Detergent

ES 2 396 568 T3

DESCRIPTION

Detergents

The present patent application describes cleaning products (detergents), especially cleaning products for dishwashers. The object of this application is in particular products for dishwashing machines, which do not contain phosphates.

Dishes that are machine washed must meet higher demands than dishes that are washed by hand. For example, after washing the dishes in the machine, the dishes must be completely free of food residues and also must not present whitish stains due to the hardness of the water or other mineral salts, which come from the drops of water dried in absence of humectant.

Modern products for dishwashers meet these requirements thanks to the integration of cleaning, care, descaling and polishing active substances and are already known to users, for example, under the name "2 in 1" or "3 in 1" dishwashing products. As an essential component for successful washing and polishing, the products for dishwashers intended for end users in the domestic sector contain carrier substances (builder). These carrier substances, on the one hand, increase the basicity of the washing bath, so that when the basicity increases, fats and oils are emulsified and saponified, and on the other hand, they reduce the hardness of the washing bath water thanks to the formation of complexes (chelates) of the calcium ions existing in the aqueous bath. Alkali phosphates, which for this reason constitute the main component of most commercial dishwasher products, have proven to be particularly effective carrier substances.

Due to their advantageous action, phosphates are highly valued as components of products for dishwashing machines, but from the point of view of environmental protection, their use is still problematic, since an important part of the phosphate in wastewater Domestic waters are discharged into river courses and play an important role, especially in over-fertilizing stagnant waters (lakes, swamps). As a result of this phenomenon, also called eutrophication, legal provisions have been issued that considerably reduce the use of pentasodium triphosphate in textile detergents in several countries, e.g. the United States, Canada, Italy, Sweden, Norway, while in Switzerland such use is totally prohibited. In Germany from 1984 onwards, detergents can only contain a maximum of 20% of these carrier substances (builder).

Nitrilotriacetic acid and especially sodium aluminum silicates (zeolites) are used as substitutes or substitutes for phosphates in textile detergents. But these substances for various reasons are not suitable for use in products for dishwashers. As an alternative to alkaline phosphates in products for dishwashing machines, a number of substitutes have therefore been discussed in the technical literature, including citrates in particular.

Phosphate-free dishwashing products, which in addition to a citrate also contain carbonates, bleaches and enzymes, have been described, for example, in European patents EP 662 117 B1 (Henkel KGaA) and EP 692 020 B1 (Henkel KGaA).

Another alternative to alkali phosphates, which is used as the sole carrier substance preferably in combination with citrates, is methylglycine acetic acid (MGDA). Products for dishwashing machines containing MGDA have been described, for example, in European patent EP 906 407 B1 (Reckitt Benckiser) or in European patent application EP 1 113 070 a2 (Reckitt Benckiser). Other relevant documents are US 5279756 and US 5308532.

Despite the efforts made to date, manufacturers of dishwasher products have failed to develop phosphate-free dishwasher products that are similar to or even superior to phosphate-bearing cleaners in cleaning performance. and polishing and especially with regard to the effectiveness to inhibit the formation of sediments. This equality in effectiveness is a prerequisite for the market launch of phosphate-free detergent products, because the majority of end consumers despite the wide public debate on environmental policy issues have always spoken out against an ecologically advantageous product, if this by price and / or by benefits it does not meet the standard level existing in the market.

In view of this initial situation, there is therefore as an object of the present application the need to develop a product for dishwashing machines without phosphates, which is similar or even superior to conventional detergents containing phosphates with regard to cleaning efficiency and even with regard to the polishing results and the inhibiting effectiveness of the formation of deposits (sediments).

It has been observed that products for dishwashers, which, apart from the carrier substance and the bleach, also contain specific non-ionic surfactants and specific copolymers modified to have

ES 2 396 568 T3 hydrophobic character, they display an excellent inhibition of sediments and a great cleaning and polishing efficiency, even without the addition of alkaline phosphates.

A first object of the present application is, therefore, a product for dishwashing machines without phosphates, which contains a carrier substance, a bleach and also

a) a copolymer formed by:

i) monomers of the group of mono- or polyunsaturated carboxylic acids, ii) monomers of the general formula R¹(R²) C = C (R³) -XR⁴, in which R¹ to R³ independently of one another signify -H, -CH3 or -C2H5, X signifies an optionally present spacer group, which is chosen from -CH2-, -C (O) O- and -C (O) -NH-, and R⁴ is a saturated, linear or branched alkyl radical of 2 to 22 carbon atoms or an unsaturated hydrocarbon radical, preferably aromatic, of 6 to 22 carbon atoms iii) optionally other monomers

b) a nonionic surfactant of the general formula R¹-CH (OH) CH2O- (AO) w (A'O) x (A "O) y- (A" 'O) zR², in which R¹means a linear or branched saturated or mono- or polyunsaturated C6-24 alkyl or alkenyl radical; and R² means a straight or branched hydrocarbon residue of 2 to 26 carbon atoms; A, A ', A "and A"' independently of one another signify a residue chosen from the group -CH2CH2, -CH2CH2-CH2, -CH2-CH (CH3), -CH2-CH2-CH2-CH2, -CH2- CH (CH3) -CH2, -CH2-CH (CH2-CH3); and "w", "x", "y" and "z" take values ​​between 0.5 and 120, where "x", "y" and / or "z" can also be 0.

A first essential component of the products for dishwashing machines of the invention is the copolymer a) modified to have hydrophobic character, formed by the monomers i) and ii).

As monomers i) of the group of mono- or polyunsaturated carboxylic acids, unsaturated carboxylic acids of the general formula R are particularly preferred.¹(R²) C = C (R³) COOH, in which R¹ to R³independently of one another mean -H, -CH3, a saturated linear or branched alkyl radical of 2 to 12 carbon atoms, a mono- or polyunsaturated, linear or branched alkenyl radical of 2 to 12 carbon atoms, substituted alkyl or alkenyl radicals by -NH2, -OH or -COOH already defined above or means -COOH or -COOR⁴, said R⁴ is a linear or branched saturated or unsaturated hydrocarbon residue of 1 to 12 carbon atoms.

Preferred according to the invention are products for dishwashers without phosphates, which contain a carrier substance, bleach and also

a) a copolymer formed by:

i) monomers of the group of carboxylic acids of the general formula R¹(R²) C = C (R³) COOH, in which R¹to R³ independently of one another mean -H, -CH3, a saturated linear or branched alkyl radical of 2 to 12 carbon atoms, a mono- or polyunsaturated, linear or branched alkenyl radical of 2 to 12 carbon atoms, substituted alkyl or alkenyl radicals by -NH2, -OH or -COOH already defined above or means -COOH or -COOR⁴, said R⁴ is a linear or branched saturated or unsaturated hydrocarbon residue of 1 to 12 carbon atoms, ii) monomers of the general formula R¹(R²) C = C (R³) -XR⁴, in which R¹ to R³ independently of one another signify -H, -CH3 or -C2H5, X signifies an optionally present spacer group, which is chosen from -CH2-, -C (O) O- and -C (O) -NH-, and R⁴ is a saturated, linear or branched alkyl radical of 2 to 22 carbon atoms or an unsaturated hydrocarbon radical, preferably aromatic, of 6 to 22 carbon atoms

b) a nonionic surfactant of the general formula R¹-CH (OH) CH2O- (AO) w (A'O) x (A "O) y- (A" 'O) zR², in which

- R¹ means a linear or branched saturated or mono- or polyunsaturated C6-24 alkyl or alkenyl radical;

- R² means a straight or branched hydrocarbon residue of 2 to 26 carbon atoms;

- A, A ', A "and A"' independently of one another signify a residue chosen from the group -CH2CH2, -CH2CH2-CH2, -CH2-CH (CH3), -CH2-CH2-CH2-CH2, -CH2 -CH (CH3) -CH2, -CH2-CH (CH2-CH3); Y

- "w", "x", "y" and "z" take values ​​between 0.5 and 120, where "x", "y" and / or "z" can also be 0.

Especially preferred monomers containing carboxyl groups i) 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, methylene malonic acid, sorbic acid, cinnamic acid or their mixtures.

The nonionic monomers ii) used are monomers of the general formula R¹(R²) C = C (R³) -XR⁴. Especially preferred monomers of this type are butene, isobutene, pentene, 3-methylbutene, 2-methyl-butene, cyclopentene, hexene, hexene-1,2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene , methylcyclohexene, 2,4,4-trimethylpentene-1, 2,4,4-trimethylpentene-2, 2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene1, 3,5-dimethylhexene -1, 4,4-dimethylhexenene-1, ethylcyclohexino, 1-octene, α-olefins of 10 or more carbon atoms, for example 1-decene, 1-hexadecene, 1-octadecene and α-olefin C22, 2-styrene, α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinyl- Naphthalene, 2-vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methyl methacrylate, N- (methyl) acrylamide, 2-ethylhethyl acrylate, 2-ethylhexylated acrylate -ethylhexyl, N- (2-ethylhexyl) acrylamide, octyl acrylate, octyl methacrylate, N- (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N- (lauryl) acrylamide,

ES 2 396 568 T3 stearyl acrylate, stearyl methacrylate, N- (stearyl) acrylamide, behenyl acrylate, behenyl methacrylate and N (behenyl) acrylamide or their mixtures.

The preferred dishwasher products of the invention, in which the total amount of the copolymer a) is between 4 and 18, have proven to be especially effective with regard to optimal deposit inhibition and cleaning and polishing results. % by weight, preferably between 6 and 15 and especially between 6 and 12% by weight.

Preferred according to the invention are phosphate-free dishwashing products, which contain a carrier substance (builder), a bleach and furthermore

a) from 4 to 18% by weight of a copolymer formed by:

i) monomers of the group of carboxylic acids of the general formula R¹(R²) C = C (R³) COOH, in which R¹to R³ independently of one another mean -H, -CH3, a saturated linear or branched alkyl radical of 2 to 12 carbon atoms, a mono- or polyunsaturated, linear or branched alkenyl radical of 2 to 12 carbon atoms, substituted alkyl or alkenyl radicals by -NH2, -OH or -COOH already defined above or means -COOH or -COOR⁴, said R⁴ is a linear or branched saturated or unsaturated hydrocarbon residue of 1 to 12 carbon atoms, ii) monomers of the general formula R¹(R²) C = C (R³) -XR⁴, in which R¹ to R³ independently of one another signify -H, -CH3 or -C2H5, X signifies an optionally present spacer group, which is chosen from -CH2-, -C (O) O- and -C (O) -NH-, and R⁴ It is a saturated, linear or branched alkyl radical of 2 to 22 carbon atoms or an unsaturated hydrocarbon radical, preferably aromatic, of 6 to 22 carbon atoms,

b) a nonionic surfactant of the general formula R¹-CH (OH) CH2O- (AO) w (A'O) x (A "O) y- (A" 'O) zR², in which

- R¹ means a linear or branched saturated or mono- or polyunsaturated C6-24 alkyl or alkenyl radical;

- R² means a straight or branched hydrocarbon residue of 2 to 26 carbon atoms;

- A, A ', A "and A"' independently of one another signify a residue chosen from the group -CH2CH2, -CH2CH2-CH2, -CH2-CH (CH3), -CH2-CH2-CH2-CH2, -CH2 -CH (CH3) -CH2, -CH2-CH (CH2-CH3); Y

- "w", "x", "y" and "z" take values ​​between 0.5 and 120, where "x", "y" and / or "z" can also be 0.

In a particularly preferred embodiment, the copolymer d) includes monomers i) and ii) and furthermore a third monomer iii) chosen from the group of monomers provided with sulfonic acid groups.

Among the monomers provided with sulfonic acid groups, those of the formula

R⁵(R⁶) C = C (R⁷) -X-SO3H, where R⁵ to R⁷ independently of one another mean -H, -CH3, a saturated linear or branched alkyl radical of 2 to 12 carbon atoms, a mono- or polyunsaturated, linear or branched alkenyl radical of 2 to 12 carbon atoms, substituted alkyl or alkenyl radicals by -NH2, -OH or -COOH, or they mean -COOH or -COOR⁴, said R⁴ is a saturated or unsaturated hydrocarbon residue, linear or branched, of 1 to 12 carbon atoms and X means an optionally present spacer group, which is chosen from - (CH2) n, said n means a number from 0 to 4, -COO - (CH2) k, said k means a number from 1 to 6, -C (O) NH-C (CH3) 2- and -C (O) -NH-CH (CH2CH3) -.

Among these monomers, those of the formulas are preferred:

H2C = CH-X-SO3H H2C = C (CH3) -X-SO3H HO3S-X- (R⁶) C = C (R⁷) -X-SO3H where R⁶ and R⁷ independently of one another they are chosen from -H, -CH3, -CH2CH3, -CH2CH2CH3, -CH (CH3) 2 and X signifies an optionally present spacer group, which is chosen from - (CH2) n- in which n is a number from 0 to 4, -COO- (CH2) k-, where k is a number from 1 to 6, -C (O) -NH-C (CH3) 2- and -C (O) -NH- CH (CH2CH3) -.

Especially 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-hydroxy-propanesulfonic 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, vinyl sulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, methacrylate, sulfomethylmethacrylamide and mixtures of these acids or their salts soluble in water.

Within polymers, the sulfonic acid groups can be present in totally or partially neutralized form, that is, the acidic hydrogen atom of some or all of the sulfonic acid groups has been replaced by metal ions, preferably alkali metal ions and especially by sodium ions. The use of copolymers provided with totally or partially neutralized sulfonic acid groups is preferred according to the invention.

ES 2 396 568 T3

The molecular weight of the copolymers containing sulfo groups and preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired purpose of use. The preferred products for dishwashing machines are characterized in that the copolymers have molecular weights of 2000 to 200,000 gmol^-1, preferably 4000 to 25,000 gmol^-1 and especially from 5000 to 15,000 gmol^-1.

Preferred according to the invention are products for dishwashers containing a carrier substance, a bleach and furthermore

a) a copolymer formed by:

i) monomers of the group of carboxylic acids of the general formula R¹(R²) C = C (R³) COOH, in which R¹to R³ independently of one another mean -H, -CH3, a saturated linear or branched alkyl radical of 2 to 12 carbon atoms, a mono- or polyunsaturated, linear or branched alkenyl radical of 2 to 12 carbon atoms, substituted alkyl or alkenyl radicals by -NH2, -OH or -COOH already defined above or means -COOH or -COOR⁴, said R⁴ is a linear or branched saturated or unsaturated hydrocarbon residue of 1 to 12 carbon atoms, ii) monomers of the general formula R¹(R²) C = C (R³) -XR⁴, in which R¹ to R³ independently of one another signify -H, -CH3 or -C2H5, X signifies an optionally present spacer group, which is chosen from -CH2-, -C (O) O- and -C (O) -NH-, and R⁴ is a saturated, linear or branched alkyl radical of 2 to 22 carbon atoms or an unsaturated hydrocarbon radical, preferably aromatic, of 6 to 22 carbon atoms, iii) monomers provided with sulfonic acid groups,

b) a nonionic surfactant of the general formula R¹-CH (OH) CH2O- (AO) w (A'O) x (A "O) y- (A" 'O) zR², in which

- R¹ means a linear or branched saturated or mono- or polyunsaturated C6-24 alkyl or alkenyl radical;

- R² means a straight or branched hydrocarbon residue of 2 to 26 carbon atoms;

- A, A ', A "and A"' independently of one another signify a residue chosen from the group -CH2CH2, -CH2CH2-CH2, -CH2-CH (CH3), -CH2-CH2-CH2-CH2, -CH2 -CH (CH3) -CH2, -CH2-CH (CH2-CH3); Y

- "w", "x", "y" and "z" take values ​​between 0.5 and 120, where "x", "y" and / or "z" can also be 0.

As a second essential component, the products for dishwashers of the invention contain nonionic surfactants nonionic surfactants of the general formula R¹-CH (OH) CH2O- (AO) w (A'O) x (A "O) y- (A" 'O) zR², in which:

- R¹ means a linear or branched saturated or mono- or polyunsaturated C6-24 alkyl or alkenyl radical;

- R² means a straight or branched hydrocarbon residue of 2 to 26 carbon atoms;

- A, A ', A "and A"' independently of one another signify a residue chosen from the group -CH2CH2, -CH2CH2-CH2, -CH2-CH (CH3), -CH2-CH2-CH2-CH2, -CH2 -CH (CH3) -CH2, -CH2-CH (CH2-CH3); Y

- "w", "x", "y" and "z" take values ​​between 0.5 and 120, where "x", "y" and / or "z" can also be 0.

The preferred products for dishwashers of the invention contain an amount of the non-ionic surfactant b) between 1 and 10% by weight, preferably between 2 and 8% by weight and especially between 3 and 6% in weigh.

Non-ionic surfactants b) of the general formula R have proven to be particularly advantageous with regard to cleaning and polishing performance.¹-CH (OH) CH2O- (AO)_w(A'O) xR², in which:

- R¹ means a linear or branched saturated or mono- or polyunsaturated C6-24 alkyl or alkenyl radical;

- R² means a straight or branched hydrocarbon residue of 2 to 26 carbon atoms;

- A and A 'independently of each other signify a residue chosen from the group -CH2CH2, -CH2CH2-CH2, -CH2CH (CH3), and

- "w" and "x" take values ​​between 0.5 and 120.

Especially preferred are products for dishwashers characterized in that the non-ionic surfactant b) has the general formula R¹-CH (OH) CH2O- (AO) w (A'O) xR², in which:

- R¹ means a linear or branched saturated or mono- or polyunsaturated C6-24 alkyl or alkenyl radical;

- R² means a straight or branched hydrocarbon residue of 2 to 26 carbon atoms;

- A means a -CH2CH2 residue and A 'means a -CH2CH2-CH2 or -CH2-CH (CH3) residue and

- "w" takes values ​​between 2 and 40, while "x" takes values ​​between 0.5 and 2.

Especially preferred are products for dishwashing machines, in which the non-ionic surfactant b) has a general formula R¹-CH (OH) cH2O- (AO) wR², in which:

- R¹ means a linear or branched saturated or mono- or polyunsaturated C6-24 alkyl or alkenyl radical;

- R² means a straight or branched hydrocarbon residue of 2 to 26 carbon atoms;

- A means a residue from the group consisting of -CH2CH2, -CH2CH2-CH2 and -CH2-CH (CH3) and

ES 2 396 568 T3

- "w" takes values ​​between 1 and 120, preferably between 10 and 80, especially between 20 and 40.

The C chain lengths and the degrees of ethoxylation or the degrees of alkoxylation indicated of the nonionic surfactants mentioned above are statistical average values, which for a given product can take whole or fractional values. Due to the procedure for obtaining it, the commercial products that conform to the aforementioned formulas are generally not formed by a single representative, but by mixtures, for which the average values ​​of both the C chain lengths and the degrees of ethoxylation or the degrees of alkoxylation can have fractional values.

Obviously, the nonionic surfactants mentioned above can be used not only individually, but also in the form of surfactant mixtures consisting of two, three, four or more surfactants. Surfactant mixtures are called not those mixtures of nonionic surfactants that in their entirety conform to one of the general formulas mentioned above, but more appropriately those mixtures that contain two, three, four or more nonionic surfactants that can be described by various general formulas previously described or by other general formulas.

As an additional essential component, the preferred dishwasher products according to the invention contain one or more carrier substances (builder). Particularly among the carrier substances are silicates, carbonates and organic complementary carrier substances (cobuilder).

As organic carrier substances, mention may be made in particular of polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and organic carrier substances. These groups of materials are described below.

Useable organic builders are, for example, polycarboxylic acids that can be used in the form of free acids and / or their sodium salts, polycarboxylic acids being understood to be carboxylic acids that carry more than one acidic functional group. Examples of this are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), on the assumption that their use does not be the object of ecological objections, as well as their mixtures. In addition to their action as carrier substances (builder), free acids also normally have the property of an acidifying component and therefore serve to adjust the pH to a lower or milder value of detergents or cleaning products. Special mention should be made of citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixture thereof.

Especially preferred dishwasher products of the invention contain citrate as one of their essential builder substances. Preferred according to the invention are products for dishwashers, characterized in that they contain between 5 and 60% by weight, preferably between 10 and 50% by weight and especially between 15 and 40% by weight of citrate. Citrate and citric acid have proven to be the most effective builders, in combination with copolymers having sulfonic acid groups, in terms of cleaning efficacy, eg brightening and especially inhibition of deposit formation.

Phosphate-free dishwasher products which contain between 5 and 60% by weight, preferably between 10 and 50% by weight and especially between 15 and 40% by weight of citrate are preferred according to the invention. , a bleach and also:

a) a copolymer formed by:

i) monomers of the group of carboxylic acids of the general formula R¹(R²) C = C (R³) COOH, in which R¹to R³ independently of one another mean -H, -CH3, a saturated linear or branched alkyl radical of 2 to 12 carbon atoms, a mono- or polyunsaturated, linear or branched alkenyl radical of 2 to 12 carbon atoms, substituted alkyl or alkenyl radicals by -NH2, -OH or -COOH already defined above or means -COOH or -COOR⁴, said R⁴ is a linear or branched saturated or unsaturated hydrocarbon residue of 1 to 12 carbon atoms, ii) monomers of the general formula R¹(R²) C = C (R³) -XR⁴, in which R¹ to R³ independently of one another signify -H, -CH3 or -C2H5, X signifies an optionally present spacer group, which is chosen from -CH2-, -C (O) O- and -C (O) -NH-, and R⁴ is a saturated, linear or branched alkyl radical of 2 to 22 carbon atoms or an unsaturated hydrocarbon radical, preferably aromatic, of 6 to 22 carbon atoms

b) a nonionic surfactant of the general formula R¹-CH (OH) CH2O- (AO) w (A'O) x (A "O) y- (A" 'O) zR², in which

- R¹ means a linear or branched saturated or mono- or polyunsaturated C6-24 alkyl or alkenyl radical;

- R² means a straight or branched hydrocarbon residue of 2 to 26 carbon atoms;

- A, A ', A "and A"' independently of one another signify a residue chosen from the group -CH2CH2, -CH2CH2-CH2, -CH2-CH (CH3), -CH2-CH2-CH2-CH2, -CH2 -CH (CH3) -CH2, -CH2-CH (CH2-CH3); Y

- "w", "x", "y" and "z" take values ​​between 0.5 and 120, where "x", "y" and / or "z" can also be 0.

Other preferred forms of execution are:

ES 2 396 568 T3

Phosphate-free dishwashing products containing between 5 and 60% by weight, preferably between 10 and 50% by weight and especially between 15 and 40% by weight of citrate, a bleach and furthermore :

a) a copolymer formed by:

i) monomers of the group of carboxylic acids of the general formula R¹(R²) C = C (R³) COOH, in which R¹to R³ independently of one another mean -H, -CH3, a saturated linear or branched alkyl radical of 2 to 12 carbon atoms, a mono- or polyunsaturated, linear or branched alkenyl radical of 2 to 12 carbon atoms, substituted alkyl or alkenyl radicals by -NH2, -OH or -COOH already defined above or means -COOH or -COOR⁴, said R⁴ is a linear or branched saturated or unsaturated hydrocarbon residue of 1 to 12 carbon atoms, ii) monomers of the general formula R¹(R²) C = C (R³) -XR⁴, in which R¹ to R³ independently of one another signify -H, -CH3 or -C2H5, X signifies an optionally present spacer group, which is chosen from -CH2-, -C (O) O- and -C (O) -NH-, and R⁴ is a saturated, linear or branched alkyl radical of 2 to 22 carbon atoms or an unsaturated hydrocarbon radical, preferably aromatic, of 6 to 22 carbon atoms, iii) monomers bearing sulfonic acid groups,

b) a nonionic surfactant of the general formula R¹-CH (OH) CH2O- (AO) w (AO) x (A'O) y- (A "O) zR², in which

- R¹ means a linear or branched saturated or mono- or polyunsaturated C6-24 alkyl or alkenyl radical;

- R² means a straight or branched hydrocarbon residue of 2 to 26 carbon atoms;

- A, A ', A "and A"' independently of one another signify a residue chosen from the group -CH2CH2, -CH2CH2-CH2, -CH2-CH (CH3), -CH2-CH2-CH2-CH2, -CH2 -CH (CH3) -CH2, -CH2-CH (CH2-CH3); Y

- "w", "x", "y" and "z" take values ​​between 0.5 and 120, where "x", "y" and / or "z" can also be 0.

Dishwashing products of the invention are preferably used which, as carrier substances, contain crystalline layered silicates of the general formula NaMSixO2x + 1. yH2O, where M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably 1.9 to 4, but especially preferred values ​​of x are 2, 3 or 4, and "y" it is a number from 0 to 33, preferably from 0 to 20.

Amorphous sodium silicates having a Na2O: SiO2 modulus of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and especially 1: 2 to 1: 2.6, can also be used. , which preferably dissolve slowly and have secondary detergent properties.

The products for dishwashing machines preferred in the context of the present application contain from 2 to 15% by weight, preferably from 3 to 12% by weight and especially from 4 to 8% by weight of silicate (s).

The use of carbonate (s) and / or hydrogen carbonate (s), preferably alkaline carbonate (s), especially sodium carbonate, in amounts of 5 to 50% by weight, preferably 10%, is particularly preferred. 40% by weight and in particular 15 to 30% by weight, percentages referred in each case to the weight of the product for dishwashing machines.

Also suitable as carrier substances are polymeric polycarboxylates, such as, for example, alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular weight of 500 to 70,000 g / mol.

Suitable polymers are especially polyacrylates, which preferably have a molecular weight of between 2,000 and 20,000 g / mol. Due to their better solubility, short-chain polyacrylates, which have molecular weights between 2000 and 10000 g / mol and with special preference between 3000 and 5000 g / mol, may be preferred among this group.

Copolymeric polycarboxylates are also suitable, especially those formed by acrylic acid and methacrylic acid or by acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid, which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid, have proven to be particularly suitable. Their relative molecular weights, based on free acids, are generally between 2,000 and 70,000 g / mol, preferably between 20,000 and 50,000 g / mol, and in particular between 30,000 and 40,000 g / mol.

Polycarboxylates (co) polymers can be used in the form of a powder or in the form of an aqueous solution. The content of the (co) polymer polycarboxylates in the products for dishwashing machines is preferably 0.5 to 20% by weight and in particular 3 to 10% by weight.

Preferred dishwasher products according to the invention additionally contain one or more bleaches. Among the compounds that act as bleaches, which give off H2O2 in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other usable bleaches are, for example, peroxypyrophosphates, citrate-perhydrates and salts of peracids which release H2O2, for example perbenzoates, peroxophthalates, diperazelaic acid, phthaliminoperacid or diperdodecanedioic acid. Bleaches from the group of organic bleaches can also be used. The blan

ES 2 396 568 T3 Typical organic cheants are diacyl peroxides, eg dibenzoyl peroxide. Other typical organic bleaches are peroxyacids, examples of which include especially alkylperoxyacids and arylperoxyacids.

Preferred according to the invention are detergents for dishwashing machines which are characterized in that they contain 1 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 12% by weight of sodium percarbonate.

Preferred according to the invention are phosphate-free dishwasher products which contain a carrier substance of 1 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 12% by weight of sodium percarbonate and what's more

a) a copolymer formed by:

i) monomers of the group of carboxylic acids of the general formula R¹(R²) C = C (R³) COOH, in which R¹to R³ independently of one another mean -H, -CH3, a saturated linear or branched alkyl radical of 2 to 12 carbon atoms, a mono- or polyunsaturated, linear or branched alkenyl radical of 2 to 12 carbon atoms, substituted alkyl or alkenyl radicals by -NH2, -OH or -COOH already defined above or means -COOH or -COOR⁴, said R⁴ is a linear or branched saturated or unsaturated hydrocarbon residue of 1 to 12 carbon atoms, ii) monomers of the general formula R¹(R²) C = C (R³) -XR⁴, in which R¹ to R³ independently of one another signify -H, -CH3 or -C2H5, X signifies an optionally present spacer group, which is chosen from -CH2-, -C (O) O- and -C (O) -NH-, and R⁴ is a saturated, linear or branched alkyl radical of 2 to 22 carbon atoms or an unsaturated hydrocarbon radical, preferably aromatic, of 6 to 22 carbon atoms

b) a nonionic surfactant of the general formula R¹-CH (OH) CH2O- (AO) w (A'O) x (A "O) y- (A" 'O) zR², in which

- R¹ means a linear or branched saturated or mono- or polyunsaturated C6-24 alkyl or alkenyl radical;

- R² means a straight or branched hydrocarbon residue of 2 to 26 carbon atoms;

- A, A ', A "and A"' independently of one another signify a residue chosen from the group -CH2CH2, -CH2CH2-CH2, -CH2-CH (CH3), -CH2-CH2-CH2-CH2, -CH2 -CH (CH3) -CH2, -CH2-CH (CH2-CH3); Y

- "w", "x", "y" and "z" take values ​​between 0.5 and 120, where "x", "y" and / or "z" can also be 0.

Other preferred forms of execution are:

Phosphate-free dishwashing products containing 1 to 20% by weight, preferably 2 to 15% by weight, and especially 4 to 12% by weight of sodium percarbonate containing carrier substance, and furthermore:

a) a copolymer formed by:

i) monomers of the group of carboxylic acids of the general formula R¹(R²) C = C (R³) COOH, in which R¹to R³ independently of one another mean -H, -CH3, a saturated linear or branched alkyl radical of 2 to 12 carbon atoms, a mono- or polyunsaturated, linear or branched alkenyl radical of 2 to 12 carbon atoms, substituted alkyl or alkenyl radicals by -NH2, -OH or -COOH already defined above or means -COOH or -COOR⁴, said R⁴ is a linear or branched saturated or unsaturated hydrocarbon residue of 1 to 12 carbon atoms, ii) monomers of the general formula R¹(R²) C = C (R³) -XR⁴, in which R¹ to R³ independently of one another signify -H, -CH3 or -C2H5, X signifies an optionally present spacer group, which is chosen from -CH2-, -C (O) O- and -C (O) -NH-, and R⁴ is a saturated, linear or branched alkyl radical of 2 to 22 carbon atoms or an unsaturated hydrocarbon radical, preferably aromatic, of 6 to 22 carbon atoms, iii) monomers bearing sulfonic acid groups,

b) a nonionic surfactant of the general formula R¹-CH (OH) CH2O- (AO) w (A'O) x (A "O) y- (A" 'O) zR², in which

- R¹ means a linear or branched saturated or mono- or polyunsaturated C6-24 alkyl or alkenyl radical;

- R² means a straight or branched hydrocarbon residue of 2 to 26 carbon atoms;

- A, A ', A "and A"' independently of one another signify a residue chosen from the group -CH2CH2, -CH2CH2-CH2, -CH2-CH (CH3), -CH2-CH2-CH2-CH2, -CH2 -CH (CH3) -CH2, -CH2-CH (CH2-CH3); Y

- "w", "x", "y" and "z" take values ​​between 0.5 and 120, where "x", "y" and / or "z" can also be 0.

Substances that release chlorine or bromine can also be used as bleaches. Suitable chlorine- or bromine-releasing materials include, for example, heterocyclic N-bromo- or N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and their salts with cations of the potassium and sodium type. Hydantoin compounds are also suitable, for example 1,3-dichloro-5,5-dimethylhydantoin.

To achieve a better bleaching effect when washed at temperatures of 60 ° C and below, the dishwasher detergents in tablet form of the invention may also contain bleach activators. As bleach activators, it is possible, for example, to use compounds which, under perhydrolysis conditions, give rise to aliphatic peroxocarboxylic acids which preferably have 1 to 10 carbon atoms, in particular 2

ES 2 396 568 T3 having 4 carbon atoms, and / or optionally perbenzoic acids. Suitable compounds are those which carry Oacyl and / or N-acyl groups and / or optionally substituted benzoyl groups. Multi-fold acylated alkylenediamines are preferred, tetraacetylethylenediamine (TAED) being especially suitable.

These bleach activators, especially TAED, are preferably used in amounts of up to 10% by weight, in particular from 0.1% by weight to 8% by weight, especially from 2 to 8% by weight and with particularly preferably 2 to 6% by weight, percentages referred in each case to the total weight of the detergent containing the bleach activator.

In addition to or instead of conventional bleach activators, so-called bleach catalysts can be used. These compounds are transition metal salts or transition metal complexes that enhance bleaching, for example salene complexes or carbonyl complexes of Mn, Fe, Co, Ru or Mo. As bleaching catalysts it is also possible to use complexes of Mn, Fe, Co, Ru, Mo, Ti, V and Cu with tripod ligands containing N as well as the amino complexes of Co, Fe, Cu and Ru.

With particular preference, manganese complexes in oxidation degree II, III, IV or VI are used, which preferably contain one or more macrocyclic ligands having N, NR, PR, O and / or S electron-donating functional groups. they preferably employ ligands bearing electron-donating nitrogen functional groups. It is especially preferred to use bleach catalyst or catalysts in the products of the invention which, as macromolecular ligands, contain 1,4,7-trimethyl-1,4,7-triazacyclononane (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^IH2 (pO) 1 (p-OAc) 2 (TACN) 2] (ClO4) 2, [Mn^mMn^IV(pO) 2 (p-OAc) 1 (TACN) 2] (BPh4) 2, [Mn^IV4 (uO) 6 (TACN) 4] (ClO4) 4, [Mn^IH2 (pO) 1 (p-OAC) 2 (Me-TACN) 2] (ClO4) 2, [Mn^mMn^IV(pO) 1 (p-OAc) 2 (Me-TACN) 2] (ClO4) 3, [Mn '^V2 (pO) 3 (Me-TACN) 2] (PF6) 2 and [Mn^{, V}2 (pO) 3 (Me / Me-TACN) 2] (PF6) 2 (where OAc is OC (O) CH3).

Preferred according to the invention are detergents for dishwashers characterized in that they also contain a bleaching catalyst chosen from the group of transition metal salts and transition metal complexes that enhance bleaching, preferably from the group of complexes. of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me3-TACN) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me4-TACN), Since, with the bleach catalysts mentioned, the cleaning or washing performance in particular can be significantly improved.

The transition metal complexes mentioned above, which enhance bleaching, especially those with central Mn or Co atoms, are used in the customary amounts, preferably in amounts of up to 5% by weight, in particular the 0.0025% by weight to 1% by weight and more preferably from 0.01% by weight to 0.30% by weight, percentages referred in each case to the total weight of the product containing the bleach activator. But in special cases, even a larger amount of bleach activator can be used.

It has been surprisingly found that the bleaching effect of catalysts from the group of salts and transition metal complexes that enhance said bleaching can be enhanced by the addition of copolymers containing acid groups and modified to have a hydrophobic character.

Therefore, a preferred object of this application is a product for dishwashing machines without phosphates, which contains a bleach and also

a) a copolymer formed by:

i) monomers of the group of mono- or polyunsaturated carboxylic acids, ii) monomers of the general formula R¹(R²) C = C (R³) -XR⁴, in which R¹ to R³ independently of one another signify -H, -CH3 or -C2H5, X signifies an optionally present spacer group, which is chosen from -CH2-, -C (O) O- and -C (O) -NH-, and R⁴ it is a saturated, linear or branched alkyl radical of 2 to 22 carbon atoms or an unsaturated hydrocarbon radical, preferably aromatic, of 6 to 22 carbon atoms, iii) optionally other monomers;

b) a nonionic surfactant of the general formula R¹-CH (OH) CH2O- (AO) w (A'O) x (A "O) y- (A" 'O) zR² in which

- R¹ means a linear or branched saturated or mono- or polyunsaturated C6-24 alkyl or alkenyl radical,

- R² means a straight or branched hydrocarbon residue of 2 to 26 carbon atoms,

- A, A ', A "and A"' independently of one another signify a residue chosen from the group -CH2CH2, -CH2CH2-CH2, -CH2CH (CH3), -CH2-CH2-CH2-CH2, -CH2-CH (CH3) -CH2, -CH2-CH (CH2-CH3), and

- "w", "x", "y" and "z" take values ​​between 0.5 and 120, where "x", "y" and / or "z" can also be 0;

c) a citrate;

d) a bleach activator chosen from the group of salts and transition metal complexes that enhance bleaching.

Some illustrative formulations of the preferred phosphate-free dishwashing products are listed in the table below.

ES 2 396 568 T3

<td>component</td><td>formulation 1 [% by weight]</td><td>formulation 2 [% by weight]</td><td>formulation 3 [% by weight]</td><td>formulation 4 [% by weight]</td>

<td>citrate</td><td> 5-60</td><td> 10-55</td><td> 15-50</td><td> 15-50</td>

<td>sodium percarbonate</td><td> 1-20</td><td> 2-15</td><td> 4-10</td><td> 4-10</td>

<td>bleach catalyst</td><td> 0,01-3</td><td> 0,02-2</td><td> 0,02-2</td><td> 0,02-1</td>

<td>copolymer¹</td><td> 0,1-30</td><td> 0,5-25</td><td> 1,0-20</td><td> 1,0-20</td>

<td>non-ionic surfactant²</td><td> 1-10</td><td> 2-8</td><td> 2-8</td><td> 3-6</td>

<td>various</td><td>up to 100</td><td>up to 100</td><td>up to 100</td><td>up to 100</td>

<td colspan="5">¹ copolymer formed by: i) monomers from the group of mono- or polyunsaturated carboxylic acids, ii) monomers of the general formula R¹(R²) C = C (R³) -XR⁴, in which R¹ to R³ independently of one another signify -H, -CH3 or -C2H5, X signifies an optionally present spacer group, which is chosen from -CH2-, -C (O) O- and -C (O) -NH-, and R⁴ It is a saturated, linear or branched alkyl radical of 2 to 22 carbon atoms or an unsaturated hydrocarbon radical, preferably aromatic, of 6 to 22 carbon atoms, iii) optionally other monomers;² nonionic surfactant of the general formula R¹-CH (OH) CH2O- (AO) w (A'O) x (A "O) y- (A" 'O) zR², in which - R¹ means a linear or branched saturated or mono- or polyunsaturated C6-24 alkyl or alkenyl radical, - R² means a straight or branched hydrocarbon residue of 2 to 26 carbon atoms, - A, A ', A "and A"' independently of one another signify a residue chosen from the group -CH2CH2, -CH2CH2-CH2, CH2-CH (CH3), -CH2-CH2-CH2-CH2, -CH2- CH (CH3) -CH2, -CH2-CH (CH2-CH3), and - "w", "x", "y" and "z" take values ​​between 0.5 and 120, where "x", "y" and / or "z" can also be 0</td>

Preferred dishwasher products according to the invention additionally contain a sequestrant (chelator), preferably 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and / or methylglycinacetic acid (MGDA).

Sequestrant (chelating) phosphonates, in addition to 1-hydroxyethane-1,1-diphosphonic acid, encompass a number of different compounds, for example diethylenetriaminepentamethylenephosphonic acid (DTPMP). Hydroxyalkane- or aminoalkanephosphonates are especially preferred in this application. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is especially important as a supplementary carrier substance (cobuilder). It is preferably used in the form of the sodium salt; the disodium salt has a neutral pH and the tetrasodium salt has a basic pH (pH 9). As aminoalkanesulfonates, preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues are taken into consideration. They are preferably used in the form of neutrally reacting sodium salts, for example as the sodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP. As carrier substance (builder) of the phosphonate group, HEDP is preferably used. The aminoalkanephosphonates also have a marked heavy metal binding power. It may therefore be preferred, especially if the products also contain bleaches, to use aminoalkanephosphonates, especially DTPMP, or to use mixtures of the phosphonates mentioned.

A preferred dishwasher product in the context of this application contains one or more phosphonates from the group consisting of:

a) aminotri (methylenephosphonic acid) (ATMP) and / or its salts;

b) ethylenediaminetetra (methylenephosphonic) acid (EDTMP) and / or its salts;

c) diethylenetriaminepenta (methylenephosphonic acid) (DTPMP) and / or its salts;

d) 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and / or its salts;

e) 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) and / or its salts;

f) hexamethylenediaminetetra (methylenephosphonic) acid (HDTMP) and / or its salts;

g) nitrilotri (methylenephosphonic acid) (NTMP) and / or its salts.

Especially preferred are products for dishwashers, which as phosphonates contain 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta (methylenephosphonic acid (DTPMP).

Obviously, the dishwasher products of the invention can contain two or more different phosphonates. Especially preferred are products for dishwashers, which, as phosphonates, contain not only 1-hydroxyethane-1,1-diphosphonic acid (HEDP) but also diethylenetriaminepenta (methylenephosphonic acid (DTPMP), the weight ratio being between HEDP and DTPMP between 20: 1 and 1:20, preferably between 15: 1 and 1:15 and especially between 10: 1 and 1:10.

In a preferred embodiment of the present invention, the weight portion of the phosphonate (s) within the total weight of the product for dishwashing machines will be less than the weight portion of the polymer (s) a). In other words, products whose ratio between the weight portion of the polymer a) and the weight portion of the phosphonate is between 200: 1 and 2: 1, preferably between 150: 1 and 2: 1, with

ES 2 396 568 T3 special preference between 100: 1 and 2: 1, with very special preference between 80: 1 and 3: 1 and especially between 50: 1 and 5: 1.

The portion by weight of these sequestrants (chelators), especially the sum of the portions by weight of 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and methylglycine diacetic acid (MGDA) will preferably be between 0.5 and 0.5%. 14% by weight, preferably between 1 and 12% by weight and especially between 2 and 8% by weight.

Preferred according to the invention are phosphate-free dishwashing products, which contain a carrier substance (builder), a bleach and furthermore:

a) a copolymer formed by:

i) monomers of the group of mono- or polyunsaturated carboxylic acids, ii) monomers of the general formula R¹(R²) C = C (R³) -XR⁴, in which R¹ to R³ independently of one another signify -H, -CH3 or -C2H5, X signifies an optionally present spacer group, which is chosen from -CH2-, -C (O) O- and -C (O) -NH-, and R⁴ It is a saturated, linear or branched alkyl radical of 2 to 22 carbon atoms or an unsaturated hydrocarbon radical, preferably aromatic, of 6 to 22 carbon atoms,

b) a nonionic surfactant of the general formula R¹-CH (OH) CH2O- (AO) wR², in which:

- R¹ means a linear or branched saturated or mono- or polyunsaturated C6-24 alkyl or alkenyl radical;

- R² means a straight or branched hydrocarbon residue of 2 to 26 carbon atoms;

- A means a residue from the group consisting of -CH2CH2, -CH2CH2-CH2 and -CH2-CH (CH3) and

- "w" takes values ​​between 1 and 120, preferably between 10 and 80, especially between 20 and 40;

c) from 2 to 8% by weight of a sequestrant from the group of 1-hydroxyethane-1,1-diphosphonic acid and methylglycine diacetic acid.

Some illustrative formulations of the preferred phosphate-free dishwashing products are listed in the table below.

<td>component</td><td>formulation 5 [% by weight]</td><td>formulation 6 [% by weight]</td><td>formulation 7 [% by weight]</td><td>formulation 8 [% by weight]</td>

<td>citrate</td><td> 5-60</td><td> 10-55</td><td> 15-50</td><td> 15-50</td>

<td>sodium percarbonate</td><td> 1-20</td><td> 2-15</td><td> 4-10</td><td> 4-10</td>

<td>phosphonate</td><td> 2-8</td><td> 2-8</td><td> 2-8</td><td> 2-8</td>

<td>copolymer¹</td><td> 0,1-30</td><td> 0,5-25</td><td> 1,0-20</td><td> 1,0-20</td>

<td>non-ionic surfactant²</td><td> 1-10</td><td> 2-8</td><td> 2-8</td><td> 3-6</td>

<td>various</td><td>up to 100</td><td>up to 100</td><td>up to 100</td><td>up to 100</td>

<td colspan="5">¹ copolymer formed by: i) monomers from the group of mono- or polyunsaturated carboxylic acids, ii) monomers of the general formula R¹(R²) C = C (R³) -XR⁴, in which R¹ to R³ independently of one another signify -H, -CH3 or -C2H5, X signifies an optionally present spacer group, which is chosen from -CH2-, -C (O) O- and -C (O) -NH-, and R⁴ It is a saturated, linear or branched alkyl radical of 2 to 22 carbon atoms or an unsaturated hydrocarbon radical, preferably aromatic, of 6 to 22 carbon atoms, iii) optionally other monomers;² nonionic surfactant of the general formula R¹-CH (OH) CH2O- (AO) w (A'O) x (A "O) y- (A" 'O) zR², in which - R¹ means a linear or branched saturated or mono- or polyunsaturated C6-24 alkyl or alkenyl radical, - R² means a straight or branched hydrocarbon residue of 2 to 26 carbon atoms, - A, A ', A "and A"' independently of one another signify a residue chosen from the group -CH2CH2, -CH2CH2-CH2, CH2-CH (CH3), -CH2-CH2-CH2-CH2, -CH2- CH (CH3) -CH2, -CH2-CH (CH2-CH3), and - "w", "x", "y" and "z" take values ​​between 0.5 and 120, where "x", "y" and / or "z" can also be 0</td>

Also preferred are phosphate-free dishwasher products, which contain a carrier substance, a bleach and in addition:

a) a copolymer formed by:

i) monomers of the group of mono- or polyunsaturated carboxylic acids, ii) monomers of the general formula R¹(R²) C = C (R³) -XR⁴, in which R¹ to R³ independently of one another signify -H, -CH3 or -C2H5, X signifies an optionally present spacer group, which is chosen from -CH2-, -C (O) O- and -C (O) -NH-, and R⁴ It is a saturated, linear or branched alkyl radical of 2 to 22 carbon atoms or an unsaturated hydrocarbon radical, preferably aromatic, of 6 to 22 carbon atoms, iii) polymers provided with sulfonic acid groups;

b) a nonionic surfactant of the general formula R¹-CH (OH) CH2O- (AO) wR², in which:

- R¹ means a linear or branched saturated or mono- or polyunsaturated C6-24 alkyl or alkenyl radical;

- R² means a straight or branched hydrocarbon residue of 2 to 26 carbon atoms;

- A means a residue from the group consisting of -CH2CH2, -CH2CH2-CH2 and -CH2-CH (CH3) and

- "w" takes values ​​between 1 and 120, preferably between 10 and 80, especially between 20 and 40;

c) from 2 to 8% by weight of a sequestrant from the group of 1-hydroxyethane-1,1-diphosphonic acid and methylglycine acid

ES 2 396 568 T3 diacetic.

Products for dishwashers containing:

a) a copolymer formed by:

i) monomers of the group of mono- or polyunsaturated carboxylic acids, ii) monomers of the general formula R¹(R²) C = C (R³) -XR⁴, in which R¹ to R³ independently of one another signify -H, -CH3 or -C2H5, X signifies an optionally present spacer group, which is chosen from -CH2-, -C (O) O- and -C (O) -NH-, and R⁴ It is a saturated, linear or branched alkyl radical of 2 to 22 carbon atoms or an unsaturated hydrocarbon radical, preferably aromatic, of 6 to 22 carbon atoms,

b) a nonionic surfactant of the general formula R¹-CH (OH) CH2O- (AO)_wrR², in which:

- R¹ means a linear or branched saturated or mono- or polyunsaturated Ce-24 alkyl or alkenyl radical;

- R² means a straight or branched hydrocarbon residue of 2 to 26 carbon atoms;

- A means a residue from the group consisting of -CH2CH2, -CH2CH2-CH2 and -CH2-CH (CH3) and

- "w" takes values ​​between 1 and 120, preferably between 10 and 80, especially between 20 and 40;

c) 10 to 50% by weight of citrate;

d) from 2 to 15% by weight of sodium percarbonate;

e) 2 to 8% by weight of a sequestrant from the group of 1-hydroxyethane-1,1-diphosphonic acid and methylglycine diacetic acid.

In addition to the components described in previous paragraphs, such as the carrier substance (builder), the bleach, the non-ionic surfactant, the copolymer a) and the sequestrants, the preferred products for dishwashing machines contain other components, preferably active substances from the group of polymers, enzymes, corrosion inhibitors, fragrances and colorants.

For example, polishing polymers and / or polymers having a descaling action belong to the group of detergent and cleaning polymers. In general, nonionic polymers can be incorporated into detergents and cleaning products, but cationic, anionic and amphoteric polymers can also be incorporated.

"Cationic polymers" in the sense of the present invention are those polymers that carry a positive charge in their molecule. This can be generated, for example, by the (alkyl) ammonium groups or other positively charged groups existing in the polymer chain. Particularly preferred cationic polymers come from the group of quaternized cellulose derivatives, polysiloxanes with quaternary groups, cationic guar derivatives, polymeric dimethylallylammonium salts and their copolymers with esters and with acrylic acid and acid amides. methacrylic, of the copolymers of vinylpyrrolidone with quaternized derivatives of dialkyl aminoacrylates and aminomethacrylates, of copolymers of vinylpyrrolidone with methoimidazolinium chloride, of quaternized polyvinylalcohols or of polymers bearing the following INCI names: Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

"Amphoteric polymers" in the sense of the present invention are those which, in addition to having a positively charged group in their chain, also have negatively charged monomer units or groups.

These groups can be, for example, carboxylic acids, sulfonic acids or phosphonic acids.

Preferred detergents or cleaning products, especially those preferred for dishwashers, are characterized in that they contain a polymer a), having monomeric units of the formula R¹R²C = CR³R⁴, in which each remainder R¹, R², R³, R⁴ independently of one another, the choice is made from hydrogen, derivatized hydroxy groups, linear or branched C1.30 alkyl groups, aryl, linear or branched C1.30 alkyl groups, substituted by aryl, polyalkoxylated alkyl groups, organic groups provided with heteroatoms having at least minus one positive charge without nitrogen being charged, at least one quaternary N atom or at least one amino group having a positive charge in the partial pH range of 2 to 11, or the salts thereof, provided that at least one R moiety¹, R², R³, R⁴ has an organic group provided with a heteroatom with at least one positive charge without nitrogen being charged, at least one quaternary N atom or at least one amino group with a positive charge.

Especially preferred cationic or amphoteric polymers in the context of the present application contain as monomeric unit a compound of the general formula

Ri R2 R4 The H₂C = C- (CH₂)₁₁-N- (CH2)_Y-C = CH2 X

R3 where R¹ and R⁴ independently of one another they mean H or a linear or branched hydrocarbon residue of 1 to 6 atoms

ES 2 396 568 T3 carbon; R² and R³ independently of each other they mean an alkyl, hydroxyalkyl or aminoalkyl group, said alkyl radicals can be linear or branched and have from 1 to 6 carbon atoms, the methyl group being preferred; "X" and "y" independently of each other mean integers between 1 and 3. X represents a counter ion, preferably a counter ion selected from the group consisting of chloride, bromide, iodide, sulfate, hydrogen sulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumenesulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or its mixtures.

The remains R¹ and R⁴ Preferred of the above formula are chosen from -CH3, -CH2-CH3, -CH2-CH2-CH3, -CH (CH3) -CH3, -CH2-OH, -CH2-CH2-OH, -CH (OH) -CH3 , -CH2-CH2-CH2-OH, -CH2-CH (OH) -CH3, -CH (OH) -CH2-CH3 and - (CH2CH2-O) nH. Polymers containing a cationic monomer unit of the above general formula, in which R¹ and R⁴ mean H, R² and R³ mean methyl and "x" and "y" are in each case the number 1. The monomeric unit in question of the formula

H2C = CH- (CH2) -N⁺(CH3) 2- (CH2) -CH = CH2 X is called DADMAC (diallyldimethylammonium chloride), in case X^- = chloride.

Other especially preferred cationic or amphoteric polymers contain a monomeric unit of the general formula

R¹HC = CR2-C (O) -NH- (CH2) xN⁺R³R⁴R⁵ X^- in which R¹, R², R³, R⁴ and R⁵ independently of one another they mean a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical of 1 to 6 carbon atoms, preferably a linear or branched alkyl radical chosen from -CH3, -CH2-CH3, -CH2-CH2- CH3, -CH (CH3) -CH3, -CH2-OH, -CH2-CH2-OH, -CH (OH) -CH3, -CH2-CH2-CH2-OH, -CH2-CH (OH) -CH3, - CH (OH) -CH2-CH3 and - (CH2CH2-O) nH and x means an integer between 1 and 6.

In the framework of the present application, polymers having a cationic monomer unit of the above general formula, in which R¹ means H and R², R³, R⁴ and R⁵ mean methyl and x means the number 3. The corresponding monomer units of the formula

H2C = C (CH3) -C (O) -NH- (CH2) xN⁺(CH3) 3 X are called MAPTAC (methylacrylamidopropyltrimethylammonium chloride), in the case that X^- = chloride.

Polymers are preferably used according to the invention, which as monomer units contain diallyldimethylammonium salts and / or acrylamidopropyltrimethylammonium salts.

The amphoteric polymers mentioned above not only possess cationic groups, but also anionic groups or monomeric units. Such anionic monomeric units come, for example, from the group of linear or branched saturated or unsaturated carboxylates, from linear or branched saturated or unsaturated phosphonates, from linear or branched saturated or unsaturated sulfates or from linear or saturated or unsaturated sulfonates or branched. Preferred monomeric units are acrylic acid, (meth) acrylic acid, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinyl acetic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, allylsulfonic acids, for example allyloxybenzenesulfonic acid and methallylsulfonic acid or allylphosphonic acids.

The amphoteric polymers that can be used with preference come from the group of alkylacrylamide / acrylic acid copolymers, from alkylacrylamide / methacrylic acid copolymers, from alkylacrylamide / methylmethacrylic acid copolymers, from alkylacrylamide / acrylic acid / methacrylic acid copolymers alkylaminoalkyl (meth) acrylic acid, from alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, of the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, of the alkylacrylamide / alkyl methacrylate copolymers) alkylaminoethyl methacrylate / alkyl methacrylate as well as the copolymers of unsaturated carboxylic acids with unsaturated carboxylic acids derivatives and optionally of other ionic and non-ionic monomers.

The bipolar (zwitterionic) polymers that can preferably be used come from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and its alkali and ammonium salts, from the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali and ammonium salts and of methacroylethylbetaine / methacrylate copolymers.

Also preferred are amphoteric polymers which, in addition to one or more anionic monomers, contain methacrylamidoalkyl-trialkylammonium chloride and dimethyl (diallyl) ammonium chloride as cationic monomers.

Especially preferred amphoteric polymers come from the group of methacrylamidoalkyl-trialkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, of the methacryl chloride copolymers13

ES 2 396 568 T3 amidoalkyltrialkylammonium / dimethyl (diallyl) ammonium chloride / methacrylic acid and of the copolymers of methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acids and their alkali and ammonium salts. Especially preferred are amphoteric polymers from the group of methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, of methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers and methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acids as well as their alkali and ammonium salts.

In an especially preferred embodiment of the present invention, the polymers are present in a pre-formulation (make-up) form. To formulate the polymers it is appropriate among others:

encapsulation of the polymers by water-soluble or water-dispersible coatings, preferably with water-soluble or water-dispersible natural or synthetic polymers;

encapsulation of the polymers with melting water-insoluble coating materials, preferably water-insoluble coating materials from the group of waxes or paraffins having a melting point greater than 30 ° C;

- the simultaneous granulation of the polymers with inert support materials, preferably with support materials from the group of detergent and cleaning substances, especially preferably from the group of support substances (builder) or complementary support substances (cobuilder).

The detergents or cleaning products contain the aforementioned cationic and / or amphoteric polymers in amounts of between 0.01 and 10% by weight, in each case based on the weight of the combination product. However, within the framework of the present application, those detergents or cleaning products are preferably used, the weight of which of cationic and / or amphoteric polymers is between 0.01 and 8% by weight, with an advantage between 0.01. and 6% by weight, preferably between 0.01 and 4% by weight, especially preferably between 0.01 and 2% by weight, especially between 0.01 and 1% by weight, percentage referred in each case to the total weight of the product for dishwashers.

To increase detergent or cleaning power, the dishwasher products of the invention may also contain enzymes. Proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, as well as preferably their mixtures, belong to them. These enzymes are in principle of natural origin; Starting from natural molecules, improved variants are available for use in detergents or cleaning products, which are therefore used with preference. Cleaning agents or detergents contain enzymes preferably in a total amount of 1 x 10^-6 5% by weight, 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 preferred. Examples are the subtilisins BPN 'and Carlsberg and the forms of their subsequent evolution, the protease PB92, the subtilisins 147 and 309, the alkaline protease of Bacillus lentus, the subtilisin DY and the enzymes termitase, proteinase K and the proteases TW3 and TW7 that belong to the group of subtilases, but that strictly speaking do not belong to the group of subtilisins.

Examples of amylases that can be used according to the invention are the α-amylases of Bacillus licheniformis, B. amyloliquefaciens, B. stearothermophilus, Aspergillus niger and A. oryzae as well as the further improved developments of the amylases mentioned above for the use in cleaning products and detergents. For the rest, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextringlucanotransferase (CGTase) from B. agaradherens (DSM 9948).

Other examples of enzymes that can be used according to the invention are lipases or cutinases, especially for their triglyceride decomposition activities, but also for generating peracids "in situ" from their previous synthetic compounds. These include, for example, lipases initially derived from Humicola lanuginosa (Thermomyces lanuginosus) or undergoing further development, especially those with the D96L amino acid substitution. For example, the cutinases that were initially isolated from Fusarium solani pisi and Humicola insolens can also be used. Lipases or cutinases can also be used, the starting enzymes of which were initially isolated from Pseudomonas mendocina and Fusarium solani.

Enzymes comprised within the term hemicellulases can also be used. These include, for example, mannanases, xanthanoliases, pectinaliases (= pectinases), pectinesterases, pectatoliases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

To increase the whitening effect, oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin-, glucose- or manganese peroxidases, dioxygenases or laccases (phenoloxidases, polyphenoloxidases) can be used according to the invention. ). More advantageously, it is also possible to preferably add organic compounds, especially aromatics, which interact with enzymes, in order to

ES 2 396 568 T3 to intensify the activity of the oxidoreductases in question (enhancers) or to guarantee the flow of electrons in the case of very different redox potentials (mediators) between oxidant enzymes and dirt.

The enzymes can be used in any way established in the state of the art. These formulations include, for example, solid preparations obtained by granulation, extrusion or lyophilization or, especially, liquid or gel detergents, enzyme solutions, most advantageously presented in the most concentrated form possible, with low water content and / or provided with stabilizers.

Alternatively, the enzymes can be encapsulated for solid or liquid presentation form, for example by spray drying or extrusion of the enzyme solution together with a naturally-preferred polymer, or incorporated into a capsule-type presentation form, for example those, in which the enzymes are entrapped within a solidified gel, or in capsules of the core-shell type, wherein the enzyme core is lined with a protective coating layer that is impermeable to water, air, and / or chemicals. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or colorants, can also be accommodated in the coating layers. These types of capsules are manufactured by methods known per se, for example by stirring or drum granulation or by fluidized bed processes. Advantageously, these granules will release little dust, for example thanks to the application of polymeric film-forming agents, and will be stable on storage thanks to the coating.

It is also possible to formulate (make up) two or more enzymes at the same time, so that a single granulate possesses several enzymatic activities.

A protein and / or enzyme can be protected in particular during storage against deterioration caused for example by inactivation, denaturation or decomposition due to eg physical factors, oxidation or proteolytic decomposition. In the microbial production of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially when the products also contain proteases. Detergents or cleaning products may contain stabilizers for this purpose; the preparation of such products constitutes a preferred embodiment of the present invention.

One or more enzymes and / or enzyme formulations are preferably used, preferably solid protease formulations and / or solid amylase formulations, in amounts between 0.1 and 5% by weight, preferably between 0.2 and 5% by weight and in particular between 0.4 and 5% by weight, percentages referred in each case to the total weight of the product containing the enzymes.

Some illustrative formulations of the preferred phosphate-free dishwashing products are listed in the tables below.

<td>component</td><td>formulation 9 [% by weight]</td><td>formulation 10 [% by weight]</td><td>formulation 11 [% by weight]</td><td>formulation 12 [% by weight]</td>

<td>citrate</td><td> 5-60</td><td> 10-55</td><td> 15-50</td><td> 15-50</td>

<td>sodium percarbonate</td><td> 1-20</td><td> 2-15</td><td> 4-10</td><td> 4-10</td>

<td>enzyme</td><td> 0,1-6</td><td> 0,2-5</td><td> 0,4-5</td><td> 0,4-5</td>

<td>copolymer¹</td><td> 0,1-30</td><td> 0,5-25</td><td> 1,0-20</td><td> 1,0-20</td>

<td>non-ionic surfactant²</td><td> 1-10</td><td> 2-8</td><td> 2-8</td><td> 3-6</td>

<td>various</td><td>up to 100</td><td>up to 100</td><td>up to 100</td><td>up to 100</td>

<td>component</td><td>formulation 13 [% by weight]</td><td>formulation 14 [% by weight]</td><td>formulation 15 [% by weight]</td><td>formulation 16 [% by weight]</td>

<td>citrate</td><td> 5-60</td><td> 10-55</td><td> 15-50</td><td> 15-50</td>

<td>carbonate / hydrogen carbonate</td><td> 2-40</td><td> 2-40</td><td> 2-40</td><td> 2-40</td>

<td>silicate</td><td> 0-15</td><td> 0-15</td><td> 0-15</td><td> 0,1-10</td>

<td>phosphonate</td><td> 0-14</td><td> 0-14</td><td> 0-14</td><td> 2-8</td>

<td>sodium percarbonate</td><td> 1-20</td><td> 2-15</td><td> 4-10</td><td> 4-10</td>

<td>bleach catalyst</td><td> 0,01-3</td><td> 0,02-2</td><td> 0,02-2</td><td> 0,02-1</td>

<td>copolymer¹</td><td> 0,1-30</td><td> 0,5-25</td><td> 1,0-20</td><td> 1,0-20</td>

<td>non-ionic surfactant²</td><td> 1-10</td><td> 2-8</td><td> 2-8</td><td> 3-6</td>

<td>enzyme</td><td> 0,1-6</td><td> 0,2-5</td><td> 0,4-5</td><td> 0,4-5</td>

<td>various</td><td>up to 100</td><td>up to 100</td><td>up to 100</td><td>up to 100</td>

<td colspan="5">¹ copolymer formed by: i) monomers from the group of mono- or polyunsaturated carboxylic acids, ii) monomers of the general formula R¹(R²) C = C (R³) -XR⁴, in which R¹ to R³ independently of one another signify -H, -CH3 or -C2H5, X signifies an optionally present spacer group, which is chosen from -CH2-, -C (O) O- and -C (O) -NH-, and R⁴ It is a saturated, linear or branched alkyl radical of 2 to 22 carbon atoms or an unsaturated hydrocarbon radical, preferably aromatic, of 6 to 22 carbon atoms, iii) optionally other monomers;</td>

ES 2 396 568 T3 ² nonionic surfactant of the general formula R¹-CH (OH) CH2O- (AO) w (A'O) x (A "O) y- (A" 'O) zR², in which

- R¹ means a linear or branched saturated or mono- or polyunsaturated C6-24 alkyl or alkenyl radical,

- R² means a straight or branched hydrocarbon residue of 2 to 26 carbon atoms,

- A, A ', A "and A"' independently of one another signify a residue chosen from the group -CH2CH2, -CH2CH2-CH2, CH2-CH (CH3), -CH2-CH2-CH2-CH2, -CH2- CH (CH3) -CH2, -CH2-CH (CH2-CH3), and

- "w", "x", "y" and "z" take values ​​between 0.5 and 120, where "x", "y" and / or "z" can also be 0

Phosphate-free dishwasher products, which contain a carrier substance (builder), a bleach and also:

a) a copolymer formed by:

i) monomers of the group of mono- or polyunsaturated carboxylic acids, ii) monomers of the general formula R¹(R²) C = C (R³) -XR⁴, in which R¹ to R³ independently of one another signify -H, -CH3 or -C2H5, X signifies an optionally present spacer group, which is chosen from -CH2-, -C (O) O- and -C (O) -NH-, and R⁴ it is a saturated, linear or branched alkyl radical of 2 to 22 carbon atoms or an unsaturated hydrocarbon radical, preferably aromatic, of 6 to 22 carbon atoms;

b) a nonionic surfactant of the general formula R¹-CH (OH) CH2O- (AO) w (A'O) x (A "O) y- (A" 'O) zR², in which

- R¹ means a linear or branched saturated or mono- or polyunsaturated C6-24 alkyl or alkenyl radical,

- R² means a straight or branched hydrocarbon residue of 2 to 26 carbon atoms,

- A, A ', A "and A"' independently of one another signify a residue chosen from the group -CH2CH2, -CH2CH2-CH2, -CH2CH (CH3), -CH2-CH2-CH2-CH2, -CH2-CH (CH3) -CH2, -CH2-CH (CH2-CH3), and

- "w", "x", "y" and "z" take values ​​between 0.5 and 120, where "x", "y" and / or "z" can also be 0;

c) 1.0 to 6% by weight of an enzyme.

Products for dishwashers, which contain:

a) a copolymer formed by:

i) monomers of the group of mono- or polyunsaturated carboxylic acids, ii) monomers of the general formula R¹(R²) C = C (R³) -XR⁴, in which R¹ to R³ independently of one another signify -H, -CH3 or -C2H5, X signifies an optionally present spacer group, which is chosen from -CH2-, -C (O) O- and -C (O) -NH-, and R⁴ it is a saturated, linear or branched alkyl radical of 2 to 22 carbon atoms or an unsaturated hydrocarbon radical, preferably aromatic, of 6 to 22 carbon atoms;

b) a nonionic surfactant of the general formula R¹-CH (OH) CH2O- (AO) wR², in which:

- R¹ means a linear or branched saturated or mono- or polyunsaturated C6-24 alkyl or alkenyl radical;

- R² means a straight or branched hydrocarbon residue of 2 to 26 carbon atoms;

- A means a residue from the group consisting of -CH2CH2, -CH2CH2-CH2 and -CH2-CH (CH3) and

- "w" takes values ​​between 1 and 120, preferably between 10 and 80, especially between 20 and 40;

c) 10 to 50% by weight of citrate;

d) from 2 to 15% by weight of sodium percarbonate;

e) from 2 to 8% by weight of a sequestrant from the group of 1-hydroxyethane-1,1-diphosphonic acid and methylglycine diacetic acid; Y

f) 1.0 to 6% by weight of an enzyme.

Glass corrosion inhibitors prevent the appearance of haze, streaks (bursts) and scratches, but also the iridescence of the glass surface that is mechanically cleaned. Preferred glass corrosion inhibitors come from the group of magnesium and / or zinc salts and / or magnesium and / or zinc complexes.

The spectrum of the preferred zinc salts, in particular of organic acids, with particular preference of organic carboxylic acids, ranges from salts, which are hardly soluble or insoluble in water, that is to say, which have a solubility of less than 100 mg / l , preferably less than 10 mg / l, especially less than 0.01 mg / l, up to salts having a solubility in water greater than 100 mg / l, preferably greater than 500 mg / l, particularly preferably greater than 1 g / l and especially greater than 5 g / l (all solubilities are determined at a water temperature of 20 ° C). Zinc citrate, zinc oleate and zinc stearate belong to the first group of zinc salts; They belong to the group of soluble zinc salts, for example zinc formate, zinc acetate, zinc lactate and zinc gluconate.

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

In the context of the present invention, the content of zinc salts in detergents or cleaning products will advantageously be between 0.1 and 5% by weight, preferably between 0.2 and 4% by weight. weight and in particular between 0.4 and 3% by weight, or the zinc content in oxidized form (calculated as Zn²⁺) will stand 16

ES 2 396 568 T3 between 0.01 and 1% by weight, preferably between 0.02 and 0.5% by weight and especially between 0.04 and 0.5% by weight, percentages referred in each case to the total weight of the product provided with the glass corrosion inhibitor.

Corrosion inhibitors serve to protect dishes or even the washing machine, silver protection products being of special importance for the dishwasher sector. Substances already known from the state of the art can be used for this. In general, silver protection agents chosen above all from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts and complexes can be used. Benzotriazole and / or alkylaminotriazoles are particularly preferred. According to the invention, the 3-amino-5-alkyl-1,2,4-triazoles or their physiologically compatible salts are preferably used, said substances being used with particular preference in a concentration of 0.001 to 10% by weight, preferably 0.0025. 2% by weight, more preferably 0.01 to 0.04% by weight.

To facilitate the disintegration of prefabricated molded articles, it is possible to incorporate disintegrating auxiliaries, also called tablet "explosives", in these products in order to shorten the decomposition period.

These substances, which are called “explosive” due to their effect, increase in volume when there is penetration of water, with which, on the one hand, their own volume increases (swelling) and, on the other hand, a release of gases and the consequent pressure can take place. , which breaks down the tablet into small particles. For example, the carbonate / citric acid systems are known disintegrators, but other organic acids can also be used. Swelling disintegrating auxiliaries are, for example, synthetic polymers of the polyvinylpyrrolidone (PVP) type, natural polymers or modified natural products, for example cellulose, starch and its derivatives, alginates and casein derivatives.

Disintegrating aids are preferably used in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight, and in particular 4 to 6% by weight, percentages in each case based on the total weight of the product containing the disintegrating aid.

Cellulose-based disintegrants are used as preferred disintegrants, so that the preferred detergents or cleaning products contain a cellulose-based disintegrant in amounts of 0.5 to 25% by weight, preferably 3 to 7% by weight and in special 4 to 6% by weight. The cellulose used as disintegrating auxiliary is preferably used not in finely divided form, but before being incorporated into the pre-pressing mixtures it is converted into a coarser form, for example it is granulated or compacted. The particle sizes of such disintegrants are generally greater than 200 pm, preferably at least 90% by weight between 300 and 1600 pm and especially at least 90% by weight between 400 and 1200 pm.

Preferred disintegrating aids, preferably based on cellulose, preferably in granulated, cogranulated or compacted form, are present in dishwasher products in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and especially from 4 to 6% by weight, percentage referred in each case to the product containing said disintegrant.

According to the invention, effervescent gas-generating systems can also preferably be used as disintegrating aids for tablets. The effervescent gas-generating system can be made up of a single substance, which releases a gas when it comes into contact with water. These compounds include especially magnesium peroxide, which in contact with water liberates oxygen. But the preferred effervescent systems are made up of at least two components, which react with each other to form a gas, they are made up for example of an alkali carbonate and / or alkaline hydrogen carbonate and an acidifying agent, which is suitable for releasing carbon dioxide from of the alkaline salts found in aqueous solution. As acidifying agents, which liberate carbon dioxide from alkaline salts in aqueous solution, there can be used, for example, boric acid and alkali metal hydrogen sulfates, alkali dihydrogen phosphates and other inorganic salts. However, organic acidifiers are preferably used, citric acid being particularly preferred. Acidifiers for an effervescent system selected from the group of organic di-, tri- and oligocarboxylic acids and mixtures thereof are preferred.

As fragrances or essential oils, individual aromatic compounds can be used in the context of the present invention, eg synthetics of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. However, mixtures of various fragrances are preferably used, which together generate an attractive aromatic note. These essential oils can contain mixtures of natural fragrances, for example those that can be obtained from plant sources, eg. the essences of pine, lemon, jasmine, patchouli, rose or ilang-ilang.

The fragrances can be processed directly, but it may also be advantageous to incorporate the fragrances into

ES 2 396 568 T3 substrates, which, due to their slower release of the aroma, make it possible to enjoy said fragrance for a longer time. As substrates of this type, for example cyclodextrins have given good results, in addition the cyclodextrin-perfume complexes can be coated with other additional auxiliaries.

Preferred colorants, the choice of which does not pose problems for experts, have high storage stability, inertia (stability) vis-à-vis the other components of the product for dishwashers, light stability, and do not exhibit marked substantivity with respect to substrates. to be treated with the products provided with colorants, for example textiles, glass, ceramics, plastic tableware, so that these substrates do not color.

The dishwasher products of the invention can be formulated in solid or liquid form and supplied for example in the form of combination of solid and liquid presentation forms.

As solid presentation forms, powders, granulated, extruded and compacted materials, in particular tablets, are especially suitable. Liquid presentation forms based on water and / or organic solvents can be presented thickened, in the form of gels.

The products of the invention can be formulated (packaged) as single-phase or polyphase products. Dishwashing products having one, two, three or four phases are especially preferred. Products for dishwashing machines characterized by being present in the form of a prefabricated dosage unit, made up of two or more phases, are especially preferred.

The individual phases of the polyphase products can have the same states of aggregation or different states. Especially preferred are products for dishwashers, which have at least two different solid phases and / or at least two liquid phases and / or at least one solid phase and at least one liquid phase.

The dishwasher products of the invention are preferably pre-formulated in dosage unit form. These dosage units preferably include the necessary amount of detergent or cleaning active substances that are needed for the washing process. Preferred dosage units have a weight of between 12 and 30 g, preferably between 14 and 26 g, and especially between 15 and 22 g.

The volume of the aforementioned dosing units and their three-dimensional shape are chosen with special preference so that the dosability of the pre-formulated units through the dosing trays of a dishwashing machine is guaranteed. The volume of the dosage unit is therefore advantageously between 10 and 35 ml, preferably between 12 and 30 ml and in particular between 15 and 25 ml.

The products for dishwashing machines of the invention, especially the pre-formulated dosage units, especially preferably have a water-soluble cover (liner).

Another object of the present application is a method of washing a tableware carried out in a dishwasher using the products for dishwashers of the invention, said products for dishwashers are dosed into the interior chamber of the machine preferably in the course of the program. before starting the main wash step or in the course of the main wash step. The dosage or the introduction of the product of the invention into the chamber of the machine can be carried out manually, but said product is preferably dosed by means of the bowl of the machine. In the course of the washing process, preferably no additional softener or rinse aid is dispensed into the inner chamber of the dishwasher.

As indicated in the introduction, the products for dishwashing machines of the invention are characterized by a better shine than conventional ones. The use of a product for dishwashing machines of the invention as a rinse aid in machine dishwashing is thus another object of the present application.

Examples

In a first washing test, dirty dishes are placed in a machine and washed with 21 g of a product for dishwashers without phosphates E2 or with 21 g of the product for dishwashers without phosphates E1, with a water hardness of 21 ° dH (German degrees of hardness).

The compositions of the products for dishwashing machines used are shown in the following table.

ES 2 396 568 T3

<td>raw material</td><td>E1</td><td>E2</td>

<td>citrate</td><td> 23</td><td> 23</td>

<td>MGDA</td><td> 8,0</td><td> 8,0</td>

<td>copolymer¹</td><td> 12,0</td><td> 12,0</td>

<td>HEDP</td><td> 2,0</td><td> 2,0</td>

<td>bland</td><td> 28,0</td><td> 28,0</td>

<td>sodium percarbonate</td><td> 10,0</td><td> 10,0</td>

<td>TAED</td><td> 2,4</td><td> 2,4</td>

<td>protease</td><td> 2,0</td><td> 2,0</td>

<td>amylase</td><td> 1,8</td><td> 1,8</td>

<td>non-ionic surfactant²</td><td> 5,0</td><td> --</td>

<td>non-ionic surfactant³</td><td> --</td><td> 5,0</td>

<td>various</td><td>up to 100</td><td>up to 100</td>

<td colspan="3">¹ copolymer modified to be hydrophobic² polyalkoxylated fatty alcohol of the general formula (C12-18 fatty alcohol) - (EO) 1-6- (PO) 1-6- (EO) 1-6- (PO) 1-6-OH</td>

<td colspan="2">mixed hydroxyether of the general formula C6-24-CH (OH) CH2O- (EO) 20-120-C2-26</td><td></td>

The general appearance of the washed dishes is evaluated according to the score below. The results are scored as indicated in the table below (the values ​​indicated are averages of the values ​​of 3 three tests).

<td></td><td>E1</td><td>E2</td>

<td>washing result</td><td> 8,0</td><td> 8,2</td>

<td>polishing result</td><td>glass 1.0 stainless steel 2.2 plastic 3.2</td><td>glass 8.0 stainless steel 9.0 plastic 6.3</td>

Wash score: 10 = no dirt observed; a 0 = heavily soiled (average values ​​obtained with seven standard soils)

Brightening Score: 10 = no droplets; a 0 = intense droplet formation.