EP1924675B1 - Cleaning formulations for machine dishwashing comprising hydrophilically modified polycarboxylates - Google Patents

Abstract

Cleaning formulation free of phosphate for dishwasher comprises: copolymer (1-20 wt.%); chelating agent (1-50 wt.%); weakly foaming non-ionic surfactant (1-15 wt.%); bleaching agent and optionally bleach activator (0-30 wt.%); further builder (0-60 wt.%); enzyme (0-8 wt.%); and one or more further additives. The copolymer comprises acrylic acid, methacrylic acid and/or alkyl-terminated polyalkylene glycol (meth)acrylate. Cleaning formulation free of phosphate for dishwasher comprises: copolymer (1-20 wt.%) from acrylic acid and/or a water-soluble salt of the acrylic acid (50-93 mol.%), methacrylic acid and/or a water soluble salt of methacrylic acid (5-30 mol.%) or at least one non-ionic monomer (I) of formula (H 2C=C(R 1>)-COO-R 2>-[R 3>-O] n-R 4>) (2-20 mol.%); chelating agent (1-50 wt.%) such as glycine-N,N-diacetic acid derivative, glutamic acid-N,N-diacetic acid and/or its salt; weakly foaming non-ionic surfactant (1-15 wt.%); bleaching agent and optionally bleach activator (0-30 wt.%); further builder (0-60 wt.%); enzyme (0-8 wt.%); and one or more further additives such as anionic or zwitterionic surfactant, bleaching catalyst, alkali carrier, corrosion inhibitor, antifoaming agent, dye, aroma material, filler, organic solvent and water (0-50 wt.%). R 1>H or methyl; R 2>a bond or 1-6C alkylene; R 3>2-4C alkylene; R 4>1-6C alkyl; and n : 3-50. Independent claims are included for: (1) a powder- or granulate mixture useful in cleaning formulation for dishwasher, comprising copolymer (10-95 wt.%), chelating agent (5-80 wt.%) and polyethylene glycol and/or non-ionic surfactant; and (2) use of a combination of copolymer and chelating agent, as a coating inhibitor in addition with cleaning formulation for the dish cleaning machine.

Description

The invention relates to cleaning formulations for machine dishwashing.

When cleaning dishes in the dishwasher, the dishes during the cleaning cycle of 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. 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 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.

In DE 102 25 594 A1 describes the use of copolymers containing alkylene oxide units in detergents and cleaners, as well as detergents and cleaners containing these copolymers. However, no combinations of these polymers with complexing agents are described.

In DE 102 33 834 A1 are described automatic dishwashing detergent containing 1 to 25 wt .-% of a copolymer containing alkylene oxide units. Dishwashing agents are also described which, in addition to the polymers mentioned, may also contain complexing agents, the use of EDTA being preferred. Glycine-N, N-diacetic acid derivatives and glutamic acid-N, N-diacetic acid and their salts are not mentioned.

WO-A-2005042684 discloses dishwashing detergents containing hydrophilically modified polycarboxylate polymers.

EP-A-778 340 discloses phosphate-free dishwashing detergents having a rinse-aid function, comprising copolymers of acrylic acid and alkylene oxide adducts of the allyl alcohol.

US-A-6172036 discloses rinse aid containing methylglycinediacetic acid and acrylic-methacrylic acid polymers.

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 also able to disperse the water-hard-forming sparingly soluble salts and the dirt present in the wash liquor. It is surprising that MGDA and GLDA in combination with the hydrophilically modified polycarboxylates have a better deposit-inhibiting effect than EDTA, although their complexation constant for Ca ions is smaller than that of EDTA.

1. a) 1 bis 20 Gew.-% Copolymere aus
   • a1) 50 bis 93 Mol-% Acrylsäure und/oder eines wasserlöslichen Salzes der Acrylsäure,
   • a2) 5 bis 30 Mol-% Methacrylsäure und/oder eines wasserlöslichen Salzes der Methacrylsäure
     und
   • a3) 2 bis 20 Mol-% mindestens eines nichtionischen Monomers der Formel (I)
     
     in der die Variablen folgende Bedeutung haben:

     R¹

     Wasserstoff oder Methyl,

     R²

     eine chemische Bindung oder unverzweigtes oder verzweigtes C₁-C₆- Alkylen,

     R³

     gleiche oder verschiedene unverzweigte oder verzweigte C₂-C₄- Alkylenreste,

     R⁴

     unverzweigtes oder verzweigtes C₁-C₆-Alkyl,

     n

     3 bis 50,

     wobei die Monomere a1) bis a3) statistisch oder blockweise einpolymerisiert sind,
2. b) 1 bis 50 Gew.-%, bevorzugt 5 bis 40 Gew.-% Komplexbildner, ausgewählt aus der Gruppe bestehend aus Glycin-N,N-diessigsäurederivaten und Glutaminsäure-N,N-diessigsäure und deren Salzen,
3. c) 1 bis 15 Gew.-%, bevorzugt 1 bis 10 Gew.-% schwach schäumende nichtionische Tenside,
4. d) 0 bis 30 Gew.-%, bevorzugt 0 bis 20 Gew.-% Bleichmittel und gegebenenfalls Bleichaktivatoren,
5. e) 0 bis 60 Gew.-%, bevorzugt 0 bis 40 Gew.-% weitere Builder,
6. f) 0 bis 8 Gew.-%, bevorzugt 0 bis 5 Gew.-% Enzyme,
7. g) 0 bis 50 Gew.-%, bevorzugt 0,1 bis 50 Gew.-% ein oder mehrere weitere Zusatzstoffe wie anionische oder zwitterionische Tenside, Bleichkatalysatoren, Alkaliträger, Korrosionsinhibitoren, Entschäumer, Farbstoffe, Duftstoffe, Füllstoffe, 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 .-% copolymers of
   • a1) from 50 to 93 mol% of acrylic acid and / or of a water-soluble salt of acrylic acid,
   • a2) 5 to 30 mol% of methacrylic acid and / or of a water-soluble salt of methacrylic acid
     and
   • a3) 2 to 20 mol% of at least one nonionic monomer of the formula (I)
     
     in which the variables have the following meaning:

     R ¹

     Hydrogen or methyl,

     R ²

     a chemical bond or unbranched or branched C ₁ -C ₆ -alkylene,

     R ³

     identical or different unbranched or branched C ₂ -C ₄ -alkylene radicals,

     R ⁴

     unbranched or branched C ₁ -C ₆ -alkyl,

     n

     3 to 50,

     the monomers a1) to a3) being copolymerized randomly or in blocks,
2. b) 1 to 50 wt .-%, preferably 5 to 40 wt .-% complexing agent selected from the group consisting of glycine-N, N-diacetic acid derivatives and glutamic acid-N, N-diacetic acid and salts thereof,
3. c) 1 to 15% by weight, preferably 1 to 10% by weight, of low-foaming nonionic surfactants,
4. d) from 0 to 30% by weight, preferably from 0 to 20% by weight, of bleach and optionally bleach activators,
5. e) 0 to 60% by weight, preferably 0 to 40% by weight, of further builders,
6. f) 0 to 8% by weight, preferably 0 to 5% by weight of enzymes,
7. g) 0 to 50% by weight, preferably 0.1 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.

The formulation can be made into tablets, powders, gel, capsules, 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 alkylene oxide units containing copolymers a) contain as copolymerized components a1) and a2) acrylic acid or methacrylic acid 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 a1) in the copolymers to be used according to the invention is 50 to 93 mol%, preferably 65 to 85 mol% and particularly preferably 65 to 75 mol%.

Methacrylic acid a2) is contained in the copolymers to be used according to the invention to 5 to 30 mol%, preferably 10 to 25 mol% and especially to 15 to 25 mol%.

in der die Variablen folgende Bedeutung haben:

R¹

Wasserstoff oder bevorzugt Methyl,

R²

unverzweigtes oder verzweigtes C₁-C₆-Alkylen oder bevorzugt eine chemische Bindung,

R³

gleiche oder verschiedene unverzweigte oder verzweigte C₂-C₄-Alkylenreste, vor allem C₂-C₃-Alkylenreste, insbesondere Ethylen,

R⁴

unverzweigtes oder verzweigtes C₁-C₆-Alkyl, bevorzugt C₁-C₂-Alkyl,

n

3 bis 50, bevorzugt 5 bis 40, besonders bevorzugt 10 bis 30.

The copolymers contain as component a3) nonionic monomers of the formula (I)

in which the variables have the following meaning:

R ¹

Hydrogen or preferably methyl,

R ²

unbranched or branched C ₁ -C ₆ -alkylene or preferably a chemical bond,

R ³

identical or different unbranched or branched C ₂ -C ₄ -alkylene radicals, especially C ₂ -C ₃ -alkylene radicals, in particular ethylene,

R ⁴

unbranched or branched C ₁ -C ₆ -alkyl, preferably C ₁ -C ₂ -alkyl,

n

3 to 50, preferably 5 to 40, particularly preferably 10 to 30.

Particularly suitable examples of the monomers (I) are: 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 a3) in the copolymers to be used according to the invention is 2 to 20 mol%, preferably 5 to 15 mol% and especially 5 to 10 mol%.

The copolymers to be used according to the invention generally have an average molecular weight M _{w of} from 3,000 to 50,000, preferably from 10,000 to 30,000 and more preferably from 15,000 to 25,000.

The K value of the copolymers is usually from 15 to 40, in particular from 20 to 35, especially from 27 to 30 (measured in 1 wt .-% aqueous solution at 25 ° C, after H. Fikentscher, Cellulose Chemistry, Vol. 13, pp. 58-64 and 71-74 (1932 )).

The copolymers to be used according to the invention can be prepared by free-radical polymerization of the monomers. It can be worked by all known radical polymerization. In addition to the bulk polymerization, the methods of solution polymerization and emulsion polymerization should be mentioned in particular, with the solution polymerization being preferred.

The polymerization is preferably carried out in water as a solvent. However, it may also in alcoholic solvents, especially C ₁ -C ₄ alcohols, such as Methanol, ethanol and isopropanol, or mixtures of these solvents are made 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.degree. C., in particular from 50 to 90.degree. 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.

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 monomers a1), a2) and a3).

The polymerization temperature is usually at 30 to 200 ° C, preferably at 50 to 150 ° C and particularly preferably at 80 to 120 ° C.

The polymerization may be carried out under atmospheric pressure, but preferably it is carried out in the closed system under the evolving autogenous pressure.

In the preparation of the copolymers a) used according to the invention, the monomers a1), a2) and a3) can be used as such, but it is also possible to use reaction mixtures which are obtained in the preparation of the monomers a3). For example, instead of methoxypolyethylene glycol methacrylate, the monomer mixture obtained in the esterification of polyethylene glycol monomethyl ether with an excess of methacrylic acid can be used. Advantageously, the esterification can also be carried out in situ in the polymerization mixture by (1) combining acrylic acid, (2) a mixture of methacrylic acid and polyethylene glycol monomethyl ether and (3) free radical initiator in parallel. If appropriate, a catalyst necessary for the esterification, such as methanesulfonic acid or p-toluenesulfonic acid, may additionally be used.

The copolymers a) used according to the invention can also be prepared by a polymer-analogous reaction, for example by reacting an acrylic acid / methacrylic acid copolymer with polyalkylene glycol monoalkyl ether. However, preferred is the radical copolymerization of the monomers.

As component b), the cleaning formulations according to the invention contain one or more complexing agents which are selected from the group consisting of glycine-N, N-diacetic acid derivatives, glutamic acid-N, N-diacetic acid and salts thereof. Preferred complexing agents b) are methylglycinediacetic acid and glutamic acid diacetic acid, particularly preferred complexing agents b) are methylglycinediacetic acid or its salts.

worin

R

C₁-C₁₂-Alkyl und

M

Alkalimetall, bevorzugt Natrium oder Kalium, besonders bevorzugt Natrium

bedeuten.Preferred glycine-N, N-diacetic acid derivatives are those in EP-A 0 845 456 described. Suitable glycine-N, N-diacetic acid derivatives are accordingly compounds of the general formula (II)

wherein

R

C ₁ -C ₁₂ alkyl and

M

Alkali metal, preferably sodium or potassium, more preferably sodium

mean.

R is a C _1-12 -alkyl radical, preferably a C _1-6 -alkyl radical, more preferably a methyl or ethyl radical. Particularly preferred component (b) 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 and, for example, in EP-A 0 845 456 and 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 general formula (III)

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

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

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

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, cationic, amphoteric 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. 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 C ₆ -C ₁₈ -alkyl betaines or C ₆ -C ₁₅ -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, 1,12-diperoxydodecanedioic acid, 1,9-diperoxyazelaic acid, diperoxoisophthalic acid or 2-decyldiperoxybutane-1,4-diacid.

• Kationische Peroxysäuren, die in den Patentanmeldungen US 5,422,028 , US 5,294,362 sowie US 5,292,447 beschrieben sind;
• Sulfonylperoxysäuren, die in der Patentanmeldung US 5,039,447 beschrieben sind.
• Sauerstoffbleichmittel werden in Mengen von im Allgemeinen 0,5 bis 30 Gew.-%, bevorzugt von 1 bis 20 Gew.-%, besonders bevorzugt von 3 bis 15 Gew.-%, bezogen auf die gesamte Reinigerformulierung, eingesetzt.
• Chlorhaltige Bleichmittel sowie die Kombination von chlorhaltigen Bleichmitteln mit peroxidhaltigen Bleichmitteln können ebenfalls verwendet werden. Bekannte chlorhaltige Bleichmittel sind beispielsweise 1,3-Dichloro-5,5-dimethylhydantoin, N-Chlorosulfamid, Chloramin T, Dichloramin T, Chloramin B, N,N'-Dichlorbenzoylharnstoff, p-Toluolsulfondichloramid oder Trichlorethylamin. Bevorzugte chlorhaltige Bleichmittel sind Natriumhypochlorit, Calciumhypochlorit, Kaliumhypochlorit, Magnesiumhypochlorit, Kaliumdichlorisocyanurat oder Natriumdichlorisocyanurat.
• Chlorhaltige Bleichmittel werden in Mengen von im Allgemeinen 0,1 bis 20 Gew.-%, bevorzugt von 0,2 bis 10 Gew.-%, besonders bevorzugt von 0,3 bis 8 Gew.-%, bezogen auf die gesamte Reinigerformulierung, eingesetzt.
• Weiterhin können in geringen Mengen Bleichmittelstabilisatoren wie beispielsweise Phosphonate, Borate, Metaborate, Metasilikate oder Magnesiumsalze zugegeben werden.
• Bleichaktivatoren sind Verbindungen, die unter Perhydrolysebedingungen aliphatische Peroxocarbonsäuren mit vorzugsweise 1 bis 10 Kohlenstoffatomen, insbesondere 2 bis 4 Kohlenstoffatomen, und/oder substituierte Perbenzoesäure ergeben. Geeignet sind Verbindungen, die eine oder mehrere N- bzw. O-Acylgruppen und/oder gegebenenfalls substituierte Benzoylgruppen enthalten, beispielsweise Substanzen aus der Klasse der Anhydride, Ester, Imide, acylierten Imidazole oder Oxime. Beispiele sind Tetracetylethylendiamin (TAED), Tetraacetylmethylendiamin (TAMD), Tetraacetylglykoluril (TAGU), Tetraacetylhexylendiamin (TAHD), N-Acylimide, wie beispielsweise N-Nonanoylsuccinimid (NOSI), acylierte Phenolsulfonate, wie beispielsweise n-Nonanoyl- oder Isononanoyloxybenzolsulfonate (n- bzw. iso-NOBS), Pentaacetylglucose (PAG), 1,5-Diacetyl-2,2-dioxohexahydro-1,3,5-triazin (DADHT) oder Isatosäureanhydrid (ISA).
• Ebenfalls als Bleichaktivatoren eignen sich Nitrilquats wie beispielsweise N-Methyl-Morpholinium-Acetonitril-Salze (MMA-Salze) oder Trimethylammoniumacetonitril-Salze (TMAQ-Salze).
• Bevorzugte Bleichaktivatoren sind aus der Gruppe bestehend aus mehrfach acylierten Alkylendiaminen, besonders bevorzugt TAED, N-Acylimide, besonders bevorzugt NO-SI, acylierte Phenolsulfonate, besonders bevorzugt n- oder iso-NOBS, MMA und TMAQ.

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 bleaches 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-toluenesulfone dichloroamide 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, 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 one or more N- or O-acyl groups and / or optionally Substituted benzoyl groups, for example, substances from the class of anhydrides, esters, imides, acylated imidazoles or oximes. Examples are tetraethylethylenediamine (TAED), tetraacetylmethylenediamine (TAMD), tetraacetylglycoluril (TAGU), tetraacetylhexylenediamine (TAHD), N-acylimides, such as N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, such as n-nonanoyl or isononanoyloxybenzenesulfonates (n- or n-nonanoyl) 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).
• Preferred bleach activators are selected from the group consisting of polyacylated alkylenediamines, particularly preferably TAED, N-acylimides, particularly preferably NO-SI, acylated phenolsulfonates, particularly 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 bzw. 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 94/27970 , WO 94/28102 , WO 94/28103 , WO 95/00626 , WO 95/14759 sowie WO 95/17498 bekannt sind.

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 and acetylated sorbitol and mannitol or 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 94/27970 . WO 94/28102 . WO 94/28103 . 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 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.

• 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, Aminopolycarboxylate und Polyasparaginsäure;
• Phosphonate wie 2-Phosphono-1,2,4-butantricarbonsäure, Aminotri-(methylenphosphonsäure), 1-Hydroxyethylen(.1,1-diphosphonsäure), Ethylendiamintetramethylenphosphonsäure, Hexamethylendiamin-tetramethylen-phosphonsäure oder Diethylentriaminpentamethylenphosphonsäure;
• Silikate wie Natriumdisilikat und Natriummetasilikat;
• wasserunlösliche Builder wie Zeolithe und kristallinen 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, 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 phyllosilicates.

As component f), the cleaning formulations according to the invention comprise one or more enzymes. The detergent can be added between 0 and 8 wt .-% of enzymes based on the total preparation in order 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 can also from EP-A 446 982 and EP-A 453 003 be known Sulfonimine and / or bleach-enhancing transition metal salts or transition metal complexes 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 19620267 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 95/27775 known.

Binuclear manganese complexes containing 1,4,7-trimethyl-1,4,7-triazacyclononane (TMTACN) such as, for example, [(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.

Bleach catalysts which are preferred are bleach-enhancing transition metal complexes or salts from the group consisting of the manganese salts and complexes and the cobalt salts and complexes. Particularly preferred 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 disilicates, ammonium and / or Alkali metal silicates and mixtures of the aforementioned substances, preference being given to using ammonium and / or alkali metal carbonates and ammonium and / or alkali disilicates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate and β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O.

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 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 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.

1. a) 10 bis 95 Gew.-% der Copolymere aus den Komponenten a1), a2) und gegebenenfalls a3) und a4), wie oben definiert,
2. b) 5 bis 80 Gew.-% Komplexbildnern, ausgewählt aus der Gruppe bestehend aus Glycin-N,N-diessigsäurederivaten und Glutaminsäure-N,N-diessigsäure und deren Salzen
   und gegebenenfalls
3. c) 0 bis 20 Gew.-% eines Polyethylenglykols, eines nichtionischen Tensids oder eines Gemisches davon.

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

1. a) from 10 to 95% by weight of the copolymers of components a1), a2) and optionally a3) and a4), as defined above,
2. b) 5 to 80 wt .-% complexing agents selected from the group consisting of glycine-N, N-diacetic acid derivatives and glutamic acid-N, N-diacetic acid and salts thereof
   and optionally
3. c) 0 to 20 wt .-% of a polyethylene glycol, a nonionic surfactant or a mixture thereof.

As component c), a polyethylene glycol, more preferably having an average molecular weight (weight average molecular weight) of 500 to 30,000 g / mol can be used.

The polyethylene glycol used as component c) preferably has OH end groups and / or C _1-6 -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 may be used as component c) 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 radical can be linear or preferably methyl-branched in the 2-position or may contain linear and branched radicals in the mixture, as they are usually present in Oxoalkoholresten. 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. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO, 4 EO or 7 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-14 -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 range 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 melted 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 all those which can dissolve components a), b) and c); preference is given, for example, to using alcohols and / or water, more preferably water.

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

Examples Examples 1 to 6 and Comparative Examples V1 to V9

Copolymer: The preparation of the copolymer (component a)) was carried out according to Example 1 of DE-A 102 25 594 as follows:

In a reactor with nitrogen inlet, reflux condenser and metering device was a mixture of 619 g of distilled water and 2.2 g of phosphorous acid under Nitrogen feed and stirring heated to 100 ° C internal temperature. Then, in parallel, (1) a mixture of 123.3 g of acrylic acid and 368.6 g of distilled water, (2) a mixture of 18.4 g of sodium peroxodisulfate and 164.6 g of distilled water, (3) a mixture of 72.0 G. Water, 49.1 g of methacrylic acid and 166.9 g of methoxypolyethylene glycol methacrylate (M _w = 1100) and (4) 46 g of a 40 wt .-% aqueous sodium hydrogen sulfite solution continuously added over 5 h. After two hours of stirring at 100 ° C, the reaction mixture was cooled to room temperature and adjusted by the addition of 190 g of 50 wt .-% sodium hydroxide solution to a pH of 7.2.

A slightly yellowish, clear solution of a copolymer having a solids content of 25.7% by weight and a K value of 27.2 (1% strength by weight aqueous solution, 25 ° C.) was obtained.

The following formulations were used to test the combinations of copolymers and complexing agents according to the invention (Table 1): Table 1: formulation 1 2 3 4 5 6 Ingredients: [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] Methylglycinediacetic acid, Na salt 22.2 13 12.4 Glutamic acid-N, N-diacetic acid, Na salt 22.2 Ethylenediaminetetraacetic acid, Na salt 13 22.2 Sodium Citrate • 2H ₂ O 11.1 11.1 26 24.7 26 11.1 sodium 35.6 35.6 7.8 7.4 7.8 35.6 sodium 24 22.9 24 Sodium disilicate (x Na ₂ O • ySiO ₂ ; x / y = 2.65; 80%) 5.6 5.6 5.2 4.9 5.2 5.6 Sodium percarbonate (Na ₂ CO ₃ • 1.5 H ₂ O ₂ ) 11.1 11.1 10.4 9.9 10.4 11.1 Tetraacetylenediamine (TAED) 3.3 3.3 3.1 3 3.1 3.3 Low-foaming nonionic surfactant based on fatty alcohol alkoxylates 5.6 5.6 5.2 4.9 5.2 5.6 copolymer 5.6 5.6 5.3 9.9 5.3 5.6

The test was carried out under the following test conditions: Dishwasher: Miele G 686 SC rinses: 2 rinses 55 ° C normal (without pre-rinse) ware: Messer (WMF table knife Berlin, Monoblock) and Fassformglasbecher (Matador, Ruhr crystal), plastic plate (SAN plate Kayser); Ballast dishes: 6 dessert plates black Rinse temperature: 65 ° C Water hardness: 14 ° dH (corresponding to 250 mg CaCO ₃ / kg) or 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.

Table 2 shows the test conditions of Examples 1 to 6 and Comparative Examples V1 and V9: Table 2: example formulation Water hardness [° dH] dirt polymer 1 1 25 without Copolymer off DE 102 25 594 V1 1 25 without without V2 6 25 without Copolymer off DE 102 25 594 2 2 25 without Copolymer off DE 102 25 594 V3 2 25 without without 3 1 25 With Copolymer off DE 102 25 594 V4 1 25 With without V5 6 25 With Copolymer off DE 102 25 594 4 1 14 without Copolymer off DE 102 25 594 V6 1 14 without without 5 3 25 without Copolymer off DE 102 25 594 V7 3 25 without Polyacrylic acid sodium salt (Mw 8000) V8 5 25 without Copolymer off DE 102 25 594 6 4 25 without Copolymer off DE 102 25 594 V9 4 25 without Polyacrylic acid sodium salt (Mw 8000)

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: Rating (grade) example knife glasses plastic 1 5.3 4.5 1.7 V1 1 1.25 1.7 V2 1.1 4.0 1.7 2 4.3 4.2 1.7 V3 1 1 1.7 3 5.5 4.4 1.7 V4 2.2 1.5 3.3 V5 1.8 3.2 1.7 4 6 5.8 1.7 V6 1 3.4 4.2 5 7.5 7 1.7 V7 5 5 1.7 V8 6.9 3.2 3.3 6 4.5 6.9 1.7 V9 5.1 3.7 1.7

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

Claims (4)

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

   a) from 1 to 20% by weight of copolymers of

   a1) from 50 to 93 mol% of acrylic acid and/or of a water-soluble salt of acrylic acid,

   a2) from 5 to 30 mol% of methacrylic acid and/or of a water-soluble salt of methacrylic acid
   and

   a3) from 2 to 20 mol% of at least one nonionic monomer of the formula I

   

   in which the variables are each defined as follows:

   R¹ is hydrogen or methyl

   R² is a chemical bond or unbranched or branched C₁-C₆-alkylene

   R³ are identical or different, unbranched or branched C₂-C₄-alkylene radicals

   R⁴ is unbranched or branched C₁-C₆-alkyl

   n is from 3 to 50,

   where monomers a1) to a3) are copolymerized in a random or block-like manner,

   b) from 1 to 50% by weight of complexing agents selected from the group consisting of glycine-N,N-diacetic acid derivatives and glutamic acid N,N-diacetic acid, and salts thereof,

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

   d) from 0 to 30% by weight of bleaches and, if appropriate, 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, the sum of components a) to g) adding up to 100% by weight.
2. The phosphate-free detergent formulation according to claim 1, wherein the complexing agent b) is methylglycinediacetic acid and/or salts thereof.
3. A mixed powder or mixed granule for use in detergent formulations for machine dishwashing, composed of

   a) from 10 to 95% by weight of the copolymers according to claim 1 composed of components a1), a2) and, a3),

   b) from 5 to 80% by weight of complexing agents selected from the group consisting of glycine-N,N-diacetic acid derivatives and glutamic acid N,N-diacetic acid and salts thereof,

   c) from 0 to 20% by weight of a polyethylene glycol, of a nonionic surfactant or of a mixture thereof.
4. The use of a combination of copolymers according to claim 1, composed of components a1), a2) and a3), and complexing agents b) selected from the group consisting of glycine-N,N-diacetic acid derivatives, glutamic acid N,N-diacetic acid and salts thereof, as a scale-inhibiting additive in detergent formulations for machine dishwashing.