EP2113024B1 - Dish detergent - Google Patents

Description

The present invention relates to the use of a phosphate-reduced builder system based on alkali metal polyphosphate and sodium iminodisuccinate for producing material-saving dishwashing detergent formulations for automatic, automatic dishwashing.

Phosphate-reduced are those formulations whose phosphate content is insufficient to bind the resulting from the water hardness and hardness-forming ions of the dish soil maximum total hardness in the wash liquor and compensate for this gap with a non-belonging to the group of phosphates complexing agent. Levels of tripolyphosphate of about 50% have been found to be adequate (+/- 5%). So phosphate-reduced formulations in the context of the present invention are characterized by a phosphate content of 25 to 40 wt.% Alkalitriphosphat.

When cleaning dishes in dishwashers during the cleaning process, the dishes from the dirt, which consists of a variety of food residues, freed. In comparison to washing dishes by hand, dishwashing in dishwashers takes place at a higher pH and a higher temperature, preferably between 45 ° and 70 ° C. The alkaline medium used in this process sapes grease and oil-like soiling and thus removes it from the items to be washed. Colored stains, such as tea stains, are removed by oxidation by a bleach system. Starch and protein components are hydrolytically split by enzymes and thus more easily removed. Surfactants play a role only as a wetting agent in low concentrations and, in contrast to hand dishwashing detergents, have low foaming properties.

However, the highly saline formulations can lead to visible residues on the cleaned items. Therefore, in automatic washing machine washing programs, the cleaning operation was separated from the rinse cycle. For this purpose, very different products have been developed: the machine dishwashing detergent and the rinse aid. The system is supplemented by the so-called regeneration salt "salt" for softening by ion exchange.

The fourth product was the "machine care" on the market, which should clean and maintain the machine itself after a certain number of operations. The previous conclusion form as deodorants designated fragrances as the fifth element. The various components are most recently integrated or combined in dishwashing tablets, e.g. "3 in 1" or "5 in 1".

• Sehr gutes Fettlösevermögen
• Quell- und Schmutzablösevermögen für protein- und stärkehaltigen Schmutz
• Entfernung von farbintensiven Flecken
• Reduzierung von Keimzahlen
• Schaumarmut
• Rückstands- und fleckenfreies Spülgut nach der Reinigung
• Materialschonung (Glas, Porzellan, Edelstahl, Silber)
• Lagerstabilität
• Günstige Umwelteigenschaften

To Hauthal, Wagner, cleaning and care products in the household, Verlag für Chemische Industrie, Augsburg, 2003, ISBN 3-87846-230-1, pages 161-168 , the requirements for automatic dishwashing detergent are as follows:

• Very good grease dissolving power
• Swelling and soil removal capacity for protein and starchy dirt
• Removal of intense spots
• Reduction of germ counts
• foaming
• Residue and stain-free items to be cleaned after cleaning
• Material protection (glass, porcelain, stainless steel, silver)
• storage stability
• Cheap environmental features

The first automatic dishwashing products consisted of more than 90% sodium tripolyphosphate (NTPP), about 3% of sodium metasilicate to increase alkalinity and corrosion protection, and contained sodium trichloroisocyanurate as a bleaching agent.

Due to the alkalinity of NTPP and Metasilikat a detachment of the fatty dirt by saponification of the fats could be ensured; In addition, NTPP combines good complexing ability for calcium and magnesium ions with a preservation of glass, porcelain and metal.

For ecological reasons (phosphates have a eutrophic effect on waters), the phosphate content was initially reduced and replaced by sodium metasilicate. However, the highly corrosive effect of metasilicates resulted in an accident risk in the household. Consequently, the first phosphate-free, low-alkaline, citrate-formulated machine dishwashing detergents were launched on the market in 1991. However, complaints about unsatisfactory cleaning results and corrosion damage to sensitive glasses and on-glass decors became more frequent. Therefore, leading manufacturers of dishwashers recommended in 1995 to return to phosphate-containing, oxygen bleaching formulations. In 1999, the phosphate-containing, oxygen-bleaching formulations again had a market share of about 90% in Germany. The role of tripolyphosphate as a complexing agent could not be sufficiently assumed by metasilicate as well as by citrate.

The question still arises of a phosphate substitute that could take over the function of the NTPP in whole or in part. Even a partial replacement of NTPP would have a favorable effect on eutrophication. There are also economic reasons for this path, since phosphates are cheaper than organic complexing agents.

In recent years biodegradable organic complexing agents with low toxicity have been developed. As an example of universally applicable products are the medium strength Complexing agent called sodium iminodisuccinate (Na-IDS) and the stronger complexing agent sodium methylglycine diacetate (Na-MGDA). These chelating agents have also been used for phosphate-free dishwashing detergents.

US 3,697,453 A describes the use of phosphate-reduced builder systems with salts of iminodisuccinic acid and up to 40% polyphosphates for the production of machine dishwashing detergents.

In the WO 2006/029806 Such a phosphate-free formulation is described for use as a cleaning formulation for machine dishwashing. This formulation contains 1 to 20 wt.% Copolymers, which are composed of the monomers maleic acid, maleic anhydride and acrylic acid, and of isobutene, styrene, etc. are. As a preferred complexing agent Methylglycindiessigsäure / MGDA and / or their Na salts claimed. Copolymers based on maleic acid / acrylic acid, which may also be hydrophobed, together with the complexing agents form the builder system in many cleaning formulations.

However, this formulation was unsatisfactory in its effect. In the case of strong complexing agents, such as the sodium salt of methylglycinediacetic acid, Na-MGDA, problems occurred with regard to the material protection of the surface to be cleaned. The glaze colors on the dishes were attacked and faded after a few cleaning cycles.

The question thus arose as to which builder systems are suitable for the automated cleaning of dishes which on the one hand are gentle on materials but on the other hand approach cleaning performance at least to the level of phosphate-containing (or phosphate-free) cleaners. Gentle on material within the meaning of the present invention means in particular corrosion protection against color decors or glazes on the dishes to be cleaned, which may preferably consist of glass, porcelain, metal, earthenware or plastic.

It has surprisingly been found that a mixture or combination consisting of an amount of 25 to 40 wt.% Alkalitripolyphosphat, preferably sodium tripolyphosphate / NTPP and 15 to 40 wt .-% Natriumiminodisuccinat Na IDS (sodium salt of Imidobernsteinsäure) in terms of cleaning performance on the one hand and material conservation on the other achieved an excellent result in the extensive test series.

1. a) 25 bis 40 Gew.% Alkalitripolyphosphat, bevorzugt Natriumtripolyphosphat (NTPP) und
2. b) 15 bis 30 Gew.-% Natriumiminodisuccinat (Na-IDS)

zur Herstellung eines phosphatreduzierten Buildersystems für materialschonende Geschirrreinigerformulierungen die in automatischen, maschinellen Geschirrreinigungsapparaten anzuwenden sind.The subject of the present application is therefore the use of a combination of

1. a) 25 to 40 wt.% Alkalitripolyphosphat, preferably sodium tripolyphosphate (NTPP) and
2. b) 15 to 30% by weight of sodiumiminodisuccinate (Na-IDS)

for the preparation of a phosphate reduced builder system for mild detergent dishwashing formulations to be used in automatic dishwashing machines.

In a preferred embodiment, the builder system to be used according to the invention contains from 25 to 35% by weight of component a) and from 15 to 25% by weight of component b). Alkali is understood according to the invention potassium and sodium.

The inventive combination of a) and b) for use in dishwashing detergents is surprising because this combination reaches the level of classic, exclusively phosphate-containing formulations, especially since Na-IDS is classified among the complexing agents only as a moderate complex and the expert had to assume that Na-IDS will not show the desired success when used in dishwashing machines. The inventive combination of a) and b) shows in the stated amounts of the individual components over the prior art significantly improved corrosion behavior compared to the material to be cleaned, as the known from the prior art combinations this being the legal requirements for a modern phosphate reduced dishwashing detergent fulfill.

The mixture to be used according to the invention may contain, in addition to the two skin constituents alkali polyphosphate and Na IDS as complexing agent, preferably NTPP and Na IDS, further constituents which support or improve the effect of the two. These components include polymers and copolymers (which may also be hydrophobed), such as polyacrylic acid or its salts, copolymers of acrylic acid with other comonomers or their salts, polycarboxylic acid based polyaspartic acid or its salts, carboxymethylcellulose or its salt, oxidized starch or cellulose , Metasilicates, phyllosilicates, orthosilicates, carbonates or bicarbonates. The complexing agents to be used according to the invention may contain, in addition to Na-IDs, one or more complexing agents of the series nitrilotriacetic acid or its salts, hydroxyethylenediaminetriacetic acid or its salts, ethylenediaminetetraacetic acid or its salts, diethylenetriaminepentaacetic acid or its salts, methylglycinediacetic acid or its salts, glutamic diacetic acid or its salts, and hydroximinodisuccinic acid or its derivatives Salts, ethylenediamine disuccinic acid or salts thereof and also aspartic acid diacetate and salts thereof.

• c) 1 bis 15 Gew.-%, bevorzugt 1 bis 10 Gew.-% schwach schäumende nichtionische Tenside und
• d) 0,1 bis 30 Gew.-%, bevorzugt 1 bis 20 Gew.-% Bleichmittel und gegebenenfalls Bleichaktivatoren.

Dishwashing detergent formulations according to the invention for machine dishwashing still contain, in addition to the combination of components a) and b) to be used according to the invention

• c) 1 to 15 wt .-%, preferably 1 to 10 wt .-% low-foaming nonionic surfactants and
• d) 0.1 to 30 wt .-%, preferably 1 to 20 wt .-% bleaching agent and optionally bleach activators.

• e) 0.1 bis 60 Gew.-%, bevorzugt 0,1 bis 40 Gew.% weitere Builder enthalten.

In a further alternative embodiment, the Gesc-hirrreinigerformulierungen invention may additionally

• e) from 0.1 to 60% by weight, preferably from 0.1 to 40% by weight, of further builders.

• f) 0,1 bis 8 Gew.-%, bevorzugt 0,1 bis 5 Gew.-% Enzyme, bevorzugt Protease, Amylase oder Lipase, enthalten.

In a further alternative embodiment, the dishwashing detergent formulations according to the invention may still be added in addition to the components a) to d) and e) or instead of e)

• f) 0.1 to 8 wt .-%, preferably 0.1 to 5 wt .-% enzymes, preferably protease, amylase or lipase containing.

• g) 0,1 bis 50 Gew.-%, bevorzugt 0,1 bis 45 Gew.% eines oder mehrere weitere Zusatzstoffe wie anionische oder zwitterionische Tenside, Bleichkatalysatoren, Alkaliträger, Korrosionsinhibitoren, Entschäumer, Farbstoffe, Duftstoffe, Füllstoffe, organische Lösungsmittel oder Wasser enthalten.

In a further alternative embodiment, the dishwashing detergent formulations according to the invention may, in addition to the components a) to d) and optionally e) and / or f) or instead of one of the components e) or f), also

• g) 0.1 to 50 wt .-%, preferably 0.1 to 45 wt.% One or more other additives such as anionic or zwitterionic surfactants, bleach catalysts, alkali carriers, corrosion inhibitors, defoamers, dyes, fragrances, fillers, organic solvents or water contain.

The sum of the components a) to g) in the respective possible combinations of the cleaning formulations according to the invention always gives 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. Cleaning apparatuses in which the combination of components a) and b) or the cleaning formulations obtainable therefrom can be used are domestic dishwashers, dishwashers in commercial kitchens and dishwashing machines on ships, in vehicles and aircraft, but also apparatus cleaning machines in medical or chemical laboratories.

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

Low-foaming or low-foaming nonionic surfactants are preferably end-capped fatty alkyl ethoxylates and obtainable from fatty alcohols and differently arranged ethylene oxide and propylene oxide / butylene oxide blocks (J. Tropsch, H. Gümbel, G. Oetter, New low-foaming surfactants for diskwasher detergents and rinse aids , SÖFW J. 2001, 127, H. 11, 2-5)

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 bis 10 C-Atomen oder H sind, wobei R¹ bevorzugt Methyl ist,

p und m

unabhängig voneinander 0 bis 300 sind.

Preferred nonionic surfactants include the surfactants of the general formula (I)

R ² -O- (CH ₂ CH ₂ O) _p - (CHR ¹ CH ₂ O) _m -R (I)

wherein

R ²

is a linear or branched alkyl radical having 8 to 22 carbon atoms,

R ¹ and R ³

are independently of one another hydrogen or a linear or branched alkyl radical having 1 to 10 C atoms or H, where R ^{1 is} preferably methyl,

p and m

independently are 0 to 300.

More preferably p is an integer from 1 to 5 and m is an integer from 0 to 30.

The surfactants of formula (I) 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 0 851 023 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 dishwashing detergent formulations according to the invention comprising component a) to d) comprise bleaching agents 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.

In addition, the following oxygen bleaches can also be used in a dishwashing detergent formulation according to the invention:

• 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 dishwashing detergent formulation.

Chlorine-containing bleaches as well as the combination of bleach with peroxide-containing bleaches may 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 trichlorethyleneamine. 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 dishwashing 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 peroxocarboxylic 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 (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 19 616 693 und DE-A 19 616 767 bekannten Enolester sowie acetyliertes Sorbitol und Mannitol und deren in EP-A 0 525 239 beschriebene Mischungen; acylierte Zuckerderivate, insbesondere Pentaacetylgkykose (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.

Furthermore, the following substances can be used as bleach activators in dishwashing detergent formulations according to the invention containing components a) and b) and also c) and d):

• 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 19 616 693 and DE-A 19 616 767 known enol esters as well as acetylated sorbitol and mannitol and their in EP-A 0 525 239 described mixtures; acylated sugar derivatives, in particular pentaacetylgkycose (PAG), pentaacetyl-fructose, tetraacetyl-xylose and octa-acetyllactose, 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 19 616 769 listed hydrophilic substituted acyl acetals and in DE-A 19 616 770 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 dishwashing detergent formulation.

As component e), the dishwashing detergent formulations according to the invention which contain components a) to d) may contain further builders. It is possible to use water-soluble and water-insoluble builders whose main task is to bind calcium and magnesium.

• Copolymere a) aus
  • a1) mindestens einem Monomeren aus der Gruppe bestehend aus monoethylenisch ungesättigen C₃-C₁₀-Mono- oder Dicarbonsäuren oder deren Anhydriden,
  gegebenenfalls mit a2) mindestens einem Monomeren der allgemeinen Formel (II),
  

wobei

R¹, R² undR³

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,

oder gegebenenfalls mit a3) mindestens einem weiteren Monomeren, ausgewählt aus der Gruppe bestehend aus Olefinen mit 10 oder 100 Kohlenstoffatomen, oder niedermolekulare Carbonsäuren sowie deren Salze wie Alkalicitrate, insbesondere wassserfreies Trinatriumcitrat oder Trinatriumcitratdihydrat, Alkalisuccinate, Alkalimalonate, Fettsäuresulfonate, Oxydisuccinat, Alkyl- oder Alkenyldisuccinate, Gluconsäuren, Oxadiacetate, Carboxymethyloxysuccinate, Tartratmonosuccinat, Tartratdisuccinat, Tartratmonoacetat, Tartratdiacetat, α-Hydroxypropionsäure;
oxidierte 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;
wasserlösliche Builder wie Zeolithe und kristalline Schichtsilikate.As further builders can be used:

• Copolymers a) from
  • a1) at least one monomer selected from the group consisting of monoethylenically unsaturated C ₃ -C ₁₀ -mono- or dicarboxylic acids or their anhydrides,
  optionally with a2) at least one monomer of the general formula (II),
  

in which

R ¹ , R ² and R ³

independently of one another are H, CH ₃ or C ₂ H ₅ ,

R ⁴

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

or optionally with a3) at least one further monomer selected from the group consisting of olefins having 10 or 100 carbon atoms, or low molecular weight carboxylic acids and their salts such as alkali citrates, in particular water-free 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, 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; 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-soluble builders such as zeolites and crystalline phyllosilicates.

Preferred monomers a1) are, for example, maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid. Preferred copolymers a) contain as monomers a1) monomers which are selected from the group consisting of maleic acid, maleic anhydride and acrylic acid.

Optionally used preferred monomers a2) are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene. Further preferred copolymers a) comprise as monomers a2) monomers which are selected from the group consisting of isobutene, diisobutene (2-methyl-3,3-dimethyl-1-butene) and styrene.

Optionally used preferred monomers a3) have at least 10, preferably 10-26 C-atoms. Particularly preferred monomers a3) are 1-decene, 1-dodecane, 1-tetradecene, 1-hexadecene, 1-octadene, 1-eicosene, 1-docoses, 1-tetracoses and 1-hexacoses. Further preferred copolymers a) contain as monomers a3) monomers which are selected from the group consisting of 1-dodecene, 1-octadecene, C ₂₂ -α-olefins and polyisobutene having an average of 12 to 100 carbon atoms.

In particular, particularly preferred copolymers a) contain both monomers a1), which are selected from maleic acid, maleic anhydride and acrylic acid, as well as monomers a2) which are selected from isobutene, diisobutene and styrene as well as monomers a3), which are selected from the group consisting of 1-dodecene, 1-octadecene, C ₂₂ -α-olefin, a mixture of C ₂₀ -C ₂₄ -α-olefins and polyisobutene having an average of 12 to 100 carbon atoms. Particular preference is given to copolymers of 30 to 70% by weight of maleic acid and maleic anhydride as monomers a1), 20 to 40% by weight of isobutene as monomers a2) and 5 to 20% by weight of octadecene as monomers a3).

Component (f) of the invention may contain enzymes containing the components of the invention containing components a) to d). The Geschmineinigungsmittel can be added between 0.1 and 8 wt .-% of enzymes, based on the total preparation, to increase its performance or to ensure the cleaning performance of the same quality under milder conditions. The most commonly used enzymes include lipases, Amylases, cellulases and proteases. Furthermore, for example, esterases, pectinases, lactases and peroxidases can be used.

The dishwashing detergent formulations according to the invention which contain components a) to d) may additionally 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 sulphonic imines and / or bleach-enhancing transition metal salts or transition metal complexes as so-called bleach catalysts in the dishwashing detergent formulations of the invention.

Examples of suitable transition metal compounds include those of DE-A 19 529 905 known manganese, iron, cobalt, ruthenium or molybdenum complexes and their DE-A 19 620 267 known N-analogues consisting of DE-A 19 536 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, which in DE-A 19 605 688 described manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, which DE-A 19 620 411 known cobalt, iron, copper and ruthenium amine complexes which are known in DE-A 4 416 438 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 443 651 . EP-A 458 397 . EP-A 458 398 . 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 19 613 103 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 transition metal 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 .

Bleaching catalysts may 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 dishwashing detergent formulation.

As further constituents of the dishwashing detergent formulations according to the invention containing components a) to d), 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 and mixtures of the abovementioned substances, preference being given to ammonium and / or Alkali carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate can be 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 / or alkylaminotriazole. In addition, in dishwashing detergent formulations, active chlorine-containing agents are often used which can markedly 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. Also salt and complex inorganic compounds such as salts of metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably from the group of cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl ) Complexes, the chlorides of cobalt or manganese and of manganese sulfate. Also, zinc compounds or bismuth compounds can be used to prevent corrosion on the items to be washed.

Paraffin oils and silicone oils can be optimally used as defoamers and for the protection of plastic and metal surfaces. Defoamers are preferably used in proportions of 0.001 wt .-% to 5 wt .-%. In addition, dyes such as patent blue, preservatives such as Kathon CG, perfumes or other fragrances may be added to the invention containing the components a) and b) and c) and d) dishwashing detergent formulations.

The dishwashing detergent formulations according to the invention for machine dishwashing on the basis of a builder system with the components a) and b) and also the components c) and d) can be used both in powder form and as tabs.

Examples

For the following experiments, a standard formulation of a low alkaline cleaner (typical phosphate content) was detected Hermann G. Hauthal, G. Wagner (Hrsg): cleaning and care products in the household, publishing house for chemical industry, Augsburg, 2003, ISBN 3-87846-230-1 used:

example 1

Pentasodium triphosphate (NTPP) 45.5% share Phosphonates (Hyodroxyethylenediamine) 5% sodium polycarboxylates 6% soda 20% sodium disilicate 5% sodium 10% Bleach activator TAED (tetraacetylethylenediamine) 2% Protease and amylase 4% Low-foaming surfactants 2% silver protection 0.2% fragrances 0.2%

In this formulation, sodium tripolyphosphate is partially replaced by sodiumiminodisuccinate, sodium methylglycine diacetate, trisodium citrate, and sodium sulfate.

• VN1: Grundrezeptur wie oben (nicht erfindungsgemäß)
• VN 2: NTPP reduziert auf 30 %, ergänzt durch 15,5 % Na-IDS (erfindungsgemäß)
• VN 3: NTPP reduziert auf 30 %, ergänzt durch 15,5 % Na-MGDA (nicht erfindungsgemäß)
• VN 4: NTPP reduziert auf 30 %, ergänzt durch 15,5 % Na-Citrat (nicht erfindungsgemäß)
• VN 5: NTPP reduziert auf 25%, ergänzt durch 20,5 % Na-IDS
• VN 6: NTPP reduziert auf 20%, ergänzt durch 25,5 % Na-IDS (nicht erfindungsgemäß)
• VN 7: NTPP reduziert auf 15%, ergänzt durch 30,5 % Na-IDS (nicht erfindungsgemäß)
• VN 8: NTPP reduziert auf 10%, ergänzt durch 35,5 % Na-IDS (nicht erfindungsgemäß)

The cleaning performance and the material protection of selected combinations were tested.

• VN1: Basic recipe as above (not according to the invention)
• VN 2: NTPP reduced to 30%, supplemented by 15.5% Na IDS (according to the invention)
• VN 3: NTPP reduced to 30%, supplemented by 15.5% Na-MGDA (not according to the invention)
• VN 4: NTPP reduced to 30%, supplemented by 15.5% Na citrate (not according to the invention)
• VN 5: NTPP reduced to 25%, supplemented by 20.5% Na IDS
• VN 6: NTPP reduced to 20%, supplemented by 25.5% Na-IDS (not according to the invention)
• VN 7: NTPP reduced to 15%, supplemented by 30.5% Na-IDS (not according to the invention)
• VN 8: NTPP reduced to 10%, supplemented by 35.5% Na-IDS (not according to the invention)

The following is a summary of the results of tests performed with these formulations. First, the cleaning performance was investigated, whereby in a series of experiments (R1) without rinse aid; in the second (R2) worked with rinse aid has been. The evaluation of the cleaning performance was carried out with a staff, where the grade 1 no cleaning effect, the grade 10 complete cleaning (= like new) represents.

The percentages for certain types of dirt are based on a gravimetric determination.

test conditions:

• Detergent dosage 20 g
• Water hardness 8-10 ° dH
• Test series 1 (= R1)

VN 1 R1 Note VN 2 R1 Note VN 3 R1 Note VN 4 R1 Note VN 5 R1 Note VN 6 R1 Note VN 7 R1 Note VN 8 R1 Note porridge 7.7 8.1 8.0 7.9 7.5 7.3 6.8 Minced meat 120 ° C 8.4 8.7 8.7 7.9 6.3 5.5 4.6 milk 6.5 6.4 6.5 6.5 6.5 6.5 6.4 tea 2.3 3.3 4.8 3.8 4.3 4.8 5.1 % Replacement. % Replacement. % Replacement. % Replacement. % Replacement. % Replacement. % Replacement. Egg / milk 96 97 97 97 96 96 97 egg yolk 64 66 68 66 68 68 70 rice starch 99 99 99 99 99 99 99 Grading Scale:
Egg yolk, rice, tomato / cheese: 0% = no cleaning effect, 100% = completely clean carrier material
Oats, minced meat, tea, milk: 0 = no cleaning effect, 10 = completely clean carrier material

In this series of experiments, the lower-phosphate variants performed better on tea than on the classic variant.

Test conditions for the cleaning test with rinse aid:

• Detergent dosage 20 g Tab
• Water hardness 8-10 ° dH
• Series 2 (= R2). When testing the cleaning performance, rinse aid was added.
• Rinse aid 3 ml IEC Type III

VN 1 R2 Note VN 2 R2 grade VN 3 R2 grade VN 4 R2 grade VN 5 R2 grade VN 6 R2 grade VN 7 R2 Note VN 8 R2 Note porridge 8.5 8.5 8.4 8.4 8.1 7.8 7.1 Minced meat 120 ° C 6.9 6.8 3 6.1 5.3 4.2 3.5 milk 6.6 6.6 6.5 6.6 6.4 6.7 6.5 tea 7.8 7.8 3.5 8.2 8.4 8.5 8.7 % Replacement. % Replacement. % Replacement. % Replacement. % Replacement. % Replacement. % Replacement. % Replacement. Egg / milk 28 26 29 26 27 26 27 egg yolk 33 29 19 28 27 28 26 rice starch 66 64 60 64 64 63 62

In the second row, the cleaning performance was examined using a rinse aid. In the case of the classic recipe and the NTPP / Na-IDS formula, better cleaning performance was achieved with tea soiling; but not when using trisodium citrate as a substitute for one third of the phosphate content.

The material-saving tests were carried out with a Miele turbothermic G 666 SC dishwasher with a universal program 65 ° C. Dosage 20 g - Tab over dosing chamber, rinse aid 3 ml IEC type III, the water hardness was 0.1 ° dH. material VN1 VN2 VN3 VN4 VN 5 VN 6 VN 7 VN 8 Glass lead crystal 3.8 3.8 3.8 3.8 3.8 3.5 3.3 3.0 Potash crystal soiree 4.4 4.0 3.5 2.9 3.6 3.3 3.1 2.8 Glass with decor soda lime 3.5 2.0 1.0 3.5 1.8 1.7 1.4 1.0 Glass 3.5 3.5 1.5 3.5 2.8 2.2 1.8 1.4 cutlery silver 5.0 5.0 5.0 5.0 5.0 5.0 4.8 4.2

Evaluation of results:

• Grade 5 = no material attack / discoloration / iridescence
• Grade 4 = low material attack / discoloration / iridescence
• Grade 3 = easy material attack / discoloration / iridescence
• Grade 2 = severe material attack / discoloration / iridescence
• Grade 1 = very strong material attack / discoloration / iridescence

The results show that the phosphate-reduced formulations according to the invention containing the combination of NTPP and Na-IDS to be used according to the invention clearly show Show differences in the material protection. Thus, the substitution of only one-third of phosphate by Na-MGDA has a significantly unfavorable effect on glass with décor, while the same substitution by Na-IDS causes less corrosivity. Even the supposedly gentle citrate showed a material-removing effect in potash crystal.

Claims (9)

1. Use of a reduced-phosphate builder system based on

   a) 25 to 40% by weight of alkali metal tripolyphosphate, preferably sodium tripolyphosphate, and

   b) 15 to 30% by weight of iminodisuccinic acid and/or its alkali metal salts, preferably sodium salts,

   for producing material-protective dishwashing detergent formulations for automatic machine dishwashing.
2. Use according to Claim 1, characterized in that the builder system, in addition to components a) and b), comprises one or more complexing agents from the group of nitrilotriacetic acid and its salts, hydroxyethylenediaminetriacetic acid and its salts, ethylenediaminetetraacetic acid and its salts, diethylenetriaminepentaacetic acid and its salts, methylglycinediacetic acid and its salts, glutaminediacetic acid and its salts, hydroxyiminodisuccinic acid and its salts, ethylenediaminedisuccinic acid and its salts, aspartic acid diacetate and its salts.
3. Use according to Claims 1 and 2, characterized in that the additional constituents used are polyacrylic acid or its salts, modified polyacrylic acid or its salts, polycarboxylates based on polyaspartic acid or their salts, carboxymethylcellulose or its salts, oxidized starch or cellulose, metasilicates, sheet silicates, ortho silicates, carbonate or hydrogencarbonate.
4. Dishwashing detergent formulations for machine dishwashing, characterized in that they comprise, as a builder system

   a) 25 to 40% by weight of alkali metal tripolyphosphate, preferably sodium tripolyphosphate, and

   b) 15 to 30% by weight of iminodisuccinic acid and/or its alkali metal salts, preferably sodium salts, and also

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

   d) 0.1 to 30% by weight of bleach and optionally bleach activators.
5. Dishwashing detergent formulations according to Claim 4, characterized in that they additionally comprise

   e) 0.1 to 60% by weight of further builders.
6. Dishwashing detergent formulations according to Claim 4 or 5, characterized in that they additionally comprise 0.1 to 8% by weight of enzymes.
7. Dishwashing detergent formulations according to one of Claims 4 to 6, characterized in that they comprise 0.1 to 50% by weight of one or more further additives.
8. Machine dishwashing process for dishware, characterized in that a dishwashing detergent formulation is used therein which comprises, as a builder system,

   a) 25 to 40% by weight of alkali metal tripolyphosphate, preferably sodium tripolyphosphate, and

   b) 15 to 30% by weight of iminodisuccinic acid and/or its alkali metal salts, preferably sodium salts, and also

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

   d) 0.1 to 30% by weight of bleach and optionally bleach activators.
9. Process according to Claim 8, characterized in that the dishwashing detergent formulation is used as a powder or as a tab.