EP1299513B1 - Machine dishwasher rinsing agent - Google Patents

Abstract

Detergents for dishwashing contain 1% up to 98.8% by weight of builders, 0.1% to 70% by weight of copolymers of unsaturated carboxylic acids and monomers containing sulfonic acid groups, and one or both of 5% to 30% by weight of nonionic surfactants and 0.1% to 30% by weight of homo- or copolymeric polycarboxylic acids or salts thereof.

Description

The present invention relates to automatic dishwashing detergents which have a content have sulfonic acid-containing polymers and beyond an additional benefit cause. The sulfonic acid-containing polymers are copolymers of i) unsaturated Carboxylic acids, ii) monomers containing sulfonic acid groups and iii) optionally further ionic or nonionic monomers. The agents may be in solid or liquid form, e.g. when Powder, granules, extrudates, tablets, liquids or gels are provided.

On machine-washed dishes are often made higher demands than manual washed dishes. Thus, even a tableware completely cleaned dishes then as not properly rated, if it still remains whitish after machine dishwashing Water hardness or other mineral salts based stains that lack of wetting agents come from dried water drops.

In order to obtain crystal-clear and spotless dishes, you are now successfully using rinse aid one. The addition of rinse aid at the end of the wash program ensures that the water is as possible completely drained, so that the different surfaces at the end of the Rinsing program are residue-free and flawlessly shiny.

The machine cleaning of dishes in household dishwashers usually includes a pre-rinse, a main rinse and a rinse cycle, the intermediate rinses to be interrupted. For most machines, the pre-rinse cycle is very dirty Harness switchable, but is selected only in exceptional cases by the consumer, so that in the Most machines have one main wash, one intermediate wash with pure water and one rinse be performed. The temperature of the main wash cycle varies depending on the machine type and program level selection between 40 and 65 ° C. In the rinse cycle are from a dosing tank In the machine rinse aid added, which is usually nonionic as a main ingredient Containing surfactants. Such rinse aids are in liquid form and are in the state of Technique broadly described. Your task consists mainly in limescale and deposits on to prevent the cleaned dishes. In addition to water and low-foaming nonionic surfactants These rinse aids often include hydrotopes, pH adjusters such as citric acid or deposit-inhibiting Polymers.

EP-B1 0 197 434 (Henkel) discloses liquid rinse aids which contain mixed ethers as nonionic surfactants. In the dishwasher, a variety of different materials (glass, metal, silver, plastic, porcelain) is cleaned. This variety of materials must be wetted as well as possible in the rinse cycle. Rinse aid formulations which contain exclusively mixed ethers as the surfactant component, do not meet these requirements or only to a small extent, so that the rinsing or drying effect is unsatisfactory, especially in the case of plastic surfaces.

The storage tank in the dishwasher must be filled with rinse aid at regular intervals depending on the type of machine for 10 to 50 rinses sufficient. Becomes forget filling the tank, so are especially glasses through limescale and deposits unsightly. In the prior art, therefore, there are some solutions, a rinse aid to integrate into the detergent for machine dishwashing. These solutions are bound to the offer form of the compact shaped body.

For example, European Patent Application EP-A-0 851 024 (Unilever) describes two-layer detergent tablets whose first layer contains peroxy bleach, builder and enzyme, while the second layer contains acidifying agent and a continuous medium having a melting point between 55 and 70 ° C and scale inhibitors contains. Due to the high-melting continuous medium, the acid (s) and scale inhibitor (s) are to be released with a delay and bring about a clear rinse effect. Powdered automatic dishwashing or surfactant-containing rinse systems are not mentioned in this document.

The object of the present invention has been to provide new means for the machine To provide dishwashing with respect to the performance characteristics deliver at least the same results as marketable funds and, in addition, further performance benefits provide. This should include the new agents as well as conventional cleaners as well be used in the form of combination products and regardless of the preparation form to develop their advantageous properties.

a) 1 bis 98,8 Gew.-% Gerüststoff(e),

b) 0,1 bis 70 Gew.-% an Copolymeren aus

i) ungesättigten Carbonsäuren

ii) Sulfonsäuregruppen-haltigen Monomeren

iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren

c) 0,1 bis 30 Gew.-% homo- und/oder copolymere Polycarbonsäuren bzw. deren Salze enthalten, wie in Anspruch 1 definiert.

This application relates to automatic dishwashing detergents which

a) 1 to 98.8% by weight of builder (s),

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

c) 0.1 to 30 wt .-% homo- and / or copolymeric polycarboxylic acids or their salts, as defined in claim 1.

The corresponding homo- or copolymeric polycarboxylic acids or polycarboxylates are described in detail below. The combination of the two polymers b) and c) in this inventive agents is particularly effective, since the polymers b) in particular phosphate-containing Counteract deposits while the polymers c) the precipitation of calcium carbonate prevent. In combination, both types of polymers show a synergistic effect Coverings on the dishes and the machine parts. The to the operation of a household dishwasher at intervals required two dosing (after a certain number of Rinses must replenish the replenisher salt in the water softening system of the machine be), can be with the above-described inventive agents to a single Summarize process, since even after a higher number of rinsing cycles, the dosage Another product (regenerating salt) and thus a double dosing not necessary is.

This effect of reduced deposit formation and thus the prevention of "limescale" on The dishes can be further supplemented by the addition of nonionic surfactants, the cause an improved drainage behavior and thus additionally streaking or banding counteract especially on glass surfaces. Such agents of the invention make the dispensing with additional dosing of rinse aids and thus represent real "3in1" products, as they combine the previous products Regeneriersalz, cleaners and rinse aid in one agent.

All of the above-mentioned agents according to the invention have the advantage that those with such agents treated utensils become significantly cleaner during subsequent cleaning operations, as dishes, which were rinsed by conventional means. The effect is independent of whether the automatic dishwashing agents are liquid, powdered or in tablet form.

As an additional positive effect occurs a shortening of the drying time of the detergent treated crockery items, i. the consumer can after the expiry of the cleaning program Take the dishes out of the machine sooner and reuse them.

The invention is characterized by an improved "cleanability" of the treated substrates later cleaning operations and by a significant reduction in the drying time 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.

As ingredient a) the agents according to the invention contain one or more builder (s). These are described below. Particularly preferred builders are within the scope of present invention phosphates and / or citrates.

In the automatic dishwashing detergents according to the invention can thereby all builders commonly used in detergents and cleaners be included, in particular So zeolites, silicates, carbonates, organic cobuilders and - if not ecological There are reservations about their use - even the phosphates. The builders listed below are all suitable as carrier materials for the rinse aid particles according to the invention, as already stated above.

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

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray-amorphous silicates, which likewise have a dissolution delay compared to the conventional water glasses, are described, for example, in German patent application DE-A-44 00 024 . Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula n Na ₂ ^O. (1-n) K ₂ ^O. Al ₂ O ₃ ^. (2 - 2.5) SiO ₂ ^. (3.5-5.5) H ₂ O can be described. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Of course, a use of the well-known phosphates as builders possible, unless such use should be avoided for environmental reasons. Among the large number of commercially available phosphates, the alkali metal phosphates have particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) in the washing and cleaning industry the greatest importance.

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 lime deposits on machine parts or lime incrustations in fabrics 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). 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 over the corresponding sodium compounds in the detergent industry.

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: hot or cold phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

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

These are according to the invention just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures can be used from these two; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate are used according to the invention.

As organic cobuilders can be used in the machine dishwashing detergents according to the invention in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, Polyacetals, dextrins, other organic cobuilders (see below) and phosphonates used become. These classes of substances are described below.

Useful organic builders are, for example, those usable in the form of their sodium salts Polycarboxylic acids, understood by polycarboxylic acids such carboxylic acids which carry more than one acidity function. For example, these are citric acid, adipic acid, Succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, Aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such use of ecological Reasons are not objectionable, as well as mixtures of these. Preferred salts are the salts polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, Sugar acids and mixtures of these.

The acids themselves can also be used. The acids have besides their builder effect typically also the property of an acidifying component and thus also serve for Setting a lower and milder pH of detergents or cleaners. Especially here are citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and to name any mixtures of these.

Builders include other polymeric polycarboxylates. These are the alkali metal salts the polyacrylic acid or the polymethacrylic acid with a relative 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 may again, the short-chain polyacrylates, the molecular weights of 2000 to 10,000 g / mol, and especially preferably from 3000 to 5000 g / mol, have to be preferred.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As especially suitable have proven copolymers of acrylic acid with maleic acid, the 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Their molecular weight, based on free acids, is from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol, and in particular 30,000 to 40,000 g / mol.

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

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

Also particularly preferred are biodegradable polymers of more than two different Monomer units, for example those containing as monomers salts of acrylic acid and the Maleic acid and vinyl alcohol or vinyl alcohol derivatives or the salts of acrylic acid as monomers and the 2-alkylallylsulfonic acid and sugar derivatives.

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

Likewise, as further preferred builder substances are polymeric aminodicarboxylic acids, their To name salts or their precursors. Particularly preferred are polyaspartic acids or their salts and derivatives, which in addition to cobuilder properties also a bleach-stabilizing Have effect.

Further suitable builder substances are polyacetals, which are prepared by reaction of dialdehydes with polyol carboxylic acids having 5 to 7 C atoms and at least 3 hydroxyl groups, can be obtained. Preferred polyacetals are selected from dialdehydes such as glyoxal, glutaraldehyde, Terephthalaldehyde and mixtures thereof and from Polyolcarbonsäuren such as gluconic acid and / or glucoheptonic acid.

Further suitable organic builder substances are dextrins, for example oligomers or Polymers of carbohydrates that can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes be performed. Preferably, they are hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. This is a polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, especially from 2 to 30 preferred, wherein DE a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 is. Useful 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 having higher molecular weights in the range of 2000 to 30,000 g / mol.

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

Also oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable cobuilders. Here, ethylenediamine-N, N'-disuccinate (EDDS) is preferred used in the form of its sodium or magnesium salts. Further preferred are in Glycerol disuccinates and glycerol trisuccinates are also linked to this context. Suitable quantities are in zeolithhaltigen and / or silicate-containing formulations at 3 to 15 wt .-%.

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

Another class of substances with co-builder properties are the phosphonates in particular hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates For example, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, wherein the disodium salt neutral and the tetrasodium salt is alkaline (pH 9). As Aminoalkanphosphonate are preferably Ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. They are preferably in shape the neutral reacting sodium salts, eg. B. as hexasodium salt of EDTMP or as hepta- and Octa-sodium salt of DTPMP used. As a builder is from the class of phosphonates preferred to use HEDP. The aminoalkanephosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it may, especially if the means also bleach may be preferred to use Aminoalkanphosphonate, in particular DTPMP, or Use mixtures of the above phosphonates.

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

The inventively used as ingredient b) sulfonic acid-containing polymers described in detail below.

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

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

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

As further ionic or nonionic monomers are in particular ethylenically unsaturated Compounds considered. The content is preferably that used according to the invention Polymers of monomers of group iii) less than 20 wt .-%, based on the polymer. Particularly preferred polymers to be used consist only of monomers of the groups i) and ii).

i) ungesättigten Carbonsäuren der Formel I. R¹(R²)C=C(R³)COOH 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 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, the use of one or more copolymers

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

iii) optionally further ionic or nonionic monomers
particularly preferred.

i) einer oder mehrerer ungesättigter Carbonsäuren aus der Gruppe Acrylsäure, Methacrylsäure und/oder Maleinsäure

ii) einem oder mehreren Sulfonsäuregruppen-haltigen Monomeren der Formeln IIa, IIb und/oder IIc: H₂C=CH-X-SO₃H H₂C=C(CH₃)-X-SO₃H HO₃S-X-(R⁶)C=C(R⁷)-X-SO₃H in der R⁶ und R⁷ unabhängig voneinander ausgewählt sind aus -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, - CH(CH₃)₂ und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n- mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)-

iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren
verwendet werden.

A particularly preferred use is characterized in that one or more copolymers of

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

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

iii) optionally further ionic or nonionic monomers
be used.

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

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

Instead of acrylic acid and / or methacrylic acid or in addition thereto, maleic acid can also be used as a particularly preferred monomer from group i). This gives rise to inventively preferred uses, which are characterized in that one or more copolymers are used, the structural units of the formula VII - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - 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 and for uses, which are characterized in that one or more copolymers are used, the structural units of the formula VIII - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - 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 the polymers, the sulfonic acid groups can be completely or partially in neutralized form, i.e. that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups against metal ions, preferably alkali metal ions and in particular against sodium ions, can be exchanged. Corresponding uses characterized are that the sulfonic acid groups in the copolymer partially or fully neutralized, are according to the invention prefers.

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

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

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

In summary, machine dishwashing detergents which contain 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 are particularly preferred - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

The amounts in which the copolymers b) are contained in the compositions according to the invention can vary depending on the desired product (dosing recommendation). General are inventive automatic dishwashing detergents containing the sulfonated copolymer (s) in quantities from 0.25 to 50% by weight, preferably from 0.5 to 35% by weight, more preferably from 0.75 to 20 wt .-% and in particular from 1 to 15 wt .-%.

In addition to the sulfonated copolymers b), the agents according to the invention contain polycarboxylic acids or their salts. In the context of the present invention, particularly suitable homo- or copolymers c) are polyacrylates, polymethacrylates, copolymers of acrylic acid and / or Methacrylic acid with maleic acid and copolymers of maleic acid with olefins. Preferred inventive Automatic dishwashing detergents are therefore characterized in that they as homo- and / or copolymeric polycarboxylic acids or their salts homo- and / or copolymers of acrylic acid and / or methacrylic acid and / or maleic acid.

Polycarboxylates are special prefers.

In summary, dishwasher detergents according to the invention are claimed as ingredient c) furthermore copolymeric polycarboxylates, in particular those of acrylic acid with Methacrylic acid and / or acrylic acid or methacrylic acid with maleic acid, wherein Copolymers of acrylic acid with maleic acid containing from 50 to 90% by weight of acrylic acid and from 50 to 10% by weight Maleic acid, preferably and polymers having molecular weights, based on free Acids, from 2000 to 70000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol are particularly preferred.

In particularly preferred automatic dishwashing agents, the weight ratio of sulfonated copolymers b) to (meth) acrylate copolymers c) 100: 1 to 1: 100, preferably 25: 1 to 1:50, more preferably 10: 1 to 1:25 and especially 5: 1 to 1:10.

In addition to the ingredients a) to c) or a) to d), the agents according to the invention can be further Contain ingredients. Important ingredients from the groups of bleaches, bleach activators, Enzymes, silver protectants, cobuilders, dyes and fragrances, etc. are detailed below described. In the context of the present invention, it is particularly preferred if the automatic dishwashing detergent additionally one or more substances from the group of acidifying agents, Chelate complexing or the deposit-inhibiting polymers included.

Substances from the group of the acidifying agents are, for example, boric acid and alkali metal hydrogen sulfates, Alkali metal dihydrogen phosphates and other inorganic salts. To be favoured However, organic Acidifizierungsmittel used, wherein the citric acid is a particularly preferred acidifying agent. In particular, the other fixed ones can be used Mono-, oligo- and polycarboxylic acids. Again preferred from this group are tartaric acid, Succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. Organic sulfonic acids such as sulfamic acid are also usable. Commercially available and as Acidifizierungsmittel in the context of the present invention also preferred Sokalan® DCS (trademark of BASF), a mixture of succinic acid (max Wt%), glutaric acid (max 50 wt%) and adipic acid (max 33 wt%).

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

Common and preferred chelate complex images within the scope of the present invention are for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Also complexing polymers, ie polymers which are either in the Main chain or self-supporting to this functional groups that act as ligands can and with suitable metal atoms usually to form chelate complexes react, can be used according to the invention. The polymer-bound ligands of the resulting Metal complexes can come from just one macromolecule or different ones Belong to polymer chains. The latter leads to the networking of the material, provided that the complex-forming Polymers were not previously crosslinked via covalent bonds.

Complexing groups (ligands) of conventional complex-forming polymers are iminodiacetic acid, Hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, amidoxime, Amino phosphoric acid, (cyclic) polyamino, mercapto, 1,3-dicarbonyl and crown ether radicals with z. T. very specific. Activities towards ions of different metals. base polymers many of the commercially important complex-forming polymers are polystyrene, polyacrylates, Polyacrylonitriles, polyvinyl alcohols, polyvinylpyridines and polyethylenimines. Also natural polymers such as cellulose, starch or chitin are complexing polymers. In addition, these can be provided by polymer analogous transformations with other ligand functionalities.

(i) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt,

(ii) stickstoffhaltigen Mono- oder Polycarbonsäuren,

(iii) geminalen Diphosphonsäuren,

(iv) Aminophosphonsäuren,

(v) Phosphonopolycarbonsäuren,

(vi) Cyclodextrine

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

(i) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5,

(ii) nitrogen-containing mono- or polycarboxylic acids,

(iii) geminal diphosphonic acids,

(iv) aminophosphonic acids,

(v) phosphonopolycarboxylic acids,

(vi) cyclodextrins

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

a) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt wie Gluconsäure,

b) stickstoffhaltige Mono- oder Polycarbonsäuren wie Ethylendiamintetraessigsäure (EDTA), N-Hydroxyethylethylendiamintriessigsäure, Diethylentriaminpentaessigsäure, Hydroxyethyliminodiessigsäure, Nitridodiessigsäure-3-propionsäure, Isoserindiessigsäure, N,N-Di-(β-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-asparaginsäure oder Nitrilotriessigsäure (NTA),

c) geminale Diphosphonsäuren wie 1-Hydroxyethan-1,1-diphosphonsäure (HEDP), deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon und 1-Aminoethan-1,1-diphosphonsäure, deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon,

d) Aminophosphonsäuren wie Ethylendiamintetra(methylenphosphonsäure), Diethylentriamin-penta(methylenphosphonsäure) oder Nitrilotri(methylenphosphonsäure),

e) Phosphonopolycarbonsäuren wie 2-Phosphonobutan-1,2,4-tricarbonsäure sowie

f) Cyclodextrine.

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

a) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, such as gluconic acid,

b) nitrogen-containing mono- or polycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, nitridodiacetic acid-3-propionic acid, isoserinediacetic acid, N, N-di- (β-hydroxyethyl) -glycine, N- (1,2- Dicarboxy-2-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid or nitrilotriacetic acid (NTA),

c) geminal diphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), their higher homologues having up to 8 carbon atoms and hydroxy- or amino-containing derivatives thereof and 1-aminoethane-1,1-diphosphonic acid whose higher homologues with up to 8 carbon atoms and hydroxyl- or amino-containing derivatives thereof,

d) aminophosphonic acids such as ethylenediaminetetra (methylenephosphonic acid), diethylenetriamine-penta (methylenephosphonic acid) or nitrilotri (methylenephosphonic acid),

e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid and

f) cyclodextrins.

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

The nonionic surfactants preferably used in the automatic dishwashing compositions of the present application are described in detail below. The quantities in which the nonionic Surfactants are used according to the invention between 5 and 30 wt .-%, wherein preferred are automatic dishwashing detergents containing from 5 to 25% by weight, preferably from 6 to 22.5 Wt .-%, particularly preferably 7.5 to 20 wt .-% and in particular 8 to 17.5 wt .-% nonionic (s) Containing 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 alone nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamide may be suitable. The amount of these nonionic surfactants is preferably no longer than that of the ethoxylated fatty alcohols, especially not more than half of them.

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

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

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

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

[Z] is preferably 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 prepared by reaction with fatty acid methyl esters in Presence of an alkoxide as a catalyst in the desired Polyhydroxyfettsäureamide converted become.

Low-foaming nonionic surfactants are used as preferred surfactants. With particular preference, the machine dishwashing detergents according to the invention contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. 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.

Particular preference is given to agents according to the invention which comprise a nonionic surfactant, which has a melting point above room temperature. Accordingly, preferred means characterized in that it comprises nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and in particular between 26.6 and 43.3 ° C, included.

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

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

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

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

Accordingly, particularly preferred rinse aids according to the invention contain ethoxylated nonionic surfactant (s) comprising 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 solid at room temperature preferably additionally has propylene oxide units in the Molecule. Preferably, such PO units make up to 25% by weight, more preferably up to to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Surfactants. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols additionally having polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules is preferably more than 30 wt .-%, more preferably more than 50 wt .-% and in particular more than 70 Wt .-% of the total molecular weight of such nonionic surfactants. Preferred rinse aids are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular bis to 15% by weight of the total molecular weight of the nonionic surfactant.

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

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

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

In place of the surfactants mentioned or in conjunction with them also cationic and / or amphoteric surfactants are used. In summary, agents according to the invention are preferred. the surfactant (s), preferably nonionic surfactant (s) and in particular nonionic (s) Surfactant (s) from the group of alkoxylated alcohols, in amounts of 0.1 to 60 wt .-%, preferably from 0.5 to 50% by weight, more preferably from 1 to 40% by weight, and especially from 2 to 30 wt .-%, each based on the agent included.

In addition to the builders are in particular substances from the groups of surfactants (see above), the Bleaching agents, bleach activators, enzymes, polymers and dyes and perfumes important Ingredients of detergents. Important representatives from the mentioned substance classes are 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-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutan-1,4-diene diacid, N, N-terephthaloyl-di (6-aminopercapronate) can be used.

As a bleaching agent in the automatic dishwashing detergents according to the invention It is also possible to use chlorine or bromine-releasing substances. Among the suitable Chloro or bromine-releasing materials include, for example, heterocyclic N-bromo and N-chloroamides, for example, trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or salts thereof with cations such as potassium and sodium in Consideration. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

Bleach activators which aid in the bleaching effect are other important ingredients. Known bleach activators are compounds which contain one or more N- or O-acyl groups such as substances from the class of anhydrides, esters, imides and acylated Imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.

As bleach activators, compounds which under perhydrolysis conditions can be aliphatic peroxycarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, are used. Suitable substances are the O- and / or N-acyl groups of said C atom number and / or optionally substituted Wear benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, Ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methylsulfate (MMA), and the German patent applications DE 19616 693 and DE 196 16 767 known enol esters and acetylated sorbitol and mannitol or their mixtures (SORMAN), acylated sugar derivatives, especially pentaacetylglucose (PAG), Pentaacetyl fructose, Tetraacetylxylose and Octaacetyllactose as well as acetylated, if necessary N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam. Hydrophilic substituted acyl acetals and acyl lactams are also preferred used. Combinations of conventional bleach activators can also be used.

In addition to or in place of the conventional bleach activators, so-called Bleaching catalysts are incorporated into the rinse aid particles. These substances are it is bleach-enhancing transition metal salts or transition metal complexes such For example, Mn, Fe, Co, Ru or Mo-salene complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru-amine complexes are useful as bleach catalysts.

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

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

As enzymes in the detergents according to the invention, in particular those from the Classes of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, Amylases, glycosyl hydrolases and mixtures of said enzymes in question. All these hydrolases contribute to the removal of stains such as protein, fat or starch containing impurities at. For bleaching and oxidoreductases can be used. Especially suitable are from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as from their genetically modified Variants obtained enzymatic agents. Preferably, subtilisin type proteases and in particular proteases derived from Bacillus lentus. there are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic acting Enzymes or protease, lipase or lipolytic enzymes, but especially protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of special interest. Examples of such lipolytic enzymes are known Cutinases. Peroxidases or oxidases have also proved 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 encapsulating substances to them to protect against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules may, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt .-% be.

Dyes and fragrances can be added to the automatic dishwasher detergents according to the invention to improve the aesthetic impression of the resulting products and to the consumer in addition to performance, a visually and sensory "typical and unmistakable" product to provide. As perfume oils or perfumes, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and type Hydrocarbons are used. Fragrance compounds of the ester type are known e.g. benzyl acetate, Phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. For example, the ethers include Benzyl ethyl ether, to the aldehydes e.g. the linear alkanals with 8-18 carbon atoms, citral, citronellal, Citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, too ketones e.g. the ionones, α-isomethylionone and methyl cedryl ketone, to the alcohols anethole, Citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons mainly include the terpenes such as limes and pinene. However, mixtures are preferred various fragrances used, which together create an appealing scent. Such perfume oils may also contain natural perfume mixtures as they come from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are Muscat, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, Cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil and orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the detergents according to the invention, it However, it may also be advantageous to apply the fragrances to carriers that the adhesion of the perfume intensify on the laundry and through a slower release of fragrance for long-lasting Fragrance of the textiles provide. Examples of such carrier materials are cyclodextrins proven, wherein the cyclodextrin-perfume complexes additionally coated with other excipients can be. Also, an incorporation of the perfumes in the rinse aid particles according to the invention is possible and leads to a fragrance impression when opening the machine (see above).

In order to improve the aesthetic impression of the agents according to the invention, it may (or parts thereof) with suitable dyes. Preferred dyes, the selection of which Expert has no difficulty, have a high storage stability and insensitivity compared with the other ingredients of the products and against light and no pronounced Substantivity to the substrates to be treated with the agents, such as glass, ceramics or Plastic dishes, so as not to stain them.

The cleaning agents according to the invention can be used to protect the items to be washed or the machine Corrosion inhibitors included, with particular silver protectants in the range of machine Dishwashing have a special meaning. It is possible to use the known substances of the prior art. In general, especially silver protectants can be selected from the Group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and the transition metal salts or complexes. Especially preferred benzotriazole and / or alkylaminotriazole are to be used. One finds in cleaner formulations In addition, frequently active chlorine-containing agents, the corrosion of the silver surface clearly can diminish. In chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. Hydroquinone, Pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives thereof Classes of compounds. Also salt and complex-like inorganic compounds, such as salts of Metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preference is given here to the transition metal salts, which are selected from the group of manganese and / or cobalt salts and / or complex, more preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the Cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds can be used to prevent corrosion on the items to be washed.

As already mentioned above, the agents according to the invention can be used in any desired manner Make up the shape. Depending on the choice of other ingredients and the "matrix" are both liquid and solid means readily produced. With the liquid means can Liquid dishwashing detergents with viscosities from a few pas to gel or even cut-resistant pastes are made. With the solid means can be both particulate Produce agents such as powders, granules, extrudates, flakes, pellets, flakes, etc., as well compact shaped articles such as blocks or tablets, the latter due to their high consumer acceptance are clearly preferred.

Detergent tablets for machine dishwashing can consist of a single Premix pressed and thus be provided in the form of a single-phase tablet. It is but also possible to use several differently composed premixes one after the other In the simplest case, tablets with a layer structure result. Yes, by number The premixes are obtained as two-layered, three-layered or four-layered tablets. The different ones Layers open up the possibility of separating active substances from one another, wherein both the inventively mandatory ingredients are separated from each other as well as other optional ingredients such as bleaches and bleach activators.

The individual phases of the shaped body can vary within the scope of the present invention Have spatial forms. The simplest realization option lies in two or multilayer tablets, each layer of the shaped article being a phase. It is but according to the invention also possible to produce multi-phase moldings in which individual Phases have the form of inclusions in (another) phase (s). Besides so-called "Ring-core tablets" are, for example, coated tablets or combinations of those mentioned Embodiments possible. The technically most prevalent spatial form of multiphase Shaped body is the two- or multi-layer tablet. It is within the scope of the present invention Therefore, it is preferred that the phases of the shaped body have the form of layers and that Shaped body is 2-, 3- or 4-phase.

The shaped bodies according to the invention can assume any geometric shape, wherein in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segmented, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, pentagonal, octagonal, prismatic and rhombohedral Shapes are preferred. Also completely irregular bases like arrow or animal forms, Trees, clouds etc. can be realized. Do the moldings of the invention corners and edges, so these are preferably rounded. As additional optical differentiation For example, an embodiment with rounded corners and chamfered edges is preferred.

Another way to separate active substances in individual areas is to to provide a tablet having a cavity (e.g., a well or a continuous well) Hole) and to fill this cavity with another part, for example by pouring with a melt or filling with powder. Also a gluing or gluing a separately prepared Shaped body or a tablet is possible, taking on the adhesive at certain geometric Conditions (mechanical adhesion) can be dispensed with. This variant has the Advantage that the second part can be made on the one hand in a variety of ways (e.g., by tabletting, sintering, pouring, extruding, etc.) and before the onor Attaching by appropriate measures (for example, by coating) are made up so can that he at a predetermined time in the program sequence of the dishwasher dissolves and releases the ingredients.

The cavity in the compressed part of such shaped bodies according to the invention can be of any shape exhibit. It can divide the shaped body, i. an opening on different sides, for example at the top and bottom of the molding, but they also can not be through the entire molding body going cavity whose opening only on a molded body side is visible. The shape of the cavity can be freely selected within wide limits. Out For reasons of process economics, there are through holes, their openings on each other lying opposite surfaces of the moldings, and troughs with an opening on a molded body side proven. In preferred detergent tablets, the cavity has the Form of a through hole, the openings on two opposite Form body surfaces are located. The shape of such a through hole can be chosen freely are preferred, wherein moldings are preferred in which the through hole circular, elliptical, triangular, rectangular, square, pentagonal, hexagonal, heptagonal or octagonal Horizontal sections also have completely irregular hole shapes such as arrow or animal shapes, Trees, clouds etc. can be realized. As with the moldings are in the case of angular holes such with rounded corners and edges or with rounded corners and chamfered edges preferred.

The aforementioned geometric realization forms can be arbitrarily with each other combine. Thus, shaped bodies with rectangular or square base and circular Holes are made as well as round shaped bodies with octagonal holes, where There are no limits to the variety of possible combinations. For the sake of procedural economy and aesthetic consumer sentiment are specially shaped with hole preferred in which the mold base body and the hole cross section of the same geometric Have shape, for example, shaped body with square base and centrally incorporated square hole. Particularly preferred are ring shaped bodies, i. circular Shaped body with a circular hole.

If the o.g. Principle of the open at two opposite sides of the molding body holes on a Opening is reduced, you get to Muldenformkörpern. Detergent tablets according to the invention, where the cavity is in the form of a trough are also preferred. As in the case of "shaped perforated bodies", the shaped bodies according to the invention can also be used in this case Embodiment take any geometric shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segmented, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, octagonal, octagonal prismatic and rhombohedral forms are preferred are. Even completely irregular surfaces such as arrow or animal shapes, trees, clouds, etc. can will be realized. If the shaped body has corners and edges, these are preferably rounded off. As an additional optical differentiation is an embodiment with rounded corners and beveled ("chamfered") edges preferred.

The shape of the trough can be chosen freely, wherein moldings are preferred in which at least one well a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segmented, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, pentagonal, octagonal, prismatic and rhombohedral Can take shape. Also completely irregular trough shapes like arrow or animal forms, Trees, clouds etc. can be realized. As with the moldings are wells with rounded corners and edges or with rounded corners and chamfered edges preferred.

The size of the trough or the through hole compared to the entire molded body depends on the intended use of the molded article. Depending on how much further active substance, the remaining hollow volume to be filled and whether a lesser or greater amount of detergent component should be included, the size of the cavity vary. Regardless of the intended use, detergent tablets are preferred. in which the volume ratio of compressed part ("base molding") to "core" 2: 1 to 100: 1, preferably 3: 1 to 80: 1, more preferably 4: 1 to 50: 1 and in particular 5: 1 to 30: 1, is.

In addition to the volume ratio mentioned, a mass ratio of the two parts can also be specified whereby the two values are greater than the densities of the basic shaped body or of the "core" correlate with each other. Regardless of the density of the individual parts are inventive Preferred detergent tablets in which the weight ratio of base molding to "Core" 1: 1 to 100: 1, preferably 2: 1 to 80: 1, more preferably 3: 1 to 50: 1 and in particular 4: 1 to 30: 1.

Analogous information can also be made for the surfaces, each of which is based on the basic molding or from the "core" are visible. Here, detergent tablets are preferred in which the after outer surface of the "core" 1 to 25%, preferably 2 to 20%, more preferably 3 to 15% and in particular 4 to 10% of the total surface of the molding

The core and the base molding are preferably colored optically distinguishable. Next The optical differentiation can application advantages by different solubilities the various molding body areas are achieved. Detergent tablets, with where the core dissolves faster than the base molding, are inventively preferred. By incorporating certain constituents, on the one hand, the solubility of the nuclei can be purposefully accelerated On the other hand, the release of certain ingredients from the kernels may increase Leading to advantages in the cleaning process.

Of course, detergent tablets according to the invention are also preferred in which the core dissolves later in the washing program than the base molding. Performance advantages from this delayed release can be achieved for example by using a slower soluble core active substance (s) are released only in later rinses. So can for example, in automatic dishwashing can be achieved by slower soluble cores, that in the rinse cycle further active substance (s) is available / stand. By additional Substances such as nonionic surfactants, Acidifizierungsmittel, soil-release polymers, etc. can be so improve the rinse results. Also, an incorporation of perfume is easily possible; due to its delayed release, the often occurring "alkaline smell" can be detected in dishwashers be eliminated when opening the machine.

The base molding in preferred embodiments of the present invention has a high specific gravity. Detergents and cleaning agent tablets, which are characterized in that the base tablet has a density above 1000 kgdm ^-3 , preferably above 1025 kgdm ^-3 , more preferably above 1050 kgdm ^-3 and in particular above 1100 kgdm ^-3 are according to the invention prefers.

In order to facilitate the disintegration of highly compacted moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrating agents, in order to shorten the disintegration times. According to Römpp (9th edition, Vol. 6, p. 4440) and Voigt " Textbook of Pharmaceutical Technology" (6th edition, 1987, pp. 182-184), excipients are understood to mean excipients which are suitable for rapid disintegration of tablets in water or gastric juice and for the release of the drugs in resorbable form.

These substances, which are also referred to as "explosives" due to their effect, increase their size when water enters their volume, on the one hand increases the intrinsic volume (swelling), on the other hand also, via the release of gases, a pressure can be generated which the tablet is in smaller particles disintegrate. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.

Preferred Reinigungsmittefformkörper contain 0.5 to 10 wt .-%, preferably 3 to 7 wt .-% and in particular 4 to 6 wt .-% of one or more disintegration aids, respectively on the molded body weight. Contains only the base molding Disintegrationshilfsmittel, so the information given refers only to the weight of the base molding. At the incorporation of disintegration aids in the detergent components of the invention include those as ingredient d).

Preferred disintegrating agents used in the present invention disintegrating agents based on cellulose, so that preferred detergent tablets such cellulose-based disintegrating agent in amounts of 0.5 to 10 wt .-%, preferably 3 to 7 wt .-% and in particular 4 to 6 wt .-% contain. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives.

The cellulose used as disintegration assistant is preferably not in finely divided form but before blending into the pre-mixes to be pressed into a coarser one Form transferred, for example, granulated or compacted. The particle sizes of such disintegrating agents are usually above 200 microns, preferably at least 90 wt .-% between 300 and 1600 microns and in particular at least 90 wt .-% between 400 and 1200 microns. The mentioned above and described in more detail in the cited documents coarser Disintegrationshilfsmittel Cellulosic are preferred in the context of the present invention as disintegration aids and commercially available, for example, under the name Arbocel® TF-30-HG available from Rettenmaier.

As another disintegrating agent based on cellulose or as a component of this component can microcrystalline cellulose. This microcrystalline cellulose is made by partial Obtained hydrolysis of celluloses under such conditions that only the amorphous regions (ca. 30% of the total cellulose mass) of the celluloses attack and completely dissolve the crystalline ones Areas (about 70%) but leave undamaged. A subsequent disaggregation of The micro-crystalline celluloses, the primary particle sizes, produce the micro-fine celluloses produced by the hydrolysis of about 5 microns and, for example, to granules with a medium Particle size of 200 microns are compacted.

In the context of the present invention, preferred detergent tablets additionally contain a disintegration aid, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of from 0.5 to 10 Wt .-%, preferably from 3 to 7 wt .-% and in particular from 4 to 6 wt .-%, each based on the molded body weight.

In addition, the detergent tablets according to the invention can be used both in the base tablet as well as in the detergent component containing a gas-developing effervescent system. The gas-evolving effervescent system may consist of a single substance which upon contact releases a gas with water. Among these compounds is in particular the magnesium peroxide to call, which releases oxygen on contact with water. Usually, the gas-releasing In its turn, however, the bubbling system consists of at least two components, one under the other Gas formation react. While here a variety of systems is thinkable and executable, the For example, release nitrogen, oxygen or hydrogen, which is in the inventive Washing and cleaning agent moldings used Sprudelsystem both by economic as well as ecological aspects. Preferred shower systems consist of alkali metal carbonate and / or bicarbonate and an acidifier, which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution.

In the alkali metal carbonates or bicarbonates, the sodium and potassium salts are made Cost reasons over the other salts clearly preferred. Of course you have to not the respective pure alkali metal carbonates or bicarbonates are used; Rather, mixtures of different carbonates and bicarbonates from washing technical Interest be preferred.

In preferred detergent tablets are used as effervescent 2 to 20 wt .-%, preferably From 3 to 15% by weight and in particular from 5 to 10% by weight of an alkali metal carbonate or hydrogen carbonate and 1 to 15, preferably 2 to 12 and in particular 3 to 10 wt .-% of a Acidifier, in each case based on the entire molded body used.

Acidifying agents which release carbon dioxide from the alkali salts in aqueous solution are For example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used. However, preferred are organic Acidifizierungsmittel used, wherein the citric acid is a particularly preferred Acidifizierungsmittel. However, it is also possible in particular to use the other solid mono-, oligo- and polycarboxylic acids. Again preferred from this group are tartaric acid, succinic acid, malonic acid, adipic acid, Maleic acid, fumaric acid, oxalic acid and polyacrylic acid. Organic sulfonic acids such as sulfamic acid are also usable. Commercially available and as Acidifizierungsmittel in Sokalan® DCS (Trademark BASF), a mixture of succinic acid (max 31 wt .-%), glutaric acid (max 50 wt .-%) and adipic acid (max 33 wt%).

In the context of the present invention, preference is given to detergent moldings in which Acidifier in effervescent system a substance from the group of organic di-, tri- and oligocarboxylic acids or mixtures of these are used.

Claims (11)

1. Machine dishwasher detergent containing

   a) 1 to 98.8% by weight of builder(s),

   b) 0.1 to 70% by weight of copolymers composed of

   i) unsaturated carboxylic acids

   ii) sulphonated monomers

   iii) optionally further ionic or nonionogenic monomers

   c) 0.1 to 30% by weight of homo- and/or copolymeric polycarboxylic acids or salts thereof from the group of the

   c1) alkali metal salts of polyacrylic acid or of polymethacrylic acid having a relative molecular mass of 500 to 70 000 g/mol and/or

   c2) copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid, more preferably 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, with a relative molecular mass, based on free acids, of 2000 to 70 000 g/mol.
2. Machine dishwasher detergent according to Claim 1, characterized in that the copolymers b) have, as monomer i), unsaturated carboxylic acids of the formula I R¹(R²)C=C(R³)COOH in which R¹ to R³ are each independently -H, -CH₃, 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, -NH₂-, -OH- or -COOH-substituted alkyl or alkenyl radicals as defined above, or -COOH or -COOR⁴ where R⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
3. Machine dishwasher detergent according to one of Claims 1 and 2, characterized in that the copolymers b) have, as monomer ii), sulphonated monomers of the formula II R⁵(R⁶)C=C(R⁷)-X-SO₃H in which R⁵ to R⁷ are each independently -H, -CH₃, 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, -NH₂-, -OH- or -COOH-substituted alkyl or alkenyl radicals as defined above, or -COOH or -COOR⁴ where R⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optionally present spacer group which is selected from -(CH₂)_n- where n = 0 to 4, -COO-(CH₂)_k- where k = 1 to 6, -C(O)-NH-C(CH₃)₂- and -C(O)-NH-CH(CH₂CH₃)-.
4. Machine dishwasher detergent according to one of Claims 1 to 3, characterized in that the copolymers b) contain only monomers from groups i) and ii), preferably in each case 5 to 95% by weight of i) or ii), more preferably 50 to 90% by weight of monomer from group i) and 10 to 50% by weight of monomer from group ii), based in each case on the polymer.
5. Machine dishwasher detergent according to one of Claims 1 to 4, characterized in that the copolymers b) contain 20 to 85% by weight of monomer from group i), 10 to 60% by weight of monomer from group ii) and 5 to 30% by weight of monomer from group iii).
6. Machine dishwasher detergent according to one of Claims 1 to 5, characterized in that the copolymers b) have molar masses of 2000 to 200 000 gmol^-1, preferably of 4000 to 25 000 gmol^-1 and in particular of 5000 to 15 000 gmol^-1.
7. Machine dishwasher detergent according to one of Claims 1 to 6, characterized in that it comprises, as homo- and/or copolymeric polycarboxylic acids or salts thereof, homo- and/or copolymers of acrylic acid and/or methacrylic acid and/or maleic acid.
8. Machine dishwasher detergent according to one of Claims 1 to 7, characterized in that the weight ratio of sulphonated copolymers b) to (meth)acrylate copolymers c) is 100:1 to 1:100, preferably 25:1 to 1:50, more preferably 10:1 to 1:25 and in particular 5:1 to 1:10.
9. Machine dishwasher detergent according to one of Claims 1 to 8, characterized in that it additionally comprises one or more substances from the group of the acidifiers, chelate complexing agents or scale-inhibiting polymers.
10. Machine dishwasher detergent according to one of Claims 7 to 9, characterized in that it contains 5 to 25% by weight, preferably 6 to 22.5% by weight, more preferably 7.5 to 20% by weight and in particular 8 to 17.5% by weight, of nonionic surfactant(s).
11. Machine dishwasher detergent according to one of Claims 1 to 10, characterized in that it contains the sulphonated copolymer(s) in amounts of 0.25 to 50% by weight, preferably of 0.5 to 35% by weight, more preferably of 0.75 to 20% by weight and in particular of 1 to 15% by weight.