EP2115113A1 - Detergent - Google Patents

Abstract

The invention relates to a phosphate-free dishwasher detergent which contains a builder, bleaching agents, and also a) a copolymer comprising i) monomers from the group of mono- or polyunsaturated carboxylic acids; ii) monomers of general formula R1(R2)C=C(R3)-X-R4, wherein R1 to R3 independently represent -H, -CH3 or -C2H5, X represents an optional spacer group that is selected from -CH2-, -C(O)O- and -C(O)-NH-, and R4 represents a straight-chain or branched saturated alkyl group with 2 to 22 carbon atoms or an unsaturated, preferably aromatic group with 6 to 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)z-R2, wherein R1 represents a straight-chain or branched, saturated or mono- or polyunsaturated C6-24 alkyl or -alkenyl group; R2 represents a linear or branched hydrocarbon group with 2 to 26 carbon atoms; A, A', A'' and A''' independently represent a group selectected from -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 between 0.5 and 120, wherein x, y and/or z can be 0. The detergent according to the invention has good cleaning and rinsing results which are comparable to those of phosphate-containing dishwasher detergents or even outdo them.

Description

 cleaning supplies

The present patent application describes detergents, in particular detergents for the machine cleaning of dishes. The subject of this application are in particular phosphate-free automatic dishwashing detergents.

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

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

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

In addition to nitrilotriacetic acid, especially sodium aluminosilicates (zeolites) are used as phosphate substitutes or substitutes in textile detergents. However, these substances are not suitable for use in automatic dishwashing detergents for various reasons. As an alternative to the alkali metal phosphates in automatic dishwashing detergents, therefore, a number of substitutes are discussed in the literature, of which the citrates are particularly noteworthy. Phosphate-free automatic dishwashing detergents which, in addition to a citrate, furthermore contain carbonates, bleaches and enzymes are described, for example, in European patents EP 662 117 B1 (Henkel KGaA) and EP 692 020 B1 (Henkel KGaA).

Another alternative to the alkali metal phosphates used as the sole builder but preferably in combination with citrates is methylglycine diacetic acid (MGDA). Machine dishwashing detergents containing MGDA are described, for example, in European patent EP 906 407 B1 (Reckitt Benckiser) or in European patent application EP 1 113 070 A2 (Reckitt Benckiser).

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

In view of this initial situation, therefore, the object of the present application was to provide a phosphate-free automatic dishwashing detergent, which is comparable in terms of its cleaning performance and with respect to its rinse results and its performance in terms of scale inhibition with conventional phosphate cleaning agents or even better.

It has been found that automatic dishwashing detergents which, in addition to builder and bleach, furthermore also contain specific nonionic surfactants and specific hydrophobically modified copolymers, also have excellent coating inhibition and cleaning and rinsing performance even without the addition of alkali metal phosphates

A first subject of the present application is therefore a phosphate-free machine

Dishwashing detergent containing builder, bleach and furthermore a) copolymer comprising i) monomers from the group of mono- or polyunsaturated

Carboxylic acids ii) monomers of the general formula R ¹ (R ² ) C =C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another are -H, -CH ₃ or -C ₂ H ₅ , X is an optionally present spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or, alternatively, other monomers b) nonionic surfactant of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A"'O) _Z -R ² in which

R ¹ is a linear or branched, saturated or mono- or polyunsaturated C ₆ - ₂₄ represents alkyl or alkenyl;

R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26

Carbon atoms;

A, A ', A "and A'" independently represent a group from the group

-CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -

-CH ₂ -CH (CH ₂ -CH ₃ ), w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0.

A first essential ingredient of automatic dishwashing detergent according to the invention is the hydrophobically modified copolymer a) comprising the monomers i) and ii).

As monomers i) from the group of mono- or polyunsaturated carboxylic acids, particular preference is given to using unsaturated carboxylic acids of the general formula R ¹ (R ² ) C =C (R ³ ) COOH in which R ¹ to R ³ independently of one another H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH as defined above or is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Phosphate-free automatic dishwashing detergent containing builder, bleaching agent, and furthermore a) copolymer comprising i) monomers from the group of carboxylic acids of the general formula

R ¹ (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ³ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched chain, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -C00R ⁴ , where R ^{4 is} a saturated or unsaturated, straight chain or branched hydrocarbon radical having 1 to 12 carbon atoms ii) monomers of the general formula R ¹ (R ² ) C = C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another are -H, -CH ₃ or -C ₂ H ₅ , X is an optional one A spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated , preferably aromatic radical having 6 to 22 carbon atoms b) nonionic surfactant of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A"'0) _z -R ² , in the

R ¹ is a linear or branched, saturated or mono- or polyunsaturated C ₆ - ₂₄ represents alkyl or alkenyl;

R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ), w, x, y and z represent values between 0.5 and 120 where x, y and / or z can also be 0 are preferred according to the invention.

Particularly preferred carboxyl-containing monomers i) are acrylic acid, methacrylic acid, ethacrylic acid, chloroacrylic acid, cyanoacrylic acid, crotonic acid, phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof.

The nonionic monomers ii) used are monomers of the general formula R ¹ (R ² ) C =C (R ³ ) -XR ⁴ . Particularly preferred such monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyne, 1-octene, olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22-olefin, 2-styrene, - Methylstyrene, 3-methylstyrene, 4-propylstryol, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2, vinylnaphthalene, methyl acrylate, ethyl acrylate, acrylic acid propyl ester, butyl acrylate, acrylic acid pentyl ester, hexyl acrylate, Methyl methacrylate, N- (methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, Λ / - (2-ethylhexyl) acrylamide, acrylic octyl acid ester, octyl acrylate, Λ / - (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, Λ / - (lauryl) acrylamide, stearyl acrylate, aryl methacrylate, Λ / - (stearyl) acrylamide, behenyl acrylate, behenyl methacrylate and N- (behenyl) acrylamide or mixtures thereof. Dishwasher detergents according to the invention have proved to be particularly effective with regard to optimum coating inhibition, cleaning and rinse-aid results, in which the weight fraction of the copolymer a) is from 4 to 18% by weight, preferably from 6 to 15 and in particular from 6 to 12% by weight. is.

Phosphate-free automatic dishwashing detergent containing builder, bleaching agent, and furthermore a) 4 to 18 wt .-% of copolymer comprising i) monomers from the group of carboxylic acids of the general formula

R ¹ (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ³ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched chain, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight chain or branched hydrocarbon radical having 1 to 12 carbon atoms ii) monomers of the general formula R ¹ (R ² ) C = C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another are -H, -CH ₃ or -C ₂ H ₅ , X is an optional spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 K. b) nonionic surfactant of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A"'O) _z -R ² , in the

R ¹ is a linear or branched, saturated or mono- or polyunsaturated C ₆ - ₂₄ represents alkyl or alkenyl;

R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ), w, x, y and z represent values between 0.5 and 120 where x, y and / or z can also be 0 are preferred according to the invention.

In a particularly preferred embodiment, the copolymer d) in addition to the monomers i) and ii) further comprises a third monomer iii) from the group of sulfonic acid group-containing monomers. In the sulfonic acid-containing monomers are those of the formula

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H

in which R ⁵ to R ⁷ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH ₂ , -OH or - COOH substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group , which is selected from - (CHz) _n - with n = O to 4, -C00- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH ₃ ) -X-SO ₃ H

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

in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = O to 4, -C00- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1 propanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3 Sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethyl methacrylamide and mixtures of said acids or their water-soluble salts.

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

The molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use. preferred Machine dishwashing detergents are characterized in that the copolymers have molar masses of 22,000,000 to 22,000,000 to 10,000,000 ^"" , preferably from 4,000 to 25,000 gmol ^"1 and especially from 5,000 to 15,000 gmol ^{" 1} .

Phosphate-free automatic dishwashing detergent containing builder, bleaching agent, and furthermore a) copolymer comprising i) monomers from the group of carboxylic acids of the general formula

R ¹ (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ³ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched chain, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight chain or branched hydrocarbon radical having 1 to 12 carbon atoms ii) monomers of the general formula R ¹ (R ² ) C = C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another are -H, -CH ₃ or -C ₂ H ₅ , X is an optional spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 K. ohlenstoffatomen stands iii) sulfonic acid group-containing monomers b) nonionic surfactant of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A '" O ) _Z -R ² , in the

R ¹ is a linear or branched, saturated or mono- or polyunsaturated C ₆ - ₂₄ represents alkyl or alkenyl;

R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ), w, x, y and z represent values between 0.5 and 120 where x, y and / or z can also be 0 are preferred according to the invention.

As a second essential ingredient, the automatic dishwashing compositions according to the invention contain nonionic surfactants of the general R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A"'O) _z -R ² , in the

R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂₄ alkyl or alkenyl radical; R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

A, A ', A "and A'" independently represent a group from the group

- (- / H ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -,

-CH ₂ -CH (CH ₂ -CH ₃ ), w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0.

Preferred automatic dishwasher detergents according to the invention have a weight fraction of this nonionic surfactant b) of from 1 to 10% by weight, preferably from 2 to 8% by weight and in particular from 3 to 6% by weight.

Nonionic surfactants b) have the general formula R ¹ -CH (OH) CH ₂ O- (AO) _W - (A'O) _X -R ² proved to be particularly advantageous in terms of cleaning and rinsing performance, in the

R ¹ is a linear or branched, saturated or mono- or polyunsaturated C ₆ - ₂₄ represents alkyl or alkenyl;

R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A, and A 'independently represent a residue from the group

- CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) stand, and w, x, stand for values between 0.5 and 120

Automatic dishwashing agents are particularly preferred in that the nonionic surfactant b) has the general formula R ¹ -CH (OH) CH ₂ O- (AO) _W - (A'O) _X -R ² , in which

R ¹ is a linear or branched, saturated or mono- or polyunsaturated C ₆ - ₂₄ represents alkyl or alkenyl;

R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

A is a radical CH ₂ CH ₂ and A 'is a radical -CH ₂ CH ₂ -CH ₂ or -CH ₂ -CH (CH ₃ ), and w is values between 2 and 40, while x is between 0.5 and 2 stands.

Machine dishwashing detergents in which the nonionic

Surfactant b) has the general formula R ¹ -CH (OH) CH ₂ O- (AO) _W -R ² in which

R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂₄ alkyl or alkenyl radical;

R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

A is a radical from the group CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), and w stands for values between 1 and 120, preferably 10 to 80, in particular 20 to 40

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

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

As a further essential constituent, machine dishwashing detergents according to the invention preferably contain one or more builders. The builders include in particular silicates, carbonates and organic cobuilders.

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

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

Particularly preferred machine dishwasher detergents according to the invention contain citrate as one of their essential builders. Automatic dishwashing agents according to the invention, characterized in that they contain from 5 to 60% by weight, preferably from 10 to 50% by weight and in particular from 15 to 40% by weight, of citrate are preferred according to the invention. Citrate or citric acid have become have proven to be the most effective builders in combination with the specific hydrophobically modified copolymers and the specific nonionic surfactants in terms of cleaning performance, such as rinse performance and scale inhibition.

Phosphate-free automatic dishwashing compositions containing 5 to 60 wt .-%, preferably 10 to 50 wt .-% and in particular 15 to 40 wt .-% citrate, bleach, and further a) copolymer comprising i) monomers from the group of carboxylic acids of the general formula

R ¹ (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ³ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched chain, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight chain or branched hydrocarbon radical having 1 to 12 carbon atoms ii) monomers of the general formula R ¹ (R ² ) C = C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another are -H, -CH ₃ or -C ₂ H ₅ , X is an optional spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 K. b) nonionic surfactant of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A"'O) _z -R ² , in the

R ¹ is a linear or branched, saturated or mono- or polyunsaturated C ₆ - ₂₄ represents alkyl or alkenyl;

R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ), w, x, y and z represent values between 0.5 and 120 where x, y and / or z can also be 0 are preferred according to the invention.

Further preferred embodiments are:

Phosphate-free automatic dishwashing compositions containing 5 to 60 wt .-%, preferably 10 to 50 wt .-% and in particular 15 to 40 wt .-% citrate, bleach, and further comprising a) copolymer i) monomers from the group of carboxylic acids of the general formula

R ¹ (R ²⁾ C = C (R ³⁾ COOH in which R ¹ to R ³ are each independently -H, - CH _3, a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, branched chain or, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight chain or branched hydrocarbon radical having 1 to 12 carbon atoms ii) monomers of the general formula R ¹ (R ² ) C = C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another are -H, -CH ₃ or -C ₂ H ₅ , X is an optional spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 K. ohlenstoffatomen stands iii) sulfonic acid group-containing monomers b) nonionic surfactant of the general formula R ¹ -CH (0H) CH ₂ 0- (A0) _w - (A'0) _x - (A "0) _y - (A"'0 ) _z -R ² , in the

R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂₄ alkyl or alkenyl radical;

R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

A, A ', A "and A'" independently represent a radical from the group - (- / H ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ), w, x, y and z represent values between 0, 5 and 120, where x, y and / or z can also be O.

With preferred machine dishwashing detergents according to the invention contain as builder crystalline layered silicates of general formula NaMSi _x O _{2x + 1} ^■ y H ₂ O wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1, 9-4 where particularly preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.

Machine dishwashing detergents preferred in the context of the present invention comprise from 2 to 15% by weight, preferably from 3 to 12% by weight and in particular from 4 to 8% by weight, of silicate (s). Particularly preferred is the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of 5 to 50 wt .-%, preferably from 10 to 40 wt .-% and in particular from 15 to 30 wt .-%, each based on the weight of the automatic dishwashing detergent.

Other suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol.

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

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

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

Preferred automatic dishwashing agents according to the invention also contain one or more bleaching agents. Among the compounds serving as bleaches in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaches that can be used are, for example, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids which yield H ₂ O ₂ , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Furthermore, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.

Machine dishwashing detergents, characterized in that they contain from 1 to 20% by weight, preferably from 2 to 15% by weight and in particular from 4 to 12% by weight, of sodium percarbonate are preferred according to the invention. Phosphate-free automatic dishwashing detergent, builder, 1 to 20 wt .-%, preferably 2 to 15 wt .-% and in particular 4 to 12 wt .-% sodium percarbonate, and further a) copolymer comprising i) monomers from the group of carboxylic acids of the general formula

R ¹ (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ³ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched chain, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight chain or branched hydrocarbon radical having 1 to 12 carbon atoms ii) monomers of the general formula R ¹ (R ² ) C = C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another are -H, -CH ₃ or -C ₂ H ₅ , X is an optional spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 K. b) nonionic surfactant of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A"'O) _z -R ² , in the

R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂₄ alkyl or alkenyl radical;

R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ), w, x, y and z represent values between 0.5 and 120 where x, y and / or z can also be 0 are preferred according to the invention.

Further preferred embodiments are:

Phosphate-free automatic dishwashing detergent containing builder, 1 to 20 wt .-%, preferably 2 to 15 wt .-% and in particular 4 to 12 wt .-% sodium percarbonate, and further a) copolymer comprising i) monomers from the group of carboxylic acids of the general formula

R ¹ (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ³ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched chain, mono- or polyunsaturated Alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms is ii) monomers of the general formula R ¹ (R ² ) C =C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another are -H, -CH ₃ or -C ₂ H ₅ , X is an optionally present spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms iii) sulfonic acid group-containing monomers b) nonionic surfactant of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A"'O) _z -R ² , in the

R ¹ is a linear or branched, saturated or mono- or polyunsaturated C ₆ - ₂₄ represents alkyl or alkenyl;

R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

A, A ', A "and A'" independently represent a radical from the group - (- / H ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ), w, x, y and z represent values between 0, 5 and 120, where x, y and / or z can also be O.

As a bleaching agent and chlorine or bromine releasing substances can be used. Among the suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

In order to achieve an improved bleaching effect when cleaning at temperatures of 60 ^° C. and below, the automatic dishwasher detergents according to the invention may additionally contain bleach activators. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylene-diamines, with tetraacetylethylenediamine (TAED) having proven particularly suitable. These bleach activators, in particular TAED, are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, especially 2 to 8% by weight and more preferably 2 to 6% by weight. , in each case based on the total weight of the bleach activator-containing agents used.

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

It is particularly preferred to use complexes of manganese in the oxidation state II, III, IV or IV, which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S. Preferably, ligands are used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the inventive compositions, which as macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triaza- cyclononan (Me-TACN), 1, 4,7-Triazacyclononan (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). Examples of suitable manganese complexes are [Mn '" ₂ (μ-O) ₁ (μ-OAc) ₂ (TACN) ₂ ] (CIO ₄ ) 2, [Mn ¹ " Mn ^lv (μ-O) 2 (μ-OAc) ₁ (TACN) ₂ ] (BPh ₄ ) 2, [Mn ' ^V 4 (μ-O) ₆ (TACN) 4] (CIO ₄ ) 4, [Mn ^I " ₂ (μ-O) ₁ (μ-OAc) ₂ (Me-TACN) ₂ ] (CIO ₄ ) 2, [Mn " ¹ Mn ^lv (μ-O) ₁ (μ-OAc) ₂ (Me-TACN) ₂ ] (CIO ₄ ) 3, [Mn ' ^v ₂ ( μ- O) ₃ (Me-TACN) _2] (PFe) ₂ and [Mn ^'v ₂ (μ-O) ₃ (Me / Me-TACN) _2] (PF _{6) 2} (OAc = OC (O) CH ₃ ).

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

The abovementioned bleach-enhancing transition metal complexes, in particular with the central atoms Mn and Co, are used in customary amounts, preferably in an amount of up to 5% by weight, in particular of 0.0025% by weight to 1% by weight and more preferably of 0, 01 wt .-% to 0.30 wt .-%, each based on the total weight of the bleach activator-containing agents used. In special cases, however, more bleach activator can also be used.

Surprisingly, it has been found that the bleaching action of lead catalysts from the group of bleach-enhancing transition metal salts and transition metal complexes can be increased by the addition of hydrophobically modified acid-containing copolymers. A preferred subject of this application is therefore a phosphate-free, bleach-containing automatic dishwashing detergent containing a) copolymer comprising i) monomers from the group of mono- or polyunsaturated carboxylic acids ii) monomers of general formula R ¹ (R ² ) C = C (R ³ ) -XR ⁴ , in which R ¹ to R ^3, independently of one another, is -H, -CH ₃ or -C ₂ H ₅ , X is an optionally present spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms iii) optionally further Monomers b) nonionic surfactant of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A"'O) _z -R ² , in of the

- R ¹ represents a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ - ₂₄ represents alkyl or alkenyl;

R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

- A, A ', A "and A'" independently of one another from the group

- (- / H ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ - CH (CH ₂ -CH ₃ ),

- w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0; c) citrate d) bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes

Some exemplary formulations for such preferred phosphate-free automatic dishwashing detergents can be found in the following table:

Copolymer comprising i) monomers from the group of mono- or polyunsaturated carboxylic acids ii) monomers of the general formula R ¹ (R ² ) C = C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another are -H, -CH ₃ or -C ₂ H ₅ , X is a optionally present spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated , preferably aromatic radical having 6 to 22 carbon atoms iii) optionally other monomers

² nonionic surfactant of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A"'O) _z -R ² in which

- R ¹ represents a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ - ₂₄ represents alkyl or alkenyl;

R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

- A, A ', A "and A'" independently of one another from the group

-CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, - CH ₂ - CH (CH ₂ -CH ₃ ), - w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0

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

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

An automatic dishwashing agent preferred in the context of this application contains one or more phosphonate (s) from the group a) aminotrimethylenephosphonic acid (ATMP) and / or salts thereof; b) ethylenediaminetetra (methylenephosphonic acid) (EDTMP) and / or salts thereof; c) diethylenetriamine penta (methylenephosphonic acid) (DTPMP) and / or salts thereof; d) 1-hydroxyethane-1, 1-diphosphonic acid (HEDP) and / or salts thereof; e) 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) and / or salts thereof; f) hexamethylenediaminetetra (methylenephosphonic acid) (HDTMP) and / or salts thereof; g) nitrilotri (methylenephosphonic acid) (NTMP) and / or salts thereof.

Particular preference is given to automatic dishwashing detergents which contain, as phosphonates, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta (methylenephosphonic acid) (DTPMP).

Of course, the automatic dishwashing compositions of the invention may contain two or more different phosphonates. Particular preference is given to those automatic dishwashing compositions which contain as phosphonates both 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylene triamine penta (methylenephosphonic acid) (DTPMP), the weight ratio of HEDP to DTPMP being between 20: 1 and 1:20, preferably between 15: 1 and 1:15 and in particular between 10: 1 and 1:10.

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

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

Phosphate-free automatic dishwashing detergent containing builder, bleach and furthermore a) copolymer comprising i) monomers from the group of mono- or polyunsaturated

Carboxylic acids ii) monomers of the general formula R ¹ (R ² ) C =C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another are -H, -CH ₃ or -C ₂ H ₅ , X is an optionally present spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms b) nonionic surfactant of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _W -R ² , in which

R ¹ is a linear or branched, saturated or mono- or polyunsaturated C ₆ - ₂₄ represents alkyl or alkenyl;

R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A is a radical from the group CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), and w is from 1 to 120, preferably from 10 to 80, in particular from 20 to 40 is c) 2 to 8 wt .-% of a complexing agent from the group 1-hydroxyethane-1, 1-diphosphonic acid and methylglycinediacetic. are preferred according to the invention.

Some exemplary formulations for such preferred phosphate-free automatic dishwashing detergents can be found in the following table:

Copolymer comprising i) monomers from the group of mono- or polyunsaturated carboxylic acids ii) monomers of the general formula R ¹ (R ² ) C =C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another represent -H , -CH ₃ or -C ₂ H ₅ , X is an optional spacer group selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms iii) optionally other monomers

² nonionic surfactant of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A"'O) _z -R ² in which

R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂₄ alkyl or alkenyl radical; R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

- A, A ', A "and A'" independently of one another from the group

- (- / H ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -

CH (CH ₂ -CH ₃ ), - w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0

Also are preferably phosphate-free automatic dishwashing agent, containing builder, bleaching agents and furthermore a) copolymer comprising i) monomers from the group of mono- or polyunsaturated carboxylic acids ii) monomers of the general formula R ¹ (R ²⁾ C = C (R ³⁾ - XR ⁴ , in which R ¹ to R ^{3 are} independently -H, -CH ₃ or -C ₂ H ₅ , X is an optional spacer group which is selected from -CH ₂ -, -C (O) O - and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms iii) sulfonic acid group-containing polymers b) nonionic surfactant of the general formula R ¹ -CH (OH) CH ₂ O. - (AO) _W -R ² , in the

R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂₄ alkyl or alkenyl radical;

R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

A is a radical from the group CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), and

- w for values between 1 and 120, preferably 10 to 80, in particular 20 to 40 is c) 2 to 8 wt .-% of a complexing agent from the group 1-hydroxyethane-1, 1-diphosphon- acid and methylglycinediacetic acid.

Especially preferred are automatic dishwashing detergents containing a) copolymer comprising i) monomers from the group of mono- or polyunsaturated carboxylic acids ii) monomers of general formula R ¹ (R ² ) C = C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another are -H, -CH ₃ or -C ₂ H ₅ , X is an optionally present spacer group which is selected from -CH ₂ -, -C (O) O- and -C ( O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms. b) nonionic surfactant of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _W -R ² , in which

R ¹ is a linear or branched, saturated or mono- or polyunsaturated C ₆ - ₂₄ represents alkyl or alkenyl;

R ^{2 is} a linear or branched hydrocarbon radical having from 2 to 26 carbon atoms;

A is a radical from the group CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), and

c is 10 to 50% by weight of citrate d) 2 to 15% by weight of sodium percarbonate e) 2 to 8% by weight of a complexing agent from the group 1-hydroxyethane-1, 1-diphosphonic acid and methylglycinediacetic acid.

In addition to the ingredients described above, such as builder, the bleach, the nonionic surfactant, the copolymer a) and the complexing agents preferred automatic dishwashing contain other ingredients, preferably active ingredients from the group of polymers, enzymes, corrosion inhibitors, fragrances or dyes.

The group of washing- or cleaning-active polymers includes, for example, the rinse aid polymers and / or polymers which act as softeners. In general, cationic, anionic and amphoteric polymers can be used in detergents or cleaners in addition to nonionic polymers.

"Cationic polymers" in the context of the present invention are polymers which carry a positive charge in the polymer molecule, which can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

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

Preferred washing or cleaning agents, in particular preferred automatic dishwashing agents, are characterized in that they contain a polymer a) which has monomer units of the formula R ¹ R ² C =CR ³ R ⁴ in which each R ¹ , R ² , R ⁴ radical ³ , R ^{4 is} independently selected from hydrogen, derivatized hydroxy, Ci- ₃₀ linear or branched alkyl groups, aryl, aryl substituted Ci _-30 linear or branched alkyl groups, polyalkoyxylierte alkyl groups, heteroatomic organic groups having at least one positive charge without charged nitrogen, at least a quaternized N atom or at least one amino group having a positive charge in the partial range of the pH range of 2 to 11, or salts thereof, with the proviso that at least one R ¹ , R ² , R ³ , R ^{4 is} a heteroatomic organic Group having at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one aminog is a group with a positive charge.

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

in which R ¹ and R ⁴ are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R ² and R ^{3 are} independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group; x and y independently represent integers between 1 and 3. X represents a counterion, preferably a counterion selected from the group consisting of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, laurylsulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.

Preferred radicals R ¹ and R ⁴ in the above formula are selected from -CH _3, -CH ₂ -CH _3, -CH ₂ - CH ₂ -CH _3, -CH (CH ₃₎ -CH _3, -CH ₂ -OH , -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , and - (CH ₂ CH ₂ -O) _n H.

Very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ¹ and R ^{4 are} H, R ² and R ^{3 are} methyl and x and y are each 1. The corresponding monomer unit of the formula H ₂ C = C H- (CH ₂ ) -N ⁺ (CH ₃ ) ₂ - (CH ₂ ) -CH = CH ₂

X ^"

in the case of X = chloride, they are also referred to as DADMAC (diallyldimethylammonium chloride).

Further particularly preferred cationic or amphoteric polymers contain a monomer unit of the general formula

R1 HC = CR2-C (O) -NH- (CH ₂₎ -N ⁺ R3R4R5

X ^" in the R ¹ , R ² , R ³ , R ⁴ and R ^{5 are} independently of one another a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , and - (CH ₂ CH ₂ -O) _{n is} H and x is an integer between 1 and 6.

For the purposes of the present application, very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ^{1 is} H and R ² , R ³ , R ⁴ and R ^{5 are} methyl and x is 3. The corresponding monomer units of the formula

H ₂ C = C (CH ₃ ) -C (O) -NH- (CH ₂ ) _X -N (C Hs) ₃

X ^"

in the case of X = chloride also referred to as MAPTAC (Methyacrylamidopropyl trimethylammonium chloride).

According to the invention, preference is given to using polymers which contain diallyldimethylammonium salts and / or acrylamidopropyltrimethylammonium salts as monomer units.

The aforementioned amphoteric polymers have not only cationic groups but also anionic groups or monomer units. Such anionic monomer units are derived, for example, 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 monomer units are the acrylic acid, the (meth) - acrylic acid, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylessingic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, the allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the like allylphosphonic.

Preferred usable amphoteric polymers are selected from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / Methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / - methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic monomers.

Preferred zwitterionic polymers are from the group of acrylamidoalkyltrialkyl ammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamido alkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the Methacroylethylbetain / methacrylate copolymers.

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

Particularly preferred amphoteric polymers are selected from the group consisting of the methacrylamidoalkyltri-alkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the methacrylamidoalkyltrialkylammonium chloride / dimethy1-diallyl ammonium chloride / alkyl ^ meth) - acrylic acid copolymers and their alkali metal and ammonium salts.

Particular preference is given to amphoteric polymers from the group of the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers and the methacrylamidopropyltrimethylammonium chloride / dimethyidiallyl ammonium chloride / Alky ^ meth) - acrylic acid copolymers and their alkali metal and ammonium salts.

In a particularly preferred embodiment of the present invention, the polymers are present in prefabricated form. For the preparation of the polymers, inter alia, the encapsulation of the polymers by means of water-soluble or water-dispersible coating compositions, preferably by means of water-soluble or water-dispersible natural or synthetic polymers; the encapsulation of the polymers by means of water-insoluble, meltable coating compositions, preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 ⁰ C; the co-granulation of the polymers with inert carrier materials, preferably with carrier materials from the group of washing- or cleaning-active substances, more preferably from the group of builders or cobuilders.

Detergents or cleaning agents contain the aforementioned cationic and / or amphoteric polymers preferably in amounts of between 0.01 and 10 wt .-%, each based on the total weight of the detergent or cleaning agent. In the context of the present application, however, preference is given to those detergents or cleaners in which the weight fraction of the cationic and / or amphoteric polymers is between 0.01 and 8% by weight, preferably between 0.01 and 6% by weight, preferably between 0.01 and 4 wt .-%, particularly preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, each based on the total weight of the automatic dishwashing agent is.

To increase the washing or cleaning performance of detergents or cleaners enzymes can be used. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly. Washing or cleaning composition preferably contain enzymes in total amounts of 1 x 10 ^"-6 to 5 wt .-% based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the biuret method.

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

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from β. amyloliquefaciens, from β. stearothermophilus, from Aspergillus niger and A. oryzae, as well as improved for use in detergents and cleaners further developments of the aforementioned amylases. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from β. agaradherens (DSM 9948). Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.

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

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

The enzymes can be used in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.

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

A protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage. In microbial recovery of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.

Preferred are one or more enzymes and / or enzyme preparations, preferably solid protease preparations and / or amylase preparations, in amounts of from 0.1 to 5 wt .-%, preferably from 0.2 to 5 wt .-% and in particular of 0.4 to 5 wt .-%, each based on the total enzyme-containing agent used.

Some exemplary formulations for such preferred phosphate-free automatic dishwashing detergents can be found in the following tables:

Copolymer comprising i) monomers from the group of mono- or polyunsaturated carboxylic acids ii) monomers of the general formula R ¹ (R ² ) C =C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another represent -H , -CH ₃ or -C ₂ H ₅ , X is an optional spacer group selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms iii) optionally other monomers

² nonionic surfactant of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A"'O) _z -R ² in which

R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂₄ alkyl or alkenyl radical;

R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

- A, A ', A "and A'" independently of one another from the group

- (- / H ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ - CH (CH ₂ -CH ₃ ), - w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0

Therefore, very particular preference is given to phosphate-free automatic dishwashing detergents containing builder, bleaching agents and furthermore a) copolymer comprising i) monomers from the group of mono- or polyunsaturated carboxylic acids ii) monomers of the general formula R ¹ (R ² ) C = C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another are -H, -CH ₃ or -C ₂ H ₅ , X is a optionally present spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated , preferably aromatic radical having 6 to 22 carbon atoms b) nonionic surfactant of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A"'0) _z -R ² , in the

R ¹ is a linear or branched, saturated or mono- or polyunsaturated C ₆ - ₂₄ represents alkyl or alkenyl;

R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ), w, x, y and z represent values between 0.5 and 120 where x, y and / or z can also be 0. c) 1, 0 to 6 wt .-% enzyme

Especially preferred are automatic dishwashing agents containing a) copolymer comprising i) monomers from the group of mono- or polyunsaturated carboxylic acids ii) monomers of the general formula R ¹ (R ² ) C = C (R ³ ) -XR ⁴ , in R ¹ to R ^{3 are} independently -H, -CH ₃ or -C ₂ H ₅ , X is an optional spacer group selected from -CH ₂ -, -C (O) O- and -C (O) -NH- and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms b) nonionic surfactant of the general formula R ^{1 is} -CH (OH) CH ₂ O- (AO) _W -R ² , in the

R ¹ is a linear or branched, saturated or mono- or polyunsaturated C ₆ - ₂₄ represents alkyl or alkenyl;

R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

A is a radical from the group CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), and w is from 1 to 120, preferably from 10 to 80, in particular from 20 to 40 is c) 10 to 50 wt .-% citrate d) 2 to 15 wt .-% sodium percarbonate e) 2 to 8 wt .-% of a complexing agent from the group 1-hydroxyethane-1, 1-diphosphon- acid and methylglycinediacetic acid; f) 1, 0 to 6 wt .-% enzyme.

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

The spectrum of the invention preferred zinc salts, preferably organic acids, particularly preferably organic carboxylic acids, ranging from salts which are difficult or insoluble in water, ie a solubility below 100 mg / l, preferably below 10 mg / l, in particular below 0.01 have mg / l, to those salts which have a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and in particular above 5 g / l (all solubilities at 2O ⁰ C. water temperature). The first group of zinc salts includes, for example, the zinc nitrate, the zinc oleate and the zinc stearate, and the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.

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

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

Corrosion inhibitors serve to protect the items to be washed or the machine, with particular silver protectants being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. According to the invention, preference is given to using 3-amino-5-alkyl-1,2,4-triazoles or their physiologically tolerated salts, these substances being particularly preferably used in a concentration of 0.001 to 10 wt .-%, preferably 0.0025 to 2 wt .-%, particularly preferably 0.01 to 0.04 wt .-% are used.

In order to facilitate the disintegration of preformed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, into these compositions in order to shorten the disintegration times.

These substances, which are also referred to as "explosives" due to their effect, increase their volume upon ingress of water, on the one hand increasing the intrinsic volume (swelling), and on the other hand creating a pressure via the release of gases which can break the tablet into smaller particles disintegrates. Known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.

Preference is given to using disintegration aids in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration aid-containing agent.

Preferred disintegrating agents are cellulosic disintegrating agents, so that preferred washing or cleaning agents comprise such cellulose-based disintegrants in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight. % contain. The cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted. The particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns.

Preferred disintegration aids, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, are present in the disintegrating agent-containing agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular of 4 to 6 wt .-%, each based on the total weight of the disintegrating agent-containing agent.

Furthermore, according to the invention, gas-evolving effervescent systems can furthermore be used as tablet disintegration auxiliaries. The gas-evolving effervescent system may consist of a single substance that releases a gas upon contact with water. Among these compounds, mention should be made in particular of magnesium peroxide, which liberates oxygen on contact with water. However, preferred effervescent systems consist of at least two components, which reacting with one another to form gas, for example from alkali metal carbonate and / or hydrogen carbonate and an acidifying agent which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution. As Acidifizierungsmittel which release carbon dioxide from the alkali metal salts in aqueous solution, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used. However, preference is given to using organic acidifying agents, the citric acid being a particularly preferred acidifying agent. Acidifying agents in the effervescent system from the group of organic di-, tri- and oligocarboxylic acids or mixtures are preferred.

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

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

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

The automatic dishwashing compositions according to the invention can be formulated in solid or liquid form but can also be present, for example, as a combination of solid and liquid forms.

Powder, granules, extrudates or compactates, in particular tablets, are particularly suitable as firm supply forms. The liquid supply forms based on water and / or organic solvents may be thickened, in the form of gels.

Inventive agents can be formulated as single-phase or multi-phase products. In particular, automatic dishwashing detergents with one, two, three or four phases are preferred. Machine dishwashing detergents, characterized in that they are in the form of a prefabricated dosing unit with two or more phases, are particularly preferred. The individual phases of multiphase agents may have the same or different states of matter. Machine dishwashing detergents which have at least two different solid phases and / or at least two liquid phases and / or at least one solid and at least one liquid phase are preferred.

Automatic dishwasher detergents according to the invention are preferably prefabricated to form metering units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g.

The volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher. The volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml and in particular between 15 and 25 ml.

The automatic dishwasher detergents according to the invention, in particular the prefabricated metering units, have a water-soluble coating, with particular preference.

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

As described at the outset, compositions according to the invention are distinguished from conventional automatic dishwashing agents by an improved rinsing action. The use of a dishwasher detergent according to the invention as a rinse aid in automatic dishwashing is therefore a further subject matter of the present application. Examples

In a first attempt at cleaning, soiled dishes were rinsed in a dishwashing machine with 21 g of a phosphate-free automatic dishwashing detergent V1 or 21 g of the phosphate-free machine dishwashing liquid E1 at a water hardness of 21 ° dH.

The composition of the dishwashing agents used can be found in the following table:

hydrophobically modified copolymer

Polyalkoxylated fatty alcohol of the general formula Ci ₂ -i ₈ - (EO) i. ₆ - (PO) i. ₆ - (EO) i. ₆ - (PO) i. ₆ -OH

Hydroxy mixed ethers of the formula C6-24-CH (OH) CH ₂ 0- (EO) 2o-i2o-C2-26

The overall appearance of the items to be washed was assessed on the basis of the rating scale listed below. The results are given in the table below (The values given are average values from 3 experiments):

Rating Scale Cleaning: 10 = no contamination to 0 = heavy contamination (mean over seven specific soils)

Rating scale rinsing: 10 = no dripping up to 0 = heavy dripping;

Claims

claims

1. A phosphate-free automatic dishwashing detergent containing builder, bleaching agent and furthermore a) copolymer comprising i) monomers from the group of mono- or polyunsaturated carboxylic acids ii) monomers of general formula R ¹ (R ² ) C =C (R ³ ) XR ⁴ , in which R ¹ to R ^{3 are} independently -H, -CH ₃ or -C ₂ H ₅ , X is an optional spacer group which is selected from -CH ₂ -, -C (O) O - and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms iii) optionally other monomers b) nonionic surfactant general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A"'0) _z -R ² in which

R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂₄ alkyl or alkenyl radical;

R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

A, A ', A "and A'" independently represent a radical from the group - (- / H ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ), w, x, y and z represent values between 0, 5 and 120, where x, y and / or z can also be 0.

2. Machine dishwashing detergent according to claim 1, characterized in that the weight fraction of the copolymer a) 4 to 18 wt .-%, preferably 6 to 15 and in particular 6 to 12 wt .-% is.

3. Phosphate-free automatic dishwashing detergent according to one of the preceding claims, characterized in that the copolymer contains a) as monomers iii) sulfonic acid group-containing monomers.

4. Machine dishwashing detergent according to one of the preceding claims, characterized in that the weight fraction of the nonionic surfactant b) 1 to 10 wt .-%, preferably 2 to 8 wt .-% and in particular 3 to 6 wt .-% is.

5. Machine dishwashing detergent according to one of the preceding claims, characterized in that the nonionic surfactant b) has the general formula R ¹ -CH (OH) CH ₂ O- (AO) _W -R ² , in which

R ¹ is a linear or branched, saturated or mono- or polyunsaturated C ₆ - ₂₄ represents alkyl or alkenyl;

R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

A is a radical from the group CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), and w is from 1 to 120, preferably from 10 to 80, in particular from 20 to 40 stands

6. Machine dishwashing detergent according to one of the preceding claims, characterized in that it contains 5 to 60 wt .-%, preferably 10 to 50 wt .-% and in particular 15 to 40 wt .-% citrate.

7. Machine dishwashing detergent according to one of the preceding claims, characterized in that it contains 1 to 20 wt .-%, preferably 2 to 15 wt .-% and in particular 4 to 12 wt .-% sodium percarbonate.

8. Machine dishwashing detergent according to one of the preceding claims, characterized in that it further contains a complexing agent, preferably 1-hydroxyethane-1, 1-diphosphonic acid and / or methylglycinediacetic acid.

9. Machine dishwashing detergent according to one of the preceding claims, comprising a) copolymer comprising i) monomers from the group of mono- or polyunsaturated carboxylic acids ii) monomers of the general formula R ¹ (R ² ) C = C (R ³ ) -XR ⁴ in which R ¹ to R ³ independently of one another are -H, -CH ₃ or -C ₂ H ₅ , X is an optional spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms b) nonionic surfactant of the general formula R ¹ -CH ( OH) CH ₂ O- (AO) _W -R ² , in which

R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂₄ alkyl or alkenyl radical;

R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A is a radical from the group CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), and w is from 1 to 120, preferably from 10 to 80, in particular from 20 to 40 is c) 10 to 50% by weight of citrate d) 2 to 15% by weight of sodium percarbonate e) 2 to 8% by weight of a complexing agent selected from the group consisting of 1-hydroxyethane-1,1-diphosphonic acid and methylglycinediacetic acid;

10. Machine dishwashing detergent according to one of the preceding claims, comprising a) copolymer comprising i) monomers from the group of mono- or polyunsaturated carboxylic acids ii) monomers of the general formula R ¹ (R ² ) C = C (R ³ ) -XR ⁴ in which R ¹ to R ³ independently of one another are -H, -CH ₃ or -C ₂ H ₅ , X is an optional spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms b) nonionic surfactant of the general formula R ¹ -CH ( OH) CH ₂ O- (AO) _W -R ² , in which

R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂₄ alkyl or alkenyl radical;

R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

A is a radical from the group CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), and w is from 1 to 120, preferably from 10 to 80, in particular from 20 to 40 is c) 10 to 50% by weight of citrate d) 2 to 15% by weight of sodium percarbonate e) 2 to 8% by weight of a complexing agent selected from the group consisting of 1-hydroxyethane-1,1-diphosphonic acid and methylglycinediacetic acid; f) 1, 0 to 6 wt .-% enzyme.

11. A method for cleaning dishes in a dishwasher, using automatic dishwashing detergent according to one of claims 1 to 10.

12. The method according to claim 11, characterized in that in the course of the cleaning process, no additional water softener and no additional rinse aid is dosed into the interior of the dishwasher.