EP1404790B1 - Aqueous "3 in 1" dish washer agent - Google Patents

Abstract

Liquid aqueous machine dishwasher products comprising a) 20 to 50% by weight of one or more water-soluble builder(s), b) 0.1 to 70% by weight of copolymers of i) unsaturated carboxylic acids ii) monomers containing sulfonic acid groups iii) optionally further ionic or nonionogenic monomers c) 5 to 30% by weight of nonionic surfactant(s). Also, the composition packaged in portions in a water-soluble enclosure.

Description

The present invention relates to liquid means for cleaning dishes in a domestic dishwasher. In particular, the invention relates to water-based liquid dishwashing detergents for machine dishwashing.

Domestic dishwashing detergents are usually offered in the form of powders or, more recently, tablets (tablets). So far, the supply form of a liquid has only played a minor role in the market in this sector. Compared to the fixed supply forms, however, liquids have advantages in terms of dosage and not to be underestimated aesthetic product advantages that make this form of supply interesting. Thus, there is also a broad state of the art both non-aqueous, mostly solvent-based and aqueous dishwashing detergents for washing dishes in a domestic dishwasher.

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

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

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

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

Viscose-elastic thixotropic dishwashing detergents containing 0.001 to 5% by weight of surfactant and enzymes and an enzyme stabilization system of boric acid and polyhydroxy compounds are described in International Patent Application WO93 / 21299 (Procter & Gamble). The agents disclosed herein also contain from 0.1% to 10% by weight of one or more thickeners.

Machine-washed dishes are often subject to more stringent requirements today than manually-washed dishes. So even a completely cleaned of leftovers dishes is then rated as not flawless if it has after dishwasher washing whitish, based on water hardness or other mineral salts stains that come from lack of wetting agent from dried water droplets.

In order to obtain crystal-clear and spotless dishes, one uses therefore successfully today rinse aid. The addition of rinse aid at the end of the washing program ensures that the water runs as completely as possible from the items to be washed, so that the different surfaces at the end of the washing program are residue-free and flawless gloss.

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

These so-called "2in1" products lead to a simplification of handling and relieve the consumer of the burden of additional dosage of two different products (cleaner and rinse aid). Nevertheless, two metering operations are required to operate a domestic dishwasher at intervals because after a certain number of rinses the regenerating salt must be replenished in the water softening system of the machine. These water softening systems consist of ion exchange polymers which soften the hard water entering the machine and are regenerated by a rinsing with salt water following the washing program.

Products which combine the conventional detergents, rinse aids and a salt substitute function as so-called "3in1" products have recently been described in the prior art. These products are only available as solids (tablets).

The present invention was based on the object to provide a pourable and thus easily and quantitatively freely dosed product that must be dosed only once per application, without even after a higher number of rinsing cycles, the dosage of another product and thus a double dosing necessary would. A liquid to gel-like product should be provided which, in addition to the "built-in rinse aid", eliminates the need to refill the regeneration brine tank, further simplifying handling. In doing so, the performance of the product should reach or exceed the performance level of conventional three-product dosing (salt-detergent rinse aid) or novel two-product dosing ("2in1" rinse-aid). The products to be provided should be superior to conventional means in terms of their many properties. In particular, the dichotomy that occurs with many pourable products - benefits in certain properties (flowability, emptiness, attractive product appearance, etc.) are associated with disadvantages in other properties (settling, storage stability, performance, etc.) - should be overcome. It therefore existed also the task to provide means that combine beneficial rheological properties (flowability, emptiness, etc.), advantageous product characteristics (appearance, cleaning power, storage stability, etc.) and a technically easy to implement and inexpensive to carry out production together.

It has now been found that castable automatic dishwashing detergents having the abovementioned positive properties on the basis of water as solvent can be formulated if these agents contain certain sulfonic acid-containing polymers and nonionic surfactants.

1. a) 20 bis 50 Gew.-% eines oder mehrerer wasserlöslicher Phosphate,
2. b) 0,1 bis 70 Gew.-% an Copolymeren aus
   • i) ungesättigten Carbonsäuren
   • ii) Sulfonsäuregruppen-haltigen Monomeren
   • iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren
3. c) 5 bis 30 Gew.-% nichtionische(s) Tensid(e).

The present invention therefore relates, in a first embodiment, to aqueous liquid dishwashing detergents containing

1. a) 20 to 50% by weight of one or more water-soluble phosphates,
2. b) 0.1 to 70 wt .-% of copolymers
   • i) unsaturated carboxylic acids
   • ii) sulfonic acid group-containing monomers
   • iii) optionally further ionic or nonionic monomers
3. c) 5 to 30% by weight of nonionic surfactant (s).

As ingredient a) the agents according to the invention contain one or more water-soluble phosphates. These water-soluble builders are used in the compositions of the invention especially for binding calcium and magnesium. These builders which are preferred in the context of the invention in amounts of 22.5 to 45 wt .-%, preferably from 25 to 40 wt .-% and in particular from 27.5 to 35 wt .-%. in each case based on the total agent, are present, phosphates. For the detergents according to the invention, pentasodium tripolyphosphate is generally preferred. In the case of the alkali metal salts, the potassium salts are to be preferred to the sodium salts, since they often have a higher water solubility.

The aqueous liquid dishwashing detergents contain, as water-soluble builders, phosphates, preferably alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate).

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

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

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

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

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals. Na ₄ P ₂ O ₇ is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.

Condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ results in higher mol. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: melting or annealing phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The industrially important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is a water-free or with 6 H ₂ O crystallizing a non-hygroscopic white water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25% K ₂ O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry.

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

organize.

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

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

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

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

As second constituent b), the agents according to the invention comprise copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers. These copolymers cause the dishware treated with such agents to become significantly cleaner in subsequent cleanings than do the dishware which has been rinsed by conventional means.

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

The invention is characterized by an improved "cleanability" of the treated substrates in subsequent cleaning operations and by a significant reduction in the drying time compared to comparable agents without the use of sulfonic acid-containing polymers.

Drying time in the context of the teaching according to the invention is generally understood to mean the meaning of the word, ie the time that elapses until a dish surface treated in a dishwasher has dried, but in particular the time that elapses, up to 90% with a cleaning or Rinse aid is dried in concentrated or diluted form treated surface.

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

R ¹ (R ² ) C = C (R ³ ) COOH (I),

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

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

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

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

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

Preferred among these monomers are those of the formulas IIa, IIb and / or IIc,

H ₂ C = CH-X-SO ₃ H (IIa),

H ₂ C = C (CH ₃ ) -X-SO ₃ H (IIb),

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

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

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

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

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

besonders bevorzugt.In summary, copolymers are made of

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

particularly preferred.

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

Particularly preferred copolymers consist of

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In summary, dishwashing detergents according to the invention are preferred which comprise as ingredient b) one or more copolymers which contain structural units of the formulas III and / or IV and / or V and / or VI and / or VII and / or VIII

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

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

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

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

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

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

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

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

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

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

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

As ingredient c) the agents according to the invention contain one or more nonionic surfactants, in short nonionic surfactants. The amounts in which the nonionic surfactants are used are, according to the invention, between 5 and 30% by weight, preference being given to machine dishwashing agents according to the invention which contain 5 to 25% by weight, preferably 6 to 22.5% by weight preferably from 7.5 to 20% by weight and in particular from 8 to 17.5% by weight of nonionic surfactant (s).

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

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

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

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

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

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

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

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

[Z] is preferably 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 converted by reaction with Feftsäuremethylestem in the presence of an alkoxide as a catalyst in the desired polyhydroxy fatty acid amides.

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

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

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

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

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

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

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

More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ^® SLF-18 from Olin Chemicals.

A further preferred rinse aid according to the invention contains nonionic surfactants of the formula

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In addition to the ingredients a) to c), the compositions according to the invention contain water and, if appropriate, further customary ingredients of cleaning agents. The agents can be completely water-based, i. contain no further solvents; but it is also possible that in addition to the water further nonaqueous solvents are included in the inventive compositions. This may for example result from certain ingredients being supplied as a solution in non-aqueous solvents, or certain formulations being more stable or having better rheological properties in the presence of certain non-aqueous solvents.

Preferably used nonaqueous solvents come, for example, from the groups of the mono-alcohols, diols, triols or polyols, the ethers, esters and / or amides. Particular preference is given to nonaqueous solvents which are water-soluble, "water-soluble" solvents in the context of the present application being solvents are that at room temperature with water completely, ie without miscibility gap, are miscible.

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

Particularly preferred automatic dishwashing detergents are characterized by containing one or more nonaqueous solvents selected from the group of polyethylene glycols and polypropylene glycols, glycerin, glycerin carbonate, triacetin, ethylene glycol, propylene glycol, propylene carbonate, hexylene glycol, ethanol, and n- Propanol and / or iso-propanol.

Preferred automatic dishwasher detergents according to the invention are characterized in that they additionally contain from 5 to 50% by weight, preferably from 7.5 to 40% by weight and in particular from 10 to 30% by weight, of nonaqueous solvents, in each case based on the total agent , contain.

In addition to the builders described above, bleaches, bleach activators, enzymes, silver protectants, dyes and fragrances, etc., are preferred ingredients of automatic dishwashing detergents. In addition, further ingredients may be present, automatic dishwashing agents according to the invention being preferred which additionally contain one or more substances from the group of acidifying agents, chelating agents or coating-inhibiting polymers.

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

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

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

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

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

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

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

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

1. a) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt wie Gluconsäure,
2. 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),
3. 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,
4. d) Aminophosphonsäuren wie Ethylendiamintetra(methylenphosphonsäure), Diethylentriamin-penta(methylenphosphonsäure) oder Nitrilotri(methylenphosphonsäure),
5. e) Phosphonopolycarbonsäuren wie 2-Phosphonobutan-1,2,4-tricarbonsäure sowie
6. f) Cyclodextrine.

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

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

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

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

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

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

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

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

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

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

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.

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

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

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives which, in addition to cobuilder properties, also have a bleach-stabilizing action.

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

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

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

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

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

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

In addition to the substances from the mentioned substance classes, the agents according to the invention may contain further customary ingredients of cleaning agents, in particular bleaching agents, bleach activators, enzymes, silver protectants, dyes and fragrances being of importance. These substances will be described below.

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

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

Bleach activators which aid in the action of the bleaches have already been mentioned above as a possible ingredient of the rinse aid particles. Known bleach activators are compounds which contain one or more N- or O-acyl groups, such as substances from the class of the anhydrides, the esters, the imides and the acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.

As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methylsulfate (MMA), and enol esters and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyl lactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam. Hydrophilic substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used.

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

Bleach activators from the group of the polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), are preferred -Methyl-morpholinium acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, particularly 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-% based on the total agent used.

Bleach-enhancing transition metal complexes, in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) Complexes of the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate are used in conventional amounts, preferably in an amount up to 5 wt .-%, in particular of 0.0025 wt % to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the total agent used. But in special cases, more bleach activator can also be used.

Suitable enzymes in the detergents according to the invention are, in particular, those from the classes of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of soils such as protein, fat or starchy stains. For bleaching and oxidoreductases can be used. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens, as well as enzymatically-derived variants derived from their genetically modified variants. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. In this case, enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or O-xidases have proven to be suitable in some cases. Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases.

The enzymes may be adsorbed to carriers or embedded in encapsulants to protect against premature degradation. The proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt .-%.

Particularly preferred in the context of the present invention is the use of liquid enzyme formulations. In this case, preference is given to automatic dishwashing agents according to the invention which additionally contain enzymes and / or enzyme preparations, preferably solid and / or liquid protease preparations and / or amylase preparations, in amounts of from 1 to 5% by weight, preferably from 1.5 to 4, 5 and in particular from 2 to 4 wt .-%, each based on the total agent included.

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

In order to improve the aesthetics of the compositions made according to the invention, it may (or parts thereof) be colored with suitable dyes. Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and against light and no pronounced substantivity to the substrates to be treated with the agents such as glass, ceramic or plastic dishes, not to stain them.

The automatic dishwashing compositions of the present invention can be further improved with respect to corrosion protection on metal surfaces (in particular on silver surfaces) and / or with regard to the protection of glassware against glass corrosion.

It is a well-known fact that silver "starts up" even when it is not in use. It is only a matter of time before it gets dark, brownish, bluish to blue-black spots or discolored altogether and is thus "tarnished" in common usage. Also in the automated cleaning of silverware occur in practice again and again problems in the form of tarnishing and discoloration of the silver surfaces. Silver can here on sulphurous substances in the rinse water dissolved or dispersed, react, because when cleaning dishes in household dishwashers (HGSM) food particles and thus, inter alia, mustard, peas, egg and other sulfur-containing compounds such as cystine and cysteine are introduced into the rinsing liquor. Also, the much higher temperatures during the mechanical rinsing and the longer contact times with the sulfur-containing food residues favor the tarnishing of silver in comparison to manual rinsing. Due to the intensive cleaning process in the dishwasher, the silver surface is also completely degreased and thus more sensitive to chemical influences.

When using active chlorine-containing cleaner, the tarnishing by sulfur-containing compounds can be largely prevented because these compounds are converted by oxidation of the sulfidic functions in secondary reaction to sulfones or sulfates.

However, the problem of silver tarnishing has again become acute when active oxygen compounds such as sodium perborate or sodium percarbonate have been used as an alternative to the active chlorine compounds which serve to eliminate bleachable soils such as tea stains / tea stains, coffee stains, vegetable dyes, lipstick residues and the like.

These active oxygen compounds are used together with bleach activators, especially in modern low-alkaline machine dishwashing detergents of the new generation of cleaners. These modern compositions generally consist of the following functional components: builder component (complexing agent / dispersant), alkali carrier, bleach system (bleach + bleach activator), enzymes and wetting agents (surfactants).

The silver surfaces are generally more sensitive to the changed formulation parameters of the new active chlorine-free cleaner generation with lowered pH values and activated oxygen bleaching. During the mechanical rinsing, these agents release the actually bleaching agent hydrogen peroxide or active oxygen during the cleaning cycle. The bleaching effect of the active oxygen-containing cleaner is enhanced by bleach activators, so that even at low temperatures, a good bleaching effect is achieved. In the presence of these bleach activators, peracetic acid forms as a reactive intermediate. Under these changed purge conditions form in the presence of silver not only sulfidic but by the oxidizing attack of intermediately formed peroxides or the active oxygen preferably oxidic deposits on the silver surfaces. Under high salt load additionally chloridic deposits can arise. The tarnishing of the silver is also reinforced by higher residual water hardness during the cleaning cycle.

Therefore, the cleaning agents according to the invention may contain corrosion inhibitors for the protection of the items to be washed or the machine, with particular silver protectants being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface. In chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds.

The problems mentioned can be solved even better with the compositions according to the invention if, in addition to the organic silver protectants or in their place, certain corrosion inhibitors are incorporated into the compositions. Another subject of the present invention are therefore inventive liquid aqueous machine dishwashing detergents, which are characterized in that they additionally contain one or more redox-active substances from the group of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium Salts and / or complexes, wherein the metals are preferably present in one of the oxidation states II, III, IV, V or VI.

Instead of or in addition to the silver protectants described above, for example the benzotriazoles, redox-active substances are used in this preferred embodiment. These substances are inorganic redox-active substances from the groups mentioned, preference being given to metal salts and / or metal complexes in which the metals are present in one of the oxidation states II, III, IV, V or VI.

The metal salts or metal complexes used should be at least partially soluble in water. The counterions suitable for salt formation comprise all customary mono-, di- or tri-positively negatively charged inorganic anions, eg. As oxide, sulfate, nitrate, fluoride, but also organic anions such. Stearate.

Metal complexes in the context of the invention are compounds which consist of a central atom and one or more ligands and optionally additionally one or more of the above-mentioned. Anions exist. The central atom is one of the o.g. Metals in one of the above Oxidation states. The ligands are neutral molecules or anions that are mono- or polydentate; The term "ligand" within the meaning of the invention is e.g. in "Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, page 2507" explained in more detail. If, in a metal complex, the charge of the central atom and the charge of the ligand (s) do not add up to zero, either one or more of the above may be provided, depending on whether there is cationic or anionic charge excess. Anions or one or more cations, e.g. As sodium, potassium, ammonium ions, for the charge balance. Suitable complexing agents are e.g. Citrate, acetylacetonate or 1-hydroxyethane-1,1-diphosphonate.

The definition of "oxidation state" common in chemistry is e.g. in "Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1991, page 3168" reproduced.

Particularly preferred metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1,1- diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) ₃ and mixtures thereof. so that preferred liquid aqueous machine dishwashing detergents according to the invention are characterized in that the metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn ( II) - [1-hydroxyethane-1,1-diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) ₃ .

In these metal salts or metal complexes are generally commercially available substances that can be used for the purpose of silver corrosion protection without prior purification in the compositions of the invention. Thus, for example, the mixture of pentavalent and tetravalent vanadium (V ₂ O ₅ , VO ₂ , V ₂ O ₄ ) known from the SO ₃ preparation (contact method) is suitable, as is the case by diluting a Ti (SO ₄ ) ₂ - Solution resulting titanyl sulfate, TiOSO ₄ .

The inorganic redox-active substances, in particular metal salts or metal complexes are preferably coated, i. completely coated with a waterproof, but easily soluble in the cleaning temperatures material to prevent their premature decomposition or oxidation during storage. Preferred coating materials, which are applied by known methods, such as Sandwik from the food industry, are paraffins, microwaxes, waxes of natural origin such as carnauba wax, candellila wax, beeswax, higher melting alcohols such as hexadecanol, soaps or fatty acids. The coating material, which is solid at room temperature, is applied in the molten state to the material to be coated, e.g. in that finely divided material to be coated is spun in continuous stream through a likewise continuously produced spray zone of the molten coating material. The melting point must be chosen so that the coating material easily dissolves or melts during the silver treatment. The melting point should ideally be in the range between 45 ° C and 65 ° C and preferably in the range 50 ° C to 60 ° C.

The metal salts and / or metal complexes mentioned are preferably present in the liquid aqueous machine dishwashing detergents according to the invention in an amount of from 0.05 to 6% by weight, preferably from 0.2 to 2.5% by weight, based on the total agent ,

In a further embodiment, the present invention relates to agents which have been further improved in terms of corrosion protection on glass surfaces.

An important criterion for the evaluation of a machine dishwashing detergent, apart from its cleaning performance, is the visual appearance of the dry dishes after cleaning. Possibly occurring calcium carbonate deposits on dishes or in the machine interior, for example, affect customer satisfaction and thus have causal influence on the economic success of such a detergent. Another longstanding problem with automatic dishwashing is the corrosion of glassware, which can usually manifest itself by the appearance of turbidity, streaks and scratches, but also by irritation of the glass surface. The observed effects are based essentially on two processes, the leakage of alkali and alkaline earth ions from the glass in conjunction with hydrolysis of the silicate network, on the other hand in a deposition of silicate compounds on the glass surface.

The stated problems can be solved even better with the compositions according to the invention if, in addition to the ingredients described above, certain glass corrosion inhibitors are incorporated in the compositions. Another object of this invention are therefore liquid aqueous machine dishwashing detergents according to the invention, which additionally contain one or more magnesium and / or zinc salts and / or magnesium and / or zinc complexes.

A preferred class of compounds that can be added to the compositions of the invention to prevent glass corrosion are insoluble zinc salts. These can accumulate on the glass surface during the dishwashing process, preventing the dissolution of metal ions from the glass network and the hydrolysis of the silicates. In addition, these insoluble zinc salts also prevent the deposition of silicate on the glass surface, so that the glass is protected from the consequences described above.

Insoluble zinc salts in the context of this preferred embodiment are zinc salts which have a solubility of a maximum of 10 grams of zinc salt per liter of water at 20 ° C. Examples of particularly preferred insoluble zinc salts according to the invention are zinc silicate, zinc carbonate, zinc oxide, basic zinc carbonate (Zn ₂ (OH) ₂ CO ₃ ), zinc hydroxide, zinc oxalate, zinc monophosphate (Zn ₃ (PO ₄ ) ₂ ), and zinc pyrophosphate (Zn ₂ (P ₂ O ₇ )).

The zinc compounds mentioned are used in the compositions according to the invention in amounts which have a content of the zinc ions of between 0.02 and 10% by weight, preferably between 0.1 and 5.0% by weight and in particular between 0.2 and 1.0 wt .-%, each based on the agent effect. The exact content of the agents on the zinc salt or zinc salts is of course dependent on the type of zinc salts - the less soluble the zinc salt used, the higher its concentration should be in the inventive compositions.

Since the insoluble zinc salts remain largely unchanged during the Geschirreinigungsvorgangs, the particle size of the salts is a criterion to be observed, so that the salts do not adhere to glassware or machine parts. Here, preference is given to aqueous liquid dishwashing detergents according to the invention in which the insoluble zinc salts have a particle size of less than 1.7 millimeters.

If the maximum particle size of the insoluble zinc salts is below 1.7 mm, insoluble residues in the dishwasher are not to be feared. Preferably, the insoluble zinc salt has an average particle size which is significantly below this value in order to further minimize the risk of insoluble residues, for example an average particle size of less than 250 μm. Again, this is even more true the less the zinc salt is soluble. In addition, the glass corrosion inhibiting effectiveness increases with decreasing particle size. For very poorly soluble zinc salts, the average particle size is preferably below 100 microns. For still less soluble salts, it may be even lower; For example, average particle sizes below 100 μm are preferred for the very poorly soluble zinc oxide.

Another preferred class of compounds are magnesium and / or zinc (s) of at least one monomeric and / or polymeric organic acid. The effect of this is that even with repeated use, the surfaces of glassware do not change corrosively, in particular, no turbidity, streaks or scratches, but also iridescence of the glass surfaces are not caused.

Compositions according to the invention containing these substances are also preferred. Liquid aqueous machine dishwashing detergents containing one or more magnesium and / or Zinc salt (s) of at least one monomeric and / or polymeric organic acid, are further preferred embodiments of the present invention.

Although, according to the invention, all magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids may be included in the claimed compositions, as described above, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids are derived from the Groups of unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the amino acids and / or the polymeric carboxylic acids are preferred. Within these groups, the acids mentioned below are again preferred in the context of the present invention:

From the group of unbranched saturated or unsaturated monocarboxylic acids: methanoic acid (formic acid), ethanoic acid (acetic acid), propionic acid (propionic acid), pentanoic acid (valeric acid), hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), Decanoic acid (capric acid), undecanoic acid, dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid (myristic acid), pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid (margaric acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid) , Hexacosanoic acid (cerotic acid), triacotinic acid (melissinic acid), 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidinic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid (elaidic acid), 9c, 12c Octadecadienoic acid (linoleic acid), 9t, 12t-octadecadienoic acid (linoleic acid ) and 9c, 12c, 15c-octadecatreic acid (linolenic acid).

From the group of branched saturated or unsaturated monocarboxylic acids: 2-methylpentanoic acid, 2-ethylhexanoic acid, 2-propylheptanoic acid, 2-butyloctanoic acid, 2-pentylnonanoic acid, 2-hexyldecanoic acid, 2-heptylundecanoic acid, 2-octyldodecanoic acid, 2-nonyltridecanoic acid, 2-decyltetradecanoic acid, 2-undecylpentadecanoic acid, 2-dodecylhexadecanoic acid, 2-tridecylheptadecanoic acid, 2-tetradecyloctadecanoic acid, 2-pentadecylnonadecanoic acid, 2-Hexadecyleicosansäure, 2-Heptadecylheneicosansäure contains.

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

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

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

From the group of hydroxy acids: hydroxyphenylacetic acid (mandelic acid), 2-hydroxypropionic acid (lactic acid), hydroxysuccinic acid (malic acid), 2,3-dihydroxybutanedioic acid (tartaric acid), 2-hydroxy-1,2,3-propanetricarboxylic acid (citric acid), ascorbic acid, 2-hydroxybenzoic acid (salicylic acid), 3,4,5-trihydroxybenzoic acid (gallic acid).

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

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

From the group of polymeric carboxylic acids: polyacrylic acid, polymethacrylic acid, alkylacrylamide / acrylic acid copolymers, alkylacrylamide / methacrylic acid copolymers, alkylacrylamide / methylmethacrylic acid copolymers, Copolymers of unsaturated carboxylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone-vinyl acrylate copolymers.

The spectrum of the inventively preferred zinc salts of organic acids, preferably organic carboxylic acids, ranging from salts which are difficult or insoluble in water, ie a solubility below 100 mg / L, preferably below 10 mg / L, in particular have no solubility, to such salts having a solubility in water above 100 mg / L, preferably above 500 mg / L, more preferably above 1 g / L and in particular above 5 g / L (all solubilities at 20 ° C water temperature). The first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate, and the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc acetate and zinc gluconate:

In a further preferred embodiment of the present invention, the agents according to the invention comprise at least one zinc salt but no magnesium salt of an organic acid, which is preferably at least one zinc salt of an organic carboxylic acid, more preferably a zinc salt selected from zinc stearate, zinc oleate, zinc gluconate, zinc acetate , Zinc acetate and / or zinc citrate. Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.

An agent preferred in the context of the present invention contains zinc salt in amounts of from 0.1 to 5% by weight, preferably from 0.2 to 4% by weight and in particular from 0.4 to 3% by weight, or zinc in oxidized form (calculated as Zn ²⁺ ) in amounts of from 0.01 to 1% by weight, preferably from 0.02 to 0.5% by weight and in particular from 0.04 to 0.2% by weight , in each case based on the total weight of the automatic dishwashing detergent.

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

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

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

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

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

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

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

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

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

Commercially available thickener based on polyurethane are, for example, under the names Acrysol ^® PM 12 V (mixture of 3-5% modified starch and 14-16% polyurethane resin in water, Rohm & Haas), Borchigel ^® L75-N (non-ionic polyurethane dispersion, 50% in water, Borchers), Coatex ^® BR-100-P (PUR-dispersion, 50% in water / butyl glycol, Dimed), Nopco ^® DSX-1514 (polyurethane dispersion, 40% in water / Butyltrigylcol, Henkel-Nopco), thickener QR 1001 (20% polyurethane emulsion in water / Digylcolether, Rohm & Haas) and Rilanit ^® VPW-3116 (polyurethane dispersion, 43% in water, Henkel) available.

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

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

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

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

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

Products of formula XVa are commercially available for example under the name Acusol ^® 820 (Rohm & Haas) in the form of 30 wt .-% strength dispersion in water available. In the said commercial product R ^{4 is} a stearyl radical, R ⁸ is a hydrogen atom, R ⁷ is H or CH ₃ and the degree of ethoxylation a is 20.

in der R³ für H oder einen verzweigten oder unverzweigten C_1-4-Alk(en)ylrest, X für N-R⁵ oder O, R⁴ für einen gegebenenfalls alkoxylierten verzweigten oder unverzweigten, evtl. substituierten C_8-22-Alk(en)ylrest, R⁵ für H oder R⁴ und n für eine natürliche Zahl steht, enthalten.Liquid automatic dishwasher detergents which are 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 wt .-% and in particular 0.1 to 1.5 wt .-%, of a polymeric thickener, preferably from the group of polyurethanes or modified polyacrylates, with particular preference of thickeners of formula XV

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

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

In a further embodiment, the present invention relates to agents which have been further improved in terms of meterability by the consumer.

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

However, it may also be desirable to provide the consumer with pre-portioned means according to the invention so that he can use the dosing advantages known to him from the "tablet" offering and combine them with the rapid dissolution and release rates as well as the performance advantages of the agents according to the invention. Such pre-portioned agents according to the invention may also be present in water-insoluble packaging, so that the consumer must open them before use in a suitable manner. However, it is also possible and preferred to package portioned agents according to the invention so that the consumer directly, i. E. together with the packaging, in the dishwasher can give. Such packages include water-soluble or decomposable packages such as bags of water-soluble film (so-called pouches), bags or other packaging of water-soluble or decomposable nonwovens or flexible or rigid bodies of water-soluble polymers, preferably in the form of filled hollow body, which for example by deep drawing, injection molding , Blow molding, calendering, etc. can be made.

Another object of the present invention are therefore inventive liquid aqueous machine dishwashing detergent, which are packaged in portions in a water-soluble wrapper.

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

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

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

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

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

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

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

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

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

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

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

contain.

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

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

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

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

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

The polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ^® (Clariant). In the present invention, particularly suitable polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^® 4-88, Mowiol ^® 5-88 and Mowiol ^® 8-88.

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

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

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

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

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

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

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

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

H- [O-CH ₂ -CH ₂ ] _n -OH

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

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

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

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

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

Preferred casings of at least partially water-soluble film comprise at least one polymer having a molecular weight between 5,000 and 500,000 g / mol, preferably between 7,500 and 250,000 g / mol and in particular between 10,000 and 100,000 g / mol. The envelope has different depending on the manufacturing process Material thicknesses, preference being given to liquid aqueous machine dishwashing detergents according to the invention in which the wall thickness of the casing is 10 to 5000 μm, preferably 20 to 3000 μm, particularly preferably 25 to 2000 μm and in particular 100 to 1500 μm.

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

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

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

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

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

It corresponds to a particularly preferred embodiment of the invention that the less well water-soluble areas or not water-soluble areas or only at higher temperature water-soluble portions of the enclosure are areas of a material which chemically substantially corresponds to those of the water-soluble or water-soluble areas, but has a higher layer thickness and / or a modified degree of polymerization of the same polymer and / or a higher degree of crosslinking thereof Having polymer structure and / or a higher degree of acetalization (in PVAL, for example with saccharides, polysaccharides, such as starch) and / or has a content of water-insoluble salt components and / or has a content of a water-insoluble polymer. Even taking into account the fact that the wrapper does not dissolve completely, so detergent portions can be provided according to the invention, which have advantageous properties in the release of the water-based liquid Geschirreinigungsmittel in the respective fleet.

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

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

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

Another class of preferably usable stabilizers are the UV absorbers. UV absorbers can improve the light stability of the formulation ingredients. These are understood to be organic substances (light protection filters) which are able to absorb ultraviolet rays and to release the absorbed energy in the form of longer-wave radiation, for example heat. Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2 and / or 4 position. In addition, substituted benzotriazoles, such as the water-soluble benzenesulfonic acid-3- (2H-benzotriazol-2-yl) -4-hydroxy-5- (methylpropyl) monosodium salt (Ciba ^® Fast H), phenyl substituted in the 3-position acrylates (cinnamic acid derivatives) , optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's urocanic acid suitable. The biphenyl and especially stilbene derivatives which are available commercially as Tinosorb ^® FD or Tinosorb ^® FR available ex Ciba. 3-benzylidene camphor or 3-benzylidene norcampher and its derivatives, eg 3- (4-methylbenzylidene) camphor, 4-aminobenzoic acid derivatives, preferably 4- (dimethylamino) benzoic acid 2-ethylhexyl ester, 4- (UV-B absorber) Dimethylamino) benzoic acid 2-octyl ester and 4- (dimethylamino) benzoic acid amyl ester; Esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester, 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene); Esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomenthyl salicylate; Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzo-phenone, 2,2'-dihydroxy-4-methoxybenzophenone; Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate; Triazine derivatives, such as 2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine and Octyl Triazone or Dioctyl Butamido Triazone (Uvasorb HEB ^®); Propane-1,3-diones such as 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione; Ketotricyclo (5.2.1.0) decane derivatives. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts; Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts; Sulfonic acid derivatives of 3-Benzylidencamphers, such as 4- (2-oxo-3-bomylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and salts thereof.

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

UV absorbers can be present in the water-based liquid dishwashing detergents in amounts of up to 5% by weight, preferably up to 3% by weight, particularly preferably from 0.01 to 2.0 and in particular from 0.03 to 1% by weight ,

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

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

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

As already mentioned above, water-based liquid dishwashing detergents according to the invention can be packaged in such a way that the packaging is, on the one hand, water-soluble and, on the other hand, tight-fitting, i. to the environment is completed. In this case, according to the invention, two embodiments can be realized:

Thus, it is a preferred embodiment of the invention that the enclosure (s) is / are closed and contains at least one anhydrous gas which does not react with the water-based liquid dishwashing detergent, more preferably in an amount such that the total pressure within the sealed one Enclosure (s) is above the external pressure, more preferably at least 1 mbar above the external pressure. Very particularly preferred embodiments of these detergent portions according to the invention comprise at least one anhydrous gas which does not react with the water-based liquid dishwashing detergent in such an amount that the total pressure within the enclosed enclosure (s) is at least 5 mbar, more preferably at least 10 mbar , most preferably in the range of 10 mbar to 50 mbar above the outside pressure. Especially in the case of the preferred embodiments with a total pressure within the enclosure (s) which is significantly above the external pressure, it is possible to surprisingly reduce or even reliably prevent access of moisture or water to the interior of the enclosure. In the context of the present invention, "external pressure" is understood to mean the pressure which prevails on the environmental side of the enclosure (s) and acts on the exterior of the enclosure (s) at the time of filling the enclosure with the respective at least one anhydrous one Gas.

According to the invention, the enclosure (s) may either contain an anhydrous gas or may contain a plurality of anhydrous gases. In practice, pressurization of the enclosure (s) with a gas is preferred because of the associated lower cost. In the context of the present invention, "anhydrous" is understood to mean that the gas (s) are carefully dried before use in the detergent portions according to the invention and thus contain no or almost no water when used; a near-zero water content is preferred. The drying process can be done in any way known to those skilled in the art for this purpose. The aim is that the gases as possible no longer contain water that could react with the components in the detergent portions and thus could lead to a deterioration in the quality of such moisture or water sensitive components. Preferred washing or cleaning agent portions according to the invention comprise as gas (s) at least one anhydrous gas selected from the group consisting of N ₂ , noble gas (s), CO ₂ , N ₂ O, O ₂ , H ₂ , air, gaseous hydrocarbons, especially N ₂ , which is inexpensive everywhere and can be completely "dried" by methods known per se. The gases mentioned are advantageously inert to the components of the detergent preparation and are therefore also sometimes referred to as "inert gases" in the context of the present invention.

According to a further, likewise preferred embodiment of the detergent portion according to the invention, the enclosure (s) is / are closed and contain at least one substance which liberates a gas which does not react with the detergent preparation (s) in an amount upon reaction with water, that the total pressure within the enclosed enclosure (s) increases. Of particular advantage are those detergent portions in which the at least one substance contained in the enclosure (s) liberates the at least one gas in an amount upon reaction with water in such a way that the total pressure within the closed enclosure (s) is at least 1 mbar above the external pressure rises, preferably by at least 5 mbar, more preferably by a value in the range of 5 to 50 mbar higher than the external pressure. This embodiment is particularly advantageous in that its preparation compared to the embodiment in which the gas is contained in the enclosed enclosure, is greatly simplified, since only the at least one substance must be added, which in contact with moisture / water in the closed Surrounding generated at least one gas. Furthermore, any moisture that has penetrated the enclosure is immediately absorbed and reacted by the substance capable of reacting with water and is therefore no longer available for a deterioration in the quality of the components of the detergent preparation. Also conceivable are mixed forms of the detergent preparation in which from the beginning both (at least) an anhydrous gas in the closed enclosure is included as well as a substance capable of reacting with water. With this embodiment, the deterioration of the components of the compositions according to the invention can be prevented in a particularly good and efficient manner by the ingress of moisture or water.

According to a preferred embodiment of the invention, the water-releasing substance is a constituent of the detergent-active preparation and is more preferably a hygroscopic substance which is compatible with the components of the detergent-active preparation (s). This has, inter alia, the advantage that this substance (s) moisture or water, as it enters the interior of the enclosure, immediately absorbs gas forming the internal pressure within the enclosure increases to a value above the atmospheric pressure and so surprisingly makes it difficult or impossible to access further moisture or other water.

Examples of such substances include, but are not limited to, substances selected from the group consisting of hydrogen peroxide-containing substances, O-containing substances, OCO-containing substances, hydrides and carbides, more preferably a substance, which is selected from the group of percarbonates (particularly preferably sodium percarbonate), persulfates, perborates, peracids, M _A M _B H ₄ , in which M _{A is} an alkali metal (particularly preferably Li or Na) (for example LiAlH ₄ , NaBH ₄ , NaAlH ₄ ) and M _{B is} B or Al, or M ' ₂ C ₂ or M ^II C ₂ , where M' is a monovalent metal and M "is a divalent metal (e.g., CaC ₂ ).

Detergent portions are preferred according to the invention in which the anhydrous gas contained in the enclosure (s), with which the enclosure (s) are directly charged, is selected from the group consisting of N ₂ , noble gas (e), CO ₂ , N ₂ O, O ₂ , H ₂ , air, gaseous hydrocarbons or mixtures thereof. Preferred gas - or at least one of the preferred gases used - is N ₂ , due to the fact that nitrogen is available inexpensively everywhere at low cost and can be readily dried by conventional means, or can be stored dried.

Likewise preferred according to the invention are those detergent portions in which the at least one gas formed within the enclosure of the water or moisture-reactive substance is selected from the group CO ₂ , N ₂ , H ₂ , O ₂ , gaseous hydrocarbons, in particular Methane, ethane, propane or a mixture of several of the gases mentioned. The gases mentioned are advantageously inert to the components of the detergent-active preparation and are therefore also sometimes referred to as "inert gases" in the context of the present invention.

Claims (20)

1. Liquid aqueous machine dishwasher product comprising

   a) 20 to 50% by weight of one or more water-soluble phosphate(s),

   b) 0.1 to 70% by weight of copolymers of

   i) unsaturated carboxylic acids

   ii) monomers containing sulfonic acid groups

   iv) optionally further ionic or nonionogenic monomers

   c) 5 to 30% by weight of nonionic surfactant(s).
2. Liquid aqueous machine dishwasher product according to Claim 1, characterized in that it comprises, as water-soluble phosphates, alkali metal phosphates, particularly preferably pentasodium or pentapotassium phosphate (sodium or potassium tripolyphospate).
3. Liquid aqueous machine dishwasher product as claimed in either of Claims 1 and 2, characterized in that it comprises the water-soluble phosphate(s) in amounts of from 22.5 to 45% by weight, preferably from 25 to 40% by weight and in particular from 27.5 to 35% by weight, in each case based on the total composition.
4. Machine dishwasher product according to any of Claims 1 to 3, characterized in that it comprises, as ingredient b), one or more copolymers which contain structural units of the formulae III and/or IV and/or V and/or VI and/or VII and/or VIII
   
           -[CH₂-CHCOOH]_m-[CH₂-CHC(O)-Y-SO₃H]_p-     (III),
   
           -[CH₂-C(CH₃)COOH]_m-[CH₂-CHC(O)-Y-SO₃H]_p-     (IV),
   
           -[CH₂-C(CH₃)COOH]_m-[CH₂-C(CH₃)C(O)-Y-SO₃H]_p-     (VI),
   
           -[HOOCCH-CHCOOH]_m-[CH₂-CHC(O)-Y-SO₃H]_p-     (VII),
   
           -[HOOCCH-CHCOOH]_m-[CH₂-C(CH₃)C(O)O-Y-SO₃H]_p-     (VIII),
   
   in which m and p are in each case a whole natural number between 1 and 2000, and Y is a spacer group which is chosen from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, where spacer groups in which Y is -O-(CH₂)_n- where n = 0 to 4, is -O-(C₆H₄)-, is -NH-C(CH₃)₂ or -NH-CH(CH₂CH₃)- are preferred.
5. Machine dishwasher product as claimed in any of Claims 1 to 4, characterized in that it comprises the sulfonated copolymer(s) in amounts of from 0.25 to 50% by weight, preferably from 0.5 to 35% by weight, particularly preferably from 0.75 to 20% by weight and in particular from 1 to 15% by weight.
6. Machine dishwasher product as claimed in any of Claims 1 to 5, characterized in that it comprises 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. Machine dishwasher product as claimed in any of Claims 1 to 6, characterized in that it additionally comprises 5 to 50% by weight, preferably 7.5 to 40% by weight and in particular 10 to 30% by weight, of nonaqueous solvent(s), in each case based on the total product.
8. Machine dishwasher product as claimed in Claim 7, characterized in that that nonaquoeus solvent(s) is/are chosen from the group of polyethylene glycols and polypropylene glycols, glycerol, glycerol carbonate, triacetin, ethylene glycol, propylene glycol, propylene carbonate, hexylene glycol, ethanol, and n-propanol and/or isopropanol.
9. Machine dishwasher product as claimed in any of Claims 1 to 8, characterized in that it additionally comprises one or more substances from the group of acidifying agents, chelate complexing agents or of the deposit-inhibiting polymers.
10. Machine dishwasher product as claimed in any of Claims 1 to 9, characterized in that it additionally comprises 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 polyurethanes or of modified polyacrylates, particularly preferably thickeners of the formula IX

    

    in which R³ is H or a branched or unbranched C_1-4-alk(en)yl radical, X is N-R⁵ or O, R⁴ is an optionally alkoxylated branched or unbranched, possibly substituted C_8-22-alk(en)yl radical, R⁵ is H or R⁴, and n is a natural number.
11. Machine dishwasher product as claimed in any of Claims 1 to 10, characterized in that it additionally comprises enzymes and/or enzyme preparations, preferably solid and/or liquid protease preparations and/or amylase preparations, in amounts of from 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 product.
12. Machine dishwasher product as claimed in any of Claims 1 to 11, characterized in that it has a viscosity of from 500 to 5000 mPas, preferably from 1000 to 4000 mPas and in particular from 1300 to 3000 mPas.
13. Machine dishwasher product as claimed in any of Claims 1 to 12, characterized in that the pH of a 1% strength by weight 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.
14. Machine dishwasher product as claimed in any of Claims 1 to 13, characterized in that it additionally comprises one or more redox-active substances from the group of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and/or complexes, where the metals are preferably present in one of the oxidation states II, III, IV, V or VI.
15. Machine dishwasher product as claimed in Claim 14, characterized in that the metal salts and/or metal complexes are present in an amount of from 0.05 to 6% by weight, preferably 0.2 to 2.5% by weight, based on the total product, where preferred metal salts and/or metal complexes are chosen from the group MnSO₄, Mn(II) citrate, Mn(II) stearate, Mn(II) acetylacetonate, Mn(II) [1-hydroxyethane-1,1-diphosphonate], V₂O₅, V₂O₄, VO₂, TiOSO₄, K₂TiF₆, K₂ZrF₆, CoSO₄, Co (NO₃)₂, Ce(NO₃)₃.
16. Machine dishwasher product as claimed in any of Claims 1 to 15, characterized in that it additionally comprises one or more magnesium and/or zinc salts and/or magnesium and/or zinc complexes, preferably one or more magnesium and/or zinc salt(s) at least of one monomeric and/or polymeric organic acid.
17. Machine dishwasher product as claimed in Claim 16, characterized in that it comprises insoluble zinc salts which have a particle size below 1.7 millimeters.
18. Machine dishwasher product as claimed in any of Claims 1 to 17, characterized in that it is packaged in portions in a water-soluble enclosure, where the enclosure preferably comprises one or more materials from the group of polymers containing acrylic acid, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters and polyethers and mixtures thereof and preferably has a wall thickness of from 10 to 5000 µm, preferably from 20 to 3000 µm, particularly preferably from 25 to 2000 µm and in particular from 100 to 1500 µm.
19. Machine dishwasher product as claimed in Claim 18, characterized in that the water-soluble enclosure comprises a sachet made of water-soluble film and/or an injection-molded part and/or a blow-molded part and/or a deep-drawn part, where the enclosure preferably comprises one or more water-soluble polymer(s), preferably a material from the group of (optionally acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and derivatives thereof and mixtures thereof, more preferably (optionally acetalized) polyvinyl alcohol (PVAL).
20. Machine dishwasher product as claimed in Claim 19, characterized in that the enclosure comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%, preference being given to polyvinyl alcohols whose molecular weight is in the range from 10 000 to 100 000 gmol^-1, preferably from 11 000 to 90 000 gmol^-1, particularly preferably from 12 000 to 80 000 gmol^-1 and in particular from 13 000 to 70 000 gmol^-1.