EP1076683B1 - Solid machine dishwashing detergent with phosphate and crystalline lamellar silicates - Google Patents

Abstract

A solid-form dishwasher detergent that contains a builder combination of conventional phosphates and crystalline layer silicates. Despite its phosphate content, the detergent provides improved protection to sensitive tableware, more particularly glasses and decorated tableware, and improved cleaning performance.

Description

The present invention relates to a machine dishwashing detergent which is in solid form and contains a builder combination of conventional phosphates and crystalline layered silicates. Such agents, despite their phosphate content improved protection for sensitive items, especially glasses and decorated items with known good cleaning performance and even partially improved cleaning performance compared to conventional phosphate-containing dishwashing detergents.

Since dishwashers have become more prevalent in households, it is known that the highly alkaline dishwashing detergents based on phosphate / metasilicate show very good cleaning performance, but behave unfavorably with regard to the corrosion of decorated dishes, i. Colored onglaze and inglaze decorations applied on porcelain, colorfully decorated glasses and gold decors lose their color intensity and shine over time.

The low-alkali citrate or phosphate based alkaline dishwashing detergents introduced on the market in recent years also show the above-mentioned effect, albeit to a lesser extent.

By adding larger amounts of water-soluble amorphous silicates, in particular amorphous disilicates, these disadvantages can be largely eliminated, but at the same time occur after a few rinse programs with disilicate-containing cleaners irreversible damage to glasses that make noticeable through opacities and Irisieren (dazzling colors).

European patent application EP-A-0 504 091 (Viking) describes phosphate-free automatic dishwashing detergents with very good cleaning performance on tea stains. The cleaners contain about 5 to 15 wt .-% crystalline layered silicates and additionally 10 to 15 wt .-% citric acid and additionally (co) polymeric polycarboxylates.

However, the total cleaning performance of such low alkaline dishwashing detergents is not sufficient in the case of problem soiling apart from tea. The tea cleaning performance is good, but it can be increased.

Machine dishwashing detergents which are described in the international patent application WO-A-94/16047 (Procter & Gamble) show by the use of builders, in a certain time released bleach and paraffin oil in amounts of 0.05 to 2.5 parts by weight. % Improvements in silver protection. Citrate-containing agents are clearly preferred. Other builders may be aluminosilicates, phosphates or else crystalline phyllosilicates. Combinations of phosphates and crystalline phyllosilicates are not suggested or advantages are not mentioned by the use of such builder combinations.

Finally, International Patent Application WO-A-96/12783 (Henkel) describes phosphate-free to low-phosphate machine dishwashing detergents with improved decorative and glass preservation and high tea cleaning performance based on citrate-containing formulations which contain crystalline layered silicates. However, the overall cleaning performance is also in this case, the improvement.

Although European Patent Application EP-A-0 416 366 (Hoechst) discloses a machine dishwashing detergent containing 30% by weight sodium tripolyphosphate, 30% by weight crystalline layered sodium silicate, preferably as proton donor mineral acid and / or polycarboxylic acids and / or hydroxypolycarboxylic acids and / or Phosphonic acids and / or their acid salts or esters and overall has a relatively low pH. Although such automatic dishwashing detergents already have good cleaning performance.

However, agents which contain crystalline layered silicates as a builder raw material also have the disadvantage that, because of the low rate of dissolution of the crystalline layered silicate, lime deposits on glass and dishes may occur. In addition, the raw material is very finely divided and with high dust content, which can lead to production problems both in the powder and granule production and in the production of dishwasher tablets.

There has not yet been a satisfactory solution to the problem, a decor and glass gentle cleaning in combination with a demanded by the consumer high cleaning performance problem soiling such as tea, milk / dairy products, egg / protein products and to ensure production-technically safe and problematic production.

The object of the present invention was therefore to provide a machine dishwashing detergent which does not have the abovementioned disadvantages, ie which does not cause damage to glass even after repeated use, at the same time has good tea cleaning performance, but also excellent total cleaning performance and both in the powder and Granule production as well as in the production of tablets without production problems can be produced.

Surprisingly, it has been found that this object can be achieved by phosphate-containing automatic dishwashing agents, if they contain, in addition to the phosphates, crystalline layered silicates in a certain processed form.

The present invention accordingly provides a solid machine dishwashing detergent which comprises conventional phosphates and further customary ingredients, wherein the agent comprises, in addition to the phosphates, as a further builder a granular additive which contains as essential constituents a crystalline layered silicate of the general formula (I)

NaMSi _x O _{2x + 1} yH ₂ O (I),

wherein M represents sodium or hydrogen, x is an integer from 1.9 to 22, preferably from 1.9 to 4, and y is a number from 0 to 33, and contains (co) polymeric polycarboxylic acid.

The conventional phosphates useful as builders in automatic dishwashing detergents include in particular alkali phosphates and polymeric alkali phosphates, which may be in the form of their alkaline neutral or acidic sodium or potassium salts. Examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium tripolyphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of from 5 to 1000, in particular from 5 to 50, and the corresponding potassium salts or mixtures of sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts , Particularly preferred are the salts of tripolyphosphate. Their amounts are based on the total formulation and calculated as anhydrous active substance, preferably in the range of above 30 wt .-% to 65 wt .-% and in particular from 35 to 60 wt .-%.

The crystalline layer-form silicates of the formula (I) are sold by Clariant GmbH (Germany) under the trade name Na-SKS, for example Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ .xH ₂ O, Kenyaite), Na. SKS-2 (Na ₂ Si ₁₄ O ₂₉ .xH ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ O ₁₇ .xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ .xH ₂ O, Makatite).

Particularly suitable for the purposes of the present invention are agents which contain crystalline sheet silicates of the formula (I) in which x is 2. Of these, especially Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O ₅ , natrosilite), Na-SKS-9 (NaH-Si ₂ O ₅ · H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ · 3H ₂ O, kanemite), Na-SKS-11 (t-Na ₂ Si ₂ O ₅₎ and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ). An overview of crystalline phyllosilicates is given, for example, in "Hoechst High Chem Magazine 14/1993" on pages 33-38 and in "Seifen-Ole-Fette-Wachse, 116 Volume, No. 20/1990" on pages 805-808 published article. According to the invention, at least part of the crystalline layer-form silicates of the formula (I) is introduced into the machine dishwashing detergent according to the invention via the builder additive used according to the invention. In a preferred embodiment of the invention, the crystalline layer-form silicates of the formula (I) are introduced into the machine dishwashing compositions according to the invention exclusively via the builder additive used according to the invention. Advantageously, the automatic dishwashing agents contain the crystalline layered silicate of the formula (I), introduced via the builder additive, in amounts of from 2 to at most 30% by weight, preferably in amounts of from 3 to 25% by weight and in particular in amounts of 4 to 20 wt .-%.

In the context of the present invention, a (co) polymeric polycarboxylic acid is understood as meaning a homopolymer or copolymer which is not or only partially neutralized. These include the homopolymers of acrylic acid or methacrylic acid or their copolymers with other ethylenically unsaturated monomers such as acrolein, dimethylacrylic acid, ethylacrylic acid, vinylacetic acid, allylacetic acid, maleic acid, fumaric acid, itaconic acid, meth (allylsulfonic acid), vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid and phosphorous groups Monomers such as vinylphosphonic acid, allylphosphoric acid and acrylamidomethylpropanephosphonic acid and salts thereof, and hydroxyethyl (meth) acrylate sulfates, allyl alcohol sulfates and allyl alcohol phosphates. Such polymers are described, for example, in the German Patent applications DE-A-23 57 036, DE-A-44 39 978 and European patent applications EP-A-0 075 820 or EP-A-0 451 508.

Preferred (co) polymers have an average molar mass of from 1000 to 100000 g / mol, preferably from 2000 to 75000 g / mol and in particular from 2000 to 35000 g / mol. The degree of neutralization of the acid groups is advantageously from 0 to 90%, preferably from 10 to 80% and in particular from 30 to 70%.

Particularly suitable polymers include homopolymers of acrylic acid and copolymers of (meth) acrylic acid with maleic acid or maleic anhydride.

Further suitable copolymers are derived from terpolymers which are obtained by polymerization of 10 to 70% by weight of monoethylenically unsaturated dicarboxylic acids having 4 to 8 C atoms or salts thereof, 20 to 85% by weight of monoethylenically unsaturated monocarboxylic acids having 3 to 10 C atoms or their salts, 1 to 50 wt .-% of monounsaturated monomers which release after hydrolysis hydroxyl groups on the polymer chain, and 0 to 10 wt .-% of further free-radically copolymerizable monomers. For the application according to the invention, saponification of the monounsaturated monomers which release a hydroxyl group on the polymer chain after saponification in an acidic medium is preferred. Products of the abovementioned type are described in German patent applications DE-A-43 00 772 and DE-A-195 16 957 and in WO-A-94/15978, respectively.

Also suitable are graft polymers of monosaccharides, oligosaccharides, polysaccharides and modified polysaccharides, as described in the German patent applications DE-A-40 03 172 and DE-A-44 15 623. The graft polymers disclosed in the European patent application with proteins of animal or vegetable origin, in particular with modified proteins, are likewise very suitable.

Copolymers are selected from the group of the graft copolymers preferably used of sugar and other polyhydroxy compounds, and a monomer mixture of the following composition 45 to 96 wt .-% of monoethylenically unsaturated C ₃ - to C ₁₀ monocarboxylic acid or mixtures of C ₃ - to C ₁₀ monocarboxylic acids and or their salts with monovalent cations, monomers containing 4 to 55% by weight of monoethylenically unsaturated monosulfonic acid groups, monoethylenically unsaturated sulfuric esters, vinylphosphonic acid and / or the salts of these acids with monovalent cations and 0 to 30% by weight of water-soluble, monoethylenically unsaturated compounds, with 2 to 50 moles of alkylene oxide per mole of monoethylenically unsaturated compound are modified. Such compounds are described in DE-A-42 21 381 and in DE-A-43 43 993.

Other suitable polymers are polyaspartic acids or their derivatives in non-neutralized or partially neutralized form. Usually, the polyaspartic acids are obtained in the form of their alkali metal or ammonium salts. From these it is possible to obtain the products which have not been neutralized or only partially neutralized by addition of appropriate amounts of organic or inorganic acids and, if appropriate, separation of the resulting salts.

Such products can also be obtained by the thermal reaction of maleic acid and ammonia or by the condensation of aspartic acid and the subsequent hydrolysis of the resulting polysuccinimide. The production of such products is described for example in DE-A-36 26 672, DE-A-43 07 114, DE-A-44 27 287, EP-A-0 612 784, EP-A-0 644 257 and WO -A-92/14753.

Also particularly suitable are graft polymers of acrylic acid, methacrylic acid, maleic acid and other ethylenically unsaturated monomers to salts of polyaspartic acid, as usually obtained in the hydrolysis of the polysuccinimide described above. This can be dispensed with the otherwise necessary addition of acid for the preparation of only partially neutralized form of polyaspartic acid. The amount of polyaspartate is usually chosen so that the degree of neutralization of all incorporated in the polymer carboxyl groups does not exceed 80%, preferably 60%. Products of the type mentioned are described in more detail in International Patent Application WO-A-94101486.

The amounts in which the (partially) neutralized (co) polymeric polycarboxylates are present in the compositions according to the invention are determined by the content of the builder additives used according to the invention and their content of these polymers.

The builder additive used according to the invention contains the crystalline layered silicate of the formula (I) and the (co) polymeric polycarboxylic acid preferably in weight ratios of (40 to 1): 1, in particular of (20 to 2): 1, where ratios of 7 : 1 to about 3: 1, in each case based on the anhydrous calculated active substances, may be particularly advantageous. The water content of the builder additives used according to the invention is preferably from 4 to 20% by weight, the upper meaningful value is made dependent on the water content thereof, that the builder additive should be stable and free-flowing even after storage at elevated temperatures of for example 40 ° C and should not clump. It has been found that the lower value for the water content influences the dissolving behavior of the builder additive. For reasons of the higher rate of dissolution of the builder additive, it is therefore preferable to use additives which contain from 5 to 15% by weight of water and in particular from 7 to 12% by weight of water. The determination of the water content takes place at a temperature of 140 ° C and a duration of 4 hours.

The builder additives used according to the invention can be prepared by simply contacting the crystalline layered silicate of the formula (I) with an aqueous solution, preferably a concentrated aqueous solution of the (co) polymeric polycarboxylic acid and optionally subsequent drying to the desired water content. Conventional mixing and granulating devices, such as the ploughshare mixer from Lödige or a Schugi mixer or an Eirich mixer or a Lödige recycler CB 30 and other apparatus known to those skilled in the art, which allow in particular the jetting of a liquid onto a solid, are just as suitable as fluidized bed apparatus. The polymer solution serves as an agglomeration aid. It is believed that in the reaction of the crystalline layered sodium silicate of formula (I) with the acidic polymer, especially at pH values of the polymer solution used of less than 4, a portion of the sodium ions of the silicate is exchanged for protons. However, the silicate framework with its layer structure and the majority of the sodium ions remain unchanged. As a result, the builder additives used according to the invention have only a slightly reduced starting alkalinity, but a significantly lower residual alkalinity than the pure crystalline layered silicate of the formula (I). The residual alkalinity can be adjusted accordingly by the content of the additives of polymer acid. The builder additive can therefore be used as a buffer substance in automatic dishwashing detergents.

The builder additives may contain high levels of (co) polymeric polycarboxylic acid, with amounts between 2 and 40% by weight being preferred and amounts between 5 and 30% by weight being particularly preferred, and amounts between 10 and 25% by weight being quite are particularly preferred. The content of the builder additives on the crystalline layered silicates of the formula (I) is preferably 50 to 90% by weight, more preferably 60 to 90% by weight and most preferably 65 to 85% by weight. The calcium binding capacity of the additives is preferably above 185 mg CaCO ₃ / g. The pH of a 0.1% strength by weight aqueous solution is preferably above 10, but below 20 ° C. of 12. The bulk density of the additives used according to the invention varies according to the nature of its preparation and is usually in the range from above 400 to about 700 g / l. While pure crystalline layered silicate of the formula (I) such as SKS6® usually obtains very finely divided and also has high amounts of dust fractions, the builder additive used according to the invention is a coarse-grained powder to agglomerate / granules, which is finer when prepared in the fluidized bed and coarser, for example when made in a high speed mixer. Coarser-grained additives have, for example, an average particle size (d50) of about 450 to 900 μm, while finer-particle additives have an average particle size (d50) of between about 280 and 330 μm. But even with the finely divided additives, the dust content is significantly lower than in the commercially available pure crystalline layered silicates of the formula (I), in particular as in SKS6®.

The content of the automatic dishwashing agents according to the invention in these builder additives can be varied within a wide range and depends both on the content of the dishwashing detergent formulation on crystalline layered silicates of the formula (I) and on the content of the selected builder additive in this crystalline layered silicate , Usual levels of the phosphate-containing automatic dishwashing agents on these builder additives are about 2 to 40 wt .-%, with contents of 5 to 35 wt .-% and in particular to 30 wt .-% are preferred.

The automatic dishwashing compositions according to the invention, which may be in the form of granules, powdered or tablet-form solids or other solid shaped bodies, may contain, in addition to the ingredients used according to the invention, in principle all known ingredients customary in such agents. The agents according to the invention may in particular be further builders, surface-active surfactants, bleaches based on organic and / or in particular inorganic peroxygen compounds, bleach activators, enzymes, sequestering agents, electrolytes, pH regulators and / or further auxiliaries, for example silver corrosion inhibitors, foam regulators and dyes and fragrances contain. In tablets or other moldings and conventional disintegrating agents can be used in conventional amounts.

In addition to the phosphates and the builder additives, the automatic dishwasher detergents according to the invention may also contain one or more further builder substances from the group consisting of carbonates, bicarbonates, amorphous silicates, crystalline layered silicates, which have not been introduced via the additive, and the polyfunctional carboxylic acids or their Salts, especially citric acid or citrate.

In a preferred embodiment of the invention, however, the compositions do not contain any crystalline layered silicates of the formula (I) which have not been incorporated into the formulation via the builder additive. The agents may additionally contain further (co) polymeric polycarboxylates of the conventional type, which are likewise water-soluble and which can serve as co-builders, in particular under hard water conditions. For example, polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymeric acids may be considered. Commercially available products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF. Further commercially available and usable polymers are, for example, POC QUAL AS 2507® (Degussa), Norasole® such as Norasol LMW 45N®, Norasol SP 02N® or Norasol 470 N® (Rohm & Haas) or Alcosperse 175 N® (Alco). Examples of suitable co-builder polymers of native origin include oxidized starch, for example as disclosed in international patent application WO 94/05762 and polyamino acids such as polyglutamic acid or polyaspartic acid. Other possible builder components are naturally occurring hydroxycarboxylic acids such as mono-, dihydroxy-succinic acid, α-hydroxypropionic acid and gluconic acid. Preferred organic builder components include the salts of citric acid, especially sodium citrate. As sodium citrate, anhydrous trisodium citrate and preferably trisodium citrate dihydrate are suitable. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder. Depending on the pH value ultimately set in the agents according to the invention, the acids corresponding to the said co-builder salts may also be present. The automatic dishwasher detergents according to the invention preferably contain not more than 2% by weight of this (co) polymeric polycarboxylates additionally and not via the builder additive; in particular, the agents are even free of such (co) polymeric polycarboxylates introduced additionally and not via the builder additive.

Carbonates and bicarbonates are among the commonly used alkali carriers. The agents according to the invention may contain their sodium and / or potassium salts, for example in an amount of from 10 to 40% by weight, preferably from 15 to 30% by weight, based on the total agent.

Because of the possible negative effects of amorphous silicates and in particular amorphous sodium silicates with a weight ratio Na ₂ O: SiO ₂ of 1: 1.8 to 1: 3.3, in particular up to 1: 2.5, these alkali carriers are preferably in amounts of less than 4% by weight, in particular less than 2% by weight in the mechanical Dishwashing agents contain, with particularly preferred means advantageously free of amorphous silicates, are also free of metasilicates.

Suitable peroxygen compounds are, in particular, organic peracids or peracid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the washing or cleaning conditions, such as perborate, percarbonate and / or persilicate. Hydrogen peroxide can also be produced by means of an enzymatic system, ie an oxidase and its substrate. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle. Particular preference is given to using alkali metal percarbonate, alkali metal perborate monohydrate, alkali metal perborate tetrahydrate or hydrogen peroxide in the form of aqueous solutions which contain from 3% by weight to 10% by weight of hydrogen peroxide. If a cleaning agent according to the invention contains peroxygen compounds, these are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight. The addition of small amounts of known bleach stabilizers such as phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.

However, typical oxygen bleaches are also the organic peracids. Among the preferred organic peracids, especially the excellent effective Phthalimidoperoxycapronsäure, but also all other known peracids are principally usable.

As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl or Isononanoyloxybenzolsulfonat (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and from German patent applications DE 196 16 693 and DE 196 16 767 known enol esters and acetylated sorbitol and mannitol or their mixtures described in European Patent Application EP 0 525 239 (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfruktose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and or N-acylated lactams, for example N-benzoyl-caprolactam, which are known from international patent applications WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95/14759 and WO 95/17498. The hydrophilic substituted acyl acetals known from the German patent application DE 196 16 769 and the acyllactams described in the German patent application DE 196 16 770 and the international patent application WO 95/14075 are also preferably used. The combinations of conventional bleach activators known from German patent application DE 44 43 177 can also be used. Such bleach activators are contained in the customary amount range, preferably in amounts of from 1% by weight to 10% by weight, in particular from 2% by weight to 8% by weight, based on the total agent.

In addition to or in place of the conventional bleach activators listed above, the sulfone imines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0 446 982 and EP 0 453 003 may also be present as so-called bleach catalysts. Suitable transition metal compounds include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum-salene complexes known from German patent application DE 195 29 905 and their N-analogues known from German patent application DE 196 20 267, which are known from US Pat German Patent Application DE 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl, the described in the German patent application DE 196 05 688 manganese, iron, cobalt, ruthenium, molybdenum, titanium , Vanadium and copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium-ammine complexes known from German patent application DE 196 20 411, the manganese described in German patent application DE 44 16 438, Copper and cobalt complexes, the cobalt complexes described in European patent application EP 0 272 030, the manganese complex known from European patent application EP 0 693 550 xe, the manganese, iron, cobalt and copper complexes known from European patent EP 0 392 592, which are known from the international Patent applications WO 96/23859, WO 96/23860 and WO 96/23861 known cobalt complexes and / or in the European patent EP 0 443 651 or the European patent applications EP 0 458 397, EP 0 458 398, EP 0 549 271, EP 0 549 272, EP 0 544 490 and EP 0 544 519 describe manganese complexes. Combinations of bleach activators and transition metal bleach catalysts are known, for example, from German patent application DE 196 13 103 and international patent application WO 95/27775. Bleach-enhancing transition metal complexes, in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in customary amounts, preferably in an amount of up to 1% by weight, in particular 0.0025% by weight. % to 0.25 wt .-% and particularly preferably from 0.01 wt .-% to 0.1 wt .-%, each based on the total agent used. A bleach-enhancing active ingredient combination which is obtainable by intimately mixing a water-soluble salt of a divalent transition metal selected from cobalt, iron, copper and ruthenium and mixtures thereof, a water-soluble ammonium salt and optionally a peroxygen-based oxidizing agent and inert carrier material is described, for example, in the earlier German patent application P 197 09 284.5 described.

Although chlorine-containing bleaching agents may in principle be present in the compositions according to the invention and the invention also includes chlorine-containing formulations, it is preferred to use exclusively chlorine-free bleaching agents.

Automatic dishwashing detergents according to the invention may contain corrosion inhibitors as ingredients for the protection of the items to be washed or the machine, with silver protectants in particular being of particular importance in the field of automatic dishwashing. Can be used, the known substances of the prior art, such as. As described in DE 43 25 922, DE 41 28 672 or DE 43 38 724. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. It can according to the above writings particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts, which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the Cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds can be used to prevent corrosion on the items to be washed. These silver protectants may usually be present in amounts of up to about 5% by weight.

Enzymes which can be used in the compositions include those from the class of proteases, lipases, cutinases, amylases, pullulanases, oxidases and peroxidases, glucanases and mixtures thereof, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem® , Alcalase®, Esperase®, Savinase®, Durazym® and / or Purafect® OxP, amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and / or Purafect® OxAm, lipases such as Lipolase®, Lipomax®, Lumafast ® and / or Lipozym®. Particularly suitable are from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia derived enzymatic agents. These optionally additionally used enzymes can also be adsorbed on carriers and / or embedded in encapsulating substances, as described, for example, in European patent EP 0 564 476 or in international patent application WO 94/23005, and / or embedded in encapsulating substances in order to protect them against premature inactivation. They are preferably present in the dishwasher detergents according to the invention in amounts of up to 10% by weight, in particular from 0.05% by weight to 5% by weight, particularly preferably enzymes which are stabilized against oxidative degradation, for example from US Pat international patent applications WO 94/02597, WO 94/02618, WO 94/18314, WO 94/23053 or WO 95/07350. Preferred proteases used in agents according to the invention include the enzymes known from international patent applications WO 91/02792, WO 92/21760 and WO 95/23221.

If appropriate, surfactants, in particular low-foaming nonionic surfactants, optionally in admixture with anionic and / or zwitterionic surfactants, which serve to better remove greasy soilings, as wetting agents and optionally as granulating aids in the preparation of the cleaning agents, may also be added to the compositions according to the invention. Their amount can be up to 10 wt .-%, in particular up to 5 wt .-% and is preferably in the range of 0.5 wt .-% to 3 wt .-%. Usually, extremely low-foam compounds are used in particular in detergents for use in automatic dishwashing processes. These include preferably C ₁₂ -C ₁₈ -Alkylpolyethylenglykolpolypropylenglykolether with in each case to 8 moles of ethylene oxide and propylene oxide in the molecule. But you can also use other known low-foam nonionic surfactants, such as C ₁₂ -C ₁₈ alkylpolyethylene glycol polybutylenglykolether with up to 8 moles of ethylene oxide and butylene oxide in the molecule, endgruppenverschlossene Alkylpolyalkylenglykolmischether and foaming, but ecologically attractive C ₈ -C ₁₄ -Alkylpolyglucoside having a degree of polymerization of about 1 to 4 (eg APG® 225 and APG® 500 from Henkel) and / or C ₁₂ -C ₁₄ alkyl polyethylene glycols having 3 to 8 ethylene oxide units in the molecule. Also suitable are surfactants from the family of glucamides, such as, for example, alkyl-N-methylglucamides, in which the alkyl moiety preferably originates from a fatty alcohol with the C chain length C ₆ -C ₁₄ . It is partially advantageous if the surfactants described are used as mixtures, for example the combination of alkyl polyglycoside with fatty alcohol alkoxylates or glucamide with alkyl polyglycosides. Also particularly preferred are the hydroxyl-containing alkoxylated alcohols, as described in EP-A-0300305. It was found that these hydroxy mixed ether surfactants show an excellent clear rinse effect. This is particularly preferred for mixtures with other nonionic surfactants, such as fatty alcohol alkoxylates, for example Dehypon LS 54®, and also in mixtures with Dehydol LS 4®, but also for mixtures of hydroxy mixed ether and APG® or for mixtures of fatty alcohol ethoxylates, hydroxy mixed ethers and alkyl polyglycoside. In addition to the clear rinsing effect, these surfactant mixtures also contribute to the fact that the stress corrosion cracking of plastic is significantly reduced.

Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations. Usable soaps are preferably the alkali salts of the saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in incompletely neutralized form. Useful surfactants of the suifat type include the salts of the sulfuric acid half-esters of fatty alcohols having 12 to 18 carbon atoms and the sulfation products of said nonionic surfactants having a low degree of ethoxylation. Suitable surfactants of the sulfonate type include linear alkylbenzenesulfonates having 9 to 14 carbon atoms in the alkyl moiety, alkane sulfonates having 12 to 18 carbon atoms, and olefin sulfonates having 12 to 18 carbon atoms, which are formed in the reaction of corresponding monoolefins with sulfur trioxide, and α-sulfofatty acid esters formed in the sulfonation of fatty acid methyl or ethyl esters.

If the cleaning agents, for example in the presence of anionic surfactants, foam too much during use, they may still contain up to 6% by weight, preferably approximately 0.5 wt .-% to 4 wt .-% of a foam-pressing compound, preferably from the group of silicone oils, mixtures of silicone oil and hydrophobized silica, paraffins, paraffin-alcohol combinations, hydrophobized silica, the Bisfettsäureamide, and other further known in the Commercially available defoamers are added. Further optional ingredients in the compositions according to the invention are, for example, perfume oils.

The automatic dishwasher detergents according to the invention are in solid form. They may be pulverulent to granular or may be in the form of a shaped body, in particular a tablet. They can be prepared conventionally, for example by mixing, granulating, compacting, such as roll compacting, tabletting and / or spray-drying. In some cases, the ingredients can also be used in precompounded form for the preparation of automatic dishwashing detergents according to the invention.

The tablets may be single-phase or multiphase, monochrome or multicolor and in particular consist of one or more layers, in particular two layers, as are already commercially available. The builder additive may be present in multilayer tablets either only in one layer, but also distributed over several to all layers.

For the preparation of detergents according to the invention in tablet form, the procedure is preferably such that all components - optionally one layer - mixed together in a mixer and the mixture by means of conventional tablet presses, such as eccentric or rotary presses, with compressive forces in the range of about 50 to 100 kN , preferably compressed at 60 to 70 kN. Particularly in the case of multilayer tablets, it may be advantageous if at least one layer is pre-compressed. This is preferably carried out at pressing forces between 5 and 20 kN, in particular at 10 to 15 kN. This gives fracture-resistant and yet sufficiently rapidly soluble tablets under application conditions with breaking and bending strengths of normally 100 to 200 N, but preferably above 150 N. Preferably, a tablet produced in this way has a weight of 15 g to 40 g, in particular 20 g up to 30 g. The spatial form of the tablets is arbitrary and can be round, oval or angular, with intermediate forms are also possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm. In particular, the size of square / cuboid-shaped tablets, which are introduced predominantly via the metering device in the dishwasher, depends on the geometry and the volume of this metering device. Exemplary preferred embodiments currently have a footprint of (20 to 30 mm) x (34 to 40 mm), in particular 26 x 36 mm or 24 x 38 mm.

The preparation of machine dishwashing detergents in the form of non-dusting, storage-stable free-flowing powders and / or granules with high bulk densities in the range of 750 to 1200 g / l is characterized in that in a first process step, the builder components with at least a proportion of liquid mixture components Increase the bulk density of this premix and subsequently - if desired after an intermediate drying - the other components of the machine dishwashing detergent combined with the thus obtained premix.

The addition of the agents according to the invention is carried out either by hand or - as already indicated above - by means of suitable metering devices. The application concentrations in the main cleaning cycle, irrespective of whether a prewash cycle has taken place or not, are preferably about 2 to 8 g / l, preferably 2 to 5 g / l.

The rinsing program is generally supplemented and terminated by an intermediate rinse with clear water following the cleaning cycle and a rinse cycle, if appropriate with a common rinse aid. After drying, a completely clean, freed from tea and other soiling residues and hygienically perfect dishes. Even after very many rinses, the advantages are significantly recognizable by the use of the agents according to the invention, such as improved glass protection or decorative protection.

However, the automatic dishwashing compositions according to the invention not only show a very good cleaning performance on tea stains; There are also compared to automatic dishwashing detergents with comparable compositions containing phosphates and crystalline layered silicates of the formula (I), but the latter as a powder and not in the form of the builder additive used in the invention, significant improvements in the removal of proteinaceous soils and soils caused by dairy products achieved. Production-technical production of the powders, granules or tablets according to the invention took place without problems, in contrast to formulations which contained finely divided crystalline stratified silicate.

Examples example 1

25 g tablets of the compositions listed in Table 1 were pressed, TE 1 being the tablet according to the invention and TV 1 the direct comparison product. <u> Table 1 </ u>: Compositions of TE1 and TV1 (in% by weight, respectively) TE1 TV1 Tripolyphosphate (based on anhydrous active substance) 51.0 51.0 amorphous sodium disilicate (based on anhydrous active substance) --- 4.5 Sodium salt of the copolymer of acrylic acid and maleic anhydride (Sokalan CP5®) --- 2.1 Builder additive consisting of 6.0 --- 71% by weight of SKS 6® 20% by weight terpolymer 9% by weight of water sodium 17.0 16.5 sodium perborate 9.0 9.0 Bielch activator TAED 2.1 2.1 phosphonate 0.9 0.8 Dehypon LS 54® 1.5 1.5 Dehypon LT 104® 0.5 0.5 enzyme 3.8 3.7 Perfume, dye, tableting aids, silver protectants and water rest rest

Dehypon LS 54® and Dehypon LT 104® are two low-foaming fatty alcohol alkoxylates from Henkel.

The terpolymer contained in the builder additive was prepared according to the disclosure of WO-A-94/15978 from 80% by weight of acrylic acid and maleic acid in a weight ratio of 7: 3 and from 20% by weight of vinyl acetate and then saponified in an acidic medium. The terpolymer was purchased from Stockhausen.

• 0 : unverändert
• 1 : leichte Veränderungen, noch akzeptabel
• 2 : mittlere Veränderung, noch akzeptabel
• 3 : starke Veränderung, nicht mehr akzeptabel
• 4 : sehr starke Veränderung, nicht mehr akzeptabel.

Tabelle 2a: Werte für TE 1 und TV 1 nach 100 Spülzyklen Material TE1 TV1 Kalknatronglas T 1-2 I 0 T 2-3 I 0 Kalikristallglas T 1 I 0 T 3 I 2 Bleikristallglas T 0 I 0 T 0 I 3 Tabelle 2b: Werte für TE1 und TV 1 nach 150 Spülzyklen Material TE1 TV1 Kalknatronglas T 1-2 I 0 2 0 Kalikristallglas T 1 I 0 T 3-4 I 1 Bleikristallglas T 0 I 0 T 0 I 3 The effects of the tablets TE1 and TV1 on sensitive dishes were in a dishwasher Miele G 570 or G 575, which were converted to continuous operation, (built in 1993) in the program Universal 65 ° C at dosages of one dishwashing tablet and 50 g of soiling mixture from fats, egg whites, starch, milk, coloring matter and preservatives in 5.0 1 water with a hardness of 0 to 1 ° d in the cleaning cycle after 100 or 150 rinsing cycles on 3 soda lime glasses, potassium crystal glasses and lead crystal glasses for turbidity (T) resp Irises (I) tested. The grading was done visually by employees trained in the screening of items to be washed. The scores given in Tables 2a and 2b were determined, with the lowest visible glass in each category being graded. The notes mean:

• 0: unchanged
• 1: slight changes, still acceptable
• 2: medium change, still acceptable
• 3: strong change, no longer acceptable
• 4: very strong change, no longer acceptable.

<u> Table 2a: </ u> Values for TE 1 and TV 1 after 100 rinse cycles material TE1 TV1 soda-lime glass T 1-2 I 0 T 2-3 I 0 Kalikristallglas T 1 I 0 T 3 I 2 Lead crystal glass T 0 I 0 T 0 I 3 material TE1 TV1 soda-lime glass T 1-2 I 0 2 0 Kalikristallglas T 1 I 0 T 3-4 I 1 Lead crystal glass T 0 I 0 T 0 I 3

Tables 2a and 2b clearly show the advantages of the tablet according to the invention TE1 compared to the comparative tablet TV1.

Example 2

Powders of the compositions shown in Table 3 were prepared in a conventional manner, with PE1 to PE3 being the agents of the invention and PV1 being the comparison agent. The powders were tested for material protection and deposit formation. The effects of the powders PE1 to PE3 and PV1 on sensitive items were measured as in Example 1 at a dosage of 25 g to 51 water after 100 (PE1 to PE3 and PV1) and 300 rinsing cycles (only PE1 and PE2, compared to PV1 after 100 Rinsing cycles). The results are shown in Tables 4a and 4b. <u> Table 3: </ u> Compositions of PE1 to PE3 and PV1 (in% by weight) PV1 PE1 PE2 PI3 Premix of: Makrophos® (tripolyphosphate) (75.83 wt.%) Sodium carbonate (21.41 wt.%) Dehypon LS 54® (2.07 wt.%) Dehypon LT 104® (0.69 wt. -% 72.53 71.9 72.8 --- Makrophos® --- --- --- 51.8 Dehypon LS 54® --- --- --- 1.5 Dehypon LT 104® 0.5 amorphous sodium disilicate (based on anhydrous active substance) 4.0 --- --- --- Builder additive consisting of --- 5.63 11.5 28.2 71% by weight of SKS 6® 20% by weight terpolymer 9% by weight of water Sodium perborate monohydrate (compact) with soda in the ratio 9: 1 10.0 10.0 10.0 10.0 Bleach activator TAED 2, 2.1 2.1 2.1 enzymes 3.4 3.4 3.4 3.4 sodium 5.75 5.75 --- 1.8 Perfume, dye, silver protectant, water rest rest Rest (no silver protectant) rest material PV1 PE1 PE2 PI3 soda-lime glass T 3 I 0 T0 I 0 T1 I 0 T3 I 0 Kalikristallglas T 3 I 0 T0 I 0 T1 I 0 T3 I 0 Lead crystal glass unchanged unchanged unchanged unchanged material PV1 PE1 PE2 soda-lime glass T 3 I 0 T 1 I 0 T 1 I 0 Kalikristallglas T 3 I 0 T1 I 0 T 1 I 0 Lead crystal glass unchanged unchanged unchanged

Tables 4a and 4b clearly show the advantages of the formulations according to the invention PE1 and PE2 compared to PV1. Even with a high content of builder additive of 28.2% by weight in PE3 corresponding to an active substance content of crystalline layered disilicate of 20% by weight, similar values are obtained as for PV1 with 4% by weight of amorphous sodium disilicate , However, as Table 5 shows, PE3 also had significant advantages over PV1 when color loss was measured on decorated glass plates. For this purpose, in addition to the above-mentioned glasses, red-decorated glass plates of the "Arcopol" brand, "Bande rouge" decor were also tested under the same cleaning conditions. The color loss FV was determined after 50 or 150 rinsing cycles. The assigned grades have the same meaning as stated above. <u> Table 5: </ u> Paint loss on decorated glass plates rinse cycles PV1 PE1 PE2 PI3 50 FV 2 FV 2 FV 2 FV 0 150 FV 4 FV 4 FV 4 FV 1

Example 3

The cleaning performance of an agent according to the invention PE4 compared to a comparison agent PV2, which contained SKS6® as a powder and not according to the invention as a builder additive, was tested (see also Table 6). The results are summarized in Table 7. Table 6: Compositions of PE4 and PV2 (in% by weight) PE4 PV2 Tripolyphosphate (Thermphos® 1018) 40.0 48.0 SKS 6® --- 20.0 Builder additive (as above) 15.5 --- sodium 27.5 15.0 sodium 10.0 10.0 TAED 2.0 2.0 Genapol 2909D® (nonionic surfactant) 2.0 2.0 protease 2.0 2.0 amylase 1.0 1.0 Genapol is a low foaming fatty alcohol alkoxylate from Clariant Anschmutzungsart PE4 PV2 oatmeal 88.0 80.0 egg 100 98.5 Minced meat, intense 100 100 spinach 100 100 tea 100 100 milk 81.0 67.0

Compared to phosphate-free formulations, the comparative formulation PV2 had clear advantages, in particular with minced meat, spinach and tea. The formulation according to the invention improved these services in addition to egg and protein-containing stains and quite clearly to milk and stains of dairy products and oatmeal.

Claims (14)

1. A solid dishwasher detergent containing conventional phosphates and other typical ingredients, characterized in that a granular additive containing a crystalline layer silicate corresponding to general formula (I):
   
           NaMSi_xO_2x+1 · y H₂O     (I)
   
   in which M is sodium or hydrogen, x is a number of 1.9 to 22 and Y is a number of 0 to 33, and (co)polymeric polycarboxylic acid as key constituents is present as another builder in addition to the phosphates.
2. A detergent as claimed in claim 1, characterized in that it contains the crystalline layer silicate corresponding to formula (I) introduced through the builder additive in quantities of 2 to at most 30% by weight, preferably in quantities of 3 to 25% by weight and more preferably in quantities of 4 to 20% by weight.
3. A detergent as claimed in claim 1 or 2, characterized in that it contains phosphates, more particularly salts of the tripolyphosphate, in quantities, expressed as water-free active substance and based on the formulation as a whole, of more than 30% by weight to 65% by weight and more particularly in the range from 35 to 60% by weight.
4. A detergent as claimed in any of claims 1 to 3, characterized in that it contains one or more other builders from the group of carbonates, hydrogen carbonates, amorphous silicates, crystalline layer silicates which have not been introduced through the additive, polybasic carboxylic acids and salts thereof.
5. A detergent as claimed in any of claims 1 to 4, characterized in that it contains amorphous silicates, more particularly amorphous sodium silicates with a ratio by weight of Na₂O to SiO₂ of 1:1.8 to 1:3.3 in quantities of less than 4% by weight and preferably in quantities of less than 2% by weight, detergents free from amorphous silicates being particularly preferred.
6. A detergent as claimed in any of claims 1 to 5, characterized in that it is present in the form of shaped bodies, more particularly in the form of tablets.
7. A detergent as claimed in any of claims 1 to 5, characterized in that it is present in the form of a powder or granules.
8. A detergent as claimed in any of claims 1 to 7, characterized in that it contains the builder additive in quantities of 2 to 40% by weight, preferably in quantities of 5 to 35% by weight and more preferably in quantities of up to 30% by weight.
9. A detergent as claimed in any of claims 1 to 8, characterized in that it contains a builder additive which contains 50 to 90% by weight, preferably 60 to 90% by weight and more preferably 65 to 85% by weight of crystalline layer silicate corresponding to formula (I), 2 to 40% by weight, preferably 5 to 30% by weight and more preferably 10 to 25% by weight of polymeric polycarboxylic acid and 4 to 20% by weight, preferably 5 to 15% by weight and more preferably 7 to 12% by weight water.
10. A detergent as claimed in claim 9, characterized in that the (co)polymeric polycarboxylic acid in the builder additive has a molecular weight of 1,000 to 100,000 g/mole, preferably 2,000 to 75,000 g/mole and more preferably 2,000 to 35,000 g/mole, the degree of neutralization of the acid groups being from 0 to 90%, preferably from 10 to 80% and more preferably from 30 to 70%.
11. A detergent as claimed in any of claims 1 to 10, characterized in that it contains oxygen bleaching agents and/or chlorine bleaching agents and optionally bleach activators and/or bleach catalysts.
12. A detergent as claimed in any of claims 1 to 11, characterized in that it contains surfactants, advantageously low-foaming nonionic surfactants.
13. A detergent as claimed in claim 12, characterized in that it contains C_12-18 alkyl polyethylene glycol polypropylene glycol ethers containing up to 8 moles ethylene oxide units and 8 moles propylene oxide units in the molecule, C_12-18 alkyl polyethylene glycol polybutylene glycol ethers containing up to 8 moles ethylene oxide units and 8 moles butylene oxide units in the molecule, end-capped alkyl polyalkylene glycol mixed ethers, C_8-14 alkyl polyglucosides with a degree of polymerization of about 1 to 4, C_12-14 alkyl polyethylene glycols containing 3 to 8 ethylene oxide units in the molecule, glucamides and/or hydroxy mixed ethers as nonionic surfactants.
14. A detergent as claimed in claim 12 or 13, characterized in that it contains mixtures of fatty alcohol alkoxylates and hydroxy mixed ethers or mixtures of alkyl polyglycoside and hydroxy mixed ethers or mixtures of fatty alcohol ethoxylates, hydroxy mixed ethers and alkyl polyglycoside.