EP2201090B1 - Dishwashing formulation comprising a mixture of hydrophobically modified polycarboxylates and hydrophilically modified polycarboxylates - Google Patents

Abstract

A phosphate-free detergent formulation for machine dishwashing, having from 1 to 20% by weight of a mixture of from 5 to 95% by weight of hydrophobically modified polycarboxylates I formed from 20 to 80 mol % of at least one monoethylenically unsaturated C3-C10-mono- or -dicarboxylic acid or anhydrides thereof, from 0 to 80 mol % of at least one monomer of the general formula (I) in which R1, R2 and R3 are each independently H, CH3 or C2H5, and R4 is a linear, branched or cyclic radical having from 1 to 6 carbon atoms or an aromatic radical having from 6 to 12 carbon atoms, and from 0 to 20 mol % of at least one further monomer, from 5 to 95% by weight of hydrophilically modified polycarboxylates II, where the sum of a1) and a2) adds up to 100% by weight.

Description

The invention relates to cleaning formulations for machine dishwashing.

In the case of machine dishwashing, the items to be washed should be produced in a residue-free, cleaned condition with an impeccably glossy surface. The items to be washed must be cleaned of food residues and the detached contaminants must be dispersed or emulsified so that they do not re-deposit on the dishes surfaces. Furthermore, no whitish spots or deposits should occur, which arise due to the presence of lime or other inorganic and organic salts in the drying of water droplets or reflected by deposition of dirt or inorganic salts already during the rinsing process.

In particular, in modern machine dishwashing detergents, the multifunctional cleaners (eg 3-in-1 cleaners), the functions of cleaning, rinsing and water softening in a single detergent formulation are combined, so that for the consumer both the refilling of salt (in water from 0 ° to 21 °) as well as rinse aid becomes superfluous.

In these dishwashing agents, polymers are frequently used for inhibiting coating. These may be, for example, sulfonate-containing polymers in phosphate-containing cleaners, which show, in particular, effects on the inhibition of calcium phosphate precipitates. The surfactants used are chosen so that they drag themselves into the rinse cycle, where they ensure optimal wetting and a good rinse aid result. Other common polymers are polycarboxylates such as polyacrylic acids.

The results achieved so far are still to be improved. In particular, the trend towards phosphate-free cleaning agents, which should continue to be used without rinse aid and ion exchangers, requires new solutions. Here, the composition of the resulting salts is different than in phosphate-containing cleaners, so that other polymers show the optimum effect. Furthermore, if the ion exchanger is not used, polymers may themselves precipitate as calcium salts. Therefore, it is necessary to use polymers which can not precipitate as calcium salts themselves under the rinsing conditions, but at the same time are nevertheless able to disperse inorganic salts.

Many of the formulations on the market are phosphate-based. The phosphate used is ideal for use because it combines many useful properties that are needed 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. Also for the products for machine dishwashing it is discussed whether a conversion 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, 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.

EP-A 0 778 340 describes the use of copolymers of allyl alcohol ethoxylates and acrylic acid in phosphate-free dishwashing detergent compositions.

WO2005 / 042684 describes the use of special copolymers of acrylic acid, methacrylic acid and acrylic acid alkoxylates as deposit-inhibiting additives in machine dishwashing.

WO2006 / 029806 describes the use of a combination of specific hydrophobically modified polycarboxylates and specific chelants as a builder system in dishwashing detergent formulations.

WO 02/34870 describes the combination of hydrophobically modified polycarboxylates, acrylic acid (co) polymers and phosphonates to give an antiscaling and antispotting effect. Both phosphate-containing and phosphate-free dishwashing detergents are described.

The object of the invention is to provide improved phosphate-free cleaning formulations for machine dishwashing which give an improved dishwashing result. 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.

1. a) 1 bis 20 Gew.-% eines Gemischs aus hydrophob modifizierten Polycarboxylaten a1) und hydrophil modifizierten Polycarboxylaten a2) aus
   • a1) 5 bis 95 Gew.-% hydrophob modifizierten Polycarboxylaten I aus
     • a11) 20 bis 80 mol-% mindestens eines Monomeren aus der Gruppe bestehend aus monoethylenisch ungesättigten C₃-C₁₀-Mono- oder Dicarbonsäuren oder deren Anhydriden,
     • a12) 0 bis 80 mol-% mindestens eines Monomeren der allgemeinen Formel (I),
       
       • worin R¹, R² und R³ unabhängig voneinander H, CH₃ oder C₂H₅ bedeuten,
       • R⁴ einen linearen, verzweigten oder cyclischen Rest mit 1 bis 6 Kohlenstoffatomen oder einen aromatischen Rest mit 6 bis 12 Kohlenstoffatomen bedeutet,
       und
     • a13) 0 bis 20 mol-% mindestens eines weiteren Monomeren, ausgewählt aus der Gruppe bestehend aus Olefinen mit 10 oder mehr Kohlenstoffatomen oder deren Gemischen und reaktiven Polyisobutenen mit im Mittel 12 bis 100 Kohlenstoffatomen,
   • a2) 5 bis 95 Gew.-% hydrophil modifizierten Polycarboxylaten II aus
     • a21) 50 bis 99 mol.-% Acrylsäure und/oder eines wasserlöslichen Salzes der Acrylsäure,
     • a22) 0 bis 50 mol.-% eines weiteren sauren Monomers und/oder eines wasserlöslichen Salzes desselben,
     • a23) 0,1 bis 20 mol.-% mindestens eines nichtionischen Monomers der allgemeinen Formel (II),
       
       in der die Variablen folgende Bedeutung haben:
       • R⁵ Wasserstoff oder Methyl;
       • Z -C(O)O- oder -CH₂O-
       • R⁶ gleiche oder verschiedene unverzweigte oder verzweigte C₂-C₄-Alkylenreste;
       • R⁷ unverzweigtes oder verzweigtes C₁-C₆-Alkyl;
       • n 3 bis 50,
   wobei die Summe aus a1) und a2) 100 Gew.-% ergibt,
2. b) 0 bis 50 Gew.-% Komplexbildner,
3. c) 0,1 bis 20 Gew.-% schwach schäumende nichtionische Tenside,
4. d) 0,1 bis 30 Gew.-% Bleichmittel und gegebenenfalls Bleichaktivatoren,
5. e) 0 bis 60 Gew.-% weitere Builder,
6. f) 0 bis 8 Gew.-% Enzyme,
7. g) 0 bis 50 Gew.-% ein oder mehrere weitere Zusatzstoffe wie anionische oder zwitterionische Tenside, Bleichkatalysatoren, Alkaliträger, Korrosionsinhibitoren, Entschäumer, Farbstoffe, Duftstoffe, Füllstoffe, Tablettensprengmittel, organische Lösungsmittel und Wasser,

wobei die Summe der Komponenten a) bis g) 100 Gew.-% ergibt.The object is achieved by phosphate-free cleaning formulations for machine dishwashing containing as components:

1. a) 1 to 20 wt .-% of a mixture of hydrophobically modified polycarboxylates a1) and hydrophilic modified polycarboxylates a2)
   • a1) from 5 to 95% by weight of hydrophobically modified polycarboxylates I
     • a11) 20 to 80 mol% of at least one monomer from the group consisting of monoethylenically unsaturated C ₃ -C ₁₀ -mono- or dicarboxylic acids or their anhydrides,
     • a12) 0 to 80 mol% of at least one monomer of the general formula (I),
       
       • in which R ¹ , R ² and R ^3, independently of one another, denote H, CH ₃ or C ₂ H ₅ ,
       • R ⁴ denotes a linear, branched or cyclic radical having 1 to 6 carbon atoms or an aromatic radical having 6 to 12 carbon atoms,
       and
     • a13) 0 to 20 mol% of at least one further monomer selected from the group consisting of olefins having 10 or more carbon atoms or mixtures thereof and reactive polyisobutenes having an average of 12 to 100 carbon atoms,
   • a2) from 5 to 95% by weight of hydrophilically modified polycarboxylates II
     • a21) from 50 to 99 mol% of acrylic acid and / or of a water-soluble salt of acrylic acid,
     • a22) 0 to 50 mol .-% of another acidic monomer and / or a water-soluble salt thereof,
     • a23) from 0.1 to 20 mol% of at least one nonionic monomer of the general formula (II),
       
       in which the variables have the following meaning:
       • R ^{5 is} hydrogen or methyl;
       • Z -C (O) O- or -CH ₂ O-
       • R ⁶ identical or different unbranched or branched C ₂ -C ₄ -alkylene radicals;
       • R ^{7 is} unbranched or branched C ₁ -C ₆ -alkyl;
       • n 3 to 50,
   the sum of a1) and a2) being 100% by weight,
2. b) 0 to 50% by weight of complexing agent,
3. c) from 0.1 to 20% by weight of low-foaming nonionic surfactants,
4. d) from 0.1 to 30% by weight of bleaching agent and optionally bleach activators,
5. e) 0 to 60% by weight of further builders,
6. f) 0 to 8% by weight of enzymes,
7. 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, tablet disintegrants, organic solvents and water,

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

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

The object is further achieved by the use of a combination of hydrophobically modified polycarboxylates a1) and hydrophilic modified polycarboxylates a2) as co-builders in cleaning formulations for machine dishwashing.

It has been found that the use of a combination of hydrophobically modified polycarboxylates and hydrophilically modified polycarboxylates in dishwashing dishwashing detergents achieves both a very good deposit-inhibiting effect and a very good rinse-off effect (anti-spotting effect).

Suitable monomers a11) for the hydrophobically modified polycarboxylates a1) are, for example, maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid. Preferred hydrophobically modified polycarboxylates a1) contain as monomers a11) monomers which are selected from the group consisting of maleic acid, maleic anhydride and acrylic acid.

Suitable monomers a12) are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene. Further preferred hydrophobically modified polycarboxylates a1) contain as monomers a12) monomers which are selected from the group consisting of isobutene, diisobutene and styrene.

Suitable monomers a13) have at least 10, generally 10-26, carbon atoms. Suitable monomers a13) are, for example, 1-decene, 1-dodecane, 1-tetradecene, 1-hexadecene, 1-octadene, 1-eicosene, 1-docoses, 1-tetracoses and 1-hexacoses. Further preferred hydrophobically modified polycarboxylates a1) contain as monomers a13) monomers which are selected from the group consisting of 1-dodecene, 1-octadecene, C ₂₂ -alpha-olefin, a mixture of C ₂₀ -C ₂₄ -alpha-olefins and Polyisobutene with an average of 12 to 100 carbon atoms.

Particularly preferred hydrophobically modified polycarboxylates contain both monomers a11), which are selected from maleic acid, maleic anhydride and acrylic acid, and also monomers a12) which are selected from isobutene, diisobutene and styrene, as well as monomers a13), which are selected from the group consisting of 1-dodecene, 1-octadecene, C ₂₂ -alpha-olefin, a mixture of C ₂₀ C ₂₄ -alpha-olefins and polyisobutene having an average of 12 to 100 carbon atoms. Particular preference is given to copolymers of 30 to 70 mol% of maleic acid and maleic anhydride as monomers a11), 30 to 50 mol% of isobutene as monomers a12) and 1 to 10 mol% of octadecene as monomers a13).

The hydrophilically modified polycarboxylates II contain as copolymerized components a21) and a22) acrylic acid, optionally a further acidic monomer, and / or water-soluble salts of these acids, in particular the alkali metal salts, such as potassium and especially sodium salts, and ammonium salts.

The proportion of acrylic acid a21) to the hydrophilically modified polycarboxylates II is 50 to 99 mol .-%, preferably 55 to 90 mol .-% and particularly preferably 60 to 85 mol .-%.

The further acidic monomer a22) is in the hydrophilically modified polycarboxylates II to 0 to 50 mol .-%, preferably to 5 to 40 mol .-%, particularly preferably from 10 to 35 mol% and especially to 15 to 30 mol. -% contain.

Acid monomers a22) are, for example, methacrylic acid, maleic acid, sulfonate groups or phosphonate group-containing monomers, preference being given to methacrylic acid and maleic acid.

Particularly suitable examples of the nonionic monomers (a23) are: allyl alcohol, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, methoxypoly (propylene oxide co-ethylene oxide) (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate , Ethoxypolypropylene glycol (meth) acrylate, ethoxypolybutylene glycol (meth) acrylate and ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, with methoxypolyethylene glycol (meth) acrylate and methoxypolypropylene glycol (meth) acrylate being preferred and methoxypolyethylene glycol methacrylate being particularly preferred.

The polyalkylene glycols contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units.

The proportion of nonionic monomers a23) to the hydrophilically modified polycarboxylates II is 0.1 to 20 mol .-%, preferably 1 to 15 mol .-% and especially 2 to 10 mol .-%.

• a21) 50 bis 99 mol.-% Acrylsäure und/oder einem wasserlöslichen Salz der Acrylsäure,
• a22) 0 bis 50 mol.-% Maleinsäure und/oder einem wasserlöslichen Salz der Maleinsäure,
• a23) 0,1 bis 20 mol.-% Allylakohol, der mit 3 bis 50 mol Ethylenoxid pro mol Allylalkohol ethoxyliert ist,

aufgebaut.Preferred hydrophilic modified polycarboxylates a2) are still made

• a21) from 50 to 99 mol% of acrylic acid and / or of a water-soluble salt of acrylic acid,
• a22) 0 to 50 mol% of maleic acid and / or a water-soluble salt of maleic acid,
• a23) from 0.1 to 20 mol% allyl alcohol ethoxylated with from 3 to 50 moles of ethylene oxide per mole of allyl alcohol,

built up.

The ethoxylated allyl alcohol a23) is preferably alkoxylated with 5 to 40 mol, more preferably with 10 to 30 mol of ethylene oxide.

The weight-average molecular weight M _{w of} the hydrophilically modified polycarboxylates a2) is generally 500 to 500,000 g / mol, preferably 1000 to 300,000 g / mol, particularly preferably 5,000 to 100,000 g / mol.

The hydrophilically modified polycarboxylates preferably have a calcium insensitivity, which corresponds to a cloud point of a solution containing 250 mg / L of the hydrophilically modified polymer at pH 10 at a calcium concentration of> 2000 mg / L Ca ²⁺ , that is to say turbidity only above this calcium concentration the polymer solution by precipitation of calcium salts.

The cleaning formulations according to the invention contain 1 to 20 wt .-%, preferably 1 to 10 wt .-% of the mixture of hydrophobically modified polycarboxylates a1) and hydrophilic modified polycarboxylates a2), wherein the proportion of hydrophobically modified polycarboxylates a1) 5 to 95 wt. %, preferably 10 to 90 wt .-% and particularly preferably 20 to 80 wt .-%, and the proportion of hydrophilically modified polycarboxylates a2) 5 to 95 wt .-%, preferably 10 to 90 wt .-% and particularly preferably 20 to 80 wt .-%, based on the sum of a1) and a2), is.

As component b), the cleaning formulations according to the invention may contain one or more complexing agents. Preferred complexing agents are selected from the group consisting of nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid and methylglycinediacetic acid, glutamic acid diacetic acid, iminodisuccinic acid, hydroxyiminodisuccinic acid, Ethylenediamine disuccinic acid, aspartic acid diacetic acid and salts thereof. Particularly preferred complexing agents b) are methylglycinediacetic acid and its salts.

As component c), the cleaning formulations according to the invention contain weakly or low-foaming nonionic surfactants. These are generally present in proportions of 0.1 to 20 wt .-%, preferably 0.1 to 15 wt .-%, particularly preferably 0.25 to 10 wt .-%.

• worin R² ein linearer oder verzweigter Alkylrest mit 8 bis 22 C-Atomen ist,
• R¹ und R³ unabhängig voneinander Wasserstoff oder ein linearer oder verzweigter Alkylrest mit 1-10 C-Atomen oder H sind, wobei R¹ bevorzugt Methyl ist,
• p und m unabhängig voneinander 0 bis 300 sind. Bevorzugt ist p = 1-100 und
• m = 0-30.

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

R ² -O- (CH ₂ CH ₂ O) _p - (CHR ¹ CH ₂ O) _m -R ³ (III)

• wherein R ^{2 is} a linear or branched alkyl radical having 8 to 22 C atoms,
• R ¹ and R ³ independently of one another are hydrogen or a linear or branched alkyl radical having 1-10 C atoms or H, where R ^{1 is} preferably methyl,
• p and m are independently 0 to 300. Preferably, p = 1-100 and
• m = 0-30.

The surfactants of formula (III) may be both random copolymers and block copolymers, preferably block copolymers.

Further, 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 are the EP-A 851 023 as well as the DE-A 198 19 187 ,

The formulations may further contain anionic or zwitterionic surfactants, preferably in admixture with nonionic surfactants. Suitable anionic and zwitterionic surfactants are also in EP-A 851 023 such as DE-A 198 19 187 called.

As component d), the cleaning formulations according to the invention comprise 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 as well as 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, 1,12-diperoxydodecanedioic acid, 1,9-diperoxyazelain 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 disclosed in the patent applications US 5,422,028 . US 5,294,362 such as US 5,292,447 are described;
Sulfonyl peroxyacids disclosed in the patent application US 5,039,447 are described.

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 bleach with peroxide-containing bleaches can also be used. Known chlorine-containing bleaching agents are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, dichloramine T, chloramine B, N, N'-dichlorobenzoylurea, p-toluenesulfondichloroamide or trichloroethylamine. 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 phosphonates, borates, metaborates, metasilicates or magnesium salts can be added in small amounts.

Bleach activators are compounds which, under perhydrolysis conditions, comprise 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 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). Also 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.

• Carbonsäureanhydride wie beispielsweise Phthalsäureanhydrid; acylierte mehrwertige Alkohole wie beispielsweise Triacetin, Ethylenglykoldiacetat oder 2,5-Diacetoxy-2,5-dihydrofuran; die aus DE-A 196 16 693 und DE-A 196 16 767 bekannten Enolester sowie acetyliertes Sorbitol und Mannitol und deren in EP-A 525 239 beschriebenen Mischungen; acylierte Zuckerderivate, insbesondere Pentaacetylglukose (PAG), Pentaacetylfructose, Tetraacetylxylose und Octaacetyllactose, sowie acetyliertes, gegebenenfalls N-alkyliertes, Glucamin und Gluconolacton, und/oder N-acylierte Lactame, beispielsweise N-Benzoylcaprolactam, die aus den Schriften WO 94/27 970 , WO 94/28 102 , WO 94/28 103 , WO 95/00 626 , WO 95/14 759 sowie WO 95/17 498 bekannt sind;
• die in DE-A 196 16 769 aufgeführten hydrophil substituierten Acylacetale sowie die in DE-A 196 16 770 und WO 95/14 075 beschriebenen Acyllactame können ebenso wie die aus DE-A 44 43 177 bekannten Kombinationen konventioneller Bleichaktivatoren eingesetzt werden.

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; from DE-A 196 16 693 and DE-A 196 16 767 known enol esters as well as acetylated sorbitol and mannitol and their in EP-A 525 239 described mixtures; acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose, as well as acetylated, optionally N-alkylated, glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, which are known from the documents WO 94/27 970 . WO 94/28 102 . WO 94/28 103 . WO 95/00626 . WO 95/14759 such as WO 95/17498 are known;
• in the DE-A 196 16 769 listed hydrophilic substituted acyl acetals and in DE-A 196 16 770 and WO 95/14075 acyl lactams described as well as those from DE-A 44 43 177 known 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 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.

• niedermolekulare Carbonsäuren sowie deren Salze wie Alkalicitrate, insbesondere wasserfreies Trinatriumcitrat oder Trinatriumcitratdihydrat, Alkalisuccinate, Alkalimalonate, Fettsäuresulfonate, Oxydisuccinat, Alkyl- oder Alkenyldisuccinate, Gluconsäuren, Oxadiacetate, Carboxymethyloxysuccinate, Tartratmonosuccinat, Tartratdisuccinat, Tartratmonoacetat, Tartratdiacetat, α-Hydroxypropionsäure;
• oxiderte Stärken, oxidierte Polysaccharide;
• homo- und copolymere Polycarbonsäuren und deren Salze wie Polyacrylsäure, Polymethacrylsäure, Copolymere aus Maleinsäure und Acrylsäure;
• Pfropfpolymerisate von monoethylenisch ungesättigten Mono- und/oder Dicarbonsäuren auf Monosaccharide, Oligosaccharide, Polysaccharide oder Polyasparaginsäure; Aminopolycarboxylate und Polyasparaginsäure;
• Phosphonate wie 2-Phosphono-1,2,4-butantricarbonsäure, Aminotri(methylenphosphonsäure), 1-Hydroxyethylen(1,1-diphosphonsäure), Ethylendiamintetramethylenphosphonsäure, Hexamethylendiamintetramethylenphosphonsäure oder Diethylentriaminpentamethylenphosphonsäure;
• Silikate wie Natriumdisilikat und Natriummetasilikat;
• wasserunlösliche Builder wie Zeolithe und kristalline Schichtsilikate.

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 malates, 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 or polyaspartic acid; Aminopolycarboxylates and polyaspartic acid;
• Phosphonates such as 2-phosphono-1,2,4-butanetricarboxylic acid, aminotri (methylenephosphonic acid), 1-hydroxyethylene (1,1-diphosphonic acid), ethylenediamine tetramethylenephosphonic 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 of the invention may contain 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, disintegrating agents, organic solvents and water.

In addition to the conventional bleach activators listed above or in their place can also from EP-A 446 982 and EP-A 453 003 known sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes may be present as so-called bleach catalysts in the inventive cleaning formulations.

Examples of suitable transition metal compounds include those of DE-A 195 29 905 known manganese, iron, cobalt, ruthenium or molybdenum-salene complexes and their DE-A 196 20 267 known N-analogues consisting of DE-A 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, which in DE-A 196 05 688 described manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, which DE-A 196 20 411 known cobalt, iron, copper and ruthenium-amine complexes which are known in DE-A 44 16 438 described manganese, copper and cobalt complexes, which in EP-A 272 030 described cobalt complexes consisting of EP-A 693 550 known manganese complexes that are made 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 544 490 and EP-A 544 519 described manganese complexes. Combinations of bleach activators and transition metal bleach catalysts are for example DE-A 196 13 103 and WO 95/27 775 known.

Dinuclear manganese complexes containing 1,4,7-trimethyl-1,4,7-triazacyclononane (TMTACN) such as [(TMTACN) ₂ Mn ^IV Mn ^IV (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 ^IV Mn ^IV (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, 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 metal silicates and mixtures of the aforementioned substances, preference being given to using ammonium and / or alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate.

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 / 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, oxygen- and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, e.g. Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol and 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. Preference is given here to the transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably from the group of the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl ) Complexes, the chlorides of cobalt or manganese and manganese sulfate used. Also, zinc compounds or bismuth compounds can be used to prevent corrosion on the items to be washed.

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 may be added to the cleaning formulation of the invention.

A suitable filler is, for example, sodium sulfate.

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

Examples Example and Comparative Examples V1 to V5

To test the copolymers of the invention, they were each added to a phosphate-free dishwashing detergent formulation having the following composition.

Geschirrspülformulierung

1.2% by weight

enzyme

3% by weight

Surfactant based on fatty alcohol alkoxylates

7% by weight

a combination of hydrophobically modified and hydrophilically modified polycarboxylate

14% by weight

percarbonate

4% by weight

TAED

12% by weight

disilicate

18.8% by weight

sodium

38% by weight

citrate

2% by weight

sulfate

• Polymer 1: Copolymer aus Maleinsäure und Diisobuten (Gewichtsverhältnis 51:49) mit einem Molekulargewicht von 12 000 g/ mol;
• Polymer 2: Copolymer aus Maleinsäureanhydrid, Isobuten und C18-Olefin (Gewichtsverhältnis 65:26:9), Molekulargewicht 3 000 g/mol;
• Polymer 3: Polyacrylsäure, Molekulargewicht 4000 g/mol;
• Polymer 4: Copolymer aus Acrylsäure, Maleinsäure und Allylalkohol, ethoxyliert mit 16,6 mol Ethylenoxid pro mol Allylalkohol, im Molverhältnis 82,5 : 15 : 2,5, mit einem K-Wert von 74,5 bei pH 7 in 1 gew.-%iger Lösung bei 25 °C;
• Polymer 5: Copolymer aus Acrylsäure, Methacrylsäure und Methoxypolyethylenglykolmethacrylat mit Mw = 1100 g/mol im Molverhältnis 11 : 4 : 1 mit einem K-Wert von 27,2 bei pH 7 in 1 gew.-%iger Lösung bei 25°C.

The following polymers were used:

• Polymer 1: copolymer of maleic acid and diisobutene (weight ratio 51:49) having a molecular weight of 12,000 g / mol;
• Polymer 2: copolymer of maleic anhydride, isobutene and C18 olefin (weight ratio 65: 26: 9), molecular weight 3,000 g / mol;
• Polymer 3: polyacrylic acid, molecular weight 4000 g / mol;
• Polymer 4: copolymer of acrylic acid, maleic acid and allyl alcohol, ethoxylated with 16.6 moles of ethylene oxide per mole of allyl alcohol, in the molar ratio 82.5: 15: 2.5, with a K value of 74.5 at pH 7 in 1 wt. -% solution at 25 ° C;
• Polymer 5: copolymer of acrylic acid, methacrylic acid and methoxypolyethylene glycol methacrylate with Mw = 1100 g / mol in the molar ratio 11: 4: 1 with a K value of 27.2 at pH 7 in 1 wt .-% solution at 25 ° C.

In the rinsing tests described below, in each case 21 g of the cleaner formulation were used.

Each 50 g ballast dirt, according to SÖFW journal, 122nd year, 03/06, p. 65, were added to the dishwasher at the beginning of the experiment. The test was carried out under the following rinsing conditions.

flushing:

Dishwasher:

Miele G 686 SC

rinses:

2 rinses 55 ° C normal (without pre-rinse)

ware:

Messer (WMF Tafelmesser Berlin, Monoblock) and Fassformglasbecher (Matador, Ruhr Kristall),

Dishwashing liquid:

21 g

dirt addition

50 g ballast dirt at the beginning

Rinse temperature:

65 ° C

Water hardness:

21 ° dH (Ca: Mg: HCO ³ = 4: 1: 8)

The evaluation of the dishes was carried out 18 hours after cleaning by visual inspection in a black painted light box with halogen spot and pinhole. The coverings on knives and glasses were rated on a grading scale from 10 (very good) to 1 (very bad). The highest grade of 10 corresponds to a surface free of deposits, from grades <5 coverings are already recognizable with normal room lighting, so are perceived as disturbing.

The spotting took place after a rating of 1-5 with 1 = very many spots to 5 = no spotting.

The test results obtained are summarized in the table below. Table: Results of rinsing tests example polymer Covering knife Spotting knife Topping glasses Spotting glasses V1 7% by weight 5 5 4.5 4.5 Polymer 2 V2 7% by weight 7 3 6.5 1.5 Polymer 5 V3 7% by weight 5 3 2 2 Polymer 1 V4 7% by weight 5.7 1 7 2 Polymer 4 1 5% by weight 6.3 5 6.0 4 Polymer 2, 2% by weight Polymer 5 V5 3.5% by weight 4.5 2 4.5 2 Polymer 1, 3.5% by weight Polymer 3

As can be seen from the table, the best results are achieved with the polymer combination according to the invention.

Claims (5)

1. A phosphate-free detergent formulation for machine dishwashing, comprising, as components:

   a) from 1 to 20% by weight of a mixture of hydrophobically modified polycarboxylates a1) and hydrophilically modified polycarboxylates a2), composed of

   a1) from 5 to 95% by weight of hydrophobically modified polycarboxylates I formed from

   a11) from 20 to 80 mol% of at least one monomer from the group consisting of monoethylenically unsaturated C₃-C₁₀-mono- or -dicarboxylic acids or anhydrides thereof,

   a12) from 0 to 80 mol% of at least one monomer of the general formula (I)

   

   in which R¹, R² and R³ are each independently H, CH₃ or C₂H₅,

   R⁴ is a linear, branched or cyclic radical having from 1 to 6 carbon atoms or an aromatic radical having from 6 to 12 carbon atoms,
   and

   a13) from 0 to 20 mol% of at least one further monomer selected from the group consisting of olefins having 10 or more carbon atoms or mixtures thereof and reactive polyisobutenes having an average of from 12 to 100 carbon atoms,

   a2) from 5 to 95% by weight of hydrophilically modified polycarboxylates II formed from

   a21) from 50 to 99 mol% of acrylic acid and/or of a water-soluble salt of acrylic acid,

   a22) from 0 to 50 mol% of a further acidic monomer and/or of a water-soluble salt thereof,

   a23) from 0.1 to 20 mol% of at least one nonionic monomer of the general formula (II)

   

   in which the variables are each defined as follows:

   R⁵ is hydrogen or methyl,

   Z is -C(O)O- or -CH₂O-,

   R⁶ are identical or different, unbranched or branched C₂-C₄-alkylene radicals,

   R⁷ is unbranched or branched C₁-C₆-alkyl,

   n is from 3 to 50,

   where the sum of a1) and a2) adds up to 100% by weight,

   b) from 0 to 50% by weight of complexing agents,

   c) from 0.1 to 20% by weight of low-foam nonionic surfactants,

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

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

   f) from 0 to 8% by weight of enzymes,

   g) from 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,

   where the sum of components a) to g) adds up to 100% by weight.
2. The phosphate-free detergent formulation according to claim 1, wherein the monomers a11) in the hydrophobically modified polycarboxylate a1) are selected from the group consisting of maleic acid, maleic anhydride and acrylic acid, the monomers a12) are selected from the group consisting of isobutene, diisobutene and styrene, and the monomers a13) are selected from the group consisting of 1-dodecene, 1-octadecene, C₂₂-alphaolefin, a mixture of C₂₀-C₂₄-alpha-olefins and polyisobutene having an average of from 12 to 100 carbon atoms.
3. The phosphate-free detergent formulation according to claim 1 or 2, wherein the hydrophilically modified polycarboxylates have a calcium insensitivity corresponding to a cloud point of a solution comprising 250 mg/l of the hydrophilically modified polymer at pH 10 at a calcium concentration of > 2000 mg/l of Ca²⁺.
4. The phosphate-free detergent formulation according to any one of claims 1 to 3, wherein the complexing agent b) is selected from the group consisting of nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and methylglycinediacetic acid, glutamic acid diacetic acid, iminodisuccinic acid, hydroxyiminodisuccinic acid, ethylenediaminedisuccinic acid, aspartic acid diacetic acid, and salts thereof.
5. The use of a mixture of hydrophobically modified polycarboxylates and hydrophilically modified polycarboxylates, composed of

   a1) from 5 to 95% by weight of hydrophobically modified polycarboxylates (I) formed from

   a11) from 20 to 80 mol% of at least one monomer from the group consisting of monoethylenically unsaturated C₃-C₁₀-mono- or -dicarboxylic acids or anhydrides thereof,

   a12) from 0 to 80 mol% of at least one monomer of the general formula (I)

   

   in which R¹, R² and R³ are each independently H, CH₃ or C₂H₅,

   R⁴ is a linear, branched or cyclic radical having from 1 to 6 carbon atoms or an aromatic radical having from 6 to 12 carbon atoms,
   and

   a13) from 0 to 20 mol% of at least one further monomer selected from the group consisting of olefins having 10 or more carbon atoms or mixtures thereof and reactive polyisobutenes having an average of from 12 to 100 carbon atoms,

   a2) from 5 to 95% by weight of hydrophilically modified polycarboxylates II formed from

   a21) from 50 to 99 mol% of acrylic acid and/or of a water-soluble salt of acrylic acid,

   a22) from 0 to 50 mol% of a further acidic monomer and/or of a water-soluble salt thereof,

   a23) from 0.1 to 20 mol% of at least one nonionic monomer of the general formula (II)

   

   in which the variables are each defined as follows:

   R⁵ is hydrogen or methyl,

   Z is -C(O)O- or -CH₂O-,

   R⁶ are identical or different, unbranched or branched C₂-C₄-alkylene radicals,

   R⁷ is unbranched or branched C₁-C₆-alkyl;

   n is from 3 to 50,

   where the sum of a1) and a2) adds up to 100% by weight,

   as a cobuilder in detergent formulations for machine dishwashing.