EP2113024A1

EP2113024A1 - Dish detergent

Info

Publication number: EP2113024A1
Application number: EP08707986A
Authority: EP
Inventors: Thomas Klein; Ralf-Johann Moritz; Thomas Staffel; Jürgen STRAUB
Original assignee: Lanxess Deutschland GmbH; BK Giulini GmbH
Current assignee: Lanxess Deutschland GmbH; BK Giulini GmbH
Priority date: 2007-01-19
Filing date: 2008-01-18
Publication date: 2009-11-04
Anticipated expiration: 2028-01-18
Also published as: MX2009007599A; JP2010516832A; TW200846463A; CA2675811A1; AR064974A1; WO2008087200A1; EP2113024B1; DE102007003885A1; CN101631848A; IL199890A0; US20100144576A1; CL2008000155A1

Abstract

The present invention relates to the use of a phosphate-reduced builder system based on alkali tripolyphosphate and sodium iminodisuccinate of gentle dish detergent formulations for automatic dishwashing by machine.

Description

Geschtrrreinigungsmittel

The present invention relates to the use of a phosphate-reduced builder system based on alkali metal polyphosphate and sodiumiminodisuccinate for the production of 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%). Thus, phosphate-reduced formulations in the sense of the present invention are characterized by a phosphate content of less than

45%, preferably 0.01 to 44.9.

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 for washing dishes by hand, the purification is carried out in dishwashing machines at higher pH and a higher temperature, preferably between 45 ° and 70 ⁰ C. In this case the alkaline medium used in fat and oil based contaminants are saponified and thus removed from the dishes. 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 to be washed. 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 introduced by the "machine care workers", who after a certain number of operations are supposed to clean and care for the machine themselves The previous conclusion is the use of deodorant fragrances as the fifth element combined, eg "3 in 1" or "5 in 1".

According to Hauthal, Wagner, Reinägungs- 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

• Queli and soil release properties for protein and starchy dirt

• Removal of color-intensive spots

• Reduction of germ counts • Low foaming

• Residue and stain-free items to be cleaned after cleaning

• Material protection (glass, porcelain, stainless steel, silver)

• storage stability

• Favorable environmental features

The first automatic dishwashing products consisted of more than 90%

Sodium tripolyphosphate (NTPP), about 3% of sodium metasilicate to increase the alkalinity as well as 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 power for calcium and magnesium ions with protection of glass, porcelain and magnesium

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 Phosphathaitigen, with oxygen bleaching formulations. In 1999, the phosphate-containing, oxygen-bleaching formulations in Germany had one again

Market share of about 90%. 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. Economic reasons also speak in favor of this path

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.

No. 3,697,453 A describes the use of phosphate-reduced builder systems with salts of iminodisuccinic acid and up to 40% of polyphosphates for the production of mechanical

Dishwashing detergents.

WO 2006/029806 describes such a phosphate-free formulation 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 0.1 to 54.9% by weight of alkali metal polyphosphate, preferably sodium tripolyphosphate / NTPP and 0.1 to 54.9% by weight of sodium iminodisuccinate Na-IDS (sodium salt imidosuccinic acid) achieved excellent results in terms of cleaning performance on the one hand and material protection on the other hand in the extensive test series.

The subject of the present application is therefore the use of a combination of

a) 25 to 54.9 wt .-% alkali polyphosphate, preferably sodium tripolyphosphate (NTPP) and

b) 0.1 to 30% by weight of sodiumiminodisuccinate (Na-IDS) for the production of a reduced-phosphate Bui Idersystem for material-saving dishwashing detergent formulations which are to be used in automatic, machine dishwashing apparatus.

In a preferred embodiment, the builder system to be used according to the invention contains from 25 to 40% by weight of component a) and from 15 to 30% by weight of component b), more preferably from 25 to 35% by weight of component a) and from 15 to 25% by weight .-% component b). Alkali is understood according to the invention potassium and sodium.

The combination according to the invention 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-fDS was classified among the complexing agents only as a moderate complex and the skilled person 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 constituents of the constituents alkali nitripolyphosphate and Na-IDS as complexing agent, preferably NTPP and Na-IDS, further constituents which support or improve the action of the two. These constituents include polymers and copolymers (which may also be hydrophobicized), such as polyacrylic acid or its salts, copolymers of acrylic acid with other comonomers or their salts, polycarboxylates based on polyaspartic acid or its salts, carboxymethylcellulose or its salt, oxidized starch or cellulose, meta-cate, 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 salts thereof, ethylenediaminetetraacetic acid or its salts, ethylenetriammapentaacetic acid or its salts, methylglycinediacetic acid or its salts, glutamic diacetic acid or its salts, or hydroxyminodisuccinic acid or its derivatives Salts, ethylenediamine disuccinic acid or salts thereof and also aspartic acid diacetate and salts thereof.

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.

In a further alternative embodiment, the dishwashing detergent formulations according to the invention may additionally be added

e) 0.1 to 60 wt .-%, preferably 0.1 to 40 wt .-% further builders.

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% by weight, preferably 0.1 to 5% by weight, of enzymes, preferably protease, amylase or lipase.

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 parts of one of the components e) or f) still

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

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 .-%.

Low-foaming or low-foaming nonionic Tensi ^'de preferred are end-capped Fettalkylethoxylate and from Fettalkohoien and differently arranged Ethylenoxäd- and propylene oxide / butylene blocks available (J. Tropsch, H.

Gümbel, G. Oetter, New low-foaming surfactants for disk washing detergents and rinse aids, SÖFW J. 2001, 127, H. 11, 2-5)

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

R 1 O- (CH ₂ CH ₂ O) _P - (CHR ¹ CH ₂ O) ₁₇₁ -R ³ (1)

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 to 10 C atoms or H, where R ^{1 is} preferably methyl,

p and m are independently 0 to 300.

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

30th

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, which (for example, under the name Pluronic ^® BASF

Aktiengesellschaft) or Tetronic ^® (BASF Corporation) are commercially available. Furthermore, reaction products of sorbitan esters with ethylene oxide and / or propylene oxide can be used. Also suitable are amine oxides or alkyl glycosides. An overview of suitable nonionic surfactants is given by EP-A 0 851 023 and 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 mentioned in EP-A 851 023 and DE-A 198 19 187.

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 bleaching center! are also organic peracids such as perbenzoic acid, peroxy-alpha-naphthoic acid, peroxylauric acid, peroxystearic acid, Phthalimidoperoxycapronsäure, 1, 12-diperoxydodecanedioic acid, 1, 9-Diperoxyazelainsäure, diperoxoisophthalic or 2-Decyldiperoxybutan-l, 4-diacid.

In addition, the following oxygen bleaches in a novel

Dishwashing detergent formulation can be used:

Cationic peroxyacids described in patent applications US 5,422,028, US 5,294,362 and US 5,292,447; Sulfonyl peroxyacids, which are described in the patent application US 5,039,447.

Oxygen bleaching agents are used in amounts of generally from 0.5 to 30% by weight, preferably from

1 to 20 wt .-%, particularly preferably from 3 to 15 wt .-%, based on the total dishwashing detergent formulation used.

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, dichloroamine

T, chloramine B, N, N'-dichlorobenzoylurea, p-toluenesulfondichloroamide or trichloroethyleneamine. 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 are aliphatic under perhydrolysis conditions

Peroxocarbonsäsuren preferably having 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), l, 5-diacetyl-2 , 2-dioxohexahydr> l, 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.

Furthermore, the following substances can be used as bleach activators in the invention

Components a) and b) and c) and d) containing dishwashing detergent formulations are used:

Carboxylic acid anhydrides such as phthalic anhydride; acylated polyhydric alcohols such as triacetin, ethylene glycol diacetate or 2,5-diacetoxy-2,5-dihydrofuran; the known from DE-A 19 616 693 and DE-A 19 616 767 enol esters and acetylated sorbitol and

Mannitol and its mixtures described in EP-A 0 525 239; acylated sugar derivatives, in particular pentaacetylgkycose (PAG), pentaacetyl-fructose, tetraacetyl-xylose and octaacetyl lactose, and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl-caprolactam, which are described in WO 94/27 970, WO 94/28 102, WO 94/28 103, WO 95/00 626, WO 95/14759 and WO 95/17 498 are known.

The hydrophilically substituted acylacetals listed in DE-A 19 616 769 and the acyl lactams described in DE-A 19 616 770 and WO 95/14075 can be used in the same way as the combinations of conventional bleach activators known from DE-A 44 43 177.

Bleach activators are used in amounts of generally from 0.1 to 10% by weight, preferably from 1 to

9 wt .-%, particularly preferably from 1, 5 to 8 wt .-%, based on the total dishwashing detergent formulation used. 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 the binding of calcium and magnesium.

As further builders can be used:

Copolymers a) from

al) at least one monomer selected from the group consisting of monoethylenically unsaturated C ₃ -C ₀ mono- or dicarboxylic acids or anhydrides thereof,

optionally with a2) at least one monomer of the general formula (II),

Rl f

R ² r \ R ^{4 (II)}

in which

R ¹ , R ² and R ^{3 are} independently 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 2 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 polyacrytic acid, polymethacrylic acid, copolymers of maleic acid and acrylic acid,

Graft polymers of monoethylenically unsaturated mono- and / or dicarboxylic acids

Monosaccharides, oligosaccharides, polysaccharides or polyaspartic acid; Amino polycarboxylates and polyaspartic acid; Phosphonates, such as 2-phosphono-1, 2,4-butanetricarboxylic acid, aminotri (trimethylenephosphonic acid), 1-hydroxyethylene (1,1-diphosphonic acid), ethylene diaminotrimethylene phosphonic acid, hexamethylenediamine tetramethylene phosphonic acid or diethylene triamine pentamethylene phosphonic acid;

Silicates such as sodium disilicate and sodium metasilicate;

water-soluble binders such as zeolites and crystalline phyllosilicates.

Examples of preferred monomers a1) are maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid. Preferred copolymers a) contain, as monomers a1), monomers 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) contain 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 to 26 carbon atoms. Particularly preferred monomers a3) are 1-decene, 1-dodecane, 1-tetradecene, 1-

Hexadecene, 1-octadene, 1-eicosene, 1-docoses, 1-tetracoses and i-hexacoses. Further preferred copolymers a) comprise as monomers a3) monomers which are selected from the group consisting of 1-dodecene, 1-octadecene, C ₂₂ -ot-olefins and polyisobutene having on average 12 to 100 carbon atoms.

Particularly particularly preferred copolymers a) comprise both monomers a1) 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 -ct-Olefϊn, a mixture of C ₂₀ -C ₂₄ -Ct-O lefinen and polyisobutene with an average of 12 to 100 carbon atoms. Particularly preferred are copolymers of 30 to 70 wt .-% maleic acid and maleic anhydride as monomers al),

From 20 to 40% by weight of isobutene as monomers a2) and from 5 to 20% by weight of octadecene as monomers a3).

As component f), the dishwashing detergent formulations according to the invention containing the components a) to d) can contain enzymes. The dishwashing detergent can be added between 0.1 and 5% by weight of enzymes, based on the total preparation, in order to increase its performance or, under milder conditions, to achieve the same cleaning performance

To ensure quality. 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, the sulfone imines and / or bleach-enhancing transition metal salts or transition metal complexes known from EP-A 446 982 and EP-A 453 003 may also be present as so-called bleach catalysts in the dishwashing detergent formulations according to the invention.

Suitable transition metal compounds include, for example, the manganese, iron, cobalt, ruthenium or molybdenum complexes known from DE-A 19 529 905 and their N-analogues known from DE-A 19 620 267, which A 19 536 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl, which in DE-A 19 605

688 manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands described in DE-A 19 620 411 known cobalt, iron, copper and ruthenium Amine complexes, the manganese, copper and cobalt complexes described in DE-A 4 416 438, the cobalt complexes described in EP-A 272 030, the manganese complexes known from EP-A 693 550, which 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 known, for example, from DE-A 19 613 103 and WO 95/27 775.

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

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 preferred are the cobalt (amane) complexes, the

Cobalt (acetate) complexes, the cobalt {carbonyl complexes, the chlorides of cobalt or manganese, manganese sulfate or [(TMTACN) ₃ 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 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. To be considered as alkali carriers

Ammonium and / or alkali metal hydroxides, ammonium and / or alkali metal carbonates,

Ammonium and / or alkali metal bicarbonates, ammonium and / or

Alkali metal sesquicarbonates, 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, silver protectants from the group of the triazoles, the Benzotriazoie, the Bisbenzotriazole, the Aminotriazoie, the Alkylaminotriazole and the transition metal salts or complexes can be used. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. In addition, dishwashing formulations often use active chlorine-containing agents which can markedly reduce the corrosion of the silver surface. In chlorine-free cleaners, preferred are 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. Preference is given here to the transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably from the group of the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt ( carbonyl) complexes, the chlorides of cobalt or manganese and of manganese sulfate. 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. Antifoams are preferably used in proportions of 0.001% by weight to 5% by weight. In addition, dyes such as patent blue, preservatives such as Kathon CG, perfumes or other fragrances may be added to the dishwashing detergent formulations according to the invention containing components a) and b) and c) and d).

The scarf cleaner formulations according to the invention for the automatic cleaning of dishes based on 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) after Hermann G. Hauthal, G. Wagner (eds): Cleaning and care agents in the household, Verlag für Chemische Industrie, Augsburg, 2003, ISBN 3-87846-230- 1 used:

example 1

Pentasodium triphosphate (NTPP) 45.5% proportion

Phosphonates (Hyodroxyethylenediamine) 5%

Sodium polycarboxylates 6%

Soda 20%

Sodium disilicate 5%

Sodium perborate 10%

Bleach activator TAED (tetraacetylethylenediamine) 2%

Protease and Amylase 4%

Low-foaming surfactants 2%

Silver protection 0.2%

Perfumes 0.2%

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

It was tested the pure aging performance and the material preservation of selected combinations.

VN 1: 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 with 5.5% Na citrate (not according to the invention) VN 5: NTPP reduced to 25%, supplemented with 20.5% Na IDS

VN 6: NTPP reduced to 20%, supplemented by 25.5% Na-IDS

VN 7: NTPP reduced to 15%, supplemented with 30.5% Na-ΪDS

VN 8: NTPP reduced to 10%, supplemented by 35.5% Na-IDS

Below are the results of a series of tests with these

Formulations were carried out. First, the cleaning performance was investigated, whereby in a series of experiments (Rl) without rinse aid; in the second (R2) worked with rinse aid has been. The assessment of the Remigungsleistung was carried out with a grading system, 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 (= Rl)

Grading scale ¹ egg yolk, rice, tomato / cheese: 0% = no cleaning effect, 100% = completely clean

support 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 rinse test with rinse aid:

Detergent dosage 20 g Tab

Water hardness 8-10 ^o dH

Series 2 (= R2). When testing the cleaning performance, rinse aid was added

Rinse aid 3 ml IEC Type III

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 formulation, better cleaning performance was achieved for tea stains; but not when using trisodium citrate as a substitute for one third of the phosphate content.

The tests with respect to protection of the material were carried out using a Miele G 666 SC turbothermic dishwasher with a Universal program 65 ⁰ C. Dosage 20 g - Tab over dosing chamber, rinse aid 3 ml IEC type IU, the water hardness was 0.1 ° dH.

Evaluation of results:

Grade 5 = no material attack / discoloration / irrigation Grade 4 = minor material attack / discoloration / iridescence Grade 3 = slight 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

claims

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

a) 25 to 54.9 wt .-% alkali metal polyphosphate, preferably Natriumtripoiyphosphat, and

b) from 0.1 to 30% by weight of odminodisuccinic acid and / or its alkali metal salts, preferably sodium salts,

for the production of material-saving dishwashing detergent formulations for automatic, automatic dishwashing.

2. Use according to claim 1, characterized in that the builder system in addition to the components a) and b) one or more complexing agents of the series nitrilotriacetic acid or its salts, hydroxyethylenediaminetriacetic acid or salts thereof,

Ethylenediaminetetraacetic acid or its salts, diethylenetriaminepentaacetic acid or its salts, methylglycinediacetic acid or its salts, glutamic diacetic acid or its salts, hydroxyiminodisuccinic acid or its salts; Ethylenediamindibernsteinsäure or their salts, aspartic acid diacetate and salts thereof.

3. Use according to claims 1 or 2, characterized in that as additional

Components polyacrylic acid or its salts, modified polyacrylic acid or its salts, polycarboxylates based Poϊyasparaginsäure or salts thereof, carboxymethylcellulose or its salts, oxidized starch or cellulose, metasilicates, phyllosilicates, orthosilicates, carbonate or bicarbonate can be used.

4. Dishwashing detergent formulations for machine dishwashing, characterized in that this as a builder system

b) 0.1 to 30 wt .-% iminodisuccinic acid and / or their Alkalisalaze, preferably sodium salts, and also

c) 1 to 15 wt .-% low-foaming nonionic surfactants and

d) 0.1 to 30 wt .-% bleach and optionally bleach activators.

5. Dishwashing detergent formulations according to claim 4, characterized in that these additionally e) 0.1 to 60 wt .-% further builders.

6. Dishwashing detergent formulations according to claim 4 or 5, characterized in that they additionally contain 0.1 to 8 wt .-% enzymes.

7. Dishwashing detergent formulations according to one of claims 4 to 6, characterized in that they contain 0.1 to 50 wt .-% of one or more other additives.

8. A machine cleaning process of crockery, characterized in that a dishwashing detergent formulation is used which acts as a builder system

a) 25 to 54.9 wt .-% alkali metal polyphosphate, preferably sodium tripolyphosphate, and

b) 0.1 to 30 wt .-% iminodisuccinic acid and / or their Alkalisalaze, preferably

Sodium salts, as well as

c) 1 to 15 wt .-% low-foaming nonionic surfactants and

d) 0.1 to 30 wt .-% bleaching agent and optionally bleach activators.

9. The method according to claim 8, characterized in that the dishwashing formulation is used as a powder or as a tab.