40 to 150 (measured at pH 7 in 1% strength by weight aqueous solution at 25 ° C.),

b) from 1 to 50% by weight, preferably from 5 to 40% by weight, of complexing agents selected from the group consisting of nitrilotriacetic acid, ethylenediaminetetraacetic acid, glycine-N, N-diacetic acid derivatives, glutamic acid-N, N-diacetic acid, iminodiacetic acid, Hydroxyiminodsuccinic acid, S, S-ethylenediamine disuccinic acid, asparagine acid diacetic acid and the salts of said complexing agents,

c) 1 to 15% by weight, preferably 1 to 10% by weight, of low-foaming nonionic surfactants,

d) from 0 to 30% by weight, preferably from 0 to 20% by weight, of bleach and optionally bleach activators,

e) 0 to 60% by weight, preferably 0 to 40% by weight, of further builders,

f) 0 to 8% by weight, preferably 0 to 5% by weight of enzymes,

g) 0 to 50 wt .-%, preferably 0.1 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,

the sum of components a) to g) being 100% by weight. - A -

The formulation may be processed as a tablet, powder, gel, capsule, extrudate or solution. These may be formulations for both household and commercial applications.

The object is further achieved by the use of a combination of copolymers a) and complexing agents b) as a builder system in cleaning formulations for machine dishwashing. The builder system takes on the task of complexing the water hardness-causing ions (calcium and magnesium ions) contained in the rinse water or in the food residues.

The object is further achieved by the use of a combination of copolymers a) and complexing agents b) as a deposit-inhibiting additive in cleaning formulations for machine dishwashing.

The copolymers a) used according to the invention comprise as copolymerized monomer a1) a monoethylenically unsaturated monocarboxylic acid, preferably a C3-C6 monocarboxylic acid, and / or a water-soluble salt, in particular an alkali metal salt, such as potassium and, above all, sodium salt, or ammonium salt of this acid.

Specific examples of suitable monomers a1) are: acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid. Of course, mixtures of these acids can also be used.

Particularly preferred monomer a1) is acrylic acid.

The copolymers a) used according to the invention contain from 50 to 99.5 mol% of the monomer a1). If the copolymers are composed only of the monomers a1) and a2), the content of the monomer a1) is generally from 80 to 99.5 mol%, preferably from 90 to 98 mol%. Terpolymers of the monomers a1), a2) and a3) generally contain 60 to 98 mol%, preferably 70 to 95 mol%, of the monomer a1).

As copolymerized monomer a2), the copolymers used according to the invention comprise an alkethoxylated monoethylenically unsaturated monomer of the formula (I)

(I) in which the variables have the following meaning:

R ^{1 is} hydrogen or methyl, preferably hydrogen; R ² - (CH ₂ ) _X -O-, -CH ₂ -NR ⁵ -, -CH ₂ -O-CH ₂ -CR ⁶ R ⁷ -CH ₂ -O- or -CONH-, preferably - (CH ₂ ) _{X is} -O-, -CH ₂ -NR ⁵ - or -CH ₂ -O-CH ₂ -CR ⁶ R ⁷ -CH ₂ -O- and particularly preferably - (CH ₂ ) _X -O- or -CH ₂ -O -CH ₂ -CR ⁶ R ⁷ -CH ₂ -O-;

R ^{3 are} identical or different C ₂ -C ₄ -alkylene radicals which may be arranged in blocks or randomly, the proportion of ethylene radicals being at least 50 mol%, preferably at least 75 mol% and particularly preferably 100 mol%;

R ⁴ is hydrogen, C _r C ₄ alkyl, -SO ₃ M or -PO ₃ M _2; R ^{5 is} hydrogen or -CH ₂ -CR ¹ = CH ₂ ;

R ⁶ -O- [R ³ -O] _n -R ⁴ , where the radicals - [R ³ -O] _n - of the other radicals contained in formula I - [R ³ -O] _n - may be different and the apply to preferred R ³ ;

R ^{7 is} hydrogen or ethyl;

M alkali metal, preferably sodium or potassium, or hydrogen; n is 4 to 250, preferably 5 to 200 and particularly preferably 10 to 100; x O or i.

Specific examples of particularly suitable monomers a2) are the alkoxylation products of the following unsaturated monomers: (meth) allyl alcohol, (meth) allylamines, diallylamines, glycerol monoallyl ethers, trimethylolpropane monoallyl ethers, vinyl ethers, vinylamides and vinylamines.

Of course, it is also possible to use mixtures of the monomers a2).

Particular preference is given to monomers a2) which are based on allyl alcohol, glycerol monoallyl ether, trimethylolpropane monoallyl ether and diallylamine.

Very particularly preferred monomers a2) are ethoxylated allyl alcohols which in particular contain from 5 to 20, especially from 10 to 100, moles of EO / mole of allyl alcohol.

The monomers a2) can be prepared by well-known standard methods of organic chemistry see, for. By amidation and transamidation of suitable (meth) acrylic acids, by alkoxylation of allyl alcohol, glycerol monoallyl ether, trimethylolpropane monoallyl ether; by etherification of allyl halides with poly-C ₂ -C ₄ -alkylene oxides and vinylation of polyalkylene oxides with OH or NH end group with acetylene. If the copolymers used according to the invention have -SO 3 M or -PO 3 M ₂ end groups, these can be introduced by sulfation or phosphation of the monomers (B) or else of the copolymers themselves, for example with chlorosulfonic acid or polyphosphoric acid.

The copolymers used according to the invention contain from 0.5 to 20 mol% of the monomer a2). If the copolymers are composed only of the monomers a1) and a2), the content of the monomer a1) is generally from 0.5 to 20 mol%, preferably from 1 to 10 mol%. Terpolymers of the monomers a1), a2) and a3) generally contain from 1 to 15 mol%, preferably from 1 to 10 mol%, of the monomer a2).

The copolymers used according to the invention may contain as copolymerized monomer a3) a monoethylenically unsaturated dicarboxylic acid, preferably a C ₄ -C 6 -dicarboxylic acid. Of course, instead of the free acid and its anhydride and / or one of its water-soluble salts, in particular an alkali metal salt, such as potassium and especially sodium, or ammonium salt are used.

Specific examples of suitable monomers a3) are: maleic acid, fumaric acid, methylenemalonic acid, citraconic acid and itaconic acid. Of course, mixtures of these acids can also be used.

Particularly preferred monomer a3) is maleic acid.

If the monomer a3) is contained in the copolymers used according to the invention, its content is generally from 1 to 30 mol%, preferably from 5 to 30 mol%.

The copolymers used according to the invention are preferably composed only of the monomers a1) and a2) or of the monomers a1), a2) and a3).

However, they may also contain another monoethylenically unsaturated monomer a4) which is different from the monomers a1) to a3) but copolymerizable with these monomers.

Examples of suitable monomers a4) are:

Esters of monoethylenically unsaturated C ₃ -C ₅ -carboxylic acids, in particular (meth) acrylic esters, such as methyl, ethyl, propyl, hydroxypropyl, n-butyl, isobutyl, 2-ethylhexyl, decyl, lauryl -, iso-bornyl, cetyl, palmityl and stearyl (meth) acrylate; (Meth) acrylamides such as (meth) acrylamide, N- (C _r Ci ₂ alkyl) - and N, N-di (C _r C ₄ alkyl) - (meth) acrylamides such as N-methyl, N, N-dimethyl, N-ethyl, N-propyl, N-tert-butyl, N-tert-octyl and N-undecyl (meth) acrylamide;

Vinyl esters of C ₂ -C 30, in particular C ₂ -C _4, carboxylic acids, such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate and vinyl laurate;

N-vinylamides and N-vinyllactams, such as N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinylpyrrolidone, N-vinylpiperidone and N-vinylcaprolactam;

Vinylsulfonic acid and vinylphosphonic acid;

Vinyl aromatics, such as styrene and substituted styrenes, e.g. Alkylstyrenes, such as methylstyrene and ethylstyrene.

If monomers a4) are contained in the copolymers used according to the invention, their content is generally from 1 to 20 mol%, preferably from 1 to 10 mol%. If hydrophobic monomers are used as monomer a4), their content should be selected such that the copolymer retains its hydrophilic character as a whole.

The copolymers used according to the invention have an average molecular weight M _{w of} from 30,000 to 500,000 g / mol, preferably from 50,000 to 300,000 g / mol (determined by gel permeation chromatography at room temperature with aqueous eluent).

Their K values are accordingly from 40 to 150, preferably from 50 to 125 (measured at pH 7 in 1% strength by weight aqueous solution at 25 ° C., according to H. Finkentscher, Cellulose-Chemie, Vol. 13, pp. 58-64 and 71-74 (1932)).

The copolymers used according to the invention can be obtained by the known free-radical polymerization processes. In addition to the bulk polymerization, in particular solution and emulsion polymerization should be mentioned, with the solution polymerization is 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 1 -C ₄ -alcohols, such as methanol, ethanol and isopropanol, or in mixtures of these solvents with water. AIs polymerization initiators are both thermally and photochemically (photoinitiators) decomposing and thereby forming radicals.

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, Benzyldi- alkylketones and their derivatives.

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 usually at 30 to 200 ° 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, but is preferably carried out in a closed system under the evolving autogenous 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 complexing agents which are selected from the group consisting of nitrilotriacetic acid, ethylenediaminetetraacetic acid, glycine-N, N-diacetic acid derivatives, glutamic acid-N, N-diacetic acid, iminodisuccinic acid, Hydroxyiminodibernsteinsäu- re, S. , S-Ethylenediamindibernsteinsäure and aspartic acid as well as their Salt. Preferred complexing agents b) are methylglycinediacetic acid and / or salts thereof.

Suitable glycine-N, N-diacetic acid derivatives are compounds of the general formula

(I) in the

R Cr to Ci ₂ alkyl and

M alkali metal mean.

In the compounds of the general formula M is an alkali metal, preferably sodium or potassium, more preferably sodium.

R is a Ci_i ₂ alkyl radical, preferably a d- ₆ alkyl radical, more preferably a methyl or ethyl radical. Particularly preferred component (a) used is an alkali metal salt of methylglycinediacetic acid (MGDA). Most preferably, the trisodium salt of methylglycinediacetic acid is used.

The preparation of such glycine-N, N-diacetic acid derivatives is known, cf. EP-A-0 845 456 and the literature cited therein.

As component c), the cleaning formulations according to the invention contain weakly or low-foaming nonionic surfactants. These are generally present in proportions of 1 to 15 wt .-%, preferably 1 to 10 wt .-%.

Suitable nonionic surfactants include the surfactants of the general formula (II)

R ¹ - (OCH ₂ CHR ² ) _p - (OCH ₂ CHR ³ ) _m -OR ⁴ (II)

wherein R ^{1 is} a linear or branched alkyl radical having 6 to 24 C atoms, R ² and R ^{3 are} independently hydrogen or a linear or branched alkyl radical having 1-16 C atoms, wherein R ² ≠ R ³ and R ^{4 is} a linear or branched alkyl radical having 1 to 8 carbon atoms, p and m are independently 0 to 300. Preferably, p = 1-50 and m = 0-30.

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

Can continue di- and multiblock copolymers composed of ethylene oxide and propylene oxide, are used, for example, under the name Pluronic ^® (BASF Aktiengesellschaft) or Tetronic ^® (BASF Corporation) are commercially available. Furthermore, 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 is provided by EP-A 851 023 and DE-A 198 19 187.

The formulations 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, C ₈ -C 16 -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-C-iβ-alkylbetaines or C ₆ -C ₅ -alkylsulfobetaines or amine oxides such as alkyldimethylamine oxides.

As component d), the cleaning formulations according to the invention may contain bleaches and optionally bleach activators.

Bleaching agents are subdivided into oxygen bleaching agents and chlorine-containing bleaching agents. Use as oxygen bleach find alkali metal perborates and their hydrates and alkali metal percarbonates. 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. phthalimidoperoxycaproic acid, 1,1-diperoxydodecanedioic acid, 1,9-diperoxyazelaic acid, diperoxoisophthalic acid or 2-decyldiperoxybutane-1,4-diacid.

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

Cationic peroxyacids described in patent applications US 5,422,028, US 5,294,362 and US 5,292,447;

Sulfonyl peroxyacids, which are described in the patent application US 5,039,447.

Oxygen bleaching agents are used in amounts of generally from 0.5 to 30% by weight, preferably from 1 to 20% by weight, particularly preferably from 3 to 15% by weight, based on the total detergent formulation.

Chlorine-containing bleaches as well as the combination of chlorine-containing bleaches with peroxide-containing bleaches can 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 sulfondichloroamid 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 0.1 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, for example, phosphonates, borates, metaborates, metasilicates or magnesium salts, can 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 (TA-GU), tetraacetylhexylenediamine (TAHD), N-acylimides, such as, for example, N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, such as, for example, n-nonanoyl- or isononanoyloxybenzenesulfonates (n- or iso-NOBS), pentaacetylglucose (PAG), 1, 5 Diacetyl-2,2-dioxohexahydro-1,3,5-triazine (DADHT) or isoic anhydride (ISA). Also suitable as bleach activators are nitrile quats such as N-methyl morpholinium acetonitrile salts (MMA salts) or trimethyl ammonium acetonitrile salts (TMAQ salts).

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

Furthermore, the following substances can be used as bleach activators in the detergent 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 and their mixtures described in EP-A 525 239; acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose, and also acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, which are known from WO 94 / 27,970, WO 94/28 102, WO 94/28 103, WO 95/00626, WO 95/14759 and WO 95/17 498 are known.

The hydrophilic substituted acyl acetals listed in DE-A 196 16 769 and the acyl lactams described in DE-A 196 16 770 and WO 95/14 075 can be used as well as the known from DE-A 44 43 177 combinations of conventional bleach activators.

Bleach activators are used in amounts of generally from 0.1 to 10% by weight, preferably from 1 to 9% by weight, particularly preferably from 1.5 to 8% by weight, based on the total detergent formulation.

As component e) the cleaning formulations of the invention may contain further builders. It is possible to use water-soluble and water-insoluble builders whose main task is the binding of calcium and magnesium.

As further builders can be used:

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 metal malate nate, fatty acid sulfonates, oxydisuccinate, alkyl or alkenyl disuccinates, gluconic acids, oxadiacetates, carboxymethyloxysuccinates, tartrate monosuccinate, tartrate disuccinate, tartrate monoacetate, tartrate diacetate, α-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 or polyaspartic acid; further aminopolycarboxylates and polyaspartic acid;

Phosphonates such as 2-phosphono-1, 2,4-butanetricarboxylic acid, aminotri (methylenephosphonic acid), 1-hydroxyethylene (1,1-diphosphonic acid), ethylenediaminetetra methylene phosphonic acid, hexamethylenediamine 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 phyllosilicates.

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

In addition, the cleaning agents according to the invention may contain, as component g), further additives such as anionic or zwitterionic surfactants, bleach catalysts, alkali carriers, corrosion inhibitors, defoamers, dyes, fragrances, fillers, organic solvents and water.

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, the manganese, iron, cobalt and copper complexes known from EP-A 392 592 and / or the manganese complexes described in EP-A 443 651, EP-A 458 397, EP-A 458 398, EP-A 549 271, EP-A 549 272, EP-A 544 490 and EP-A 544 519 , Combinations of bleach activators and transition metal bleach catalysts are known, for example, from DE-A 196 13 103 and WO 95/27 775.

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-O ) ₃ ] ²⁺ (PF ₆ -) ₂ .

Bleach catalysts can be used in amounts of from 0.0001 to 5% by weight, preferably from 0.0025 to 1% by weight, particularly preferably from 0.01 to 0.25% by weight, based on the total detergent formulation ,

As further constituents of the cleaner formulation, one or more alkali carriers may be present. Suitable alkali carriers are ammonium and alkali metal hydroxides, ammonium and alkali metal carbonates, ammonium and alkali metal hydrogencarbonates, ammonium and alkali metal sesquicarbonates, ammonium and alkali silicates, ammonium and alkali metal silicates, ammonium and alkali disilicates and mixtures of the abovementioned substances, preference being given to ammonium and Alkali carbonates and ammonium and Alkalidisilikate, in particular sodium carbonate, sodium bicarbonate, Natriumsesquicarbonat and ß- and δ-sodium disilicate Na ₂ Si ₂ O ₅ y H ₂ O are used. As corrosion inhibitors, it is possible to use 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 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 are preferably oxygen and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, such as hydroquinone, pyrocatechol, hydroxyhydroquinone, 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 the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (Carbonyl) complexes, the chlorides of cobalt or manganese and of manganese sulfate. It is likewise possible to use zinc compounds or bismuth compounds for preventing corrosion on items to be washed, in particular of glass.

Paraffin oils and silicone oils can 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 of the cleaning formulation according to the invention can be added.

A suitable filler is, for example, sodium sulfate.

The present invention also provides mixed powders or mixed granules for use in cleaning formulations for machine dishwashing

a) from 30 to 95% by weight of the copolymers of components a1), a2) and optionally a3) and a4), as defined above,

b) from 5 to 70% by weight of complexing agents selected from the group consisting of nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid and glycine-N, N-diacetic acid and its derivatives, glutamic acid-N, N-diacetic acid, iminodisuccinate, xyiminodisuccinate, S, S-ethylenediamine disuccinate and aspartic acid diacetic acid and the salts of the abovementioned substances, and optionally

c) 0 to 20 wt .-% of a polyethylene glycol, a nonionic surfactant or a mixture thereof.

As component (c), it is preferable to use a polyethylene glycol, more preferably having an average molecular weight (weight average molecular weight) of 500 to 30,000 g / mol.

The polyethylene glycol used as component (c) preferably has OH end groups and / or Ci _-6 alkyl end groups. Particular preference is given to using in the mixture according to the invention as component (c) a polyethylene glycol which has OH and / or methyl end groups.

Preferably, the polyethylene glycol has a molecular weight (weight average molecular weight) of 1000 to 5000 g / mol, most preferably from 1200 to 2000 g / mol.

Suitable compounds which may be used as component (c) are nonionic surfactants. These are preferably selected from the group consisting of alkoxylated primary alcohols, alkoxylated fatty alcohols, alkyl glycosides, alkoxylated fatty acid alkyl esters, amine oxides and polyhydroxy fatty acid amides.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue is linear or preferably methyl-branched in the 2-position may contain linear or branched radicals in the mixture, as they are usually present in Oxoal- koholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. Preferred ethoxylated alcohols include, for example, Ci ₂ - ₁₄ alcohols containing 3 EO, 4 EO or 7 EO, n-alcohols containing 7 EO, C _3- I ₅ alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, Ci ₂ -i8-alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci ₂ - ₁₄ -alcohol with 3 EO and Ci ₂ - ₁₄ -alcohol with 7 EO. The degrees of ethoxylation given represent statistical means that may be a whole or fractional number for a particular product. Preferred alcohol ethoxylates have a narrow homolog distribution ("narrow rank ethoxylates", NRE). The preparation of the mixed powders or mixed granules according to the invention is carried out by mixing the components (a), (b) and (c) as a powder, heating the mixture and adjusting the powder properties in the subsequent cooling and shaping process.

Furthermore, it is possible to granulate the components (a) and (b) with the already molten component (c) and then to cool it. The subsequent solidification and shaping takes place in accordance with the known processes of melt fabrication, for example by prilling or on cooling belts with, if necessary, downstream steps for adjusting the powder properties, such as grinding and sieving.

The mixed powders or mixed granules according to the invention can also be prepared by dissolving the components (a), (b) and (c) in a solvent and spray-drying the resulting mixture, wherein a granulation step can follow. In this case, the components (a) to (c) can be dissolved separately, wherein the solutions are subsequently mixed, or a powder mixture of the components can be dissolved in water. As solvents, it is possible to use those which are capable of dissolving components (a), (b) and (c). For example, alcohols and / or water, more preferably water, are preferably used.

The invention is explained in more detail by the following examples.

Examples

Examples 1 to 3 and Comparative Examples V1 to V3

The following formulations were used to test the combinations of copolymers and complexing agents according to the invention (Table 1):

Table i:

The test was carried out under the following test conditions:

Dishwasher: Miele G 686 SC Rinses: 2 rinses 55 ° C Normal (without pre-rinsing) Wash ware: Knife (WMF table knife Berlin, Monoblock) and keg-shaped glass beaker (Matador by Ruhr Kristall), plastic dish (SAN)

Plate of Kayser); Ballast dishes: 6 dessert plates black

Rinse 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 following polymers were used:

Polymer 1: Copolymer of acrylic acid, maleic acid and allyl alcohol, ethoxylated with 16.6 mol EO / mol allyl alcohol in the molar ratio 82.5: 15: 2.5, K value = 74.5, measured at pH 7 in 1 wt. % solution at 25 ° C, Polymer 2: copolymer of acrylic acid and glycerol monoallyl ether, ethoxylated with 20 mol EO / mol glyerin monoallyl ether in the molar ratio 97.7: 2.3, K value = 61, 7, measured at pH 7 in 1 wt .-% aqueous solution at 25 ° C,

Polymer 3: polyacrylic acid having a molecular weight Mw of 8000 g / mol,

Polymer 4: copolymer of acrylic acid and allyl alcohol, ethoxylated with 16.6 mol EO / mol allyl alcohol, in the molar ratio 99.2: 0.8, K value = 34.3, measured at pH 7 in 1 wt.% Aqueous solution at 25 ° C with a molecular weight Mw of 12,500 g / mol

In Table 2, the test conditions of Examples 1 to 3 and Comparative Examples V1 to V3 are listed:

Table 2:

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:

The experiments show that the use of copolymers according to the invention in combination with selected complexing agents can markedly reduce the formation of deposits, in particular on glass and stainless steel.

Claims

claims

1. Phosphate-free cleaning formulation for machine dishwashing containing as components:

a) 1 to 20 wt .-% copolymers of

a1) 50 to 99.5 mol% of a monoethylenically unsaturated monocarboxylic acid and / or a salt thereof,

a2) 0.5 to 20 mol% of an alkoxylated monoethylenically unsaturated

Monomers of the formula (I)

R ¹ H ₂ C = C-R ² -> RO ⁴ R ⁴ (I)

in which the variables have the following meaning:

R ^{1 is} hydrogen or methyl;

R ^{2 is} - (CH ₂ ) _X -O-, -CH ₂ -NR ⁵ -, -CH ₂ -O-CH ₂ -CR ⁶ R ⁷ -CH ₂ -O- or -CONH-; R ^{3 are} identical or different C ₂ -C ₄ -alkylene radicals which may be arranged in blocks or randomly, the proportion of ethylene radicals being at least 50 mol%;

R ⁴ is hydrogen, C _r C ₄ alkyl, -SO ₃ M or -PO ₃ M _2;

R ^{5 is} hydrogen or -CH ₂ -CR ¹ = CH ₂ ; R ^{6 is} -O- [R ³ -O] _n -R ⁴ , where the radicals - [R ³ -O] _n - may be different from the other radicals contained in formula I - [R ³ -O] _n -;

R ^{7 is} hydrogen or ethyl;

M alkali metal or hydrogen; n 4 to 250; x O or i,

a3) 0 to 50 mol% of a monoethylenically unsaturated dicarboxylic acid, an anhydride and / or a salt thereof,

a4) 0 to 20 mol% of a further copolymerizable monoethylenically unsaturated monomer, the copolymer having an average molecular weight M _{w of} from 30,000 to 500,000 g / mol and a K value of from 40 to 150, measured at pH 7 in 1% strength by weight aqueous solution at 25 ° C.,

b) from 1 to 50% by weight of complexing agents selected from the group consisting of nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid and glycine-N, diacetic acid and derivatives thereof, glutamic acid-N, N-diacetic acid, iminodisuccinate, Hydroxyiminodisuccinat, S, S-ethylenediamine disuccinate and aspartic acid diacetic acid and the salts of the aforementioned substances,

c) from 1 to 15% by weight of low-foaming nonionic surfactants,

d) from 0.1 to 30% by weight of bleaching agent and optionally bleach activators,

e) 0 to 60% by weight of further builders,

f) 0 to 8% by weight of enzymes,

g) 0 to 50% by weight of one or more further additives, such as anionic or zwitterionic surfactants, bleach catalysts, alkali carriers, corrosion inhibitors, defoamers, dyes, fragrances, fillers, organic solvents and water,

the sum of components a) to g) being 100% by weight.

2. phosphate-free cleaning formulation according to claim 1, characterized in that the complexing agent b) methylglycinediacetic acid and / or salts thereof.

3. Mixed powder or mixed granules for use in cleaning formulations for machine dishwashing

a) from 30 to 95% by weight of the copolymers of claim 1 from the components a1), a2) and optionally a3) and a4),

b) from 5 to 70% by weight of 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, iminodiacetic acid succinic acid, hydroxyiminodisuccinic acid, S, S-ethylenediamine succinic acid and aspartic acid diacetic acid and the salts of the abovementioned acids,

c) 0 to 20 wt .-% of a polyethylene glycol, a nonionic surfactant or a mixture thereof.

4. Use of a combination of copolymers according to claim 1 from the components a1), a2) and optionally a3) and a4) and complexing agents b), selected from the group consisting of nitriloacetic acid, ethylenediaminetetraacetic acid and glycine-N, N-diacetic acid Derivatives, glutamic acid-N, N-diacetic acid, iminodisuccinic acid, Hydroxyiminodibernstein- acid, SS-ethylenediamine disuccinic acid and aspartic acid diacetic acid and the salts of the aforementioned acids, as a deposit-inhibiting additive in cleaning formulations for machine dishwashing.