DE10133136B4 - Non-aqueous "3in1" -Geschirrspülmittel - Google Patents

Abstract

Use of a pourable machine dishwashing detergent containing
a) from 1 to 60% by weight of nonaqueous solvent (s),
b) 0.1 to 70 wt .-% of copolymers
i) unsaturated carboxylic acids
ii) sulfonic acid group-containing monomers
c) 5 to 30% by weight of nonionic surfactant (s).
as a machine dishwashing detergent in a dishwashing process without the addition of regenerating salt and rinse aid.

Description

The The present invention relates to liquid means for cleaning Dishes in a domestic dishwasher. In particular, the invention relates to nonaqueous liquid dishwashing detergents for automatic dishwashing.

Machinery Dishwashing liquid for the Household use become common in the form of powders or more recently also shaped articles (tablets) offered. The supply form of a liquid has in this sector so far only a minor importance in the market. Compared to the fixed supply forms have liquids However, advantages in the dosage and not to be underestimated aesthetic Product advantages that make this offer form interesting. Thus, there is also a broad state of the art both to non-aqueous, mostly solvent-based as well as to aqueous dishwashing detergents for the do the washing up of dishes in a common household Dishwasher.

That's how it describes DE 20 29 598 A liquid detergent compositions containing 14 to 35 wt .-% sodium tripolyphosphate, 0.1 to 50 wt .-% of a potassium and / or ammonium salt of an inorganic or organic acid, water and optionally surfactants, solubilizers, sequestering agents, persalts and other ingredients.

Linear viscoelastic automatic dishwashing detergent compositions are also described in the European patent application EP 446 761 A1 (Colgate). The compositions disclosed herein contain up to 2% by weight of a long chain fatty acid or set thereof, 0.1 to 5% by weight of surfactant, 5 to 40% by weight of water soluble builder, and up to 20% by weight of chlorine bleach and a polycarboxylate thickener wherein the ratio of potassium to sodium ions in the compositions is 1: 1 to 45: 1.

Machine dishwashing detergents in the form of clear, translucent gels are described in the European patent application EP 439 878 A1 (Union Camp Corp.). The compositions disclosed herein contain a polyacrylate thickener which forms a gel matrix with water, surfactant, bleach, builder and water.

Gelled automatic dishwashing detergents are also disclosed in the European patent application EP 611 206 A1 (Colgate). These compositions contain 1 to 12% by weight of a liquid nonionic surfactant, 2 to 70% by weight of builder, as well as enzymes and a stabilizing system composed of swelling substances and hydroxypropylcellulose.

viscoelastic, Thixotropic dishwashing detergent with 0.001 to 5 wt .-% surfactant and enzymes and an enzyme stabilization system of boric acid and Polyhydroxy compounds are described in the international patent application WO93 / 21299 A1 (Procter & Gamble) described. The means disclosed here also contain 0.1 to 10% by weight of one or more thickeners.

At mechanically rinsed Dishes are common today higher Requirements placed as on manually rinsed dishes. So will be one of leftovers completely cleaned dishes then rated as not flawless when it after machine dishwashing still whitish, on water hardness or other mineral salts has stains that lack of wetting agent come from dried-up water drops.

Around To obtain crystal-clear and spotless dishes, one therefore sets Today rinse aid with success one. The addition of rinse aid at the end of the washing program makes sure that this Water as possible completely from ware expires So that the different surfaces at the end of the washing program residue-free and immaculate shiny are.

The automatic cleaning of dishes in household dishwashers usually includes a pre-wash, a main wash, and a rinse cycle interrupted by intermediate rinses. In most machines, the pre-rinse for heavily soiled dishes is switchable, but is selected only in exceptional cases by the consumer, so that in most machines a main rinse, an intermediate rinse with pure water and a rinse cycle are performed. The temperature of the main wash cycle varies between 40 and 65 ° C, depending on the machine type and program level selection. In the rinse cycle, rinse aids are added from a dosing tank in the machine, which usually contain nonionic surfactants as the main constituent. Such rinse aids are in liquid form and are in the State of the art widely described. Your task is primarily to prevent limescale and deposits on the cleaned dishes.

These so-called "2in1" products lead to simplify the handling and take away the consumer Load of additional Dosing two different products (cleaner and rinse aid) from. Nevertheless, to operate a household dishwasher at intervals two dosing operations required, because after a certain number of rinses the regenerating salt in water softening system the machine refilled must become. These water softening systems consist of Ionenaustauscherpolymeren that of the machine soften incoming hard water and following the washing program through a conditioner be regenerated with salt water.

Products, soft as so-called "3in1" products the conventional Cleaner, rinse aid and a salt substitute function are more recent State of the art described. These products are only as solid (Tablets) available.

Of the Present invention was based on the object, a pourable and so light and free in quantity To provide a dosable product, the application per application only once must be dosed without that too after a higher one Number of rinsing cycles the dosage of another product and thus a double Dasiervorgang would be necessary. It should be a liquid until gelatinous product is provided, which in addition to the "built-in rinse aid" filling the Regenerationsalzbehälters superfluous makes and thus further simplifies handling. This should be the performance of the product the performance level of conventional three-product dosing (Salt-cleaner rinse aid) or novel two-product dosing ("2in1" -reiniger rinse aid) reach or exceed. The products to be provided should be as close as possible many features conventional Superior means be. In particular, the occurring in many pourable products Dichotomy - benefits for certain properties (flowability, residual emptying, appealing product appearance, etc.) have disadvantages with others Properties (settling behavior, storage stability, performance etc.) - should be overcome become. It was therefore also the task to provide funds, the advantageous rheological properties (flowability, Residual emptying, etc.), favorable product characteristics (appearance, Cleaning power, storage stability etc.) and a technically easy to implement and inexpensive to carry out production combine with each other.

It it has now been found that castable automatic dishwashing detergent with the aforementioned positive properties based on nonaqueous solvents can be formulated if these agents contain certain sulfonic acid groups Contain polymers and nonionic surfactants.

• a) 1 bis 60 Gew.-% nichtwäßrige(s) Lösungsmittel,
• b) 0,1 bis 70 Gew.-% an Copolymeren aus i) ungesättigten Carbonsäuren ii) Sulfonsäuregruppen-haltigen Monomeren iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren
• c) 5 bis 30 Gew.-% nichtionische(s) Tensid(e), als maschinelles Geschirrspülmittel in einem Geschirrspülverfahren ohne Zusatz von Regeneriersatz Klarspüler.

The present invention is therefore in a first embodiment, the use of a pourable machine dishwashing agent containing

• a) from 1 to 60% by weight of nonaqueous solvent (s),
• b) 0.1 to 70 wt .-% of copolymers of i) unsaturated carboxylic acids ii) sulfonic acid group-containing monomers iii) optionally further ionic or nonionic monomers
• c) 5 to 30 wt .-% of nonionic (s) surfactant (s), as a machine dishwashing detergent in a dishwashing process without the addition of rinse aid rinse aid.

When Ingredient a) contain the agents used in the invention one or several non-aqueous solvents. These come, for example, from the groups of mono-alcohols, Diols, triols or polyols, ethers, esters and / or amides. Especially preferred are nonaqueous solvents, the water-soluble are, being "water-soluble" solvents For the purposes of the present application, solvents are those at room temperature with water completely, i.e. without miscibility gap, are miscible.

Non-aqueous solvents which can be used in the compositions according to the invention preferably originate from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the given concentration range. Preferably, the solvents are selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, etheylene glycol mono-n-butyl ether, diethylene glycol methyl ether , Diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t butyl ether like that such as mixtures of these solvents.

Especially preferred automatic dishwashing detergents are characterized that the non-aqueous (s) solvent selected is / are from the group of polyethylene glycols and polypropylene glycols, Glycerol, glycerin carbonate, triacetin, ethylene glycol, propylene glycol, Propylene carbonate, hexylene glycol, ethanol and n-propanol and / or iso-propanol.

Polyethylene glycols (abbreviation PEG) which can be used according to the invention are liquid at room temperature. PEG are polymers of ethylene glycol, those of the general formula H- (O-CH ₂ -CH ₂ ) _n -OH n, where n can assume values between 1 (ethylene glycol, see below) and about 16. For polyethylene glycols there are various nomenclatures that can lead to confusion. Technically common is the indication of the average relative molecular weight following the indication "PEG", so that "PEG 200" characterizes a polyethylene glycol having a relative molecular weight of about 190 to about 210. According to this nomenclature, the commercially available polyethylene glycols PEG 200, PEG 300, PEG 400 and PEG 600 can be used in the context of the present invention.

For cosmetic ingredients, a different nomenclature is used, in which the abbreviation PEG is hyphenated and directly followed by the hyphen a number corresponding to the number n in the above-mentioned formula 1. According to this nomenclature (so-called INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 ^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997) according to the invention, for example, PEG-4, PEG-6, PEG-8, PEG- 9, PEG-10, PEG-12, PEG-14 and PEG-16 can be used according to the invention.

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

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

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

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

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

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

from Propylene glycol exist two isomers, the 1,3-propanediol and the 1,2-propanediol. 1,3-propanediol (Trimethylene glycol) is a neutral, colorless and odorless, sweet-tasting liquid of density 1.0597, which solidifies at -32 ° C and at 214 ° C boils. The preparation of 1,3-propanediol succeeds 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 prepared from propylene oxide by water addition.

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

In preferred used in the invention automatic dishwashing detergents will the non-aqueous (s) solvent in amounts of from 5 to 50% by weight, preferably from 7.5 to 40% by weight and in particular from 10 to 30 wt .-%, each based on the total Medium, used.

there is to be understood in the context of this invention by "non-aqueous" a state in which the Free water content in the means well below 5% by weight, based on the means lies. It is preferred that the content the agents according to the invention on free, i. not in the form of water of hydration and / or water of constitution present water below 2% by weight, preferably below 1% by weight. and in particular even below 0.5 wt .-%, each based on the Means, lies. Water can therefore essentially only in chemically and / or physically bound form or as a component the present as a solid raw materials or compounds, but not as a liquid, solution or dispersion are introduced into the agent.

When second component b) contain the inventively used Means Copolymers of unsaturated Carboxylic acids, Containing sulfonic acid Monomers and optionally further ionic or nonionic Monomers. These copolymers cause the be treated with such agents Dishes become cleaner during subsequent cleaning processes, as tableware, with conventional Rinsed agents were.

When additional positive effect occurs a shortening the drying time of the dishes treated with the detergent on, i. the consumer can after the expiry of the cleaning program the dishes earlier Remove from the machine and reuse.

The Invention is characterized by an improved "cleanability" of the treated substrates in subsequent cleaning operations and by a considerable shortening compared to the drying time Comparable agents without the use of sulfonic acid-containing polymers out.

Under Drying time is in the context of the teaching of the invention in general the literal meaning understood, that is, the time that elapses until one in a dishwasher treated dish surface dried, but in particular the time that elapses until 90% of one with a detergent or rinse aid in concentrated or diluted Form treated surface dried.

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

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

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

Preferred among these monomers are those of the formulas IIa, IIb and / or IIc, H ₂ C = CH-X-SO ₃ H (IIa), H ₂ C = C (CH ₃ ) -X-SO ₃ H (IIb), HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (IIc), in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -.

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

When other ionic or nonionic monomers are used in particular ethylenically unsaturated compounds into consideration. Preferably the content of the invention used Polymers to monomers of group iii) less than 20 wt .-%, based on the polymer. Particularly preferred polymers to use only from monomers of groups i) and ii).

• i) ungesättigten Carbonsäuren der Formel I. R¹(R²)C=C(R³)COOH (I),in der R¹ bis R³ unabhängig voneinander für -H -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist,
• ii) Sulfonsäuregruppen-haltigen Monomeren der Formel II R⁵(R⁶)C=C(R⁷)-X-SO₃H (II),in der R⁵ bis R⁷ unabhängig voneinander für -H -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n- mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)
• iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren

besonders bevorzugt.In summary, copolymers are made of

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

particularly preferred.

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

Particularly preferred copolymers consist of

• i) one or more unsaturated carboxylic acids from the group of acrylic acid, methacrylic acid and / or maleic acid
• ii) one or more sulfonic acid group-containing monomers of the formulas IIa, IIb and / or IIc: H ₂ C = CH-X-SO ₃ H (IIa), H ₂ C = C (CH ₃ ) -X-SO ₃ H (IIb), HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (IIc), in which R ⁶ and R ⁷ are independently selected from -H, -CH _3, -CH ₂ CH _3, -CH ₂ CH ₂ CH _3, -CH (CH _{3) 2} and X is an optionally present spacer group is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -
• iii) optionally further ionic or nonionic monomers.

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

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

These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative. Copolymerizing the sulfonic acid-containing acrylic acid derivative with methacrylic acid, one arrives at another polymer whose use in the agents according to the invention is likewise preferred and characterized in that the agents contain one or more copolymers which contain structural units of the formula IV - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (IV) in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with sulfonic acid-containing methacrylic acid derivatives, whereby the structural units in the molecule are changed. Thus, agents according to the invention which comprise one or more copolymers which are structural units of the formula V - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (V) in which m and p respectively represent a whole natural number between 1 and 2000 and Y for a space which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y is -O- (CH ₂ ) _n - where n = 0 to 4, for -O- ( C ₆ H ₄ ) -, -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are preferred, also a preferred embodiment of the present invention, just as agents are preferred, which are characterized in that they contain one or more copolymers, the structural units of the formula VI - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (VI), in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

Instead of acrylic acid and / or methacrylic acid or in addition thereto, maleic acid can also be used as a particularly preferred monomer from group i). In this way, one obtains according to the invention preferred agents, which are characterized in that they contain one or more copolymers, the structural units of the formula VII - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (VII) in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, are preferred and to agents which are characterized in that they contain one or more copolymers, the structural units of the formula VIII - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - (VIII), in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

In summary, according to the invention, the use of automatic dishwasher detergent is preferred which contains as ingredient b) one or more copolymers which contain structural units of the formulas III and / or IV and / or V and / or VI and / or VII and / or VIII - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (III), - [CH ₂ -C (CH ₃ ) COOH] _m - (CH ₂ -CHC (O) -Y-SO ₃ H] _p - (IV), - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (VI), - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (VII) - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - (VIII), in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

In the polymers can the sulfonic acid groups wholly or partly in neutralized form, i. that the acidic Hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups against metal ions, preferably alkali metal ions and in particular against sodium ions, can be replaced. Appropriate means which are characterized in that the sulfonic acid groups present in the copolymer partially or fully neutralized, are preferred according to the invention.

The Monomer distribution of those used in the compositions used in the invention Copolymer is for copolymers containing only monomers from groups i) and ii), preferably in each case from 5 to 95% by weight of i) or ii), particularly preferably 50 to 90% by weight of monomer from group i) and 10 to 50% by weight Monomer from group ii), in each case based on the polymer.

at Terpolymers are particularly preferred which contain from 20 to 85% by weight. Monomer from group i), 10 to 60 wt .-% monomer from the group ii) and 5 to 30 wt .-% of monomer from group iii).

The molecular weight of the polymers used in the compositions according to the invention can be varied in order to adapt the properties of the polymers to the desired end use. Preferred automatic dishwashing detergents are characterized in that the copolymers have molar masses of 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 .

Of the Content of one or more copolymers in the invention used Means may vary depending on the purpose and desired product performance, preferred machine according to the invention Dishwashing liquid characterized in that they the copolymer (s) in amounts of 0.25 to 50 wt .-%, preferably from 0.5 to 35 wt .-%, particularly preferably from 0.75 to 20 wt .-% and in particular from 1 to 15% by weight.

When Ingredient c) contain the agents used in the invention one or several nonionic surfactants, in short nonionic surfactants. The quantities in which the nonionic surfactants are used according to the invention between 5 and 30 wt .-%, whereby inventive automatic dishwashing detergents are preferred, the 5 to 25 wt .-%, preferably 6 to 22.5 wt .-%, particularly preferably 7.5 to 20 wt .-% and in particular 8 to 17.5 % By weight of nonionic surfactant (s).

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

In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) _x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

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

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamide can 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 from that.

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

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

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

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

[Z] is preferably by reductive amination of a reduced sugar obtained, for example, glucose, fructose, maltose, lactose, galactose, Mannose or xylose. The N-alkoxy or N-aryloxy-substituted Connections can by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxyfatty acid amides are transferred.

When preferred surfactants are low-foaming nonionic surfactants used. With particular preference contain the machine according to the invention Dishwashing liquid a nonionic surfactant that has a melting point above room temperature having. Accordingly, preferred means are characterized that she nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, contain.

suitable nonionic surfactants, the melting or softening points in said Temperature range, for example, low-foaming nonionic Surfactants which may be solid or highly viscous at room temperature. Become used at room temperature highly viscous nonionic surfactants, it is preferred that these a viscosity above 20 Pas, preferably above 35 Pas and especially above 40 Pas. Also nonionic surfactants which are waxy at room temperature Consistency are preferred.

Prefers as at room temperature fixed to be used nonionic surfactants derived the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary Alcohols and mixtures of these surfactants with structurally complicated built-up surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control out.

In a preferred embodiment The present invention is the nonionic surfactant having a Melting point above room temperature an ethoxylated nonionic surfactant, that from the reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 moles, in particular at least 20 moles of ethylene oxide per Mol alcohol or alkylphenol emerged.

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

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

The Nonionic surfactant preferably additionally has propylene oxide units in the molecule. Preferably, such PO units make up to 25% by weight, especially preferably up to 20 wt .-% and in particular up to 15 wt .-% of total molecular weight of the nonionic surfactant. Especially preferred nonionic surfactants are ethoxylated monohydroxyalkanols or Alkylphenols, in addition Having polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules is involved preferably more than 30% by weight, particularly preferably more than 50 Wt .-% and in particular more than 70 wt .-% of the total molecular weight such nonionic surfactants. Preferred rinse aids are characterized that she contain ethoxylated and propoxylated nonionic surfactants in which the Propylene oxide units in the molecule up to 25% by weight, preferably up to 20% by weight and in particular to constitute 15% by weight of the total molecular weight of the nonionic surfactant, contain.

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

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

A further preferred rinse aid according to the invention contains nonionic surfactants of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ], in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is a value of at least 15.

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

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

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula is to R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

Summarizing the latter statements, rinse aids according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, x is n-butyl, 2-butyl or 2-methyl-2-butyl, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, surfactants of the type R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² in which x is from 1 to 30, preferably from 1 to 20 and especially from 6 to 18, are particularly preferred.

In Compounds with said surfactants may also be anionic, cationic and / or amphoteric surfactants are used, these because their foaming behavior in automatic dishwashing detergents only have subordinate importance and mostly only in quantities below of 10 wt .-%, usually even below 5 wt .-%, for example from 0.01 to 2.5 wt .-%, each based on the agent used. The agents according to the invention can Thus, as a surfactant also anionic, cationic and / or contain amphoteric surfactants.

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

Further Suitable anionic surfactants are sulfated fatty acid glycerol esters. Among fatty acid glycerol esters are to understand the mono-, di- and triesters and their mixtures, such as they are produced 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 to be obtained. Preferred sulfated fatty acid glycerol esters are included the sulphonated products of saturated fatty acids with 6 to 22 carbon atoms, for example the caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or Behenic acid.

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

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

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

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

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

worin jede Gruppe R¹ unabhängig voneinander ausgewählt ist aus C_1-6-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R² unabhängig voneinander ausgewählt ist aus C_8-28-Alkyl- oder -Alkenylgruppen; R³ = R¹ oder (CH₂)_n-T-R²; R⁴ = R¹ oder R² oder (CH₂)_n-T-R²; T = -CH₂-, -O-CO- oder -CO-O- und n eine ganze Zahl von 0 bis 5 ist.As cationic active substances, the agents used according to the invention may contain, for example, cationic compounds of the formulas XI, XII or XIII:

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 addition to the ingredients a) to c), the compositions used according to the invention may contain other customary ingredients of cleaning agents. In particular, the builders are of particular importance. Builders are in the compositions of the invention especially for binding of Calcium and magnesium used. Usual builders which are preferred in the context of the invention in amounts of 22.5 to 45 wt .-%, preferably from 25 to 40 wt .-% and in particular from 27.5 to 35 wt .-%, each based on the total agent , are present, 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 silicatic builders from the class of alkali disilicates are preferably used for the cleaning agents according to the invention. In general, with the alkali metal salts, the potassium salts are preferable to the sodium salts because they often have a higher water solubility. Preferred water-soluble builders are, for example, tripotassium citrate, potassium carbonate and the potassium water glasses.

Especially preferred automatic dishwashing agents contain as builders Phosphates, preferably alkali metal phosphates, with particular preference of pentasodium or pentakalium triphosphate (sodium or potassium tripolyphosphate).

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

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉₎ and Maddrell's salt (see below), pass. NaH ₂ PO _{4 is} acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (potassium phosphate primary or monobasic potassium phosphate, KDP), KH ₂ PO ₄ , is a white salt of 2.33 gcm ^-3 density, has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is light soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm ^-3 , loss of water at 95 °), 7 moles (density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 moles water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na ₄ P ₂ O ₇ . Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is readily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which have a density of 1.62 gcm ^-3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH. Tripotassium phosphate (tertiary or three-basic potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder of density 2.56 gcm ^-3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred in the detergent industry compared to corresponding sodium compounds.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals. Na ₄ P ₂ O ₇ is formed on heating of 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 agents and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.

Condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ results in higher mol. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: melting or annealing phosphates, Graham's salt, Kurrolsches 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 O ₁₀ (sodium tripolyphosphate), is an anhydrous or with 6 H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25% K ₂ O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry.

preferred automatic dishwashing detergent included in addition to the ingredients a) to c) 20 to 50 wt .-% of one or more water Builders, preferably citrates and / or phosphates, preferably alkali metal phosphates with particular preference of pentasodium or pentakalium triphosphate (sodium or potassium tripolyphosphate).

In preferred embodiments In the present invention, the content of the agents is water-soluble builders within narrower limits. Here are machine dishwashing detergents preferably containing the water-soluble builder (s) in amounts of 22.5 to 45 wt .-%, preferably from 25 to 40 wt .-% and in particular from 27.5 to 35% by weight, based in each case on the total agent, contain.

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

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

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

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

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

Next the builders especially bleaches, bleach activators, enzymes, silver protectants, Dyes and fragrances, etc. preferred ingredients of machine Dishwashing detergents. In addition, more can Ingredients be present, wherein automatic dishwashing detergents according to the invention preferred are the additional one or more substances from the group of acidifying agents, Chelate complexing or the deposit-inhibiting polymers included.

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

A more possible Group of ingredients are the chelating agents. Chelated chelating agents are substances that are cyclic with metal ions Form connections, with a single ligand more than one coordination site occupied by a central atom, i. H. at least "bidentate". In this case, so usually elongated compounds closed by complex formation via an ion into rings. The number of bound ligands depends on the coordination number of the central ion.

common and in the context of the present invention, preferred chelate complex images are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Also complexing polymers, ie polymers which are either in the Main chain itself or side by side to carry functional groups that can act as ligands and with suitable metal atoms usually forming chelate complexes react, can be used according to the invention. The polymer-bound ligands of the resulting metal complexes can thereby originate from only one macromolecule or belong to different polymer chains. The latter leads to Crosslinking of the material, unless the complexing polymers already above covalent bonds were crosslinked.

complexing Groups (ligands) more common complexing polymers are iminodiacetic acid, hydroxyquinoline, thiourea, Guanidine, dithiocarbamate, hydroxamic, amidoxime, aminophosphoric, (cycl.) Polyamino, mercapto, 1,3-dicarbonyl and crown ether radicals with z. Very much specif. Activities towards ions different metals. Many base polymers are also commercially available important complexing polymers are polystyrene, polyacrylates, Polyacrylonitriles, polyvinyl alcohols, polyvinylpyridines and polyethylenimines. Also natural Polymers such as cellulose, starch or chitin are complexing polymers. In addition, these can provided by polymer-analogous transformations with other ligand functionalities become.

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

in Mengen oberhalb von 0,1 Gew.-%, vorzugsweise oberhalb von 0,5 Gew.-%, besonders bevorzugt oberhalb von 1 Gew.-% und insbesondere oberhalb von 2,5 Gew.-%, jeweils bezogen auf das Gewicht des Geschirrspülmittels, enthalten.In the context of the present invention, particular preference is given to automatic dishwasher detergents which contain one or more chelate complexing agents from the groups of

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

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

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

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

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

When polycarboxylic a) in the context of this patent application, carboxylic acids - also monocarboxylic acids - are understood, where the sum of carboxyl and contained in the molecule Hydroxyl groups is at least 5. Complexing agent from the Group of nitrogen-containing polycarboxylic acids, in particular EDTA, are prefers. In the invention required alkaline pH values of the treatment solutions are these Komplexbilner at least partially as anions. It does not matter if they are in the form of acids or in the form of salts. In case of use Salts are alkali, ammonium or alkylammonium salts, in particular Sodium salts, preferred.

Deposit-inhibiting Polymers can also in the invention used Be included means. These substances, which are chemically different could be are for example from the groups of low molecular weight polyacrylates having molecular weights between 1000 and 20,000 daltons, with polymers having Molar masses below 15,000 daltons are preferred.

Deposit-inhibiting Polymers can also have co-builder properties. As organic cobuilders can in the machine according to the invention dishwashing detergents in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, Polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used. These classes of substances are hereafter described.

useful organic builders For example, they can be used in the form of their sodium salts polycarboxylic where among polycarboxylic acids such carboxylic acids be understood that 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), if such an application for ecological reasons not is objectionable, as well as mixtures of these. Preferred salts are the salts of polycarboxylic acids like citric acid, adipic acid, Succinic acid, glutaric, Tartaric acid, sugar acids and mixtures of these.

Also the acids in itself can be used. The acids In addition to their builder effect, they also typically have the property an acidifying component and thus serve to set a lower and milder one pH value of detergents or cleaning agents. In particular, here are citric acid, Succinic acid, glutaric, adipic acid, gluconic and to name any mixtures of these.

When Builder or coating inhibitor are further polymeric polycarboxylates suitable, these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those having a molecular weight of 500 to 70,000 g / mol.

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

suitable Polymers are in particular polyacrylates, which preferably have a molecular mass of 2000 to 20,000 g / mol. Because of their superior solubility can from this group again the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and more preferably from 3000 to 5000 g / mol, may be preferred.

Suitable are furthermore copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and the acrylic acid or methacrylic acid with maleic acid. Particularly suitable are copolymers of acrylic acid with maleic which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid. Your molecular weight, based on free acids, is in general from 2000 to 70000 g / mol, preferably from 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 the (co) polymeric polycarboxylates is preferably 0.5 to 20 wt .-%, in particular 3 to 10 wt .-%.

Especially Biodegradable polymers of more than two are also preferred various monomer units, for example, those as monomers Salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers Salts of acrylic acid and 2-alkylallyl sulfonic acid and sugar derivatives. Further preferred copolymers are those containing as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

As well are as further preferred builders polymeric aminodicarboxylic acids whose Salts or their precursors to call. Particular preference is given to polyaspartic acids or their salts and derivatives, in addition to cobuilder properties also have a bleach-stabilizing effect.

Further Suitable builders are polyacetals, which by reaction of dialdehydes with polyol carboxylic acids containing 5 to 7 carbon atoms and at least 3 hydroxyl groups can be obtained. preferred Polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic receive.

Further suitable organic builders are dextrins, for example Oligomers or polymers of carbohydrates by partial Hydrolysis of starches can be obtained. The hydrolysis can be carried out according to usual, for example acidic or enzyme-catalyzed processes. Preferably These are hydrolysis products with average molecular weights in the range from 400 to 500,000 g / mol. It is a polysaccharide with a Dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 preferred where DE is a common one Measure of the reducing Effect of a polysaccharide compared to dextrose, which DE of 100 is. Useful are both maltodextrins with a DE between 3 and 20 and dry glucose syrup with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher Mot masses in the range of 2000 to 30,000 g / mol.

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

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

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

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

In addition to The substances from the classes of substances mentioned can be used according to the invention more usual Ingredients of cleaning agents contain, in particular Bleaching agents, bleach activators, enzymes, silver protectants, colorants and perfumes are of importance. These substances are below described.

Among the compounds serving as bleaches in water H ₂ O ₂ , sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Cleaning agents according to the invention may also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)] , o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutan-1,4-diene diacid, N, N-terephthaloyl-di (6-aminopercapronate) can be used.

When Bleaching agent in the detergents used according to the invention for the automatic dishwashing can Chlorine or bromine releasing substances are used. Among the suitable chlorine or bromine releasing materials come for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric (DICA) and / or their salts with cations such as potassium and sodium into consideration. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

Bleach activators, which support the effect of bleaches, have already gone further above as possible Ingredient of rinse aid particles mentioned. Known bleach activators are compounds containing one or more Contain N- or O-acyl groups, such as substances from the class of Anhydrides, esters, imides and acylated imidazoles or Oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.

When Bleach activators can Compounds which, under perhydrolysis conditions, are aliphatic peroxycarboxylic acids preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, are used. Suitable substances are the O- and / or N-acyl groups of the mentioned C atom number and / or optionally substituted benzoyl groups wear. Preference is given to polyacylated alkylenediamines, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methylsulfate (MMA), and enol ester, as well as acetylated sorbitol and mannitol, respectively their mixtures (SORMAN), acylated sugar derivatives, in particular Pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyl lactose and acetylated, optionally N-alkylated Glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl. Hydrophilic substituted acyl acetals and acyl lactams are also used preferably used. Also combinations of conventional bleach activators can be used.

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

Prefers become bleach activators from the group of the multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methylsulfate (MMA), preferably in amounts up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, especially 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-% based on the entire remedy, used.

Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate in usual Quantities, preferably in an amount up to 5 wt .-%, in particular from 0.0025 wt.% to 1 wt.%, and more preferably from 0.01 % By weight to 0.25% by weight, in each case based on the total agent, used. But in special cases it is also possible to use more bleach activator.

When Enzymes come in the detergents used in the invention especially those from the classes of hydrolases such as proteases, Esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures of said enzymes in question. All these hydrolases contribute to the removal of stains such as protein, fat or starchy Stains in. To bleach can Oxidoreductases are also used. Particularly well suited from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens and their genetically modified variants obtained enzymatic agents. Preferably, subtilisin-type proteases and in particular Proteases derived from Bacillus lentus. These are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, in particular however, protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples for such Lipolytic enzymes are the known cutinases. Also peroxidases or oxidases have been found to be suitable in some cases. Among the suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases.

The Enzymes can on carriers adsorbed or in enveloping substances be embedded to protect them against premature decomposition. Of the Proportion of enzymes, enzyme mixtures or enzyme granules, for example about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt .-% amount.

Especially Within the scope of the present invention, the use of liquid enzyme formulations is preferred. Here are machine according to the invention Dishwashing liquid b preferred, the additional Enzymes and / or enzyme preparations, preferably solid and / or liquid Protease preparations and / or amylase preparations, in amounts of 1 to 5 wt .-%, preferably from 1.5 to 4.5 and especially from 2 to 4 wt .-%, each based on the entire remedy, included.

Dyes and fragrances can be added to the automatic dishwashing agents used according to the invention in order to improve the aesthetic impression of the resulting products and to provide the consumer with a visual and sensory "typical and unmistakable" product in addition to performance. As perfume oils or fragrances, individual perfume compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals with 8-18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the ionone, α-isomethylionone and Methylcedrylketon to the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol; the hydrocarbons mainly include the terpenes such as limonene and pinene. However, mixtures of different fragrances are preferably ver which together create an appealing scent. Such perfume oils may also contain natural fragrance mixtures as are available from vegetable sources, eg pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.

Around the aesthetic Impression of the invention used Means to improve they (or parts thereof) are colored with suitable dyes. Preferred dyes whose selection the expert no difficulty prepares, have a high storage stability and insensitivity to the other ingredients the agent and against light and no pronounced substantivity to the with the means to be treated substrates such as glass, ceramics or Plastic dishes, so as not to stain them.

The used according to the invention Cleaning agents can to protect the dishes or the machine contain corrosion inhibitors, taking particular Silver protection agent in the field of automatic dishwashing have special meaning. It is possible to use the known substances of the prior art. In general, especially silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes are used. Particularly preferable to use are benzotriazole and / or alkylaminotriazole. One finds in cleaner formulations beyond that often Active chlorine-containing agents, the corrosion of the silver surface clearly can diminish. In chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, z. Hydroquinone, catechol, hydroxyhydroquinone, gallic acid, phloroglucinol, Pyrogallol or derivatives of these classes of compounds. Also salt and complex inorganic compounds, such as salts of metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Prefers here are the transition metal salts, the selected are from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds can help prevent it corrosion on the items to be washed be used.

to viscosity control can the invention used Means contain other ingredients, with their use, for example the settling behavior or pourability or flowability can be controlled selectively. In non-aqueous systems have become in particular combinations of texturizers and thickeners proven.

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

Machine dishwashing detergents preferred in the context of the present invention also contain

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

Of the Structurant a) comes from the group of bentonites and / or at least partially etherified sorbitol. These substances are used for the physical stability to ensure the means and the viscosity adjust. Although conventional Thickeners such as polyacrylates or polyurethanes in nonaqueous media fail, the viscosity control succeeds with the substances mentioned in the non-aqueous system.

bentonite are contaminated clays caused by weathering of volcanic tuffs have arisen. Because of its high content of montmorillonite Bentonites have valuable properties such as swellability, Ion exchange capacity and thixotropy. It is possible the properties of bentonite according to the purpose to modify. Bentonites are as an ingredient in tropical Soils are frequent and become as sodium bentonite e.g. mined in Wyoming / USA. Sodium bentonite has the cheapest application properties (swelling capacity), so that its Use in the context of the present invention is preferred. Naturally occurring For example, calcium bentonites come from Mississippi / USA or Texas / USA resp. From Landshut / D. The naturally derived Ca-bentonites be artificially through Exchange of Ca for Na converted into the swellable Na bentonites.

The main constituents of the bentonites form so-called montmorillonites, which can also be used in their pure form in the context of the present invention. Montmorillonites are clay minerals belonging to the phyllosilicates and here to the dioctahedral smectites, which crystallize monoclinic pseudohexagonal Montmorillonite form predominantly white, grayish-white to yellowish, completely amorphous appearing, easily friable, in the water swelling, but not plasticizing masses, by the general formulas Al ₂ [(OH) ₂ / Si ₄ O ₁₀ ] .nH ₂ O respectively. Al ₂ O ₃ · 4SiO ₂ · H ₂ O · nH ₂ O respectively. Al ₂ [(OH) ₂ / Si ₄ O ₁₀ ] (dried at 150 °) can be described.

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

In Combination with the bentonites or as a substitute for them when their use not desired, can At least partially etherified sorbitol used as a structurizer become.

sorbitol is one of the witches 6-valent alcohol (sugar alcohol), intramolecularly relatively easy one or two moles of water splits off and forms cyclic ethers (for example Sorbitan and Sorbid). The splitting off of water is also intermolecular possible, wherein noncyclic ethers of sorbitol and the respective Form alcohols. Again, the training of mono-ethers and Bis-ethers possible, although higher Etherification levels such as 3 and 4 may occur. In the context of the present Invention preferably used at least partially etherified Sorbitols are di-etherified sorbitols, of which the dibenzylidenesorbitol is particularly preferred. Here are machine dishwashing detergents preference is given to the structurally doubly etherified sorbitols, especially dibenzylidenesorbitol.

The used according to the invention Means can the structurant in amounts of 0.1 to 1.0 wt .-%, based on contain the entire agent and to the active substance of the structure generator. Preferred agents contain the modifier in amounts of 0.2 to 0.9 wt .-%, preferably in amounts of 0.25 to 0.75 wt .-% and in particular in amounts of 0.3 to 0.5 wt .-%, respectively on the entire remedy.

When Thickeners can the preferred ones used in the invention Medium inorganic salts from the group of carbonates, sulfates and amorphous or crystalline disilicates. in principle can in this case, the said salts of all metals are used, wherein the alkali metal salts are preferred. Particularly preferred in the context of the present invention as thickener alkali carbonate (e), Alkali sulphate (s) and / or amorphous (s) and / or crystalline alkali disilicate (s), preferably sodium carbonate, sodium sulfate and / or amorphous or crystalline sodium disilicate used.

The preferred used in the invention Agents contain the thickener in amounts of 5 to 30 wt .-%, based on the entire means. Particularly preferred agents contain the or Thickener in amounts of 7.5 to 28 wt .-%, preferably in amounts from 10 to 26 wt .-% and in particular in amounts of 12.5 to 25 Wt .-%, each based on the total agent.

in the With regard to an increased sedimentation it is preferred that the in the invention used Agents contained solids as possible be used finely divided. This is especially the case with the inorganic ones Thickeners and bleaches of advantage. Here are machine according to the invention Dishwashing liquid preferred in which the average particle size of the bleaching agent and thickener and the optionally use builder less than 75 microns, preferably less than 50 μm and in particular less than 25 microns is.

The used according to the invention liquid automatic dishwashing detergent can for setting a possibly higher viscosity and others viscosity regulators or thickeners. Here are all known thickeners can be used, ie those based on natural or synthetic Polymers.

Out naturally derived polymers used as thickening agents For example, agar-agar, carrageenan, gum tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, Gelatin and casein.

modified Natural products come mainly from the group of modified starches and Celluloses, examples being carboxymethylcellulose and others Cellulose ethers, hydroxyethyl and Propyl cellulose and Kernmehlether called.

A size Group of thickeners, widely used in the most diverse Fields of application are the fully synthetic polymers such as Polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic Polyethers, polyimines, polyamides and polyurethanes.

Thickeners from said substance classes are widely available commercially and are sold for example under the trade name Acusol ^® -820 (methacrylic acid (stearyl alcohol 20 EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral ^® -GT- 282-S (alkyl polyglycol ethers, Akzo), DEUTEROL ^® polymer-11 (dicarboxylic acid copolymer, Schoner GmbH) deuteron ^® -xg (anionic heteropolysaccharide based on β-D-glucose, D-mannose, D-glucuronic acid, Schoner GmbH ) deuteron ^® -XN (nonionic polysaccharide Schoner GmbH), DICRYLAN ^® -Verdicker-O (ethylene oxide adduct, 50% solution in water / isopropanol, Pfersse Chemie), EMA ^® -81 and EMA ^® -91 (ethylene-maleic anhydride copolymer, Monsanto), thickener QR-1001 (polyurethane emulsion, 19-21% in water / diglyme, Rohm & Haas), Mirox ^® -AM (anionic acrylic acid-acrylate copolymer dispersion, 25% in water, Stockhausen), SER-AD FX 1100 (hydrophobic urethane polymer, servo Delden), Shellflo ^® -S (hochmol ekulares polysaccharide, stabilized with formaldehyde, Shell), and Shellflo XA ^® (xanthan biopolymer, stabilized with formaldehyde, Shell).

One preferably used polymeric thickener is xanthan, a microbial anionic heteropolysaccharide derived from Xanthomonas campestris and some other species under aerobic conditions is produced and a molecular weight of 2 to 15 million daltons having. Xanthan gum is made from a chain of β-1,4-bound glucose (cellulose) formed with side chains. The structure of the subgroups consists of Glucose, mannose, glucuronic acid, Acetate and pyruvate, where the number of pyruvate units is the viscosity of xanthan certainly.

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

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

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

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

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

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

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

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

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

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

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

in der R³ für H oder einen verzweigten oder unverzweigten C_1-4-Alk(en)ylrest, X für N-R⁵ oder O, R⁴ für einen gegebenenfalls alkoxylierten verzweigten oder unverzweigten, evtl. substituierten C_8-22-Alk(en)ylrest, R⁵ für H oder R⁴ und n für eine natürliche Zahl steht, enthalten.Liquid automatic 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 wt .-%, of a polymeric thickener, preferably from the group of polyurethanes or modified polyacrylates, with particular preference of thickeners of the formula XV

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

The viscosity the invention used Medium can with usual Standard methods (for example, Brookfield Viscometer LVT-II at 20 rpm and 20 ° C, Spindle 3) are measured and is preferably in the range of 500 to 5000 mPas. Preferred detergent compositions have viscosities from 1000 to 4000 mPas whereby values between 1300 to 3000 mPas are particularly are preferred. The pH of the compositions according to the invention is 1% by weight solution in distilled water, preferably within the range of 7 to 11, more preferably between 8 and 10 and in particular between 8.5 and 9.5.

The used according to the invention Means can on conventional Kind, i. in bottles or similar containers, be packed. But it is also possible to use the invention To offer means pre-portioned to the consumer the dosage of detergents and cleaners. In the case of such single dose amounts of detergents have particular bag packaging and below this again bags enforced by water-soluble film, the ripping make the packaging by the consumer unnecessary. In this way is a convenient dosing of a single serving by inserting the Bag directly into the dishwasher or in their Einspülkammer possible.

The used according to the invention Means can preferably packed in bags of water-soluble film. Such bag materials or films are known from the prior art known and originate, for example, the group (acetalized) Polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, gelatin and mixtures thereof.

The term "polyvinyl alcohols" in the present invention comprises homopolymers of vinyl alcohol, copolymers of vinyl alcohol with copolymerizable monomers or hydrolysis products of vinyl ester homopolymers or vinyl ester copolymers with copolymerizable monomers. Homo- or copolymers of vinyl alcohol can not be obtained by polymerization of vinyl alcohol (H ₂ C = CH-OH), since its concentration in the tautomeric equilibrium with acetaldehyde (H ₃ C-CHO) is too low. These polymers are therefore prepared above all from polyvinyl esters, in particular polyvinyl acetates, via polymer-analogous reactions such as hydrolysis, but in particular technically by alkaline catalyzed transesterification with alcohols (preferably methanol) in solution.

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

enthalten.In the context of the present invention, polyvinyl alcohols (abbreviation PVAL, occasionally also PVOH) are particularly preferred as bag materials. PVAL is the name for polymers of the general structure

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

contain.

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

polyvinyl alcohols are dependent soluble in the degree of hydrolysis in water and a few highly polar organic solvents (Formamide, dimethylformamide, dimethyl sulfoxide); of (chlorinated) Hydrocarbons, esters, fats and oils are not attacked. Polyvinyl alcohols are classified as toxicologically harmless and are at least partially biodegradable biologically. The water solubility can be by post-treatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid od. Reduce borax. The coatings of polyvinyl alcohol are broad impenetrable for Gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.

in the Within the scope of the present invention, preferred bag materials are characterized in that the Degree of hydrolysis of the polyvinyl alcohol 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol% is.

Polyvinyl alcohols of a certain molecular weight range are preferably used as bag materials, with bags being preferred in which the polyvinyl alcohol has a molecular weight in the range of 10,000 to 100,000 gmol ^-1 , preferably 11,000 to 90,000 gmol ^-1 , more preferably 12,000 to 80,000 gmol ^-1 and especially from 13,000 to 70,000 gmol ^-1 .

Of the Degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680 and especially between about 260 to about 1500th

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. Commercially available PVAL (for example, Mowiol ^® grades Hoechst) come as a white yellowish powders or granules having degrees of polymerization in the range of about 500-2500 (corresponding to molecular weights of about 20,000-100,000 g / mol) in the trade and have different degrees of hydrolysis of 98 -99 and 87-89 mol%, respectively. So they are partially hydrolyzed polyvinyl acetates with a residual content of acetyl groups of about 1-2 or 11-13 mol%.

The Water of PVAL can be achieved by post-treatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid, Reduce borax and thus set specifically to desired values. films made of PVAL are largely impermeable to gases such as oxygen, nitrogen, Helium, hydrogen, carbon dioxide, however, allow water vapor to pass through.

beschreiben.Polyvinylpyrrolidones, referred to as PVP for short, may be represented by the general formula

describe.

PVP are prepared by radical polymerization of 1-vinylpyrrolidone. commercial PVP have molecular weights in the range of about 2500-750,000 g / mol and are considered as white, hygroscopic powders or offered as aqueous solutions.

Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula H- [O-CH ₂ -CH ₂ ] _n -OH the technically by alkaline-catalyzed polyaddition of ethylene oxide (oxirane) in mostly small amounts of water-containing systems are prepared with ethylene glycol as the starting molecule. They have molar masses in the range of about 200-5,000,000 g / mol, corresponding to degrees of polymerization n of about 5 to> 100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and show only weak glycol properties.

gelatin is a polypeptide (molecular weight: about 15,000-> 250,000 g / mol), which is mainly by Hydrolysis of the collagen contained in the skin and bones of animals is obtained under acidic or alkaline conditions. The amino acid composition The gelatin largely corresponds to that of the collagen from which they are made and varies depending on its provenance. The use of gelatin as the water-soluble coating material is in particular in pharmacy in the form of hard or soft gelatin capsules extremely far common. In the form of slides, gelatin is because of their compared to the above-mentioned polymers of high price only small Use.

Prefers are also used portioned according to the invention in the context of the present invention Detergents whose bags of water-soluble film of at least a polymer from the group starch and starch derivatives, Cellulose and cellulose derivatives, especially methylcellulose and Mixtures consists of this.

Strength is a homoglycan, wherein the glucose units are linked α-glycosidically. Strength is composed of two components of different molecular weight: From about 20-30% straight chain amylose (MW about 50,000-150,000) and 70-80% branched chain Amylopectin (MG, approximately 300,000-2,000,000), In addition, there are still small amounts of lipids, phosphoric acid and Contain cations. While the amylose due to binding in the 1,4-position long, helical, entangled Chains with about 300-1200 Glucose molecules Forms chain at amylopectin branches on average 25 glucose building blocks by 1,6-binding to a branch-like Structures with about 1500-12000 molecules Glucose. Besides pure strength are for producing water-soluble Bag in the context of the present invention also starch derivatives, which are obtainable from starch by polymer-analogous reactions. Such chemically modified starches include, for example, products of esterification or etherification, in which hydroxy hydrogen atoms have been substituted. But also Strengthen, in which the hydroxy groups against functional groups that do not have a Oxygen atom bound, replaced, can be used as starch derivatives deploy. Into the group of starch derivatives fall, for example, alkali, carboxymethyl (CMS), starch ester and ethers, and amino acids.

Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.

Preferred bags of water-soluble film consist of a polymer having a molecular weight between 5000 and 500,000 daltons, preferably between 7500 and 250,000 daltons and in particular between 10,000 and 100,000 daltons. The water-soluble film forming the bag preferably has a thickness of 1 to 150 μm, preferably 2 to 100 μm, more preferably 5 to 75 μm, and in particular der from 10 to 50 microns, on.

Claims (19)

Use of a pourable machine dishwashing detergent, containing a) from 1 to 60% by weight of nonaqueous solvent (s), b) 0.1 to 70 wt .-% of copolymers i) unsaturated carboxylic acids ii) Containing sulfonic acid monomers c) 5 to 30% by weight of nonionic surfactant (s). when machine dishwashing detergent in a dishwashing process without the addition of regenerating salt and rinse aid. Use according to claim 1, characterized that the non-aqueous (n) Solvent is / are selected from the group of polyethylene glycols and polypropylene glycols, glycerol, Glycerin carbonate, triacetin, ethylene glycol, propylene glycol, propylene carbonate, Hexylene glycol, ethanol and n-propanol and / or iso-propanol. Use according to one of claims 1 or 2, characterized that it the non-aqueous (s) solvent in amounts of from 5 to 50% by weight, preferably from 7.5 to 40% by weight and in particular from 10 to 30 wt .-%, each based on the total Means containing. Use according to one of claims 1 to 3, characterized in that it contains as ingredient b) one or more copolymers which contain structural units of the formulas III and / or IV and / or V and / or VI and / or VII and / or VIII - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (III), - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (IV) - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (VI), - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (VII) - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - (VIII), in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred. Use according to one of Claims 1 to 4, characterized that it additionally one or more substances from the group of acidifying agents, Chelatkomplexbildner or the deposit-inhibiting polymers contains. Use according to one of claims 1 to 5, characterized that it From 5 to 25% by weight, preferably 6 to 22.5% by weight, particularly preferably 7.5 to 20% by weight and in particular from 8 to 17.5% by weight of nonionic surfactant (s). Use according to one of claims 1 to 6, characterized that it the sulfonated copolymer (s) in amounts of from 0.25 to 50% by weight, preferably from 0.5 to 35% by weight, more preferably from 0.75 to 20 wt .-% and in particular from 1 to 15 wt .-%. Use according to one of claims 1 to 7, characterized that the Content of free, i. not in the form of water of hydration and / or water of constitution present water below 2% by weight, preferably below 1% by weight. and in particular even below 0.5 wt .-%, each based on the Means, lies. Use according to one of claims 1 to 8, characterized in that it also aa) 0.1 to 1.0 wt .-% of one or more structurants from the group of bentonites and / or at least partially etherified sorbitol and bb) contains 5.0 to 30 wt .-% of one or more thickeners from the group of carbonates, sulfates and amorphous or crystalline disilicates. Use according to claim 9, characterized that as Structured Montmorillonite be used. Use according to one of claims 9 or 10, characterized that as Structurally doubly etherified sorbitols, especially dibenzylidenesorbitol, be used. Use according to one of Claims 9 to 11, characterized that it the structurant in amounts of 0.2 to 0.9 wt .-%, preferably in amounts of 0.25 to 0.75 wt .-% and in particular in amounts of 0.3 to 0.5 wt .-%, each based on the total agent contains. Use according to one of Claims 9 to 12, characterized that the average particle size of bleach and thickener as well as the optionally used builder less than 75 μm, preferably less than 50 microns and in particular less than 25 microns is. Use according to one of claims 1 to 13, characterized that it additionally From 20 to 50% by weight of one or more water-soluble builders, preferably citrates and / or phosphates, preferably alkali metal phosphates under particular Preference of pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphate) contains. Use according to claim 14, characterized that it the one or more water-soluble ones Builder (s) in amounts of from 22.5 to 45% by weight, preferably from 25 to 40% by weight and in particular from 27.5 to 35 wt .-%, each based on the entire means, contains. Use according to one of Claims 1 to 14, 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 wt .-%, of a polymeric thickener, preferably from the group of polyurethanes or modified polyacrylates, with particular preference to thickeners of the formula XV

in the R ^{3 is} H or a branched or unbranched C _1-4 -alk (en) yl radical, X is NR ⁵ or O, R ^{4 is} an optionally alkoxylated branched or unbranched, possibly substituted C _8-22 -alk (s ) yl radical, R ^{5 is} H or R ⁴ and n is a natural number. Use according to one of claims 1 to 13, characterized that it additionally Enzymes and / or enzyme preparations, preferably solid and / or liquid Protease preparations and / or amylase preparations, in amounts of 1 to 5 wt .-%, preferably from 1.5 to 4.5 and especially from 2 to 4 wt .-%, each based on the entire remedy, contains. Use according to one of claims 1 to 18, characterized that it at 20 ° C a viscosity from 500 to 5000 mPas, preferably from 1000 to 4000 mPas, and in particular from 1300 to 3000 mPas. Use according to one of claims 1 to 19, characterized that the pH of a 1% by weight solution the composition in distilled water between 7 and 11, preferably between 8 and 10 and in particular between 8.5 and 9.5.