EP2235153B1 - Cleaning agent - Google Patents

Abstract

The invention relates to one- or two-phase dishwasher tablets that are produced of a compacted, particulate material, characterized in that at least one tablet phase A comprises, based on its total weight, a) 5 to 50% by weight of citrate, b) 1 to 20% by weight of citric acid, c) 0.1 to 40% by weight of anionic polymer(s), comprising i) acid group-containing monomers, ii) other non-ionic monomers. The dishwasher tablets according to the invention have excellent cleaning and rinsing results and disintegration properties with an improved hardness.

Description

The present patent application describes detergents, in particular detergents for the machine cleaning of dishes. The subject of this application are, in particular, citrate-containing automatic dishwashing detergent tablets.

Machine-washed dishes are often subject to more stringent requirements today than manually-washed dishes. So the dishes after machine cleaning should not only be completely free of food particles free but also, for example, no whitish, based on water hardness or other mineral salts stains that come from lack of wetting agent from dried water drops.

Modern automatic dishwashing detergents meet these requirements by integrating cleansing, caring, water-softening and clear-rinsing active ingredients and are known to the consumer, for example, as "2in1" or "3in1" dishwashing detergents. As essential for the cleaning as for the rinse aid success constituent intended for the private consumer dishwasher automatic dishwashing contain builders. On the one hand, these builders increase the alkalinity of the cleaning liquor, whereby fats and oils are emulsified and saponified with increasing alkalinity, and on the other hand reduce the water hardness of the cleaning liquor by complexing the calcium ions contained in the aqueous liquor. Particularly effective builders have proved to be the alkali metal phosphates which, for this reason, form the main constituent of the vast majority of commercially available automatic dishwashing detergents.

Thus, while the phosphates are highly valued for their beneficial effect as a component of automatic dishwashing detergents, their use is not unproblematic from the environmental point of view, since a substantial portion of the phosphate enters the water via the domestic effluent and especially in stagnant waters (lakes , Barrages) plays a critical role in their over-fertilization. As a result of this phenomenon, also referred to as eutrophication, the use of pentasodium triphosphate in laundry detergents in a number of countries, e.g. USA, Canada, Italy, Sweden, Norway, significantly reduced by law and regulations. completely prohibited in Switzerland. In Germany, detergents since 1984 may contain no more than 20% of this builder.

In addition to nitrilotriacetic acid, especially sodium aluminosilicates (zeolites) are used as phosphate substitutes or substitutes in textile detergents. However, these substances are not suitable for use in automatic dishwashing detergents for various reasons. As an alternative to the alkali metal phosphates in automatic dishwashing detergents, therefore, a number of substitutes are discussed in the literature, of which the citrates are particularly noteworthy.

Phosphate-free automatic dishwashing detergents which, in addition to a citrate, furthermore contain carbonates, bleaches and enzymes are described, for example, in the European patents EP 662 117 B1 (Henkel KGaA) and EP 692 020 B1 (Henkel KGaA).

Despite the efforts so far, the manufacturers of automatic dishwashing detergents have hitherto not succeeded in providing phosphate-free automatic dishwashing detergents which are comparable or even exceed phosphate-containing detergents in terms of their cleaning and rinsing performance and, in particular, their coating-inhibiting performance. However, such an equality of performance is a prerequisite for the successful market introduction of phosphate-free detergents, since the vast majority of end consumers will always decide against an ecologically advantageous product despite wide public discussion of environmental issues, if this does not meet the market standard in terms of its price and / or performance.

In view of this initial situation, therefore, the object of the present application was to provide a reduced-phosphate or phosphate-free automatic dishwashing detergent, which is comparable or even comparable with conventional phosphate-containing cleaning agents in terms of its cleaning performance as well as its rinse results and its performance in terms of scale inhibition surpasses and preferably in the form of convenience of the tablet for the consumer can be offered.

It has been found that a combination of hydrophobically modified anionic polymers with a mixture of citrate and citric acid can provide automatic dishwashing detergent tablets with very good cleaning and rinse-off results with simultaneously improved hardness and disintegration properties.

1. a) 5 bis 50 Gel.-% Citrat
2. b) 1 bis 20 Gew.-% Citronensäure
3. c) 0,1 bis 40 Gew.-% hydrophob modifizierte(s) anionische(s) Polymer(e), umfassend
   1. i) 5 bis 95 Gew.-% Säuregruppen-haltige Monomere
   2. ii) 5 bis 95 Gew.-% weitere nichtionische Monomere

umfasst.A first subject of the present application is therefore a single-phase or multi-phase automatic dishwashing tablet of a compressed particulate material, characterized in that at least one tablet phase A, based on their total weight,

1. a) 5 to 50 gel .-% citrate
2. b) 1 to 20 wt .-% citric acid
3. c) from 0.1 to 40% by weight of hydrophobically modified anionic polymer (s) comprising
   1. i) from 5 to 95% by weight of acid group-containing monomers
   2. ii) from 5 to 95% by weight of other nonionic monomers

includes.

The basis for the advantageous cleaning and rinsing performance of automatic dishwasher detergents according to the invention is their content of citrate a), citric acid b) and anionic polymer c).

The basis for the advantageous hardness and disintegration properties of the tablet phases A according to the invention is their content of a combination of citrate a), citric acid b) and anionic

Polymer c). In other words, the hardness and disintegration properties of a tablet phase containing two of the three aforementioned components a), b) and c) are surprisingly improved by the addition of the respective third component.

For example, starting from a tablet phase containing citrate and citric acid, the hardness and the disintegrating property of this tablet phase are improved by the addition of the copolymer c). The observed improvement in phase hardness and phase decay is observed with the addition of anionic copolymers with nonionic monomers, but not with the addition of anionic copolymers containing no nonionic monomers.

Dishwashing detergent tablets according to the invention may have one or more phases. Automatic dishwashing detergent tablets which are preferred according to the invention are characterized in that the tablet has two or more phases.

The dishwasher tablets according to the invention are produced by compression of particulate premixes. For the purposes of this application, a "tablet phase" is therefore a body produced by tableting a particulate premix and, for example, not a granulate contained in the particulate premix. These phases may, for example, be in the form of layers, inserts (e.g., cores in a well tablet) or inclusions. Preferably, a dishwasher tablet according to the invention has at least one layer, preferably two, three or more layers. At least one of these layers corresponds in composition to the abovementioned tablet phase A.

A first characteristic constituent of agents according to the invention is the citrate. The term "citrate" includes the salts of citric acid, in particular their alkali metal salts. Particularly preferred machine dishwasher detergents according to the invention contain citrate, preferably sodium citrate, in amounts of 10 to 45% by weight, preferably 15 to 40% by weight, in each case based on the total weight of the dishwashing tablet phase.

A second characteristic constituent of agents according to the invention is citric acid. The term "citric acid" includes the citric acid itself and not its salts. Particularly preferred machine dishwasher detergents according to the invention contain citric acid in amounts of from 2 to 15% by weight and in particular from 5 to 12% by weight, in each case based on the total weight of the dishwashing tablet phase.

In terms of tablet hardness and tablet disintegration, such automatic dishwashing agents have proven particularly advantageous in which the weight ratio of citrate to citric acid in at least one of the tablet phases is 40: 1 to 2: 1, preferably 30: 1 to 2: 1 and especially 20 : 1 to 2: 1.

As a third essential ingredient, the automatic dishwashing compositions according to the invention contain anionic polymer (s) comprising acid group-containing monomer (s) and nonionic monomer (s). The proportion by weight of this copolymer in the total weight of the tablet phase is preferably 0.2 to 20 wt .-%, preferably 0.5 to 15 wt .-% and in particular 1.0 to 10 wt .-%.

Some example formulations for such preferred tablet phases A can be found in the following table: ingredient Recipe 1 Recipe 2 Recipe 3 Recipe 4 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] citrate 5 to 50 10 to 45 15 to 40 15 to 40 citric acid 2 to 15 2 to 15 2 to 15 5 to 12 Copolymer ¹ 0.1 to 40 0.2 to 20 0.5 to 15 1.0 to 10 Misc Add 100 Add 100 Add 100 Add 100 ¹ copolymer (s) comprising
i) monomers containing acid groups
ii) other nonionic monomers

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

The aforementioned copolymers c) may vary in the chemical nature of their monomers. Thus, in addition to the monomers i) and ii), further ionic or nonionic monomers may be present in the copolymer.

In a first preferred embodiment, the copolymers c) comprise at least one unsaturated carboxylic acid as the acid group-containing monomer. As unsaturated carboxylic acids i) unsaturated carboxylic acids of the formula R ¹ (R ² ) C =C (R ³ ) COOH are used in these special copolymers c), in which R ¹ to R ³ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH 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.

Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyl-acrylic acid, maleic acid, maleic anhydride, Fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof.

Dishwashing detergent tablet according to the invention, characterized in that the anionic polymer c) is a copolymer of a carboxylic acid, preferably acrylic acid or methacrylic acid or maleic acid, are preferred according to the invention.

In the polymers, the carboxylic acid groups may be wholly or partially in neutralized form, i. in that the acidic carbon atom of the carboxylic acid group in some or all of the carboxylic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or fully neutralized carboxylic acid group-containing copolymers is preferred according to the invention.

The molar mass of the carboxylic acid group-containing copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use. Preferably, the molecular weights of the copolymers are between 2000 and 200,000 gmol ^-1 , preferably between 4000 and 25,000 gmol ^-1 and in particular between 5000 and 15,000 gmol ^-1 .

Some example formulations for such preferred tablet phases A can be found in the following table: ingredient Recipe 5 Recipe 6 Recipe 7 Recipe 8 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] citrate 5 to 50 10 to 45 15 to 40 15 to 40 citric acid 2 to 15 2 to 15 2 to 15 5 to 12 Copoylmer ¹ 0.1 to 40 0.2 to 20 0.5 to 15 1.0 to 10 Misc Add 100 Add 100 Add 100 Add 100 ¹ copolymer (s) comprising
i) monomers containing carboxylic acid groups
ii) other nonionic monomers

In a first preferred embodiment, the copolymers c) comprise at least one unsaturated sulfonic acid as acid group-containing monomer. These sulfonic acid-containing copolymers used with preference contain as monomer i) preferably sulfonic acid-containing monomers of the formula R ⁵ (R ⁶ ) C =C (R ⁷ ) X-SO ₃ H, in which R ⁵ to R ⁷ independently of one another represent -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 or -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-H (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas

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, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1 propanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate , 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble salts.

In the polymers, the sulfonic acid groups may be wholly or partially in neutralized form, i. in that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.

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

Some example formulations for such preferred tablet phases A can be found in the following table: ingredient Recipe 9 Recipe 10 Recipe 11 Recipe 12 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] citrate 5 to 50 10 to 45 15 to 40 15 to 40 citric acid 2 to 15 2 to 15 2 to 15 5 to 12 Copolymer ¹ 0.1 to 40 0.2 to 20 0.5 to 15 1.0 to 10 Misc Add 100 Add 100 Add 100 Add 100 ¹ copolymer (s) comprising
i) sulfonic acid group-containing monomers
ii) other nonionic monomers

As nonionic monomers ii), preferred copolymers c) preferably comprise monomers ii) selected from the group of mono- or polyunsaturated hydrocarbon radicals having 2 to 26 carbon atoms.

1. i) Monomeren aus der Gruppe Säuregruppen-haltigen Monomere
2. ii) Monomere aus der Gruppe der ein- oder mehrfach ungesättigten Kohlenwasserstoffreste mit 2 bis 26 Kohlenstoffatomen

enthält.A first group of preferred automatic dishwashing detergents is therefore characterized in that the dishwashing detergent comprises copolymer (e) c)

1. i) monomers from the group of acid group-containing monomers
2. ii) monomers from the group of mono- or polyunsaturated hydrocarbon radicals having 2 to 26 carbon atoms

contains.

Some example formulations for such preferred tablet phases A can be found in the following table: ingredient Recipe 13 Recipe 14 Recipe 15 Recipe 16 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] citrate 5 to 50 10 to 45 15 to 40 15 to 40 citric acid 2 to 15 2 to 15 2 to 15 5 to 12 Copolymer ¹ 0.1 to 40 0.2 to 20 0.5 to 15 1.0 to 10 Misc Add 100 Add 100 Add 100 Add 100 ¹ copolymer (s) comprising
i) monomers from the group of acid group-containing monomers
ii) monomers from the group of mono- or polyunsaturated hydrocarbon radicals having 2 to 26 carbon atoms

As unsaturated hydrocarbon radicals ii) are in the copolymers c), so for example in the previously described preferred copolymers c) having a carboxylic acid or sulfonic acid-containing monomer i), preferably monomers of the general formula R ¹ (R ² ) C = C. (R ³ ) -XR ⁴ used, in which R ¹ to R ³ independently of one another is -H, -CH ₃ or -C ₂ H ₅ , X is an optional spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 represents} a straight or branched chain saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.

Particularly preferred unsaturated hydrocarbon radicals are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexene, 1-octene, α-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22-α-olefin, 2-styrene, α Methylstyrene, 3-methylstyrene, 4-propylstryol, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2, vinylnaphthalene, Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methyl methacrylate, N- (methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N- (2-ethylhexyl) acrylamide, octyl acrylate, octyl methacrylate, N- (octyl ) acrylamide, acryloyl acrylate, lauryl methacrylate, N- (lauryl) acrylamide, stearyl acrylate, stearyl methacrylate, N- (stearyl) acrylamide, behenyl acrylate, behenyl methacrylate and N- (behenyl) acrylamide or mixtures thereof.

As an alternative to the abovementioned embodiments, the anionic polymers c) used in tablet phases A according to the invention may also contain a combination of monomers containing carboxylic acid groups and monomers containing sulfonic acid groups.

1. i) Carbonsäuregruppen-haltigem Monomer
2. ii) Sulfonsäuregruppen-haltigem Monomer
3. iii) nichtionogenem Monomer

handelt, werden erfindungsgemäß bevorzugt.Dishwashing tablet according to one of the preceding claims, characterized in that the anionic polymer c) is a copolymer of

1. i) monomer containing carboxylic acid groups
2. ii) sulfonic acid group-containing monomer
3. iii) nonionic monomer

are preferred according to the invention.

The above-described dishwashing detergent tablets according to the invention may contain, in addition to the aforementioned ingredients, further washing or cleaning-active substances, preferably from the group of builders, surfactants, polymers, bleaches, bleach activators, enzymes, glass corrosion inhibitors, corrosion inhibitors, disintegration aids, fragrances and perfume carriers. These preferred ingredients will be described in more detail below.

The builders include in particular silicates, carbonates and organic cobuilders as well as the phosphates.

With preference, automatic dishwashing agents according to the invention contain as builder crystalline layered silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4 where particularly preferred values for x are 2, 3 or 4 and y is a number from 0 to 33, preferably from 0 to 20.

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 preferably delayed release and have secondary washing properties.

Machine dishwashing detergents preferred in the context of the present invention comprise from 2 to 15% by weight, preferably from 3 to 12% by weight and in particular from 4 to 8% by weight, of silicate (s).

Particularly preferred is the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of 1 to 60 wt .-%, preferably from 5 to 55 wt .-% and in particular from 10 to 50 wt .-%, each based on the weight of the automatic dishwashing detergent.

Dishwashing detergent tablets according to the invention, characterized in that the tablet, based in each case on its total weight, contains between 1 and 60% by weight, preferably between 5 and 55 and in particular between 10 and 50% by weight of carbonate, are preferred according to the invention.

Some example formulations for preferred carbonate-containing tablet phases A can be found in the following table: ingredient Recipe 17 Recipe 18 Recipe 19 Recipe 20 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] citrate 5 to 50 10 to 45 15 to 40 15 to 40 citric acid 2 to 15 2 to 15 2 to 15 5 to 12 Copolymer ¹ 0.1 to 40 0.2 to 20 0.5 to 15 1.0 to 10 Sodium carbonate / bicarbonate 1 to 60 5 to 55 10 to 50 10 to 50 Misc Add 100 Add 100 Add 100 Add 100 ¹ copolymer (s) comprising
i) monomers containing acid groups
ii) other nonionic monomers

Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and other organic cobuilders. These classes of substances are described below.

Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. For example, these are in addition to the above citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for environmental reasons, as well as mixtures of these. In addition to their builder effect, the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Among the large number of commercially available phosphates, the alkali metal phosphates, with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.

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.

Technically particularly important phosphates are the pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate). The sodium potassium tripolyphosphates are also preferably used according to the invention.

If phosphates are used as washing or cleaning substances in automatic dishwashing detergent tablets within the scope of the present application, preferred tablets comprise this phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or pentasodium). Potassium tripolyphosphate), in amounts of less than 20% by weight, preferably less than 10% by weight and in particular less than 5% by weight. Particularly preferred machine dishwashing detergent tablets according to the invention are free of inorganic phosphates.

Some example formulations for preferred tablet phases A as a constituent of phosphate-free automatic dishwasher tablets can be found in the following table: ingredient Recipe 21 Recipe 22 Recipe 23 Recipe 24 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] citrate 5 to 50 10 to 45 15 to 40 15 to 40 citric acid 2 to 15 2 to 15 2 to 15 5 to 12 Copolymer ¹ 0.1 to 40 0.2 to 20 0.5 to 15 1.0 to 10 Misc Add 100 Add 100 Add 100 Add 100 ¹ copolymer (s) comprising
i) monomers containing acid groups
ii) other nonionic monomers

In addition to the active ingredient combination of citrate, citric acid and anionic polymer, complexing agents, preferably phosphonates, are used in preferred dishwasher tablets. Particularly preferred dishwashing detergent tablets according to the invention are characterized in that the tablets contain at least one complexing agent, preferably 1-hydroxyethane-1,1-diphosphonic acid and / or methylglycine diacetic acid.

In addition to 1-hydroxyethane-1,1-diphosphonic acid, the complex-forming phosphonates comprise a number of different compounds such as, for example, diethylene triamine penta (methylene phosphonic acid) (DTPMP). Hydroxyalkane or aminoalkane phosphonates are particularly preferred in this application. Among the hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

1. a) Aminotrimethylenphosphonsäure (ATMP) und/oder deren Salze;
2. b) Ethylendiamintetra(methylenphosphonsäure) (EDTMP) und/oder deren Salze;
3. c) Diethylentriaminpenta(methylenphosphonsäure) (DTPMP) und/oder deren Salze;
4. d) 1-Hydroxyethan-1,1-diphosphonsäure (HEDP) und/oder deren Salze;
5. e) 2-Phosphonobutan-1,2,4-tricarbonsäure (PBTC) und/oder deren Salze;
6. f) Hexamethylendiamintetra(methylenphosphonsäure) (HDTMP) und/oder deren Salze;
7. g) Nitrilotri(methylenphosphonsäure) (NTMP) und/oder deren Salze.

An automatic dishwashing agent A preferred in the context of this application contains one or more phosphonate (s) from the group

1. a) aminotrimethylenephosphonic acid (ATMP) and / or salts thereof;
2. b) ethylenediaminetetra (methylenephosphonic acid) (EDTMP) and / or salts thereof;
3. c) diethylenetriamine penta (methylenephosphonic acid) (DTPMP) and / or salts thereof;
4. d) 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and / or salts thereof;
5. e) 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) and / or salts thereof;
6. f) hexamethylenediaminetetra (methylenephosphonic acid) (HDTMP) and / or salts thereof;
7. g) nitrilotri (methylenephosphonic acid) (NTMP) and / or salts thereof.

Particularly preferred are automatic dishwashing detergents which contain as phosphonates 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta (methylenephosphonic acid) (DTPMP).

Of course, the automatic dishwashing compositions of the invention may contain two or more different phosphonates.

In a preferred embodiment of the present invention, the weight fraction of the phosphonate (s) in the total weight of the automatic dishwashing agent is less than the weight proportion of the polymer (s) b). In other words, those agents are particularly preferred in which the ratio of the weight fraction of polymer b) to the weight fraction of the phosphonate is 200: 1 to 2: 1, preferably 150: 1 to 2: 1, particularly preferably 100: 1 to 2: 1, most preferably 80: 1 to 3: 1 and in particular 50: 1 to 5: 1.

The proportion by weight of these complexing agents, in particular the sum of the proportions by weight of 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and methylglycinediacetic acid (MGDA) is preferably 0.5 to 14% by weight, preferably 1 to 12% by weight and in particular 2 to 8 wt .-%.

To increase the washing or cleaning performance, preferred automatic dishwashing detergent tablets contain enzyme (s). These include in particular proteases, amylases, lipases, Hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly. Detergents or cleaning agents contain enzymes preferably in total amounts of 1 × 10 ^-6 to 5 wt .-% based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferable. Examples of these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, B. amyloliquefaciens, B. stearothermophilus, Aspergillus niger and A. oryzae, as well as the further developments of the aforementioned amylases which are improved for use in detergents and cleaners. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.

Furthermore, enzymes can be used, which are summarized by the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

Oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect. Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.

Washing or cleaning-active enzymes such as proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storable and transportable preparations. Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.

Alternatively, the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.

Furthermore, it is possible to assemble two or more enzymes together so that a single granule has several enzyme activities.

As can be seen from the previous comments, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Preferred enzyme preparations according to the invention, such as protease and amylase preparations, contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, more preferably between 0.4 and 20% by weight and in particular between 0.8 and 10% by weight of the enzyme protein.

Preferred dishwasher tablets are characterized in that the tablet, in each case based on their total weight, 0.2 to 5 wt .-%, preferably 0.5 to 5 wt .-% and in particular 0.1 to 4 wt .-% of one or more Enzyme preparation (s) contains.

Preferred automatic dishwashing agents according to the invention also contain one or more bleaching agents. Among the compounds serving as bleaches in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

Furthermore, bleaching agents from the group of organic bleaching agents can also be used. 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 dishwashing detergent tablets according to the invention are characterized in that the tablet, based in each case on their total weight, contains 1 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 12% by weight of sodium percarbonate.

In order to achieve an improved bleaching effect when cleaning at temperatures of 60 ° C and below, the automatic dishwashing detergent tablets according to the invention may additionally contain bleach activators. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, with tetraacetylethylenediamine (TAED) having proven particularly suitable.

These bleach activators, in particular TAED, are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, especially 2 to 8% by weight and more preferably 2 to 6% by weight. , in each case based on the total weight of the bleach activator-containing agents used.

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

It is particularly preferred to use complexes of manganese in the oxidation state II, III, IV or IV, which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S. Preferably, ligands are used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononan (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and or 2-methyl-1,4,7-triazacyclononane (Me / TACN). Suitable manganese complexes are, for example, [Mn ^III ₂ (μ-O) ₁ (μ-OAc) ₂ (TACN) ₂ ] (CIO ₄ ) ₂ , [Mn ^III Mn ^IV (μ-O) ₂ (μ-OAc) ₁ (TACN ) ₂ ] (BPh ₄ ) ₂ , [Mn ^IV ₄ (μ-O) ₆ (TACN) ₄ ] (CIO ₄ ) ₄ , [Mn ^III ₂ (μ-O) ₁ (μ-OAc) ₂ (Me-TACN ) ₂ ] (ClO ₄ ) ₂ , [Mn ^III Mn ^IV (μ-O) ₁ (μ-OAc) ₂ (Me-TACN) ₂ ] (ClO ₄ ) ₃ , [Mn ^IV ₂ (μ-O) ₃ ( Me-TACN) ₂ ] (PF ₆ ) ₂ and [Mn ^IV ₂ (μ-O) ₃ (Me / Me-TACN) ₂ ] (PF ₆ ) ₂ (OAc = OC (O) CH ₃ ).

Automatic dishwasher tablets, characterized in that it further comprises a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me ₃ -TACN ) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me ₄ -TACN), are preferred according to the invention, since in particular the cleaning result can be significantly improved by the abovementioned bleach catalysts.

The abovementioned bleach-enhancing transition metal complexes, in particular with the central atoms Mn and Co, are used in customary amounts, preferably in an amount of up to 5% by weight. Dishwashing detergent tablets, characterized in that the tablet contains, based on their total weight, 0.01 to 2 wt .-%, preferably 0.02 to 1 wt .-% and in particular 0.05 to 0.8 wt .-% bleach catalyst are preferred according to the invention.

As an additional ingredient, preferred dishwashing detergents according to the invention may contain surfactants. The addition of surfactants has been found to be particularly advantageous in terms of cleaning performance and drying, the nonionic gave the best results from the group of non-ionic surfactants used with particular preference, anionic surfactants and amphoteric surfactants. Anionic and amphoteric surfactants are preferably used in combination with defoamers or foam inhibitors.

As nonionic surfactants, it is possible to use all nonionic surfactants known to the person skilled in the art. Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) _x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which is 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.

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

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

Low-foaming nonionic surfactants are used as preferred surfactants. With particular preference, washing or cleaning agents, in particular automatic dishwashing detergents, contain 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 is linear or preferably methyl-branched in the 2-position may contain or linear and methyl-branched radicals in the mixture, 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 moles of 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 stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of 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 therefore given to ethoxylated nonionic surfactants consisting of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol of ethylene oxide per mol Alcohol was used. A particularly preferred 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 mol, preferably at least 15 mol and especially at least 20 mol of ethylene oxide. Of these, the so-called "narrow range ethoxylates" are particularly preferred.

With particular preference further combinations of one or more tallow fatty alcohols with 20 to 30 EO and silicone defoamers are used.

Particular preference is given to nonionic surfactants which have a melting point above room temperature. Nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, is / are particularly preferred ,

Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pa · s, preferably above 35 Pa · s and in particular above 40 Pa · s. Also, nonionic surfactants having waxy consistency at room temperature are preferred depending on their purpose.

Nonionic surfactants from the group of alkoxylated alcohols, more preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO-Niotenside, are also used with particular preference.

The nonionic surfactant solid at room temperature preferably has propylene oxide units in the molecule. Preferably, such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol content of such nonionic surfactant molecules preferably makes up more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight, of the total molecular weight of such nonionic surfactants. Preferred agents 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 up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.

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

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

bevorzugt, in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht; jede Gruppe R² bzw. R³ unabhängig voneinander ausgewählt ist aus -CH₃, -CH₂CH₃, -CH₂CH₂-CH₃, CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.In the context of the present invention, particularly preferred nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here are nonionic surfactants of the general formula

in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical; each group R ² or R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently stand for integers from 1 to 6.

The preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R'-OH and ethylene or alkylene oxide. The radical R ¹ in the above formula may vary depending on the origin of the alcohol. If native sources are used, the radical R ^{1 has} an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of natural origin having 12 to 18 C atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred. Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions, preference is given to nonionic surfactants in which R ¹ in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.

As the alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide. But also other alkylene oxides in which R ² or R ^{3 are} independently selected from -CH ₂ CH ₂ -CH ₃ or -CH (CH ₃ ) ₂ are suitable. Preference is given to using nonionic surfactants of the above formula in which R ² or R ^{3 is} a radical -CH ₃ , w and x independently of one another for values of 3 or 4 and y and z independently of one another are values of 1 or 2.

In summary, particularly preferred are nonionic surfactants having a C _9-15 alkyl group having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units. These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.

Surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A"'O) _z -R ² , in which R ¹ and R ² independently of one another represents a straight-chain or branched, saturated or mono- or polyunsaturated C _2-40 -alkyl or -alkenyl radical; A, A ', A "and A"' independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0 are preferred according to the invention.

Preference is given in particular to those end-capped poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² , in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 2 to 30 carbon atoms, preferably having from 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having from 1 to 30 carbon atoms, where x is from 1 to 30 carbon atoms 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.

Particularly preferred are 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 with 4 R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1.5 and y is a value of at least 15.

Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² , in which R ¹ and R ² independently of one another is a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ , - CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ , but preferably -CH ₃ , and x and y are independently from each other values between 1 and 32, wherein nonionic surfactants with R ³ = -CH ₃ and values of x from 15 to 32 and y of 0.5 and 1.5 are very particularly preferred.

By using the above-described nonionic surfactants having a free hydroxyl group on one of the two terminal alkyl radicals, the formation of deposits in machine dishwashing can be markedly improved compared to conventional polyalkoxylated fatty alcohols without a free hydroxyl group.

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. When the value x ≥ 2, each R ³ in the above formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ^{2 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 R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² simplified. In the latter 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.

The stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.

Of course, the aforementioned nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants. Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas ,

In a preferred embodiment, the dishwashing tablet according to the invention contains, based on its total weight, nonionic surfactant in amounts of from 0.1 to 10% by weight, preferably from 0.2 to 8% by weight and in particular from 3 to 6% by weight.

Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group of magnesium and zinc salts and magnesium and zinc complexes.

The spectrum of the invention preferred zinc salts, preferably organic acids, particularly preferably organic carboxylic acids, ranging from salts which are difficult or insoluble in water, ie a solubility below 100 mg / l, preferably below 10 mg / l, in particular below 0.01 have mg / l, to those salts which have a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and in particular above 5 g / l (all solubilities at 20 ° C. water temperature). The first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate, and the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.

With particular preference as glass corrosion inhibitor at least one zinc salt of an organic carboxylic acid, particularly preferably a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, Zinc acetate, zinc lactate and zinc citrate used. Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.

In the context of the present invention, the content of zinc salt in detergents or cleaners is preferably between 0.1 and 5% by weight, preferably between 0.2 and 4% by weight and in particular between 0.4 and 3% by weight. , or the content of zinc in oxidized form (calculated as Zn ²⁺ ) between 0.01 to 1 wt .-%, preferably between 0.02 to 0.5 wt .-% and in particular between 0.04 to 0, 2 wt .-%, each based on the total weight of the glass corrosion inhibitor-containing agent.

Corrosion inhibitors serve to protect the items to be washed or the machine, with particular silver protectants being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. According to the invention, preference is given to using 3-amino-5-alkyl-1,2,4-triazoles or their physiologically tolerated salts, these substances being particularly preferably used in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2 Wt .-%, particularly preferably 0.01 to 0.04 wt .-% are used. Preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulphurous acid, organic carboxylic acids such as acetic, glycolic, citric and succinic acid. Especially effective are 5-pentyl, 5-heptyl, 5-nonyl, 5-undecyl, 5-isononyl, 5-Versatio-10-acid alkyl-3-amino-1,2,4-triazoles and mixtures of these substances.

In order to facilitate the disintegration of preformed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, into these compositions in order to shorten the disintegration times. By tablet disintegrants or disintegrants are meant excipients which ensure the rapid disintegration of tablets in water or other media and for the rapid release of the active ingredients.

These substances, which are also referred to as "explosives" due to their effect, increase their volume upon ingress of water, on the one hand increasing the intrinsic volume (swelling), and on the other hand creating a pressure via the release of gases which can break the tablet into smaller particles disintegrates. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also 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.

Disintegration aids are preferably used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration assistant-containing agent.

As perfume oils or perfumes, within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, Citrus, Jasmine, Patchouly, Rose or Ylang-Ylang oil.

The fragrances can be processed directly, but it can also be advantageous to apply the fragrances on carriers that provide a slower fragrance release for long-lasting fragrance. As such carrier materials, for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.

Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to the substrates to be treated with the dye-containing agents such as textiles, glass, ceramics or plastic dishes do not stain them.

When choosing the colorant, it must be taken into account that the colorants have a high storage stability and insensitivity to light. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. In the case of readily water-soluble colorants, colorant concentrations in the range of a few 10 ^-2 to 10 ^-3 % by weight are typically selected. By contrast, in the case of the particularly preferred, but less readily water-soluble, pigment dyes due to their brilliance, the suitable concentration of the colorant in detergents or cleaners is typically about 10 ^-3 to 10 ^-4 % by weight.

Dyeing agents which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners, are preferred. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic colorants, for example anionic nitrosofarbstoffe.

Preferred automatic dishwashing detergent tablets contain a binder in addition to the washing and cleaning-active substances. Particularly preferred is the integration of such a binder into the tablet phase A of the dishwasher tablet. The group of preferred binders includes organic materials from the group of (modified) celluloses and starches. However, particularly preferred binders are nonionic polymers, preferably polyethylene glycols or polyvinylpyrrolidones.

Dishwashing detergent tablets, characterized in that the tablet phase A contains a nonionic polymer, preferably a nonionic polymer from the group polyalkylene glycols, are preferred according to the invention. The proportion by weight of the polyethylene glycol in the total weight of the tablet phase A is preferably 0.1 to 10 wt .-%, preferably 0.1 to 5 wt .-% and in particular 0.1 to 3 wt .-%

Some example formulations for preferred binder-containing tablet phases A can be found in the following table: ingredient Recipe 25 Recipe 26 Recipe 27 Recipe 28 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] citrate 5 to 50 10 to 45 15 to 40 15 to 40 citric acid 2 to 15 2 to 15 2 to 15 5 to 12 Copolymer ¹ 0.1 to 40 0.2 to 20 0.5 to 15 1.0 to 10 polyethylene glycol 0.1 to 5 0.1 to 5 0.1 to 5 0.1 to 3 Misc Add 100 Add 100 Add 100 Add 100 ¹ copolymer (s) comprising
i) monomers containing acid groups
ii) other nonionic monomers

The manufacture of the dishwasher tablets preferably takes place in a manner known to the person skilled in the art by compressing particulate premixes. In this case, it is preferred according to the invention that the particulate premix has an average particle size between 0.4 and 3.0 mm, preferably between 0.6 and 2.5 mm and in particular between 0.8 and 2.0 mm.

The tabletting, during which the particulate premix is compressed in a so-called matrix between two punches to form a solid compress, is divided into four sections: metering, compaction (elastic deformation), plastic deformation and expulsion. The tabletting is preferably carried out on so-called rotary presses.

• Verwendung von Kunststoffeinlagen mit geringen Dickentoleranzen
• Geringe Umdrehungszahl des Rotors
• Große Füllschuhe
• Abstimmung des Füllschuhflügeldrehzahl auf die Drehzahl des Rotors
• Füllschuh mit konstanter Pulverhöhe
• Entkopplung von Füllschuh und Pulvervorlage

When tableting with rotary presses, it has proven to be advantageous to carry out the tableting with the lowest possible weight fluctuations of the tablet. In this way, the hardness fluctuations of the tablet can be reduced. Small variations in weight can be achieved in the following ways:

• Use of plastic inserts with small thickness tolerances
• Low number of revolutions of the rotor
• Big filling shoes
• Tuning of the filling paddle speed to the speed of the rotor
• Filling shoe with constant powder height
• Decoupling of filling shoe and powder template

To reduce Stempelanbackungen offer all known from the art non-stick coatings. Plastic coatings, plastic inserts or plastic stamps are particularly advantageous. Rotary punches have also proved to be advantageous, whereby upper and lower punches should, if possible, be rotatable. With rotating punches can be dispensed with a plastic insert usually. Here, the stamp surfaces should be electropolished.

Preferred processes in the context of the present invention are characterized in that the pressing takes place at pressing pressures of 0.01 to 50 kNcm ^-2 , preferably of 0.1 to 40 kNcm ^-2 and in particular of 1 to 25 kNcm ^-2 .

The density of dishwasher tablets preferred according to the invention is between 1.1 and 1.8 g / cm ³ , preferably between 1.2 and 1.7 cm ³ and in particular between 1.3 and 1.6 g / cm ³ .

1. a) 5 bis 50 Gew.-% Citrat
2. b) 1 bis 20 Gew.-% Citronensäure
3. c) 0,1 bis 40 Gew.-% anionische(s) Polymer(e)

hergestellt und zu einer Tablette verpresst wird.A further subject of the present application is therefore a process for the preparation of a dishwashing detergent tablet, characterized in that a particulate premix comprising

1. a) 5 to 50 wt .-% citrate
2. b) 1 to 20 wt .-% citric acid
3. c) from 0.1 to 40% by weight of anionic polymer (s)

prepared and compressed into a tablet.

Concentric presses can be provided to increase the throughput with two filling shoes, which only a semicircle must be run through to produce a tablet.

As mentioned above, the tablets in the context of the present invention can also be multi-phase, in particular multi-layered. The moldings can be made in a predetermined spatial form and predetermined size. As a form of space practically all useful manageable configurations come into consideration, for example, the training as a blackboard, the bar or bar shape, cubes, cuboids and corresponding space elements with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section. This last embodiment covers the presentation form of the tablet up to compact cylinder pieces with a ratio of height to diameter above 1.

To produce two-layered and multi-layered shaped bodies, several filling shoes are arranged one after the other without the slightly pressed-on first layer being ejected before further filling. By suitable process control coat and point tablets can be produced in this way, which have a zwiebelschalenartigen structure, wherein in the case of the point tablets, the top of the core or the core layers is not covered and thus remains visible. Producible are further mortar tablets, which have on their upper side a trough (a one-sided opened by webs and a base limited cavity).

1. a) 5 bis 50 Gew.-% Citrat
2. b) 1 bis 20 Gew.-% Citronensäure
3. c) 0,1 bis 40 Gew.-% anionische(s) Polymer(e)

hergestellt und zu einer Muldentablette verpresst wird, werden erfindungsgemäß bevorzugt.Corresponding processes for producing a dishwashing detergent tablet, characterized in that a particulate premix comprising

1. a) 5 to 50 wt .-% citrate
2. b) 1 to 20 wt .-% citric acid
3. c) from 0.1 to 40% by weight of anionic polymer (s)

prepared and pressed into a well tablet, are preferred according to the invention.

After pressing, the detergent tablets have a high stability. The breaking strength of cylindrical shaped bodies can be detected by the measurand of the diametric breaking load. This is determinable $$\sigma =\frac{2P}{\mathit{\pi Dt}}$$

Herein, σ is the diametrical fracture stress (DFS) in Pa, P is the force in N which results in the pressure applied to the molded article causing the breakage of the molded article, D is the molded article diameter in meters and t the height of the moldings.

1. a) eine erfindungsgemäße maschinelle Geschirrspülmitteltablette;
2. b) eine Anleitung, die den Verbraucher darauf hinweist, das maschinelle Geschirrspülmittel ohne Zusatz eines Klarspülers und/oder eines Enthärtersalzes zu verwenden ist, ist ein weiterer Gegenstand dieser Anmeldung.

The subject matter of the present application is furthermore a method for cleaning dishes in a dishwasher using automatic dishwasher tablets according to the invention, wherein the automatic dishwashing tablets are preferably metered into the interior of a dishwasher during the passage of a dishwashing program, before the main wash cycle or during the main wash cycle. The metering or the entry of the agent according to the invention into the interior of the dishwasher can be done manually, but preferably the agent is metered into the interior of the dishwasher by means of the metering chamber of the dishwasher. In the course of the cleaning process preferably no additional water softener and no additional rinse aid is dosed into the interior of the dishwasher. A kit for a dishwasher, comprising

1. a) a dishwasher automatic tablet according to the invention;
2. (b) instructions instructing the consumer to use the automatic dishwashing detergent without the addition of a rinse aid and / or a softening salt are another subject of this application.

The automatic dishwasher detergents according to the invention show their advantageous cleaning properties, in particular also low-temperature cleaning processes. Preferred dishwashing processes using agents according to the invention are therefore characterized in that these processes are carried out at temperatures up to a maximum of 55 ° C., preferably up to a maximum of 50 ° C.

Examples

Each 20 g of three different particulate premixes were pressed with a force of 50 kN into tablets weighing 20 g.

The composition of the particulate premixes can be found in the following table: raw material V1 V2 E1 phosphonate 1.94 1.94 1.94 Nonionic surfactant 5.66 5.66 5.66 Sodium citrate dihydrate 22.39 22.39 22.39 Citric acid anhydrate 5.76 5.76 5.76 soda 32.36 32.36 32.36 sodium 17,04 17,04 17,04 TAED 4.17 4.17 4.17 Polyacrylic acid ¹ 9.06 - - Polysulfonic acid ² - 9.06 - Anionic polymer ³ - - 9.06 Misc Add 100 Add 100 Add 100 ¹ polyacrylic acid, sodium salt
² sulfonic acid-containing copolymer without nonionic monomers, sodium salt
³ anionic polymer, sodium salt, comprising
i) monomers containing acid groups
ii) other nonionic monomers

The breaking hardness of the obtained tablets was determined. The results are given in the table below (The values given are averages of 10 measurements each): V1 V2 E1 Tablet hardness [N] 224 245 301

As can be seen from these results, the hardness of citrated and citric acid-containing tablets is markedly improved by the addition of hydrophobically modified anionic copolymers.

Claims (15)

1. A mono- or multiphasic automatic dishwashing agent tablet made from a press-moulded particulate material, characterised in that at least one tablet phase A, relative to the total weight thereof, comprises

   a) 5 to 50 wt.% of citrate

   b) 1 to 20 wt. % of citric acid

   c) 0.1 to 40 wt.% of hydrophobically modified anionic polymer(s), comprising

   i) 5 to 95 wt.% of monomers containing acid groups

   ii) 5 to 95 wt.% of further nonionic monomers.
2. A dishwashing agent tablet according to claim 1, characterised in that the tablet phase A, in each case relative to the total weight thereof,
   contains 10 to 45 wt.% and in particular 15 to 40 wt.% of citrate, preferably sodium citrate.
3. A dishwashing agent tablet according to either one of the preceding claims, characterised in that the tablet phase A, in each case relative to the total weight thereof, contains 2 to 15 wt.% and in particular 5 to 12 wt.% of citric acid.
4. A dishwashing agent tablet according to any one of the preceding claims, characterised in that the weight ratio of citrate to citric acid in the tablet phase A amounts to 40:1 to 2:1, preferably 30:1 to 2:1 and in particular 20:1 to 2:1.
5. A dishwashing agent tablet according to any one of the preceding claims, characterised in that the tablet phase A, in each case relative to the total weight thereof, contains the anionic polymer c) in quantities of 0.2 to 20 wt.%, preferably 0.5 to 15 wt.% and in particular of 1.0 to 10 wt.%.
6. A dishwashing agent tablet according to any one of the preceding claims, characterised in that the anionic polymer c) is a copolymer of a carboxylic acid, preferably of acrylic acid or methacrylic acid or maleic acid.
7. A dishwashing agent tablet according to any one of the preceding claims, characterised in that the anionic polymer c) is a copolymer of

   i) monomer containing carboxylic acid groups

   ii) monomer containing sulfonic acid groups

   iv) nonionogenic monomer.
8. A dishwashing agent tablet according to any one of the preceding claims, characterised in that the tablet phase A, in each case relative to the total weight thereof, contains less than 20 wt.%, preferably less than 10 wt.% and in particular less than 5 wt.% of phosphate.
9. A dishwashing agent tablet according to any one of the preceding claims, characterised in that the tablet phase A, in each case relative to the total weight thereof, contains between 1 and 60 wt.%, preferably between 5 and 55 and in particular between 10 and 50 wt.% of carbonate.
10. A dishwashing agent tablet according to any one of the preceding claims, characterised in that the tablet, in each case relative to the total weight thereof, contains 0.2 to 5 wt.%, preferably 0.5 to 5 wt.% and in particular 0.1 to 4 wt.% of enzyme preparation(s).
11. A dishwashing agent tablet according to any one of the preceding claims, characterised in that the tablet, in each case relative to the total weight thereof, contains 1 to 20 wt.%, preferably 2 to 15 wt.% and in particular 4 to 12 wt.% of sodium percarbonate.
12. A method for producing a dishwashing agent tablet according to any one of the preceding claims, characterised in that a particulate premix comprising

    a) 5 to 50 wt.% of citrate

    b) 1 to 20 wt.% of citric acid

    c) 0.1 to 40 wt.% of anionic polymer(s)

    is produced and press-moulded to form a tablet phase.
13. A method according to claim 12, characterised in that the particulate premix exhibits an average particle size of between 0.4 and 3.0 mm, preferably between 0.6 and 2.5 mm and in particular between 0.8 and 2.0 mm.
14. A method for cleaning dishes in a dishwashing machine using automatic dishwashing agents according to any one of claims 1 to 11.
15. A method according to claim 14, characterised in that no additional water softener and no additional rinse aid is dispensed into the interior of the dishwashing machine in the course of the cleaning method.