Detergent

European).

OK II-12 / P31659EN00

EP 2 115 113 B1

Cleaning agents

This patent application describes cleaning agents, in particular cleaning agents for machine cleaning of machines. The subject of this application are in particular phosphate-free machine dishwashing agents.

Today, machine-washed dishes are often placed at higher demands than hand-washed ones. Thus, the dishes after machine cleaning should not only be completely free of food residues, but also should not show any whitish stains resulting from the hardness of water or other mineral salts, which due to the lack of wetting agents come from dried water droplets.

Modern detergents for machine-washed dishes meet these requirements by combining cleaning, care, water softening and rinsing active substances together and are known to the user as "2 in 1" or "3 in 1" dishwashing agents. As an essential ingredient for the success of both cleaning and washing, machine dishwashing agents intended for private end users contain skeletal substances. First of all, these skeletal substances increase the alkalinity of the cleaning bath, while the increasing alkalinity emulsify and saponify fats and oils, and secondly, by complexing calcium ions contained in the water bath, they reduce the hardness of the cleaning bath water. Lithium phosphates have proven to be particularly effective skeletal substances, which are therefore a major component of the vast majority of commercially available machine dishwashing agents.

- 2 So, while phosphates are very highly valued as a component of machine dishwashing agents due to their beneficial effects, their use from an environmental point of view is problematic, however, because a substantial part of phosphate enters the water through domestic sewage surface, and especially plays a dubious role in stagnant surface waters (lakes, damming water steps) in the event of their fertilization. As a result of this phenomenon also known as eutrophy, the use of pentasodium triphosphate in textile washing agents has been significantly reduced in some countries, e.g. the USA, Canada, Italy, Sweden, Norway, and they have been banned completely in Switzerland. In Germany, detergents can contain at most 20% of this skeletal substance since 1984.

In addition to nitrilotriacetic acid, mainly sodium aluminosilicates (zeolites) are used as replacements for phosphates in textile washing agents. For various reasons, however, these substances are not suitable for use in machine dishwashing agents. Hence, as an alternative to alkali metal phosphates in machine dishwashing agents, substitute substances are discussed in the literature, among which citrates should be highlighted in particular.

Phosphate-free machine dishwashing agents which, in addition to citrate, further contain carbonates, bleaches and enzymes, are described e.g. in European patent documents EP 662 117 B1 (Henkel KGaA) and EP 692 020 (Henkel KGaA).

A further alternative for alkali metal phosphates, in which the only skeletal substance, however, is preferably used in a mixture with citrates, is methylglycine diacetic acid (MGDA). MGDA-containing machine dishwashing agents are described in e.g. European Patent Document EP 906 407 B1 (Reckitt Benckiser) or European Patent Application EP 1 113

- 3,070 A2 (Reckitt Benckiser). Further suitable documents are US 5279756 and US 5308532.

Despite the efforts made to date, manufacturers of machine dishwashing agents have not yet been able to develop phosphate-free machine dishwashing agents which, in terms of their cleaning and rinsing performance, and in particular their effectiveness in inhibiting the formation of deposits, would be comparable to or containing phosphate-containing cleaning agents. They exceeded. However, such performance equality is a prerequisite for successful commercialization of phosphate-free cleaners, since the overwhelming number of end users, despite extensive public discussion of environmental policy, are still opting for an ecologically beneficial product when it does not meet the market standard in terms of price and / or your performance.

As regards this initial situation, the task of the present application was accordingly to develop a phosphate-free machine dishwashing agent which, both in terms of its cleaning performance and in terms of its rinsing results and its efficiency in terms of inhibiting the formation of sludge is comparable to or exceeds traditional phosphate-containing cleaners.

It was found that machine dishwashing agents which, in addition to the skeletal substance and bleaching agent, also display specific non-ionic surfactants and specific, hydrophobically modified copolymers, also without the addition of alkali metal phosphates, show excellent inhibition of deposit formation and cleaning and rinsing performance .

The first object of the present invention is therefore a phosphate-free machine dishwashing agent containing a skeletal substance, a bleaching agent and further

a) a copolymer containing

- 4 i) monomers from the group of mono- or polyunsaturated carboxylic acids, ii) monomers of general formula R¹(R²) C = C (R³) XR⁴in which R¹-R³ are independently -H, -CH₃ or -C₂H₅, X is an optionally existing spacer group which is selected from -CH2-, -C (O) O- and -C (O) -NH-, and R⁴ is a straight or branched chain saturated alkyl radical with 2-22 carbon atoms or an unsaturated, preferably aromatic radical with 6-22 carbon atoms, iii) optionally further monomers,

b) a nonionic surfactant of general formula

R¹-CH (OH) CH2O- (AO) w- (A'O) x- (A''O) y- (A '' 'O) zR², wherein

- R¹ is a straight or branched chain, saturated or mono- or polyunsaturated C6-24 alkyl or -alkenyl radical,

- R² is a linear or branched hydrocarbon radical with 2-26 carbon atoms,

- A, A ', A' 'and A' '' are each independently a radical from the group consisting of -CH2CH2, -CH2CH2-CH2, -CH2-CH (CH3), -CH2-CH2-CH2-CH2, -CH2- CH (CH3) -CH2-, -CH2-CH (CH2-CH3),

- w, x, y and z represent values ​​of 0.5-120, with x, y and / or z also representing 0.

The first essential component of the machine dishwashing agents according to the invention is the hydrophobically modified copolymer a) containing monomers

i) and ii).

As monomers i) from the group of mono- or polyunsaturated carboxylic acids, carboxylic acids of general formula R are particularly preferably used.¹(R²) C = C (R³) COOH, in which R¹-R³ are independently from each other -H, -CH3, a straight or branched, saturated alkyl radical with 2-12 carbon atoms, a straight or branched saturated, mono- or polyunsaturated unsaturated alkenyl radical with 2-12 carbon atoms, substituted with -NH₂, -OH or -COOH alkyl or alkenyl radicals as previously defined or are -COOH or -COOR⁴, with R⁴ is a saturated or unsaturated straight or branched chain hydrocarbon radical with 1-12 carbon atoms.

According to the invention, phosphate-free machine dishwashing agents containing a skeletal substance, bleaching agent and further are preferably used.

a) a copolymer containing

i) monomers from the group consisting of carboxylic acids of general formula R¹(R²) C = C (R³) COOH, in which R¹-R³ are independently from each other -H, -CH3, a straight or branched, saturated alkyl radical with 2-12 carbon atoms, a straight or branched saturated, mono- or multiple unsaturated alkenyl radical with 2-12 carbon atoms, substituted with -NH2, -OH or -COOH alkyl or alkenyl radicals as previously defined or are -COOH or -COOR⁴, with R⁴ is a saturated or unsaturated, straight or branched chain hydrocarbon radical of 1-12 carbon atoms, ii) monomers of the general formula R¹(R²) C = C (R³) XR⁴in which R¹-R³ are each independently -H, -CH3 or -C2H5, X is an optionally existing spacer group which is selected from -CH2-, -C (O) O- and -C (O) -NH-, and R⁴ is a straight or branched chain saturated alkyl radical with 2-22 carbon atoms or an unsaturated, preferably aromatic radical with 6-22 carbon atoms,

b) a nonionic surfactant of formula

- 6 general

R¹-CH (OH) CH2O- (AO) w- (A'O) x- (A''O) y- (A '' 'O) zR², wherein

- R¹ is a straight chain or branched, saturated or mono- or polyunsaturated C6-24 alkyl or -alkenyl radical,

- R² is a linear or branched hydrocarbon radical with 2-26 carbon atoms,

- A, A ', A' 'and A' '' represent, independently of each other, a radical from the group consisting of -CH₂CH₂,

-CH2CH2-CH2, -CH2-CH (CH3), -CH2-CH2-CH2-CH2,

-CH2-CH (CH3) -CH2-, -CH2-CH (CH2-CH3),

- w, x, y and z represent values ​​of 0.5-120, with x, y and / or z also representing 0.

Particularly preferred monomers i) containing carboxyl groups are acrylic acid, methacrylic acid, ethacrylic acid, etachloroacrylic acid, ethanoacrylic acid, crotonic acid, phenylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylene malonic acid sorbic, mandelic acid or mixtures thereof.

As nonionic monomers ii) monomers of formula R are used¹(R²) C = C (R³) -X-R⁴. Particularly preferred monomers of this type are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexane, 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-dimethylhexene-1,3,5-dimethylhexene-1, 4,4-dimethylhexene 1, ethylcyclohexine, 1-octene, 10 olefins or more carbon atoms, e.g. 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22-olefin, 2-styrene, 2-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2- ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, acrylic acid methyl ester, acrylic acid ethyl ester, ester

- 7 propyl acrylic acid, acrylic acid butyl ester, acrylic acid pentyl ester, acrylic acid hexyl ester, methacrylic acid methyl ester, N- (methyl) acrylamide, acrylic acid 2-ethylhexyl ester, methacrylic acid 2-ethylhexyl ester, N- ( 2-ethylhexyl) acrylamide, acrylic acid octyl ester, methacrylic acid octyl ester, N- (octyl) acrylamide, acrylic acid lauryl ester, methacrylic acid lauryl ester, N- (lauryl) acrylamide, acrylic acid stearyl ester, methacrylic acid stearyl ester, N- (stearyl) acrylamide, acrylic acid behenyl ester, methacrylic acid behenyl ester and N- (behenyl) acrylamide or mixtures thereof.

The machine-dishwashing agents according to the invention in which the copolymer by weight of the copolymer a) is 4-18% by weight, preferably 6-15, preferably 6-15, have proved to be particularly effective in terms of optimal inhibition of deposit formation and cleaning and rinsing results. 12% by weight.

According to the invention, phosphate-free machine dishwashing agents containing a skeletal substance, bleaching agent and further are preferred.

a) 4-18% by weight containing copolymer

i) monomers from the group consisting of carboxylic acids of the general formula

R¹(R²) C = C (R³) COOH, in which R¹-R³ are independently -H, -CH₃, a straight or branched chain saturated alkyl radical with 2-12 carbon atoms, a straight chain or branched chain, single or multiple unsaturated alkenyl radical with 2-12 carbon atoms, substituted with -NH2, -OH or -COOH alkyl or alkenyl radicals, as previously defined, or are -COOH or -COOR⁴, with R⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical with 1-12 carbon atoms , ii) monomers of the general formula R¹(R²) C = C (R³) XR⁴in which R¹-R³ are independently -H, -CH₃ or -C₂H₅, X is an optionally existing spacer group which is selected from

-CH2-, -C (O) O- and -C (O) -NH-, and R⁴ is a straight or branched chain saturated alkyl radical with 2-22 carbon atoms or an unsaturated, preferably aromatic radical with 6-22 carbon atoms,

b) a nonionic surfactant of general formula

R¹-CH (OH) CH2O- (AO) w- (A'O) x- (A''O) y- (A '' 'O) zR², wherein

- R¹ is a straight or branched chain, saturated or mono- or polyunsaturated C6-24 alkyl or -alkenyl radical,

- R² is a linear or branched hydrocarbon radical with 2-26 carbon atoms,

- A, A ', A' 'and A' '' are each independently a radical from the group consisting of -CH2CH2, -CH2CH2-CH2, -CH2-CH (CH3), -CH2-CH2-CH2-CH2, -CH2- CH (CH3) -CH2-, -CH2-CH (CH2-CH3),

- w, x, y and z represent values ​​of 0.5-120, with x, y and / or z also representing 0.

In a particularly preferred embodiment, the copolymer d) contains, in addition to the monomers i) and ii) further a third monomer iii) selected from the group consisting of sulfonic acid containing monomers.

For monomers containing sulfonic acid groups, monomers of the formula are preferred

R⁵(R⁶) C = C (R⁷) -X-SO3H, in which R⁵-R⁷ are independently from each other -H, -CH3, straight or branched, saturated alkyl radical with 2-12 carbon atoms, straight or branched, single or multiple unsaturated alkenyl radical with 2-12 carbon atoms, substituted with - 9 NH2, -OH or -COOH alkyl or alkenyl radicals, or are -COOH or -COOR⁴, with R⁴ is a saturated or unsaturated, straight or branched chain hydrocarbon radical with 1-12 carbon atoms, and X is an optionally existing spacer group which is selected from - (CH2) n-, where n = 0-4, -COO (CH2) k- , where k = 1-6, -C (O) -NH-C (CH3) 2- and -C (O) -NHCH (CH2CH3) -.

Of these monomers, monomers having formulas are preferred

H2C = CH-X-SO3H

H2C = C (CH3) -X-SO3H

HO3S-X- (R⁶) C = C (R⁷) -X-SO3H, in which R⁶ and R⁷ is independently selected from -H, -CH3, -CH2CH3, -CH2CH2CH3, -CH (CH3) 2, and X is an optionally existing spacer group which is selected from - (CH2) n-, where n = 0-4 , -COO (CH2) k-, where k = 1-6, -C (O) -NH-C (CH3) 2- and -C (O) -NHCH (CH2CH3) -.

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, methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, metallylsulfonic acid, allyloxybenzenesulfonic acid, metallyloxybenzenesulfonic acid, acid

2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrene sulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of these acids and their soluble in salt water.

The sulfonic acid groups can be present in polymers in full or in partial form, which means that the hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali ions, especially sodium ions. According to the invention, it is preferred to use partially or completely neutralized copolymers containing sulfonic acid groups.

The molar mass of the sulfo-copolymers preferably used according to the invention can be varied to adapt the polymer properties to the desired application. Preferred agents for machine dishwashing are characterized in that the copolymers have a molar mass of 2000-200000 gmol^-1, preferably 4000-25000 gmol^-1, especially 5000-15000 gmol^-1.

According to the invention, phosphate-free machine dishwashing agents containing a skeletal substance, bleaching agent and further are preferred.

a) a copolymer containing

i) monomers from the group consisting of carboxylic acids of the general formula

R¹(R²) C = C (R³) COOH, in which R¹-R³ are independently -H, -CH₃, straight or branched chain, saturated alkyl radical with 2-12 carbon atoms, straight or branched chain, single or multiple unsaturated alkenyl radical with 212 carbon atoms, substituted with -NH2, -OH or -COOH alkyl or alkenyl radicals as previously defined, or are -COOH or -COOR⁴, with R⁴is a saturated or unsaturated, straight or branched chain hydrocarbon radical of 1-12 carbon atoms, ii) monomers of the general formula R¹(R²) C = C (R³) -X-R⁴in which R¹-R³ are each independently -H, -CH3 or -C2H5, X is an optionally existing spacer group which is selected from -CH2-, -C (O) O- and -C (O) -NH-, and R⁴ is a straight or branched chain saturated alkyl radical with 2-22 carbon atoms or unsaturated, preferably aromatic

- 11 radical with 6-22 carbon atoms, iii) monomers containing sulfonic acid groups,

b) a nonionic surfactant of general formula

R¹-CH (OH) CH2O- (AO) w- (A'O) x- (A''O) y- (A '' 'O) zR², wherein

- R¹ is a straight chain or branched, saturated or mono- or polyunsaturated C6-24 alkyl or -alkenyl radical,

- R² is a linear or branched hydrocarbon radical with 2-26 carbon atoms,

- A, A ', A' 'and A' '' represent, independently of each other, a radical from the group consisting of -CH₂CH₂,

-CH2CH2-CH2, -CH2-CH (CH3), -CH2-CH2-CH2-CH2,

-CH2-CH (CH3) -CH2-, -CH2-CH (CH2-CH3),

- w, x, y and z represent values ​​of 0.5-120, with x, y and / or z also representing 0.

As a second important ingredient, the dishwashing agents according to the invention contain nonionic surfactants of general formula R¹-CH (OH) CH2O- (AO) w- (A'O) x- (A''O) y- (A '' 'O) zR², wherein

- R¹ is a straight or branched chain, saturated or mono- or polyunsaturated C6-24 alkyl or -alkenyl radical,

- R² is a linear or branched hydrocarbon radical with 2-26 carbon atoms,

- A, A ', A' 'and A' '' are each independently a radical from the group consisting of -CH₂CH₂, -CH2CH2-CH2, -CH2-CH (CH3), -CH2-CH2-CH2-CH2, -CH2-CH (CH3) -CH2-, -CH2-CH (CH2-CH3),

- w, x, y and z represent values ​​of 0.5-120, with x, y and / or z also representing 0.

Preferred dishwashing agents according to the invention have a weight fraction of this nonionic surfactant b) 1-10% by weight, preferably 2-8% by weight and especially 3-6% by weight.

As particularly advantageous in terms of performance

- cleaning and rinsing proved to be nonionic surfactants b) of the general formula R¹-CH (OH) CH2O (AO) w (A'O) x R², wherein

- R¹ is a straight or branched chain, saturated or mono- or polyunsaturated C6-24 alkyl or -alkenyl radical,

- R² is a linear or branched hydrocarbon radical with 2-26 carbon atoms,

- A and A 'are each independently a radical from the group consisting of -CH2CH2, -CH2CH2-CH2, -CH2CH (CH3), and

- w, x denote values ​​0.5-120.

Especially preferred are dishwashing agents which are characterized in that the non-ionic surfactant b) has the general formula R¹-CH (OH) CH2O- (AO) w (A'O) x R², wherein

- R¹ is a straight or branched chain, saturated or mono- or polyunsaturated C6-24 alkyl or -alkenyl radical,

- R² is a linear or branched hydrocarbon radical with 2-26 carbon atoms,

- A represents the CH2CH2 radical, A 'represents the -CH2CH2-CH2 or -CH2-CH (CH3) radical, and

- w means values ​​2-40, while x means values ​​0.5-2.

Especially preferred are dishwashing agents in which the nonionic surfactant has the general formula R¹-CH (OH) -CH 2 O (AO) wR², wherein

- R¹ is a straight or branched chain, saturated or mono- or polyunsaturated C6-24 alkyl or -alkenyl radical,

- R² is a linear or branched hydrocarbon radical with 2-26 carbon atoms,

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

w means values ​​1-120, preferably 10-80, especially 20-40.

- The given C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the previously discussed nonionic surfactants are statistical average values ​​that can be an integer or a fractional number for a special product. Due to the method of production, commercial products of the formulas discussed usually consist not of one representative, but of mixtures, which may result in average values ​​of both chain lengths and degrees of ethoxylation or alkoxylation, and hence fractional numbers.

The nonionic surfactants discussed above can of course not only be used as individual substances, but also as mixtures of two, three, four or more surfactants. Mixtures of surfactants are not mixtures of non-ionic surfactants which in their entirety correspond to one of the general formulas discussed above, but rather mixtures which contain two, three, four or more non-ionic surfactants which can be described by different from the general formulas discussed above.

Preferably, according to the invention, the mechanical dishwashing agents contain one or more skeletal substances as a further essential component. Skeletal substances include, in particular, silicates, carbonates and organic builders.

As organic co-fillers, in particular, polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and other organic co-fillers should be mentioned. These substance classes will be described later.

Useful organic skeletal substances are e.g. polycarboxylic acids used in the form of free acids and / or their sodium salts, with polycarboxylic acids being understood as carboxylic acids that contain more than one acid group

- functional, and for example they are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, amino carboxylic acids, nitrilotriacetic acid (NTA), unless this type of use is prohibited for ecological reasons and mixtures thereof. In addition to their activity as an active filler, the free acids also typically have the property of an acidifying component and are therefore also used to set lower and milder pH values ​​for washing and cleaning agents. Of these, mention should in particular be made of citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof.

Particularly preferred machine dishwashing agents according to the invention contain citrate as one of their essential skeletal substances. Preferred according to the invention are the machine dishwashing agents according to the invention which are characterized in that they contain 5-60% by weight, preferably 10-50% by weight and especially 15-40% by weight of citrate. Citrate or citric acid proved to be the most effective skeletal substances in a mixture with specific, hydrophobically modified copolymers and specific nonionic surfactants in terms of cleaning efficiency, such as rinsing efficiency, and inhibition of deposit formation.

According to the invention, phosphate-free machine dishwashing agents containing 560% by weight, preferably 10-50% by weight, in particular 15-40% by weight of citrate, bleach and further are preferred

a) a copolymer containing

i) monomers from the group consisting of carboxylic acids of general formula R¹(R²) C = C (R³) COOH, in which R¹-R³ are independently from each other -H, -CH3, a straight or branched chain saturated alkyl radical with 2-12 carbon atoms, a straight or branched chain saturated mono or multiple unsaturated alkenyl radical with 212 carbon atoms, substituted with -NH2, -OH or -COOH alkyl or alkenyl radicals as previously defined or are -COOH or -COOR⁴, with R⁴is a saturated or unsaturated, straight or branched chain hydrocarbon radical of 1-12 carbon atoms, ii) monomers of the general formula R¹(R²) C = C (R³) -X-R⁴in which R¹-R³ are each independently -H, -CH3 or -C2H5, X is an optionally existing spacer group which is selected from -CH2-, -C (O) O- and -C (O) -NH-, and R⁴ is a straight or branched chain saturated alkyl radical with 2-22 carbon atoms or an unsaturated, preferably aromatic radical with 6-22 carbon atoms,

b) a nonionic surfactant of general formula

R¹-CH (OH) CH2O- (AO) w- (A'O) x- (A''O) y- (A '' 'O) zR², wherein

- R¹ is a straight or branched chain, saturated or mono- or polyunsaturated C6-24 alkyl or -alkenyl radical,

- R² is a linear or branched hydrocarbon radical with 2-26 carbon atoms,

- A, A ', A' 'and A' '' are each independently a radical from the group consisting of -CH2CH2, -CH2CH2-CH2, -CH2-CH (CH3), -CH2-CH2-CH2-CH2, -CH2- CH (CH3) -CH2-, -CH2-CH (CH2-CH3),

- w, x, y and z represent values ​​of 0.5-120, with x, y and / or z also representing 0.

Further preferred embodiments are phosphate-free machine dishwashing agents containing 5-60% by weight, preferably 10-50% by weight, in particular 15-40% by weight of citrate, bleaching agent and

- 16 next

a) a copolymer containing

i) monomers from the group consisting of carboxylic acids of general formula R¹(R²) C = C (R³) COOH, in which R¹-R³ are independently -H, -CH₃, straight or branched chain, saturated alkyl radical with 2-12 carbon atoms, straight or branched chain, single or multiple unsaturated alkenyl radical with 212 carbon atoms, substituted with -NH2, -OH or -COOH alkyl or alkenyl radicals as previously defined, or are -COOH or -COOR⁴, with R⁴is a saturated or unsaturated, straight or branched chain hydrocarbon radical of 1-12 carbon atoms, ii) monomers of the general formula R¹(R²) C = C (R³) -X-R⁴in which R¹-R³ are each independently -H, -CH3 or -C2H5, X is an optionally existing spacer group which is selected from -CH2-, -C (O) O- and -C (O) -NH-, and R⁴ is a straight or branched chain saturated alkyl radical with 2-22 carbon atoms or an unsaturated, preferably aromatic radical with 6-22 carbon atoms, iii) monomers containing sulfonic acid groups,

b) a nonionic surfactant of general formula

R¹-CH (OH) CH2O- (AO) w- (A'O) x- (A''O) y- (A '' 'O) zR², wherein

- R¹ is a straight or branched chain, saturated or mono- or polyunsaturated C6-24 alkyl or -alkenyl radical,

- R² is a linear or branched hydrocarbon radical with 2-26 carbon atoms,

- 17 - A, A ', A' 'and A' '' are each independently a radical from the group consisting of -CH2CH2, -CH2CH2-CH2, -CH2-CH (CH3), -CH2-CH2-CH2-CH2, - CH2-CH (CH3) -CH2-, -CH2-CH (CH2-CH3),

- w, x, y and z are 0.5-120, with x, y and / or z also being 0. Machine dishwashing agents according to the invention preferably contain as skeletal material crystalline layered silicates with the general formula NaMSixO2x + 1.yH2O wherein M is sodium or hydrogen, x is 1.9-22, preferably 1.9-4, with particularly preferred values ​​for x being 2, 3 or 4, and y being 0-33, preferably 0-20 .

Amorphous sodium silicates with Na2O: SiO2 modulus from 1: 2 to 1.33, preferably from 1: 2 to 1: 2.8, in particular from 1: 2 to 1: 2.6, which dissolve preferably with delayed and have secondary washing properties.

In the context of the present invention, preferred dishwashing agents contain 2-15% by weight, preferably 3-12% by weight and especially 4-8% by weight of silicate (s).

Particularly preferred is the use of carbonate (s) and / or bicarbonate (s), preferably alkali carbonate (s), particularly preferably sodium carbonate, in amounts of 5-50% by weight, preferably 10-40% by weight, especially 15-30% by weight , in relation to the weight of the machine dishwashing agent.

Polymeric polycarboxylates are further suitable as skeletal substances, e.g. alkali polycarboxylic acid or poly methacrylic acid salts, e.g. salts with a relative molecular weight of 500,000,000 g / mol.

Suitable polymers are especially polyacrylates, which preferably have a molecular weight of 2000-20000 g / mol. Due to their better solubility in this group, short chain polyacrylates which have a molecular weight of 2000-10000 may again be preferred

- 18 g / mol, particularly preferably 3000-5000 g / mol.

Also suitable are copolymeric polycarboxylates, especially acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid, which contain 50-90% by weight acrylic acid and 50-10% by weight maleic acid have proved to be particularly suitable. Their relative molecular weight is generally 2000-70000 g / mol, preferably 20,000-50000 g / mol relative to free acids, especially 30,000-40,000 g / mol.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of (co) polymeric polycarboxylates in machine dishwashing agents is preferably 0.520% by weight, especially 3-10% by weight.

Preferred dishwashing agents according to the invention further comprise one or more bleaching agents. Among the compounds serving as bleaching agents, which provide H2O2 in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further useful bleaching agents are e.g. peroxopyrophosphates, citrate perhydrates, and H2O2-providing peracid or peracid salts, such as perbenzoates, peroxophthalates, dinadazelaic acid, phthalimine acid or dinaddodecanoic acid. Bleaching agents from the group of organic bleaching agents may also be used. Typical organic bleaching agents are diacyl peroxides, such as dibenzoyl peroxide, for example. Further typical organic bleaching agents are peroxy acids, in particular alkyl peroxy acids and peroxy peroxy acids being given as examples.

According to the invention, machine dishwashing agents are preferred which are characterized by containing 1-20% by weight, preferably 2-15% by weight and especially 4-12% by weight of sodium percarbonate.

According to the invention, phosphate-free salts are preferred

19 dishwashing agents which as a skeletal substance contain 1-20% by weight, preferably 2-15% by weight, in particular 4-12% by weight of sodium percarbonate, and further

a) a copolymer containing

i) monomers from the group consisting of carboxylic acids of general formula R¹(R²) C = C (R³) COOH, in which R¹-R³ are independently -H, -CH₃, straight or branched chain, saturated alkyl radical with 2-12 carbon atoms, straight or branched chain, single or multiple unsaturated alkenyl radical with 212 carbon atoms, substituted with -NH2, -OH or -COOH alkyl or alkenyl radicals as previously defined, or are -COOH or -COOR⁴, with R⁴is a saturated or unsaturated, straight or branched chain hydrocarbon radical of 1-12 carbon atoms, ii) monomers of the general formula R¹(R²) C = C (R³) -X-R⁴in which R¹-R³ are each independently -H, -CH3 or -C2H5, X is an optionally existing spacer group which is selected from -CH2-, -C (O) O- and -C (O) -NH-, and R⁴ is a straight or branched chain saturated alkyl radical with 2-22 carbon atoms or an unsaturated, preferably aromatic radical with 6-22 carbon atoms,

b) a nonionic surfactant of general formula

R¹-CH (OH) CH2O- (AO) w- (A'O) x- (A''O) y- (A '' 'O) zR², wherein

- R¹ is a straight or branched chain, saturated or mono- or polyunsaturated C6-24 alkyl or -alkenyl radical,

- R² is a linear or branched radical

- 20 hydrocarbon with 2-26 carbon atoms,

- A, A ', A' 'and A' '' are each independently a radical from the group consisting of -CH2CH2, -CH2CH2-CH2, -CH2-CH (CH3), -CH2-CH2-CH2-CH2, -CH2- CH (CH3) -CH2-, -CH2-CH (CH2-CH3),

- w, x, y and z represent values ​​of 0.5-120, with x, y and / or z also representing 0.

Further preferred embodiments are phosphate-free machine dishwashing agents containing 1-20% by weight, preferably 2-15% by weight, in particular 4-12% by weight of sodium percarbonate as skeletal material, and further

a) a copolymer containing cy

i) monomers from the group consisting of carboxylic acids of general formula R¹(R²) C = C (R³) COOH, in which R¹-R³ are independently from each other -H, -CH3, straight or branched, saturated alkyl radical with 2-12 carbon atoms, straight or branched, single or multiple unsaturated alkenyl radical with 212 carbon atoms, substituted with -NH2, -OH or -COOH alkyl or alkenyl radicals as previously defined or are -COOH or -COOR⁴, with R⁴is a saturated or unsaturated, straight or branched chain hydrocarbon radical of 1-12 carbon atoms, ii) monomers of the general formula R¹(R²) C = C (R³) -X-R⁴in which R¹-R³ are each independently -H, -CH3 or -C2H5, X is an optionally existing spacer group which is selected from -CH2-, -C (O) O- and

-C (O) -NH-, and R⁴ is a straight or branched chain saturated alkyl radical with 2-22 carbon atoms or an unsaturated, preferably aromatic radical with 6-22 carbon atoms,

- 21 iii) monomers containing sulfonic acid groups,

b) a nonionic surfactant of general formula

R¹-CH (OH) CH2O- (AO) w- (A'O) x- (A''O) y- (A '' 'O) zR², wherein

- R¹ is a straight or branched chain, saturated or mono- or polyunsaturated C6-24 alkyl or -alkenyl radical,

- R² is a linear or branched hydrocarbon radical with 2-26 carbon atoms,

- A, A ', A' 'and A' '' are each independently a radical from the group consisting of -CH2CH2, -CH2CH2-CH2, -CH2-CH (CH3), -CH2-CH2-CH2-CH2, -CH2- CH (CH3) -CH2-, -CH2-CH (CH2-CH3),

- w, x, y and z represent values ​​of 0.5-120, with x, y and / or z also representing 0.

Chlorine or bromine releasing agents can also be used as bleaching agents. Among the suitable chlorine or bromine releasing materials, e.g. heterocyclic N-bromo- and N-chloramides, e.g. trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such like potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

In order to achieve a better bleaching effect when cleaning at 60 ° C and below, the machine dishwashing agents according to the invention may additionally contain bleach activators. As bleach activators, compounds which give aliphatic percarboxylic acids, preferably 1-10 C atoms, especially 2-4 C atoms, and / or optionally substituted perbenzoic acid may be used under perhydrolysis conditions. Substances that contain O- and / or N-acyl groups with the above-mentioned number of C atoms and / or optionally substituted benzoyl groups are suitable. Multi-acylated alkylene diamines are preferred, tetraacetyl ethylenediamine (TAED) being particularly suitable.

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

In addition to conventional bleach activators or instead of them so-called bleaching catalysts. These substances are bleaching enhancing transition metal salts or transition metal complexes such as e.g. Mn, Fe, Co, Ru or Mo salen or carbonyl complexes, while Mn, Fe, Co, Ru complexes can also be used as bleaching catalysts , Mo, Ti, V and Cu with N-containing tripod ligands and amine complexes of Co, Fe, Cu and Ru.

Manganese complexes with oxidation state II, III, IV or VI, which preferably contain one or more macrocyclic ligands with N, NR, PR, O and / or donor functional groups, are preferably used. Ligands that have nitrogenous, donor functional groups. It is particularly advantageous to use bleach catalysts in the compositions according to the invention which contain 1,4,7-trimethyl-1,4,7-triazacyclononate (Me-TACN), 1,4,7-triazacyclononate (TACN) as high-molecular ligands.

1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononan (Me / MeTACN) and / or 2-methyl- 1,4,7-triazacyclononan (Me / TACN). Suitable manganese complexes are, for example, [Μη^ΙΙΙ2 (μ-Ο) ₁(μOAc) 2 (TACN) 2] (ClO4) 2, [Mn^IIIMn^IV (μ-ΘΜμ-ΘΑοΜΤΑΟΝ ^] (BPh4) 2, [Mn^IV4 ^ -O) 6 ^ -OAch (TACN) 4] (ClO4) 4, [Mn ^ -Oh ^ -OAch (Me-TACN) 2] (ClO4) 2, [Mn^IIIMn^IV ^ -O) and ^ -OAch (MeTACN) 2] (ClO4) 3, [Mn^IV2 ^ -O) 3 (Me-TACNh (PF6) 2 and [Mn^IV2 ^ -O) 3 (Me / Me-TACN) 2] (PF6) 2 (OAc = OC (O) CH3).

According to the invention, machine dishwashing agents are preferred which are characterized in that they further comprise a bleach catalyst selected from the group of bleach enhancers of transition metal salts and transition metal complexes, preferably from the group of manganese complexes with 1,4,7-trimethyl -1,4,7-triazacyclononate (Me3TACN) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononate (Me4-TACN), because the bleaching catalysts previously discussed can, in particular, significantly improve the cleaning result.

The previously discussed bleach-enhancing transition metal complexes, especially with central Mn and Co atoms, are used in ordinary amounts, preferably in an amount of up to 5% by weight, in particular 0.0025-1% by weight, especially preferably 0.01 -0.30% by weight, in each case based on the total weight of agents containing bleach activators. In special cases, however, you can also use more bleach activator.

It has been surprisingly found that the bleaching effect of bleach catalysts from the group of bleach enhancers of transition metal salts and transition metal complexes can be increased by the addition of acid-containing hydrophobically modified copolymers.

A preferred subject of the present application is therefore a phosphate-free, machine-containing bleaching agent containing

a) a containing copolymer

i) monomers from the group consisting of mono- or polyunsaturated carboxylic acids, ii) monomers of general formula R¹(R²) C = C (R³) -X-R⁴in which R¹-R³ are each independently -H, -CH3 or -C2H5, X is an optionally existing spacer group which is selected from -CH2-, -C (O) O- and -C (O) -NH-, and R⁴ is a straight or branched chain saturated alkyl radical with 2-22 carbon atoms or

- 24 unsaturated, preferably aromatic radical with 6-22 carbon atoms, iii) optionally further monomers,

b) a nonionic surfactant of general formula

R¹-CH (OH) CH2O- (AO) w- (A'O) x- (A''O) y- (A '' 'O) zR², wherein

- R¹ is a straight or branched chain, saturated or mono- or polyunsaturated C6-24 alkyl or -alkenyl radical,

- R² is a linear or branched hydrocarbon radical with 2-26 carbon atoms,

- A, A ', A' 'and A' '' are each independently a radical from the group consisting of -CH2CH2, -CH2CH2-CH2, -CH2-CH (CH3), -CH2-CH2-CH2-CH2, -CH2- CH (CH3) -CH2-, -CH2-CH (CH2-CH3),

- w, x, y and z are values ​​0.5-120, with x, y and / or z also being 0,

c) citrate,

d) a bleach catalyst selected from the group of bleaching agents for transition metal salts and transition metal complexes.

Some examples of recipes of this kind of beneficial, phosphate-free machine dishwashing agents can be found in the following table:

<td>Ingredient</td><td>Recipe 1 (Wt-%).</td><td>Recipe 2 (Wt-%).</td><td>Recipe 3 (Wt-%).</td><td>Recipe 4 (Wt-%).</td>

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

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

<td>Catalyst bleaching</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>nonionic center surfactant active</td><td> 1-10</td><td> 2-8</td><td> 2-8</td><td> 3-6</td>

<td>Different</td><td>up to 100</td><td>up to 100</td><td>up to 100</td><td>up to 100</td>

- 25 ¹Copolymer containing

i) monomers from the group consisting of mono- or polyunsaturated carboxylic acids, ii) monomers of general formula R¹(R²) C = C (R³) -X-R⁴in which R¹-R³ are each independently -H, -CH3 or -C2H5, X is an optionally existing spacer group which is selected from -CH2-, -C (O) O- and -C (O) -NH-, and R⁴ is a straight or branched chain saturated alkyl radical with 2-22 carbon atoms or an unsaturated, preferably aromatic radical with 6-22 carbon atoms, iii) optionally further monomers, ²nonionic surfactant of general formula R¹-CH (OH) CH2O- (AO) w- (A'O) x- (A''O) y- (A '' 'O) zR², wherein

- R¹ is a straight or branched chain, saturated or mono- or polyunsaturated C6-24 alkyl or -alkenyl radical,

- R² is a linear or branched hydrocarbon radical with 2-26 carbon atoms,

- A, A ', A' 'and A' '' are each independently a radical from the group consisting of -CH2CH2, -CH2CH2-CH2, -CH2-CH (CH3), -CH2-CH2-CH2-CH2, -CH2- CH (CH3) -CH2-, -CH2-CH (CH2-CH3),

- w, x, y and z represent values ​​of 0.5-120, with x, y and / or z also representing 0.

Preferred dishwashing agents according to the invention further comprise a complexing agent, preferably 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and / or methylglycine diacetic acid (MGDA).

Complex-forming phosphonates include, in addition to 1-hydroxyethane-1,1-diphosphonic acid, a number of different compounds, such as e.g. diethylenetriamine penta (methylene phosphonic acid) (DTPMP). Hydroxyalkane or aminoalkane phosphonates are particularly preferred in this application.

Of the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as the active co-filler and is preferably used as the sodium salt, the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9) . Preferred as aminoalkanephosphonates are ethylenediaminetetramethylene phosphonate (EDTMP), diethylenetriaminepentamethylene phosphonate (DTPMP) and their higher homologues and are preferably used in the form of inert sodium salts, e.g. as EDTMP hexasodium salt or as hepta- and octasodium salt. Of the phosphonate class, HEDP is preferably used as the builder. Aminoalkane phosphonates also have a pronounced heavy metal binding capacity. Accordingly, especially when the compositions also contain bleaching agents, it may be advantageous to use amino-alkanophosphonates, especially DTPMP, or mixtures of the phosphonates discussed.

A preferred machine dishwashing agent within this application contains one or more phosphonates of the group

a) aminotrimethylene phosphonic acid (ATMP) and / or its salts,

b) ethylenediaminetetra (methylene phosphonic acid) (EDTMP) and / or its salts,

c) diethylenetriaminepenta (methylene phosphonic 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) hexamethylene diamine tetra (methylene phosphonic acid) (HDTMP) and / or its salts,

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

Especially preferred are dishwashing agents which contain 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta (methylene phosphonic acid) (DTPMP) as phosphonates.

The machine dishwashing agents according to the invention may of course contain two or more different phosphonates. Especially preferred are dishwashing agents which, as phosphonates, contain both 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylenetriaminepenta- (methylene phosphonic acid) (DTPMP), with the weight ratio of HEDP to DTPMP being from 20: 1 to 1:20, preferably from 15: 1 to 1:15, and especially from 10: 1 to 1:10.

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

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

According to the invention, phosphate-free machine dishwashing agents containing a skeletal substance, a bleaching agent and further

a) a copolymer containing

i) monomers from the group consisting of mono- or polyunsaturated carboxylic acids, ii) monomers of general formula R¹(R²) C = C (R³) -X-R⁴in which R¹-R³ are each independently -H, -CH3 or -C2H5, X is an optionally existing spacer group which is selected from -CH2-,

- 28 -C (O) O- and -C (O) -NH-, and R⁴ is a straight or branched chain saturated alkyl radical with 2-22 carbon atoms or an unsaturated, preferably aromatic radical with 6-22 carbon atoms,

b) a non-ionic surfactant of general formula R¹-CH (OH) CH2O- (AO) wR², wherein

- R¹ is a straight or branched chain, saturated or mono- or polyunsaturated C6-24 alkyl or -alkenyl radical,

- R² is a linear or branched hydrocarbon radical with 2-26 carbon atoms,

- A is a radical selected from the group consisting of CH2CH2, -CH2CH2-CH2, -CH2-CH (CH3), and

w means values ​​1-120, preferably 10-80, especially 20-40,

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

Some examples of recipes of this kind of beneficial, phosphate-free machine dishwashing agents can be found in the following table:

<td>Ingredient</td><td>Recipe 5 (Wt-%).</td><td>Recipe 6 (Wt-%).</td><td>Recipe 7 (Wt-%).</td><td>Recipe 8 (Wt-%).</td>

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

<td>percarbonate soda</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>nonionic center surfactant 2 active²</td><td> 1-10</td><td> 2-8</td><td> 2-8</td><td> 3-6</td>

<td>Different</td><td>up to 100</td><td>up to 100</td><td>up to 100</td><td>up to 100</td>

¹Copolymer containing

i) monomers from the group consisting of mono- or polyunsaturated carboxylic acids, ii) monomers of general formula R¹(R²) C = C (R³) -X-R⁴in

- 29 which R¹-R³ mean independently of each other

-H, -CH3 or -C2H5, X is an optionally existing spacer group which is selected from -CH2-, -C (O) O- and -C (O) -NH-, and R⁴is a straight or branched chain saturated alkyl radical with 2-22 carbon atoms or an unsaturated, preferably aromatic radical with 6-22 carbon atoms, iii) optionally further monomers, ²nonionic surfactant of general formula R¹-CH (OH) CH2O- (AO) w- (A'O) x- (A''O) y- (A '' 'O) zR², wherein

- R¹ is a straight or branched chain, saturated or mono- or polyunsaturated C6-24 alkyl or -alkenyl radical,

- R² is a linear or branched hydrocarbon radical with 2-26 carbon atoms,

- A, A ', A' 'and A' '' are each independently a radical from the group consisting of -CH2CH2, -CH2CH2-CH2, -CH2-CH (CH3), -CH2-CH2-CH2-CH2, -CH2- CH (CH3) -CH2-, -CH2-CH (CH2-CH3),

- w, x, y and z represent values ​​of 0.5-120, with x, y and / or z also representing 0.

In addition, phosphate-free machine dishwashing agents containing a skeletal substance, bleaching agent and further are preferred.

a) a copolymer containing cy

i) monomers from the group consisting of mono- or polyunsaturated carboxylic acids, ii) monomers of general formula R¹(R²) C = C (R³) -X-R⁴in which R¹-R³ are each independently -H, -CH3 or -C2H5, X is an optionally existing spacer group which is selected from -CH2-, -C (O) O- and C (O) -NH-, and R⁴ is a straight or branched chain saturated alkyl radical with 2-22 carbon atoms, iii) polymers containing acid groups

- 30 sulfone,

b) a non-ionic surfactant of general formula R¹-CH (OH) CH2O- (AO) wR², wherein

- R¹ is a straight or branched chain, saturated or mono- or polyunsaturated C6-24 alkyl or -alkenyl radical,

- R² is a linear or branched hydrocarbon radical with 2-26 carbon atoms,

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

- w means values ​​1-120, preferably 10-80, especially 20-40,

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

Especially preferred are machine dishwashing agents containing

a) a containing copolymer

i) monomers from the group consisting of mono- or polyunsaturated carboxylic acids, ii) monomers of general formula R¹(R²) C = C (R³) -X-R⁴in which R¹-R³ are each independently -H, -CH3 or -C2H5, X is an optionally existing spacer group which is selected from -CH2-, -C (O) O- and -C (O) -NH-, and R⁴ is a straight or branched chain saturated alkyl radical with 2-22 carbon atoms or an unsaturated, preferably aromatic radical with 6-22 carbon atoms,

b) a non-ionic surfactant of general formula R¹-CH (OH) CH2O- (AO) wR², wherein

- R¹ is a straight or branched chain, saturated or mono- or polyunsaturated C6-24 alkyl or -alkenyl radical,

- R² is a linear or branched hydrocarbon radical with 2-26 carbon atoms,

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

- 31 - w means values ​​1-120, preferably 10-80, especially 20-40,

c) 10-50% by weight of citrate,

d) 2-15% by weight sodium percarbonate,

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

In addition to the above-described components, such as skeletal substance, bleaching agent, nonionic surfactant, copolymer a) and complexing agents, preferred dishwashing agents contain further components, preferably active substances from the group of polymers, enzymes, corrosion inhibitors, fragrances or dyes.

The group of polymers active in washing or cleaning include, for example, rinsing polymers and / or polymers effective as emollients. In addition to nonionic polymers, cationic, anionic and amphoteric polymers can generally be used in washing or cleaning agents.

"Cationic polymers" in the sense of the present invention are polymers that have a positive charge in their molecule. This charge can be realized, e.g., by (alkyl) ammonium moieties or other positively charged groups present in the polymer chain. Particularly preferred cationic polymers are derived from quaternized groups of cellulose derivatives, polysiloxanes with quaternary groups, cationic guar derivatives, polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, vinyl pyrrolidone copolymolacrylacrylate copolymeric acid copolymers - metimimidazolinium chloride, quaternized polyvinyl alcohols or polymers listed under INCI Polyquaternium 2, Poly-quaternium 17, Polyquaternium 18 and Polyquaternium 27.

In the sense of the present invention, "amphoteric polymers" exhibit, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be, for example, carboxylic acids, sulfonic acids or phosphonic acids.

Preferred washing or cleaning agents, and especially preferred dishwashing agents, are characterized in that they contain a polymer a) which has monomeric units of formula R¹R²C = CR³R⁴in which each radical R¹, R^2, R³, R⁴ selected independently of each other from hydrogen, a derivatized hydroxyl group, linear or branched C1-30 alkyl groups, aryl, aryl substituted linear or branched C1-30 alkyl groups, polyalkoxylated alkyl groups, heteroatom organic groups with at least one positive charge without charged nitrogen , at least one quaternized N atom or at least one amino group with a positive charge in the partial range of pH 2-11, or their salts, provided that at least one radical R¹, R², R³, R⁴ is a heteroatom organic group with at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one amino group without positive charge.

Within the framework of the present application, particularly preferred cationic or amphoteric polymers contain as a monomer unit a compound of the general formula

R¹ R² R⁴

II II

H2C = C- (CH2) xN⁺- (CH2) yC = CH2 X^- ,

AND

R³ in which R¹ and R⁴ independently of each other H or a linear or branched hydrocarbon radical with 1-6 carbon atoms, R² and R³ are independently of each other an alkyl, hydroxyalkyl or aminoalkyl group in which the alkyl radical is linear or branched and has 1-6 carbon atoms, preferably

- 33 for a methyl group, x and y are, independently of each other, integers 1-3. X is a counterion, preferably a counterion from the group consisting of chloride, bromide, iodide, sulfate, bisulfate, metosulfate, lauryl sulfate, dodecylbenzene sulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylene sulfonate, phosphate, citrate, formate, acetate or mixtures thereof.

Preferred R radicals¹ and R⁴ in the above formula is selected from -CH3, -CH2-CH3, -CH2-CH2-CH3, -CH (CH3) -CH3, -CH2-OH, -CH2-CH2-OH, -CH (OH) -CH3, - CH2-CH2CH2-OH, -CH2-CH (OH) -CH3, -CH (OH) -CH2-CH3 and - (CH2CH2-O) nH.

Polymers that exhibit a cationic monomer unit of the above general formula wherein R is particularly preferred¹ and R⁴ are H, R² and R³are methyl, and x and y each represent 1. A suitable monomeric unit of formula

H2C = CH- (CH2) -N⁺- (CH3) 2- (CH2) -CH = CH2 X^- determined in the case where X^- = chloride, also as DADMAC (diallyldimethylammonium chloride).

Further particularly preferred cationic or amphoteric polymers comprise a polymer unit of the general formula

R¹HC = CR²-C (O) -NH- (CH₂)_x-N⁺R³R⁴R⁵ X^- in which R¹, R², R³, R⁴ and R⁵ are independently of each other a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical with 1-6 carbon atoms, preferably a linear or branched alkyl radical selected from -CH3, -CH2-CH3, -CH2-CH2-CH3, -CH (CH3) -CH3, -CH2-OH, -CH2-CH2-OH, -CH (OH) -CH3, -CH2-CH2CH2-OH, -CH2-CH (OH) -CH3, -CH (OH) -CH2-CH3 and - (CH2CH2-O) nH, ax is an integer 1-6.

Polymers which exhibit a cationic monomeric unit of the above general formula in which R¹ is H and R², R³, R⁴ and R⁵ are methyl, and x is 3. Suitable monomer units of formula H2C = C (CH3) 2-C (O) -NH- (CH2) xN⁺(CH3) 3 X^- determined in the case where X^- = chloride, also as

- 34 MAPTAC (methylacrylamidopropyltrimethylammonium chloride).

The invention preferably uses polymers that contain diallyldimethylammonium salts and / or acrylamidopropyltrimethylammonium salts as monomer units.

The previously mentioned amphoteric polymers show not only cationic groups, but also anionic groups or monomeric units. Such anionic monomer units are e.g. from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates or linear or branched, saturated or unsaturated sulfonates. Preferred monomeric units are acrylic acid, (meth) acrylic acid, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylacetic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, acids allylsulfone, such as e.g.

allyloxybenzenesulfonic acid and methallylsulfonic acid or allylphosphonic acids.

Preferred amphoteric polymers used are from the group of alkylacrylamide / acrylic acid copolymers, alkylacrylamide / methacrylic acid copolymers, alkylacrylamide / methyl methacrylate copolymers, alkylcrylamide / acrylic acid copolymers / alkylamino-alkyl methacrylate / methacrylate / ) alkylaminoalkyl acyan, alkyl-acrylamide / methyl meacrylate / alkylaminoalkyl (meth) acrylate copolymers, alkylacrylamide / alkyl methacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionogenic monomers.

Preferably the zwitterionic polymers used are from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their salts with alkali and ammonium salts, alkylamidoalkyltrialylammonium chloride copolymers and their salts with alkali and ammonium salts as well as methacroleethylethylmethrylate /

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

Particularly preferred amphoteric polymers are from the group of methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid / methylmethylchlorylmethylchlorylmethylchloro chloride, and methacrylate chloride and their alkali and ammonium salts.

Especially preferred are amphoteric polymers from the group of copolymers: methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid, copolymers of methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid / methyl methacrylate chloride and methyl methacrylate chloride alkyl and their alkali and ammonium salts.

In a particularly preferred embodiment of the present invention, the polymers are in pre-assembled form. Suitable for packaging polymers include

- encapsulation of polymers with water-soluble or water-dispersible coating agents, preferably with water-soluble or water-dispersible coatings, natural or synthetic polymers,

- encapsulation of polymers by means of water-insoluble, fusible coating agents, preferably by means of water-insoluble coating agents from the group of waxes or paraffins with a melting point above 30 ° C,

- co-granulating polymers with inert carrier materials, preferably with carrier materials from the group of active substances in washing or cleaning, particularly preferably from the group of active fillers (skeletal substances) or active co-fillers.

The washing or cleaning agents contain the previously discussed cationic and / or amphoteric polymers preferably in amounts of 0.01-10% by weight, in each case based on the total weight of the washing or cleaning agent. Within the scope of this application, however, washing or cleaning agents are preferred in which the weight proportion of cationic and / or amphoteric polymers is 0.01-8% by weight, preferably 0.01-6% by weight, in particular 0.01-4% by weight , particularly preferably 0.01-2% by weight, in particular 0.01-1% by weight, in each case based on the total weight of the machine dishwashing agent.

Enzymes can be used to increase the efficiency of washing or cleaning of washing or cleaning agents and include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases and preferably mixtures thereof. These enzymes are essentially of natural origin. Starting from natural particles for use in washing or cleaning agents, better variants are available that can be suitably used advantageously. Washing or cleaning agents contain enzymes preferably in total amounts from 1 χ 10^-6 up to 5% by weight based on active protein. Protein concentration can be determined using known methods, e.g., the BCA method or the biuret method.

Of the proteases, subtilisin-type proteases are preferred and examples thereof are BPN 'and Carlsberg subtilisins and their further developed forms, PB92 proteases, subtilisin 147 and 309, Bacillus alkaline protease

- 37 lentus, DY subtilisin and subtilisins, but no longer subtilisins in the narrower sense, enzymes thermitase, proteinase K and proteases TW3 and TW7.

Examples of amylases used according to the invention are α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and

A. oryzae and improved for use in washing and cleaning agents, further development of the previously discussed amylases. Therefore, for this purpose, α-amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin-glucanotransferase (CGTase) from B. agaradherens (DSM 9948) should be emphasized.

According to the invention, lipases or cutinases can be further used, in particular due to their triglyceride cleavage activities, and to generate superacids in situ from suitable precursors, and include, e.g., those obtained originally from Humicola lanuginosa (Thermomyces lanuginosus) or further developed lipases, in particular with D96L amino acid exchange. Further, e.g. cutinases that were originally isolated from Fusarium solani pisi and Humicola insolens can be used. Lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii can be used further.

Further, enzymes that are included in the term hemicellulase can be used and include, e.g., mannanases, xanthanolases, pectinolases (= pectinases), pectinesterases, pectanolases, xyloglucanases (= xylanases), pululanases and β-glucanases.

According to the invention, oxidoreductases, e.g. oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo-, lignino, glucose or manganese-peroxidase, dioxygenase or lactase (phenoloxidase, polyphenoloxidase) can be used to increase the bleaching effect. To increase the activity of the respective oxidoreductases (enhancers) or to provide a stream of electrons (mediators) with strongly different redox potentials between oxidizing enzymes and soils, preferably further preferred organic, especially preferably aromatic compounds interacting with enzymes are added.

The enzymes can be used in any form known in the art and include, e.g., solid preparations obtained, e.g., by granulation, extrusion or lyophilization, or, especially in the case of liquid or gel compositions, enzyme solutions, preferably as concentrated as possible, low in water and / or set with stabilizers.

Alternatively, the enzymes can be encapsulated in both the solid and liquid form offered, e.g. by spray drying or extrusion of the enzyme solution together with preferably a natural polymer, or in the form of capsules, e.g. capsules in which the enzymes are enclosed as in a solid gel or capsules core-sheath type, in which the core containing the enzyme is coated with a protective film impermeable to water, air and / or chemicals. In the applied layers, further active substances, e.g. stabilizers, emulsifiers, pigments, bleaching substances or dyes, may additionally be applied. Capsules of this type are applied by known methods, e.g. by shock granulation or turning granulation, or in fluidized bed processes. Such granules, e.g. by applying polymeric film-forming agents, are preferably low in dust and, thanks to the coating, stable in storage.

Furthermore, it is also possible to pack two or more enzymes together so that a single granulate has more enzymatic activities.

The protein and / or enzyme can be protected, especially during storage, against damage such as e.g. inactivation, denaturation or degradation, e.g. due to physical influences, oxidation or proteolytic cleavage. In the case of bacterial production of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially when the agents also contain proteases. Washing or cleaning agents may contain stabilizers for this purpose and the production of such agents is a preferred embodiment of the present invention.

One or more enzymes and / or enzyme preparations, preferably solid protease preparations and / or amylase preparations, are preferably used in amounts of 0.1-5% by weight, more preferably 0.2-5% by weight, in particular 0.4- 5% by weight, in each case based on the whole enzyme-containing agent.

Some examples of recipes of this kind of beneficial, phosphate-free machine washing agents can be found in the following tables:

<td>Ingredient</td><td>Recipe 9 (Wt-%).</td><td>Recipe 10 (Wt-%).</td><td>Recipe 11 (Wt-%).</td><td>Recipe 12 (Wt-%).</td>

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

<td>percarbonate soda</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>nonionic center surfactant active²</td><td> 1-10</td><td> 2-8</td><td> 2-8</td><td> 3-6</td>

<td>Different</td><td>up to 100</td><td>up to 100</td><td>up to 100</td><td>up to 100</td>

<td>Ingredient</td><td>Recipe 13 (Wt-%).</td><td>Recipe 14 (Wt-%).</td><td>Recipe 15 (Wt-%).</td><td>Recipe 16 (Wt-%).</td>

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

<td>Carbonate / bicarbonate</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>Catalyst bleaching</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>Nonionic agent surfactant active²</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>Different</td><td>up to 100</td><td>up to 100</td><td>up to 100</td><td>up to 100</td>

¹Containing copolymer

- i) monomers from the group consisting of mono- or polyunsaturated carboxylic acids, ii) monomers of general formula R¹(R²) C = C (R³) -X-R⁴in which R¹-R³ are each independently -H, -CH3 or -C2H5, X is an optionally existing spacer group which is selected from -CH2-, -C (O) O- and -C (O) -NH-, and R⁴is a straight or branched chain saturated alkyl radical with 2-22 carbon atoms or an unsaturated, preferably aromatic radical with 6-22 carbon atoms, iii) optionally further monomers, ²nonionic surfactant of general formula

R¹-CH (OH) CH2O- (AO) w- (A'O) x- (A''O) y- (A '' 'O) zR², wherein

- R¹ is a straight or branched chain, saturated or mono- or polyunsaturated C6-24 alkyl or -alkenyl radical,

- R² is a linear or branched hydrocarbon radical with 2-26 carbon atoms,

- A, A ', A' 'and A' '' are each independently a radical from the group consisting of -CH2CH2, -CH2CH2-CH2, -CH2-CH (CH3), -CH2-CH2-CH2-CH2, -CH2- CH (CH3) -CH2-, -CH2-CH (CH2-CH3),

- w, x, y and z represent values ​​of 0.5-120, with x, y and / or z also representing 0.

Phosphate-free machine dishwashing agents containing a skeletal substance, a bleaching agent and furthermore are therefore particularly preferred.

a) a copolymer containing

i) monomers from the group consisting of mono- or polyunsaturated carboxylic acids, ii) monomers of general formula R¹(R²) C = C (R³) -X-R⁴in which R¹-R³ are each independently -H, -CH3 or -C2H5, X is an optionally existing spacer group which is selected from -CH2-, -C (O) O- and -C (O) -NH-, and R⁴ means straight chain or

- a 41 branched, saturated alkyl radical with 222 carbon atoms or an unsaturated, preferably aromatic radical with 6-22 carbon atoms,

b) a nonionic surfactant of general formula

R¹-CH (OH) CH2O- (AO) w- (A'O) x- (A''O) y- (A '' 'O) zR², wherein

- R¹ is a straight or branched chain, saturated or mono- or polyunsaturated C6-24 alkyl or -alkenyl radical,

- R² is a linear or branched hydrocarbon radical with 2-26 carbon atoms,

- A, A ', A' 'and A' '' are each independently a radical from the group consisting of -CH₂CH₂,

-CH2CH2-CH2, -CH2-CH (CH3), -CH2-CH2-CH2-CH2,

-CH2-CH (CH3) -CH2-, -CH2-CH (CH2-CH3),

- w, x, y and z are values ​​0.5-120, with x, y and / or z also being 0,

c) 1.0-6% by weight of enzyme.

Especially preferred are machine dishwashing agents containing

a) a copolymer containing

i) monomers from the group consisting of mono- or polyunsaturated carboxylic acids, ii) monomers of general formula R¹(R²) C = C (R³) -X-R⁴in which R¹-R³ are independently -H, -CH₃ or -C₂H₅, X is an optionally existing spacer group which is selected from -CH2-, -C (O) O- and -C (O) -NH-, and R⁴is a straight or branched chain saturated alkyl radical with 2-22 carbon atoms,

b) a non-ionic surfactant of general formula R¹-CH (OH) CH2O- (AO) wR², wherein

- R¹ is a straight or branched chain, saturated or mono- or polyunsaturated C6-24 alkyl or -alkenyl radical,

- R² is a linear or branched radical

- 42 hydrocarbon with 2-26 carbon atoms,

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

- w means values ​​1-120, preferably 10-80, especially 20-40,

c) 10-50% by weight of citrate,

d) 2-15% by weight sodium percarbonate,

e) 2-8% by weight of a complexing agent from the group consisting of 1-hydroxyethane-1,1-diphosphonic acid and methylglycine diacetic acid,

f) 1.0-6% by weight of enzyme.

Glass corrosion inhibitors prevent the occurrence of cloudiness, streaks and scratches, as well as the irrigation of the surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group of magnesium and zinc salts as well as magnesium and zinc complexes.

The spectrum of preferred zinc salts according to the invention, preferably with organic acids, particularly preferably with organic carboxylic acids, ranges from salts that are sparingly soluble or insoluble in water, and thus have a solubility below 100 mg / L, preferably below 10 mg / L, and especially below 0.01 mg / l, for those salts which in water have a solubility above 100 mg / l, preferably above 500 mg / l, particularly preferably above 1 g / l, especially above 5 g / l (all solubilities at 20 ° C water temperature). The first group of zinc salts include, e.g., zinc citrate, zinc oleate and zinc stearate, and the group of soluble zinc salts include, e.g., zinc formate, zinc acetate, zinc lactate and zinc gluconate.

As a glass corrosion inhibitor, it is particularly preferred to use at least one zinc salt of the organic carboxylic acid, particularly preferably the zinc salt from the group consisting of zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and zinc citrate. Zinc ricinolate, zinc abietate and oxalate are also preferred

- 43 zinc.

In the context of the present invention, the zinc salt content of the washing or cleaning agents is preferably 0.1-5% by weight, more preferably 0.2-4% by weight, in particular 0.4-3% by weight, or the zinc content in the oxidized form (in converted to Zn²⁺) is 0.01-1% by weight, preferably 0.02-0.5% by weight, especially 0.04-0.5% by weight, based on the total weight of the agent containing the glass corrosion inhibitor.

Corrosion inhibitors are used to protect the items to be washed or the machine, with silver protection agents being particularly important in the field of machine dishwashing agents and substances known from the technique set can be used. In general, silver protection agents selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and salts or transition metal complexes can generally be used. Benzotriazole and / or alkylaminotriazole are particularly preferred for use. Preferably, according to the invention, 3-amino-5-alkyl-1,2,4-triazoles or their physiologically compatible salts are used, these substances being used particularly preferably in a concentration of 0.001-10% by weight, preferably 0.0025-2% by weight, and particularly preferably 0.01-0.04% by weight.

To facilitate the disintegration of previously prepared shaped products, it is possible to introduce disintegration enhancers, i.e. tablet disintegration agents to reduce disintegration times.

These substances, which due to their action are also known as "raising agents", increase their volume with water access, on the one hand the own volume (swelling) increases, and on the other hand, by releasing gases, pressure is generated, which allows the tablet to disintegrate into smaller particles. For example, carbonate / citric acid systems have long been known to disintegrate, and other organic acids can also be used. Swelling disintegrants 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.

Disintegrants are preferably used in amounts of 0.5-10 wt.%, Preferably 3-7 wt.%, Especially 4-6 wt.%, Each time based on the total weight of the disintegrant containing agent.

As preferred disintegrants, cellulose-based disintegrating agents are used, such that the preferred washing or cleaning agents contain such a cellulose-based disintegrating agent in amounts of 0.5-10% by weight, preferably 3-7% by weight, especially 4- 6% by weight. The cellulose used as a disintegrant is preferably used not in fine form, but before being mixed into the pressed master batches it is converted into a thicker form, e.g. granulating or pressing. The particle size of such disintegrants is at least above 200 pm, preferably at least 90% by weight of the particles are in the range 300-1600 pm, and especially at least 90% of the particles are in the range 400-1200 pm.

Preferred disintegrants, in particular a cellulose based disintegrant, preferably in granular, co-granulated or compacted form, are included in the compositions containing the disintegrant in amounts of 0.5-10% by weight, preferably 3-7% by weight, especially 4-6% by weight, in each case based on the total weight of the disintegrant containing agent.

According to the invention, it is furthermore possible to further use gas-evolving effervescent systems as tablet disintegrating agents. The effervescent gas system may consist of a single substance that releases gas when in contact with water. Among these

- 45 compounds should be mentioned in particular magnesium peroxide, which in contact with water releases oxygen. Preferred effervescent systems, however, consist of at least two components that react with each other to form a gas, e.g., alkali metal carbonate and / or bicarbonate, and an acidifying agent that is suitable for releasing alkali salts in an aqueous carbon dioxide solution. As acidifying agents which release carbon dioxide from aqueous alkali salts, e.g. boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts. Preferably, however, organic acidulants are used, with citric acid being a particularly preferred acidulant. In the effervescent system, acidifying agents from the group of organic di-, tri- and oligocarboxylic acids or mixtures thereof are preferred.

Individual perfume compounds, e.g. synthetic products of the type esters, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used as perfume oils or fragrances. Preferably, however, mixtures of different aromas are used which together give a pleasant aroma. Such perfume oils may also contain natural mixtures of fragrances, such as are available from plant sources, e.g. pine oil, citrus oil, jasmine oil, patchouli oil, rose oil and ilang oil.

Fragrances can be processed directly, however it is also advantageous to apply the fragrances to the carriers which, due to the slowed release of the fragrances, ensure a long-lasting aroma. Cyclodextrins, for example, have proven to be such carrier materials, with cyclodextrin-perfume complexes being able to be coated with further excipients.

Preferred dyes, the choice of which is not difficult for the specialist, have a high durability

- during storage and insensitivity to other components of the agents and to light, and show no clear affinity for substrates treated with dye-containing agents so as not to dye them.

The dishwashing agents according to the invention may be in the form of solid or liquid as well as a mixture of solid and liquid forms.

Powders, granules, extrusion products or pressing products, in particular tablets, are particularly suitable as the solid forms offered. The liquid forms offered based on water and / or organic solvents may be in concentrated form, e.g. in the form of gels.

The compositions according to the invention can be packaged as single-phase or multi-phase products. Particularly preferred are dishwashing machines with one, two, three or four phases. Especially preferred are dishwashing agents which are characterized in that they are in the form of a pre-prepared dispensing unit with one or more phases.

The individual phases of the multi-phase agents may exhibit the same or different physical states, with machine dishwashing agents having at least two different solid phases and / or at least two liquid phases and / or at least one solid phase being particularly preferred at least one liquid phase.

Preferably, the machine dishwashing agents according to the invention are pre-packaged into dispensing units which preferably contain the amount of active substance for washing or cleaning necessary for the cleaning process. Preferred dosing units have a weight of 12-30 g, preferably 14-26 g, especially 15-22 g.

The volume of the dispensing units previously discussed and their spatial shape are particularly preferably chosen in such a way that it is ensured

- 47 susceptibility to dispensing pre-assembled units through the dispensing chamber of the dishwasher. The volume of the dispensing unit is 10-35 ml, preferably

12-30 ml, especially 15-25 ml.

The dishwashing agents according to the invention, and especially the previously prepared dispensing units, particularly preferably have a water-soluble casing.

The present invention further relates to a method of cleaning dishes in a dishwashing machine using the dishwashing agents of the invention, wherein the dishwashing agents are preferably dispensed into the interior space of the dishwasher during the course of the dishwashing program, before starting the main wash cycle or during the main wash cycle. The dispensing or introduction of the agent according to the invention into the inner space of the dishwasher can be done manually, however, the agent is dosed into the inner space of the dishwasher preferably via the dispensing chamber of the dishwasher. During the cleaning process, preferably no additional water softener and no additional rinsing agent are metered into the interior space of the dishwasher.

As described at the outset, the compositions according to the invention have a better rinsing effect compared to conventional dishwashing agents. Therefore, a further object of the present application is the use of the machine dishwashing agent according to the invention as a rinse aid for machine dishwashing.

Examples

In the first cleaning test, the soiled dishes were washed in a dishwasher with 21 g of E2 phosphate-free machine dishwashing agent or 21 g of E1 phosphate-free machine dishwashing agent with a water hardness of 21 ° dH.

With the composition of the dishwashing agent used

- 48 you can refer to the following table:

<td>Raw</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>Soda</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>Nonionic agent</td><td> 5,0</td><td> -</td>

<td>surfactant</td><td></td><td></td>

<td>active²</td><td></td><td></td>

<td>Nonionic agent</td><td> -</td><td> 5,0</td>

<td>surfactant</td><td></td><td></td>

<td>active³</td><td></td><td></td>

<td>Different</td><td>up to 100</td><td>up to 100</td>

¹ hydrophobically modified copolymer ² polyalkoxylated fatty alcohol of the general formula

C 12-18 (EO) 1-6- (PO) 1-6- (EO) 1-6-OH ³ mixed hydroxyether with the general formula C6-24-CH (OH) CH2O- (EO) 20-120-C2-26.

The overall picture of the washed material was assessed using the rating scale shown below. The results are presented in the table below (the values ​​given are the mean values ​​of 3 trials).

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

<td>Score cleaning</td><td> 8, 0</td><td> 8,2</td>

<td>Rinse result</td><td>glass 1.0 stainless steel 2.2 visual artist 3.2</td><td>glass 8.0 stainless steel 9.0 plastic 6.3</td>

Cleaning evaluation scale: from 10 = no soil to 0 = heavy soil (average value of seven specific soils)

Wash rating scale: from 10 = no drop formation to 0 = strong drop formation.

Henkel AG &amp; Co. KGaA

Deputy:

- 49 OK II-12 / P31659EN B1