EP1657295A1 - Compound comprising a zink salt and a crystalline, layered silicate - Google Patents

Abstract

Automatic dishwasher detergent or rinse aid contains zinc salt(s) and crystalline foliated silicate(s) (I), which may contain metal(s) selected from alkali and alkaline earth metals, a sub-group element, preferably zinc, iron or manganese, a main group III element and/or a main group V element. Automatic dishwasher detergent or rinse aid contains zinc salt(s) and crystalline foliated silicate(s) of formula (I); aA2O.bBO.cC2O3.dD2O5.xSiO2.fH2O (I); A : alkali metal and/or H; B : alkaline earth metal and/or a sub-group element, preferably Zn, Fe, Mn; C : main group III element and/or a sub-group element, preferably Fe; D : a main group V element and/or a sub-group element; a : 0.1; b : 0-0.5; c/x : 0-0.05; d/x : 0-0.25; x : 1.9-22; f : 0-40.

Description

The present invention is in the field of automatic dishwashing detergents. In particular, the present invention relates to automatic dishwashing detergents containing zinc salts and certain silicates.

With the progressive automation of various washing and cleaning processes in the home and industry, machine washing and cleaning agents for textiles and tableware have become increasingly important in recent decades.
The so-called lower alkaline cleaners required for automatic dishwashing frequently contain mixtures of sodium disilicate and soda as alkali carriers, builders such as citric acid, for example in conjunction with polycarboxylates, and preferably low-foaming nonionic surfactants. Furthermore, bleaching agents, bleach activators, silver and corrosion inhibitors and, to enhance the cleaning power, enzymes may be included. In a typical machine cleaning cycle, the dishes set in baskets are cleaned by intensive contact with the aqueous detergent solution at about 65 ° C and pH values between 9 and 11 and then rinsed clear.
An important criterion for the evaluation of a machine dishwashing detergent, apart from its cleaning performance, is the visual appearance of the dry dishes after cleaning. Possibly occurring calcium carbonate deposits on dishes or in the machine interior, for example, affect customer satisfaction and thus have causal influence on the economic success of such a detergent. Another long-standing problem with automatic dishwashing is the corrosion of glassware, which can usually manifest itself by the appearance of turbidity, streaks and scratches, but also by iridescence of the glass surface. The observed effects are based essentially on two processes, the leakage of alkali and alkaline earth ions from the glass in conjunction with hydrolysis of the silicate network, on the other hand in a deposition of silicate compounds on the glass surface. To avoid such corrosion processes, there are in the prior art a number of proposals, for example with regard to the use of zinc salts.

According to the teaching of US Pat. No. 3,677,820 (Whirlpool Corporation), a zinc strip mounted in the interior of the dishwasher prevents the corrosion of glass surfaces during the cleaning process.

Finally, European Patent Application EP 0 383 482 (Procter & Gamble Company) describes automatic dishwashing detergents containing insoluble zinc salts which are distinguished by improved glass corrosion protection. The insoluble zinc salts must have a particle size below 1.7 millimeters to achieve such an effect.

However, the use of silicates to prevent glass corrosion in automatic dishwashing has also been described.

For example, international patent application WO 96/12783 (Henkel KGaA) discloses phosphate-free to low-phosphate machine dishwashing detergents with improved decorative and glass protection based on citrate-containing formulations which contain crystalline layered silicates.

The subject of the international patent application WO 99/57237 (Clariant GmbH, Henkel KGaA) are phosphate-containing automatic dishwashing agents which contain a powdery to granular additive which contains as essential components a crystalline layered silicate of the general formula NaMSi _x O _{2x + 1} · y H ₂ O, wherein M represents sodium or hydrogen, x is a number from 1.9 to 22 and y is a number from 0 to 33, and have (co) polymeric polycarboxylic acid and also have excellent cleaning performance in addition to glass or decor-preserving effects.

It is an object of the present invention to provide a machine dishwashing detergent which does not corrosively change the surfaces of glassware, even after repeated use, in particular does not cause turbidity, streaks or scratches, nor iridescence of the glass surfaces. Preferably, an automatic dishwashing detergent additive should be provided which is suitable as a component of automatic dishwashing detergent of any kind, for example, as a component of powder, tablet, liquid formulations, cleaning foams or depot products, without restricting them by formulation.

It has now been found that the abovementioned objects are achieved by those compounds which contain at least one zinc salt and at least one crystalline layered silicate of the general formula (I)

a A ₂ O • b BO • c C ₂ O ₃ • d D ₂ O ₅ • x SiO ₂ • f H ₂ O (I),

in the A is an alkali metal and / or hydrogen, B is an alkaline earth metal and / or a sub-group element, preferably an element from the group zinc, iron manganese, C. Element of the third main group of the Periodic Table and / or a subgroup element, preferably iron, and D is an element of the Fifth Main Group of the Periodic Table and / or a subgroup element and further that 0 ≤ a ≤ 1; 0 ≤ b ≤ 0.5; 0 ≤ c / x ≤ 0.05; 0 ≤ d / x ≤ 0.25; 1.9 ≤ x ≤ 22; 0 ≤ f ≤ 40, characterized in that the contained zinc salt (s) and the contained crystalline layered silicate (s) with one or more further active and / or framework substance (s) formulated, in particulate form, as a compound present / present.

In a preferred embodiment of the present invention, the automatic dishwashing detergent or automatic dishwashing auxiliary comprises at least one zinc salt and at least one crystalline layered silicate of the general formula (I)

a A ₂ O • b BO • C ₂ O ₃ • d D ₂ O ₅ • x SiO ₂ • y H ₂ O (I),

in which A is an alkali metal and / or hydrogen, B is an alkaline earth metal and / or zinc, C is an element of the third main group of the Periodic Table and D is an element of the Fifth Main Group of the Periodic Table, and furthermore that 0 ≤ a ≤ 1; 0 ≤ b ≤ 0.5; 0 ≤ c / x ≤ 0.05; 0 ≤ d / x ≤ 0.25; 1.9 ≤ x ≤ 22; 0≤f≤40.

Finally, it is particularly preferred that the automatic dishwashing or machine dishwashing auxiliary comprises at least one zinc salt and at least one crystalline layered silicate of the general formula (I)

a A ₂ O • b BO • c C ₂ O ₃ • d D ₂ O ₅ • x SiO ₂ • y H ₂ O (I),

in which A is an alkali metal and / or hydrogen, B is an alkaline earth metal, C is an element of the third main group of the Periodic Table and D is an element of the Fifth Main Group of the Periodic Table, and further that 0 ≤ a ≤ 1; 0 ≤ b ≤ 0.5; 0 ≤ c / x ≤ 0.05; 0 ≤ d / x ≤ 0.25; 1.9 ≤ x ≤ 22; 0≤f≤40.

In particularly preferred agents according to the invention, the crystalline layered silicate contains, by weight, up to 10 mol%, preferably between 0.01 and 10 mol%, preferably between 0.01 and 8 mol% and in particular between 0.01 and 5 mole% boron.

In a further preferred embodiment of the agents according to the invention, the crystalline, layered silicate contains up to 50 mol%, preferably between 0.01 and 50 mol%, preferably between 0.01 and 40 mol% and in particular between 0.01 and 20 Mol% phosphorus.

In a further preferred embodiment of the composition according to the invention, for the formula (I): a = 1 and b = c = d = 0; A is sodium or sodium or hydrogen. The preferred subject matter of the present application is therefore dishwasher detergents or dishwashing assistants containing at least one zinc salt and at least one crystalline layered silicate of the general formula (Ia)

NaMSi _x O _{2x + 1} · y H ₂ O (Ia),

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.
It has proved to be particularly advantageous for the corrosion-inhibiting action of agents according to the invention if the zinc salt (s) and / or the crystalline layered silicate (s) of the general formula (I) or the general formula (la) in the ratio 10: 1 to 1:50, preferably from 5: 1 to 1:30 and in particular from 3: 1 to 1:10 are contained in these agents.

The crystalline layer-form silicates of the formula (Ia) are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS, eg 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 (Ia) 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 (NaHSi 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 sheet silicates can be found, for example, in the article published on pages 805-808 in "Soaps Oils-Fette-Wachse, 116 Volume, No. 20/1990".

In the context of the present application, preferred automatic dishwashing detergents or dishwashing assistants have a weight fraction of the crystalline layered silicate of the general formula (I) or of the general formula (Ia) of from 0.1 to 20% by weight, preferably from 0.2 to 15 Wt .-% and in particular from 0.4 to 10 wt .-%, each based on the total weight of these agents, on.

Compositions according to the invention contain, in addition to the crystalline layered silicates mentioned, zinc salts, it being possible to use both inorganic and organic salts. A non-exhaustive list of some preferred zinc salts is shown in the following table: zinc salt solubility Zinc acetate dihydrate 430 g / l (20 ° C) zinc acetylacetonate 4 g / l (20 ° C) zinc bromide 820 g / l (25 ° C) zinc chloride 4320 g / l (25 ° C) zinc gluconate 100 g / l (20 ° C) zinc hydroxycarbonate Almost insoluble (20 ° C) zinc iodide 4500 g / l (20 ° C) Zinc nitrate hexahydrate 1843 g / l (20 ° C) Zinc nitrate tetrahydrate Slightly soluble (20 ° C) zinc oxide Insoluble zinc stearate 0.9 mg / l (20 ° C) Zinc sulfate Heptahydat 960 g / l (20 ° C) Zinc sulphate monohydrate ~ 350 g / l (20 ° C)

In addition to the insoluble inorganic zinc salts, ie salts which have a solubility below 100 mg / L (20 ° C), preferably below 10 mg / L (20 ° C), in particular no solubility (20 ° C) (Ex .: zinc oxide ), are in the context of the present application, the soluble inorganic interest salts, that is, salts having a solubility in water above 100 mg / L, preferably above 500 mg / L, more preferably above 1 g / L and especially above 5 g / L , preferred ingredient of agents according to the invention. Preferred soluble inorganic salts include zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate. Another preferred subject matter of the present application is therefore automatic dishwashing or dishwashing auxiliaries which contain at least one zinc salt selected from the group of inorganic zinc salts, preferably from the group of soluble inorganic zinc salts, in particular from the group zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate ,

The spectrum of the inventively preferred zinc salts of organic acids, preferably organic carboxylic acids, ranging from salts which are not soluble in water, ie a solubility below 100 mg / L, preferably below 10 mg / L, in particular have no solubility, to such salts, the in water a solubility above 100 mg / L, preferably above 500 mg / L, more preferably above 1 g / L and in particular above 5 g / L (all solubilities at 20 ° C water temperature). The first group of zinc salts include, for example, zinc citrate, zinc laureate, zinc oleate, zinc oxalate, zinc tartrate, and zinc stearate. The group of soluble organic zinc salts includes, for example, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, the zinc gluconate, the zinc valerate and the zinc salt of p-toluenesulfonic acid.

In a further preferred embodiment, automatic dishwasher detergents or dishwashing auxiliaries according to the invention therefore comprise at least one zinc salt selected from the group of organic zinc salts, preferably from the group of soluble organic zinc salts, more preferably from the group of soluble zinc salts of monomeric or polymeric organic acids, in particular from Group zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate, zinc p-toluenesulfonate.

Of course, preferred compositions of the invention may also mixtures of organic and inorganic zinc salts, in particular mixtures of soluble organic zinc salts with insoluble inorganic zinc salts or mixtures of soluble organic zinc salts with soluble inorganic zinc salts or mixtures of insoluble organic zinc salts with insoluble inorganic zinc salts or mixtures of insoluble organic zinc salts with soluble inorganic zinc salts.

For the purposes of the present application, automatic dishwashing or automatic dishwashing aids in which the proportion by weight of the zinc salt relative to the total weight of this agent is 0.1 to 10% by weight, preferably 0.2 to 7% by weight and in particular 0, are preferred , 4 to 4 wt .-% and regardless of which zinc salts are used, in particular therefore irrespective of whether organic or inorganic zinc salts, soluble or non-soluble zinc salts or mixtures thereof are used.

Compositions according to the invention are not subject to any restrictions with regard to their packaging and forms of presentation. Machine dishwashing or machine dishwashing aids in the context of the present invention can therefore be provided both in solid and in liquid form.

Depending on the scope of the method of the invention, it may be necessary or desirable to use different or the same in the compositions of the invention Release active ingredients and / or active ingredient preparations in a timely manner. This time-controlled release can take place through different mechanisms or, in other words, due to different "switches". Based on the zinc salts and layered silicates contained in the compositions according to the invention, this means that these active substances are preferably added together but with a time offset to one or more further active ingredients and / or active substance preparations, such as builders (builders, cobuilders), surfactants, bleaches, bleach activators, enzymes , Dyes, fragrances, corrosion inhibitors or polymers are released. The zinc salt and / or the phyllosilicate can be released into the aqueous liquor both before and after the release of these active substances.

• der Aggregatzustand und die Konfektionsform der Mittel; flüssige Mittel lösen sich häufig schneller als feste Mittel; feste Mittel mit großer Oberfläche (z.B. Pulver, Granulate) lösen sich schneller als feste Mittel mit vergleichsweise kleiner Oberfläche (z.B. Tabletten);
• die mechanische Stabilität, welche - in Abhängigkeit von der Zeit, von der Temperatur oder von anderen Parametern - ein die Desintegration bestimmender Faktor sein kann;
• die Temperatur, d. h. das Erreichen eines bestimmten Temperaturwertes im Verlauf des Temperaturprofils des Wasch-, Reinigungs- oder Spülvorgangs; die Steuerung über die Temperatur stellt insbesondere bei Geschirrspülmitteln wegen der mit jeder Stufe des Spülvorgangs steigenden Temperatur eine zuverlässige und damit bevorzugte Ausführungsform dar;
• der pH-Wert, d. h. die Einstellung eines bestimmten pH-Wertes im Verlauf eines Wasch-, Reinigungs- oder Spülvorgangs durch Komponenten der waschaktiven, reinigungsaktiven oder spülaktiven Zubereitung oder das Verlassen eines bestimmten pH-Wertes nach Zerfall einer den pH-Wert beeinflussenden oder bestimmenden Komponente;
• die lonenstärke;
• die Anwesenheit von Enzymen
• der Einsatz von vorzugsweise wasserlöslichen Verpackungsmaterialien, sowie deren Permeabilität für eine bestimmte - vornehmlich gasförmige oder flüssige - Komponente; usw..

Possible "switches" which influence the release behavior of active substances or active substance preparations are, for example

• the state of aggregation and the ready-made form of the means; Liquid funds often dissolve faster than fixed funds; Solid agents with a large surface area (eg powder, granules) dissolve faster than solid agents with a comparatively small surface (eg tablets);
• the mechanical stability, which - depending on time, temperature or other parameters - may be a factor determining disintegration;
• the temperature, ie the achievement of a certain temperature value in the course of the temperature profile of the washing, cleaning or rinsing process; the control over the temperature represents a reliable and therefore preferred embodiment, in particular for dishwashing detergents, because of the rising temperature with each stage of the flushing process;
• the pH value, ie the setting of a specific pH value during the course of a washing, cleaning or rinsing process by components of the detergent-active, cleaning-active or rinse-active preparation or the leaving of a specific pH value after decomposition of a pH influencing or determining agent Component;
• the ionic strength;
• the presence of enzymes
• the use of preferably water-soluble packaging materials, as well as their permeability to a specific - primarily gaseous or liquid - component; etc..

The aforementioned parameters are only examples which are not intended to limit the invention.

If the agents according to the invention are prepared, for example, as combination products of two or more substances or mixtures of substances in different preparation / physical state, then the composition according to the invention which contains the zinc salt and the layered silicate is preferably contained only in one of these agents. In the present application, for example, liquids, powders, granules, compactates, extrudates, casting bodies, gels, dispersions are considered as different types of preparation / physical states. The assembly of such different means to a combination product can be done for example by means of a common, preferably water-soluble packaging having one, two, three, four or more receiving chambers. Methods for producing such packages are known in the art. These methods include, for example, thermoforming, injection molding or casting. In the following, with reference to single and two-chamber packaging, some preferred combinations of differently prepared compositions are described:

Water-soluble or water-dispersible packaging with a receiving chamber: Receiving chamber 1 Inventive agent in a powder and liquid Composition according to the invention in a powder and further powder Inventive agent in a powder and granules Inventive agent in a powder and Kompaktat Inventive agent in a powder and extrudate Inventive agent in a powder and casting Inventive agent in a powder and dimensionally stable gel Inventive agent in a melt and liquid Composition according to the invention in a melt and further powder Inventive agent in a melt and granules Inventive agent in a melt and Kompaktat Composition according to the invention in a melt and extrudate Inventive agent in a melt and casting Inventive agent in a melt and dimensionally stable gel Inventive agent in a granule and liquid Composition according to the invention in granules and further powder Inventive agent in granules and granules Inventive agent in a granule and Kompaktat Composition according to the invention in a granulate and extrudate Inventive agent in a granule and casting Inventive agent in a granule and dimensionally stable gel

Water-soluble or water-dispersible packaging with two receiving chambers: Receiving chamber 1 Receiving chamber 2 Composition according to the invention in a dispersion liquid Composition according to the invention in a dispersion powder Composition according to the invention in a dispersion granules Composition according to the invention in a dispersion compacted Composition according to the invention in a dispersion extrudate Composition according to the invention in a dispersion casting body Composition according to the invention in a dispersion Dimensionally stable gel Composition according to the invention in a dispersion dispersion Inventive agent in a powder liquid Inventive agent in a powder powder Inventive agent in a powder granules Inventive agent in a powder compacted Inventive agent in a powder extrudate Inventive agent in a powder casting body Inventive agent in a powder Dimensionally stable gel Inventive agent in a powder dispersion Inventive agent in a granule liquid Inventive agent in a granule powder Inventive agent in a granule granules Inventive agent in a granule compacted Inventive agent in a granule extrudate Inventive agent in a granule casting body Inventive agent in a granule Dimensionally stable gel Inventive agent in a granule dispersion Inventive agent in a Kompaktat liquid Inventive agent in a Kompaktat powder Inventive agent in a Kompaktat granules Inventive agent in a Kompaktat compacted Inventive agent in a Kompaktat extrudate Inventive agent in a Kompaktat casting body Inventive agent in a Kompaktat Dimensionally stable gel Inventive agent in a Kompaktat dispersion Composition according to the invention in an extrudate liquid Composition according to the invention in an extrudate powder Composition according to the invention in an extrudate granules Composition according to the invention in an extrudate compacted Composition according to the invention in an extrudate extrudate Composition according to the invention in an extrudate casting body Composition according to the invention in an extrudate Dimensionally stable gel Composition according to the invention in an extrudate dispersion Inventive agent in a casting liquid Inventive agent in a casting powder Inventive agent in a casting granules Inventive agent in a casting compacted Inventive agent in a casting extrudate Inventive agent in a casting casting body Inventive agent in a casting Dimensionally stable gel Inventive agent in a casting dispersion

For the preparation of the water-soluble and / or water-dispersible film, in principle all substances or mixtures of substances which can be formulated in the form of a film are suitable. However, particularly preferred is a process in which the water-soluble and / or water-dispersible film of (acetalized) Polyvinylakohol, polyvinylpyrrolidone, polyethylene oxide, gelatin, starch and starch derivative (s), cellulose and cellulose derivative (s), in particular methylcellulose and / or mixtures of these substances this listing being exemplary and not limiting the invention.

In a further, likewise preferred embodiment, it is advantageous according to the invention for the film (s) to comprise one or more materials from the group of acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters and polyethers and mixtures thereof ,

• Mischungen aus 50 bis 100 % Polyvinylalkohol oder Poly(vinylalkohol - co - vinylacetat) mit Molekulargewichten im Bereich von 10.000 bis 200.000 g/mol und Acetatgehalten von 0 bis 30 Mol-%; diese können Verarbeitungszusätze wie Weichmacher (Glycerin, Sorbit, Wasser, PEG usw.), Gleitmittel (Stearinsäure und andere Mono-, Di- und Tricarbonsäuren), sogenannte "Slipmittel" (z. B. "Aerosil"), organische und anorganische Pigmente, Salze, Blasformmittel (Citronensäure-Natriumbicarbonat-Mischungen) enthalten;
• Acrylsäure-haltige Polymere, wie z. B. Copolymere, Terpolymere oder Tetrapolymere, die mindestens 20 % Acrylsäure enthalten und ein Molekulargewicht von 5.000 bis 500.000 g/mol besitzen; als Comonomere sind besonders bevorzugt Acrylsäureester wie Ethylacrylat, Methylacrylat, Hydroxy-ethylacrylat, Ethylhexylacrylat, Butylacrylat, und Salze der Acrylsäure wie Natriumacrylat, Methacrylsäure und deren Salze und deren Ester wie Methylmethacrylat, Ethylmethacrylat, Trimethylammoniummethylmethacrylatchlorid (TMAEMC), Methacrylatamidopropyl-trimethylammoniumchlorid (MAPTAC). Weitere Monomere wie Acrylamid, Styrol, Vinylacetat, Maleinsäureanhydrid, Vinylpyrrolidon sind ebenfalls mit Vorteil verwendbar;
• Polyalkylenoxide, bevorzugt Polyethylenoxide mit Molekulargewichten von 600 bis 100.000 g/mol und deren durch Pfropfcopolymerisation mit Monomeren wie Vinylacetat, Acrylsäure und deren Salzen und deren Estern, Methacrylsäure und deren Salzen und deren Estern, Acrylamid, Styrol, Styrolsulfonat und Vinylpyrrolidon modifizierte Derivate (Beispiel: Poly-(ethylenglykol - graft - vinylacetat). Der Polyglykol-Anteil sollte 5 bis 100 Gew.-% betragen, der Pfropfanteil sollte 0 bis 95 Gew.-% betragen; letzterer kann aus einem oder aus mehreren Monomeren bestehen. Besonders bevorzugt ist ein Pfropfanteil von 5 bis 70 Gew.-%; dabei sinkt die Wasserlöslichkeit mit dem Pfropfanteil;
• Polyvinylpyrrolidon (PVP) mit einem Molekulargewicht von 2.500 bis 750.000 g/mol;
• Polyacrylamid mit einem Molekulargewicht von 5.000 bis 5.000.000 g/mol;
• Polyethyloxazolin und Polymethyloxazolin mit einem Molekulargewicht von 5.000 bis 100.000 g/mol;
• Polystyrolsulfonate und deren Copolymere mit Comonomeren wie Ethyl-(meth-)acrylat, Methyl(meth-)acrylat, Hydroxyethyl(meth-)acrylat, Ethylhexyl(meth-)acrylat, Butyl(meth)acrylat und den Salzen der (Meth-) Acrylsäure wie Natrium-(meth-)acrylat, Acrylamid, Styrol, Vinylacetat, Maleinsäureanhydrid, Vinylpyrrolidon; der Comonomer-Gehalt sollte 0 bis 80 Mol-% betragen, und das Molekulargewicht sollte im Bereich von 5.000 bis 500.000 g/mol liegen;
• Polyurethane, insbesondere die Umsetzungsprodukte von Diisocyanaten (z. B. TMXDI) mit Polyalkylenglykolen, insbesondere Polyethylenglykolen des Molekulargewichts 200 bis 35.000, oder mit anderen difunktionellen Alkoholen zu Produkten mit Molekulargewichten von 2.000 bis 100.000 g/mol;
• Polyester mit Molekulargewichten von 4.000 bis 100.000 g/mol, basierend auf Dicarbonsäuren (z. B. Terephthalsäure, Isophthalsäure, Phthalsäure, Sulfoisophthalsäure, Oxalsäure, Bernsteinsäure, Sulfobernsteinsäure, Glutarsäure, Adipinsäure, Sebacinsäure usw.) und Diolen (z. B. Polyethylenglykole, beispielsweise mit Molekulargewichten von 200 bis 35.000 g/mol);
• Celluloseether/ester, z. B. Celluloseacetate, Cellulosebutyrate, Methylcellulose, Hydroxypropylcellulose, Hydroxyethylcellulose, Methylhydroxypropylcellulose usw.;
• Polyvinylmethylether mit Molekulargewichten von 5.000 bis 500.000 g/mol.

With particular advantage, one or more materials may be cited from the following illustrative but non-limiting list:

• Mixtures of 50 to 100% polyvinyl alcohol or poly (vinyl alcohol-co-vinyl acetate) having molecular weights in the range of 10,000 to 200,000 g / mol and acetate contents of 0 to 30 mol%; these may include processing additives such as plasticizers (glycerin, sorbitol, water, PEG, etc.), lubricants (stearic acid and other mono-, di- and tricarboxylic acids), so-called "slip agents" (eg "Aerosil"), organic and inorganic pigments, salts, blowing agents (citric acid-sodium bicarbonate mixtures);
• Acrylic acid-containing polymers, such as. Copolymers, terpolymers or tetrapolymers containing at least 20% of acrylic acid and having a molecular weight of from 5,000 to 500,000 g / mol; Particularly preferred comonomers are acrylic acid esters such as ethyl acrylate, methyl acrylate, hydroxyethyl acrylate, ethylhexyl acrylate, butyl acrylate, and salts of acrylic acid such as sodium acrylate, methacrylic acid and their salts and their esters such as methyl methacrylate, ethyl methacrylate, trimethylammonium methyl methacrylate chloride (TMAEMC), methacrylatamidopropyl trimethyl ammonium chloride (MAPTAC). Other monomers such as acrylamide, styrene, vinyl acetate, maleic anhydride, vinyl pyrrolidone are also useful with advantage;
• Polyalkylene oxides, preferably polyethylene oxides having molecular weights of 600 to 100,000 g / mol and their derivatives by graft copolymerization with monomers such as vinyl acetate, acrylic acid and their salts and their esters, methacrylic acid and its salts and their esters, acrylamide, styrene, styrenesulfonate and vinylpyrrolidone modified derivatives (Example: The amount of polyglycol should be from 5 to 100% by weight, the amount of graft should be from 0 to 95% by weight, the latter being composed of one or more monomers Graft content of from 5 to 70% by weight, in which case the solubility in water drops with the grafting component;
• Polyvinylpyrrolidone (PVP) having a molecular weight of 2,500 to 750,000 g / mol;
• Polyacrylamide having a molecular weight of 5,000 to 5,000,000 g / mol;
• Polyethyloxazoline and polymethyloxazoline having a molecular weight of 5,000 to 100,000 g / mol;
• Polystyrenesulfonates and their copolymers with comonomers such as ethyl (meth) acrylate, methyl (meth) acrylate, hydroxyethyl (meth) acrylate, ethylhexyl (meth) acrylate, butyl (meth) acrylate and the salts of (meth) acrylic acid such as sodium (meth) acrylate, acrylamide, styrene, vinyl acetate, maleic anhydride, vinylpyrrolidone; the comonomer content should be 0 to 80 mol%, and the molecular weight should be in the range of 5,000 to 500,000 g / mol;
• Polyurethanes, in particular the reaction products of diisocyanates (eg TMXDI) with polyalkylene glycols, in particular polyethylene glycols of molecular weight 200 to 35,000, or with other difunctional alcohols to products with molecular weights of 2,000 to 100,000 g / mol;
• Polyesters having molecular weights of 4,000 to 100,000 g / mol, based on dicarboxylic acids (eg terephthalic acid, isophthalic acid, phthalic acid, sulfoisophthalic acid, oxalic acid, succinic acid, sulfosuccinic acid, glutaric acid, adipic acid, sebacic acid etc.) and diols (eg polyethylene glycols, for example, with molecular weights of 200 to 35,000 g / mol);
• Cellulose ethers / esters, eg. Cellulose acetates, cellulose butyrates, methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, methyl hydroxypropyl cellulose, etc .;
• Polyvinyl methyl ether with molecular weights of 5,000 to 500,000 g / mol.

Embodiments of the water-soluble films which are particularly preferred according to the invention also take account of the fact that the active substances and / or active-substance preparations contained in the receiving troughs are particularly-if not necessarily-water-soluble, preferably controllable, of the film material at a particular point in time of the washing, cleaning or Rinsing process, for example, upon reaching a certain temperature, or upon reaching a certain pH or a certain ionic strength of the wash liquor or due to other controllable events or conditions in the aqueous liquor can be fed.

The quality of the material as well as its quantity / strength directly influence these solubility properties. It is therefore in the context of the present invention, such a method is particularly preferred, which is characterized in that the thickness of the water-soluble film is between 1 .mu.m and 1000 .mu.m, preferably between 5 .mu.m and 500 .mu.m and in particular between 10 .mu.m and 200 .mu.m. Various film thicknesses with the aim of a delayed release of active substances and / or active substance preparations can also be realized, for example, advantageously by the multiple sealing of one or more receiving chambers by means of one or more identical or different water-soluble films. The thickness of the water-soluble film in the sense of the present invention then results as the sum of the thicknesses of the water-soluble individual films sealing one receiving trough.

Particular preference is given to materials for the water-soluble films, which-based on a certain thickness, which determines the thickness-dissolve at certain temperatures, pH values, ionic strengths, or after a certain residence time in the aqueous liquor. In this case, such a release process can capture the film as a whole or only a part thereof, so that parts of the film solve when setting a certain parameter combination, while other parts are not yet (but later) or not at all solved. The latter can be achieved by different quality of the material as well as by different amounts of material (thickness) or different geometries of the water-insoluble container. For example, it is possible to impede the access of water by the outer shape of the water-insoluble container and thus delay the dissolution process. In another preferred embodiment, it is possible to make the films of different thicknesses (nevertheless of the same material) and thus to allow earlier dissolution at the thinner locations. Be such different thicknesses of water-soluble films to cover used different receiving troughs, the active substances contained in these receiving troughs are released at different times. In a further likewise preferred embodiment, the films may be made of materials of different water solubility, for example of polyvinyl alcohols (PVAL) with different residual acetate content.

In a particularly preferred embodiment, the water-soluble and / or water-dispersible film can also contain one or more washing and cleaning-active substances or consist of these substances (for example: polyvinyl alcohols as film material and builder) in addition to the ingredients mentioned. In the former case, for example, washing active, cleaning active or active ingredients that are only present in small amounts in the preparations and their uniform incorporation is therefore not unproblematic, in the film or a part of the film, for example, one which is in the state of Washing, cleaning or rinsing dissolves, in which just the active ingredient is needed to be incorporated, whereby it is released when dissolving the film at the right time in the fleet. An example of this may be fragrances which are desired in the final stage of the washing or cleaning or rinsing process, but also optical brighteners, UV protectants, dyes and other detergent-active, cleaning-active or rinse-active preparations.

A further embodiment of agents according to the invention which is likewise preferred in the context of the present application is the time-controlled release of one or more of the active substances (s) and / or active substance preparation (s) contained in these agents by the incorporation of matrix or coating materials of different solubility or melting temperature.
According to the above, differences in the release rate of active substances and / or active substance mixtures can be achieved by the use of matrix materials or coatings which have different melting temperatures. The use of fusible or softenable substances as matrix or coating material for the active substances or active substance preparations is particularly preferred. In the context of the present invention, the term "coating" encompasses not only the coating of one or more sides or surfaces of an article, such as a solid particulate agent, but also the complete coating, ie, the coating of this particulate article, as well as the sealing of a receiving well by a meltable substance by coating such a substance on a particulate or gel-like active / active substance preparation is referred to as a coating. The term "active substances" or "active substance preparations" includes both the zinc salts / sheet silicates which characterize the compositions according to the invention all others optionally included Ingredients.) According to preferred fusible substances have a melting point above 30 ° C. If active substance preparations are to be released at different times, for example during the various rinses of a cleaning process, this can be done, for example, by using one or different fusible matrices or coatings. If two or more different fusible matrices are used, the melting points are preferably adapted to the temperature profile of this cleaning process, the difference in the melting points being sufficient to ensure the separate dissolution of the individual matrices or coatings. Such substances are preferred for the different matrices and / or coatings, which differ in their melting point by at least 5 ° C, preferably by 10 ° C, more preferably by 15 ° C and in particular by at least 20 ° C, wherein it further preferred in that the melting point of at least one of the fusible substances forming a matrix or a coating is below 30 ° C, while the melting point of at least one further substance forming a further matrix or coating is above 30 ° C.

If it is envisaged to use a softenable substance as a matrix for an active substance or an active substance formulation, then this mass softenable under the influence of temperature can be mixed by mixing the desired further ingredients with this meltable or softenable substance and heating the mixture to temperatures in the softening range of this substance is processed shaping at these temperatures. If the softenable substances are used as coating agents, then such a coating can take place, for example, by dipping, spraying or circulating in a drum coater or coating pan. Particular preference is given to using waxes, paraffins, polyalkylene glycols, etc. as meltable or softenable substances for the matrices or the coatings.

It has proved to be advantageous if the meltable or softenable substances do not show a sharply defined melting point, as usually occurs in the case of pure, crystalline substances, but instead have a melting range which may be several degrees Celsius. The meltable or softenable substances preferably have a melting range of between about 35 ° C and about 75 ° C. That is, in the present case, the melting range occurs within the specified temperature interval and does not denote the width of the melting range. Preferably, the width of the melting range is at least 1 ° C, preferably from about 2 to about 3 ° C.

Apart from paraffins and polyethylene glycols, the abovementioned properties are as a rule also fulfilled by so-called waxes. Find more detailed descriptions of these groups of substances further down in the description. Reference is made to these statements to avoid repetition at this point.

Another preferred possibility for the delayed release of active substances or active substance preparations is the staggered spatial arrangement of these substances in the receiving chamber of a preferably water-soluble packaging or within a casting or compact (onion model) with the aim of a staggered release. Such a spatially staggered arrangement is, for example, the layer or phase arrangement of the active ingredients or active substance preparations, for example, the layered tabletting or the layered pouring liquid active substances or mixtures of active ingredients and their subsequent solidification by solidification and / or crystallization are suitable. Since access of the solvent in compressed or cast moldings can take place only over their surface, this layered arrangement leads to the release of those active substances or active substance mixtures which are located on the surface of such a multiphase mixture. The phases are thus removed offset in time, the ingredients are released with a time delay.

Of course, the previously described methods for the timely release of active substances and / or mixtures of active substances are not an end in themselves, but are used for targeted control of the purification process. Thus, a program for the automatic cleaning of dishes usually includes various cleaning cycles, the nature and number of these cleaning cycles can be determined by the consumer by means of a program selection. Examples of such cleaning cycles are the pre-wash cycle, intermediate and main washes or the rinse cycle. All these different cleaning operations require for an optimum result of the targeted dosage of appropriate active ingredients or active mixtures. In particular, for optimizing the active ingredient combination of zinc salts with phyllosilicates used according to the invention, a controlled early or delayed release of zinc salts and / or phyllosilicates and / or other active substances may be beneficial, depending on the nature of the other active ingredients used.

Solid forms of the machine dishwashing detergents or dishwashing auxiliaries according to the invention are, for example, fine- to coarse-grained powders, as obtained, for example, by spray-drying or granulation, compacted mixtures of roll compacting, but also solidified melts or shaped articles obtained by extrusion or tabletting. Such moldings can in the context of the present invention have virtually all useful manageable embodiments, for example, in the form of a bar, in bar or bar form, a cube, a cuboid and the like Room element with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section. This last embodiment covers the presentation form of the actual tablet to compact cylinder pieces with a height-to-diameter ratio above 1. Preferred tabletted or extruded means in the present invention, two or more phases, for example, by their composition, their Share of the total volume of the molding and / or can distinguish their visual appearance.

The phases of such multiphase moldings can additionally be distinguished by a different dissolving behavior in the aqueous phase. Such moldings are suitable for the time-controlled release of certain ingredients (controlled release), for example in certain rinses of the machine wash program. In a preferred embodiment, one of the phases of the shaped body as the main constituent has meltable or softenable substances from the group of waxes, paraffins and / or polyalkylene glycols. Furthermore, it has proved to be advantageous if the melted or softenable substances contained molded body or molded body component is at least largely water insoluble. The solubility in water should not exceed about 10 mg / l at a temperature of about 30 ° C and preferably be below 5 mg / l. In such cases, however, the meltable or softenable substances should have the lowest possible water solubility, even in water at elevated temperature, in order to avoid as much as possible a temperature-independent release of the active substances. The release of the active substance takes place in this way upon reaching the melting or softening point. A further preferred procedure for obtaining a controlled release of ingredients, in particular the combination of zinc salt and sheet silicate according to the invention, from multiphase tablets is the compaction of the two or more individual phases with different pressures. Since the disintegration and dissolution properties of tablets or tablet phases are known to depend inter alia on the compaction pressure exerted on the tablet phase during tabletting, tablet phases having different disintegration and dissolution properties can be prepared solely by using different compaction pressures. It may be preferred according to the invention that the combination of zinc salt and layered silicate according to the invention are together in the phase which was exposed to the comparatively higher tabletting pressure and therefore decomposes later. However, it may also be advantageous, depending on the composition of the cleaning agent, to prepare zinc salt and layered silicate together in the tablet phase, which was tabletted with the comparatively lower pressure. Finally, it is also preferred to formulate zinc salt and phyllosilicate in different tablet phases, wherein the zinc salt is in an advantageous embodiment in the comparatively highly compacted tablet phase, while in another preferred embodiment is in the comparatively less compacted tablet phase.

In the context of the present application, automatic dishwashing assistants are those which are added in addition to a commercial detergent, for example in the form of a special glass preservative. Such a dosage can take place both before the beginning of each rinsing program and in the form of a depot product which causes a continuous release of the agent according to the invention.

Preferred solid agents according to the invention are in the form of a dosing unit sufficient for a cleaning cycle. An example of such Konfektionsformen are dishwashing (auxiliary) mitteleltabletten.

If the agents according to the invention are in solid particulate form, but not in the form of separate metering units, the problem of segregation of individual constituents arises for these agents, and the segregation of the zinc salts and silicates contained in the agents according to the invention must be avoided. Examples of such particulate forms of supply are powders or granules. In a preferred embodiment of the present invention, the zinc salt (s) contained in the automatic dishwashing detergent or automatic dishwashing auxiliary and / or the contained crystalline layered silicate (s) with one or more further active and / or builder substance (s) pre-formed, in particulate form, as a compound before.

Since the zinc salts and crystalline layered silicates make up only a small proportion by weight of preferred automatic dishwashing detergents, compounding on the basis of their "dilution effect" simplifies the metering of these salts in the preparation of automatic dishwasher detergents according to the invention. But even in the event that an inventive agent in the form of a special product for glass corrosion protection a commercial cleaning agent is added only by the consumer, the dosage is facilitated by the compounding. The advantages of compounding are completely independent of whether the automatic dishwashing agent, to which the corresponding compounds are added, is solid, liquid or gel-like.

Preferred solid forms of the machine dishwashing detergent according to the invention contain, for example, fine to coarse-grained powders, as obtained, for example, by spray-drying or granulation. Such powders can be marketed as a commercial product or used as a premix for compaction, for example for tableting, and generally have a particle size in the range from 0.1 to 10 mm. In order to prevent segregation of these powders from the dosed silicate and / or zinc salt compounds, it is preferred that these compounds have a particle size comparable to the powders.

A preferred subject matter of the present application is therefore a machine dishwashing detergent, characterized in that the particle size of the zinc salts and / or crystalline layered silicates compounded with one or more active and / or builder substances is 0.1 and 10 mm, preferably 0.2 and 8 mm and in particular 0.5 and 5 mm, wherein preferred particulate compounds to avoid segregation additionally a density of 0.1 to 2.0 g / cm ³ , preferably from 0.2 to 1.6 g / cm ³ and in particular from 0.4 to 1.2 g / cm ³ .

Automated dishwashing agents preferred according to the invention are characterized in particular by the particles of the zinc salts and / or crystalline layered silicates synthesized with one or more active and / or builder substances containing from 0.1 to 80% by weight of the zinc salts or crystalline layered silicates, particularly preferably from 0.2 to 70% by weight and particularly preferably from 0.5 to 60% by weight, in each case based on the total weight of the particles.

The abovementioned particulate compounds are obtained according to the invention preferably by spray drying and / or granulation and / or extrusion and / or roller compaction and / or tabletting and / or solidification and / or crystallization, but in particular by spray drying and / or granulation.

In spray drying, an aqueous slurry ("slurry") is prepared in a first step of the process, which may contain other thermally stable active and / or builders in addition to the zinc salts according to the invention, which neither volatilize nor decompose under the conditions of spray drying and this then transported via pumps in the spray tower and sprayed via located in the head of the tower nozzles. Ascending hot air dries the slurry and evaporates the adhering water so that the detergent ingredients at the outlet of the tower are obtained as fine powders. These may, if necessary, further Tempertur labile ingredients such. As bleaching agents or perfumes, are admixed.

The preparation of compositions according to the invention can be carried out not only by the spray drying described above but also by a fluidized bed process in which fine granular bulk material stored on horizontal, perforated trays, which besides the zinc salts according to the invention can contain further active and / or builder substances, from below by gases (eg hot air) is flowed through. Under certain flow conditions, this creates a state that is similar to that of a boiling liquid; the layer causes bubbles, and the particles of the bulk material are within the layer in a constant, swirling up and down movement and remain so to speak in the balance. The large surface of the fluidized material then allows, for example, the reaction with other substances such as solvents, solutions of active and / or builders, liquid active substances or other ingredients that are present as solid at room temperature, by increasing the temperature and / or addition of very limited amounts of liquid But soften additives at least superficially and / or form an adhesive and adhesive strength under the influence of temperature. Typical examples of the aforementioned substances are water and aqueous solutions, for example, aqueous solutions of zinc salts according to the invention can be used at room temperature liquid or solid surfactant compounds, especially nonionic surfactants, or polymer compounds of synthetic and / or natural origin, for example (co) -polymere carboxylates ,

Another preferred procedure for the granulation is the use of mixers / compressors, as they are provided for this purpose, among other providers, for example, by the company Lödige and which are particularly suitable for the production of preformed particles according to the invention, as by the user Variation of different process parameters such as the number of revolutions of the mixer, the residence time of the individual components, the dosing of individual components during the mixing process, the geometry of the mixing elements used or the energy input offer the possibility of targeted control of the product properties of the resulting granules. The grain size and / or density of granules can be influenced in this way, and the assembly of zinc salts according to the invention with one or more further active and / or builder substance (s) in the aforementioned mixers / compressors is therefore within the scope of the present invention particularly preferred.

Finally, it is possible to mix the zinc salts and / or silicates according to the invention with further individual components which differ only slightly in their bulk densities from those of the salts mentioned. Such mixtures have only slight separation tendencies of the components during storage, transport and processing and are therefore also particularly suitable for the desired safe and reliable dosing of the silicates and / or zinc salts according to the invention. Preferred in the context of the present invention are therefore mixtures of silicates and / or zinc salts with further active and / or builders, characterized in that the bulk densities of the individual components mixed with one another by a maximum of 200 g / l, preferably by a maximum of 150 g / l, preferably differ by a maximum of 100 g / l and in particular by a maximum of 50 g / l.

The scaffolding and / or active substances which can be used in the above-described formulation of preferred automatic dishwashing compositions according to the invention include, among other conventional ingredients of detergents, for example builders, co-builders, surfactants, bleaches, bleach activators, enzymes, dyes, fragrances, corrosion inhibitors or polymers.

Whilst all the substances mentioned are generally suitable as active and / or builder substances for the formulation of zinc salts according to the invention, those automatic dishwashing or machine dishwashing auxiliaries are particularly preferred in the context of the present invention in which the one or more active and / or builder substances are formulated Zinc salt compounds, active substances and / or builders from the group of phosphates, carbonates, bicarbonates, sulfates, silicates, citrates, citric acid, acetates, preferably in amounts of from 20 to 99% by weight, particularly preferably from 30 to 98% by weight and particularly preferably from 40 to 95 wt .-%, each based on the total weight of the particles.

Other active and / or builder substances which are particularly preferred for the preparation of the zinc salts in the context of the present invention are the surfactants, preferably the nonionic surfactants, and / or the polymeric carboxylates, in particular the polysulfocarboxylates.

For further description of particularly preferred surfactants or polymeric carboxylates and polysulfocarboxylates, reference is made to the following statements to avoid repetition.

The silicates present in the machine dishwashing detergents or dishwashing auxiliaries according to the invention are also preferably packaged with other active ingredients or builders in these compositions, in which case active or builder substances from the group of organic monocarboxylic or polycarboxylic acids, hydroxypolycarboxylic acids and phosphonic acids are used ,

A further preferred subject matter of the present application is therefore dishwasher detergents or automatic dishwashing assistants, characterized in that the crystalline layered silicate (s) of the general formula (I) or of the general formula (Ia) has a or more further active and / or builder substance (s), preferably with one or more further active and / or builder substances from the group of the organic monocarboxylic or polycarboxylic acids, hydroxypolycarboxylic acids and phosphonic acids, in particulate form, as compound available.

The particulate present, with one or more active and / or builders formulated zinc salts and / or crystalline layered silicates may be provided to protect environmental influences and thus to improve their storage stability or to influence the dissolution behavior with a coating (coating). Coating materials and methods for coating particulate agents are widely described in the literature and will be explained below only with respect to particularly preferred embodiments.

Particularly preferred is the use of fusible or softenable substances as coating material. (The term "coating" means in the context of the present invention, in addition to the coating of single or multiple sides or surfaces of a particulate, inventively prepared agent also a complete coating, so the envelope of this particulate article.) According to the invention preferred fusible substances have a melting point above 30 ° C on. If the ready-made zinc salts and / or crystalline layered silicates are to be released at different times, for example during the various rinses of a cleaning process, this can be done, for example, by the use of different fusible coatings which differ in their melting point, the melting points of these substances preferably being on the Adjusted temperature course of this cleaning process and the difference of the melting points is sufficient to ensure the separate dissolution of the individual matrices or coatings. If, for example, it is envisaged to release zinc salts and crystalline layer-form silicates at separate times, then such substances are preferred for the different coatings which, with respect to their melting point, are at least 5 ° C., preferably around 10 ° C., more preferably around 15 ° C. and in particular around at least 20 ° C, wherein it is further preferred that the melting point of at least one of the fusible substances forming a coating is below 30 ° C, while the melting point of at least one further substance forming another matrix or coating, above 30 ° C is.

Such coatings can be applied, for example, by dipping, spraying or tumbling in a drum coater or coating pan. Particular preference is given to using waxes, paraffins, polyalkylene glycols, etc., as the meltable or softenable substances for the coatings.

It has proved to be advantageous if the meltable or softenable substances do not show a sharply defined melting point, as usually occurs in the case of pure, crystalline substances, but instead have a melting range which may be several degrees Celsius. The meltable or softenable substances preferably have a melting range of between about 45 ° C and about 75 ° C. That is, in the present case, that the melting range occurs within the specified temperature interval and does not indicate the width of the melting range. Preferably, the width of the melting range is at least 1 ° C, preferably from about 2 to about 3 ° C.

The above properties are usually met by so-called waxes. "Waxing" is understood to mean a series of naturally or artificially produced substances which generally melt above 40 ° C. without decomposition and are already relatively low-viscosity and non-stringy just above the melting point. They have a strong temperature-dependent consistency and solubility.

According to their origin, the waxes are divided into three groups, the natural waxes, chemically modified waxes and the synthetic waxes.

The natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, Japan wax, Espartograswachs, cork wax, guaruma wax, rice germ oil wax, sugarcane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, spermaceti, lanolin (wool wax), or crepe fat, mineral waxes such as ceresin or ozokerite (groundwax), or petrochemical waxes such as petrolatum, paraffin waxes or microwaxes.

The chemically modified waxes include, for example, hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.

Synthetic waxes are generally understood as meaning polyalkylene waxes or polyalkylene glycol waxes. It is also possible to use as meltable or softenable substances for the compositions which cure by cooling, and compounds from other substance classes which meet the stated requirements with regard to the softening point. Suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl phthalate, which is commercially available under the name Unimoll® 66 (Bayer AG), proved. Also suitable are synthetically produced waxes from lower carboxylic acids and fatty alcohols, for example dimyristyl tartrate, which is available under the name Cosmacol® ETLP (Condea). Conversely, synthetic or partially synthetic esters of lower alcohols can be used with fatty acids from natural sources. This class of substances includes, for example, Tegin® 90 (Goldschmidt), a glycerol monostearate palmitate. Shellac, for example shellac KPS three-ring SP (Kalkhoff GmbH) can also be used as meltable or softenable substances.

Likewise to the waxes in the context of the present invention, for example, the so-called wax alcohols are calculated. Wax alcohols are higher molecular weight, water-insoluble Fatty alcohols with usually about 22 to 40 carbon atoms. The wax alcohols are, for example, in the form of wax esters of higher molecular weight fatty acids (wax acids) as the main constituent of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The coating of the prepared zinc salts or crystalline layered silicates may optionally also contain wool wax alcohols, which are understood to mean triterpenoid and steroid alcohols, for example lanolin, which is obtainable, for example, under the trade name Argowax® (Pamentier & Co). In the context of the present invention, fatty acid glycerol esters or fatty acid alkanolamides but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds may likewise be used as part of the meltable or softenable substances.

Particularly preferred meltable or softenable substances are those from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) contains, with polyethylene glycols having molecular weights between 1500 and 36,000 are preferred, those with molecular weights from 2000 to 6000 particularly preferred and those with molecular weights of 3000 to 5000 are particularly preferred. Also, corresponding processes, which are characterized in that the plastically deformable mass (s) at least one substance from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) contains / are preferred.

genügen, wobei n Werte zwischen 10 und 2000 annehmen kann. Bevorzugte PPG weisen Molmassen zwischen 1000 und 10.000, entsprechend Werten von n zwischen 17 und ca. 170, auf.Coating agents which contain propylene glycols (PPG) and / or polyethylene glycols (PEG) as sole meltable or softenable substances are preferred here. Polypropylene glycols which can be used according to the invention (abbreviated PPG) are polymers of propylene glycol which have the following general formula

satisfy, where n can take values between 10 and 2000. Preferred PPG have molecular weights between 1000 and 10,000, corresponding to values of n between 17 and about 170.

Polyethylene glycols (abbreviated to PEG) which can preferably be used according to the invention are polymers of ethylene glycol, those of the general formula

H- (O-CH ₂ -CH ₂ ) _n -OH

satisfy, where n can take values between 20 and about 1000. The abovementioned preferred molecular weight ranges correspond to preferred ranges of the value n in formula IV of about 30 to about 820 (exactly: from 34 to 818), more preferably from about 40 to about 150 (exactly: from 45 to 136). and especially from about 70 to about 120 (exactly: from 68 to 113).

In a further preferred embodiment, the coating materials contain paraffin wax.

In the context of the present invention, paraffin waxes have the advantage over the other natural waxes mentioned that no hydrolysis of the waxes takes place in an alkaline detergent environment (as is to be expected, for example, in the case of wax esters), since paraffin wax contains no hydrolyzable groups.

Paraffin waxes consist mainly of alkanes, as well as low levels of iso- and cycloalkanes. The paraffin to be used according to the invention preferably has substantially no constituents with a melting point of more than 70 ° C., more preferably of more than 60 ° C. Shares of high-melting alkanes in the paraffin can fall below this melting temperature in the detergent leaving unwanted wax residue on the surfaces to be cleaned or the property to be cleaned. Such wax residues usually lead to an unsightly appearance of the cleaned surface and should therefore be avoided.

Preferably melt or softenable substances to be processed contain at least one paraffin wax with a melting range of 50 ° C to 60 ° C, preferred coating materials being characterized in that they contain a paraffin wax having a melting range of 50 ° C to 55 ° C.

Preferably, the content of the paraffin wax used at ambient temperature (usually about 10 to about 30 ° C) solid alkanes, isoalkanes and cycloalkanes as high as possible. The more solid wax constituents in a wax at room temperature, the more useful it is within the scope of the present invention. As the proportion of solid wax constituents increases, the end-of-processability of the process end products increases against impacts or friction on other surfaces, resulting in longer-lasting protection. High levels of oils or liquid wax components can weaken the coating, opening pores and exposing the active ingredients to environmental conditions.

The meltable or softenable substances may contain, in addition to paraffin as the main constituent, one or more of the abovementioned waxes or waxy substances. In a In another preferred embodiment of the present invention, the mixture forming the meltable or softenable substances should be such that the composition and the coating formed therefrom are at least substantially insoluble in water. The solubility in water should not exceed about 10 mg / l at a temperature of about 30 ° C and preferably be below 5 mg / l.

In such cases, however, the meltable or softenable substances should have the lowest possible water solubility, even in water at elevated temperature, in order to avoid as much as possible a temperature-independent release of the active substances.

Preferred coating materials to be processed according to the invention are characterized in that they contain, as meltable or softenable substances, one or more substances having a melting range from 40 ° C. to 75 ° C. in amounts of from 6 to 30% by weight, preferably from 7.5 to 25 Wt .-% and in particular from 10 to 20 wt .-%, each based on the weight of the coating material.

Apart from the choice of a suitable coating, the dissolution behavior of the zinc salt or silicate compounds can also be influenced by the abovementioned compaction methods. Here, in addition to the amount of pressure used and the use of aids, such as binders, in particular the choice of / the co-assembled active and / or builders of great importance. For example, compacted silicates, in particular disilicates, and / or polycarboxylates and / or mixtures of various polycarboxylates are suitable as "depot substances" for the zinc salts or crystalline layered form due to their delayed solution / dispersion or due to gelling of these substances or substance mixtures in aqueous liquor silicates.

Another particularly preferred form of compounding machine dishwashing or automatic dishwashing auxiliaries according to the present invention is polymer matrices. Such polymer matrices are universally applicable in various programs, are characterized by a simple and cost-effective method of preparation and may contain varying amounts of active agent.

The preferred subject matter of the present application is therefore furthermore dishwasher detergents or dishwashing auxiliaries in which the zinc salt (s) and / or the crystalline layered silicate (s) are packaged in a polymer matrix.

The active ingredient-containing polymer matrices can be produced cheaply and in a high variety of forms. By selecting water-soluble or water-insoluble polymers, the composition of the present invention can even be formulated as a package of automatic dishwashing detergents or as a basket into which the compositions are incorporated. It is also possible to combine both types of incorporation by, for example, a carrier basket of water-insoluble, active ingredient-containing polymer matrix containing a polymer body of water-soluble, active ingredient-containing polymer matrix. Such products can release different levels of active agents from the various matrices at different times, resulting in an optimal concentration of active ingredient at each point in the cleansing program.

If, in accordance with the invention, both the zinc salt and the silicates are packaged in a polymer matrix, this preparation can be carried out in the same polymer matrix as well as in different matrices in preferred embodiments of the present invention, ie the zinc salt can be converted, for example, into polymer A pre-assembled, while the silicate was formulated in a polymer B. Finally, zinc salt and silicate can also be formulated by means of the same polymer, but in separate matrices.

The compositions of the invention can therefore be realized both with water-insoluble and with water-soluble polymers or mixtures thereof. Preferred automatic dishwashing or machine dishwashing aids are characterized in that the polymer matrix comprises one or more water-soluble polymer (s).

The polymer matrices according to the invention can be formulated universally. For example, it is possible to provide pre-softeners, pre-rinsing agents, cleaning agents for the main rinse or rinse aid according to the invention. In addition, compositions according to the invention may also be combination products which combine two or more of the aforementioned agents. Also, the formulation of inventive compositions as an addition product, which is hung for example in the dishwasher, is easily possible. The active ingredient-containing polymer matrix can be particulate incorporated into the compositions of the invention, but it can also be a compact molded body, for example, either a core which fills a trough of a detergent tablet, or a shaped product, which as an addition product equal to a deodorant hanger in the dishwasher is introduced. Also, baskets which are suitable for receiving detergent tablets, can be prepared from the active ingredient-containing polymer matrix. Last but not least, the active ingredient-containing polymer matrix can also be used as a packaging for automatic dishwasher detergents. This is especially true for completely water-soluble active substance-containing polymer matrices attractive, since the consumer does not have to unpack the product, the direct contact with the product, which is perceived as undesirable, avoids and other packaging materials are saved.

• ) 5 bis 99,5 Gew.-% eines oder mehrerer Polymere,
• ) mindestens ein Zinksalz sowie mindestens ein kristallines schichtförmiges Silikat der allgemeinen Formel (la)
  
           NaMSi_xO_2x+1 · y H₂O     (Ia),
  
  worin M Natrium oder Wasserstoff darstellt, x eine Zahl von 1,9 bis 22, vorzugsweise von 1,9 bis 4, ist und y für eine Zahl von 0 bis 33 steht, enthält, wobei die Summe der Gewichtsanteile des/der Zinksalze(s) und des/der kristallinen Silikate(s) 0,5 bis 95 Gew.-% beträgt,
• ) 0 bis 30 Gew.-% weiterer Wirk- und/oder Hilfsstoffe
  umfaßt, wobei sich die Gewichtsangaben jeweils auf das Gesamtgewicht der wirkstoffhaltigen Polymermatrix beziehen.

Particularly preferred agents according to the invention are characterized in that the polymer matrix

• ) 5 to 99.5% by weight of one or more polymers,
• ) at least one zinc salt and at least one crystalline layered silicate of the general formula (Ia)
  
  NaMSi _x O _{2x + 1} · y H ₂ O (Ia),
  
  wherein M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, and y is a number from 0 to 33, wherein the sum of the weight proportions of the zinc salt (s ) and of the crystalline silicate (s) is from 0.5 to 95% by weight,
• ) 0 to 30 wt .-% of other active ingredients and / or adjuvants
  includes, wherein the weights are each based on the total weight of the active ingredient-containing polymer matrix.

The polymer matrix of the agents preferred according to the invention comprises from 5 to 99.5% by weight of one or more polymers. The term "polymers" in the context of the following application, based on the IUPAC definition, denotes substances which are composed of a collective of chemically uniformly structured, but generally differing in terms of degree of polymerization, molecular weight and chain length macromolecules. According to this IUPAC definition, which does not take into account the concept of the term, a polymer is "a substance composed of a plurality of molecules in which one kind or more kinds of atoms or atomic groups" so-called constitutive units, basic units or repeating units repeats The different sized macromolecules of a polymer are composed of so many identical or similar low molecular weight building blocks (monomers) that the physical properties of the substance, especially the viscoelasticity, do not appreciably change with a slight increase or decrease in the number of building blocks The size of the macromolecules implies that the end groups have relatively little effect on the properties of the polymers, so that their explicit specification in the structural formulas given below is usually dispensed with.

The matrix-forming polymers of the compositions according to the invention may be of natural or synthetic origin. Preferred agents according to the invention are characterized in that the polymer matrix from 7.5 to 95 wt .-%, preferably 10 to 90 wt .-%, particularly preferably 12.5 to 85 wt .-%, more preferably 15 to 82.5 wt .-% and in particular 20 to 80 wt .-% of one or more polymers, wherein the weights are based on the active ingredient-containing polymer matrix.

The average molar mass of the polymers contained in the preferred agents according to the invention is preferably at least 5000 g / mol, particularly preferably at least 10,000 g / mol and in particular at least 12,000 g / mol.

As already mentioned, the agents preferred according to the invention may contain both water-insoluble and water-soluble polymers and mixtures of these polymers. According to preferred compositions based on water-insoluble polymer matrices are characterized in that the polymer matrix comprises one or more water-insoluble polymers from the group polyethylene, polypropylene, polytetrafluoroethylene, polystyrene, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polyurethanes, polyamides and mixtures thereof.

• i) Polyacrylsäuren und deren Salzen
• ii) Polymethacrylsäuren und deren Salzen
• iii) Polyvinylpyrrolidon,
• iv) Vinylpyrrolidon/Vinylester-Copolymeren,
• v) Celluloseethern
• vi) Polyvinylacetaten, Polyvinylalkoholen und ihren Copolymeren
• vii) Pfropfcopolymeren aus Polyethylenglykolen und Vinylacetat
• viii) Alkylacrylamid/Acrylsäure-Copolymeren und deren Salzen
• ix) Alkylacrylamid/Methacrylsäure-Copolymeren und deren Salzen
• x) Alkylacrylamid/Methylmethacrylsäure-Copolymeren und deren Salzen
• xi) Alkylacrylamid/Acrylsäure/Alkylaminoalkyl(meth)acrylsäure -Copolymeren und deren Salzen
• xii) Alkylacrylamid/Methacrylsäure/Alkylaminoalkyl(meth)acrylsäure -Copolymeren und deren Salzen
• xiii) Alkylacrylamid/Methylmethacrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymeren und deren Salzen
• ) Alkylacrylamid/Alkymethacrylat/Alkylaminoethylmethacrylat/Alkylmethacrylat-Copolymeren und deren Salzen
• ) Copolymeren aus
  • xv-i) ungesättigten Carbonsäuren und deren Salzen
  • xv-ii) kationisch derivatisierten ungesättigten Carbonsäuren und deren Salzen
• ) Acrylamidoalkyltrialkylammoniumchlorid/Acrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze
• ) Acrylamidoalkyltrialkylammoniumchlorid/Methacrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze
• ) Methacroylethylbetain/Methacrylat-Copolymere
• ) Vinylacetat/Crotonsäure-Copolymere
• ) Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere
• ) Pfropfpolymere aus Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch, copolymerisiert mit Crotonsäure, Acrylsäure oder Methacrylsäure mit Polyalkylenoxiden und/oder Polykalkylenglykolen
• ) gepropften Copolymere aus der Copolymerisation von
  • xxii-i) mindesten einem Monomeren vom nicht-ionischen Typ,
  • xxii-ii) mindestens einem Monomeren vom ionischen Typ,
• ) durch Copolymerisation mindestens eines Monomeren jeder der drei folgenden Gruppen erhaltenen Copolymere:
  • xxiii-i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesättigter Alkohole und ungesättigter Carbonsäuren,
  • xxiii-i) ungesättigte Carbonsäuren,
  • xxiii-iii) Ester langkettiger Carbonsäuren und ungesättigter Alkohole und/oder Ester aus den Carbonsäuren der Gruppe d6ii) mit gesättigten oder ungesättigten, geradkettigen oder verzweigten C_8-18-Alkohols.

Instead of water-insoluble polymers or in admixture with them, water-soluble polymers of natural or synthetic origin can also form the polymer matrix. Further preferred agents according to the invention are characterized in that the polymer matrix comprises one or more water-soluble polymers, wherein the water-soluble polymer (s) is / are preferably selected from:

• i) polyacrylic acids and their salts
• ii) polymethacrylic acids and their salts
• iii) polyvinylpyrrolidone,
• iv) vinyl pyrrolidone / vinyl ester copolymers,
• v) cellulose ethers
• vi) polyvinyl acetates, polyvinyl alcohols and their copolymers
• vii) graft copolymers of polyethylene glycols and vinyl acetate
• viii) alkylacrylamide / acrylic acid copolymers and their salts
• ix) alkylacrylamide / methacrylic acid copolymers and their salts
• x) alkylacrylamide / methylmethacrylic acid copolymers and their salts
• xi) alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and their salts
• xii) alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and their salts
• xiii) alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and their salts
• ) Alkylacrylamide / Alkymethacrylate / Alkylaminoethylmethacrylat / Alkylmethacrylat copolymers and their salts
• ) Copolymers
  • xv-i) unsaturated carboxylic acids and their salts
  • xv-ii) cationically derivatized unsaturated carboxylic acids and their salts
• ) Acrylamidoalkyltrialkylammoniumchlorid / acrylic acid copolymers and their alkali metal and ammonium salts
• ) Acrylamidoalkyltrialkylammoniumchlorid / methacrylic acid copolymers and their alkali metal and ammonium salts
• ) Methacroylethylbetaine / methacrylate copolymers
• ) Vinyl acetate / crotonic acid copolymers
• ) Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers
• ) Graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid alone or in admixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols
• ) grafted copolymers from the copolymerization of
  • xxii-i) at least one nonionic type monomer,
  • xxii-ii) at least one ionic type monomer,
• ) by copolymerization of at least one monomer of each of the following three groups of copolymers obtained:
  • xxiii-i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids,
  • xxiii-i) unsaturated carboxylic acids,
  • xxiii-iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters of the carboxylic acids of group d6ii) with saturated or unsaturated, straight-chain or branched C _8-18 -alcohols.

The active substance-containing polymer matrix has, in addition to the polymer (s), a content of at least one zinc salt and / or at least one crystalline layered silicate of the general formula (I) or the general formula (Ia) which can be released from the matrix. Agents preferred according to the invention are characterized in that they comprise at least one zinc salt and at least one crystalline layered silicate of the general formula (I) or of the general formula (Ia), the sum of the proportions by weight of these constituents being from 1 to 90% by weight, preferably 1.5 to 80 wt .-%, particularly preferably 2 to 70 wt .-%, more preferably 2.5 to 60 wt .-% and in particular 3 to 50 wt .-%, each based on the total weight of the active ingredient-containing polymer matrix is.

The automatic dishwasher detergents or automatic dishwashing auxiliaries according to the invention can contain the active ingredient-containing polymer matrix in different amounts. Depending on whether the active ingredient-containing polymer matrix is contained in the compositions, for example as a finely divided powder or granules, as part of a shaped body, or whether it encloses the composition as packaging, the proportions of the active ingredient-containing polymer matrix can vary in the overall composition. Preferred compositions according to the invention are those which, based on the total mass of the composition, are 1 to 40% by weight, preferably 1.5 to 35% by weight, more preferably 2 to 30% by weight and in particular 2.5 to 20 Wt .-% of the active ingredient-containing polymer matrix included.

Particularly preferred polymer matrices contain at least one zinc salt in such amounts that the composition comprises zinc in oxidized form in proportions by weight of from 0.01 to 1% by weight, preferably from 0.02 to 0.5% by weight and in particular from 0.04 to 0.2 wt .-%, each based on the total weight of the polymer matrix contains.

As mentioned at the beginning, incorporation of preferred active ingredient-containing polymer matrices into the compositions according to the invention does not entail any restriction with regard to the forms of preparation or the formulations of these compositions. Thus, in addition to conventional automatic dishwashing agents, pre-soaking or pre-rinsing products, rinse aid, machine care or additional products can be provided as a composition according to the invention. A preferred embodiment of the composition of the invention provides that the polymer matrix is provided as a separate part to be introduced into the dishwasher, which releases the agents from the polymer matrix over several rinse cycles. This molding can either be a Dosierkörbchen for other products, such as the cleaner, but it can also embody the added benefit of glass preservation as a separate and independent molding. Possible shapes are based, for example, on the known dishwasher Dodorantien. Visually attractive is the design of the plastic part in translucent, opalescent or completely clear form, for example in the form of a stylized diamond. By such product designs, the gloss resulting from the glass preservation can be visualized close to the consumer.

There are no limits to the variety of shape due to the possibilities of plastics processing. The active ingredient-containing polymer matrices can be easily converted by conventional methods.

The shaping processing takes place according to the usual in the plastics processing industry process, in particular, the film production and processing, blow molding and injection molding are preferred. All methods have in common that a plastic granules are melted by means of an extruder and fed to forming tools. In this case, the plastic granules may already contain the agents for glass corrosion inhibition, but these can also be added during the melting in the extruder, which allows a particularly cost-effective production of the inventively preferred active ingredient-containing polymer matrices.

In an additional preferred embodiment, the automatic dishwasher detergents or automatic dishwashing auxiliaries according to the invention are packaged in a manner which makes it possible to selectively apply and meter the active substances contained in these agents. For this purpose are in the context of the present application, in particular pen-shaped offer form, similar to a glue stick, do not change their spatial-geometric shape during storage and transport, but these, the offer form is moved under the influence of pressure over a surface, in their contact area loses with the surface due to the shear forces occurring there. The agent is smeared as a result of the shearing forces acting on the surface and remains there after the end of the action of the shear forces in its new spatial-geometric shape, so in turn is dimensionally stable. With the aid of such a preferred assembly, compositions according to the invention can be applied and metered in a targeted manner.

Such dimensionally stable automatic dishwashing detergents or dishwashing auxiliaries, which due to their material properties can be spread on a surface when subjected to a shearing force but remain in its spatial form without the action of a shearing force, can advantageously be characterized by their penetration numbers. Penetration number in the context of the present invention is the numerical value which results when determining the hardness of the agents according to the invention by means of a texture analyzer, model TA-XT2-I from Stable Micro Systems. To perform this measurement, the following test parameters are set: TA Fashion: Mass force in compression direction TA option: Simple test Trigger Value 0.2 g PPS 200

The penetration rate is determined by pressing a specific measuring tool (TA-15 45 ° cone made of stainless steel) at a defined feed rate (0.5 mm / s) to a defined penetration depth (5.0 mm) into the test material and then with a defined speed (0.2 mm / s) is pulled out of this material. The tested test materials had a temperature of 23 ° C, the measurements were carried out at 20 ° C room temperature. Based on the test setup described above, the measuring instrument determined a numerical value in units of grams [g]. This numerical value is referred to in the context of the present application as a penetration number. The measurements according to the described method have now shown that the preferred dimensionally stable automatic dishwashing or machine dishwashing auxiliary penetration numbers of 200 to 1000 g, preferably from 250 to 900 g, more preferably from 300 to 800 g and in particular from 350 to 700 g.

Another preferred subject of the present invention are therefore automatic dishwashing detergents or dishwashing auxiliaries according to the invention which are dimensionally stable and have a penetration number of from 200 to 1000 g, preferably from 250 to 900 g, more preferably from 300 to 800 g and in particular from 350 to 700 g.

The term "dimensionally stable" in the context of the present invention denotes automatic dishwashing detergents or dishwashing auxiliaries which have an intrinsic dimensional stability which enables them, under normal conditions of manufacture, storage, transport and handling by the consumer, to be stable against breakage, to have non-disintegrating spatial form, which does not change even under the conditions mentioned for a long time, that is under the usual conditions of manufacture, storage, transport and handling by the consumer persists in the caused by the production spatial-geometric shape that is, for example, does not melt.

The penetration number of 200 to 1000 g, which is characteristic for preferred agents according to the invention, can not be realized in their pure form by active substances such as zinc salts or layered silicates. It is therefore necessary to provide a carrier material or matrix material for these active substances, which corresponds to the stated physical requirements for an agent according to the invention. In addition, such a matrix should be compatible with active agents contained in it, ie in particular should not react with them, but stabilize them. In addition, the carrier materials should not jeopardize the intended cleaning process, ie they should also be compatible with all other substances used during the cleaning and / or maintenance process. Finally, the matrix material should preferably be water-soluble or water-dispersible in order to prevent the occurrence of residues to avoid after the application of the agent according to the invention. Particular preference is given to support materials which, in addition to the function as matrix for the active substance, simultaneously have a cleaning or care function. From the large number of possible carrier materials, a number of substance groups have proven to be particularly advantageous in the context of the present invention. These substances will be discussed in more detail below.

In the context of the present application, preferably dimensionally stable dishwashing detergents or dishwashing auxiliaries according to the invention are characterized in that they contain polyvinylpyrrolidone (s) and / or polyvinyl alcohol (s) and / or polyvinyl acetate (s) and / or polyacrylate (s) and / or Polyalkylene glycol (s) and / or fat (s) and / or fatty acid (s) and / or fatty acid esters and / or fatty acid amide (s) and / or fatty alcohols and / or wax (s) and / or parrafin (s) and / or Wax alcohols and / or surfactant (s), preferably nonionic (s) surfactant (s), and / or dextrin (s) and / or starch ethers, wherein the proportion by weight of this component / these components in the total weight of dimensionally stable machine dishwashing and / or Dishwashing auxiliary preferably between 30 and 99 wt.%, Particularly preferably between 40 and 95 wt .-% and in particular between 50 and 95 wt .-% is.

Automatic dishwashing detergents or automatic dishwashing auxiliaries according to the invention can also be formulated in the form of liquid or flowable agents, in addition to the solid or dimensionally stable forms described. In a further preferred embodiment of the present invention, the automatic dishwashing or machine dishwashing aids therefore have a viscosity of from 500 to 500,000 mPas, preferably from 900 to 200,000 mPas and in particular from 1300 to 100,000 mPas. The viscosity of the compositions according to the invention is measured by conventional standard methods (for example Brookfield LVT-II viscosimeter at 20 rpm and 20 ° C., spindle 3). The term "liquid or flowable agents" will be used hereafter for agents which have a viscosity of from 500 to 500,000 mPas, preferably from 900 to 200,000 mPas and especially from 1300 to 100,000 mPas.

As a preferred ingredient, such preferred liquid or flowable compositions of the invention contain one or more non-aqueous solvents. These are derived, for example, from the groups of monoalcohols, diols, triols or polyols, ethers, esters and / or amides. Particular preference is given to nonaqueous solvents which are water-soluble, "water-soluble" solvents in the sense of the present application being solvents which are completely miscible with water at room temperature, ie without a miscibility gap.

Suitable nonaqueous solvents are preferably from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the given concentration range. Preferably, the solvents are selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, etheylene glycol mono-n-butyl ether, diethylene glycol methyl ether , Diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents.

Nonionic surfactants which are liquid at room temperature are also preferred nonaqueous solvents in the context of the application.

A liquid or free-flowing machine dishwashing detergent or machine dishwashing auxiliary which is particularly preferred in the context of the present invention is characterized in that it contains nonaqueous solvents, the solvent (s) preferably being selected from the group of polyethylene glycols and polypropylene glycols, glycerol, glycerol carbonate , Triacetin, ethylene glycol, propylene glycol, propylene carbonate, hexylene glycol, ethanol, and n-propanol and / or iso-propanol.

Polyethylene glycols (abbreviated to PEG) which can preferably be used according to the invention are liquid at room temperature. PEG are polymers of ethylene glycol which are of the general formula (II)

H- (O-CH ₂ -CH ₂ ) _n -OH (II)

n, where n can assume values between 1 (ethylene glycol, see below) and about 16. For polyethylene glycols there are various nomenclatures that can lead to confusion. Technically common is the indication of the average relative molecular weight following the indication "PEG", so that "PEG 200" characterizes a polyethylene glycol having a relative molecular weight of about 190 to about 210. According to this nomenclature, the commercially available polyethylene glycols PEG 200, PEG 300, PEG 400 and PEG 600 can be used in the context of the present invention.

For cosmetic ingredients, another nomenclature is used in which the abbreviation PEG is hyphenated and directly followed by the hyphen followed by a number corresponding to the number n in the above formula. According to this nomenclature (so-called INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 ^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997) according to the invention, for example PEG-4, PEG-6, PEG-8, PEG-9, PEG-10, PEG-12, PEG-14 and PEG-16 can be used according to the invention.

Commercially available are polyethylene glycols, for example, under the trade name Carbowax® PEG 200 (Union Carbide), Emkapol® 200 (ICI Americas), Lipoxol® 200 MED (HUBS America), Polyglycol® E-200 (Dow Chemical), Alkapol® PEG 300 (Rhone -Poulenc), Lutrol® E300 (BASF) and the corresponding trade name with higher numbers.

genügen, wobei n Werte zwischen 1 (Propylenglycol, siehe unten) und ca. 12 annehmen kann. Technisch bedeutsam sind hier insbesondere Di-, Tri- und Tetrapropylenglycol, d.h. die Vertreter mit n=2, 3 und 4 in der vorstehenden Formel.Polypropylene glycols (abbreviation PPG) which can be used according to the invention are polymers of propylene glycol which correspond to the general formula (III)

n, where n can assume values between 1 (propylene glycol, see below) and about 12. Of particular technical importance here are di-, tri- and tetrapropylene glycols, ie the representatives with n = 2, 3 and 4 in the above formula.

Glycerin is a colorless, clear, heavy-bodied, odorless sweet-tasting hygroscopic liquid of density 1.261 that solidifies at 18.2 ° C. Glycerol was originally a by-product of fat saponification but is now technically synthesized in large quantities. Most technical processes are based on propene, which is processed into glycerol via the intermediates allyl chloride, epichlorohydrin. Another technical process is the hydroxylation of allyl alcohol with hydrogen peroxide at the WO ₃ contact via the step of the glycide.

Glycerol carbonate is accessible by transesterification of ethylene carbonate or dimethyl carbonate with glycerol, as by-products of ethylene glycol or methanol incurred. Another synthetic route is based on glycidol (2,3-epoxy-1-propanol), which is converted under pressure in the presence of catalysts with CO ₂ to glycerol carbonate. Glycerine carbonate is a clear, easily agitated liquid with a density of 1.398 gcm ^-3 , which boils at 125-130 ° C (0.15 mbar).

Ethylene Glycol (1,2-Ethanediol, "Glycol") is a colorless, viscous, sweet-tasting, highly hygroscopic liquid that is miscible with water, alcohols and acetone and has a density of 1.113. The solidification point of ethylene glycol is -11.5 ° C, the liquid boils at 198 ° C. Technically, ethylene glycol is recovered from ethylene oxide by heating with water under pressure. Promising manufacturing processes can also be built on the acetoxylation of ethylene and subsequent hydrolysis or on synthesis gas reactions.

There are two isomers of propylene glycol, 1,3-propanediol and 1,2-propanediol. 1,3-Propanediol (trimethylene glycol) is a neutral, colorless and odorless, sweet-tasting liquid of density 1,0597, which solidifies at -32 ° C and boils at 214 ° C. The preparation of 1,3-propanediol succeeds from acrolein and water with subsequent catalytic hydrogenation.

Technically much more significant is 1,2-propanediol (propylene glycol), which is an oily, colorless, almost odorless liquid, density 1.0381, which solidifies at -60 ° C and boils at 188 ° C. 1,2-Propanediol is prepared from propylene oxide by water addition.

Propylene carbonate is a water-bright, easily mobile liquid, with a density of 1.21 gcm ^-3 , the melting point is -49 ° C, the boiling point at 242 ° C. Also propylene carbonate is industrially accessible by reaction of propylene oxide and CO ₂ at 200 ° C and 80 bar.

In preferred liquid or flowable automatic dishwashing or machine dishwashing auxiliaries according to the invention, the nonaqueous solvent (s) is / are in amounts of from 0.1 to 70% by weight, preferably from 0.5 to 60% by weight, more preferably from 1 to 50 wt .-%, most preferably from 2 to 40 wt .-% and in particular from 2.5 to 30 wt .-%, each based on the total agent included.

In the context of this invention, "non-aqueous" is to be understood as meaning a state in which the content of free water in the agents is significantly below 5% by weight, based on the agent. It is preferred that the level of the automatic dishwashing or machine dishwashing aids of the invention be free, i. not present in the form of water of hydration and / or water of constitution below 10% by weight, preferably below 8% by weight and in particular even below 6% by weight, in each case based on the agent. Accordingly, water can be introduced into the agent substantially only in chemically and / or physically bound form or as a constituent of the raw materials or compounds present as solid, but not as a liquid, solution or dispersion.

As a further preferred ingredient, preferred liquid or free-flowing automatic dishwasher detergents or dishwashing auxiliaries according to the invention comprise one or more nonionic surfactants, in short nonionic surfactants. The amounts in which the nonionic surfactants are used are according to the invention preferably between 5 and 30% by weight, whereby according to the invention those agents which are 1 to 25% by weight are particularly preferred, preferably 2 to 22.5 wt .-%, particularly preferably 3 to 20 wt .-% and in particular 4 to 17.5 wt .-% nonionic (s) surfactant (s) included.

For a detailed description of these nonionic surfactants, reference is made to the following remarks on the preferred washing or cleaning-active ingredients of preferred compositions according to the invention in order to avoid repetitions at these points.

For viscosity control, the compositions according to the invention may comprise further ingredients, the use of which, for example, the settling behavior or the pourability or flowability can be specifically controlled. In non-aqueous systems in particular combinations of structurizers and thickeners have proven to be useful.

• ) 0,1 bis 1,0 Gew.-% eines oder mehrerer Strukturgeber aus der Gruppe der Bentonite und/oder mindestens teilweise veretherten Sorbitole sowie
• ) 5,0 bis 30 Gew.-% eines oder mehrerer Verdicker aus der Gruppe der Carbonate, Sulfate und amorphen oder kristallinen Disilikate.

In the context of the present invention, preferred automatic dishwashing detergents contain

• ) 0.1 to 1.0 wt .-% of one or more structurants from the group of bentonites and / or at least partially etherified sorbitol and
• ) 5.0 to 30 wt .-% of one or more thickeners from the group of carbonates, sulfates and amorphous or crystalline disilicates.

The structurant a) comes from the group of bentonites and / or at least partially etherified sorbitols. These substances are used to ensure the physical stability of the agents and to adjust the viscosity. Although conventional thickeners such as polyacrylates or polyurethanes fail in non-aqueous media, the viscosity control with the substances mentioned succeeds in the non-aqueous system.

Bentonites are contaminated clays caused by the weathering of volcanic tuffs. Due to their high content of montmorillonite, bentonites have valuable properties such as swellability, ion exchange capacity and thixotropy. It is possible to modify the properties of the bentonite according to the intended use. Bentonites are common as clay constituents in tropical soils and are used as sodium bentonite, e.g. mined in Wyoming / USA. Sodium bentonite has the most favorable application properties (swelling capacity), so that its use is preferred in the context of the present invention. Naturally occurring calcium bentonites originate, for example, from Mississippi / USA or Texas / USA or from Landshut / D. The naturally obtained Ca-bentonites are artificially converted by exchange of Ca for Na in the more swellable Na-bentonites.

The main constituents of the bentonites form so-called montmorillonites, which can also be used in their pure form in the context of the present invention. Montmorillonites are too the clay silicates and here to the dioctahedral smectites belonging clay minerals, which crystallize monoclinic pseudohexagonal. Montmorillonite form predominantly white, grayish-white to yellowish, completely amorphous appearing, easily friable, in the water swelling, but not plasticizing masses, by the general formulas

Al ₂ [(OH) ₂ / Si ₄ O ₁₀ ] .nH ₂ O

respectively.

Al ₂ O ₃ · 4SiO ₂ · H ₂ O · nH ₂ O

respectively.

Al ₂ [(OH) ₂ / Si ₄ O ₁₀ ]

(dried at 150 °)
can be described.

Preferred automatic dishwashing detergents or dishwashing auxiliaries are characterized in that montmorillonites are used as structurants. Montmorillonites have a three-layer structure consisting of two tetrahedral layers, which are electrostatically crosslinked via the cations of an octahedral intermediate layer. The layers are not rigidly connected, but can swell by reversible incorporation of water (in 2-7 times the amount) and other substances such as alcohols, glycols, pyridine, □ -picolin, ammonium compounds, hydroxy-aluminosilicate ions, etc. The above. Formulas are only approximate formulas since montmorillonites have a large ion exchange capacity. Thus Al can be exchanged for Mg, Fe ²⁺ , Fe ³⁺ , Zn, Cr, Cu and other ions. As a result of such substitution, a negative charge of the layers results, which is balanced by other cations, especially Na ⁺ and Ca ²⁺ .

In combination with the bentonites or as a substitute for them, if their use is not desired, at least partially etherified sorbitols can be used as structurants.

Sorbitol is a hexavalent 6-valent alcohol (sugar alcohol) that is relatively easy to split one or two moles of water intramolecularly and forms cyclic ethers (eg, sorbitan and sorbide). The removal of water is also possible intermolecularly, forming noncyclic ethers of sorbitol and the alcohols in question. Again, the formation of mono-ethers and bis-ethers is possible, with higher degrees of etherification such as 3 and 4 may occur. At least partially etherified sorbitols to be used in the context of the present invention are doubly etherified sorbitols, of which the dibenzylidenesorbitol is particularly preferred. Here, automatic dishwashing detergents which contain twice etherified sorbitols, in particular dibenzylidenesorbitol, as structurants are preferred.

The preferred liquid or flowable compositions according to the invention may contain the structurants in amounts of from 0.1 to 1.0% by weight, based on the total agent and on the active substance of the structurizer. Preferred agents contain the modifier in amounts of from 0.2 to 0.9% by weight, preferably in amounts of from 0.25 to 0.75% by weight and in particular in amounts of from 0.3 to 0.5% by weight. %, in each case based on the total mean.

As thickeners, the preferred liquid or flowable agents according to the invention may contain inorganic salts from the group of carbonates, sulfates and amorphous or crystalline disilicates. In principle, the said salts of all metals can be used, the alkali metal salts being preferred. Alkaline carbonate (s), alkali metal sulphate (s) and / or amorphous (s) and / or crystalline alkali metal disilicate (s), preferably sodium carbonate, sodium sulphate and / or amorphous or crystalline sodium disilicate, are particularly preferably used in the context of the present invention as thickener ,

The preferred liquid or flowable compositions according to the invention contain the thickeners in amounts of from 5 to 30% by weight, based on the total agent. Particularly preferred compositions contain the thickener (s) in amounts of 7.5 to 28 wt .-%, preferably in amounts of 10 to 26 wt .-% and in particular in amounts of 12.5 to 25 wt .-%, each based on the entire remedy.

With regard to an increased settling stability, it is preferred that the solids present in the agents according to the invention are used as finely divided as possible. This is particularly advantageous in the case of inorganic thickeners and bleaching agents. Here, automatic dishwashing detergents according to the invention are preferred in which the average particle size of the bleaching agents and thickeners and of the optionally used builder is less than 75 μm, preferably less than 50 μm and in particular less than 25 μm.

The liquid automatic dishwashing compositions according to the invention may also contain other viscosity regulators or thickeners for adjusting a possibly desired higher viscosity. In this case, all known thickening agents can be used, ie those based on natural or synthetic polymers.

Naturally derived polymers which are used as thickening agents are, for example, agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and casein. Modified natural products come mainly from the group of modified starches and celluloses, examples which may be mentioned here carboxymethylcellulose and other cellulose ethers, hydroxyethyl and propylcellulose and core flour ethers.

In the context of the present invention, preferred liquid or free-flowing automatic dishwashing or machine dishwashing aids comprise, as thickening agents, hydroxyethylcellulose and / or hydroxypropylcellulose, preferably in amounts of from 0.01 to 4.0% by weight, more preferably in amounts of from 0.01 to 3, 0 wt .-% and in particular in amounts of 0.01 to 2.0 wt .-%, each based on the total agent.

A large group of thickeners, which find wide use in a variety of applications, are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes.

Thickeners from the substance classes mentioned are commercially widely available and are described, for example, under the trade names Acusol®-820 (methacrylic acid (stearyl alcohol-20-EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral® GT 282-S (alkyl polyglycol ether, Akzo), Deuterol® polymer 11 (dicarboxylic acid copolymer, Schöner GmbH), Deuteron®-XG (anionic heteropolysaccharide based on β-D-glucose, D-mannose, D-glucuronic acid, Schöner GmbH ), Deuteron®-XN (nonionic polysaccharide, Schöner GmbH), Dicrylan® thickener-O (ethylene oxide adduct, 50% in water / isopropanol, Pfersse Chemie), EMA®-81 and EMA®-91 (ethylene-maleic anhydride Copolymer, Monsanto), thickener-QR-1001 (polyurethane emulsion, 19-21% in water / diglycol ether, Rohm & Haas), Mirox®-AM (anionic acrylic acid-acrylic ester copolymer dispersion, 25% in water, Stockhausen), SER-AD-FX-1100 (hydrophobic urethane polymer, Servo Delden), Shellflo®-S (high molecular weight polysaccharide stabilized with formaldehyde, Shell) and Shellflo®-XA (xanthan biopolymer stabilized with formaldehyde, Shell).

A preferred polymeric thickener is xanthan gum, a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and having a molecular weight of from 2 to 15 million daltons. Xanthan is formed from a chain of β-1,4-linked glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan gum.

Also preferably used in the context of the present invention thickeners are polyurethanes or modified polyacrylates, which, based on the total agent, for example, in amounts of 0.1 to 5 wt .-% can be used.

in der R¹ für einen niedermolekularen oder polymeren Diol-Rest, R² für eine aliphatische oder aromatische Gruppe und n für eine natürliche Zahl steht. R¹ ist dabei vorzugsweise eine lineare oder verzweigte C_2-12-Alk(en)ylgruppe, kann aber auch ein Rest eines höherwertigen Alkohols sein, wodurch quervernetzte Polyurethane gebildet werden, die sich von der oben angegebenen Formel VIII dadurch unterscheiden, daß an den Rest R¹ weitere -O-CO-NH-Gruppen gebunden sind.Polyurethanes (PUR) are prepared by polyaddition from dihydric and higher alcohols and isocyanates and can be described by the general formula IV

in which R ^{1 is} a low molecular weight or polymeric diol radical, R ^{2 is} an aliphatic or aromatic group and n is a natural number. R ¹ is preferably a linear or branched C _2-12 -alk (en) yl group, but may also be a residue of a higher-valent alcohol, whereby crosslinked polyurethanes are formed, which differ from the formula VIII given above in that the Rest R ¹ further -O-CO-NH groups are bonded.

Technically important PU are from polyester and / or polyether diols and, for example, from 2,4- and 2,6-toluene diisocyanate (TDI, R ² = C ₆ H ₃ -CH ₃ ), 4,4'-methylenedi (phenyl isocyanate) (MDI, R ² = C ₆ H ₄ -CH ₂ -C ₆ H ₄ ) or hexamethylene diisocyanate [HMDI, R ² = (CH ₂ ) ₆ ].

Commercially available polyurethane-based thickeners are known, for example, under the names Acrysol®PM 12 V (3-5% modified starch mixture and 14-16% PUR resin in water, Rohm & Haas), Borchigel® L75-N (nonionic PUR dispersion, 50% in water, Borchers), Coatex® BR-100-P (PUR dispersion, 50% in water / butylglycol, Dimed), Nopco® DSX-1514 (polyurethane dispersion, 40% in water / butyltriglycol, Henkel-Nopco), thickener QR 1001 (20% PUR emulsion in water / diglycol ether, Rohm & Haas) and Rilanit® VPW-3116 (PUR dispersion, 43% in water, Henkel). For the purposes of the present invention, when using aqueous dispersions, care must be taken that the water content of the agents according to the invention remains within the abovementioned limits. If the use of the aqueous dispersions for these reasons is not possible, dispersions in other solvents, or even the solids can be used.

in der R³ für H oder einen verzweigten oder unverzweigten C_1-4-Alk(en)ylrest, X für N-R⁵ oder O, R⁴ für einen gegebenenfalls alkoxylierten verzweigten oder unverzweigten, evtl. substituierten C_8-22-Alk(en)ylrest, R⁵ für H oder R⁴ und n für eine natürliche Zahl steht. Allgemein sind solche modifizierten Polyacrylate Ester oder Amide von Acrylsäure bzw. einer α-substituierten Acrylsäure. Unter diesen Polymeren bevorzugt sind solche, bei denen R³ für H oder eine Methylgruppe steht. Bei den Polyacrylamiden (X = N-R⁵) sind sowohl einfach (R⁵ = H) als auch zweifach (R⁵ = R⁴) N-substituierte Amidstrukturen möglich, wobei die beiden Kohlenwasserstoffreste, die an das N-Atom gebunden sind, unabhängig voneinander aus gegebenenfalls alkoxylierten verzweigten oder unverzweigten C_8-22-Alk(en)ylresten ausgewählt werden können. Unter den Polyacrylestern (X = O) sind solche bevorzugt, in denen der Alkohol aus natürlichen oder synthetischen Fetten bzw. Ölen gewonnen wurde und zusätzlich alkoxyliert, vorzugsweise ethoxyliert ist. Bevorzugte Alkoxlierungsgrade liegen zwischen 2 und 30, wobei Alkoxylierungsgrade zwischen 10 und 15 besonders bevorzugt sind.Modified polyacrylates which can be used in the context of the present invention are derived, for example, from acrylic acid or methacrylic acid and can be described by the general formula V.

in the R ^{3 is} H or a branched or unbranched C _1-4 -alk (en) yl radical, X is NR ⁵ or O, R ^{4 is} an optionally alkoxylated branched or unbranched, possibly substituted C _8-22- Alk (en ) ylrest, R ^{5 is} H or R ⁴ and n is a natural number. In general, such modified polyacrylates are esters or amides of acrylic acid or of an α-substituted acrylic acid. Preferred among these polymers are those in which R ^{3 is} H or a methyl group. In the polyacrylamides (X = NR ⁵ ), both simple (R ⁵ = H) and also doubly (R ⁵ = R ⁴ ) N-substituted amide structures are possible, the two hydrocarbon radicals which are bonded to the N atom being independent of one another from optionally alkoxylated branched or unbranched C _8-22 -alk (en) ylresten can be selected. Among the polyacrylic esters (X = O), preference is given to those in which the alcohol was obtained from natural or synthetic fats or oils and additionally alkoxylated, preferably ethoxylated. Preferred alkoxylation levels are between 2 and 30, with degrees of alkoxylation between 10 and 15 being particularly preferred.

Since the polymers which can be used are technical compounds, the designation of the radicals bound to X represents a statistical mean value which, in individual cases, can vary with regard to chain length or degree of alkoxylation. The formula V indicates only formulas for idealized homopolymers. In the context of the present invention, however, it is also possible to use copolymers in which the proportion of monomer units which satisfy the formula V is at least 30% by weight. For example, it is also possible to use copolymers of modified polyacrylates and acrylic acid or salts thereof which still have acidic H atoms or basic -COO ^- groups.

in der R⁴ für einen vorzugsweise unverzweigten, gesättigten oder ungesättigten C_8-22-Alk(en)ylrest, R⁶ und R⁷ unabhängig voneinander für H oder CH₃ stehen, der Polymerisationsgrad n eine natürliche Zahl und der Alkoxylierungsgrad a eine natürliche Zahl zwischen 2 und 30, vorzugsweise zwischen 10 und 20 ist. R⁴ ist dabei vorzugsweise ein Fettalkoholrest, der aus natürlichen oder synthetischen Quellen gewonnen wurde, wobei der Fettalkohol wiederum bevorzugt ethoxyliert (R⁶=H)ist.Modified polyacrylates which are preferably used for the purposes of the present invention are polyacrylate-polymethacrylate copolymers which satisfy the formula Va

in which R ^{4 is} a preferably unbranched, saturated or unsaturated C _8-22- alk (en) yl radical, R ⁶ and R ⁷ independently of one another are H or CH ₃ , the degree of polymerization n is a natural number and the degree of alkoxylation a is a natural number between 2 and 30, preferably between 10 and 20. R ⁴ is preferably a fatty alcohol radical which has been obtained from natural or synthetic sources, the fatty alcohol in turn preferably ethoxylated (R ⁶ = H).

Products of the formula Va are commercially available, for example, under the name Acusol® 820 (Rohm & Haas) in the form of 30% strength by weight dispersions in water. In the commercial product mentioned, R ⁴ is a stearyl radical, R ⁶ is a hydrogen atom, R ⁷ is H or CH ₃ and the degree of ethoxylation a is 20. In this dispersion, the above applies to the water content of the Mitttel said.

in der R³ für H oder einen verzweigten oder unverzweigten C_1-4-Alk(en)ylrest, X für N-R⁵ oder O, R⁴ für einen gegebenenfalls alkoxylierten verzweigten oder unverzweigten, evtl. substituierten C_8-22-Alk(en)ylrest, R⁵ für H oder R⁴ und n für eine natürliche Zahl steht, enthalten.In the context of the present invention, preferred liquid or free-flowing automatic dishwasher detergents or dishwashing auxiliaries are characterized in that they additionally contain 0.01 to 5 wt.%, Preferably 0.02 to 4 wt.%, Particularly preferably 0.05 to 3 wt .-% and in particular 0.1 to 1.5 wt .-%, of a polymeric thickener, preferably from the group of polyurethanes or modified polyacrylates, with particular preference to thickeners of formula VI

in the R ^{3 is} H or a branched or unbranched C _1-4 -alk (en) yl radical, X is NR ⁵ or O, R ^{4 is} an optionally alkoxylated branched or unbranched, possibly substituted C _8-22- Alk (en ) yl radical, R ^{5 is} H or R ⁴ and n is a natural number.

The solid or dimensionally stable and liquid or free-flowing automatic dishwashing or dishwashing auxiliaries according to the invention can be offered to the consumer in conventional containers, for example bottles, screw jars, canisters, balloons, cups or spray vessels, from which they are dosed for use. Higher viscosity products can also be offered in tubes or dispensers as known from toothpaste or sealants. Such containers are today usually made of non-water-soluble polymers and may for example consist of all common water-insoluble packaging materials, which are well known to those skilled in the art. In particular, polymers based on hydrocarbons may be mentioned as preferred polymers. Particularly preferred polymers include polyethylene, polypropylene (more preferably oriented polypropylene) and polymer blends such as blends of said polymers with polyethylene terephthalate. Also suitable are one or more polymers from the group consisting of polyvinyl chloride, polysulfones, polyacetals, water-insoluble cellulose derivatives, cellulose acetate, cellulose propionate, cellulose acetobutyrate and mixtures of said polymers or copolymers comprising said polymers.

A particularly preferred embodiment of the present invention, however, aims to provide the consumer with pre-portioned means according to the invention so that he can use the dosing advantages known to him from the "tablet" offering and combine them with the rapid dissolution and release rates and the performance advantages of the agents according to the invention can. Such pre-portioned agents according to the invention may also be present in water-insoluble packaging, so that the consumer must open them before use in a suitable manner. However, it is also possible and preferred to package portioned compositions according to the invention so that the consumer can give them without further handling steps directly, ie together with the packaging, into the dishwasher. Such packages include water-soluble or decomposable packages such as bags of water-soluble film (so-called pouches), bags or other packaging of water-soluble or decomposable nonwovens or flexible or rigid bodies of water-soluble polymers, preferably in the form of filled hollow body, which for example by deep drawing, injection molding , Blow molding, calendering, etc. can be made.

A preferred subject matter of the present invention are therefore automatic dishwashing detergents or dishwashing auxiliaries according to the invention, which are packaged in portions in a water-soluble casing.

Dishwasher detergents or dishwashing auxiliaries according to the invention preferably comprise a completely or partially water-soluble coating. The shape of the wrapper is not limited to specific shapes. Basically, all Archimedean and Platonic bodies, ie three-dimensional shaped bodies, come into question as forms of envelopment. Examples of the shape of the wrapper are capsules, cubes, spheres, ovoid moldings, cuboids, cones, rods or bags. Also hollow body with one or more compartments are suitable as a sheath for the Geschirreinigungsmittel. In preferred embodiments of the invention, the wrappers are in the form of capsules, such as those used in pharmacy for the administration of drugs, spheres or bags. The latter are preferably welded or glued on at least one side, wherein the adhesive used in particularly preferred embodiments of the invention is an adhesive that is water-soluble.

According to a preferred embodiment of the invention, the water-soluble polymer material which partially or completely surrounds the automatic dishwashing or dishwashing auxiliary is a water-soluble packaging. This is understood to mean a flat part which partially or completely surrounds the dishwashing detergent. The exact form of such packaging is not critical and can be largely adapted to the conditions of use. For example, processed plastic foils or sheets, capsules and other conceivable forms come into consideration for various forms (such as hoses, cushions, cylinders, bottles, disks or the like). Particularly preferred according to the invention are films which, for example, can be bonded and / or sealed to packagings such as hoses, cushions or the like, after they have been filled with partial portions of the cleaning agents according to the invention or with the cleaning agents according to the invention.

Further preferred are, according to the invention, due to the excellent adaptable to the desired physical conditions properties plastic film packaging of water-soluble polymer materials. Such films are basically known from the prior art.

In summary, both hollow body of any shape, which can be produced by injection molding, bottle blowing, deep drawing, etc., as well as hollow body of films, in particular bags (so-called pouches) as packages for portioned inventive Medium preferred. Preferred automatic dishwasher detergents or dishwashing auxiliaries according to the invention are thus characterized in that the water-soluble casing comprises a bag of water-soluble film and / or an injection-molded part and / or a blow-molded part and / or a deep-drawn part.

According to the invention, it is preferred that the one or more enclosures are / are completed. This has the advantage that the Geschirreinigungsmittel are optimally protected against the effects of the environment, especially against moisture. In addition, with these closed enclosures, the invention can be further developed such that the detergents contain at least one gas to protect the contents of the enclosure (s) from moisture, see below.

Suitable materials for the completely or partially water-soluble coating are in principle all materials in question, which can completely or partially dissolve in the aqueous phase under the given conditions of a washing process, rinsing or cleaning process (temperature, pH, concentration of detergent components). The polymer materials may particularly preferably the groups (optionally partially acetalized) polyvinyl alcohol, polyvinylpyrrolidone, poly-ethylene oxide, gelatin, cellulose and derivatives thereof, starch and derivatives thereof, in particular modified starches, and mixtures (polymer blends, composites, coextrudates, etc.) of belong to the materials mentioned. Particularly preferred are gelatin and polyvinyl alcohols and the two materials mentioned in each case in combination with starch or modified starch. There are also inorganic salts and mixtures thereof as materials for the at least partially water-soluble envelope in question.

Preferred automatic dishwasher detergents or dishwashing auxiliaries according to the invention are characterized in that the coating comprises one or more materials from the group of acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters and polyethers and mixtures thereof.

Particularly preferred automatic dishwasher detergents or dishwashing auxiliaries according to the invention are characterized in that the coating comprises one or more water-soluble polymer (s), preferably a material from the group (optionally acetalised) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and their derivatives and mixtures thereof, more preferably (optionally acetalized) polyvinyl alcohol (PVAL).

die in geringen Anteilen (ca. 2%) auch Struktureinheiten des Typs

enthalten."Polyvinyl alcohols" (abbreviated PVAL, occasionally PVOH) is the name for polymers of the general structure

in small proportions (about 2%) also structural units of the type

contain.

Commercially available polyvinyl alcohols, which are available as white-yellowish powders or granules with degrees of polymerization in the range of about 100 to 2500 (molar masses of about 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , so still contain a residual content of acetyl groups. The polyvinyl alcohols are characterized by the manufacturer by indicating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and a few highly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically safe and are biologically at least partially degradable. The water solubility can be reduced by aftertreatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid or borax. The coatings of polyvinyl alcohol are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.

In the context of the present invention it is preferred that the coating comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol% ,

Polyvinyl alcohols of a certain molecular weight range are preferably used as materials for the coating, it being preferred according to the invention for the coating to comprise a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol ^-1 , preferably from 11,000 to 90,000 gmol ^-1 , more preferably from 12,000 to 80,000 gmol ^-1 and in particular from 13,000 to 70,000 gmol ^-1 .

The degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and most preferably between about 260 to about 1500.

The polyvinyl alcohols described above are widely available commercially, for example under the trademark Mowiol® (Clariant). Polyvinyl alcohols which are particularly suitable for the purposes of the present invention are, for example, Mowiol® 3-83, Mowiol® 4-88, Mowiol® 5-88 and Mowiol® 8-88.

Further polyvinyl alcohols which are particularly suitable as material for the hollow bodies are shown in the following table: description Degree of hydrolysis [%] Molecular weight [kDa] Melting point [° C] Airvol® 205 88 15-27 230 Vinex® 2019 88 15-27 170 Vinex® 2144 88 44 - 65 205 Vinex® 1025 99 15-27 170 Vinex® 2025 88 25 - 45 192 Gohsefimer® 5407 30 - 28 23,600 100 Gohsefimer® LL02 41 - 51 17,700 100

Other suitable polyvinyl alcohols for the mold are ELVANOL® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX ® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.), Gohsenol® NK-05, A-300, AH-22, C -500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (Trademark of Nippon Gohsei KK ).

The water solubility of PVAL can be altered by post-treatment with aldehydes (acetalization) or ketones (ketalization). Polyvinyl alcohols which are acetalated or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly advantageous and particularly advantageous on account of their pronounced cold water solubility. To use extremely advantageous are the reaction products of PVAL and starch.

Furthermore, the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus set specifically to desired values. Films made of PVAL are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.

Examples of suitable water-soluble PVAL films are the PVAL films available under the name "SOLUBLON®" from Syntana Handelsgesellschaft E. Harke GmbH & Co. Their solubility in water can be adjusted to the exact degree, and films of this product series are available which are soluble in aqueous phase in all temperature ranges relevant for the application.

Polyvinylpyrrolidones, referred to as PVP for short, can be described by the following general formula:

PVP are prepared by radical polymerization of 1-vinylpyrrolidone. Commercially available PVP have molecular weights in the range of about 2,500 to 750,000 g / mol and are offered as white, hygroscopic powders or as aqueous solutions.

Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula

H- [O-CH ₂ -CH ₂ ] _n -OH

the technically by alkaline-catalyzed polyaddition of ethylene oxide (oxirane) in mostly small amounts of water-containing systems are prepared with ethylene glycol as the starting molecule. They have molar masses in the range of about 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n of about 5 to> 100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and show only weak glycol properties.

Gelatin is a polypeptide (molecular weight: about 15,000 to> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions. The amino acid composition of gelatin is broadly similar to that of the collagen from which it was obtained and varies depending on its provenance. The use of gelatin as the water-soluble shell material is especially in pharmacy in the form of hard or soft gelatin capsule extremely widespread. In the form of films, gelatin has little use because of its high price compared to the polymers mentioned above.

Also preferred in the context of the present invention are dishwashing detergents whose packaging consists of at least partially water-soluble film of at least one polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methylcellulose and mixtures thereof.

Starch is a homoglycan, wherein the glucose units are linked α-glycosidically. Starch is composed of two components of different molecular weight: from about 20 to 30% straight chain amylose (MW about 50,000 to 150,000) and 70 to 80% branched chain amylopectin (MW about 300,000 to 2,000,000). In addition, small amounts of lipids, phosphoric acid and cations are still included. While the amylose forms long, helical, entangled chains with about 300 to 1,200 glucose molecules as a result of the binding in the 1,4-position, the chain branched in amylopectin after an average of 25 glucose building blocks by 1,6-bonding to a branch-like structure with about 1,500 to 12,000 molecules of glucose. In addition to pure starch, starch-derivatives which are obtainable from starch by polymer-analogous reactions are also suitable for the preparation of water-soluble coatings of the detergent, detergent and cleaner portions in the context of the present invention. Such chemically modified starches include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. But even starches in which the hydroxy groups have been replaced by functional groups that are not bound by an oxygen atom, can be used as starch derivatives. The group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and ethers, and amino starches.

Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5,000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives.

The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.

Preferred casings of at least partially water-soluble film comprise at least one polymer having a molecular weight between 5,000 and 500,000 g / mol, preferably between 7,500 and 250,000 g / mol and in particular between 10,000 and 100,000 g / mol. Depending on the production method, the casing has different material thicknesses, automatic dishwashing agents or automatic dishwashing auxiliaries according to the invention being preferred in which the wall thickness of the casing is 10 to 5000 μm, preferably 20 to 3000 μm, particularly preferably 25 to 2000 μm and in particular 100 to 1500 μm ,

If film pouches (so-called pouches) are selected as the packaging, then the water-soluble film forming the coating preferably has a thickness of 1 to 300 μm, preferably 2 to 200 μm, more preferably 5 to 150 μm and in particular 10 to 100 μm, up.

These water-soluble films can be produced by various production methods. Blow molding, calendering and casting processes should be mentioned here in principle. In a preferred method, the films are blown starting from a melt with air through a mandrel to a hose. In the case of the calendering process, which is likewise one of the preferred production processes, the raw materials plasticized by suitable additives are atomized to form the films. In particular, it may be necessary to attach drying to the atomizations. In the casting process, which is also one of the preferred production methods, an aqueous polymer preparation is placed on a heatable drying roller, after the evaporation of the water is optionally cooled and the film is peeled off as a film. Optionally, this film is additionally powdered before or during the removal.

According to the invention, an embodiment is preferred in accordance with which the coating is water-soluble as a whole, ie, dissolves completely under normal use during mechanical cleaning when the conditions for release are reached. Particularly preferred as completely water-soluble coatings z. B. gelatin capsules, advantageously of soft gelatin, or bags of (optionally partially acetalized) PVAL or balls of gelatin or (optionally partially acetalized) PVAL or of one or more organic and / or inorganic salts, preferably spheres of soft gelatin. The essential advantage of this embodiment is that the sheath within a practically relevant short time - as a non-limiting example can be a few seconds to 5 min - at least partially dissolves under precisely defined conditions in the cleaning liquor and thus according to the requirements, the coated content, ie the cleaning-active material or several materials in the fleet brings.

In another embodiment of the invention, which is also preferred because of its advantageous properties, the water-soluble coating comprises regions which are less soluble or not water-soluble or only water-soluble at relatively high temperatures and regions which are readily soluble in water or soluble in water at low temperature. In other words, the coating does not consist of a uniform material that has the same water solubility in all areas, but of materials of different water solubility. On the one hand, areas of good water solubility are to be distinguished from areas with less good water solubility, with poor or even absent water solubility or areas in which the water solubility reaches the desired value only at a higher temperature or only at a different pH value or only when the electrolyte concentration has changed achieved, on the other hand. This may result in certain areas of the enclosure becoming disengaged under normal conditions of use, while other areas remain intact. Thus, an envelope provided with pores or holes is formed, into which water and / or liquor can penetrate, which can dissolve washing-active, rinse-active or cleaning-active ingredients and remove them from the casing. In the same way, wrapping systems in the form of multi-chamber bags or in the form of nested hollow bodies (eg balls: "onion system") can also be provided. Thus, controlled release systems of the detergent-active, rinse-active or cleaning-active ingredients can be produced.

To form such systems, the invention is not limited. Thus, wraps can be provided in which a uniform polymeric material comprises small areas of incorporated compounds (for example, salts) which are more rapidly soluble in water than the polymeric material. On the other hand, several polymer materials with different water solubility can be mixed (polymer blend), so that the faster soluble polymer material is disintegrated faster under defined conditions by water or the liquor than the slower soluble.

It is in accordance with a particularly preferred embodiment of the invention that the less readily water-soluble or water-insoluble areas or areas of the enclosure which are water-soluble at higher temperatures are areas of a material chemically substantially that of the water-soluble or water-soluble areas but has a higher layer thickness and / or has a modified degree of polymerization of the same polymer and / or has a higher degree of crosslinking of the same polymer structure and / or a higher degree of acetalization (in PVAL, for example with saccharides, polysaccharides, such as starch) and / or has a content of water-insoluble salt components and / or has a content of a water-insoluble polymer. Even taking into account the fact that the enclosure does not dissolve completely, it is thus possible to provide detergent portions according to the invention which have advantageous properties in the release of the dishwashing detergent into the respective liquor.

The water-soluble shell material is preferably transparent. For the purposes of this invention, transparency means that the transmittance within the visible spectrum of the light (410 to 800 nm) is greater than 20%, preferably greater than 30%, more preferably greater than 40% and in particular greater than 50%. Thus, once a wavelength of the visible spectrum of the light has a transmittance greater than 20%, it is to be regarded as transparent within the meaning of the invention.

Dishwashing detergents according to the invention, which are packaged in transparent envelopes or containers, can contain a stabilizing agent as an essential constituent. Stabilizing agents in the context of the invention are materials which protect the detergent components in their water-soluble, transparent sheaths from decomposition or deactivation by light irradiation. Antioxidants, UV absorbers and fluorescent dyes have proven to be particularly suitable here.

Particularly suitable stabilizing agents in the context of the invention are the antioxidants. In order to prevent undesirable changes in the formulations caused by light irradiation and thus radical decomposition, the formulations may contain antioxidants. Examples of antioxidants which may be used here are sterically hindered groups, substituted phenols, bisphenols and thiobisphenols. Further examples are propyl gallate, butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), t-butylhydroquinone (TBHQ), tocopherol and the long chain (C8-C22) esters of gallic acid, such as dodecyl gallate. Other classes of compounds are aromatic amines, preferably secondary aromatic amines and substituted p-phenylenediamines, phosphorus compounds with trivalent phosphorus such as phosphines, phosphites and phosphonites, citric acids and citric acid derivatives such as isopropyl citrate, endiol group-containing compounds, so-called reductones such as ascorbic acid and its derivatives, such as ascorbic palmitate, organosulfur compounds, such as the esters of 3,3'-thiodipropionic acid with C _1-18 alkanols, especially C _10-18 alkanols, metal ion deactivators capable of auto-oxidation catalyzing metal ions, such as Copper, such as nitrilotriacetic acid and its derivatives and their mixtures. Antioxidants may be present in the formulations in amounts of up to 35% by weight, preferably up to 25% by weight, particularly preferably from 0.01 to 20 and in particular from 0.03 to 20% by weight.

Another class of preferably usable stabilizers are the UV absorbers. UV absorbers can improve the light stability of the formulation ingredients. By this are meant organic substances (sunscreen filters) capable of absorbing ultraviolet rays and absorbing the absorbed energy in the form of longer wavelength radiation, e.g. Heat again. Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. Furthermore, substituted benzotriazoles, such as the water-soluble benzenesulfonic acid 3- (2H-benzotriazol-2-yl) -4-hydroxy-5- (methylpropyl) monosodium salt (Cibafast® H), in the 3-position phenyl-substituted acrylates (cinnamic acid derivatives) , optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's urocanic acid suitable. Of particular importance are biphenyl derivatives, in particular stilbene derivatives, which are commercially available as Tinosorb® FD or Tinosorb® FR ex Ciba. As UV-B absorbers there may be mentioned 3-benzylidene camphor or 3-benzylidene norcamphor and its derivatives, e.g. 3- (4-methylbenzylidene) camphor; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and 4- (dimethylamino) benzoic acid ester; Esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester, 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene); Esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomenthyl salicylate; Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate; Triazine derivatives, e.g. 2,4,6-trianilino (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine and octyl triazone or dioctyl butamido triazone (Uvasorb® HEB); Propane-1,3-diones, such as e.g. 1- (4-tert-butylphenyl) -3- (4'methoxyphenyl) propane-1,3-dione; Ketotricyclo (5.2.1.0) decane derivatives. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts; Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts; Sulfonic acid derivatives of the 3-benzylidene camphor, e.g. 4- (2-Oxo-3-bomylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) -sulfonic acid and its salts.

As a typical UV-A filter in particular derivatives of benzoylmethane are suitable, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl 4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) -propane-1,3-dione and enamine compounds. Of course, the UV-A and UV-B filters can also be used in mixtures be used. In addition to the soluble substances mentioned, insoluble photoprotective pigments, namely finely dispersed, preferably nano-metal oxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are in particular zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof. As salts silicates (talc), barium sulfate or zinc stearate can be used. The oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They may have a spherical shape, but it is also possible to use those particles which have an ellipsoidal or otherwise deviating shape from the spherical shape. The pigments can also be surface-treated, ie hydrophilized or hydrophobized. Typical examples are coated titanium dioxides, such as titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Suitable hydrophobic coating agents are in particular silicones and in particular trialkoxyoctylsilanes or simethicones. Preferably, micronized zinc oxide is used.

UV absorbers may be present in the dishwashing detergents in amounts of up to 5% by weight, preferably up to 3% by weight, particularly preferably from 0.01 to 2.0 and in particular from 0.03 to 1% by weight.

Another preferred class of stabilizers to be used are the fluorescent dyes. These include the 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methyl umbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole, benzisoxazole and Benzimidazole systems and substituted by heterocycles pyrene derivatives. Of particular importance are the sulfonic acid salts of diaminostilbene derivatives, as well as polymeric fluorescent substances, as disclosed in US 5,082,578.

Fluorescent substances can be present in the formulations in amounts of up to 5% by weight, preferably up to 1% by weight, particularly preferably from 0.01 to 0.5 and in particular from 0.03 to 0.1% by weight.

In a preferred embodiment, the abovementioned stabilizers are used in any mixtures. The stabilizers are used in amounts of up to 40% by weight, preferably up to 30% by weight, particularly preferably from 0.01 to 20% by weight, in particular from 0.02 to 5% by weight.

Irrespective of the nature of their preparation, preferred automatic dishwashing or machine dishwashing aids comprise at least one washing or cleaning substance from the group of bleaching agents, bleach activators, polymers, builders, surfactants, enzymes, electrolytes, pH adjusters, fragrances, perfume carriers, dyes, hydrotropes, Foam inhibitors, antimicrobial agents, germicides, fungicides, corrosion inhibitors, non-aqueous solvents. These substances will be described in more detail in the following.

Builder

According to the present invention, all builders commonly used in detergents and cleaning agents, in particular silicates, carbonates, organic cobuilders and also the phosphates, may be incorporated in the automatic dishwashing or dishwashing auxiliaries.

Suitable crystalline layered sodium silicates have the general formula NaMSi _x O _{2x + 1} H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ yH ₂ O are preferred.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

As carbonates, both the monoalkali metal salts and the dialkali metal salts of carbonic acid as well as sesquicarbonates can be contained in the compositions. Preferred alkali metal ions represent sodium and / or potassium ions. In one embodiment, it may be preferable to mix the carbonate and / or bicarbonate at least partially as a further component separately or subsequently. Compounds of, for example, carbonate, silicate and optionally other auxiliaries such as, for example, anionic surfactants or other, in particular organic builders, may be present as a separate component in the finished compositions.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Among the large number of commercially available phosphates, the alkali metal phosphates, with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.

Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent limescale deposits on machine parts or limescale deposits on the items to be washed and also contribute to the cleaning performance.

Suitable phosphates are the sodium dihydrogen phosphate, NaH ₂ PO ₄ , the disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , the trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , the tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , by condensation of NaH ₂ PO ₄ and KH ₂ PO ₄ , respectively, form relatively high molecular weight sodium and potassium phosphates, in which cyclic representatives, which can distinguish sodium or potassium metaphosphates and chain types, the sodium and potassium polyphosphates, as well as the pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate).

In addition to the sodium phosphate, it is also possible to use the corresponding potassium salts or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.

In the context of the present invention, preferred automatic dishwashing or machine dishwashing aids contain no sodium and / or potassium hydroxide.

Further preferred water-soluble builders are, for example, tripotassium citrate and the potassium water glasses.

Preferred automatic dishwashing or dishwashing auxiliaries contain from 20 to 60% by weight of one or more water-soluble builders, preferably citrates and / or phosphates, preferably alkali metal phosphates, with particular preference of pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate).

In preferred embodiments of the present invention, the level of water-soluble builders is within narrower limits. Here, preference is given to automatic dishwashing detergents or dishwashing auxiliaries which contain the water-soluble builder (s) in amounts of from 22.5 to 55% by weight, preferably from 25 to 50% by weight and in particular from 27.5 to 45% by weight. -%, in each case based on the total mean.

With particular preference, the compositions according to the invention may contain phosphates condensed as water-softening substances. These substances form a group of - because of their production also mentioned melting or annealing phosphates - phosphates, which can be derived from acidic salts of orthophosphoric acid (phosphoric acids) by condensation. The condensed phosphates can be classified into the metaphosphates [Mnn (PO ₃ ) _n ] and polyphosphates (M ^I _{n + 2} P _n O _{3n + 1} or M ^I _n H ₂ P _n O _{3n + 1} ).

The term "metaphosphates" was originally the general term for condensed phosphates of the composition M _n [P _n O _3n ] (M = monovalent metal), but today is usually limited to salts with cyclic cyclo (poly) phosphate anions. At n = 3, 4, 5, 6, etc. one speaks of tri-, tetra-, penta-, hexa-metaphosphates. etc. According to the systematic nomenclature of isopolyanions z. B. called the anion with n = 3 as cyclo triphosphate.

Metaphoaphates are obtained as accompanying substances of Graham's salt - mistakenly referred to as sodium hexametaphosphate - by melting NaH ₂ PO ₄ to temperatures above 620 ° C., so-called Maddrell's salt also being produced as an intermediate. This and Kurrolsches salt are linear polyphosphates, which are usually not one of the metaphosphates today, but also in the context of the present invention are also used with preference as water-softening substances.

The crystalline, water-insoluble Maddrell salt, (NaPO ₃ ) _x with x> 1000, which can be obtained at 200-300 ° C from NaH ₂ PO ₄ , passes at about 600 ° C into the cyclic metaphosphate [Na ₃ (PO ₃ ) ₃ ] melting at 620 ° C. The quenched, glassy melt is depending on Reaction conditions, the water-soluble Graham's salt, (NaPO ₃ ) _40-50 , or a glassy condensed phosphate of the composition (NaPO ₃ ) _15-20 , which is known as Calgon. For both products, the misleading term hexametaphosphate is still in use. The so-called Kurrol's salt, (NaPO ₃ ) _n with n »5000, is also produced from the 600 ° C hot melt of Maddrell's salt, if this is left for a short time at about 500 ° C. It forms high polymer water-soluble fibers.

Particularly preferred water-softening substances from the abovementioned classes of condensed phosphates are the "hexametaphosphates" Budit® H6 or H8 from Budenheim.

For the purposes of the present application, automatic dishwashing or machine dishwashing auxiliaries which additionally comprise one or more substances from the group of acidifying agents, chelating agents or coating-inhibiting polymers are particularly preferred.

Acidifying agents are both inorganic acids and organic acids, provided that they are compatible with the other ingredients. For reasons of consumer protection and handling safety in particular the solid mono-, oligo- and polycarboxylic acids are used. Again preferred from this group are citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and also polyacrylic acid. Also, the anhydrides of these acids can be used as Acidifizierungsmittel, in particular maleic anhydride and succinic anhydride are commercially available. Organic sulfonic acids such as sulfamic acid are also usable. Commercially available and likewise preferably usable as acidifying agent in the context of the present invention is Sokalan® DCS (trademark of BASF), a mixture of succinic acid (maximum 31% by weight), glutaric acid (maximum 50% by weight) and adipic acid ( at most 33% by weight).

Another possible group of ingredients are the chelating agents. Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination site on a central atom, i. H. at least "bidentate". In this case, normally stretched compounds are closed by complex formation over an ion to rings. The number of bound ligands depends on the coordination number of the central ion.

Customary and preferred in the context of the present invention chelate complex images are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and Nitrilotriacetic acid (NTA). Also, complex-forming polymers, ie polymers which carry functional groups either in the main chain itself or laterally to it, which can act as ligands and react with suitable metal atoms generally with the formation of chelate complexes, can be used according to the invention. The polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.

Complexing groups (ligands) of conventional complexing polymers are iminodiacetic, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic, amidoxime, aminophosphoric, (cyclic) polyamino, mercapto, 1,3-dicarbonyl and Crown ether residues with z. T. very specific. Activities towards ions of different metals. Base polymers of many also commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinylpyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided by polymer-analogous transformations with other ligand functionalities.

• (i) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt,
• (ii) stickstoffhaltigen Mono- oder Polycarbonsäuren,
• (iii) geminalen Diphosphonsäuren,
• (iv) Aminophosphonsäuren,
• (v) Phosphonopolycarbonsäuren,
• (vi) Cyclodextrine

in Mengen oberhalb von 0,1 Gew.-%, vorzugsweise oberhalb von 0,5 Gew.-%, besonders bevorzugt oberhalb von 1 Gew.-% und insbesondere oberhalb von 2,5 Gew.-%, jeweils bezogen auf das Gewicht des Geschirrspülmittels, enthalten.In the context of the present invention, machine dishwashing or dishwashing auxiliaries which comprise one or more chelate complexing agents from the groups of

• (i) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5,
• (ii) nitrogen-containing mono- or polycarboxylic acids,
• (iii) geminal diphosphonic acids,
• (iv) aminophosphonic acids,
• (v) phosphonopolycarboxylic acids,
• (vi) cyclodextrins

in amounts above 0.1 wt .-%, preferably above 0.5 wt .-%, more preferably above 1 wt .-% and in particular above 2.5 wt .-%, each based on the weight of Dishwashing detergent, included.

• a) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt wie Gluconsäure,
• b) stickstoffhaltige Mono- oder Polycarbonsäuren wie Ethylendiamintetraessigsäure (EDTA), N-Hydroxyethylethylendiamintriessigsäure, Diethylentriaminpentaessigsäure, Hydroxyethyliminodiessigsäure, Nitridodiessigsäure-3-propionsäure, Isoserindiessigsäure, N,N-Di-(β-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-asparaginsäure oder Nitrilotriessigsäure (NTA),
• c) geminale Diphosphonsäuren wie 1-Hydroxyethan-1,1-diphosphonsäure (HEDP), deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon und 1-Aminoethan-1,1-diphosphonsäure, deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon,
• d) Aminophosphonsäuren wie Ethylendiamintetra(methylenphosphonsäure), Diethylentriaminpenta(methylenphosphonsäure) oder Nitrilotri(methylenphosphonsäure),
• e) Phosphonopolycarbonsäuren wie 2-Phosphonobutan-1,2,4-tricarbonsäure sowie
• f) Cyclodextrine.

In the context of the present invention, all complexing agents of the prior art can be used. These can belong to different chemical groups. Preferably, used individually or in admixture with each other:

• a) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, such as gluconic acid,
• b) nitrogen-containing mono- or polycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, nitridodiacetic acid-3-propionic acid, isoserinediacetic acid, N, N-di (β-hydroxyethyl) glycine, N- (1,2- Dicarboxy-2-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid or nitrilotriacetic acid (NTA),
• c) geminal diphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), their higher homologues having up to 8 carbon atoms and hydroxy- or amino-containing derivatives thereof and 1-aminoethane-1,1-diphosphonic acid whose higher homologues with up to 8 carbon atoms and hydroxyl- or amino-containing derivatives thereof,
• d) aminophosphonic acids, such as ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) or nitrilotri (methylenephosphonic acid),
• e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid and
• f) cyclodextrins.

For the purposes of this patent application, polycarboxylic acids a) are understood as meaning carboxylic acids, including monocarboxylic acids, in which the sum of carboxyl and the hydroxyl groups contained in the molecule is at least 5. Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. In the case of the alkaline pH values of the treatment solutions required according to the invention, these complexing agents are at least partially present as anions. It is irrelevant whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali metal, ammonium or alkylammonium salts, in particular sodium salts, are preferred.

Scale-inhibiting polymers can likewise be present in the agents according to the invention. These substances, which could be constructed chemically different, for example, from the groups of low molecular weight polyacrylates having molecular weights between 1000 and 20,000 daltons, with polymers having molecular weights below 15,000 daltons are preferred.

Scale-inhibiting polymers may also have co-builder properties. As organic cobuilders, it is possible in particular to use polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and phosphonates in the dishwasher detergents according to the invention. These classes of substances are described below.

Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning such carboxylic acids which carry more than one acidity function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

As a builder or coating inhibitor further polymeric polycarboxylates are suitable, these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a molecular weight of 500 to 70000 g / mol.

For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

In the context of the present invention, the organic cobuilders used may in particular be polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and also phosphonates. These classes of substances are described below.

Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, methylglycinediacetic acid, sugar acids and mixtures thereof.

The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1000 to 20 000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1,000 to 10,000 g / mol, and more preferably from 1,200 to 4,000 g / mol, may again be preferred from this group.

Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers are particularly preferably used in the compositions according to the invention. The sulfonic acid-containing copolymers will be described in detail below.

• i) ungesättigten Carbonsäuren
• ii) Sulfonsäuregruppen-haltigen Monomeren
• ii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren

enthalten.However, it is also possible to provide products according to the invention which, as so-called "3in1" products, combine the conventional cleaners, rinse aids and a salt replacement function. For this purpose, automatic dishwashing agents according to the invention are preferred which additionally comprise from 0.1 to 70% by weight of copolymers

• i) unsaturated carboxylic acids
• ii) sulfonic acid group-containing monomers
• ii) optionally further ionic or nonionic monomers

contain.

These copolymers cause the dishware treated with such agents to become significantly cleaner in subsequent cleanings than do the dishware which has been rinsed by conventional means.

As an additional positive effect, a shortening of the drying time of the dishes treated with the detergent occurs, i. the consumer can take the dishes from the machine earlier and reuse them after the cleaning program has ended.

In the context of the present invention, unsaturated carboxylic acids of the formula VII are preferred as the monomer,

R ¹ (R ² ) C = C (R ³ ) COOH (VII),

in which R ¹ to R ³ each independently -H, -CH _3, a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, -NH _2, -OH or - COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or - COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids which can be described by the formula VII are in particular acrylic acid (R ¹ = R ² = R ³ = H), methacrylic acid (R ¹ = R ² = H, R ³ = CH ₃ ) and / or maleic acid (R ¹ = COOH; R ² = R ³ = H) is preferred.

In the sulfonic acid-containing monomers, those of the formula VIII are preferred,

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (VIII),

in the R ⁵ to R ⁷ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or - COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - _N (CH ₂₎ - where n = 0 to 4, -COO- (CH _{2) k} - with k = 1 to 6, -C (O) -NH-C (CH _{3) 2} - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas VIIIa, VIIIb and / or VIIIc,

H ₂ C = CH-X-SO ₃ H (VIIIa),

H ₂ C = C (CH ₃ ) -X-SO ₃ H (VIIIb),

HO ₃ SX- (R ⁶ ) C =C (R ⁷ ) -X-SO ₃ H (VIIIc),

in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -.

Sulfonic acid group-containing Particularly preferred monomers are 1-acrylamido-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₂ CH ₃₎ in formula IIa), 2-acrylamido-2-propanesulfonic acid (X = -C ( O) NH-C (CH ₃ ) ₂ in formula VIIIa), 2-acrylamido-2-methyl-1-propanesulfonic acid (X = - C (O) NH-CH (CH ₃ ) CH ₂ - in formula VIIIa), 2 -Methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula VIIIb), 3-methacrylamido-2-hydroxypropanesulfonic acid (X = -C (O) NH-CH ₂ CH (OH) CH ₂ - in formula VIIIb), allylsulfonic acid (X = CH ₂ in formula VIIIa), methallylsulfonic acid (X = CH ₂ in formula IIb), allyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula VIIIa), methallyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula VIIIb), 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid (X = CH ₂ in formula VIIIb), styrenesulfonic acid (X = C ₆ H ₄ in formula VIIIa), vinylsulfonic acid (X not present in formula VIIIa), 3-sulfopropyl acrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ in formula VIIIa), 3-sulfopropyl methacrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in formula VIIIb), sulfomethacrylamide (X = -C (O) NH- in formula VIIIb), sulfomethylmethacrylamide (X = -C (O) NH-CH ₂ - in formula VIIIb) as well as water-soluble salts of said acids.

Suitable further ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds. The content of the polymers used according to the invention to monomers of group iii) is preferably less than 20% by weight, based on the polymer. Particularly preferred polymers to be used consist only of monomers of groups i) and ii).

• i) ungesättigten Carbonsäuren der Formel VII.
  
           R¹(R²)C=C(R³)COOH     (VII),
  
  in der R¹ bis R³ unabhängig voneinander für -H -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder - COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder - COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist,

• i) Sulfonsäuregruppen-haltigen Monomeren der Formel VIII
  
           R⁵(R⁶)C=C(R⁷)-X-SO₃H     (VIII),
  
  in der R⁵ bis R⁷ unabhängig voneinander für -H -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n- mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)-
• iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren

besonders bevorzugt.In summary, copolymers are made of

• i) unsaturated carboxylic acids of the formula VII.
  
  R ¹ (R ² ) C = C (R ³ ) COOH (VII),
  
  in the R ¹ to R ³ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or - COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,

• i) sulfonic acid group-containing monomers of the formula VIII
  
  R ⁵ (R ⁶⁾ C = C (R ⁷⁾ -X-SO ₃ H (VIII)
  
  in the R ⁵ to R ⁷ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -
• iii) optionally further ionic or nonionic monomers

particularly preferred.

• i) einer oder mehrerer ungesättigter Carbonsäuren aus der Gruppe Acrylsäure, Methacrylsäure und/oder Maleinsäure
• ii) einem oder mehreren Sulfonsäuregruppen-haltigen Monomeren der Formeln VIIIa, VIIIb und/oder VIIIc:
  
           H₂C=CH-X-SO₃H     (VIIIa),
  
           H₂C=C(CH₃)-X-SO₃H     (VIIIb),
  
           HO₃S-X-(R⁶)C=C(R⁷)-X-SO₃H     (VIIIc),
  
  in der R⁶ und R⁷ unabhängig voneinander ausgewählt sind aus -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH(CH₃)₂ und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n- mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)-
• iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren.

Particularly preferred copolymers consist of

• i) one or more unsaturated carboxylic acids from the group of acrylic acid, methacrylic acid and / or maleic acid
• ii) one or more sulfonic acid group-containing monomers of the formulas VIIIa, VIIIb and / or VIIIc:
  
  H ₂ C = CH-X-SO ₃ H (VIIIa),
  
  H ₂ C = C (CH ₃ ) -X-SO ₃ H (VIIIb),
  
  HO ₃ SX- (R ⁶ ) C =C (R ⁷ ) -X-SO ₃ H (VIIIc),
  
  in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -
• iii) optionally further ionic or nonionic monomers.

The copolymers used in the compositions may contain the monomers from groups i) and ii) and optionally iii) in varying amounts, all representatives of group i) with all representatives from group ii) and all representatives from group iii) can be combined. Particularly preferred polymers have certain structural units, which are described below.

Thus, for example, agents according to the invention are preferred, which are characterized in that they contain one or more copolymers, the structural units of the formula IX

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (IX),

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative. Copolymerizing the sulfonic acid-containing acrylic acid derivative with methacrylic acid, one arrives at another polymer whose use in the agents according to the invention is also preferred and characterized in that the agents contain one or more copolymers, the structural units of the formula X.

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (X),

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Thus, agents according to the invention which comprise one or more copolymers which are structural units of the formula XI

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XI),

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH _{2) n} - with n = 0 to 4, is -O- (C ₆ H ₄₎ -, -NH-C (CH _{3) 2} - or -NH-CH (CH ₂ CH ₃₎ - are, are preferred, also a preferred embodiment of the present invention, just as are also preferred agents which are characterized are characterized in that they contain one or more copolymers, the structural units of the formula XII

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XII),

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

Instead of acrylic acid and / or methacrylic acid or in addition thereto, maleic acid can also be used as a particularly preferred monomer from group i). This gives way to inventively preferred agents, which are characterized in that they contain one or more copolymers, the structural units of the formula XIII

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XIII)

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, are preferred and to agents which are characterized in that they contain one or more copolymers, the structural units of the formula XIV

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - (XIV),

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

In summary, machine dishwashing detergents or dishwashing auxiliaries according to the invention are preferred which comprise one or more copolymers as ingredient b), the structural units of the formulas IX and / or X and / or XI and / or XII and / or XIII and / or XIV

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (IX),

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (X),

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃₎ C (O) -Y-SO ₃ H] _p - (XI),

- [CH ₂ -C (CH ₃ ) COOH] _m - (CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XII),

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XIII)

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - (XIV),

in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

In the polymers, the sulfonic acid groups may be wholly or partially in neutralized form, i. in that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. Corresponding agents, which are characterized in that the sulfonic acid groups are partially or fully neutralized in the copolymer, are preferred according to the invention.

The monomer distribution of the copolymers used in the agents according to the invention in the case of copolymers which contain only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight i) or ii), particularly preferably from 50 to 90% by weight. % Of monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer.

In the case of terpolymers, particular preference is given to those containing from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii) ,

The molecular weight of the polymers used in the agents according to the invention can be varied in order to adapt the properties of the polymers to the desired use. Preferred automatic dishwashing detergents are characterized in that the copolymers Molar masses of 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 have.

The content of one or more copolymers in the compositions according to the invention can vary depending on the intended use and the desired product performance, preferred machine dishwashing agents according to the invention being characterized in that they contain the copolymer (s) in amounts of from 0.25 to 50% by weight. %, preferably from 0.5 to 35 wt .-%, particularly preferably from 0.75 to 20 wt .-% and in particular from 1 to 15 wt .-%.

As already mentioned above, in the agents according to the invention it is particularly preferable to use both polyacrylates and the above-described copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers. The polyacrylates were described in detail above. Particularly preferred are combinations of the above-described sulfonic acid-containing copolymers with low molecular weight polyacrylates, for example in the range between 1000 and 4000 daltons. Such polyacrylates are commercially available under the trade names Sokalan® PA15 and Sokalan® PA25 (BASF).

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their molecular weight relative to free acids is generally from 2000 to 100,000 g / mol, preferably from 20,000 to 90,000 g / mol and in particular from 30,000 to 80,000 g / mol.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of (co) polymeric polycarboxylates in the compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

To improve the water solubility, the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.

Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ,

Further preferred copolymers preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives.

Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and also so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 to 30,000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. A product oxidized to C _{6 of} the saccharide ring may be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates. Suitable amounts are in zeolithhaltigen and / or silicate-containing formulations at 3 to 15 wt .-%.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition, all compounds capable of forming complexes with alkaline earth ions can be used as co-builders.

In the context of the present application, agents according to the invention are characterized in that they comprise builders, preferably from the group of silicates, carbonates, organic cobuilders and / or phosphates, in amounts of from 0.1 to 99.5% by weight, preferably from 1 to 95% Wt .-%, particularly preferably from 5 to 90 wt .-% and in particular from 10 to 80 wt .-%, each based on the composition.

surfactants

For the purposes of the present application, preferred cleaners comprise one or more surfactants from the groups of anionic, nonionic, cationic and / or amphoteric surfactants.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. As surfactants of the sulfonate type preferably come C _9-13 alkyl benzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and Disulfonates, as obtained for example from C _12-18 monoolefins having terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation, into consideration. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical having an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. Also 2,3-alkyl sulfates, which can be obtained as commercial products of the Shell Oil Company under the name DAN®, are suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C _7-21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or C _12-18 . Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

As further anionic surfactants are particularly soaps into consideration. Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants, including the soaps, may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

Another group of detergent substances are the nonionic surfactants. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated Fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters.

Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG). Usable Alkypolyglycoside meet the general formula RO (G) _z , in which R is a linear or branched, especially in the 2-position methyl branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4. Preference is given to using linear alkyl polyglucosides, that is to say alkyl polyglycosides which consist of a glucose residue and an n-alkyl chain.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Further suitable surfactants are polyhydroxy fatty acid amides of the formula (XV)

wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R ^{1 is} hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder Propxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula (XVI)

in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having from 1 to 8 carbon atoms, with C _1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

In detergents and cleaners for automatic dishwashing come as surfactants in general all surfactants in question. However, the nonionic surfactants described above and, above all, the low-foaming nonionic surfactants are preferred for this purpose. Particularly preferred are the alkoxylated alcohols, especially the ethoxylated and / or propoxylated alcohols. The person skilled in the art generally understands, under alkoxylated alcohols, the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the context of the present invention, the longer-chain alcohols (C ₁₀ to C ₁₈ , preferably between C ₁₂ and C ₁₆ , such as, for example, C ₁₁ , C ₁₂ , C ₁₃ , C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ and C ₁₈ alcohols). As a rule, n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions, form a complex mixture of addition products of different degrees of ethoxylation. A further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. Also, if desired, by a final etherification with short-chain alkyl groups, such as preferably the butyl group, the substance class of "closed" alcohol ethoxylates reach, which can also be used in the context of the invention. Very particularly preferred for the purposes of the present invention are highly ethoxylated fatty alcohols or mixtures thereof with end-capped fatty alcohol ethoxylates.

in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht; jede Gruppe R² bzw. R³ unabhängig voneinander ausgewählt ist aus -CH₃; -CH₂CH₃, -CH₂CH₂-CH₃, -CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.In the context of the present invention, particularly preferred nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Machine dishwashing agents according to the invention which contain surfactants of the general formula XVII as nonionic surfactant (s) are preferred here

in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical; each group R ² or R ^{3 is} independently selected from -CH ₃ ; -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ and the indices w, x, y, z independently of one another are integers from 1 to 6.

The preferred nonionic surfactants of formula XVII can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in the above formula XVII may vary depending on the origin of the alcohol. If native sources are used, the radical R ^{1 has} an even number of carbon atoms and is usually undisplayed, wherein the linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred. Alcohols accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position in the mixture, as they are usually present in oxo alcohol radicals. Irrespective of the nature of the alcohol used to prepare the nonionic surfactants according to the invention contained in the agents are preferred machine dishwashing detergents according to the invention in which R ¹ in formula XVII is an alkyl group having 6 to 24, preferably 8 to 20, more preferably 9 to 15 and in particular 9 to 11 carbon atoms.

As the alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide. But also other alkylene oxides in which R ² or R ^{3 are} independently selected from - CH ₂ CH ₂ -CH ₃ or -CH (CH ₃ ) ₂ are suitable. Preferred automatic dishwashing detergents are characterized in that R ² and R ³ are each a residue -CH ₃ , w and x independently of one another for values of 3 or 4 and y and z independently of one another represent values of 1 or 2.

In summary, for use in the compositions of the invention, particular preference is given to nonionic surfactants which have a C _9-15 -alkyl radical having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units.

Low-foaming nonionic surfactants are used as preferred additional surfactants. With particular preference, the automatic dishwasher detergents according to the invention contain a nonionic surfactant which has a melting point above room temperature. Accordingly, preferred agents are characterized by containing nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C, and most preferably between 26.6 and 43, 3 ° C, included.

Suitable nonionic surfactants in addition to the nonionic surfactants according to the invention which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If high-viscosity nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have waxy consistency at room temperature are also preferred.

Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols, and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

In a preferred embodiment of the present invention, the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.

A particularly preferred room temperature solid nonionic surfactant is selected from a straight chain fatty alcohol of 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ -alcohol and at least 12 moles, preferably at least 15 moles and in particular at least 20 moles of ethylene oxide. Of these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

Accordingly, particularly preferred agents according to the invention contain ethoxylated nonionic surfactant (s) consisting of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was recovered (n).

The nonionic surfactant preferably additionally has propylene oxide units in the molecule. Preferably, such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants. Preferred automatic dishwashing detergents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule contain up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic surfactant.

More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Nonionic surfactants which may be used with particular preference are available, for example, under the name Poly Tergent® SLF-18 from Olin Chemicals.

A further preferred machine dishwashing detergent according to the invention contains nonionic surfactants of the formula

R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ].

in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is a value of at least 15.

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value x ≥ 2, each R ³ in the above formula may be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula may be different if x ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula is to

R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²

simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

Summarizing the latter statements, dishwashing agents according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, x is n-butyl, 2-butyl or 2-methyl-2-butyl, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, surfactants of the type

R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²

in which x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

Anionic, cationic and / or amphoteric surfactants may also be used in conjunction with the surfactants mentioned, these having only minor importance because of their foaming behavior in dishwasher detergents and usually only in amounts below 10% by weight, in most cases even below 5% by weight .-%, for example, from 0.01 to 2.5 wt .-%, each based on the agent used. The agents according to the invention can thus also contain anionic, cationic and / or amphoteric surfactants as surfactant component.

In the context of the present invention, it is preferred that the automatic dishwashing or machine dishwashing aids comprise surfactant (s), preferably nonionic surfactant (s), in amounts of from 0.5 to 10% by weight, preferably from 0.75 to 7.5 wt .-% and in particular from 1.0 to 5 wt .-%, each based on the total agent included.

bleach

Bleaching agents and bleach activators are important constituents of detergents and cleaners, and a preferred automatic dishwashing detergent or automatic dishwashing auxiliary may in the context of the present invention comprise one or more substances from the said groups. Among the compounds which serve as bleaches and deliver H ₂ O ₂ in water, sodium percarbonate has particular significance. Further useful bleaching agents are, for example, sodium perborate tetrahydrate and the sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

"Sodium percarbonate" is a term used in unspecified form for sodium carbonate peroxohydrates, which strictly speaking are not "percarbonates" (ie salts of percarbonic acid) but hydrogen peroxide adducts of sodium carbonate. The commercial product has the average composition 2 Na ₂ CO ₃ · 3 H ₂ O ₂ and is therefore no peroxycarbonate. Sodium percarbonate forms a white, water-soluble powder with a density of 2.14 gcm ^-3 , which readily decomposes into sodium carbonate and bleaching or oxidizing oxygen.

Dishwashing detergents may also contain bleaches from the group of organic bleaches. Typical organic bleaching agents which can be used as ingredients in the present invention are the diacyl peroxides, e.g. Dibenzoyl. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutan-1, 4-diacid, N, N-terephthaloyl-di (6-aminopercapronate) can be used.

As a bleaching agent for automatic dishwashing, chlorine or bromine releasing substances can also be used according to the present invention. Among the suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

Advantageous agents in the context of the present invention contain one or more bleaching agents, preferably from the group of the oxygen or halogen bleaches, in particular the chlorine bleach, with particular preference of sodium percarbonate and / or sodium perborate monohydrate, in amounts of 0.5 to 40 wt .-%, preferably from 1 to 30 wt .-%, particularly preferably from 2.5 to 25 wt .-% and in particular from 5 to 20 wt .-%, each based on the total agent.

Bleach activators

In order to achieve an improved bleaching effect when cleaning at temperatures of 60 ° C. and below, cleaning agents in the context of the present invention may contain bleach activators. 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, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran.

In addition to or in place of the conventional bleach activators, so-called bleach catalysts can also be incorporated into the detergents according to the present invention. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.

According to the invention, agents are preferred which comprise one or more substances from the group of bleach activators, in particular from the groups of the polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), the acylated phenolsulfonates, in particular Nonanoyl or Isononanoyloxybenzolsulfonat (n- or iso-NOBS) and n-methyl-morpholinium acetonitrile-methyl sulfate (MMA), in amounts of 0.1 to 20 wt .-%, preferably from 0.5 to 15 wt .-% and in particular from 1 to 10 wt .-%, each based on the total agent.

in denen R¹ für -H, -CH₃, einen C_2-24-Alkyl- oder -Alkenylrest, einen substituierten C_2-24-Alkyl- oder -Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN, einen Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe und mindestens einem weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -CH₂-CN, - CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, -CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH_2-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, -(CH₂CH₂-O)_nH mit n = 1, 2, 3, 4, 5 oder 6 und X ein Anion ist.The bleach activators preferred in the context of the present invention furthermore include the "nitrile quats", cationic nitriles of the formula (XVIII),

in which R ^{1 is} -H, -CH ₃ , a C _2-24 -alkyl or -alkenyl radical, a substituted C _2-24 -alkyl or -alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH _2, -CN, an alkyl or alkenylaryl radical with a C _1-24 alkyl group, or a substituted alkyl- or alkenylaryl radical with a C _1-24 alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ - OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH _3, -CH _2- CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH _3, -CH (OH) - CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H where n = 1, 2, 3, 4, 5 or 6 and X is an anion.

The general formula (XVIII) includes a variety of cationic nitriles useful in the present invention. With particular advantage, the detergent tablets according to the invention comprise cationic nitriles in which R ^{1 represents} methyl, ethyl, propyl, isopropyl or an n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-butyl Tetradecyl, n-hexadecyl or n-octadecyl stands. R ² and R ³ are preferably selected from methyl, ethyl, propyl, isopropyl and hydroxyethyl, wherein one or both radicals may advantageously also be a Cyanomethylenrest.

For ease of synthesis, preference is given to compounds in which the radicals R ¹ to R ^{3 are} identical, for example (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^-, (CH ₃ CH ₂ CH _{2) 3} N ⁽⁺⁾ CH ₂ -CN X ^-, (CH ₃ CH (CH _{3)) 3} N ⁽⁺⁾ CH ₂ -CN X ^-, or (HO -CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , where X ^{- is} preferably an anion selected from the group consisting of chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate is selected.

Automatic dishwashing or dishwashing assistants preferred in the context of the present invention are characterized in that they contain the cationic nitrile of the formula (XVIII) in amounts of 0.1 to 20 wt .-%, preferably from 0.25 to 15 wt .-% and in particular from 0.5 to 10 wt .-%, each based on the total weight of the composition.

enzymes

Particularly suitable enzymes are those from the classes of hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying. In addition, cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. It is also possible to use oxidoreductases for bleaching or inhibiting color transfer. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens, as well as enzymatically-derived variants derived from their genetically modified variants. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. In this case, enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases.

Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferably cellobiohydrolases, endoglucanases and - glucosidases, which are also called cellobiases, or mixtures thereof used. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

The enzymes may be adsorbed to carriers or embedded in encapsulants to protect against premature degradation. Preferred agents according to the invention contain enzymes, preferably in the form of liquid and / or solid enzyme preparations, in amounts of from 0.1 to 10% by weight, preferably from 0.5 to 8% by weight and in particular from 1 to 5% by weight. , in each case based on the total mean.

dyes

In order to improve the aesthetic impression of automatic dishwashing or machine dishwashing aids, they can be colored with suitable dyes. Dyes which are preferred in the context of the present invention and whose selection does not present any difficulty to a person skilled in the art have a high storage stability and insensitivity to the other ingredients of the compositions and to light, as well as no pronounced substantivity towards the items to be dyed.

Preferred for use in the machine dishwashing detergents or dishwashing auxiliaries according to the invention are all colorants which can be oxidatively destroyed in the cleaning process and mixtures thereof with suitable blue dyes, so-called blue toners. It has proved to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable are, for example, anionic colorants, e.g. anionic nitrosofarads. A possible colorant is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1, Part 2: 10020), which is available as a commercial product, for example as Basacid® Green 970 from BASF, Ludwigshafen, and mixtures thereof with suitable blue dyes. Further dyeing agents used are Pigmosol® Blue 6900 (CI 74160), Pigmosol® Green 8730 (CI 74260), Basonyl® Red 545 FL (CI 45170), Sandolan® Rhodamine EB400 (CI 45100), Basacid® Yellow 094 (CI 47005), Sicovit® Patent Blue 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), Pigment Blue 15 (CI 74160), Supranol® Blue GLW (CAS 12219-32-8, CI Acidblue 221 ), Nylosan® Yellow N-7GL SGR (CAS 61814-57-1, CI Acidyellow 218) and / or Sandolan® Blue (CI Acid Blue 182, CAS 12219-26-0).

fragrances

Fragrances are added to the compositions within the scope of the present invention in order to improve the aesthetics of the products and to provide the consumer, in addition to the performance of the product, with a visually and sensory "typical and unmistakable" product.

As perfume oils or fragrances, individual fragrance compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons, can be used in the context of the present invention. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, Ethyl methyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals with 8-18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the ionone, α-isomethylionone and methyl cedrylketone , the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene.

Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.

Corrosion inhibitors

Detergents for machine dishwashing may contain corrosion inhibitors to protect the items to be washed or the machine, with silver protectants in particular being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. 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. In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface. In chlorine-free cleaners are 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 of manganese sulfate and the manganese complexes [Me-TACN) Mn ^IV (m-O) ₃ Mn ^IV (Me-TACN)] ²⁺ (PF ₆ ^- ) ₂ ,
[Me-MeTACN) Mn ^IV (m-0) ₃ Mn ^IV (Me-MeTACN)] ²⁺ (PF ₆ ^- ) ₂ ,
[Me-TACN) Mn ^III (m-0) (m-OAc) ₂ Mn ^III (Me-TACN)] ²⁺ (PF ₆ ^- ) ₂ and
[Me-MeTACN) Mn ^III (m-O) (m -OAc) ₂ Mn ^III (Me-MeTACN)] ²⁺ (PF ₆ ^- ) ₂ , wherein Me-TACN is 1,4,7-trimethyl-1, 4,7-triazacyclononane and Me-MeTACN stands for 1,2,4,7-tetramethyl-1,4,7-triazacyclononane. Also, zinc compounds can be used to prevent corrosion on the items to be washed.

In the context of the present invention, preference is given to automatic dishwasher detergents or dishwashing auxiliaries which additionally contain at least one silver protectant selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles, preferably benzotriazole and / or alkylaminotriazole, in amounts of from 0.001 to 1 Wt .-%, preferably from 0.01 to 0.5 wt .-% and in particular from 0.05 to 0.25 wt .-%, each based on the total agent included.

A further subject of the present application is the use of a machine dishwashing detergent or automatic dishwashing auxiliary according to the invention for reducing the glass corrosion in automatic dishwashing.

Claims (9)

1. Compound containing at least one zinc salt and at least one crystalline layered silicate of the general formula (I)

a A ₂ O • b BO • c C ₂ O ₃ • d D ₂ O ₅ • x SiO ₂ • f H ₂ O (I),

in the A is an alkali metal and / or hydrogen, B is an alkaline earth metal and / or a sub-group element, preferably an element from the group zinc, iron manganese, C is an element of the third main group of the Periodic Table and / or a sub-group element, preferably iron, and D Mean element of the Fifth Main Group of the Periodic Table and / or a subgroup element and further that 0 ≤ a ≤ 1; 0 ≤ b ≤ 0.5; 0 ≤ c / x ≤ 0.05; 0 ≤ d / x ≤ 0.25; 1.9 ≤ x ≤ 22; 0 ≤ f ≤ 40, characterized in that the contained zinc salt (s) and the contained crystalline layered silicate (s) with one or more further active and / or or framework substance (s) formulated, in particulate form, as a compound present / present. 1. Compound according to claim 1, characterized in that the further active and / or builder substance (s) is a scaffold, a surfactant, a bleaching agent, a bleach activator, enzyme, dye, fragrance, corrosion inhibitor or polymer , 2. Compound according to one of the preceding claims, characterized in that it is in the / the further active and / or builder substance (s) is a polymeric polycarboxylate, preferably alkali metal salt of the polyacrylic acid or polymethacrylic acid. 3. Compound according to claim 3, characterized in that the polymeric polycarboxylate has a molecular weight of 500 to 70000 g / mol. 4. Compound according to one of the preceding claims, characterized in that it is in the / the further active and / or builder (s) to a polyacrylate, preferably a polyacrylate having a molecular weight of 1000 to 20,000 g / mol. 5. Compound according to one of the preceding claims, characterized in that it is at the / the further active and / or builder substance (s) is a copolymer unsaturated carboxylic acids, sulfonic acid group-containing monomers and optionally further ionic or nonionic monomers. 6. Compound according to one of the preceding claims, characterized in that it is in the / the further active and / or builder (s) is a copolymeric polycarboxlate of acrylic acid with methacrylic acid, acrylic acid with maleic acid or methacrylic acid with maleic acid. 7. Compound according to one of the preceding claims, characterized in that it is in the / the further active and / or builder (s) is a copolymer of acrylic acid with methacrylic acid, wherein the copolymer 50 to 90 wt .-% of acrylic acid and Contains 50 to 10 wt .-% maleic acid. 8. A process for the preparation of a compound according to any one of the preceding claims, by spray drying, granulation, extrusion, roll compaction, tableting, solidification or crystallization.