DE10133136A1 - Liquid detergent for automatic dishwashers contains non-aqueous solvent, copolymer of unsaturated carboxylic acid and monomer containing sulfo groups and nonionic surfactant - Google Patents

Abstract

Detergent for automatic dishwashers contains 1-60 wt.% non-aqueous solvent(s), 0.1-70 wt.% copolymer of unsaturated carboxylic acid, monomer containing sulfo groups and optionally other ionic or nonionic monomers and 5-30 wt.% nonionic surfactant(s).

Description

The present invention relates to liquid agents for cleaning dishes in one household dishwasher. In particular, the invention relates to non-aqueous liquid Dishwashing detergent for automatic dishwashing.

Machine dishwashing detergents for household use are usually in the form of Powders or, more recently, moldings (tablets) are offered. The offer form of a So far, liquid has only become of minor importance in the market in this sector. Compared to the fixed supply forms, however, liquids have advantages in dosage and not to be underestimated aesthetic product advantages that make this offer interesting do. So there is also a broad state of the art for both non-aqueous, mostly solvent-based as well as aqueous dishwashing detergents for washing dishes in one household dishwasher.

For example, DE 20 29 598 describes liquid detergent compositions which 14 to 35% by weight sodium tripolyphosphate, 0.1 to 50% by weight of a potassium and / or ammonium salt an inorganic or organic acid, water and optionally surfactants, solubilizers, Contains sequestering agents, persalts and other ingredients.

Linear viscoelastic detergent compositions for automatic dishwashing are also described in European patent application EP 446 761 (Colgate). The one here disclosed compositions contain up to 2% by weight of a long-chain fatty acid or a salt thereof, 0.1 to 5% by weight of surfactant, 5 to 40% by weight of water-soluble builder and to contain 20 wt .-% chlorine bleach and a polycarboxylate thickener, which Ratio of potassium to sodium ions in the compositions should be 1: 1 to 45: 1.

Machine dishwashing detergents in the form of clear, translucent gels are used in Europe Patent application EP 439 878 (Union Camp Corp.). The ones disclosed herein Compositions contain a polyacrylate thickener that forms a gel matrix with water, Surfactant, bleach, a builder and water.

Gel-like automatic dishwashing detergents are also used in the European patent application EP 611 206 (Colgate). These compositions contain 1 to 12% by weight of one liquid nonionic surfactant, 2 to 70 wt .-% builder, as well as enzymes and a stabilization system, which consists of swelling substances and hydroxypropyl cellulose is composed.

Viscose-elastic, thixotropic dish detergent with 0.001 to 5% by weight of surfactant and Enzymes and an enzyme stabilization system from boric acid and polyhydroxy compounds in international patent application WO 93/21299 (Procter & Gamble). This one Disclosed agents also contain 0.1 to 10% by weight of one or more thickeners.

Today, machine-washed dishes are often subject to higher requirements than they are manually washed dishes. In this way, dishes that have been completely cleaned of leftovers are then used as not rated properly if it is whitish after machine dishwashing Water hardness or other mineral salts has spots that are lacking Wetting agents come from dried water drops.

In order to obtain crystal-clear and spotless dishes, rinse aid is successfully used today on. The addition of rinse aid at the end of the wash program ensures that the water runs as completely as possible from the wash ware, so that the different surfaces at the end of the Washing programs are residue-free and spotlessly shiny.

The automatic cleaning of dishes in domestic dishwashers usually includes a pre-rinse, a main rinse and a rinse cycle that of intermediate rinse to be interrupted. On most machines, the pre-rinse cycle is for heavily soiled items Dishes can be switched on, but is only selected by the consumer in exceptional cases, so that in the Most machines have a main wash, an intermediate wash with pure water and a Rinse aid. The temperature of the main wash cycle varies depending on Machine type and program level selection between 40 and 65 ° C. In the final rinse cycle, one Dosing tank in the machine added rinse aid, usually as the main ingredient contain nonionic surfactants. Such rinse aids are in liquid form and are in the state of the art Technology broadly described. Your job primarily consists of lime stains and toppings to prevent the cleaned dishes.

These so-called "2-in-1" products simplify handling and take the consumer the burden of additional dosing of two different products (cleaner and rinse aid). Nevertheless, in order to operate a household dishwasher Intervals two dosing processes required, because after a certain number of rinsing the Regeneration salt in the water softening system of the machine must be refilled. This Water softening systems consist of ion exchange polymers, which are those of the machine Incoming hard water soften and after rinsing with a rinse Salt water can be regenerated.

Products which, as so-called "3-in-1" products, include conventional detergents, rinse aids and a Combining salt replacement functions have recently been described in the prior art. These products are only available as solids (tablets).

The present invention was based on the object of being castable and therefore light and to provide a quantity that can be dosed freely and doses only once per application must be without the dosing even after a higher number of rinsing cycles other product and thus a double dosing process would be necessary. It should be a liquid until gel-like product are provided, which in addition to the "built-in rinse aid" Refilling the regeneration salt container makes it unnecessary and thus further handling simplified. The performance of the product should be the level of performance more traditional Three-product doses (salt detergent rinse aid) or new two-product doses ("2-in-1" detergent) Rinse Aid) The products to be provided should be related to as many properties as possible are superior to conventional agents. Especially with many pourable products occurring dichotomy - advantages with certain properties (Flowability, residual emptiness, appealing product appearance, etc.) come with disadvantages other properties (settling behavior, storage stability, performance, etc.) - should be overcome. There was therefore also the task of providing means that are advantageous rheological properties (flowability, residual emptiness, etc.), advantageous product characteristics (Appearance, cleaning power, storage stability etc.) and a technically easy to implement and combine production to be carried out inexpensively.

It has now been found that pourable machine dishwashing detergents are compatible with the above have the stated positive properties formulated on the basis of non-aqueous solvents, if these agents certain polymers containing sulfonic acid groups and nonionic surfactants contain.

• a) 1 bis 60 Gew.-% nichtwäßrige(s) Lösungsmittel,
• b) 0,1 bis 70 Gew.-% an Copolymeren aus
  • a) ungesättigten Carbonsäuren
  • b) Sulfonsäuregruppen-haltigen Monomeren
  • c) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren
• c) 5 bis 30 Gew.-% nichtionische(s) Tensid(e).

The subject of the present invention is therefore in a first embodiment a machine dishwashing detergent containing

• a) 1 to 60% by weight of non-aqueous solvent (s),
• b) 0.1 to 70 wt .-% of copolymers
  • a) unsaturated carboxylic acids
  • b) monomers containing sulfonic acid groups
  • c) optionally further ionic or nonionic monomers
• c) 5 to 30% by weight of nonionic surfactant (s).

The agents according to the invention contain one or more non-aqueous ingredients as ingredient a) Solvent. These come from the groups of mono-alcohols, diols, and triols, for example or polyols, the ethers, esters and / or amides. Non-aqueous are particularly preferred Solvents that are water-soluble, "water-soluble" solvents in the sense of present application are solvents which are completely with water at room temperature, ie. H. without Mix gap, are miscible.

Non-aqueous solvents which can be used in the agents according to the invention, preferably come from the group of mono- or polyhydric alcohols, alkanolamines or Glycol ether, provided that they are miscible with water in the concentration range specified. The solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, Propane or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, Ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, Diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and Mixtures of these solvents.

Particularly preferred automatic dishwashing detergents are characterized in that the non-aqueous solvent (s) is / are selected from the group of polyethylene glycols and Polypropylene glycols, glycerin, glycerol 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, which have the general formula

H- (O-CH ₂ -CH ₂ ) _n -OH

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

A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and immediately after the hyphen is followed by a number which corresponds to the number n in the formula I mentioned above. According to this nomenclature (known as INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997) according to the invention, for example, PEG-4, PEG-6, PEG-8, PEG 9, PEG-10, PEG-12, PEG-14 and PEG-16 can be used according to the invention.

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

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


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

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

Glycerol carbonate can be obtained by transesterification of ethylene carbonate or dimethyl carbonate with glycerin, ethylene glycol or methanol being obtained as by-products. Another synthetic route starts from glycidol (2,3-epoxy-1-propanol), which is converted under pressure in the presence of catalysts with CO ₂ to form glycerol carbonate. Glycerol carbonate is a clear, easily movable 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, strong 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 198 ° C. Technically, ethylene glycol is made from ethylene oxide by heating with water under pressure won. Promising manufacturing processes can also be carried out on the acetoxylation of Build ethylene and subsequent hydrolysis or synthesis gas reactions.

There are two isomers of propylene glycol, 1,3-propanediol and 1,2-propanediol. 1,3-propanediol (trimethylene glycol) is a neutral, colorless and odorless, sweet tasting Liquid with a density of 1.0597 that solidifies at -32 ° C and boils at 214 ° C. The production of 1,3-propanediol can be obtained from acrolein and water with subsequent catalytic hydrogenation.

Technically far more important is 1,2-propanediol (propylene glycol), which is an oily, colorless, almost odorless liquid, density 1.0381, which solidifies at -60 ° C and boils at 188 ° C. 1,2-propanediol is made from propylene oxide by adding water.

Propylene carbonate is a bright, easily moving liquid with a density of 1.21 gcm ^-3 , the melting point is -49 ° C, the boiling point is 242 ° C. Large quantities of propylene carbonate can also be obtained by reacting propylene oxide and CO ₂ at 200 ° C and 80 bar.

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

In the context of this invention, “non-aqueous” is understood to mean a state in which the Free water content in the compositions is clearly below 5% by weight, based on the composition. It it is preferred that the content of the agents according to the invention is free, i. H. not in the form of Water of hydration and / or constitutional water less than 2% by weight, preferably is below 1% by weight and in particular even below 0.5% by weight, in each case based on the agent. Accordingly, water can essentially only be chemically and / or physically bound form or as part of the raw materials or compounds present as a solid, but not be introduced into the product as a liquid, solution or dispersion.

As a second component b), the agents according to the invention contain copolymers of unsaturated Carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic ones or nonionic monomers. These copolymers cause those with such agents treated dishes become much cleaner in subsequent cleaning processes than Parts of dishes that have been washed using conventional means.

As an additional positive effect, the drying time is reduced with that Detergent treated dishes on d. H. after the expiry of the Cleaning programs take the dishes out of the machine earlier and reuse them.

The invention features improved "cleanability" of the treated substrates later cleaning processes and by significantly reducing the drying time compared to comparable agents without the use of sulfonic acid-containing polymers.

The drying time in the context of the teaching according to the invention is generally the understood the meaning in the sense of the word, i.e. the time that passes until one in one Dishwasher-treated dish surface has dried, but especially the time that elapses until 90% one with a detergent or rinse aid in concentrated or diluted form treated surface is 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 which R ¹ to R ³ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids which can be described by 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) preferred.

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

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

in which R ⁵ to R ⁷ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group , which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k with k = 1 to 6, -C (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 selected independently of one another from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally present spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (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-hydroxy-propanesulfonic 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-propen1-sulfonic acid (X = CH ₂ in formula IIb), styrene sulfonic acid (X = C ₆ H ₄ in formula IIa), vinyl sulfonic acid (X not present in formula IIa), 3-sulfopropylacrylate (X = -C (O) NH- CH ₂ CH ₂ CH ₂ - in Formula IIa), 3-sulfopropyl methacrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in formula IIb), sulfomethacrylamide (X = -C (O) NH- in formula IIb), sulfomethyl methacrylamide (X = -C (O) NH-CH ₂ - in formula IIb) and water-soluble salts of the acids mentioned.

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

• a) 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,
• b) 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)-
• c) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren

besonders bevorzugt. In summary, copolymers are made of

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

particularly preferred.

• a) einer oder mehrerer ungesättigter Carbonsäuren aus der Gruppe Acrylsäure, Methacrylsäure und/oder Maleinsäure
• b) 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)-
• c) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren.

Particularly preferred copolymers consist of

• a) one or more unsaturated carboxylic acids from the group consisting of acrylic acid, methacrylic acid and / or maleic acid
• b) one or more monomers of the formulas IIa, IIb and / or IIc containing sulfonic acid groups:
  
  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 selected independently of one another from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally present spacer group which is selected from - (CH ₂ ) _n -with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -
• c) optionally further ionic or nonionic monomers.

The copolymers which persist in the compositions according to the invention can be obtained from the monomers Groups i) and ii) and optionally iii) in varying amounts, all representatives from group i) with all representatives from group ii) and all representatives from the Group iii) can be combined. Particularly preferred polymers have certain Structural units that are described below.

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

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

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

These polymers are produced by copolymerization of acrylic acid with an acrylic acid derivative containing sulfonic acid groups. If the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained, the use of which in the agents according to the invention is also preferred and is characterized in that the agents contain one or more copolymers which have structural units of the formula IV

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

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

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

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

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

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -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 or in addition to acrylic acid and / or methacrylic acid, maleic acid can also be used as a particularly preferred monomer from group i). In this way, preferred agents according to the invention are obtained which are characterized in that they contain one or more copolymers, the structural units of the formula VII

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

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O- (CH ₂ ) with n = 0 to 4, represents -O- (C ₆ H ₄ ) -, represents -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - , 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 I [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - (VIII),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -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, automatic dishwashing agents according to the invention are preferred which contain, as ingredient b), one or more copolymers which have structural units of the formulas 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),

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

The sulfonic acid groups in the polymers can be wholly or partly in neutralized form are present, d. H. that the acidic hydrogen atom of the sulfonic acid group in some or all Sulphonic acid groups against metal ions, preferably alkali metal ions and in particular against Sodium ions, can be exchanged. Corresponding means, which are characterized in that the According to the invention, sulfonic acid groups in the copolymer are partially or fully neutralized prefers.

The monomer distribution of the copolymers used in the agents according to the invention is preferred for copolymers containing only monomers from groups i) and ii) each 5 to 95 wt .-% i) or ii), particularly preferably 50 to 90 wt .-% monomer from the group i) and 10 to 50 wt .-% monomer from group ii), each based on the polymer.

In the case of terpolymers, those which contain 20 to 85% by weight of monomer from the Group i), 10 to 60% by weight of monomer from group ii) and 5 to 30% by weight of monomer group iii) included.

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

The content of one or more copolymers in the agents according to the invention may vary Application and desired product performance vary, with preferred Machine dishwashing detergents according to the invention are characterized in that they are the Copolymer (s) in amounts of 0.25 to 50% by weight, preferably 0.5 to 35% by weight, particularly preferably contain from 0.75 to 20% by weight and in particular from 1 to 15% by weight.

The agents according to the invention contain one or more nonionic surfactants as ingredient c), for short non-ionic surfactants. The amounts in which the nonionic surfactants are used are according to the invention between 5 and 30 wt .-%, wherein automatic dishwashing detergent according to the invention preferred are 5 to 25% by weight, preferably 6 to 22.5% by weight, particularly preferably 7.5 Contain up to 20 wt .-% and in particular 8 to 17.5 wt .-% nonionic surfactant (s).

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

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

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

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


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

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


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

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

Low-foaming nonionic surfactants are used as preferred surfactants. With The automatic dishwashing detergents according to the invention contain a particular preference nonionic surfactant that has a melting point above room temperature. As a result preferred agents, characterized in that they contain nonionic surfactant (s) with a Melting point above 20 ° C, preferably above 25 ° C, particularly preferably between 25 and 60 ° C and in particular between 26.6 and 43.3 ° C, included.

Suitable nonionic surfactants, the melting or softening points in the above Have temperature range are, for example, low-foaming nonionic surfactants, which Room temperature can be solid or highly viscous. Become highly viscous at room temperature Nonionic surfactants used, it is preferred that this has a viscosity above 20 Pa.s, preferably have above 35 Pa.s and in particular above 40 Pa.s. Also non-ionic surfactants that are used in Room temperature waxy consistency are preferred.

Preferred nonionic surfactants to be used as solid at room temperature come from the groups of alkoxylated nonionic surfactants, especially the ethoxylated primary alcohols and mixtures thereof Surfactants with structurally complicated surfactants such as Polyoxypropylene / Polyoxyethylene / Polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

In a preferred embodiment of the present invention, the nonionic surfactant is included a melting point above room temperature an ethoxylated nonionic surfactant resulting from the reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 carbon atoms with preferably at least 12 moles, particularly preferably at least 15 moles, in particular at least 20 moles Ethylene oxide per mole of alcohol or alkylphenol has emerged.

A particularly preferred nonionic surfactant which is solid at room temperature is obtained 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 mol, preferably at least 15 mol and in particular at least 20 mol, of ethylene oxide , Among 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 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained.

The nonionic surfactant preferably additionally has propylene oxide units in the molecule. Preferably make such PO units up to 25 wt .-%, particularly preferably up to 20 wt .-% and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. Especially preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or Alkylphenol part of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total Molecular weight of such nonionic surfactants. Preferred rinse aids are characterized in that they contain ethoxylated and propoxylated nonionic surfactants, in which the propylene oxide units in Molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the make up the total molecular weight of the nonionic surfactant.

Other nonionic surfactants to be used with particular preference with melting points above Room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene Block polymer blends containing 75% by weight of an inverted 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 Copolymers of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Examples of nonionic surfactants that can be used with particular preference are available 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 represents} a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y stands for a value of at least 15.

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

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

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

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

R ¹ 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 represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 represents} H and x assumes values from 6 to 15.

If the latter statements are summarized, 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

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

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

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

In combination with the surfactants mentioned, anionic, cationic and / or amphoteric surfactants are used, which because of their foaming behavior in machine dishwashing detergents are of minor importance and mostly only in quantities below 10% by weight, mostly even below 5% by weight, for example from 0.01 to 2.5 % By weight, based in each case on the agent. The agents according to the invention can thus also contain anionic, cationic and / or amphoteric surfactants as the surfactant component.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C _12-18 monoolefins with a terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfofatty acids (ester sulfonates), e.g. B. the α-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures, as in the case of Manufactured by esterification of a monoglycerin with 1 to 3 moles of fatty acid or in the Transesterification of triglycerides with 0.3 to 2 mol of glycerol can be obtained. Preferred sulfated Fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 Carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, Lauric acid, palmitic acid, stearic acid or behenic acid.

As alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which can be obtained as commercial products from Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

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

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-11 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Soaps are particularly suitable as further anionic surfactants. Saturated ones are suitable Fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural fatty acids, e.g. B. coconut, Palm kernel or tallow fatty acids, derived soap mixtures.

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

The agents according to the invention can contain, for example, cationic compounds of the formulas XI, XII or XIII as cationic active substances:


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 agents according to the invention can contain other conventional agents Contain ingredients of cleaning agents. The builders in particular are from special meaning. Builders are used in the compositions according to the invention mainly used to bind calcium and magnesium. Usual builders working under the Invention preferably 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 composition, are present the low molecular weight polycarboxylic acids and their salts, the homopolymers and copolymers Polycarboxylic acids and their salts, the carbonates, phosphates and sodium and potassium silicates. For the cleaning agents according to the invention are preferably trisodium citrate and / or Pentasodium tripolyphosphate and silicate builders from the class of alkali disilicates are used. As a general rule In the case of the alkali metal salts, the potassium salts are preferable to the sodium salts, since they are often have a higher water solubility. Preferred water-soluble builders are for example tripotassium citrate, potassium carbonate and the potassium water glasses.

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

Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid 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 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, water-soluble powders that lose water of crystallization when heated and at 200 ° C into the weakly acidic 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). Na ₄ H 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 (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt with a density of 2.33 gcm ^-3 , 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 easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ³ , water loss at 95 °), 7 mol. (Density 1.68 gcm 3, melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water (density 1 , 52 gcm ^-3 melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to diphosphate Na ₄ P ₂ O ₇ when heated more strongly. Disodium hydrogen phosphate is produced by neutralizing phosplioric 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 easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₂ PO ₄ , are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm ³ 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 with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 gm. Has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises e.g. B. when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gm, melting point 988 °, also stated 880 °) and as decahydrate (density 1.815-1.836 g cm 3, melting point 94 ° with loss of water). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), 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 of the 1% solution at 25 ° is 10.4.

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

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 H ₂ O. -Na with n = 3. In 100 g of water about 17 g of the salt of water free of crystal water dissolve at room temperature, about 20 g at 60 ° and about 32 g at 100 °; after heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry.

Preferred machine dishwashing detergents contain 20 in addition to the ingredients a) to c) up to 50% by weight of one or more water-soluble builders, preferably citrates and / or Phosphates, preferably alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate).

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

The agents according to the invention can particularly preferably contain condensed phosphates as water-softening substances. These substances form a group of phosphates - also called melting or glow phosphates due to their production - which can be derived from acid salts of orthophosphoric acid (phosphoric acids) by condensation. The condensed phosphates can be divided into the metaphosphates [Mln (PO ₃ ) _n ] and polyphosphates (M ^l _{n + 2} P _n O _{3n + 1} or M ^l _n H ₂ P _n O _{3n + 1} ).

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

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

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

As particularly preferred water-softening substances from the above classes of the condensed phosphates are the "Hexametaphosphate" Budit® H6 or H8 from Budenheim proved.

In addition to the builders, bleaching agents, bleach activators, enzymes, Silver preservatives, dyes and fragrances etc. preferred ingredients of mechanical Dishwashing detergents. In addition, other ingredients may be present, with mechanical ones according to the invention Dishwashing detergents are preferred which additionally contain one or more substances from the group of Acidifying agents, chelating agents or the deposit-inhibiting polymers contain. Both inorganic acids and organic acids are suitable as acidifiers, if they are compatible with the other ingredients. For consumer protection reasons and the handling safety are in particular the solid mono-, oligo- and polycarboxylic acids used. From this group citric acid, tartaric acid, Succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. Also the Anhydrides of these acids can be used as acidifying agents, in particular Maleic anhydride and succinic anhydride are commercially available. organic Sulfonic acids such as amidosulfonic acid can also be used. Commercially available and as Sokalan® can also preferably be used in the context of the present invention DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight).

Another possible group of ingredients are the chelating agents. Chelating agents are substances that form cyclic compounds with metal ions, with a single Ligand occupies more than one coordination site on a central atom, i. H. at least "bidentate" is. In this case, elongated connections are usually formed by complex formation closed to rings via an ion. The number of ligands bound depends on the Coordination number of the central ion.

Common chelate complex images which are preferred in the context of the present invention are for example polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and Nitrilotriacetic acid (NTA). Also complex-forming polymers, i.e. polymers that are either in the Main chain itself or laterally to this functional groups that act as ligands can and with suitable metal atoms usually with the formation of chelate complexes react, can be used according to the invention. The polymer-bound ligands of the resulting Metal complexes can originate from just one macromolecule or different ones Polymer chains belong. The latter leads to the networking of the material, provided that the complex-forming Polymers were not previously cross-linked via covalent bonds.

Complexing groups (ligands) are common complex-forming polymers iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, Amidoxime, aminophosphoric acid, (cycl.) Polyamino, mercapto, 1,3-dicarbonyl and crown ether Leftovers with z. T. very specific Activities against ions of different metals. base polymers of many commercially important complex-forming polymers are polystyrene, polyacrylates, Polyacrylonitriles, polyvinyl alcohols, polyvinyl pyridines and polyethylene imines. Even natural Polymers such as Ceulose, starch or chitin are complex-forming polymers. In addition, this can be provided with further ligand functionalities by polymer-analogous conversions.

• a) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt,
• b) stickstoffhaltigen Mono- oder Polycarbonsäuren,
• c) geminalen Diphosphonsäuren,
• d) Aminophosphonsäuren,
• e) Phosphonopolycarbonsäuren,
• f) Cyclodextrine

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

• a) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5,
• b) nitrogen-containing mono- or polycarboxylic acids,
• c) geminal diphosphonic acids,
• d) aminophosphonic acids,
• e) phosphonopolycarboxylic acids,
• f) cyclodextrins

in amounts above 0.1% by weight, preferably above 0.5% by weight, particularly preferably above 1% by weight and in particular above 2.5% by weight, in each case based on the weight of the Dishwashing detergent included.

• 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.

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

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

Polycarboxylic acids a) are carboxylic acids in the context of this patent application Monocarboxylic acids - understood, in which the sum of carboxyl and those contained in the molecule Hydroxyl groups is at least 5. Complexing agents from the group of nitrogenous Polycarboxylic acids, especially EDTA, are preferred. With those required according to the invention These complex bilgeers are at least partially alkaline pH values of the treatment solutions as anions. It is immaterial whether they are in the form of acids or in the form of salts be introduced. When used as salts are alkali, ammonium or Alkyl ammonium salts, especially sodium salts, are preferred.

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

Deposit-inhibiting polymers can also have cobuilder properties. As organic Cobuilders can be used in particular in the dishwasher detergents according to the invention Polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, Dextrins, other organic cobuilders (see below) and phosphonates can be used. This Substance classes are described below.

Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, polycarboxylic acids being understood to mean such carboxylic acids that have 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), provided that such use from ecological Reasons is not objectionable, as well as mixtures of these. Preferred salts are the salts polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, Sugar acids and mixtures of these.

The acids themselves can also be used. The acids have besides theirs Builder effect typically also the property of an acidifying component and thus also serve for Setting a lower and milder pH value for detergents or cleaning agents. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and to name any mixtures of these.

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

In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), 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 to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2000 have up to 20,000 g / mol. Because of their superior solubility, this group can again the short-chain polyacrylates, the molar masses from 2000 to 10,000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may be preferred.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As particularly suitable have proven copolymers of acrylic acid with maleic acid, the 50 to 90 wt .-% acrylic acid and contain 50 to 10% by weight of maleic acid. Their relative molecular mass, based on free Acids is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

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

Biodegradable polymers of more than two are also particularly preferred various monomer units, for example those which are salts of acrylic acid and Maleic acid and vinyl alcohol or vinyl alcohol derivatives or the salts of the monomers Acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives. More preferred Copolymers are those which, as monomers, preferably acrolein and acrylic acid / acrylic acid salts or Have acrolein and vinyl acetate.

Likewise, other preferred builder substances are polymeric aminodicarboxylic acids, their To name salts or their precursors. Polyaspartic acids are particularly preferred or their salts and derivatives which, in addition to cobuilder properties, also have a bleach-stabilizing effect Have effect.

Other suitable builder substances are polyacetals, which are obtained by reacting dialdehydes with polyol carboxylic acids which have 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 acid.

Other suitable organic builder substances are dextrins, for example oligomers or Polymers of carbohydrates that can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes be performed. It is preferably hydrolysis products with medium Molar masses in the range from 400 to 500000 g / mol. A polysaccharide with a dextrose Equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 is. Both maltodextrins with a DE between 3 can be used and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called Yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30,000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with Oxidizing agents which are capable of at least one alcohol function of the saccharide ring to oxidize to the carboxylic acid function. A product oxidized at C6 of the saccharide ring can be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates are also preferred Ethylene diamine disuccinate are other suitable cobuilders. Ethylene diamine N, N'-disuccinate (EDDS) is preferred used in the form of its sodium or magnesium salts. Are further preferred in this Also related to glycerol disuccinates and glycerol trisuccinates. Suitable quantities in zeolite-containing and / or silicate-containing formulations are 3 to 15% by weight. Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which at least 4 carbon atoms and at least one hydroxyl group and a maximum of two Acid groups included.

Another class of substances with cobuilder properties are the phosphonates it is especially hydroxyalkane or aminoalkanephosphonates. Among the Hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) are of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt being neutral and the tetrasodium salt is alkaline (pH 9). Coming as aminoalkane phosphonates preferably ethylenediaminetetramethylenephosphonate (EDTMP), Diethylene triamine pentamethylene phosphonate (DTPMP) as well as their higher homologues in question. They are preferably in shape the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as hepta- and Octa sodium salt of DTPMP, used. As a builder, the class of phosphonates preferably HEDP used. The aminoalkanephosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it can, especially if the means too Contain bleach, be preferred to use aminoalkane phosphonates, in particular DTPMP, or To use mixtures of the phosphonates mentioned.

In addition to the substances from the substance classes mentioned, the agents according to the invention can contain further usual ingredients of cleaning agents, in particular bleaching agents, Bleach activators, enzymes, silver preservatives, colors and fragrances are important. This Substances are described below.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Cleaning agents according to the invention can also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaching agents are the diacyl peroxides, such as. B. dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. 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-phthalimidanoic acid paprooxyacrylic acid , o-Carboxybenzamidoperoxycapronsäure, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, Diperocysebacinsäure, diperoxybrassylic acid, diperoxyphthalic acids, the 2-decyldiperoxybutane-1,4- diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

As a bleaching agent in the cleaning agents according to the invention for automatic dishwashing can also be used to release chlorine or bromine. Among the appropriate ones Chlorine or bromine releasing materials come for example heterocyclic N-bromine and N- Chloramides, for example trichloroisocyanuric acid, tribromo isocyanuric acid, dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium in Consideration. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

Bleach activators that support the action of the bleach have already been described above possible ingredient of the rinse aid particles mentioned. Known bleach activators are Compounds which contain one or more N- or O-acyl groups, such as substances from the class of Anhydrides, the esters, the imides and the acylated imidazoles or oximes. examples are Tetraacetylethylenediamine TAED, tetraacetylmethylene diamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine DADHT and Isatoic anhydride ISA.

Compounds which are aliphatic under perhydrolysis conditions can be used as bleach activators Peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid result can be used. Are suitable Substances containing O- and / or N-acyl groups of the number of carbon atoms mentioned and / or if appropriate carry substituted benzoyl groups. Multi-acylated alkylenediamines are preferred, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4- dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), Carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, in particular Triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile- Methyl sulfate (MMA), and enol esters, as well as acetylated sorbitol and mannitol, respectively their mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetyl glucose (PAG), Pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, if necessary N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N- Benzoyl. Hydrophilically substituted acylacetals and acyllactams are also used preferably used. Combinations of conventional bleach activators can also be used.

In addition to the conventional bleach activators or in their place, too so-called bleaching catalysts are incorporated into the rinse aid particles. With these fabrics are bleach-enhancing transition metal salts or transition metal complexes such as for example Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also Mn-, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru-amine complexes can be used as bleaching catalysts.

Bleach activators from the group of multi-acylated alkylenediamines are preferred, especially tetraacetylethylenediamine (TAED), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), preferably in Amounts up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6 wt .-% based on the total agent used.

Bleach-enhancing transition metal complexes, especially with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group consisting 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, des Manganese sulfate is used in conventional amounts, preferably in an amount of up to 5% by weight, in particular from 0.0025% by weight to 1% by weight and particularly preferably from 0.01% by weight to 0.25% by weight, each based on the total agent used. But in special cases, more can be done Bleach activator can be used.

In the cleaning agents according to the invention, the enzymes in particular come from Classes of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, Amylases, glycosyl hydrolases and mixtures of the enzymes mentioned in question. All these Hydrolases help remove soiling such as protein, fat or starchy Stains on. Oxidoreductases can also be used for bleaching. Particularly good are suitable from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens and from their genetic engineering modified variants obtained enzymatic active ingredients. Proteases are preferably from Subtilisin type and in particular proteases obtained from Bacillus lentus are used. there are enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytic enzymes or protease, amylase and lipase or lipolytic Enzymes or protease, lipase or lipolytically active enzymes, in particular, however Protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of special interest. Examples of such lipolytically active enzymes are the known ones Cutinases. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases.

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

The use of liquid is particularly preferred in the context of the present invention Enzyme formulations. Here, automatic dishwashing agents according to the invention are preferred, which additionally Enzymes and / or enzyme preparations, preferably solid and / or liquid protease Preparations and / or amylase preparations, in amounts of 1 to 5% by weight, preferably from 1.5 to 4.5 and in particular from 2 to 4% by weight, in each case based on the total composition, contain.

Dyes and fragrances can be added to the automatic dishwashing detergents according to the invention to improve the aesthetic impression of the resulting products and the Consumers in addition to performance a visually and sensory "typical and distinctive" To provide product. Individual as perfume oils or fragrances Fragrance compounds, e.g. B. the synthetic products of the type of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons are used. Fragrance compounds of the ester type are e.g. B. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, Dimethylbenzylcarbinylacetate, phenylethyl acetate, linalylbenzoate, benzyl formate, ethylmethylphenylglycinate, Allytcyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example Benzyl ethyl ether, to the aldehydes z. B. the linear alkane with 8-18 C atoms, citral, Citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, among the Ketones e.g. B. the Jonone, α-isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, Citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol Hydrocarbons mainly belong to the terpenes like limonene and pinene. However, are preferred Mixtures of different fragrances are used, which together have an appealing fragrance produce. Such perfume oils can also contain natural fragrance mixtures such as those from plant sources are accessible, e.g. B. pine, citrus, jasmine, patchouly, rose or ylang Ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, Cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and Labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

In order to improve the aesthetic impression of the agents produced according to the invention, it can (or parts thereof) with suitable dyes. Preferred dyes whose Selection presents no difficulty to the person skilled in the art, has a high storage stability and Insensitivity to the other ingredients of the agent and to light and none pronounced substantivity towards the substrates to be treated with such agents, such as glass, Ceramic or plastic dishes so as not to stain them.

The cleaning agents according to the invention can protect the dishes or the machine Corrosion inhibitors contain, especially silver protection in the field of mechanical Dishwashing have a special meaning. The known substances can be used the state of the art. In general, silver protection agents can be selected from the Group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the Alkylaminotriazoles and the transition metal salts or complexes are used. Particularly preferred to benzotriazole and / or alkylaminotriazole are used. One finds in cleaner formulations In addition, agents often containing active chlorine, which clearly corrode the silver surface can reduce. Chlorine-free cleaners contain oxygen and nitrogen in particular organic redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, Pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives thereof Classes of compounds. Also salt-like and complex-like inorganic compounds, such as salts of Metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. The are preferred here Transition metal salts which are selected from the group consisting of the 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. Zinc compounds can also be used to prevent corrosion on the wash ware become.

To regulate the viscosity, the agents according to the invention can contain further ingredients, with their use, for example, specifically the settling behavior or the pourability or flowability can be controlled. In particular, combinations have been found in non-aqueous systems proven from structure donors and thickeners.

• a) 0,1 bis 1,0 Gew.-% eines oder mehrerer Strukturgeber aus der Gruppe der Bentonite und/oder mindestens teilweise veretherten Sorbitole sowie
• b) 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 further contain

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

The structuring agent a) comes from the group of bentonites and / or at least partially etherified sorbitols. These substances are used to increase the physical stability of the agent ensure and adjust the viscosity. Although conventional thickeners like The viscosity control also works if polyacrylates or polyurethanes fail in non-aqueous media the substances mentioned in the non-aqueous system.

Bentonites are contaminated clays that are formed by weathering volcanic tuffs. Due to their high montmorillonite content, bentonites have valuable properties such as Swellability, ion exchange capacity and thixotropy. It is possible the properties to modify the bentonite according to the intended use. Bentonites are considered Clay component common in tropical soils and are known as sodium bentonite z. B. in Wyoming / USA reduced. Sodium bentonite has the most favorable application properties (Swellability), so that its use is preferred in the context of the present invention. Naturally Occurring calcium bentonites originate, for example, from Mississippi / USA or Texas / USA or from Landshut / D. The naturally obtained Ca bentonites are made artificially through exchange converted from Ca against Na into the more swellable Na bentonites.

The main constituents of the bentonites are so-called montmorillonites, which can also be used in pure form in the context of the present invention. Montmorillonites belong to the phyllosilicates and here to the dioctahedral smectites clay minerals that crystallize monoclinic-pseudohexagonal. Montmorillonite predominantly form white, gray-white to yellowish, completely amorphous appearing, easily friable, swelling in the water, but not becoming plastic, by the general formulas

Al ₂ [(OH) ₂ / Si ₄ O ₁₀ ] .nH ₂ O or

Al ₂ O ₃ .4SiO ₂ .H ₂ O.nH ₂ O or

Al ₂ [(OH) ₂ / Si ₄ O ₁₀ ] (dried at 150 °)

can be described.

Preferred machine dishwashing detergents are characterized in that montmorillonites are used as structuring agents. Montmorillonites have a three-layer structure, which consists of two tetrahedral layers that are electrostatically cross-linked via the cations of an intermediate octahedral layer. The layers are not rigidly connected, but can be reversibly incorporated by water (in 2-7 times the amount) and other substances such as. As alcohols, glycols, pyridine, α-picoline, ammonium compounds, hydroxy aluminosilicate ions, etc. swell. The above. Formulas are only approximate formulas because montmorillonites have a large ion exchange capacity. Al can be exchanged for Mg, Fe ²⁺ , Fe ³⁺ , Zn, Cr, Cu and other ions. As a result of such a substitution, the layers are negatively charged, which is balanced by other cations, especially Na ⁺ and Ca ²⁺ .

In combination with the bentonites or as a replacement for them if you do not want to use them , at least partially etherified sorbitols can be used as structure donors.

Sorbitol is a hexahydric alcohol (sugar alcohol), the intramolecular removes one or two moles of water relatively easily and forms cyclic ethers (for example Sorbitan and sorbide). The elimination of water is also possible intermolecularly Form noncyclic ethers from sorbitol and the alcohols concerned. Here too is the training of Monoethers and bisethers possible, although higher degrees of etherification such as 3 and 4 also occur can. In the context of the present invention, preferably to be used at least partially etherified sorbitols are double etherified sorbitols, of which the dibenzylidene sorbitol is particularly preferred. Here, automatic dishwashing detergents are preferred, which are used as structuring agents double etherified sorbitols, especially dibenzylidene sorbitol.

The agents according to the invention can contain the structuring agents in amounts of 0.1 to 1.0% by weight, based on the total agent and on the active substance of the structuring agent. preferred Agents contain the structuring agent in amounts of 0.2 to 0.9% by weight, preferably in amounts from 0.25 to 0.75% by weight and in particular in amounts of 0.3 to 0.5% by weight, in each case based on the entire mean.

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

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

In view of increased settling stability, it is preferred that the in the invention Solids contained agents are used as fine as possible. This is particularly the case with the inorganic thickeners and an advantage for bleaching agents. Here are inventive machine dishwashing detergent preferred, in which the average particle size of the bleach and Thickener and the optional builder less than 75 microns, preferably less is less than 50 µm and in particular less than 25 µm.

The liquid dishwasher detergents according to the invention can be used to adjust a any desired higher viscosity also other viscosity regulators or thickeners contain. Here, all known thickeners can be used, ie those on the Based on natural or synthetic polymers.

Natural polymers that are used as thickeners for example agar agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar Flour, locust bean gum, starch, dextrins, gelatin and casein.

Modified natural products mainly come from the group of modified starches and Celluloses, examples include carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and -propyl cellulose and core meal ether called.

A large group of thickeners, widely used in a wide variety Find application areas are the fully synthetic polymers such as polyacrylic and polymethacrylic Compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and Polyurethanes.

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

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

In the context of the present invention, thickeners are also to be used with preference Polyurethanes or modified polyacrylates, based on the total agent, for example can be used in amounts of 0.1 to 5 wt .-%.

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

Technically important PUR are made from polyester and / or polyether diols and, for example, z. B. from 2,4- or 2,6-toluenediisocyanate (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 ].

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

Modified polyacrylates which can be used in the context of the present invention are derived, for example, from acrylic acid or methacrylic acid and can be described by the general formula XV


in which R ^{3 represents} H or a branched or unbranched C ₁₄ alk (en) yl radical, X represents NR ⁵ or O, R ^{4 represents} an optionally alkoxylated branched or unbranched, possibly substituted C _8-22 alk (en) yl radical , R ^{5 stands} for H or R ⁴ and n stands for a natural number. Such modified polyacrylates are generally esters or amides of acrylic acid or an α-substituted acrylic acid. Preferred among these polymers are those in which R ^{3 represents} H or a methyl group. In the case of the polyacrylamides (X = NR ⁵ ), both single (R ⁵ = H) and double (R ⁵ = R ⁴ ) N-substituted amide structures are possible, the two hydrocarbon radicals which are bonded to the N atom being optionally independent of one another alkoxylated branched or unbranched C _8-22 alk (en) yl residues can be selected. Among the polyacrylic esters (X = O), preference is given to those in which the alcohol has been obtained from natural or synthetic fats or oils and is additionally alkoxylated, preferably ethoxylated. Preferred degrees of alkoxylation are between 2 and 30, with degrees of alkoxylation between 10 and 15 being particularly preferred.

Since the polymers that can be used are technical compounds, the designation of the radicals bound to X represents a statistical mean, which can vary in individual cases with regard to chain length or degree of alkoxylation. Formula II only provides formulas for idealized homopolymers. However, copolymers in which the proportion of monomer units which satisfy the formula II is at least 30% by weight can also be used in the context of the present invention. As well as copolymers of modified polyacrylates and acrylic acid or salts thereof are usable, for example, the still acidic hydrogen atoms or basic -C00 ^- - possess groups.

Modified polyacrylates to be 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 alk (en) yl radical, R ⁶ and R ⁷ independently of one another are H or CH ₃ , the degree of polymerization n is a natural number and the degree of alkoxylation a is a natural number is between 2 and 30, preferably between 10 and 20. R ⁴ is preferably a fatty alcohol residue obtained from natural or synthetic sources, the fatty alcohol in turn preferably being ethoxylated (R ⁶ = H).

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

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


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

The viscosity of the agents according to the invention can be determined using customary standard methods (for example Brookfield viscometer LVT-11 measured at 20 rpm and 20 ° C, spindle 3) and lies preferably in the range from 500 to 5000 mPas. Preferred detergent compositions have viscosities from 1000 to 4000 mPas with values between 1300 to 3000 mPas are particularly preferred. The pH of the agents according to the invention is in 1% by weight solution distilled water preferably within the range of 7 to 11, particularly preferred between 8 and 10 and in particular between 8.5 and 9.5.

The agents according to the invention can in a conventional manner, i. H. in bottles or the like Container to be packed. However, it is also possible to pre-portion the agents according to the invention to make it easier for consumers to dose detergents and cleaning agents. in the Such single dose amounts of detergents have been found in particular Pouch packaging and, in turn, pouches made of water-soluble film, which tear open make packaging unnecessary by the consumer. This way is a convenient one Dosage of a single portion by inserting the bag directly into the dishwasher or in their induction chamber possible.

The agents according to the invention can preferably be packaged in bags made of water-soluble film become. Such bag materials or foils are known from the prior art and come, for example, from the group (acetalized) polyvinyl alcohol, polyvinyl pyrrolidone, Polyethylene oxide, gelatin and mixtures thereof.

According to the invention, the generic term “polyvinyl alcohols” 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. Homopolymers or copolymers of vinyl alcohol cannot be obtained by polymerizing vinyl alcohol (H ₂ C = CH-OH) since its concentration in tautomer equilibrium with acetaldehyde (H ₃ C-CHO) is too low. These polymers are therefore primarily prepared from polyvinyl esters, in particular polyvinyl acetates, via polymer-analogous reactions such as hydrolysis, but technically in particular by alkaline-catalyzed transesterification with alcohols (preferably methanol) in solution.

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


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


contain.

Commercially available polyvinyl alcohols with white-yellow powder or granules Degree of polymerization in the range from approx. 100 to 2500 (molar masses from approx. 4000 to 100,000 g / mol) are offered have degrees of hydrolysis of 98-99 or 87-89 mol%, so they still contain one Residual content of acetyl groups. The polyvinyl alcohols are characterized by the manufacturers by specifying the degree of polymerization of the starting polymer, the degree of hydrolysis, the Saponification number or the solution viscosity.

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and a few strongly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); from (chlorinated) They do not attack hydrocarbons, esters, fats and oils. polyvinyl alcohols are classified as toxicologically safe and are at least partially biodegradable. Water solubility can be achieved by post-treatment with aldehydes (acetalization) Complexation with Ni or Cu salts or by treatment with dichromates, boric acid or Reduce borax. The polyvinyl alcohol coatings are largely impenetrable for Gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, however, leave water vapor pass.

This makes bag materials preferred in the context of the present invention characterized in that the degree of hydrolysis of the polyvinyl alcohol is 70 to 100 mol%, preferably 80 to 90 mol% %, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.

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

The degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, particularly preferred 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 trademark Mowiol® (Clariant). Particularly within the scope of the present invention Suitable polyvinyl alcohols are, for example, Mowiol® 3-83, Mowiol 4-88, Mowiol® 5-88 and Mowiol® 8-88. Commercial PVAL (e.g. Mowiol® types from Hoechst) come as white-yellow powder or granules with degrees of polymerization in the range of approx. 500-2500 (corresponding to molar masses of approx. 20,000-100,000 g / mol) in the trade and have different Degrees of hydrolysis of 98-99 and 87-89 mol%. So they are partially saponified polyvinyl acetates with one Residual acetyl group content of approx. 1-2 or 11-13 mol%.

The water solubility of PVAL can be improved by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, Reduce borax and adjust it to the desired values. Foils are made of PVAL largely impenetrable for gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but let water vapor pass through.

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


describe.

PVPs are made by radical polymerization of 1-vinyl pyrrolidone. commercial PVP have molar masses in the range of approx. 2500-750,000 g / mol and are hygroscopic powder 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

which are produced industrially by base-catalyzed polyaddition of ethylene oxide (oxirane) in systems containing mostly small amounts of water with ethylene glycol as the starting molecule. They have molar masses in the range of approx. 200-5,000,000 g / mol, corresponding to degrees of polymerization n of approx. 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 (molar mass: approx. 15,000-> 250,000 g / mol), which is mainly due to Hydrolysis of the collagen contained in animal skin and bones under acidic or alkaline Conditions is won. The amino acid composition of the gelatin corresponds largely that of the collagen from which it was obtained and varies depending on it Provenance. The use of gelatin as a water-soluble coating material is particularly in the Pharmaceuticals in the form of hard or soft gelatin capsules are extremely widespread. In the form of Gelatine is found in films because of its high level compared to the abovementioned polymers Price only minor use.

In the context of the present invention, portioned portions according to the invention are also preferred Detergents whose bags are made of water-soluble film made of at least one polymer from the Starch and starch derivatives group, cellulose and cellulose derivatives, in particular methyl cellulose and Mixtures of this consists.

Starch is a homoglycan, with the glucose units linked α-glycosidically. Strength is made up of two components of different molecular weights: approx. 20-30% straight chain amylose (MW. approx. 50,000-150,000) and 70-80% branched chain amylopectin (MG. approx. 300,000-2,000,000), as well as small amounts of lipids, phosphoric acid and cations contain. While the amylose is long, helical forms intertwined chains with about 300-1200 glucose molecules, the chain branches at Amylopectin after an average of 25 glucose units through 1,6 binding to one knot-like structures with about 1500-12000 molecules of glucose. In addition to pure starch are used to manufacture Water-soluble pouches within the scope of the present invention also contain starch derivatives polymer-analogous reactions from starch are available. Such chemically modified starches include, for example, products from esterifications or etherifications in which Hydroxy hydrogen atoms have been substituted. But also strengths in which the hydroxy groups with functional groups that are not bound via an oxygen atom work as a starch derivative. The starch derivatives group, for example Alkaline starches, carboxymethyl starch (CMS), starch esters and ethers and amino starches.

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

Preferred bags made of water-soluble film consist of a polymer with a molecular weight between 5000 and 500,000 daltons, preferably between 7500 and 250,000 daltons and especially between 10,000 and 100,000 daltons. The water-soluble film that forms the pouch preferably has a thickness of 1 to 150 microns, preferably from 2 to 100 microns, particularly preferably from 5 to 75 μm and in particular from 10 to 50 μm.

Claims (19)

1. Containing automatic dishwashing detergent a) 1 to 60% by weight of non-aqueous solvent (s), b) 0.1 to 70 wt .-% of copolymers a) unsaturated carboxylic acids b) monomers containing sulfonic acid groups c) optionally further ionic or nonionic monomers c) 5 to 30% by weight of nonionic surfactant (s). 2. Automatic dishwashing detergent according to claim 1, characterized in that the / non-aqueous solvent (s) is / are selected from the group of polyethylene glycols and Polypropylene glycols, glycerin, glycerol carbonate, triacetin, ethylene glycol, propylene glycol, Propylene carbonate, hexylene glycol, ethanol and n-propanol and / or iso-propanol. 3. Automatic dishwashing detergent according to one of claims 1 or 2, characterized in that that it is the non-aqueous solvent (s) in amounts of 5 to 50 wt .-%, preferably from 7.5 to 40% by weight and in particular from 10 to 30% by weight, in each case based on the total funds. 4. Automatic dishwashing agent according to one of claims 1 to 3, characterized in that it contains, as ingredient b), one or more copolymers which have 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),

contain, in which m and p each represent an integer between 1 and 2000 and Y stands for a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -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. 5. Automatic dishwashing detergent according to one of claims 1 to 4, characterized in that that there are additionally one or more substances from the group of acidifying agents, Contains chelating agents or the deposit-inhibiting polymers. 6. Automatic dishwashing detergent according to one of claims 1 to 5, characterized in that that it is 5 to 25% by weight, preferably 6 to 22.5% by weight, particularly preferably 7.5 to 20 % By weight and in particular 8 to 17.5% by weight of nonionic surfactant (s). 7. Automatic dishwashing detergent according to one of claims 1 to 6, characterized in that that it is the sulfonated copolymer (s) in amounts of 0.25 to 50 wt .-%, preferably from 0.5 to 35% by weight, particularly preferably from 0.75 to 20% by weight and in particular from 1 contains up to 15 wt .-%. 8. Automatic dishwashing detergent according to one of claims 1 to 7, characterized in that that the content of free, i.e. H. not in the form of water of hydration and / or constitutional water water present below 2% by weight, preferably below 1% by weight and in particular even is less than 0.5% by weight, based in each case on the agent. 9. Automatic dishwashing detergent according to one of claims 1 to 8, characterized in that it continues a) 0.1 to 1.0 wt .-% of one or more structurants from the group of bentonites and / or at least partially etherified sorbitols and b) 5.0 to 30% by weight of one or more thickeners from the group of the carbonates, sulfates and amorphous or crystalline disilicates
contains. 10. Automatic dishwasher detergent according to claim 9, characterized in that as Structure donor Montmorillonite can be used. 11. Automatic dishwashing detergent according to one of claims 9 or 10, characterized characterized in that double-etherified sorbitols, especially dibenzylidene sorbitol, be used. 12. Automatic dishwashing detergent according to one of claims 9 to 11, characterized in that that the structuring agent 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 whole means. 13. Automatic dishwashing detergent according to one of claims 9 to 12, characterized in that that the average particle size of the bleaches and thickeners as well as the optional Builder to be used less than 75 microns, preferably less than 50 microns and in particular less than 25 µm. 14. Automatic dishwashing detergent according to one of claims 1 to 13, characterized in that that there is an additional 20 to 50% by weight of one or more water-soluble builders, preferably citrates and / or phosphates, preferably alkali metal phosphates with particular Preference for pentasodium or pentapotassium triphosphate (sodium or Potassium tripolyphosphate) contains. 15. Automatic dishwashing detergent according to claim 14, characterized in that it is the or the water-soluble builders (e) in amounts of 22.5 to 45% by weight, preferably 25 up to 40% by weight and in particular from 27.5 to 35% by weight, in each case based on the total Means, contains. 16. Automatic dishwashing detergent 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% by weight, of a polymeric thickener, preferably from the group of the polyurethanes or the modified polyacrylates, with particular preference for thickeners of the formula XV


in which R ^{3 represents} H or a branched or unbranched C _1-4 alk (en) yl radical, X represents NR ⁵ or O, R ^{4 represents} an optionally alkoxylated branched or unbranched, possibly substituted C _8-22 alk (en ) yl radical, R ^{5 is} H or R ⁴ and n is a natural number. 17. Automatic dishwashing detergent according to one of claims 1 to 13, characterized in that that there are additionally enzymes and / or enzyme preparations, preferably solid and / or liquid protease preparations and / or amylase preparations, in amounts of 1 to 5% by weight, preferably from 1.5 to 4.5 and in particular from 2 to 4% by weight, in each case based on the total funds. 18. Automatic dishwashing detergent according to one of claims 1 to 18, characterized in that it has a viscosity of 500 to 5000 mPas, preferably from 1000 to 4000 mPas and in particular from 1300 to 3000 mPas. 19. Automatic dishwasher detergent according to one of claims 1 to 19, characterized in that that the pH of a 1 wt .-% solution of the composition in distilled water between 7 and 11, preferably between 8 and 10 and in particular between 8.5 and 9.5 lies.