EP1417291A2

EP1417291A2 - Dishwasher detergent with improved protection against glass corrosion n

Info

Publication number: EP1417291A2
Application number: EP02767346A
Authority: EP
Inventors: Arnd Kessler; Rainer Sorg; Melanie Baumann; Wolfgang Wick
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2001-08-17
Filing date: 2002-08-08
Publication date: 2004-05-12
Anticipated expiration: 2022-08-08
Also published as: EP1417291B1; HUP0401286A2; US7153816B2; WO2003016444A2; DE50214339D1; ATE463555T1; PL367794A1; PL202632B1; US20050075258A1; AU2002331215A1; HUP0401286A3; WO2003016444A3

Abstract

A dishwasher detergent containing one or several builders and optionally other components of detergents and cleaning agents, also containing zinc salts and/or magnesium salts of organic acids, characterized by significantly improved glass corrosion properties.

Description

"Automatic dishwashing detergent with improved glass corrosion protection"

The present invention is in the field of automatic dishwashing detergents. In particular, the present invention relates to automatic dishwashing detergents which contain zinc salts.

With the progressive automation of various washing and cleaning processes in the household and industry, mechanical washing and cleaning agents for textiles and dishes have become increasingly important in recent decades.

The so-called low-alkaline cleaners required for automatic dishwashing often contain, as alkali carriers, mixtures of sodium disilicate and soda, builders such as cttronic acid. for example in combination with polycarboxylates and preferably low-foaming, nonionic surfactants. Bleaching agents, bleach activators, silver and corrosion protection agents and, to enhance the cleaning ability, enzymes can also be present. In a typical machine cleaning cycle, the dishes placed in baskets are cleaned by intensive contact with the aqueous cleaning solution at about 65 ° C and pH values between 9 and 11 and then rinsed clear.

In addition to its cleaning performance, an important criterion for evaluating a machine dishwashing detergent is the visual appearance of the dry dishes after cleaning. Possible calcium carbonate deposits on dishes or in the interior of the machine can, for example, affect customer satisfaction and thus have a causal influence on the economic success of such a cleaning agent. Another long-standing problem with machine dishwashing is the corrosion of glassware, which can usually manifest itself through the appearance of cloudiness, streaks and scratches, but also through iridescence of the glass surface. The observed effects are essentially based on two processes, the emergence of alkali and alkaline earth ions from the glass in connection with hydrolysis of the silicate network, and on the other hand in the deposition of silicate compounds on the glass surface. In order to avoid such corrosion processes, there are a number of proposals in the prior art, for example with regard to the use of different silicates.

International patent application WO 96/12783 (Henkel KGaA) describes phosphate-free to low-phosphate machine dishwashing detergents with improved decoration and glass protection based on citrate-containing formulations which contain crystalline layered silicates. Subject of the international patent application WO 99/57237 (Claπ ^' ant, Henkel KGaA) are phosphate-containing automatic dishwashing detergents which contain a powdery to granular additive which, as essential components, comprises a crystalline layered silicate of general formula NaMSi _x 0 _{2x + 1} y H ₂ 0, in which M represents sodium or hydrogen, x is a number from 1.9 to 22 and y stands for a number from 0 to 33, and have (co) polymeric polycarboxylic acid and in addition to glass or decor-protecting effects, also have excellent cleaning performance.

The use of zinc or zinc salts to prevent glass corrosion in automatic dishwashing has also been described.

According to the teaching of the American patent US 3,677,820 (whirlpool), for example, a zinc strip attached 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) describes machine 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.

The international patent application WO 00/39259 (Reckitt Benckiser) discloses water-soluble glasses according to DIN ISO 719, which contain at least one glass corrosion-inhibiting active ingredient, the proportion by weight of which in the glass is not more than 85% by weight and which under the conditions of cleaning and / or Rinse cycle is released from this glass.

The present invention was based on the object of providing a machine dishwashing detergent which, even when used repeatedly, does not corrosively change the surfaces of glassware, in particular does not cause clouding, streaks or scratches but also does not cause the glass surfaces to become iridescent. Preferably, an additive for a machine dishwashing detergent should be provided, which is suitable as a component of automatic dishwashing detergents in any form of offer, for example as a component of powder, tablet, liquid formulations, cleaning foams or depot products, without imposing any restrictions on the recipes for these forms of offer.

It has now been found that the aforementioned objects are achieved by machine dishwashing detergents, the builders and optionally further constituents of cleaning agents and one or more magnesium and / or zinc salt (s) of at least one monomeric and / or polymeric organic acid with the exception of zinc ricinoleate , Zincabietats and zinc oxalate contain, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids from the group of unbranched saturated or unsaturated monocarboxylic acids, branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and Tncarbonsauren, the sugar acids, the hydroxy acids, the oxo acids, the amino acids and / or the polymeric carboxylic acids are preferred, and it is further preferred that these automatic dishwashing agents do not contain magnesium or zinc salts contain unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acids with at least 8 carbon atoms and / or resin acids

Although all other magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids may be present in the claimed agents with the exception of zinc pincoleate, zinc abietate and zinc oxalate according to the invention, as described above, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids from the groups of the unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and t-carboxylic acids, the sugar acids, the hydroxy acids, the oxo acids , the amino acids and / or the polymeric carboxylic acids are preferred. Within these groups, the acids mentioned below are preferred in the context of the present invention

From the group of unbranched saturated or unsaturated monocarboxylic acids methanoic acid (formic acid), ethanoic acid (acetic acid), propanoic acid (propionic acid), pentanoic acid (valenanoic acid), hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid) (Capric acid), undecanoic acid, dodecanoic acid (launnic acid), tndecanoic acid, tetradecanoic acid (mypinic acid), pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid (margaric acid), octadecanoic acid (stearic acid), arachanoic acid tetraacid (eicosanoic acid), arachanoic acid tetraacid Hexacosanoic acid (cerotinic acid), tnacotanoic acid (messic acid), 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-laic acid, 9t Octadecadienoic acid (linoleic acid), 9t, 12t-octadecadienoic acid

(Linolaidic acid) and 9c, 12c, 15c-Octadecatreιnsaure (linolenic acid)

From the group of branched saturated or unsaturated monocarboxylic acids 2-

Methylpentanoic acid, 2-ethylhexanoic acid, 2-propylheptanoic acid, 2-butyloctanoic acid, 2-

Pentylnonanoic acid, 2-hexyldecanoic acid, 2-heptylundecanoic acid, 2-octyldodecanoic acid, 2-

Nonyltπdecanoic acid, 2-decyltetradecanoic acid, 2- undecylpentadecanoic acid, 2-

Contains dodecylhexadecanoic acid, 2-trιdecylheptadecansaure, 2-tetradecyloctadecanoic acid, 2-pentadecylnonadecanoic acid, 2-hexadecyleιcosansaure, 2-heptadecylheneιcosansaure From the group of unbranched saturated or unsaturated di- or t-carboxylic acids: propanedioic acid (malonic acid), butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), octanedioic acid (suberic acid), nonanedioic acid (decanedioic acid) Sebacic acid), 2c-butenedioic acid (maleic acid), 2t-butenedioic acid (fumaric acid), 2-butynedicarboxylic acid (acetylenedicarboxylic acid).

From the group of aromatic mono-, di- and t-carboxylic acids: benzoic acid, 2-carboxybenzoic acid (phthalic acid), 3-carboxybenzoic acid (isophthalic acid), 4-carboxybenzoic acid (terephthalic acid), 3,4-dicarboxybenzoic acid (trimellitic acid), 3,5-dicarboxybenzoic acid (Trimesionsäure).

From the group of sugar acids: galactonic acid, mannonic acid, fructonic acid, arabinonic acid, xylonic acid, ribonic acid, 2-deoxy-ribonic acid, alginic acid.

From the group of hydroxy acids: hydroxyphenylacetic acid (mandelic acid), 2-hydroxypropionic acid (lactic acid), hydroxy succinic acid (malic acid), 2,3-

Dihydorxybutanedioic acid (tartaric acid), 2-hydroxy-1, 2,3-propanetricarboxylic acid (citric acid), ascorbic acid, 2-hydroxybenzoic acid (salicylic acid), 3,4,5-trihydroxybenzoic acid (gallic acid).

From the group of oxo acids: 2-oxopropionic acid (pyruvic acid), 4-oxopentanoic acid (levulinic acid).

From the group of amino acids: alanine, valine, leucine, isoleucine, proline, tryptophan, phenylalanine, methionine, glycine, serine, tyrosine, threonine, cysteine, asparagine, glutamine, aspartic acid, glutamic acid, lysine, arginine, histidine.

From the group of the polymeric carboxylic acids: polyacrylic acid, polymethacrylic acid, alkyl acrylamide / acrylic acid copolymers, alkyl acrylamide / methacrylic acid copolymers,

Alkyl acrylamide / methyl methacrylic acid copolymers, copolymers of unsaturated carboxylic acids, vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers.

The spectrum of the zinc salts of organic acids, preferably organic carboxylic acids, which are preferred according to the invention, extends from salts which are sparingly or not soluble in water, ie have a solubility below 100 mg / L, preferably below 10 mg / L, in particular no solubility, up to such salts which have a solubility in water above 100 mg / L, preferably above 500 mg / L, particularly preferably above 1 g / L and in particular above 5 g / L (all solubilities at 20 ° C. water temperature). To the first group zinc salts include, for example, zinc citrate, zinc oleate and zinc stearate; the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate:

In a further preferred embodiment of the present invention, the agents according to the invention contain at least one zinc salt but no magnesium salt of an organic acid, it preferably being at least one zinc salt of an organic carboxylic acid, particularly preferably a zinc salt from the group consisting of zinc stearate, zinc oleate and zinc gluconate, Zinc acetate, zinc lactate and / or zinc citrate.

A preferred agent in the context of the present invention contains zinc salt in amounts of 0.1 to 5% by weight, preferably 0.2 to 4% by weight and in particular 0.4 to 3% by weight, or zinc in oxidized form in amounts of 0.01 to 1 wt .-%, preferably from 0.02 to 0.5 wt .-% and in particular from 0.04 to 0.2 wt .-%, each based on the total weight of the automatic dishwashing detergent.

Another object of the present invention is the use of salts of the metals magnesium and zinc with organic acids, with the exception of formic acid, acetic acid, gluconic acid and oxalic acid, as glass corrosion inhibitors.

As mentioned at the beginning, the incorporation of magnesium and / or zinc salts according to the invention of organic acids into the automatic dishwashing detergents according to the invention does not impose any restriction with regard to the forms of supply or the recipes for these detergents. Automatic dishwashing detergents in the context of the present invention can therefore be provided both in solid and in liquid form.

Liquid cleaning agents, in the context of the present invention, are aqueous and non-aqueous agents based on liquid constituents, with dynamic viscosities in the range between 0.2 and 1000 mPa-s, but also more viscous agents with viscosities above 1000 mPa-s up to cut-resistant and dimensionally stable gels are possible forms of offer. Preferred non-aqueous liquid cleaning agents contain solvents from the group consisting of ethanol, n-propanol, i-propanol, 1-butanol, 2-butanol, glycol, propanediol, butanediol, glycerin, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol -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 butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether or mixtures thereof. To adjust the viscosity of liquid forms of supply of the cleaning agents according to the invention, these typically also contain one or more thickeners. Preferred thickeners are agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose,

Hydroxypropylmethylcellulose, powdered meal ether, polyacrylic and. Polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides, polysilicic acids, clay minerals such as montmorillonites, zeolites and silicas.

Another typical component of liquid aqueous cleaning agents are hydrotropes. The addition of such substances causes a poorly soluble substance to become water-soluble in the presence of the hydrotrope, which is not itself a solvent. Substances that bring about such an improvement in solubility are referred to as hydrotropes or hydrotropes. Typical hydrotropes, e.g. xylene and cumene sulfonate are used in the assembly of liquid detergents or cleaning agents. Other substances, e.g. Urea or N-methylacetamide, increase the solubility through a structure-breaking effect, in which the water structure in the vicinity of the hydrophobic group of a poorly soluble substance is broken down.

An im. Machine dishwashing detergent preferred in the context of this application is characterized in that it has a viscosity of 500 to 500,000 mPas, preferably 900 to 200,000 mPas and in particular 1300 to 100,000 mPas. The viscosity of the agents according to the invention is measured using customary standard methods (for example Brookfield viscometer LVT-II at 20 rpm and 20 ° C., spindle 3).

The agents according to the invention contain one or more non-aqueous solvents as a preferred ingredient. These come, for example, from the groups of monoalcohols, diols, triols or polyols, ethers, esters and / or amides. Non-aqueous solvents which are water-soluble are particularly preferred, "water-soluble" solvents in the sense of the present application being solvents which are completely miscible with water at room temperature, i.e. without a miscibility gap.

Non-aqueous solvents that can be used in the agents according to the invention preferably come from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the concentration range indicated. The solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerin, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene 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 butoxytriglycol, 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 particularly preferred automatic dishwashing agent in the context of the present invention is characterized in that it contains non-aqueous solvent (s), 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 isopropanol.

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

H- (0-CH ₂ -CH ₂ ) _n -OH (I)

are sufficient, where n can have values between 1 (ethylene glycol, see below) and approx. 16. There are various nomenclatures for polyethylene glycols that can lead to confusion. The specification of the average relative molecular weight following the specification "PEG" is customary in technical terms, so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210. According to this nomenclature, the technically customary polyethylene glycols PEG 200, PEG 300, PEG 400 and PEG 600 can be used in the context of the present invention.

A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and immediately after the hyphen is followed by a number that corresponds to the number n in the above-mentioned formula. According to this nomenclature (known as INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th 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 polyethylene glycols, for example, under the trade names Carbowax ^® PEG 200 (Union Carbide), Emkapol ^® 200 (ICI Americas), Lipoxol ^® 200 MED (HÜLS America), Polyglycol ^® E-200 (Dow Chemical), Alkapol ^® PEG 300 (Rhone-Poulenc), Lutrol ^® E300 (BASF) and the corresponding trade names with higher numbers.

Polypropylene glycols (abbreviation PPG) which can be used according to the invention are polymers of propylene glycol which have the general formula (II)

H- (0-CH-CH ₂ ) _n -OH (II)

I CH ₃

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

Glycerin is a colorless, clear, difficult to move, odorless, sweet-tasting hygroscopic liquid with a density of 1, 261 that solidifies at 18.2 ° C. Glycerin was originally only 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 intermediate stages allyl chloride, epichlorohydrin. Another technical process is the hydroxylation of allyl alcohol with hydrogen peroxide at the W0 ₃ contact via the glycide stage.

Glycerol carbonate can be obtained by transesterification of ethylene carbonate or dimethyl carbonate with glycerin, ethylene glycol or methanol being obtained as by-products. Another synthetic route starts from glycidol (2,3-epoxy-1-propanol), which is reacted under pressure in the presence of catalysts with CO ₂ to give glycerol carbonate. Glycerol carbonate is a clear, easily movable liquid with a density of 1, 398 ^"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 obtained from ethylene oxide by heating with water under pressure, and promising manufacturing processes can also be based 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 with a density of 1, 0597 that solidifies at -32 ° C and boils at 214 ° C. 1,3-propanediol can be prepared from acrolein and water with subsequent catalytic hydrogenation.

Technically far more important 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 made from propylene oxide by adding water.

Propylene carbonate is a water-bright, easily movable liquid with a density of 1, 21 like ^"3 , the melting point is → 49 ° C, the boiling point is 242 ° C. Propylene carbonate is also commercially available through the reaction of propylene oxide and C0 ₂ at 200 ° C and 80 bar accessible.

In preferred automatic dishwashing detergents according to the invention, the content of the non-aqueous solvent (s) is from 0.1 to 70% by weight, preferably from 0.5 to 60% by weight, particularly preferably from 1 to 50% by weight particularly preferably from 2 to 40% by weight and in particular from 2.5 to 30% by weight, in each case based on the total composition.

In the context of this invention, “non-aqueous” is understood to mean a state in which the free water content in the compositions is clearly below 5% by weight, based on the composition. It is preferred that the content of the agents according to the invention is free, i.e. water not present in the form of water of hydration and / or constitutional water is below 10% by weight, preferably below 8% by weight and in particular even below 6% by weight, in each case based on the composition. Accordingly, water can essentially only be introduced into the agent in chemically and / or physically bound form or as a constituent of the raw materials or compounds present as a solid, but not as a liquid, solution or dispersion.

As a further preferred ingredient, the agents according to the invention contain one or more nonionic surfactants, in short nonionic surfactants. The amounts in which the nonionic surfactants are used are, according to the invention, between 1 and 30% by weight, machine dishwashing detergents according to the invention being preferred, which are 1 to 25% by weight, preferably 2 to 22.5% by weight, particularly preferably contain 3 to 20% by weight and in particular 4 to 17.5% by weight of nonionic surfactant (s).

For a detailed description of these surfactant ingredients, please refer to the following sections to avoid repetition.

In addition to the previously mentioned ingredients, the agents according to the invention can contain further usual ingredients of cleaning agents. Here are the builders in particular really important. Builders are mainly used in the compositions according to the invention for binding calcium and magnesium. Usual builders, which in the context of the invention are preferably present in amounts of 22.5 to 45% by weight, preferably 25 to 40% by weight and in particular 27.5 to 35% by weight, in each case based on the total agent , are present are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and sodium and potassium silicates. Trisodium citrate and / or pentasodium tripolyphosphate and silicate builders from the class of alkali disilicates are preferably used for the cleaning agents according to the invention. In general, in the case of the alkali metal salts, the potassium salts are preferable to the sodium salts, since they often have a higher solubility in water. Preferred water-soluble builders are, for example, tripotassium citrate, potassium carbonate and the potassium water glasses.

Particularly preferred automatic dishwashing detergents contain phosphates, preferably alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate).

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

A detailed description of the builders mentioned, in particular the phosphates, can be found under the heading “Builder” further down in the text. This part of the description is referred to here to avoid repetition.

In preferred embodiments of the present invention, the content of water-soluble builders in the compositions is within narrow limits. Machine dishwashing detergents which contain the water-soluble builder (s) in quantities of 22.5 to 55% by weight, preferably 25 to 50% by weight and in particular 27.5 to 45% by weight, are preferred here. in each case based on the total composition.

The agents according to the invention can particularly preferably contain condensed phosphates as water-softening substances. These substances form a group of phosphates - also called melt or glow phosphates due to their production - which can be derived from acidic salts of orthophosphoric acid (phosphoric acids) by condensation. The condensed phosphates can be divided into the metaphosphates [Mln (P0 ₃ ) _n ] and polyphosphates (M'n + zP-Oan + i or M ' _n H ₂ P _n 0 ₃ n ₊ ι). The term "metaphosphate" was originally the general term for condensed phosphates with the composition M _n [P _n 0 _3n ] (M = monovalent metal), but today is mostly limited to salts with ring-shaped cyclo (poly) phosphate anions. With n = 3, 4, 5, 6 etc. are referred to as tri-, tetra-, penta-, hexa-metaphosphates etc. etc. According to the systematic nomenclature of the isopolyanions, the anion with n = 3 is called cyclo-triphosphate.

Metaphosphates are obtained as accompanying substances of the Graham's salt - wrongly called sodium hexametaphosphate - by melting NaH ₂ P0 ₄ at temperatures above 620 ° C, whereby so-called Maddrell's salt is also formed as an intermediate. This and Kurrol's salt are linear polyphosphates, which today are usually not counted among the metaphosphates, but which can also be used with preference as water-softening substances in the context of the present invention.

The crystalline, water-insoluble Maddrell salt, (NaP0 ₃ ) _x with x> 1000, which can be obtained from NaH ₂ P0 at 200-300 ° C, goes into the cyclic metaphosphate at about 600 ° C [Na ₃ (P0 ₃ ) ₃ ], which melts at 620 ° C. Depending on the reaction conditions, the quenched, glassy melt is the water-soluble Graham's salt, (NaP0 ₃ ) ₄ or ₅ o, or a glassy condensed phosphate of the composition (NaP0 ₃ ) ₁₅ . ₂ o, known as Calgon. The misleading name hexametaphosphate is still used for both products. The so-called Kurrol's salt, (NaP0 ₃ ) _n with n »5000, also arises from the melt of the Maddrell salt, which is hot at 600 ° C, if it is left at 500 ° C for a short time. It forms highly polymeric water-soluble fibers.

Particularly preferred water-softening substances from the above classes of condensed phosphates, the "hexametaphosphates" Budit ^® H6 and H8 from. Budenheim have proven.

In addition to the surfactants and builders, bleaches, bleach activators, enzymes, silver preservatives, colorants and fragrances, etc. are preferred ingredients of automatic dishwashing detergents. In addition, other ingredients may be present, machine dishwashing detergents according to the invention being preferred which additionally contain one or more substances from the group of the acidifying agents, chelate complexing agents or the deposit-inhibiting polymers.

Both inorganic acids and organic acids are suitable as acidifiers, provided they are compatible with the other ingredients. For reasons of consumer protection and handling safety, the solid mono-, oligo- and polycarboxylic acids in particular can be used. From this group, preference is again given to citric acid, Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. The anhydrides of these acids can also be used as acidifying agents, maleic anhydride and succinic anhydride in particular being commercially available. Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 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 point on a central atom, i. H. is at least "bidentate". In this case, normally elongated compounds are closed to form rings by complex formation via an ion. The number of ligands bound depends on the coordination number of the central ion.

Common chelate complexing agents preferred in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Complex-forming polymers, that is to say polymers which carry functional groups either in the main chain itself or laterally to it, which can act as ligands and which generally react with suitable metal atoms to form 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 can 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 complex-forming polymers are iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, amidoxime, aminophosphoric acid, (cyclic) polyamino, mercapto, 1,3-dicarbonyl - And crown ether residues with z. T. very specific Activities against ions of different metals. The base polymers of many commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinyl pyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided with further ligand functionalities by polymer-analogous conversions.

In the context of the present invention, machine dishwashing detergents which contain one or more chelating complexing agents from the groups of (i) polycarboxylic acids in which the sum of the carboxylic 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% by weight, preferably above 0.5% by weight, particularly preferably above 1% by weight and in particular above 2.5% by weight, in each case based on the weight of the Dishwashing detergent included.

All complexing agents of the prior art can be used in the context of the present invention. These can belong to different chemical groups. The following are preferably used individually or in a mixture:

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-hydroxyethylethylenediamine triacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, nitridodiacetic acid, nitridodiacetic acid, nitridodiacetic acid , 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 with up to 8 carbon atoms, and derivatives thereof containing hydroxyl or amino groups, and 1-aminoethane-1, 1-diphosphonic acid, their higher homologues with up to 8 carbon atoms as well as derivatives thereof containing hydroxyl or amino groups, d) aminophosphonic acids such as ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methy lenphosphonic acid) or nitrilotri (methylenephosphonic acid), e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1, 2,4-tricarboxylic acid and f) cyclodextrins.

In the context of this patent application, polycarboxylic acids a) are understood to mean carboxylic acids, including monocarboxylic acids, in which the sum of carboxyl groups 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. These are at the alkaline pH values of the treatment solutions required according to the invention Complex bilens at least partially as anions. It is immaterial 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.

Deposit-inhibiting polymers can also be contained in the agents according to the invention. These substances, which can have different chemical structures, originate, for example, from the groups of low molecular weight polyacrylates with molecular weights between 1000 and 20,000 daltons, polymers with molecular weights below 15,000 daltons being preferred.

Deposit-inhibiting polymers can also have cobuilder properties. Organic cobuilders which can be used in the dishwasher detergents according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.

Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as 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 of these.

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 value of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

Polymeric polycarboxylates are also suitable as builders or scale inhibitors, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was made against an external polyacrylic acid standard, which is due to its structural relationship to the investigated polymers provides realistic molecular weight values. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.

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 relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 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 agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

Also particularly preferred are biodegradable polymers composed of more than two different monomer units, for example those which are salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which are salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers contain. Further preferred copolymers are those which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Polyaspartic acids or their salts and derivatives are particularly preferred which, in addition to cobuilder properties, also have a bleach-stabilizing effect.

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

Other 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 processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. 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 customary measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used.

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 at C _{6 of} the saccharide ring can be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable cobuilders. Ethylenediamine-N, N ^'- disuccinate (EDDS) is preferably in the form of its sodium or magnesium salts. Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts for use in formulations containing zeolite and / or silicate are 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be 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 aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9). Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

To regulate the viscosity, the agents according to the invention can contain further ingredients, with the use of which, for example, the settling behavior or the pourability or flowability can be specifically controlled. In non-aqueous systems, combinations of structuring agents and thickeners have proven particularly useful.

Machine dishwashing detergents preferred in the context of the present invention further comprise a) 0.1 to 1.0% by weight of one or more structurants from the group of the bentonites and / or at least partially etherified sorbitols, and b) 5.0 to 30% by weight % of one or more thickeners from the group of carbonates, sulfates and amorphous or crystalline disilicates.

The structuring agent 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 can be controlled with the substances mentioned in the non-aqueous system.

Bentonites are contaminated clays that are formed by weathering volcanic tuffs. Due to their high montmorillonite content, bentonites have valuable properties such as swellability, ion exchange capacity and thixotropy. It is possible to modify the properties of the bentonites according to the intended use. Bentonites are a common clay component in tropical soils and are mined as sodium bentonite, for example in Wyoming / USA. Sodium bentonite has the most favorable application properties (swellability), 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 into the more swellable Na bentonites by exchanging Ca for Na. The main constituents of bentonites are so-called montmorillonites, which can also be used in pure form in the context of the present invention. Montmorillonites belong to the phyllosilicates and here to the dioctahedral smectites clay minerals that crystallize monoclinic-pseudohexagonal. Montmorillonites predominantly form white, gray-white to yellowish, completely amorphous appearing, easily friable, swelling in the water, but not becoming plastic, by the general formulas

AI ₂ [(OH) ₂ / Si ₄ Oι ₀ ] nH ₂ O or AI ₂ 0 ₃ -4Si0 ₂ H ₂ O nH ₂ 0 or AI ₂ [(OH) ₂ / Si ₄ O ₁₀ ] (at 150 ° dried)

can be described.

Preferred machine dishwashing detergents are characterized in that montmorillonites are used as structure donors. Montmorillonites have a three-layer structure that consists of two tetrahedral layers that are electrostatically cross-linked via the cations of an intermediate octahedral 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, D-picoline, ammonium compounds, hydroxy-aluminosilicate ions etc. The above. Formulas are only approximate formulas since montmorillonites have a large ion exchange capacity. AI can be exchanged for Mg, Fe ²⁺ , Fe ³⁺ , Zn, Cr, Cu and other ions. As a result of such a substitution, the layers are negatively charged, 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 structure donors.

Sorbitol is a hexavalent alcohol (sugar alcohol) that is relatively easy to split off one or two moles of water intramolecularly and forms cyclic ethers (for example sorbitan and sorbide). Splitting off of water is also possible intermolecularly, noncyclic ethers being formed from sorbitol and the alcohols concerned. The formation of monoethers and bisethers is also possible here, although higher degrees of etherification such as 3 and 4 can also occur. At least partially etherified sorbitols to be preferably used in the context of the present invention are double etherified sorbitols, of which dibenzylidene sorbitol is particularly preferred. Machine dishwashing detergents are preferred here which contain double etherified sorbitols, in particular dibenzylidene sorbitol, as structuring agents. The agents according to the invention can contain the structuring agents in amounts of 0.1 to 1.0% by weight, based on the total agent and on the active substance of the structuring agents. Preferred agents contain the structuring agent in amounts of 0.2 to 0.9% by weight, preferably in amounts of 0.25 to 0.75% by weight and in particular in amounts of 0.3 to 0.5% by weight. %, each based on the total mean.

The preferred agents according to the invention can contain inorganic salts from the group of carbonates, sulfates and amorphous or crystalline disilicates as thickeners. In principle, the salts of all metals mentioned can be used, the alkali metal salts being preferred. Alkali carbonate (s), alkali sulfate (s) and / or amorphous (s) and / or crystalline (s) alkali disilicate (s), preferably sodium carbonate, sodium sulfate and / or amorphous or crystalline sodium disilicate, are particularly preferably used as thickeners in the context of the present invention ,

The preferred agents according to the invention contain the thickeners in amounts of 5 to 30% by weight, based on the total agent. Particularly preferred agents contain the thickener (s) in amounts of 7.5 to 28% by weight, preferably in amounts of 10 to 26% by weight and in particular in amounts of 12.5 to 25% by weight, in each case based on the entire mean.

In view of increased settling stability, it is preferred that the solids contained in the agents according to the invention are used as finely as possible. This is particularly advantageous for inorganic thickeners and bleaches. Machine dishwashing detergents according to the invention are preferred here, in which the average particle size of the bleaching agents and thickeners and of the optional builders is less than 75 μm, preferably less than 50 μm and in particular less than 25 μm.

The liquid machine dishwashing detergents according to the invention can also contain other viscosity regulators or thickening agents in order to set a possibly higher viscosity. All known thickeners can be used here, that is to say those based on natural or synthetic polymers.

Polymers derived from nature that are used as thickeners are, for example, agar agar, carrageenan, tragacanth, acacia, alginates, pectins, polyoses, guar flour, carob bean flour, starch, dextrins, gelatin and casein. Modified natural products come primarily from the group of modified starches and celluloses, examples include carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and core meal ether. Automatic dishwashing agents preferred in the context of the present invention contain hydroxyethyl cellulose and / or hydroxypropyl cellulose as thickeners, preferably in amounts of 0.01 to 4.0% by weight, particularly preferably in amounts of 0.01 to 3.0% by weight and in particular in quantities of 0.01 to 2.0% by weight, in each case based on the total agent.

A large group of thickeners that are widely used in a wide 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 said substance classes are widely commercially available and are, 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, Schoener GmbH), Deuteron ^® -XG (anionic heteropolysaccharide based on β-D-glucose, D-manose, D-glucuronic acid, Schoener GmbH), Deuteron ^® -XN (non-ionic polysaccharide, Schoener GmbH), dicrylan ^® thickener-0 (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 acid ester copolymer dispersion, 25% ig in Wasser, Stockhausen), SER-AD-FX-1100 (hydrophobic urethane polymer, Servo Delden), Shellflo ^® -S (high molecular polysaccharide, stabilized with formaldehyde, Shell) and Shellflo ^® -XA (xanthan biopolymer, stabilized with formaldehyde, Shell) available.

A preferred polymeric thickener is xanthan, a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and having a molecular weight of 2 to 15 million daltons. Xanthan is formed from a chain with ß-1, 4-bound 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.

In the context of the present invention, thickeners which are likewise preferably to be used are polyurethanes or modified polyacrylates which, based on the total agent, can be used, for example, in amounts of 0.1 to 5% by weight. Polyurethanes (PUR) are produced by polyaddition from dihydric and higher alcohols and isocyanates and can be described by the general formula III

[-0-R ¹ -0-C-NH-R ² -NH-C-] _n

O O

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 can also be a residue of a higher alcohol, whereby cross-linked polyurethanes are formed which differ from the formula VIII given above in that the R ¹ further -O-CO-NH groups are bound.

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

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

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 IV R ³

[-CH ₂ -C-] _n IV,

I CXR ⁴

II o

in which R ^{3 is} H or a branched or unbranched C ₁ . Alk (en) yl radical, X for NR ⁵ or O, R ⁴ for 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. Such modified polyacrylates are generally esters or amides of acrylic acid or an α-substituted acrylic acid. Preferred among these polymers are those in which R ^{3 represents} H or a methyl group. In the case of the polyacrylamides (X = NR ⁵ ), both single (R ⁵ = H) and double (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 can be selected from optionally alkoxylated branched or unbranched C _8-22 alk (en) yl radicals. Among the polyacrylic esters (X = O), preference is given to those in which the alcohol has been obtained from natural or synthetic fats or oils and is additionally alkoxylated, preferably ethoxylated. Preferred degrees of alkoxylation are between 2 and 30, with degrees of alkoxylation between 10 and 15 being particularly preferred.

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

Modified polyacrylates to be used preferably in the context of the present invention are polyacrylate-polymethacrylate copolymers which satisfy the formula V. R ⁷

I [-CH ₂ -C-] "V,

I C- (0-CH-CH ₂ ) _a OR ⁴

II IOR ⁶

in which R ^{4 represents} 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 is between 2 and 30, preferably between 10 and 20. R ⁴ is preferably a fatty alcohol residue obtained from natural or synthetic sources, the fatty alcohol in turn preferably being ethoxylated (R ⁶ = H).

Products of formula V are commercially strength, for example under the name Acusol ^® 820 (Rohm & Haas) in the form of 30 wt .-% dispersions in water available. In the case of the commercial product mentioned, R ⁴ stands for a stearyl radical, R ⁶ is a hydrogen atom, R ⁷ is H or CH ₃ and the degree of ethoxylation a is 20. Also in this dispersion, what has been said above about the water content of the compositions applies.

Liquid machine dishwashing detergents preferred in the context of the present invention are characterized in that they additionally contain 0.01 to 5% by weight, preferably 0.02 to 4% by weight, particularly preferably 0.05 to 3% by weight and in particular 0.1 to 1.5% by weight of a polymeric thickener, preferably from the group of the polyurethanes or the modified polyacrylates, with particular preference for thickeners of the formula IV

R ³

I

CXR ⁴

O in which R ^{3 is} H or a branched or unbranched C _1-4 alk (en) yl radical, X is NR ⁵ or 0, 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.

Solid forms of the automatic dishwashing agent according to the invention are, for example, fine to coarse-grained powders, such as are obtained, for example, by spray drying or granulation, compacted substance mixtures from roller compaction, but also solidified melts or moldings obtained by extrusion or tableting. In the context of the present invention, shaped bodies of this type can have practically all expediently manageable configurations, for example in the form of a table, in the form of bars or bars, a cube, a cuboid and a corresponding spatial element with flat side surfaces, and in particular cylindrical configurations with a circular or oval cross section , This last embodiment encompasses the form of presentation from the actual tablet to compact cylinder pieces with a ratio of height to diameter above 1. Preferred tableted or extruded agents have two or more phases in the context of the present invention, which can be determined, for example, by their composition Share in the total volume of the molded body and / or their visual appearance.

The phases of such multiphase molded articles can additionally be distinguished by a different dissolution behavior in the aqueous phase. Shaped bodies of this type are suitable for the time-controlled release of certain ingredients (controlled release), for example in certain rinse cycles of the automatic washing program. In a preferred embodiment, one of the phases of the molded body has meltable or softenable substances from the group of waxes, paraffins and / or polyalkylene glycols as the main constituent. Furthermore, it has proven to be advantageous if the molded body or molded body component containing these meltable or softenable substances 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 should preferably be below 5 mg / l. In such cases, however, the meltable or softenable substances should have the lowest possible solubility in water, even in water at an elevated temperature, in order to largely avoid a temperature-independent release of the active substances. The active substance is released in this way when the melting or softening point is reached.

As already mentioned at the beginning, the incorporation of magnesium and / or zinc salts of organic acids according to the invention into the automatic dishwashing detergents according to the invention does not impose any restriction with regard to the forms of supply or the recipes this means. Automatic dishwashing detergents in the context of the present invention can therefore be provided both in solid and in liquid form.

In the context of this application, however, automatic dishwashing agents according to the invention are preferred which contain the magnesium and / or zinc salts described for glass corrosion protection, these salts being prepared in such a way that they can be safely and reliably metered into an automatic dishwashing agent even in small amounts and continue to be present do not separate a fully assembled powder or granular machine dishwashing detergent.

Another preferred subject of this application is therefore an automatic dishwashing agent according to the invention, characterized in that one or more magnesium and / or zinc salt (s) is / are present in particulate form and in a form prepared with one or more further active and / or framework substances.

Since the zinc and / or magnesium salts only make up a small proportion by weight of preferred automatic dishwashing detergents, compounding simplifies the metering of these salts in the manufacture of inventive automatic dishwashing detergents on account of their “dilution effect”. But even in the event that an agent according to the invention in the form of a special product for glass corrosion protection is only added to a commercially available cleaning agent by the consumer, the metering is facilitated by the compounding. The advantages of compounding arise completely irrespective of whether the automatic dishwashing detergent to which the corresponding compounds are added is solid, liquid or gel.

Solid forms of the automatic dishwashing detergent according to the invention contain, for example, fine to coarse-grained powders, such as those obtained by spray drying or granulation. Such powders can be marketed as a commercial product or used as a premix for compacting, 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 added magnesium and / or zinc salt compounds, it is preferred that these compounds have a particle size comparable to that of the powders.

A preferred subject of the present application is therefore a machine dishwashing detergent, characterized in that the particle size of the magnesium and / or zinc salts made up 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, preferred particulate compounds to avoid segregation processes additionally having a density of 0.1 to 2.0 g / cm, preferably from 0.2 to 1.6 g / cm ³ and in particular from 0.4 to 1.2 g / cm ³ .

Machine dishwashing detergents preferred according to the invention are characterized in particular in that the particles of the magnesium and / or zinc salts assembled with one or more active and / or builder substances have a weight fraction of these magnesium and / or zinc salt (s) of 0.1 to 80% by weight. %, 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 assembled magnesium and / or zinc salts.

According to the invention, the aforementioned particulate compounds are preferably obtained by spray drying and / or granulation and / or extrusion and / or roller compaction and / or tableting and / or solidification and / or crystallization, but in particular by spray drying and / or granulation.

In the spray drying, in a first step of the process, an aqueous slurry (“slurry”) is produced which, in addition to the magnesium and / or zinc salts according to the invention, can contain further thermally stable active and / or framework substances which cannot be removed under the spray drying conditions volatilize and decompose and then pump them into the spray tower and spray them through nozzles located in the top of the tower. Rising hot air dries the slurry and evaporates the adhering water, so that the detergent components at the outlet of the tower are obtained as fine powders If necessary, further temperature-unstable components, such as bleach or fragrances, can be added.

In addition to the spray drying described above, the compositions according to the invention can also be packaged using a granulation process, a fluidized bed process being particularly preferred in which fine-grained bulk material stored on horizontal, perforated floors which, in addition to the magnesium and / or zinc salts according to the invention, contains further active and / or or may contain scaffolding substances, through which gases (eg hot air) flow from below. Under certain flow conditions, a state arises that resembles that of a boiling liquid; the layer creates bubbles and the particles of the bulk material are in a constant, swirling up and down movement within the layer and thus remain in a state of suspension. The large surface of the fluidized material then enables, for example, the reaction with other substances such as solvents, solutions of active and / or framework substances, liquid active substances or other ingredients which are present as a solid at room temperature by increasing the temperature and / or adding very limited amounts of liquid Additives soften at least superficially and / or develop 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 the magnesium and / or zinc salts according to the invention can also be used, surfactant compounds which are liquid or solid at room temperature, in particular nonionic surfactants, or polymer compounds of synthetic and / or natural origin, for example ( co) polymeric carboxylates.

Another preferred procedure for the granulation is the use of mixers / compressors, as they are provided for this purpose in addition to other providers, for example also by the company Lödige, and which are particularly suitable for the production of particles made up according to the invention because they are produced by the user Variation of various process parameters such as the number of revolutions of the mixer, the dwell time of the individual components, the dosing time 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 granules obtained. The grain size and / or density of granules can also be influenced in a targeted manner in this way, and the packaging of magnesium and / or zinc salts according to the invention with one or more further active and / or framework substance (s) in the aforementioned mixers is therefore compact particularly preferred in the context of the present invention.

Finally, there is the possibility of mixing the magnesium and / or zinc salts according to the invention with the aforementioned individual components which differ only slightly in their bulk densities from those of the salts mentioned. Mixtures of this type have only a low tendency to segregate the components during storage, transport and processing and are therefore also particularly suitable for the desired safe and reliable metering of the magnesium and / or zinc salts according to the invention. For the purposes of the present invention, preference is therefore given to mixtures of magnesium and / or zinc salts according to the invention with further active and / or builder substances, characterized in that the bulk densities of the individual components mixed with one another are not more than 200 g / l, preferably not more than 150 g / l, preferably differ by a maximum of 100 g / l and in particular by a maximum of 50 g / l.

The framework and / or active substances which can be used in the above-described packaging of preferred automatic dishwashing agents according to the invention include, in addition to other customary constituents of cleaning agents, for example builders (builders, cobuilders), surfactants, bleaching agents, bleach activators, enzymes, dyes, fragrances, corrosion inhibitors or polymers. A more detailed description of these active and / or framework substances can be found in the following sections. While all of the substances mentioned are generally suitable as active and / or builders for the manufacture of magnesium and / or zinc salts according to the invention, machine dishwashing detergents are particularly preferred in the context of the present invention in which those with one or more active and / or Builder substances made up of magnesium and / or zinc salts, active and / or builder substances from the group of phosphates, carbonates, bicarbonates, sulfates, silicates, citrates, citric acid, acetates, preferably in amounts of 20 to 99% by weight, particularly preferably of 30 to 98 wt .-% and particularly preferably from 40 to 95 wt .-%, each based on the total weight of the assembled magnesium and / or zinc salts.

In order to avoid repetitions, reference is made to the corresponding explanations in the following sections with regard to the phosphates, carbonates, hydrogen carbonates and silicates.

In the context of the present invention, sulfates are salts of sulfuric acid which arise when one or both of the two H ions of the H ₂ S0 molecule is replaced by metal ion residues (M ¹ ). In the first case, the easily soluble, easily melting "acid sulfates" (hydrogen sulfates) of the general formula MΗsθ are formed. In the second case, sulfates, "neutral" or normal sulfates, M ₂ S04, which mostly crystallize with water of crystallization, are formed of double salts and are usually also readily soluble in water. Preferred metal ions are the alkali metal ions and the ammonium ion, but in particular the sodium and / or potassium and / or ammonium ion.

Citrates and acetates are the salts of citric or acetic acid, and in the case of citrates one, two or three H ions of the original citric acid can be replaced by metal ions. Sodium and / or potassium ions and the ammonium ion are particularly suitable as metal ions.

As stated in the context of the preferred packaging methods, surfactants, in particular nonionic surfactants, or (co) -polymeric carboxylates are particularly suitable as active and / or builder substances for the packaging of magnesium and / or zinc salts according to the invention. Therefore, preferred subject matter of the present application are machine dishwashing detergents in which the magnesium and / or zinc salts assembled with one or more active and / or framework substances, one or more active and / or framework substance (s) from the group of the surfactants, preferably the nonionic surfactants and / or the polymeric carboxylates, in particular the polysulfocarboxylates. For a further description of particularly preferred surfactants or polymeric carboxylates and the polysulfocarboxylates, reference is again made to the statements in the following sections.

The particulate magnesium and / or zinc salts, which are made up with one or more active and / or framework substances, can be provided with a coating (coating) in order to protect environmental influences and thus to improve their storage stability or to influence the dissolution behavior. Coating materials and methods for coating particulate agents are widely described in the literature and are only to be explained below with respect to particularly preferred embodiments.

The use of meltable or softenable substances as coating material for the magnesium and / or zinc salts made up according to the invention is particularly preferred. (In the context of the present invention, the term “coating” means, in addition to the coating of one or more sides or surfaces of a particulate agent which is made up according to the invention, also a complete coating, that is to say the encapsulation of this particulate object.) Meltable substances preferred according to the invention have a melting point above this 30 ° C. If magnesium and / or zinc salts made up according to the invention are to be released at different times, for example during the different rinsing stages of a cleaning process, this can be done, for example, by using different meltable coatings which differ in terms of their melting point, the melting points of these substances preferably depending on the temperature profile adapted to this cleaning process and the difference in melting points is sufficient to ensure the separate dissolution of the individual matrices or coatings. If, for example, provision is made for the magnesium and / or zinc salts prepared according to the invention to be released at different times, then those substances are preferred for the different coatings which have a melting point of at least 5 ° C., preferably 10 ° C., particularly preferably 15 ° C. and in particular differ by at least 20 ° C., it being further preferred that the melting point of at least one of the fusible substances that form a coating is below 30 ° C., while the melting point of at least one further substance that form a further matrix or coating, is above 30 ° C.

Such coatings can be applied, for example, by dipping, spraying or circulating in a drum coater or coating pan. Waxes, paraffins, polyalkylene glycols, etc. are particularly preferably used as meltable or softenable substances for the coatings. It has proven to be advantageous if the meltable or softenable substances do not have a sharply defined melting point, as is usually the case with pure, crystalline substances, but instead have a melting range that may include several degrees Celsius. The meltable or softenable substances preferably have a melting range which is between approximately 45 ° C. and approximately 75 ° C. In the present case, this means that the melting range occurs within the specified temperature interval and does not indicate the width of the melting range. The width of the melting range is preferably at least 1 ° C., preferably about 2 to about 3 ° C.

The properties mentioned above are usually fulfilled by so-called waxes. "Waxing" is understood to mean a number of natural or artificially obtained substances which generally melt above 40 ° C. without decomposition and which are relatively low-viscosity and not stringy even a little above the melting point. They have a strongly temperature-dependent consistency and solubility.

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

Natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, walnut, lanolin (wool wax), or broom wax, mineral wax or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or micro waxes.

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

Synthetic waxes are generally understood to mean polyalkylene waxes or polyalkylene glycol waxes. Compounds from other classes of material which meet the stated softening point requirements can also be used as meltable or softenable substances for the masses hardening by cooling. As suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl, which is commercially available under the name Unimoll 66 ^® (Bayer AG), proved. Are also suitable Synthetic waxes of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ^® ETLP (Condea). Conversely, synthetic or partially synthetic esters from lower alcohols with fatty acids from native sources can also be used. Tegin ^® 90 (Goldschmidt), for example, falls into this class of substances Glyceryl palmitate. Shellac, for example Shellac-KPS-Dreiring-SP (Kalkhoff GmbH), can also be used according to the invention as meltable or softenable substances.

The so-called wax alcohols are also included in the waxes in the context of the present invention, for example. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols with usually about 22 to 40 carbon atoms. The wax alcohols occur, for example, in the form of wax esters of higher molecular fatty acids (wax acids) as the main component of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The sheath according to the invention prefabricated magnesium and / or zinc salts may optionally also contain wool wax alcohols which are understood to be triterpenoid and steroid alcohols, for example lanolin understood, 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 also, if appropriate, water-insoluble or only slightly water-soluble polyalkylene glycol compounds can likewise be used at least in part as a constituent 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), polyethylene glycols with molecular weights between 1500 and 36,000 being preferred, those with molecular weights from 2000 to 6000 being particularly preferred and those with molecular weights of 3000 to 5000 are particularly preferred. Corresponding processes which are characterized in that the plastically deformable mass (s) contain / contain at least one substance from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) are preferred.

Here, coating agents are preferred which contain propylene glycols (PPG) and / or polyethylene glycols (PEG) as the only meltable or softenable substances. Polypropylene glycols (abbreviation PPG) which can be used according to the invention are polymers of propylene glycol which have the general formula below

H- (0-CH-CH ₂ ) _n -OH

I CH ₃

are sufficient, where n can take values between 10 and 2000. Preferred PPGs have molar masses between 1000 and 10,000, corresponding to values of n between 17 and approximately 170. Polyethylene glycols (abbreviation PEG) which can preferably be used according to the invention are polymers of ethylene glycol which have the general formula

H- (0-CH ₂ -CH ₂ ) _n -OH

are sufficient, where n can have values between 20 and approx. 1000. The preferred molecular weight ranges mentioned above correspond to preferred ranges of the value n in formula IV from approximately 30 to approximately 820 (exactly: from 34 to 818), particularly preferably from approximately 40 to approximately 150 (precisely: from 45 to 136) and in particular from about 70 to about 120 (exactly: from 68 to 113).

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

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

Paraffin waxes consist mainly of alkanes and low levels of iso- and cycloalkanes. The paraffin to be used according to the invention preferably has essentially no constituents with a melting point of more than 70 ° C., particularly preferably of more than 60 ° C. Portions of high-melting alkanes in the paraffin can leave undesired wax residues on the surfaces to be cleaned or the goods to be cleaned if the melting temperature in the detergent solution drops below this. Such wax residues usually lead to an unsightly appearance on the cleaned surface and should therefore be avoided.

Preferred fusible or softenable substances contain at least one paraffin wax with a melting range from 50 ° C to 60 ° C, preferred coating materials are characterized in that they contain a paraffin wax with a melting range from 50 ° C to 55 ° C.

Preferably, the paraffin wax content of alkanes, isoalkanes and cycloalkanes which are solid at ambient temperature (generally about 10 to about 30 ° C.) is as high as possible. The more solid wax components present in a wax at room temperature, the more useful it is within the scope of the present invention. As the percentage of solid wax components increases, the process end products' ability to withstand impacts or friction on other surfaces increases, which leads to longer-lasting protection. High proportions Oils or liquid wax components can weaken the coating, opening pores and exposing the active substances to the environment.

In addition to paraffin, the meltable or softenable substances can also contain one or more of the above-mentioned waxes or wax-like substances as the main constituent. In a further preferred embodiment of the present invention, the mixture forming the meltable or softenable substances should be such that the mass and the coating formed from it are at least largely water-insoluble. The solubility in water should not exceed about 10 mg / l at a temperature of about 30 ° C. and should preferably be below 5 mg / l.

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

Preferred according to the invention to be processed coating materials 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 C in amounts of 6 to 30 wt .-%, preferably from 7.5 to 25 Wt .-% and in particular from 10 to 20 wt .-%, each based on the weight of the coating material.

A starting point for the technical implementation of such "controlled release" concepts is the temperature dependence of the solubility of different ingredients or

Coating materials, in particular in processes in which temperature curves are run through, for example in the sterilization and pasteurization of foods or in washing and cleaning processes, which can have several heating and cooling phases. In washing and cleaning processes, in particular in the last process step, e.g. it may be advantageous to add various active substances, such as fabric softener or rinse aid, to the last rinse cycle of a washing machine or in the last rinse cycle of a dishwasher.

A group of coating materials which are used as so-called "inverse temperature switches" with the aim of controlled release of active substances and are particularly suitable for coating magnesium and / or zinc salts prepared according to the invention in the context of the present invention are the LCST polymers, substances, which have better solubility at low temperatures than at higher temperatures. LCST polymers are also referred to as substances with a lower critical segregation temperature (LCST). With the help of coatings containing LCST polyemer it is possible to Release active substances in a controlled manner after a heat treatment when the cooling phase occurs and when the temperature drops below the lower critical separation temperature (LCST).

LCST substances are usually polymers. Depending on the application conditions, the lower critical solution temperature between room temperature and the temperature of the heat treatment should lie for example between 20 ° C, preferably 30 ° C and 100 ° C, in particular between 30 ^C C and 50 ° C. Suitable LCST substances are preferably cellulose derivatives, mono- or di-N-alkylated acrylamides, copolymers of mono- or di-N-substituted acrylamides with acrylamides and / or acrylates or acrylic acids and / or polyvinylcaprolactam, in particular the alkylated and / or or hydroxyalkylated polysaccharides, cellulose ethers, polyisopropylacrylamides, copolymers of polyisopropylacrylamide and blends of these substances are preferred.

Examples of alkylated and / or hydroxyalkylated polysaccharides are methylhydroxypropyl methyl cellulose (MHPC), ethyl (hydroxyethyl) cellulose (EHEC), hydroxypropyl cellulose (HPC), methyl cellulose (MC), ethyl cellulose (EC), carboxymethyl cellulose (CMC), carboxymethyl methyl cellulose (CMMC) ), Hydroxybutylcellulose (HBC), Hydroxybutylmethylcellulose (HBMC), Hydrdoxyethylcellulose (HEC), Hydroxyethylcarboxymethylcellulose (HECMC), Hydroxyethylethylcellulose (HEEC), Hydroxypropylcellulose (HPC), Hydroxypropylcarboxymethylcellulose (HPCMCMC), Hydroxyethylpylmethylcellulose (Hydroxyethylmethyl) Cellulose (HPCMMC), Hydroxyethylmethylcellulose (Hydroxyethylmethyl) Cellulose (MHEPC), methyl cellulose (MC) and propyl cellulose (PC) and mixtures thereof, carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose and methyl hydroxypropylene cellulose as well as the alkali salts of CMC and the slightly ethoxylated MC or mixtures of the above being preferred.

Further examples of LCST substances are cellulose ethers and mixtures of cellulose ethers with carboxymethyl cellulose (CMC). Other polymers which show a lower critical segregation temperature in water and which are also suitable are polymers of mono- or di-N-alkylated acrylamides, copolymers of mono- or di-N-substituted acrylamides with acrylates and / or acrylic acids or mixtures of intertwined networks of the above (co) polymers. Also suitable are polyethylene oxide or copolymers thereof, such as ethylene oxide / propylene oxide copolymers and graft copolymers of alkylated acrylamides with polyethylene oxide, polymethacrylic acid, polyvinyl alcohol and copolymers thereof, polyvinyl methyl ether, certain proteins such as poly (VATGW), a repeating unit in the natural protein elastin and certain alginates. Mixtures of these polymers with salts or surfactants can also be used as the LCST substance. By such additives or by copolymerization with more hydrophilic or The LCST (lower critical separation temperature) can be modified accordingly for more hydrophobic comonomers.

In order to prevent the LCST layer from dissolving in the period before the start of the heat treatment, it can optionally be provided with a further coating which only begins to dissolve or melt when the heat treatment begins. The coating materials mentioned above are particularly suitable for such a second coating.

The application of a coating to agents with LCST coating, which should effectively prevent the functional layer from softening or dissolving in the first minutes of the cleaning cycle and therefore only begins to dissolve or melt when the heat treatment is started, can be done, for example, by immersion processes (immersing the particles in a Melt) or spraying the particles with the melt or the solution of a coating material in a drum coater. Finally, it is particularly preferred to provide magnesium and / or zinc salt compounds according to the invention which have an LCST coating with a coating material in the form of a dispersion, preferably a PIT emulsion or a suspension, which

(1) 1 to 80% by weight of a coating agent solid at 20 ° C.,

(2) 0.1 to 30% by weight of a dispersant and

(3) 0.1 to 30% by weight of a co-dispersant, each based on the mixture of components (1) to (3), in 15 to 99% by weight of water, based on the dispersion. It is important for the preparation of the dispersion that the ratio of components (2) and (3) is in the range from 0.5: 1 to 20: 1.

PIT emulsions are emulsions that undergo phase inversion at certain temperatures (phase inversion temperature, PIT), the phase inversion temperature characterizing the transition of the surfactant solubility from water to oil or from oil to water. For example, it is known that oil-in-water emulsions (O / W emulsions) that are produced and stabilized with nonionic emulsifiers invert when heated to water-in-oil emulsions (W / O emulsions). This process is usually reversible, which means that the original emulsion type is reduced when it cools down. It is known that emulsions which undergo phase inversion in their production are distinguished by particular stability and fineness, while those which are produced above the phase inversion temperature are less finely divided. In the context of the present invention, it is particularly preferred if the dispersions provided for the coating (preferably PIT emulsions or suspensions) have a particle size between 0.05 and 10 μm, preferably between 0.1 and 5 μm and particularly preferably between 0.15 and 2 μm, the particle size relating to the size of the particles of the dispersed phase.

As a coating agent, i.e. Component (1), all substances are suitable which are solid at 20 ° C (for example kneadable or coarse to fine crystalline) and only change to a pasty to flowable, low-viscosity state above about 40 ° C without decomposition. Preferred coating agents are especially lipids, in particular higher-chain hydrocarbons (e.g. Paraffinum durum) and / or wax esters (e.g. cetyl palmitate).

Preferred dispersants, i.e. Component (2) are hydrophilic nonionic dispersants, particularly preferably hydrophilic nonionic dispersants, which have an HLB value of 8 to 18. The HLB value (hydrophile-lipophile balance) is to be understood as a value which according to

HLB = (100-L) / 5

can be calculated, where L is the percentage by weight of the lipophilic groups, ie the fatty alkyl or fatty acyl groups, in the ethylene oxide adducts. Preferably ethylene oxide are suitable to C ₁₆ _ ₂₂ fatty alcohols. Such commercially available products are mixtures of homologous polyglycol ethers of the starting fatty alcohols. Ethylene oxide addition products onto partial esters made from a polyol can also be used as dispersants

3 to 6 carbon atoms and C ₁₄ . ₂₂ fatty acids can be used. Particularly suitable as dispersants (2) are fatty alcohol polyglycol ethers of the general formula

R ¹ - (0-CH ₂ -CH ₂ ) _n -OH,

in which R ^{1 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 8 to 22 carbon atoms, preferably 12 to 22 carbon atoms and n is an integer from 10 to 50, preferably from 10 to 30, and addition products of

4 to 20 moles of ethylene oxide to one or more fatty acid partial glycerides.

Fatty acid partial glycerides of saturated or unsaturated fatty acids having 10 to 20 carbon atoms are technical mixtures of fatty acid mono-, di- and triglycerides which are obtained by esterification of 1 mole of glycerine with 1 to 2 moles of a C _{_10-2} fatty acid or o- can be obtained by transesterification of 1 mol of a C _10-20 fatty acid triglyceride with 0.5 to 2 mol of glycerol. Addition products of 8 to 12 mol ethylene oxide onto saturated fatty alcohols having 16 to 22 carbon atoms are particularly suitable as dispersants.

In addition to the dispersant (2), the preparation of a dispersion which is suitable for the aforementioned coating requires the presence of a co-dispersant (3), preferably a hydrophobic co-dispersant. Particularly suitable as co-dispersants are those of the fatty alcohol type with 16 to 22 carbon atoms, e.g. Cetyl alcohol, stearyl alcohol, arachidyl alcohol or behenyl alcohol or mixtures of these alcohols are preferred, as are obtained in the technical hydrogenation of vegetable or animal fatty acids with 16 to 22 carbon atoms or the corresponding fatty acid methyl ester. Other particularly preferred co-dispersants (3) are partial esters made of a polyol with 3 to 6 C atoms and fatty acids with 14 to 22 C atoms. Such partial esters are e.g. the monoglycerides of palmitin and / or stearic acid, the sorbitan mono- and / or diesters of myristic acid, palmitic acid, stearic acid or of mixtures of these fatty acids, the monoesters of trimethylolpropane, erythritol or pentaerythritol and saturated fatty acids with 14 to 22 carbon atoms. Technical monoesters which are obtained by esterification of 1 mol of polyol with 1 mol of fatty acid and which are a mixture of monoesters, diesters and unesterified polyol are also understood as monoesters.

Particularly preferred co-dispersants are cetyl alcohol, stearyl alcohol or a glycerol, sorbitan or trimethylolpropane monoester of a fatty acid with 14 to 22 carbon atoms or mixtures of these substances.

As already mentioned, the ratio of components (2) and (3) is a critical parameter for the preparation of the dispersion. The ratio of (2) and (3) should be in the range from 0.5: 1 to 20: 1, with a range from 1: 1 to 10: 1 being preferred. In a particularly preferred variant of the process according to the invention, the ratio of components (2) and (3) is adjusted such that the phase inversion temperature of the entire composition is above the melting point of the solid coating composition (1) and below 100 ° C.

All devices with which coatings can be produced from an aqueous solution are suitable for applying the dispersions, preferably the PIT emulsions or the suspensions, to the respective substrates. Larger objects can be sprayed directly with spray nozzles, preferably two-substance nozzles, with simultaneous or subsequent drying. Smaller objects can be sprayed in drum coaters, such as those used for example in pharmacy, or coating pans.

The homogeneity and impermeability to diffusion of coatings produced in this way using dispersions (preferably PIT emulsions or suspensions) can be ensured by brief melting of the wax layer, for example under a heating lamp, can be further increased.

The preferred subject of the present invention are therefore automatic dishwashing detergents, characterized in that the magnesium and / or zinc salts, which are assembled with one or more active and / or framework substances, additionally have a coating.

In addition to the choice of a suitable coating, the dissolution behavior of magnesium and / or zinc salts made up according to the invention can also be influenced by the above-mentioned compacting processes. In addition to the level of pressure used and the use of auxiliaries, such as binders, the choice of co-assembled active and / or framework substances is of particular importance. Compact silicates, in particular disilicates, and / or polycarboxylates and / or mixtures of various polycarboxylates are particularly suitable because of their delayed solution / dispersion or because of the gelation of these substances or mixture of substances in aqueous liquor as "depot substances" for the magnesium and / or zinc salts.

For a detailed description of the packaging of silicates or polycarboxylates that can be used, reference is made to the following sections.

Finally, in a special embodiment of the present invention, it is preferred to add an agent containing the zinc and / or magnesium salts of an organic acid, preferably an organic carboxylic acid, to the rinsing process in addition to a commercially available cleaning agent, for example in the form of a special glass protective agent. Such a dosage can take place both before the start of each washing program and in the form of a depot product which brings about a continuous release of the zinc and / or magnesium salts according to the invention over several washing cycles.

In addition to the builders (builder, cobuilder) and the zinc and / or magnesium salts of organic acids, preferred automatic dishwashing agents according to the invention furthermore contain one or more substances from the group of the surfactants, bleaches, bleach activators, enzymes, dyes, fragrances, corrosion inhibitors, polymers, or one another common ingredient of detergents and cleaning agents. These ingredients are described below. Builder

According to the present invention, all builders usually used in detergents and cleaning agents can be incorporated into the washing and cleaning agents, in particular silicates, carbonates, organic cobuilders and also the phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x 0 _{2x + 1} H ₂ 0, 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 represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ θ ₅ 'yH ₂ 0 are preferred.

Amorphous sodium silicates with a module Na ₂ 0: Si0 ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression 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 in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

Both monoalkali metal salts and dialkali metal salts of carbonic acid as well as sesquicarbonates can be included in the compositions as carbonates. Preferred alkali metal ions are sodium and / or potassium ions. In one embodiment, it may be preferred to add the carbonate and / or bicarbonate at least partially as a further component separately or subsequently. Compounds made of, for example, carbonate, silicate and optionally other auxiliaries such as anionic surfactants or other, in particular organic builder substances, can also be present as separate components in the finished compositions. Of course, it is also possible to use the generally known phosphates as builders, provided that such use should not be avoided for ecological reasons. Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of the greatest importance in the detergent and cleaning agent industry.

Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HP0 ₃ ) _n and orthophosphoric acid H ₃ P0 _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and limescale deposits on the wash ware and also contribute to cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ P0, exists as a dihydrate (density 1.91, preferably ^"3 , melting point 60 °) and as a monohydrate (density 2.04, preferably ^{" 3} ). Both salts are white powders, which are very easily soluble in water, lose the water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ p ₂ θ ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O _g ) and Maddrell's salt (see below). NaH ₂ P0 _{4 is} acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ P0 ₄ , is a white salt with a density of 2.33 ^"3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KP0 ₃ ) _x ] and is light soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HP0 ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gladly ^"3 , water loss at 95 °), 7 mol. (Density 1, 68 gladly ^{" 3} , melting point 48 ° with loss of 5 H ₂ 0) and 12 mol. Water ( Density 1, 52 like ^"3 , melting point 35 ° with loss of 5 H ₂ 0), becomes anhydrous at 100 ° and changes to diphosphate Na P ₂ 0 ₇ when heated. Disodium hydrogenphosphate is used by neutralizing phosphoric acid with soda solution produced by phenolphthalein as an indicator Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HP0 ₄ , is an amorphous, white salt, which is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ P0 ₄ , are colorless crystals that like a dodecahydrate a density of 1.62 ^"3 and a melting point of 73-76 ° C (decomposition), as a decahydrate (corresponding to 19-20% P ₂ 0 ₅ ) have a melting point of 100 ° C. and, in anhydrous form (corresponding to 39-40% P ₂ 0 ₅ ), a density of 2.536 ^{″ 3} . trisodium phosphate is easily soluble in water with an alkaline reaction and is prepared by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or three-base potassium phosphate), K ₃ P0 ₄ , is a white, deliquescent, granular powder with a density of 2.56 ^"3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction Heating of Thomas slag with coal and potassium sulfate Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

Tetranate diphosphate (sodium pyrophosphate), Na ₄ P ₂ 0 ₇ , exists in anhydrous form (density 2.534 like ^"3 , melting point 988 °, also given 880 °) and as decahydrate (density 1, 815-1, 836 like ^{" 3} , melting point 94 ° with water loss). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ 0 ₇ is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 ^"3 , which is soluble in water, the pH of the 1% solution at 25 ° being 10.4.

Condensation of NaH ₂ P0 ₄ or KH ₂ P0 ₄ produces higher moles. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ Oι ₀ (sodium tripolyphosphate), is an anhydrous or 6 H ₂ 0 crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (0) (ONa) -0] _n -Na with n = 3. Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and around 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% by weight solution (> 23% P ₂ 0 ₅ , 25% K ₂ 0). The Potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

(NaP0 ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ 0

According to the invention, these can be used just like sodium tripolyphosphate, potassium tripolyphosphate 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.

Automatic dishwashing detergents preferred in the context of the present invention contain no sodium and / or potassium hydroxide. Dispensing with sodium and / or potassium hydroxide as the alkali source has proven to be particularly advantageous if zinc gluconate, zinc formate and zinc acetate are used as zinc salts.

builders

Organic cobuilders which can be used in the cleaning agents in the context of the present invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.

Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as 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 of these.

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 value of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular. Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or poly methacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 1000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights from 1000 to 10000 g / mol, and particularly preferably from 1200 to 4000 g / mol, can in turn be preferred from this group.

Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally other ionic or nonionic monomers are particularly preferably used in the agents according to the invention. The copolymers containing sulfonic acid groups are described in detail below.

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 detergents according to the invention are preferred which additionally contain 0.1 to 70% by weight of copolymers from i) unsaturated carboxylic acids ii) sulfonic acid group-containing monomers iii) optionally further ionic or nonionic monomers

contain.

These copolymers have the effect that the items of crockery treated with such agents become significantly cleaner in subsequent cleaning operations than items of crockery that have been washed with conventional agents. As an additional positive effect, there is a shortening of the drying time of the dishes treated with the cleaning agent, ie the consumer can take the dishes out of the machine and reuse them earlier after the cleaning program has ended.

The invention is characterized by an improved “cleanability” of the treated substrates in later cleaning processes and by a considerable reduction in the drying time compared to comparable agents without the use of polymers containing sulfonic acid groups.

In the context of the teaching according to the invention, drying time is generally understood to mean the meaning, i.e. the time which elapses until a dish surface treated in a dishwasher is dried, but in particular the time which elapses, up to 90% of one with a cleaning or Rinse aid is dried in a concentrated or diluted form treated surface.

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

R ¹ (R ² ) C = C (R ³ ) COOH (VI),

in which 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 represents -COOH or - COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

The unsaturated carboxylic acids which can be described by formula VI include, 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) preferred.

In the case of the monomers containing sulfonic acid groups, preference is given to those of the formula VII

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (VII),

in which 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 groups as defined above or represents -COOH or - COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally available spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and -C ( 0) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas VIIa, VIIb and / or VIIc,

H ₂ C = CH-X-S0 ₃ H (Vlla),

H ₂ C = C (CH ₃ ) -X-S0 ₃ H (Vllb),

H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (Vllc),

in which R ⁶ and R ⁷ are selected independently of one another from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally present spacer group which is selected is from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and -C (0) -NH- CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid (X = -C (0) NH-CH (CH ₂ CH ₃ ) in the formula VIIa), 2-acrylamido-2-propanesulfonic acid (X = -C ( 0) NH-C (CH ₃ ) ₂ in formula VIIa), 2-acrylamido-2-methyl-1-propanesulfonic acid (X = -C (0) NH-CH (CH ₃ ) CH ₂ - in formula VIIa), 2 -Methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (0) NH-CH (CH ₃ ) CH ₂ - in formula VIIIb), 3-methacrylamido-2-hydroxypropanesulfonic acid (X = -C (0) 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 VIIIb), allyloxybenzenesulfonic acid (X = -CH ₂ - 0-C ₆ H ₄ - in formula VIIa), methallyloxybenzenesulfonic acid (X = -CH ₂ -0-C ₆ H ₄ - in formula VIIb), 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid (X = CH ₂ in formula VIII), styrene sulfonic acid (X = C ₆ H in formula VIII), vinyl sulfonic acid (X not present in formula VIII), 3-sulfopropyl acrylate (X = -C (0) NH-CH ₂ CH ₂ CH ₂ - in Formula VIII), 3-sulfopropyl methacrylate (X = -C (0) NH-CH ₂ CH ₂ CH ₂ - in formula VIIIb), sulfomethacrylamide (X = - C (0) NH- in formula VIIIb), sulfomethyl methacrylamide (X = - C (0) NH-CH ₂ - in formula VIIIb) and water-soluble salts of the acids mentioned.

Other ionic or nonionic monomers that can be used are, in particular, ethylenically unsaturated compounds. The content of monomers of group iii) in the polymers used according to the invention is preferably less than 20% by weight, based on the polymer. Polymers to be used with particular preference consist only of monomers of groups i) and ii). In summary, copolymers are made of

i) unsaturated carboxylic acids of formula VI.

R ¹ (R ² ) C = C (R ³ ) COOH (VI),

in which 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 represents -COOH or - COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,

ii) Monomers of the formula VII containing sulfonic acid groups

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (VII),

in which 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 represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group , which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and -C (0) -NH- CH (CH ₂ CH ₃ ) -

iii) optionally further ionic or nonionic monomers

particularly preferred.

Particularly preferred copolymers consist of

i) one or more unsaturated carboxylic acids from the group consisting of acrylic acid, methacrylic acid and / or maleic acid

ii) one or more monomers containing sulfonic acid groups of the formulas VIIa, VIIb and / or VIIc: H ₂ C = CH-X-S0 ₃ H (Vlla),

H ₂ C = C (CH ₃ ) -X-S0 ₃ H (Vllb),

H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (Vllc),

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 represents an optionally present spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH- C (CH ₃ ) ₂ - and - C (0) -NH-CH (CH ₂ CH ₃ ) -

iii) optionally further ionic or nonionic monomers.

The copolymers contained in the compositions according to the invention can contain the monomers from groups i) and ii) and optionally iii) in varying amounts, all representatives from 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.

For example, agents according to the invention are preferred which are characterized in that they contain one or more copolymers which have structural units of the formula VIII

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (VIII),

contain, in which m and p each represent an integer between 1 and 2000 and Y stands for a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -0- (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 produced by copolymerization of acrylic acid with an acrylic acid derivative containing sulfonic acid groups. If the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained, the use of which in the agents according to the invention is also preferred and is characterized in that the agents contain one or more copolymers which have structural units of the formula IX

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (IX), contain, in which m and p each represent an integer between 1 and 2000 and Y stands for a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -0- (CH ₂ ) _n - with n = 0 to 4, for -O- (C _β H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

Completely analogously, acrylic acid and / or methacrylic acid can also be copolymerized with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Agents according to the invention which contain one or more copolymers are structural units of the formula X

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p - (X),

contain, in which m and p each represent an integer between 1 and 2000 and Y stands for a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -0- (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 ) - is, are also preferred, a preferred embodiment of the present invention, just like agents are preferred, which are characterized in that they contain one or more copolymers, the structural units of the formula XI

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p - (XI),

Instead of or in addition to acrylic acid and / or methacrylic acid, maleic acid can also be used as a particularly preferred monomer from group i). In this way, preferred agents according to the invention are obtained which are characterized in that they contain one or more copolymers, the structural units of the formula XII

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (XII), contain, in which m and p each represent an integer between 1 and 2000 and Y stands for a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -0- (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 and to agents which are characterized in that they contain one or more copolymers, the structural units of the formula XIII

- [H00CCH-CHCO0H] _m - [CH ₂ -C (CH ₃ ) C (0) 0-Y-SO ₃ H] _p - (XIII),

In summary, automatic dishwashing agents according to the invention are preferred which contain, as ingredient b), one or more copolymers which have structural units of the formulas VIII and / or IX and / or X and / or XI and / or XII and / or XIII

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (VIII),

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (IX),

- [CH ₂ -CHCO0H] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (X),

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (XII),

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) 0-Y-S0 ₃ H] _p - (XIII),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -0- (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.

The sulfonic acid groups in the polymers can be wholly or partly in neutralized form, ie the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular by sodium ions. Corresponding means, which are characterized by that the sulfonic acid groups in the copolymer are partially or fully neutralized are preferred according to the invention.

The monomer distribution of the copolymers used in the agents according to the invention is preferably 5 to 95% by weight i) or ii), particularly preferably 50 to 90% by weight, in the case of copolymers which contain only monomers from groups i) and ii). % 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, those which contain 20 to 85% by weight of monomer from group i), 10 to 60% by weight of monomer from group ii) and 5 to 30% by weight of monomer from group iii) are particularly preferred ,

The molar mass 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 intended use. Preferred automatic dishwashing detergents are characterized in that the copolymers have molar masses from 2000 to 200,000 gmol ^"1 , preferably from 4000 to 25,000 gmol ^{" 1} and in particular from 5000 to 15,000 gmol ^"1 .

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

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

Surprisingly, it was found that when a combination of zinc salts according to the invention, in particular zinc stearate, zinc oleate, zinc citrate, zinc gluconate, zinc lactate and / or zinc acetate with the above-described copolymers containing sulfonic acid groups in a MGSM, the corrosion-inhibiting effect of the zinc salts is significantly increased, and consequently the amount of the zinc salt used can be reduced. Preferred machine Dishwashing detergents in the context of the present invention therefore contain, in addition to odorant (s) and optionally further constituents of cleaning agents, also one or more zinc salts, preferably from the group zinc stearate, zinc oleate, zinc citrate, zinc gluconate, zinc lactate and / or zinc acetate and one or more copolymers containing sulfonic acid groups , The preferred weight ratio of zinc salt (calculated on Zn ²⁺ ) to copolymer containing sulfonic acid groups in such a preferred automatic dishwashing detergent is between 20: 1 and 1: 500, in particular between 1: 1 and 1: 400 and particularly preferably between 1:10 and 1: 250th

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 relative molecular weight, based on free acids, is generally 2,000 to 100,000 g / mol, preferably 20,000 to 90,000 g / mol and in particular 30,000 to 80,000 g / mol.

To improve water solubility, the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.

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

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

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Polyaspartic acids or their salts and derivatives are particularly preferred.

In addition, all compounds that are able to form complexes with alkaline earth metal ions can be used as cobuilders.

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

surfactants

In the context of the present application, preferred cleaning agents contain one or more surfactant (s) from the groups of anionic, nonionic, cationic and / or amphoteric surfactants.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _g . ₁₃ -Alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates as obtained, for example, from C ₁₂ .ι _B monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products , into consideration. Also suitable are alkanesulfonates, which are for example derived from C ₁₂ .ι ₈ alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. The esters of sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures, as obtained in the production 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 Sul- Fixed fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

The alk (en) yl sulfates are the alkali and, in particular, the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from 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 this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 2,3-alkyl sulfates, which can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched Cg-n alcohols with an average of 3.5 mol of ethylene oxide (EO) or C ₁₂ . ₁₈ fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

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

Soaps are particularly suitable as further anionic surfactants. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. The anionic surfactants, including the soaps, can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

Another group of washing-active substances are the non-ionic surfactants. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁ -alcohols with 3 EO or 4 EO, C ₉ -n alcohols with 7 EO, C ₁₃ . ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Cι ₂ . ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, 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 averages, which can be an integer or a fraction for a specific product. 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 of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Another class of preferably used nonionic surfactants, which are 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 with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester.

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Alkypolyglycosides which can be used satisfy the general formula RO (G) _z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is Is symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for 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. Prefers linear alkyl polyglucosides are used, ie alkyl polyglycosides consisting of a glucose residue and an n-alkyl chain.

Another class of preferably used nonionic surfactants, which are 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 with 1 to 4 carbon atoms in the alkyl chain.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (XIV),

R '

R-CO-N- [Z] (XIV)

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R 'for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 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.

The group of polyhydroxy fatty acid amides also includes compounds of the formula (XV)

R ¹ -0-R ²

I R-CO-N- [Z] (XV)

in which 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 is 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic Is an alkyl radical or an aryl radical or an oxy-alkyl radical with 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated derivatives of this radical.

[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 the case of detergents and cleaning agents for automatic dishwashing, all surfactants are generally suitable as surfactants. However, the nonionic surfactants described above, and above all the low-foaming nonionic surfactants, are preferred for this purpose. The alkoxylated alcohols are particularly preferred, especially the ethoxylated and / or propoxylated alcohols. The person skilled in the art generally understands by alkoxylated alcohols the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the sense of the present invention the longer-chain alcohols (C ₁₀ to C ₁₈ , preferably between C ₁₂ and C ₁₆ , such as Cn- , C ₁₂ -, C ₁₃ -, C ₁₄ -, C ₁₅ -, C ₁₆ -, Cιτ- and C ₁₈ - alcohols). As a rule, a complex mixture of addition products of different degrees of ethoxylation is formed from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions. A further embodiment consists in using mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. If desired, final etherification with short-chain alkyl groups, such as preferably the butyl group, can also give the class of "closed" alcohol ethoxylates, which can also be used in the context of the invention. Highly preferred for the purposes of the present invention are highly ethoxylated fatty alcohols or their mixtures with end-capped fatty alcohol ethoxylates.

Low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred nonionic surfactants within the scope of the present invention. Among these, surfactants with EO-AO-EO-AO blocks are preferred, with one to ten EO or AO groups being bonded to one another before a block follows from the other groups. Machine dishwashing detergents according to the invention which contain surfactants of the general formula XVI as nonionic surfactant (s) are preferred here R ¹ -0- (CH ₂ -CH ₂ -0) _w - (CH ₂ -CH-0) _x - (CH ₂ -CH ₂ -Ö) _y - (CH ₂ -CH-0) _z -H (XVI )

I I

R ² R ³

in R ¹ for a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂ 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 represent integers from 1 to 6.

The preferred nonionic surfactants of the formula XVI can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in formula XVI above can 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 generally not shown, the linear radicals being from alcohols of native origin with 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, in the mixture, methyl-branched or linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions according to the invention, preferred dishwasher detergents according to the invention are those in which R ¹ in formula XVI for an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 is up to 11 carbon atoms.

In addition to propylene oxide, butylene oxide is particularly suitable as the alkylene oxide unit which is present in the preferred nonionic surfactants in alternation with the ethylene oxide unit. However, other alkylene oxides in which R ² or R ³ are selected independently of one another from - CH ₂ CH ₂ -CH ₃ or -CH (CH ₃ ) ₂ are also suitable. Preferred automatic dishwashing agents are characterized in that R ² and R ³ for a radical -CH ₃ , w and x independently of one another stand for values of 3 or 4 and y and z independently of one another for values of 1 or 2.

In summary, nonionic surfactants are particularly preferred for use in the agents according to the invention with 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. The dishwasher detergents according to the invention particularly preferably contain a nonionic surfactant which has a melting point above room temperature having. Accordingly, preferred agents are characterized in that they contain nonionic surfactant (s) with a melting point above 20 ° C., preferably above 25 ° C., particularly preferably between 25 and 60 ° C. and in particular between 26.6 and 43, 3 ° C.

Suitable, in addition to the nonionic surfactants contained in the compositions according to the invention, which have melting or softening points in the temperature range mentioned, are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If highly viscous 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 that have a waxy consistency at room temperature are also preferred.

Preferred nonionic surfactants to be used at room temperature originate from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols, and mixtures of these surfactants with structurally more complex 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 with a melting point above room temperature is an ethoxylated nonionic surfactant which results from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has resulted.

A particularly preferred solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C _{_16-2} alcohol), preferably a Ci _B alcohol and at least 12 mole, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide won. Among these, the so-called "narrow ranks ethoxylates" (see above) are particularly preferred.

Accordingly, particularly contain (s) the / preferred inventive ethoxylated (s) nonionic surfactant selected from C ₆ - ₂ o-monohydroxy alkanols or C. ₆ ₂ o-alkylphenols or C ₁₆ . ₂₀ fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained.

The nonionic surfactant preferably additionally has propylene oxide units in the molecule. Such PO units preferably make up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols, which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol portion of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly 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 make up nonionic surfactant.

Other nonionic surfactants with melting points above room temperature which are particularly preferably used contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which contains 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol 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 that may be used with particular preference are available, for example under the name Poly Tergent ^® SLF-18 from Olin Chemicals.

A further preferred automatic dishwashing agent according to the invention contains nonionic surfactants of the formula

R ¹ 0 [CH ₂ CH (CH ₃ ) 0] _x [CH ₂ CH ₂ 0] _y [CH ₂ CH (OH) R ² ],

in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y stands for a value of at least 15.

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

R ¹ 0 [CH ₂ CH (R ³ ) 0] _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 one Methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j for values between 1 and 12, preferably between 1 and 5. If the value x ≥ 2, each R ³ in the above formula can 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, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH ₃ or - CH ₂ CH _{3 are} particularly preferred for the radical R ³ . 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 can be different if x ≥ 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, if 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 can be joined together 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 chosen here by way of example and may well be larger, the range of variation 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 can be used

R ¹ 0 [CH ₂ CH (R ³ ) 0] _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 stands for numbers 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 have} 9 to 14 carbon atoms, R ^{3 represents} H and x assumes values from 6 to 15.

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

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _] OR ²

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

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x CH ₂ CH (OH) CH ₂ OR ²

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

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

The agents according to the invention can contain, for example, cationic compounds of the formulas XVII, XVIII or XIX as cationic active substances:

R ¹

1

R ¹ -N ⁽⁺⁾ - (CH ₂ ) "- -TR ² (XVII)

I 1

(CH ₂ ) _n -TR ²

R ¹

1

R ¹ -N ⁽⁺⁾ - (CH ₂ ) "- -CH-CH ₂ (XVIII)

| I 1 1

1

R ¹ TT

1 1 R ² R ²

R ¹ IR ³ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (XIX) R ⁴

wherein each R ^{1 group is} independently selected from C _1-6 alkyl, alkenyl or hydroxyalkyl groups; each R ^{2 group is} independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O- CO- or -CO-O- and n is an integer from 0 to 5.

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

bleach

Bleaching agents and bleach activators are important constituents of washing and cleaning agents and a washing and cleaning agent can contain one or more substances from the groups mentioned within the scope of the present invention. Sodium percarbonate is of particular importance among the compounds which serve as bleaching agents and supply H ₂ 0 ₂ in water. Other usable bleaching agents are, for example, sodium perborate tetrahydrate and the sodium perborate monohydrate. Peroxypyrophosphates, citrate perhydrates and H ₂ 0 ₂ -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.

“Sodium percarbonate” is a non-specific term for sodium carbonate peroxohydrates, which strictly speaking are not “percarbonates” (ie salts of percarbonic acid) but hydrogen peroxide adducts with sodium carbonate. The merchandise has the average composition 2 Na ₂ C0 ₃ -3 H ₂ 0 ₂ and is therefore not peroxycarbonate. Sodium percarbonate often forms a white, water-soluble powder with a density of 2.14 ^"3 , which easily breaks down into sodium carbonate and bleaching or oxidizing oxygen.

Sodium carbonate peroxohydrate was first obtained in 1899 by ethanol precipitation from a solution of sodium carbonate in hydrogen peroxide, but was mistakenly regarded as peroxy carbonate. It was not until 1909 that the compound was recognized as a hydrogen peroxide addition compound, however the historical name "sodium percarbonate" has become established in practice.

The industrial production of sodium percarbonate is mainly produced by precipitation from an aqueous solution (so-called wet process). Here, aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium percarbonate Salting agents (predominantly sodium chloride), kneading aids (for example polyphosphates, polyacrylates) and stabilizers (for example Mg ²⁺ ions) are precipitated. The precipitated salt, which still contains 5 to 12% by weight of mother liquor, is then removed by centrifugation and in fluidized bed dryers at 90 ° C dried The bulk weight of the finished product can vary between 800 and 1200 g / l depending on the manufacturing process. In general, the percarbonate is stabilized by an additional coating. Coating processes and substances used for coating are widely described in the patent literature Percarbonate types are used, such as those offered by the companies Solvay Interox, Degussa, Kemira or Akzo

Detergents for automatic dishwashing can also contain bleaches from the group of organic bleaches. Typical organic bleaches that can be used as ingredients in the context of the present invention are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaches are the peroxy acids, examples of which especially the alkyl peroxy acids and the aryl peroxy acids are mentioned. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkyl peroxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacidic acid, such as peroxlauic acid , ε-phtha midoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1, 12-D ιperoxycarbonsaure, 1, 9-Dιperoxyazelaιnsäure, Diperocysebacinsaure,

Diperoxybrassyl acid, the diperoxyphthalic acids, 2-decyldipperoxybutane-1,4-dic acid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used

According to the present invention, chlorine or bromine-releasing substances can also be used as bleaching agents for automatic dishwashing. Among the suitable chlorine or bromine-releasing materials are, for example, heterocyclic N-bromine and N-chloramides, for example trichloroisocyanuric acid, tbromoisocyanuric acid, dibromoisocyanuric acid and / or dichlorosocyanuric acid ( DICA) and / or their salts with cations such as potassium and sodium are also suitable for hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydanthoion

Advantageous agents in the context of the present invention contain one or more bleaching agents, preferably from the group of oxygen or halogen bleaching agents, in particular chlorine bleaching agents, with particular preference for sodium percarbonate and / or sodium piperborate monohydrate, in amounts of 0.5 to 40% by weight %, preferably from 1 to 30% by weight, particularly preferably from 2.5 to 25% by weight and in particular from 5 to 20% by weight, in each case based on the total composition Bleach activators

In order to achieve an improved bleaching effect when cleaning at temperatures of 60 ° C. and below, cleaning agents can contain bleach activators within the scope of the present invention. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic 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 number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are multiply acylated 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, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetate, ethylene glycol, diacetoxy-2,5-dihydrofuran. In addition to the conventional bleach activators or instead of them, so-called bleach catalysts can also be incorporated into the cleaning agents 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 salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.

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

The bleach activators preferred in the context of the present invention also include the “nitrile quats”, cationic nitriles of the formula (XX),

R ¹

R -N ^(t, - (CH ₂ ) -CN X (-) (XX),

R ³ in which R ^{1 represents} -H, -CH ₃ , a C _2-24 alkyl or alkenyl radical, a substituted C _2-24 alkyl or alkenyl radical with 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 for a substituted alkyl or alkenylaryl radical with a C _1-2 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 -0) _n H with n = 1, 2, 3, 4, 5 or 6 and X is an anion.

General formula (XX) includes a large number of cationic nitriles which can be used in the context of the present invention. The laundry detergent tablets according to the invention particularly advantageously contain cationic nitriles in which R ^{1 is} methyl, ethyl, propyl, isopropyl or an n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n- Tetradecyl, n-hexadecyl or n-octadecyl radical. R ² and R ³ are preferably selected from methyl, ethyl, propyl, isopropyl and hydroxyethyl, where one or both radicals can advantageously also be a cyanomethylene radical.

For reasons of easier synthesis, compounds are preferred 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 ^" preferably represents an anion selected from the group consisting of chloride, bromide, iodide, hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate) or xylene sulfonate.

Washing and cleaning agents preferred in the context of the present invention are characterized in that they contain the cationic nitrile of the formula (XX) in amounts of 0.1 to 20% by weight, preferably 0.25 to 15% by weight and in particular from 0.5 to 10% by weight, based in each case on the weight of the shaped body.

Enzymes In particular, those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned are suitable. All of these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. To bleach or inhibit the Color transfer can also be used with oxidoreductases. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes.

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

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

dyes

In order to improve the aesthetic impression of the detergents and cleaning agents, they can be colored with suitable dyes. Dyes preferred in the context of the present invention, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity towards textile fibers, in order not to dye them.

Preferred for use in the washing and cleaning agents according to the invention are all colorants which can be oxidatively destroyed in the washing process, and also mixtures thereof with suitable blue dyes, so-called blue tones. It has proven to be advantageous to use colorants in water or at room temperature in liquid organic Substances are soluble. For example, anionic colorants, for example anionic nitroso dyes, are suitable. One possible dye is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020)., That is as a commercial product, for example as Basacid ^® Green 970 from BASF, Ludwigshafen available, as well as mixtures thereof with suitable blue dyes. Other colorants include Pigmosol ^® Blue 6900 (Cl 74160), Pigmosol ^® Green 8730 (Cl 74260), Basonyl ^® Red 545 FL (Cl 45170), Sandolan ^® Rhodamine EB400 (Cl 45100), Basacid ^® Yellow 094 (Cl 47005), Sicovit ^® Patentblau 85 E 131 (Cl 42051), Acid Blue 183 (CAS 12217-22-0, Cl Acidblue 183), Pigment Blue 15 (Cl 74160), Supranol ^® Blau GLW (CAS 12219-32- 8, Cl Acidblue 221 )), Nylosan ^® Yellow N-7GL SGR (CAS 61814-57-1, Cl Acidyellow 218) and / or Sandolan ^® Blue (Cl Acid Blue 182, CAS 12219-26-0).

When choosing the colorant, care must be taken to ensure that the colorants do not have too strong an affinity for the textile surfaces and especially for synthetic fibers. At the same time, when choosing suitable colorants, it must also be taken into account that colorants have different stabilities against oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the washing or cleaning agents varies. In the case of readily water-soluble colorants, for example the above-mentioned Basacid ^® green or the above-mentioned Sandolan ^® blue, colorant concentrations in the range from a few 10 ^{~ 2} to 10 ^"3 % by weight are typically chosen. In the case of those, in particular, on account of their brilliance preferred, but are less readily water-soluble pigment dyes, for example the above-mentioned Pigmosol ^® - dyes, the appropriate concentration of the colorant is in washing or cleaning agents, however, typically a few 10 ^"3 to ^{10" 4} wt .-%.

fragrances

Fragrances are added to the compositions in the context of the present invention in order to improve the aesthetic impression of the products and, in addition to the performance of the product, to provide the consumer with a visually and sensorially "typical and distinctive" product.

In the context of the present invention, individual fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert.-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allylcyclohexyl benzylatepylpropionate, and The ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, for the ketones e.g. the jonones, oc-isomethylionone and methyl cedryl ketone, for the alcohols anethole, citronellol, eugenol, geraniol, linal Phenylethyl alcohol and terpineol, the hydrocarbons mainly include terpenes such as limonene and pinene.

However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures as are available from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

Corrosion inhibitors

Detergents for machine dishwashing can contain corrosion inhibitors to protect the wash ware or the machine, silver protection agents in particular being particularly important in the area of machine dishwashing. The known substances of the prior art can be used. In general, silver protection agents selected from the group consisting of the triazoles, the benzotriazoles, the bisbeπzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. In addition, active chlorine-containing agents are often found in cleaner formulations, which can significantly reduce the corroding of the silver surface. In chlorine-free cleaners, especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Preferred here are the transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate, as well as the manganese complexes

[Me-TACN) Mn ^IV (m-0) ₃ Mn ^I (Me-TACN)] ²⁺ (PF ₆ -) ₂ , [Me-MeTACN) Mn ^IV (m-0) ₃ Mn ^I (Me-MeTACN) ] ²⁺ (PF ₆ -) ₂ , [Me-TACN) Mn ^lll (m-0) (m-0Ac) ₂ Mn ^{l, l} (Me-TACN)] ²⁺ (PF ₆ ^_ ) ₂ and [Me-MeTACN) Mn ^III (m-0) (m-0Ac) ₂ Mn ^III (Me-MeTACN)] ²⁺ (PF ₆ -) ₂ , where 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. Zinc compounds can also be used to prevent corrosion on the wash ware.

In the context of the present invention, automatic dishwashing agents are preferred which additionally have at least one silver protective agent selected from the group consisting of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles, preferably benzotriazole and / or alkylaminotriazole, in amounts of 0.001 to 1% by weight. %, preferably from 0.01 to 0.5% by weight and in particular from 0.05 to 0.25% by weight, in each case based on the total composition.

The dishwashing detergents according to the invention for machine dishwashing can be offered to the consumer in conventional containers, for example bottles, screw-top jars, canisters, balloons, cups or spraying vessels, from which he doses them for use. Highly viscous products can also be offered in tubes or dispensers as they are known from toothpaste or sealants. Today, such containers are usually made from water-insoluble polymers and can consist, for example, of all the usual water-insoluble packaging materials that are well known to those skilled in the art. In particular, hydrocarbon-based plastics are to be mentioned as preferred polymers. The particularly preferred polymers include polyethylene, polypropylene (more preferably oriented polypropylene) and polymer mixtures, such as, for example, mixtures of the polymers mentioned 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 the polymers mentioned or copolymers comprising the polymers mentioned.

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

A preferred subject of the present invention are therefore automatic dishwashing detergents which are packaged in portions in a water-soluble envelope.

Dishwashing detergents according to the invention preferably comprise a completely or partially water-soluble covering. The shape of the wrapper is not limited to certain shapes. Basically, all Archimedean and Platonic bodies, i.e. three-dimensional shaped bodies, can be used as forms of wrapping. Examples of the shape of the covering are capsules, cubes, spheres, egg-shaped moldings, cuboids, cones, rods or bags. Hollow bodies with one or more compartments are also suitable as a covering for the dishwashing detergents. In preferred embodiments of the invention, the envelopes are in the form of capsules, such as are also used, for example, in pharmacy for the administration of medicaments, spheres or sachets. The latter are preferably welded or glued on at least one side, an adhesive which is water-soluble being used as the adhesive in particularly preferred embodiments of the invention.

According to a preferred embodiment of the invention, the water-soluble polymer material partially or completely surrounding the dishwashing detergent 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. There are, for example, different shapes (such as hoses, pillows, cylinders, bottles, disks, etc.), processed plastic foils or plates, capsules and other conceivable shapes. According to the invention, particular preference is given to films which, for example, can be glued and / or sealed to packaging such as hoses, pillows or the like after they have been filled with partial portions of the cleaning agents according to the invention or with the cleaning agents themselves.

Plastic film packaging made of water-soluble polymer materials is further preferred according to the invention on account of the properties which can be adapted excellently to the desired physical conditions. Such films are basically known from the prior art. In summary, both hollow bodies of any shape, which can be produced by injection molding, bottle blowing, deep drawing, etc., and hollow bodies made of foils, in particular pouches, are preferred as packaging for portioned agents according to the invention. Preferred automatic dishwashing agents according to the invention are thus characterized in that the water-soluble covering comprises a bag made 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 completed. This has the advantage that the dishwashing detergents are optimally protected against environmental influences, in particular against moisture. In addition, with these enclosed enclosures, the invention can be further developed such that the cleaning agents contain at least one gas to protect the contents of the enclosure (s) from moisture, see below.

In principle, all materials that can dissolve completely or partially in the aqueous phase under the given conditions of a washing process, rinsing process or cleaning process (temperature, pH value, concentration of detergent components) are suitable as materials for the completely or partially water-soluble coating. The polymer materials can particularly preferably be the groups (optionally partially acetalized) of polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and their derivatives, starch and their derivatives, in particular modified starches, and mixtures (polymer blends, composites, coextrudates etc.) of the belong to the materials mentioned. Gelatin and polyvinyl alcohols and the two materials mentioned are particularly preferred in each case in combination with starch or modified starch. Inorganic salts and mixtures thereof can also be used as materials for the at least partially water-soluble coating.

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

Particularly preferred automatic dishwashing detergents according to the invention are characterized in that the casing contains one or more water-soluble polymer (s), preferably a material from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and their derivatives and mixtures thereof, more preferably (optionally acetalized) polyvinyl alcohol (PVAL). "Polyvinyl alcohols" (abbreviation PVAL, occasionally also PVOH) is the name for polymers of the general structure

- CH2 - CH - CH2 - CH -

OH OH

which in small proportions (approx. 2%) also structural units of the type

contain.

Commercial polyvinyl alcohols, which are offered as white-yellowish powders or granules with degrees of polymerization in the range from approx. 100 to 2500 (molar masses from approx. 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , therefore still contain a residual content of acetyl groups. The manufacturers characterize the polyvinyl alcohols by stating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number and the solution viscosity.

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and a few strongly 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 at least partially biodegradable. The water solubility can be reduced by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid or borax. The polyvinyl alcohol coatings are largely impervious 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 covering comprises a polyvinyl alcohol, the degree of hydrolysis of which 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 specific molecular weight range are preferably used as materials for the covering, it being preferred according to the invention that the covering comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol ^" ¹ , preferably from 1 1,000 to 90,000 gmol ^{" 1} , particularly 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 approximately 200 to approximately 2100, preferably between approximately 220 to approximately 1890, particularly preferably between approximately 240 to approximately 1680 and in particular between approximately 260 to approximately 1500.

The polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ^® (Clariant). In the present invention, particularly suitable polyvinyl alcohols 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 can be found in the table below:

Other polyvinyl alcohols suitable as material for the hollow 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 changed by post-treatment with aldehydes (acetalization) or ketones (ketalization). Polyvinyl alcohols which have been acetalized or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly preferred and particularly advantageous because of their extremely good solubility in cold water. The reaction products made of PVAL and starch are extremely advantageous to use. Furthermore, the solubility in water can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus specifically adjusted to the desired values. PVAL films are largely impenetrable for 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 from Syntana Handelsgesellschaft E. Harke GmbH & Co. under the name "SOLUBLON ^® ". Their solubility in water can be adjusted to the exact degree, and films of this product range are available which are soluble in the aqueous phase in all temperature ranges relevant to the application.

Polyvinylpyrrolidones, abbreviated as PVP, can be described by the following general formula:

PVP are made by radical polymerization of 1-vinyl pyrrolidone. Commercial PVPs have molar masses in the range from approx. 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- [0-CH ₂ -CH ₂ ] _n -OH

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

Gelatin is a polypeptide (molecular weight: approx. 15,000 to> 250,000 g / mol), which is primarily obtained by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions. The amino acid composition of the gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on it of its provenance. The use of gelatin as a water-soluble coating material is extremely widespread, especially in the pharmaceutical industry in the form of hard or soft gelatin capsules. In the form of films, gelatin is used only to a minor extent because of its high price in comparison to the abovementioned polymers.

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

Starch is a homoglycan, with the glucose units linked α-glycosidically. Starch is made up of two components of different molecular weights: approx. 20 to 30% straight-chain amylose (MW. Approx. 50,000 to 150,000) and 70 to 80% branched-chain amylopectin (MW. Approx. 300,000 to 2,000,000). It also contains small amounts of lipids, phosphoric acid and cations. While the amylose forms long, helical, intertwined chains with about 300 to 1,200 glucose molecules due to the binding in the 1,4-position, the chain in the amylopectin branches to an knot-like structure after an average of 25 glucose units through 1,6-binding with about 1,500 to 12,000 molecules of glucose. In addition to pure starch, starch derivatives which can be obtained by polymer-analogous reactions from starch are also suitable for producing water-soluble coatings for the detergent, dishwashing detergent and cleaning agent portions. Such chemically modified starches include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Starches in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as starch derivatives. The group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and starches and amino starches.

Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, formally speaking, is a ß-1,4 polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5,000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses

Preferred wrappings made of at least partially water-soluble film contain at least one polymer with 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 Manufacturing process on different material thicknesses, wherein automatic dishwashing agents according to the invention are 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 bags (so-called pouches) are chosen as packaging, the water-soluble film which forms the wrapper preferably has a thickness of 1 to 300 μm, preferably 2 to 200 μm, particularly preferably 5 to 150 μm and in particular 10 to 100 μm

These water-soluble films can be produced by various manufacturing processes. Blowing, calendering and casting processes are to be mentioned here in principle. In a preferred process, the films are blown from a melt with air via a blowing mandrel to form a tube. In the calendering process, which also belongs to the production process used preferably, the raw materials plasticized by suitable additives are atomized to form the films. Here it may be necessary, in particular, to connect drying to the evaporation. In the casting process, which is also one of the preferred production processes, an aqueous polymer preparation is placed on a heatable drying roller given, after the evaporation of the water is optionally cooled and the film is removed as a film. If necessary, this film is additionally powdered before or during the removal

According to the invention, an embodiment is preferred according to which the casing as a whole is water-soluble, that is to say it dissolves completely when used as intended in machine cleaning when the conditions provided for the dissolution have been reached. Particularly preferred as completely water-soluble casings are, for example, capsules made of gelatin Advantage from soft gelatin, or pouch made from (optionally partially acetated) PVAL or balls made from gelatin or (optionally partially acetated) PVAL or from one or more organic and / or inorganic salts, preferably balls made from soft gelatin. A major advantage of this embodiment is that the Wrapping within a practically relevant short time - as a non-limiting example, a few seconds to 5 minutes - can be at least partially dissolved in the cleaning liquor under precisely defined conditions and thus introduces the encapsulated content, ie the cleaning-active material or several materials, into the fleet in accordance with the requirements.

In another embodiment of the invention, which is also preferred on account of advantageous properties, the water-soluble covering comprises areas which are less or not water-soluble or only water-soluble at a higher temperature and areas which are water-soluble or water-soluble at a low temperature. In other words, the covering does not consist of a uniform material which has the same water solubility in all areas, but of materials of different water solubility. Areas of good water solubility are to be distinguished on the one hand from areas with less good water solubility, with poor or no water solubility or from areas in which water solubility is only at a higher temperature or at a different pH value or only when the electrolyte concentration has changed achieved, on the other hand. This can lead to certain areas of the wrapping becoming detached when used as intended under adjustable conditions, while other areas remain intact. This creates an envelope with pores or holes into which water and / or liquor penetrate, detach active, rinse-active or cleaning-active ingredients and can discharge them from the envelope. In the same way, encapsulation systems in the form of multi-chamber bags or in the form of hollow bodies arranged one inside the other (eg spheres: “onion system”) can also be provided. In this way, systems with controlled release of the wash-active, rinse-active or cleaning-active ingredients can be manufactured.

The invention is not subject to any restrictions for the formation of such systems. Enclosures can be provided in which a uniform polymer material comprises small areas of incorporated compounds (for example salts) which are more water-soluble than the polymer material. On the other hand, several polymer materials with different water solubility can also be mixed (polymer blend), so that the more rapidly soluble polymer material is disintegrated faster under defined conditions by water or the liquor than the more slowly soluble one.

It corresponds to a particularly preferred embodiment of the invention that the less water-soluble areas or non-water-soluble areas or only at higher temperatures water-soluble areas of the casing are areas made of a material which chemically essentially corresponds to that of the readily water-soluble areas or at lower temperatures water-soluble areas corresponds, but has a higher layer thickness and / or a changed degree of polymerization of the same polymer and / or a higher degree of crosslinking of the same polymer structure and / or a higher degree of acetalization (in the case of 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 covering does not completely dissolve, portions of detergent according to the invention can thus be provided which have advantageous properties when released have the dishwashing detergent in the respective fleet

The water-soluble Hull material is preferably transparent. For the purposes of this invention, transparency is understood to mean that the transmittance within the visible spectrum of light (410 to 800 nm) is greater than 20%, preferably greater than 30%, most preferably greater than 40% and in particular is greater than 50% As soon as a wavelength of the visible spectrum of the light has a transmittance greater than 20%, it is to be regarded as transparent in the sense of the invention

Dishwashing detergents according to the invention, which are packaged in transparent wrappings or containers, can contain a stabilizing agent as an essential constituent , UV absorbers and fluorescent dyes

Particularly suitable stabilizers for the purposes of the invention are the antioxidants. In order to prevent undesirable changes to the formulations caused by light irradiation and hence radical decomposition, the formulations can contain antioxidants. Phenols, bisphenols and thiobisphenols substituted by rigidly blocked groups can be used as antioxidants Examples are propyl gallate, butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), t-butylhydroquinone (TBHQ), tocopherol and the long-chain (C8-C22) esters of gallic acid, such as dodecyl gallate. Other classes of substances are aromatic names, preferably secondary aromatic names 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, compounds containing endiol groups, so-called reductones, such as ascorbic acid and its Derivatives, such as ascorbic acid palmitate, organosulfur compounds, such as the esters of 3,3 ^' -Thιodιpropιonsaure with Cviβ-alkanols, especially Cι ₀ ι ₈ alkanols, metal ion deactivators, which are able to catalyze the auto-oxidation Me-tal onen, such as B complexing copper, such as nitrous oxide and its derivatives and their mixtures. Antioxidants can 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 stabilizers that can preferably be used are the UV absorbers. UV absorbers can improve the light resistance of the recipe components. These include organic substances (light protection filters) that are able to absorb ultraviolet rays and release the absorbed energy in the form of longer-wave radiation, eg heat. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position. Substituted benzotriazoles, such as, for example, the water-soluble benzenesulfonic acid 3- (2H-benzotriazol-2-yl) -4-hydroxy-5- (methylpropyl) monosodium salt (Cibafast ^® H), are phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position. , optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbeiliferone and the body's own urocanoic acid. Biphenyl and especially stilbene derivatives, which are commercially available as Tinosorb ^® FD or Tinosorb ^® FR ex Ciba, are of particular importance. Examples of UV-B absorbers are 3-benzylidene camphor and 3-benzylidene norcampher and their derivatives, for example 3- (4-methylbenzylidene) camphor; 4-aminobenzoic acid derivatives, preferably 4-

2-ethylhexyl (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate; Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, 4

Isamyl methoxy cinnamate, 2-ethylhexyl 2-cyano-3,3-phenyl cinnamate (octocrylene); Esters of salicylic acid, preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropylbenzyl ester, salicylic acid homomethyl ester; 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-dione, 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, alkaline earth, 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 3-benzylidene camphor, e.g. 4- (2-oxo-3-bornylidene methyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.

Derivatives of benzoylmethane, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1, 3-dione, 4-tert-butyl, are particularly suitable as typical UV-A filters -4'-meth-oxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione and enamine compounds. The UV-A and UV-B filters can of course also be used in mixtures be used. In addition to the soluble substances mentioned, insoluble light-protection pigments, namely finely dispersed, preferably nanoized 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. Silicates (talc), barium sulfate or zinc stearate can be used as salts. 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 can have a spherical shape, but it is also possible to use particles which have an ellipsoidal shape or shape which differs from the spherical shape in some other way. The pigments can also be surface-treated, ie hydrophilized or hydrophobicized. Typical examples are coated titanium dioxides such as titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Silicones, and in particular trialkoxyoctylsilanes or simethicones, are particularly suitable as hydrophobic coating agents. Micronized zinc oxide is preferably used.

UV absorbers can be contained 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 is the fluorescent dyes. They include the ^{^{4,4'-diamino-2,2'-stilbenedisulfonic}} acids (flavonic), 4,4 ^{'-Distyrylbiphenylen,} methyl umbelliferone, coumarins, dihydroquinolinones, 1, 3- diarylpyrazolines, naphthalimides, benzoxazole, benzisoxazole, and Benzimidazole systems as well as the pyrene derivatives substituted by heterocycles. Of particular importance are the sulfonic acid salts of the diaminostilbene derivatives and polymeric fluorescent substances, as are disclosed in US Pat. No. 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 aforementioned stabilizing agents are used in any mixtures. The stabilizing agents 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. Examples:

1) Uncleaned glasses were in a continuously operated

Dishwasher washed with a standard dishwasher detergent at a water hardness of 0-1 ° dH.

In comparative example V1, only 25 g of a commercially available dishwasher detergent were metered in for each cleaning cycle, while in example E1 according to the invention, an additional 440 mg of zinc gluconate were metered in (total dosage amount 25.44 g). The rinsing process was repeated 50 times under the conditions described above. The overall appearance of the wash ware was assessed using the rating scale below. The results are shown in the table below:

Evaluation scale: T0 = no turbidity until T4 = severe turbidity

2) In a second series of experiments, non-soiled glasses were washed in a continuously operated dishwasher with a commercially available dishwasher detergent at a water hardness of 0-1 ° dH. In comparative example V1, only 24.5 g of a commercially available dishwasher detergent were metered in for each cleaning cycle, while in example E1 according to the invention 250 mg of zinc acetate were metered in simultaneously with the 24.5 g of the commercially available dishwasher detergent. The rinsing process was repeated 50 times under the conditions described above. The overall appearance of the wash ware was assessed using the rating scale below. The results are shown in the table below:

Evaluation scale: T0 = no turbidity until T4 = severe turbidity

Examples 1 and 2 show that the machine dishwashing detergent according to the invention has significantly better gas corrosion properties under the conditions mentioned. The addition of zinc gluconate or zinc acetate suppresses clouding on the glasses.

Claims

claims:

1. Automatic dishwashing detergent, containing builders and optionally further constituents of cleaning agents, characterized in that it contains one or more magnesium and / or zinc salt (s) of at least one monomeric and / or polymeric organic acid with the exception of zinc ricinoleate, zinc abietate and zinc oxalate contains.

2. Automatic dishwashing detergent according to claim 1, characterized in that it contains magnesium and / or zinc salts of at least one monomeric and / or polymeric organic acid from the group of the unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids , the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the amino acids and / or the polymeric carboxylic acids.

3. Automatic dishwashing detergent according to one of claims 1 or 2, characterized in that it contains no magnesium or zinc salts of unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acids with at least 8 carbon atoms and / or resin acids.

4. Automatic dishwashing detergent according to one of claims 1 to 3, characterized in that the unbranched (s) saturated (s) or unsaturated (s) monocarboxylic acid (s) is (are) selected from the group: methanoic acid (formic acid), ethanoic acid ( Acetic acid), propanoic acid (propionic acid), pentanoic acid (valeric acid), hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid ), Pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid (margaric acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), hexacosanoic acid (cerotinic acid), triacoteinic acid (meliacinic acid) (triacoteinic acid) (triacoteinic acid) , 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (Oleic acid), 9t-octadecenoic acid (elaidic acid), 9c, 12c-octadecadienoic acid (linoleic acid), 9t, 12t-octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c-octadecatreic acid (oleolenic acid).

5. Automatic dishwashing detergent according to one of claims 1 to 4, characterized in that the branched (s) saturated (s) or unsaturated (s) monocarboxylic acid (s) is (are) selected from the group: 2-methylpentanoic acid, 2-ethylhexanoic acid , 2-propylheptanoic acid, 2-butyloctanoic acid, 2-pentylnonanoic acid, 2-hexyldecanoic acid, 2-heptylundecanoic acid, 2-octyldodecanoic acid, 2-nonyltridecanoic acid, 2-decyltetradecanoic acid, 2- undecylpentadecanoic acid, 2-dodecyladadecanoic acid, 2-dodecylhexadecanoic acid, -Pentadecylnonadecanoic acid, 2- hexadecyleicosanoic acid, 2-heptadecylheneicosanoic acid.

6. Automatic dishwashing detergent according to one of claims 1 to 5, characterized in that the unbranched (n) saturated (s) or unsaturated (s) di- or tricarboxylic acid (s) is (are) selected from the group: propanedioic acid (malonic acid) , Butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), octanedioic acid (suberic acid), nonanedioic acid (azelaic acid), decanedioic acid (sebacic acid), 2c-butenedioic acid (maleic acid), 2t-butendic acid 2-butynedicarboxylic acid (acetylenedicarboxylic acid).

7. Automatic dishwashing detergent according to one of claims 1 to 6, characterized in that the aromatic mono-, di- and tricarboxylic acid (s) is (are) selected from the group: benzoic acid, 2-carboxybenzoic acid (phthalic acid), 3rd - Carboxybenzoic acid (isophthalic acid), 4-carboxybenzoic acid (terephthalic acid), 3,4-dicarboxybenzoic acid (trimellitic acid), 3,5-dicarboxybenzoic acid (trimesionic acid).

8. Automatic dishwashing detergent according to one of claims 1 to 7, characterized in that the sugar acid (s) is (are) selected from the group: gluconic acid, galactonic acid, mannonic acid, fructonic acid, arabinonic acid, xylonic acid, ribonic acid, 2-deoxy-ribonic acid, alginic acid.

9. Automatic dishwashing detergent according to one of claims 1 to 8, characterized in that the hydroxy acid (s) is (are) selected from the group: hydroxyphenylacetic acid (mandelic acid), 2-hydroxypropionic acid (lactic acid), hydroxy succinic acid (malic acid), 2.3 -Dihydorxybutanedioic acid (tartaric acid), 2-hydroxy-1, 2,3-propanetricarboxylic acid (citric acid), ascorbic acid, 2-hydroxybenzoic acid (salicylic acid), 3,4,5-trihydroxybenzoic acid (gallic acid).

10. Automatic dishwashing detergent according to one of claims 1 to 9, characterized in that the oxo acid (s) is (are) selected from the group: 2-oxopropionic acid (pyruvic acid), 4-oxopentanoic acid (levulinic acid).

11. Automatic dishwashing detergent according to one of claims 1 to 10, characterized in that the amino acid (s) is (are) selected from the group: alanine, valine, leucine, isoleucine, proline, tryptophan, phenylalanine, methionine, Glyciπ, serine, Tyrosine, threonine, cysteine, asparagine, glutamine, aspartic acid, glutamic acid, lysine, arginine, histidine.

12. Automatic dishwashing detergent according to one of claims 1 to 11, characterized in that the polymeric (s) carboxylic acid (s) is (are) selected from the group: polyacrylic acid, polymethacrylic acid, alkyl acrylamide / acrylic acid copolymers, alkyl acrylamide / methacrylic acid copolymers, Alkyl acrylamide / methyl methacrylic acid copolymers, copolymers of unsaturated carboxylic acids, vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers.

13. Automatic dishwashing detergent according to one of claims 1 to 12, characterized in that it contains at least one zinc salt, but no magnesium salt of an organic acid.

14. Automatic dishwashing detergent according to claim 13, characterized in that it contains at least one zinc salt of an organic carboxylic acid.

15. Automatic dishwashing detergent according to one of claims 13 or 14, characterized in that it contains zinc oleate, zinc stearate, zinc gluconate, zinc acetate, zinc lactate and / or zinc citrate as zinc salt.

16. Automatic dishwashing detergent according to one of claims 1 to 15, characterized in that it contains at least one zinc salt in amounts of 0.1 to 5% by weight, preferably 0.2 to 4% by weight and in particular 0.4 up to 3 wt .-%, based in each case on the total weight of the automatic dishwashing detergent.

17. Automatic dishwashing agent according to one of claims 13 to 17, characterized in that it contains at least one zinc salt, the automatic dishwashing agent zinc in oxidized form in amounts of 0.01 to 1% by weight, preferably 0.02 to 0 , 5 wt .-% and in particular from 0.04 to 0.2 wt .-%, each based on the total weight of the dishwasher detergent.

18. Automatic dishwashing detergent according to one of claims 1 to 17, characterized in that it contains surfactant (s), preferably nonionic (s) surfactant (s), in quantities from 0.5 to 10% by weight, preferably from 0.75 to 7.5% by weight and in particular from 1.0 to 5% by weight, in each case based on the total composition.

19. Dishwasher detergent according to one of claims 1 to 18, characterized in that it has a viscosity of 500 to 500,000 mPas, preferably from 900 to 200,000 mPas and in particular from 1300 to 100,000 mPas.

20. Automatic dishwashing detergent according to claim 19, characterized in that it contains non-aqueous solvent (s), 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.

21. Automatic dishwashing detergent according to one of claims 19 or 20, characterized in that it contains the non-aqueous solvent (s) in amounts of 0.1 to 70% by weight, preferably 0.5 to 60% by weight, particularly preferably from 1 to 50% by weight, very particularly preferably from 2 to 40% by weight and in particular from 2.5 to 30% by weight, in each case based on the total composition.

22. Automatic dishwashing detergent according to one of claims 19 to 21, characterized in that it additionally contains one or more substances from the group of acidifying agents, chelating agents or the deposit-inhibiting polymers.

23. Automatic dishwashing agent according to one of claims 19 to 22, characterized in that it is 1 to 25% by weight, preferably 2 to 22.5% by weight, particularly preferably 3 to 20% by weight and in particular 4 to Contains 17.5% by weight of nonionic surfactant (s).

24. Automatic dishwashing detergent according to one of claims 19 to 23, characterized in that the content of free, i.e. water not present in the form of water of hydration and / or constitutional water is below 10% by weight, preferably below 8% by weight and in particular even below 6% by weight, in each case based on the composition.

25. Automatic dishwashing detergent according to one of claims 19 to 24, characterized in that it contains 20 to 60% by weight of one or more water-soluble builders, preferably citrates and / or phosphates, preferably alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate).

26. Automatic dishwashing detergent according to claim 25, characterized in that it contains the water-soluble builder (s) in amounts from 22.5 to 55% by weight, preferably from 25 to 50% by weight and in particular from 27.5 to 45 wt .-%, each based on the total agent contains.

27. Automatic dishwashing detergent according to one of claims 19 to 26, characterized in that it additionally contains 0.01 to 5% by weight, preferably 0.02 to 4% by weight, particularly preferably 0.05 to 3% by weight and in particular 0.1 to 1.5% by weight, of a polymeric thickener, preferably from the group of the polyurethanes or the modified polyacrylates, with particular preference for thickeners of the formula IV

R ^Λ

I

[-CH ₂ -C-] _n IV,

I

CXR ⁴

in which R 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 represents} H or R ⁴ and n represents a natural number.

28. Automatic dishwashing detergent according to one of claims 19 to 27, characterized in that it contains hydroxyethyl cellulose and / or hydroxypropyl cellulose as thickening agent.

29. Automatic dishwashing detergent according to claim 28, characterized in that it contains the thickener in amounts of 0.01 to 4.0% by weight, preferably in amounts of 0.01 to 3.0% by weight and in particular in amounts of 0.01 to 2.0 wt .-%, each based on the total agent contains.

30. Automatic dishwashing detergent according to one of claims 1 to 18, characterized in that one or more magnesium and / or zinc salt (s) are present in particulate form and in one or more other active and / or framework substance (s) formulated / available.

31. Automatic dishwashing detergent according to claim 30, characterized in that the particle size of the magnesium and / or zinc salts made up with one or more active and / or framework substances is 0.1 and 10 mm, preferably 0.2 and 8 mm and in particular 0, 5 and 5 mm.

32. Automatic dishwashing detergent according to one of claims 30 or 31, characterized in that the particulate compounds by spray drying and / or granulation and / or extrusion and / or roller compaction and / or tableting and / or solidification, but especially by spray drying and / or granulation be preserved.

33. Automatic dishwashing detergent according to one of claims 30 to 32, characterized in that the particulate compounds have a density of 0.1 to 2.0 g / cm ³ , preferably of 0.2 to 1.6 g / cm ³ and in particular of Have 0.4 to 1.2 g / cm ³ .

34. Automatic dishwashing detergent according to one of claims 30 to 33, characterized in that the particles of the magnesium and / or zinc salts made up with one or more active and / or builder substances have a weight fraction of these magnesium and / or zinc salt (s) of 0 , 1 to 80 wt .-%, particularly preferably from 0.2 to 70 wt .-% and particularly preferably from 0.5 to 60 wt .-%, each based on the total weight of the assembled magnesium and / or zinc salts.

35. Automatic dishwashing detergent according to one of claims 30 to 34, characterized in that the magnesium and / or zinc salts, active and / or framework substances from the group of the phosphates, carbonates, hydrogen carbonates, compounded with one or more active and / or framework substances , Sulfates, silicates, citrates, citric acid, acetates, preferably in amounts of 20 to 99% by weight, particularly preferably 30 to 98% by weight and particularly preferably 40 to 95% by weight, in each case based on the total weight the assembled magnesium and / or zinc salts.

36. Automatic dishwashing detergent according to one of claims 30 to 35, characterized in that the magnesium and / or zinc salts compounded with one or more active and / or builder substances, one or more active and / or builder substances from the group of surfactants, preferably the nonionic surfactants and / or the polymeric carboxylates, in particular the polysulfocarboxylates.

37. Automatic dishwashing detergent according to one of claims 30 to 36, characterized in that the magnesium and / or zinc salts made up with one or more active and / or framework substances additionally have a coating.

38. Automatic dishwashing detergent according to one of claims 1 to 37, characterized in that it is packed in portions in a water-soluble envelope.

39. Automatic dishwashing detergent according to one of claims 1 to 38, characterized in that the water-soluble covering comprises a bag made of water-soluble film and / or an injection molded part and / or a blow molded part and / or a deep-drawn part.

40. Automatic dishwashing detergent according to one of claims 1 to 39, characterized in that 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.

41. Automatic dishwashing detergent according to one of claims 1 to 40, characterized in that it has a film bag as the covering, the water-soluble film which forms the covering preferably having a thickness of 1 to 300 μm, preferably 2 to 200 μm, particularly preferably from 5 to 150 μm and in particular from 10 to 100 μm.

42. Automatic dishwashing detergent according to one of claims 1 to 41, characterized in that the covering comprises one or more materials from the group consisting of acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters and polyethers and mixtures thereof.

43. Automatic dishwashing detergent according to one of claims 1 to 42, characterized in that the coating one or more water-soluble (s) polymer (s), preferably a material from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinyl pyrrolidone, polyethylene oxide, gelatin , Cellulose, and their derivatives and their mixtures, more preferably (optionally acetalized) polyvinyl alcohol (PVAL).

44. Automatic dishwashing detergent according to claim 43, characterized in that the covering comprises a polyvinyl alcohol, the degree of hydrolysis of which is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol% % is.

45. Automatic dishwashing detergent according to one of claims 43 or 44, characterized in that the covering comprises a polyvinyl alcohol, the molecular weight of which is in the range from 10,000 to 100,000 gmol ^"1 , preferably from 11,000 to 90,000 gmol ^{" 1} , particularly preferably from 12,000 to 80,000 gmol ^"1 and in particular from 13,000 to 70,000 gmol ^{" 1} .

46. Use of salts of the metals magnesium and zinc with organic acids, with the exception of formic acid, acetic acid, gluconic acid and oxalic acid, as glass corrosion inhibitors.