EP1664256A1

EP1664256A1 - Dishwasher detergents comprising specific polymers

Info

Publication number: EP1664256A1
Application number: EP04764838A
Authority: EP
Inventors: Rolf Bayersdörfer; Arnd Kessler; Silke Menke
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2003-09-15
Filing date: 2004-09-04
Publication date: 2006-06-07
Anticipated expiration: 2024-09-04
Also published as: DE502004010325D1; EP1664256B1; US7514395B2; DE10342632A1; US20070054833A1; ES2334504T3; ATE447603T1; PL1664256T3; WO2005026304A1

Abstract

The present invention relates to detergents and rinse agents for machine dishwashing and to supply forms which combine detergent and rinse agent containing certain polymers in a single product comprising at least one polymer modified with phosphorus-containing groups, characterized in that the pH value of a 1% by weight solution of the anionic polymer in distilled water at 20° C. is less than pH 6.

Description

"Machine dishwashing detergents with special polymers"

The present invention relates to automatic dishwashing detergents and rinse aids. More particularly, the invention relates to automatic dishwashing detergents and rinse aids, as well as to dosage forms which provide detergents and rinse aids in a product containing certain polymers. These agents are hereinafter summarized under the generic term "detergent for machine dishwashing" or "automatic dishwashing detergent".

Machine-washed dishes are often subject to more stringent requirements today than manually-washed dishes. So even a completely cleaned of leftovers dishes is then rated as not flawless if it has after dishwasher washing whitish, based on water hardness or other mineral salts stains that come from lack of wetting agent from dried water droplets.

In order to obtain glossy and spotless dishes, it is therefore successfully used today rinse aid. The addition of rinse aid at the end of the wash program ensures that the water runs as completely as possible from the items to be washed, so that the different surfaces at the end of the wash program are residue-free and flawless gloss.

The automatic cleaning of dishes in household dishwashers usually includes a pre-wash, a main wash, and a rinse cycle interrupted by intermediate rinses. In most machines, the pre-rinse for heavily soiled dishes is switchable, but is selected only in exceptional cases by the consumer, so that in most machines a main rinse, an intermediate rinse with pure water and a rinse cycle are performed. The temperature of the main wash cycle varies between 40 and 65 ° C, depending on the machine type and program level selection. In the rinse cycle, rinse aids are added from a dosing tank in the machine, which usually contain nonionic surfactants as the main constituent. Such rinse aids are in liquid form and are widely described in the art. Your task consists primarily in limescale. and to prevent deposits on the cleaned dishes. In addition to water and low-foaming nonionic surfactants, these rinse aids often also contain hydrotopes, pH regulators such as citric acid or scale-inhibiting polymers.

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

The storage tank in the dishwasher must be filled with rinse aid at regular intervals, with a filling sufficient for 10 to 50 rinses, depending on the machine type. If the filling of the tank is forgotten, then glasses in particular by lime stains and coverings become unsightly. In the prior art, therefore, there are some solutions proposed to integrate a rinse aid in the detergent for machine dishwashing. These proposed solutions are tied to the offer form of the compact molded article.

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

The object of the present invention was to provide new rinse aid, which provide at least the same results in terms of performance properties as marketable rinse aid and also provide further performance benefits. The new rinse aid should be used both as conventional rinse aid and in the form of combination products and develop their advantageous properties regardless of the formulation. Last but not least, the use of the new rinse aids should also be possible in conventional automatic dishwashing detergents, i. the funds should also provide performance benefits as an additional component.

It has now been found that the use of polymers modified with P-containing groups brings about advantageous effects in automatic dishwashing detergents. It is particularly advantageous if the polymers are used in the rinse cycle.

The present invention therefore relates, in a first embodiment, to a machine dishwashing detergent comprising at least one polymer which is modified with phosphorus-containing groups, wherein the polymer in 1% strength by weight solution in distilled water at 20 ° C. has a pH of 20%. Value below 6. According to the invention, the compositions comprise at least one polymer which has P-containing groups and has a pH of less than 6 in 1% strength by weight solution in distilled water at 20 ° C. These polymers can come from different groups. Preference is given to polymers which have, in addition to unsaturated carboxylic acids, P-group-containing monomers as monomer building blocks. Preference is given to polymers which additionally contain further ionic or nonionic monomers.

Preferred automatic dishwasher detergents according to the invention comprise a polymer of i) unsaturated carboxylic acids ii) monomers containing phosphate groups iii) optionally further ionic or nonionic monomers.

In the context of the present invention, unsaturated carboxylic acids of the formula I are preferred as the monomer,

R ¹ (R ² ) C = C (R ³ ) COOH (I),

in the R ¹ to R ³ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or - COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids which can be described by the formula I are in particular acrylic acid (R ¹ = R ² = R ³ = H), methacrylic acid (R ¹ = R ² = H, R ³ = CH ₃ ) and / or maleic acid (R ¹ = COOH; R ² = R ³ = H) is preferred.

The phosphate group-containing monomers can be described by the formula II,

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-PO ₄ H (II),

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

Preferred among these monomers are those of the formulas Ha, Mb and / or IIc,

H ₂ C = CH-X-PO ₄ H (Ha). H ₂ C = C (CH ₃ ) -X-PO ₄ H (Mb), H0 ₄ PX- (R ⁶ ) C = C (R ⁷ ) -X-PO ₄ H (IIc) 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 selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and -C (0) -NH - CH (CH ₂ CH ₃ ) -.

Further preferred monomers are compiled with their radicals R ⁵ , R ⁶ and R ⁷ and the spacer groups X in the following table:

As component iii), the polymers may contain further ionic or nonionic monomers. Examples of suitable compounds are vinylpyrrolidones, vinyl esters, vinyl acetate, alkylacrylamide, alkylaminoalkyl (meth) acrylic acid, cationically derivatized unsaturated carboxylic acids, acrylamidoalkyltrialkylammonium chloride, methacroylethylbetaine, crotonic acid, N-tert-butylacrylamide. In the polymers, the phosphate groups can ^'be present wholly or partially in neutralized form, ie the acidic hydrogen atom of the phosphate group in some or all of phosphate groups against metal ions, preferably alkali metal ions and in particular with sodium ions can be exchanged. It is of course to pay attention to the observance of the pH value criterion.

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

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

The molecular weight of the polymers can be varied to match the properties of the polymers to the desired use. Preferred copolymers have molar masses of 2000 to 200,000 gmol ^"1 , preferably from 4000 to 25,000 gmol ^{" 1} and in particular from 5000 to 15,000 gmol ^"1 .

A further preferred automatic dishwashing agent according to the invention is characterized in that it comprises a polymer of i) unsaturated carboxylic acids ii) monomers containing phosphonate groups iii) optionally further ionic or nonionogenic monomers.

Because of the description of the monomers i), reference may be made to the above statements. The phosphonate group-containing monomers can be described by the general formula III,

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-P O ₃ H (III),

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

Preferred among these monomers are those of the formulas IIIa, IIIb and / or Never,

H ₂ C = CH-X-PO ₃ H (purple), H ₂ C = C (CH ₃ ) -X-PO ₃ H (IIIb), H0 ₄ PX- (R ⁶ ) C = C (R ⁷ ) - X-P0 ₃ H (IIIc),

in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -.

Further preferred monomers are combined with their radicals R ⁵ , R ⁶ and R ⁷ and the spacer groups X in the table listed above.

In the polymers, the phosphonate groups may be wholly or partially in neutralized form, i. the acidic hydrogen atom of the phosphonate group in some or all of the phosphonate groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. It is of course to pay attention to the observance of the pH value criterion.

The molecular weight of the polymers can be varied to match the properties of the polymers to the desired use. Preferred copolymers have molecular weights of 2000 to 200,000 gmol ^"1 , preferably from 4000 to 25,000 gmol ^{" 1} and in particular from 5000 to 15,000 gmol ^"1 on.

Another preferred machine dishwashing detergent according to the invention is characterized in that it comprises a polymer of i) unsaturated carboxylic acids ii) phosphite-containing monomers iii) optionally further ionic or non-ionogenic monomers.

Because of the description of the monomers i), reference may be made to the above statements. The phosphite group-containing monomers can be described by the general formula IV,

R ⁵ (R ⁶ ) C = C (R ⁷ ) -XP (0) (OM ¹ ) ₂ (IV)

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

Preferred among these monomers are those of the formulas IVa, IVb and / or IVc,

H ₂ C = CH-X-P (O) (OM ¹ ) ₂ (IVa), H ₂ C = C (CH ₃ ) -X-P (O) (OM ¹ ) ₂ (IVb), H0 ₄ PX- (R ⁶ ) C = C (R ⁷ ) -X- P (O) (OM ¹ ) ₂ (IVc),

in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -, wherein M is hydrogen or a monovalent metal ion, preferably sodium. Further preferred monomers are combined with their radicals R ⁵ , R ⁶ and R ⁷ and the spacer groups X in the table listed above.

In the polymers, the phosphite groups may be wholly or partially in neutralized form, i. in that the acidic hydrogen atom of the phosphite group in some or all of the phosphite groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. It is of course to pay attention to the observance of the pH value criterion.

A further preferred automatic dishwashing agent according to the invention is characterized in that it comprises a polymer of i) unsaturated carboxylic acids ii) monomers containing phosphine oxide groups iii) optionally further ionic or nonionogenic monomers.

Because of the description of the monomers i), reference may be made to the above statements. The phosphine oxide group-containing monomers can be described by the general formula V,

R ⁵ (R ⁶ ) C = C (R ⁷ ) -XP (0) R ⁸ R ⁹ (V), in the R ⁵ to R ⁹ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or --COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas Va, Vb and / or Vc,

H ₂ C = CH-X-P (0) R ⁸ R ⁹ (Va), H ₂ C = C (CH ₃ ) -X- P (0) R ⁸ R ⁹ (Vb), H0 ₄ PX- (R ⁶ ) C = C (R ⁷ ) -X- P (O) R ⁸ R ⁹ (Vc), 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 optionally present spacer group which is selected from - (CH ₂ ) _n - where n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Further preferred monomers are combined with their radicals R ⁵ , R ⁶ and R ⁷ and the spacer groups X in the table listed above. The tables below show preferred monomers of the formula V, wherein with regard to the radicals R ⁵ , R ⁶ and R ⁷ and the spacer groups X reference is made to the table above.

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Z.88600 / 00Zda / X3d t0ε9Z0 / £ 00Z OΛV

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Z.88600 / 00Zda / X3d t0ε9Z0 / £ 00Z OΛV

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Z.88600 / 00Zda / X3d t0ε9Z0 / S00Z OΛV

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Z.88600 / 00Zda / X3d Mε9Z0 / S00Z OΛV

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Particularly preferred machine dishwasher detergents according to the invention are characterized in that the polymer modified with phosphorus-containing groups has at least partially terminal phosphorus-containing groups.

The agents of the invention may contain varying amounts of said polymers. Preferred automatic dishwashing agents according to the invention are characterized in that they contain the polymer (s) modified with phosphorus-containing groups, preferably in amounts of from 0.1 to 20% by weight, particularly preferably from 0.2 to 10% by weight. -% and in particular from 0.5 to 7.5 wt .-%, each based on the total agent included.

Irrespective of the comments made on the individual polymers, automatic dishwasher detergents according to the invention are preferred in which the polymer (s) modified with phosphorus-containing groups have average molecular weights of from 1000 to 10 000 000 gmol ^-1 , preferably from 1500 to 1000 .000 gmol ^"1 , particularly preferably from 2000 to 100,000 gmol ^{" 1} and in particular from 2500 to 50,000 gmol ^"1 .

Corresponding details can also be made of the degrees of polymerization. Here automatic dishwashing agents according to the invention are preferred in which the polymer (s) modified with phosphorus-containing groups has a degree of polymerization of from 10 to 10000, preferably from 20 to 5000, particularly preferably from 40 to 2000 and in particular from 80 to 1000.

In preferred polymers to be used - regardless of whether they are phosphates, phosphonates, phosphites or phosphine oxides - the molar ratio of the monomers i) to ii) is 1: 1 to 200: 1, preferably 1: 1 to 100: 1 and in particular 1: 1 to 10: 1.

Particularly preferred machine dishwasher detergents according to the invention are characterized in that the phosphorus-containing group-modified polymer (s) has a phosphorus content of from 0.5 to 5.0% by weight, preferably from 0.7 to 4.0 Wt .-% and in particular from 0.9 to 3.0 wt .-%, each based on the total weight of the / the phosphorus-containing polymer (s) s, have.

Also, irrespective of whether they are phosphates, phosphonates, phosphites or phosphine oxides, machine dishwashing agents according to the invention are preferred in which the content of the polymers in monomers iii) is at most 20 mol%, preferably at most 10 mol% and in particular maximum 5 mol.%.

In addition to the P-group-containing polymers, the automatic dishwashing compositions according to the invention may contain further polymers. Here, automatic dishwasher detergents are preferred which additionally contain one or more cationic and / or amphoteric polymer (s), preferably in amounts of from 0.1 to 20% by weight, particularly preferably from 0.2 to 10% by weight .-% and in particular from 0.5 to 7.5 wt .-%, each based on the total agent included.

These polymers are described below.

Preferred amphoteric polymers are from the group of

1) Alkylacrylam id / acrylic acid copolymers

2) Alkylacrylamide / methacrylic acid copolymers

3) Alkylacrylam id / methylmethacrylic acid copolymers

4) Alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers

5) Alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers

6) Alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers

7) Alkylacrylamide / Alkymethacrylate / Alkylaminoethylmethacrylate Alkylmethacrylate Copolymers

8) Copolymers of 8i) unsaturated carboxylic acids 8ii) cationically derivatized unsaturated carboxylic acids 8iii) optionally further ionic or nonionogenic monomers

Preferred zwitterionic polymers are selected from the group of

1) Acrylamidoalkyltrialkylammoniumchlorid / acrylic acid copolymers and their alkali metal and ammonium salts

2) Acrylamidoalkyltrialkylammoniumchlorid / methacrylic acid copolymers and their alkali metal and ammonium salts

3) Methacroylethylbetaine / methacrylate copolymers

Preferred water-soluble cationic polymers are preferably selected from the group of

1) quaternized cellulose derivatives

2) polysiloxanes with quaternary groups

3) cationic guar derivatives

4) polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid

5) Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate

6) Vinylpyrrolidone-methoimidazolinium chloride copolymers

7) quaternized polyvinyl alcohol

8) under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 indicated polymers.

A particularly preferred ingredient for automatic dishwashing agents is a polymer containing sulfonic acid groups. Preferred compositions according to the invention are therefore characterized in that they comprise at least one copolymer of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers

Preferred automatic dishwasher detergents according to the invention are therefore characterized in that they additionally comprise one or more polymer (s) of i) unsaturated carboxylic acids ii) monomers containing sulfonic acid groups iii) optionally further ionic or nonionogenic monomers preferably in amounts of 0.1 to 20 wt .-%, particularly preferably from 0.2 to 10% by weight and in particular from 0.5 to 7.5 wt .-%, each based on the total agent.

In the context of the present invention, unsaturated carboxylic acids of the formula I as monomer are also preferred for the polymers containing sulfonic acid groups,

R ¹ (R ² ) C = C (R ³ ) COOH (I),

Among the unsaturated carboxylic acids which can be described by the formula I are in particular acrylic acid (R = R ² = R ³ = H), methacrylic acid (R ¹ = R ² = H, R ³ = CH ₃ ) and / or maleic acid ( R ¹ = COOH; R ² = R ³ = H) is preferred.

In the sulfonic acid-containing monomers, those of the formula VI are preferred,

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (VI),

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

Preferred among these monomers are those of the formulas Via, Vlb and / or Vlc,

H ₂ C = CH-X-SO ₃ H (Via), H ₂ C = C (CH ₃ ) -X-SO ₃ H (VIb), H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) - X-S0 ₃ H (Vlc), in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -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-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts of said acids.

Suitable further ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds. The content of the monomers used according to the invention to monomers of group iii) is preferably less than 20% by weight, based on the polymer. Particularly preferred polymers to be used consist only of monomers of groups i) and ii).

In summary, copolymers are made of

i) unsaturated carboxylic acids of the formula I.

R ¹ (R ² ) C = C (R ³ ) COOH (I),

in the R ¹ to R ³ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or - COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,

ii) sulfonic acid group-containing monomers of the formula VI

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (VI), in the R ⁵ to R ⁷ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or - COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -

iii) optionally further ionic or nonionic monomers

particularly preferred.

Particularly preferred copolymers consist of i) one or more unsaturated carboxylic acids from the group of acrylic acid, methacrylic acid and / or maleic acid ii) one or more monomers containing sulfonic acid groups of the formulas Via, Vlb and / or Vlc:

H ₂ C = CH-X-SO ₃ H (Via), H ₂ C = C (CH ₃ ) -X-SO ₃ H (VIb), H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) - X-S0 ₃ H (Vlc),

in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and - C (0) -NH-CH (CH ₂ CH ₃ ) - iii) optionally further ionic or nonionic monomers.

The copolymers may contain the monomers from groups i) and ii) and, if appropriate, iii) in varying amounts, it being possible for all representatives from group i) to be combined with all representatives from group ii) and all representatives from group iii). Particularly preferred polymers have certain structural units, which are described below. Thus, for example, preferred are compositions according to the invention which are characterized in that they contain one or more copolymers which contain structural units of the formula VII

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (VII)

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative. If the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained whose use in the compositions according to the invention is likewise preferred and which is characterized in that the compositions contain one or more copolymers which contain structural units of the formula VIII

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (VIII)

Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Thus, compositions according to the invention which comprise one or more copolymers which are structural units of the formula IX

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (IX),

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -0- (CH ₂ ) _n - where n = 0 to 4, for -O- (C ₆ H ₄ ) -, -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are preferred, also a preferred embodiment of the present invention, as well as compositions are preferred , which are characterized in that they contain one or more copolymers, the structural units of the formula X.

[CH ₂ -C (CH 3) COOH] m - [CH ₂ -C (CH 3) C (O) -Y-SO ₃ H] p- (IX),

Instead of acrylic acid and / or methacrylic acid or in addition thereto, maleic acid can also be used as a particularly preferred monomer from group i). In this way, one obtains according to the invention preferred compositions, which are characterized in that they contain one or more copolymers, the structural units of the formula X.

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (X),

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, are preferred and to compositions which are characterized in that they contain one or more copolymers, the structural units of the formula XI

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) O-Y-SO ₃ H] _p - (XI),

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred. In summary, compositions according to the invention which contain one or more copolymers which contain structural units of the formulas VI and / or VII and / or VIII and / or IX and / or X and / or XI are preferred

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] p- (VI), - [CH ₂ -C (CH ₂ ) COOH] _rn - [CH ₂ -CHC (0 ) -Y-S0 ₃ H] _p - (VII), - [CH ₂ -CHC00H] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] p- (VIII), [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SOsH] _p - (IX), - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (X), - [HOOCCH-CHCOOH] _rn - [CH ₂ -C (CH ₃ ) C (O) O-Y-SO ₃ H] _p - (XI) .

in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

In the polymers, the sulfonic acid groups may be wholly or partially in neutralized form, i. in that the acidic hydrogen atom 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. Corresponding compositions which are characterized in that the sulfonic acid groups are partially or fully neutralized in the copolymer are preferred according to the invention.

The monomer distribution of the copolymers used in the compositions according to the invention in the case of copolymers containing only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight i) or ii), particularly preferably from 50 to 90% by weight. % Of monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer.

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

Preferred automatic dishwashing agents according to the invention additionally contain one or more surfactants, preferably nonionic surfactant (s), preferably in amounts of from 0.1 to 20% by weight, more preferably from 0.2 to 15% by weight and in particular of 0.5 to 12% by weight, in each case based on the total agent.

These are derived from the groups of anionic, nonionic, cationic and / or amphoteric surfactants, nonionic surfactants being clearly preferred in the context of automatic dishwashing and the surfactants from the other groups being used only in minor amounts or preferably not at all.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. Suitable surfactants of the sulfonate type are preferably C _9-13 alkyl benzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example from Cι _2- i8 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained. Also suitable are alkanesulfonates which are obtained from C _2-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfo fatty acids (ester sulfonates), for example, the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or Taigfettsäuren are suitable.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₀ -C ₂₀ -oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length which are synthetic, petrochemical Basis produced straight-chain alkyl radical containing an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest are the C ₂ -C ₁₆ alkyl sulfates and C ₁₂ -C- | ₅ alkyl sulfates and Cι -Cι ₅ - alkyl sulfates are preferred. Also 2,3-alkyl sulfates, which can be obtained as commercial products of Shell Oil Company under the name DAN ^® , are suitable anionic surfactants.

Also, the sulfuric monoesters of ethoxylated with 1 to 6 moles of ethylene oxide straight-chain or branched C _7-2 -ι-alcohols, such as 2-methyl-branched C ₉ .ι alcohols having an average of 3.5 moles of ethylene oxide (EO) or C _12-8 Fatty alcohols containing 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8- i ₈ fatty alcohol radicals or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

As further anionic surfactants are particularly soaps into consideration. Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants, including the soaps, may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

Another group of cleaning-active substances are the nonionic surfactants. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical is linear or preferred may be methyl branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C-ι _2- ι ₄ - alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C ₁₃ -ι ₅ -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ ι ₈ alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-1 linear alcohol with 3 EO and C _12-i ₈ alcohol containing 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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

Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG). Usable Alkypolyglycoside meet the general formula RO (G) _z , in which R is a linear or branched, especially in the 2-position methyl branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Symbol that represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of glycosidation z is between 1, 0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1, 1 and 1.4. Preference is given to using linear alkyl polyglucosides, that is to say alkyl polyglycosides which consist of a glucose residue and an n-alkyl chain.

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

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylaminoxid and N-tallow alkyl-N, N-dihydroxyethylaminoxid, and the fatty acid alkanolamides may be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

Further suitable surfactants are polyhydroxy fatty acid amides of the formula (XII)

R ¹

R-CO-N- [Z] (XII)

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

The group of polyhydroxy fatty acid amides also includes compounds of the formula (XIII)

R ¹ -O-R ² I

R-CO-NZ] (XIII)

in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein Cι _-4 -alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives this rest.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst. In detergents and cleaners for automatic dishwashing come as surfactants in general all surfactants in question. However, the nonionic surfactants described above and, above all, the low-foaming nonionic surfactants are preferred for this purpose. Particularly preferred are the alkoxylated alcohols, especially the ethoxylated and / or propoxylated alcohols. The person skilled in the art generally means, under alkoxylated alcohols, the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the context of the present invention, the longer-chain alcohols (C ₁₀ to C ₁₈ , preferably between C ₁₂ and C ₁₆ , such as, for example, C 1) -, C ₁₂ -. C ₁₃ -, -C -, C ₁₅ -, C ₁₆ - .C ^ - and C ₁₈ - alcohols). As a rule, n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions, form a complex mixture of addition products of different degrees of ethoxylation. A further embodiment consists in the use of mixtures of alkylene oxides, preferably of the mixture of ethylene oxide and propylene oxide. Also, if desired, by a final etherification with short-chain alkyl groups, such as preferably the butyl group, the substance class of "closed" alcohol ethoxylates reach, which can also be used in the context of the invention. Very particularly preferred for the purposes of the present invention are highly ethoxylated fatty alcohols or mixtures thereof with end-capped fatty alcohol ethoxylates.

In the context of the present invention, particularly preferred nonionic surfactants have been low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Machine dishwashing detergents according to the invention which contain surfactants of the general formula XIV as nonionic surfactant (s) are preferred here

R ¹ -O- (CH ₂ -CH ₂ -O) _w - (CH ₂ -CH-O) _x - (CH ₂ -CH ₂ -O) _y - (CH ₂ -CH-O) _z -H (XIV IIR ² R ³

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

The preferred nonionic surfactants of formula III can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in the formula I above may vary depending on the origin of the alcohol. Become native sources used, the radical R ^{1 has} an even number of carbon atoms and is usually not shown, wherein the linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, are preferred are. Alcohols accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position in the mixture, as they are usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions according to the invention, automatic dishwasher detergents according to the invention are preferred in which R ¹ in formula I is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.

As the alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide. But also other alkylene oxides in which R ² or R ^{3 are} independently selected from - CH ₂ CH ₂ -CH ₃ or -CH (CH ₃ ) ₂ are suitable. Preferred automatic dishwashing agents are characterized in that R ² and R ³ are each a residue -CH ₃ , w and x independently of one another for values of 3 or 4 and y and z independently of one another represent values of 1 or 2.

In summary, nonionic surfactants are particularly preferred for use in the inventive compositions, the C ₉ . ₁₅ alkyl having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed byi to 4 ethylene oxide units, followed byi to 4 propylene oxide units.

Low-foaming nonionic surfactants are used as preferred additional surfactants. With particular preference, the automatic dishwasher detergents according to the invention contain a nonionic surfactant which has a melting point above room temperature. Accordingly, preferred agents are characterized by containing nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C, and most preferably between 26.6 and 43, 3 ° C, included.

Suitable nonionic surfactants in addition to the nonionic surfactants according to the invention which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If high-viscosity nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have waxy consistency at room temperature are also preferred. Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

In a preferred embodiment of the present invention, the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.

A particularly preferred nonionic surfactant which is solid at room temperature is selected from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _6-2 o-alcohol), preferably a C ₁₈ -alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol of ethylene oxide won. Of these, the so-called "narrow rank ethoxylates" (see above) are particularly preferred.

Accordingly, particularly preferred compositions according to the invention contain ethoxylated nonionic surfactant (s) comprising C _6-20 monohydroxyalkanols or C _6-2 o-alkylphenols or C _6-20 fatty alcohols and more than 12 mol, preferably more than 15 Mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was won (n).

The nonionic surfactant preferably additionally has propylene oxide units in the molecule. Preferably, such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants. Preferred automatic dishwashing detergents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule contain up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic surfactant. Further particularly preferably used nonionic surfactants with melting points. above room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of Polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

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

A further preferred machine dishwashing detergent according to the invention contains nonionic surfactants of the formula

R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ],

in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y is a value of at least 15.

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R 0 [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value x> 2, each R ³ in the above formula may be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula may be different if x ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. Stands For example, for 3, the radical R ^{3 may be} selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO) (PO ) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) (PO ) (PO). The value 3 for x has been selected here by way of example and may well be greater, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula is to

R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²

simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

Summarizing the latter statements, dishwashing agents according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, x is n-butyl, 2-butyl or 2-methyl-2-butyl, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, surfactants of the type

R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²

in which x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

It is also possible to use anionic, cationic and / or amphoteric surfactants in conjunction with the surfactants mentioned, these having only secondary importance owing to their foaming behavior in automatic dishwashing detergents and in most cases only in Amounts below 10 wt .-%, usually even below 5 wt .-%, for example, from 0.01 to 2.5 wt .-%, each based on the agent used. The agents according to the invention can thus also contain anionic, cationic and / or amphoteric surfactants as surfactant component.

Preferred automatic dishwashing agents according to the invention contain, in addition to the ingredients mentioned above, one or more substances from the group of builders, co-builders, bleaches, bleach activators, enzymes, dyes, fragrances, corrosion inhibitors, polymers, or another common constituent of detergents and cleaners , These ingredients are described below.

Builder

According to the present invention, all builders commonly used in detergents and cleaners, in particular silicates, carbonates, organic cobuilders and also the phosphates, may be incorporated in the detergents and cleaners.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} H ₂ O, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ "yH ₂ O are preferred.

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

As carbonates, both the monoalkali metal salts and the dialkali metal salts of carbonic acid as well as sesquicarbonates can be contained in the compositions. Preferred alkali metal ions are sodium and / or potassium ions. In one embodiment, it may be preferable to mix the carbonate and / or bicarbonate, at least partially, as a further component, separately or subsequently. Compounds of, for example, carbonate, silicate and optionally other auxiliaries such as, for example, anionic surfactants or other, in particular organic builders, may be present as a separate component in the finished compositions.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Among the large number of commercially available phosphates, the alkali metal phosphates, with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.

Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids in which metaphosphoric acids (HP0 ₃ ) _n and orthophosphoric H ₃ P0 ₄ can distinguish in addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent limescale deposits on machine parts or limescale deposits on the items to be washed and also contribute to the cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ P0 ₄ , exists as dihydrate (density 1, 91 like ^"3 , melting point 60 °) and as monohydrate (density 2.04 like ^{" 3} ). Both salts are white powders which are very slightly soluble in water and which lose the water of crystallization on heating and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ 0 ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ 0 ₉ ) and Maddrell's salt (see below). NaH ₂ P0 is acidic; It is formed when phosphoric acid is adjusted to pH 4.5 with narcotic eye and the mash is sprayed. Potassium dihydrogen phosphate (potassium phosphate primary or monobasic phosphate, potassium biphosphate, KDP), KH ₂ P0, is a white salt of density 2.33 ^"3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KP0 ₃ ) χ] and is readily soluble in water. Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 like ^"3 , water loss at 95 °), 7 moles (density 1.68 like ^{" 3} , melting point 48 ° with loss of 5 H ₂ 0) and 12 moles water ( Density 1.52 ^"3 , melting point 35 ° with loss of 5 H ₂ 0), becomes anhydrous at 100 ° and on more intense heating in the diphosphate Na ₄ P ₂ 0 _7. Disodium hydrogen phosphate is by neutralization of phosphoric acid with sodium carbonate solution under Use of phenolphthalein as an indicator Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HP0 ₄ , is an amorphous, white salt that is readily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ P0 ₄ , are colorless crystals which have a density of 1, 62 ^"3 and a melting point of 73-76 ° C (decomposition) as dodecahydrate, as decahydrate (corresponding to 19-20% P ₂ 0 ₅ ) a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ θ _s ) aufeisen a density of 2.536 like ^"3 . Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ P0 ₄ , is a white, deliquescent, granular powder with a density of 2.56 ^"3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction Heating of Thomas slag with coal and potassium sulfate Despite the higher price, in the detergent industry, the more soluble, hence highly effective, potassium phosphates are often preferred over corresponding sodium compounds.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O, exists in anhydrous form (density 2.534 like ^"3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 like ^{" 3} , melting point 94 ° with loss of water). For substances are colorless, in water with alkaline reaction soluble crystals. Na P ₂ 0 ₇ is formed when heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and the solution is dehydrated by spraying. The decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), KP ₂ 0 ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 ^"3 ", which is soluble in water, the pH of the 1% solution at 25 ° is 10.4.

Condensation of the NaH ₂ P0 or the KH ₂ P0 gives higher mol. Sodium and potassium phosphates, where one can distinguish cyclic representatives, the sodium or Kaliummetaphoshate and chain types, the sodium or potassium polyphosphates. Especially for the latter, a variety of names are in use: hot or cold phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ Oι ₀ (sodium tripolyphosphate), is an anhydrous or with 6 H ₂ 0 crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (0) (ONa) -0] _n -Na with n = 3. In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K ₅ P Oι ₀ (potassium tripolyphosphate), for example in the form of a 50 wt .-% - solution (> 23% P ₂ 0 ₅ , 25% K ₂ 0) in the trade. Potassium polyphosphates are widely used in the detergents and cleaners industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH - NasKzPsO ™ + H ₂ O

These are used according to the invention exactly as sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.

Automatic dishwashing detergents preferred in the context of the present invention contain no sodium and / or potassium hydroxide. A waiver of sodium and / or potassium hydroxide as the alkali source has proved to be particularly advantageous if zinc gluconate, zinc formate and zinc acetate are used as zinc salts.

builders

As organic cobuilders in the detergents in the context of the present invention, in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and Phosphonates are used. The polymers may also be part of the active ingredient-containing matrix, but they may also be contained completely independently of these in the inventive compositions. The mentioned classes of substances are described below.

Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, 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 of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, methylglycinediacetic acid, sugar acids and mixtures thereof.

The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve for setting 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 thereof ,

Further 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 from 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1000 to 20 000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1,000 to 10,000 g / mol, and more preferably from 1,200 to 4,000 g / mol, may again be preferred from this group. Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers are particularly preferably used in the compositions according to the invention. The sulfonic acid-containing copolymers will be described in detail below.

In addition, of course, the sulfonic acid group-containing polymers described above may also be present in the agents according to the invention, without necessarily having to be part of the active ingredient-containing matrix zuu.

As already mentioned above, in the agents according to the invention it is particularly preferable to use both polyacrylates and the above-described copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers. The polyacrylates were described in detail above. Particularly preferred are combinations of the above-described sulfonic acid-containing copolymers with low molecular weight polyacrylates, for example in the range between 1000 and 4000 daltons. Such polyacrylates are commercially available under the trade name Sokalan ^® PA15 and PA25 Sokälan ^® (BASF).

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 molecular weight relative to free acids is generally from 2000 to 100,000 g / mol, preferably from 20,000 to 90,000 g / mol and in particular from 30,000 to 80,000 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 the compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

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

Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives , Other preferred copolymers have as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives.

Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 to 30,000 g / mol.

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

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable co-builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates. Suitable amounts are in zeolithhaltigen and / or silicate-containing formulations at 3 to 15 wt .-%. Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. 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 aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or hepta- and octa-sodium salt of DTPMPr 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.

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

In the context of the present application, agents according to the invention are characterized in that they comprise builders, preferably from the group of silicates, carbonates, organic cobuilders and / or phosphates, in amounts of from 0.1 to 99.5% by weight, preferably from 1 to 95% Wt .-%, particularly preferably from 5 to 90 wt .-% and in particular from 10 to 80 wt .-%, each based on the composition.

bleach

Bleaching agents and bleach activators are important constituents of detergents and cleaners, and a washing and cleaning agent may in the context of the present invention contain one or more substances from the groups mentioned. Among the compounds which serve as bleaches and deliver H ₂ O ₂ in water, sodium percarbonate has particular significance. Other useful bleaching agents are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate .Peroxypyrophosphate, citrate as well as H ₂ 0 ₂ -yielding peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

"Natnumper carbonate" is a nonspecific name used for sodium carbonate peroxohydrates, which strictly speaking are not "percarbonates" (ie salts of percarbonic acid) but hydrogen peroxide adducts of sodium carbonate. The commercial commodity has the average composition 2 Na ₂ C0 ₃ -3 H ₂ 0 ₂ and is therefore no peroxycarbonate. Sodium percarbonate forms a white, water-soluble powder of density 2.14 ^"3 , which readily decomposes into sodium carbonate and bleaching or oxidizing oxygen.

Sodium carbonate peroxohydrate was first obtained in 1899 by precipitation with ethanol from a solution of sodium carbonate in hydrogen peroxide, but mistakenly regarded as peroxycarbonate. It was not until 1909 that the compound was recognized as a hydrogen peroxide addition compound, yet the historical name "sodium percarbonate" has prevailed in practice.

The industrial production of sodium percarbonate is predominantly produced by precipitation from aqueous solution (so-called wet process). Here, aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium by salting-out agent (mainly sodium chloride), Kristallisierhilfsmittel (for example, polyphosphates, polyacrylates) and stabilizers (for example, Mg ²⁺ ions). The precipitated salt, which still contains 5 to 12 wt .-% mother liquor, is then removed by centrifugation and dried in fluid bed dryers at 90 ° C. The bulk density of the finished product may vary between 800 and 1200 g / l, depending on the manufacturing process. As a rule, the percarbonate is stabilized by an additional coating. Coating methods and materials used for coating are widely described in the patent literature. In principle, all commercially available percarbonate types can be used according to the invention, as offered for example by the companies Solvay Interox, Degussa, Kemira or Akzo.

Dishwashing detergents may also contain bleaches from the group of organic bleaches. Typical organic bleaches that can be used as ingredients in the present invention are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [Phthaloiminoperoxyhexanoic acid (PAP )], o- Carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid,

Diperoxybrassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronate) can be used.

As a bleaching agent for automatic dishwashing, chlorine or bromine releasing substances can also be used according to the present invention. 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 into consideration. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

Advantageous agents in the context of the present invention comprise one or more bleaching agents, preferably from the group of the oxygen or halogen bleaches, in particular the chlorine bleach, with particular preference of sodium percarbonate and / or sodium perborate monohydrate, in amounts of from 0.5 to 40 Wt .-%, preferably from 1 to 30 wt .-%, particularly preferably from 2.5 to 25 wt .-% and in particular from 5 to 20 wt .-%, each based on the total agent.

Bleach activators

In order to achieve an improved bleaching effect when cleaning at temperatures of 60 ° C. and below, cleaning agents in the context of the present invention may contain bleach activators. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydro drofuran. In addition to or in place of the conventional bleach activators, so-called bleach catalysts can also be incorporated into the detergents according to the present invention. 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.

According to the invention, agents are preferred which comprise one or more substances from the group of bleach activators, in particular from the groups of the polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), the acylated phenolsulfonates, in particular Nonanoyl or Isononanoyloxybenzolsulfonat (n- or iso-NOBS) and n-methyl-morpholinium acetonitrile methyl sulfate (MMA), in amounts of 0.1 to 20 wt .-%, preferably from 0.5 to 15 wt. -% and in particular from 1 to 10 wt .-%, each based on the total agent included.

The bleach activators preferred in the context of the present invention furthermore include the "nitrile quats", cationic nitriles of the formula (XV),

R ¹ IR ² -N ⁽⁺⁾ - (CH ₂ ) -CN X ^w (XV), IR ³

in which R ^{1 is} -H, -CH ₃ , a C _2-24 -alkyl or -alkenyl radical, a substituted C _2-24 -alkyl or -alkenyl radical having at least one substituent from the group - Cl, -Br, - OH, -NH ₂ , -CN, an alkyl or Alkenylarylrest with a _-24- alkyl group, or represents a substituted alkyl or Alkenylarylrest with a _-24- alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -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 , - (CH ₂ CH ₂ -O) _n H where n = 1, 2, 3, 4, 5 or 6 and X is an anion.

The general formula (XXI) includes a variety of cationic nitriles useful in the present invention. With particular advantage, the detergent tablets according to the invention contain cationic nitriles in which R ^{1 represents} methyl, ethyl, propyl, isopropyl or an n-butyl, n-hexyl, n-octyl, n-decyl ,. n-dodecyl, n-tetradecyl, n- Hexadecyl or n-octadecyl stands. R ² and R ³ are preferably selected from methyl, ethyl, propyl, isopropyl and hydroxyethyl, wherein one or both radicals may advantageously also be a Cyanomethylenrest.

For ease of synthesis, preference is given to compounds in which the radicals R ¹ to R ^{3 are} identical, for example (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH (CH ₃ )) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , or (HO -CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , where X ^{" is} preferably an anion selected from the group consisting of chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate is selected.

Detergents and cleaning agents which are preferred in the context of the present invention are characterized in that they contain the cationic nitrile of the formula (XXI) in amounts of from 0.1 to 20% by weight, preferably from 0.25 to 15% by weight, and in particular from 0.5 to 10 wt .-%, each based on the molding weight.

enzymes

Particularly suitable enzymes are those from the classes of hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying. In addition, cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. It is also possible to use oxidoreductases for bleaching or inhibiting color transfer. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens, as well as enzymatically-derived variants derived from their genetically modified variants. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. In this case, enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferably cellobiohydrolases, endoglucanases and - glucosidases, which are also called cellobiases, or mixtures thereof used. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

The enzymes may be adsorbed to carriers or embedded in encapsulants to protect against premature degradation. Preferred agents according to the invention contain enzymes, preferably in the form of liquid and / or solid enzyme preparations, in amounts of from 0.1 to 10% by weight, preferably from 0.5 to 8% by weight and in particular from 1 to 5% by weight. , in each case based on the total mean.

dyes

In order to improve the aesthetic impression of detergents and cleaners, they can be dyed with suitable dyes. Dyes which are preferred in the context of the present invention and whose selection does not present any difficulty to a person skilled in the art have a high storage stability and insensitivity to the other ingredients of the compositions and to light and no pronounced substantivity to textile fibers so as not to stain them.

Preferred for use in the detergents and cleaning agents according to the invention are all colorants which can be oxidatively destroyed in the cleaning process and mixtures thereof with suitable blue dyes, so-called blue toners. It has proved to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic colorants, for example anionic nitrosofarbstoffe. One possible dye is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020)., That is as a commercial product, for example as Basacid ^® Green 970 from BASF, Ludwigshafen available, as well as mixtures thereof with suitable blue dyes. Further suitable colorants Pigmosol come ^® Blue 6900 (CI 74160), Pigmosol ^® Green 8730 (CI 74260), Basonyl ^® Red 545 FL (CI 45170), Sandolan® ^® rhodamine EB400 (CI 45100), Basacid® ^® Yellow 094 (CI 47005) Sicovit ^® Patentblau 85 e 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, Cl Acidblue 183), pigment Blue 15 (Cl 74160), Supranol Blue ^® GLW (CAS 12219-32- 8, Cl Acidblue 221 )), Nylosan Yellow ^® N-7GL SGR (CAS 61814-57-1, Cl Acidyellow 218) and / or Sandolan Blue ^® (Cl Acid Blue 182, CAS 12219-26-0) is used. When choosing the colorant, it must be taken into account that the colorants do not have too high an affinity for the textile surfaces and, in particular, for synthetic fibers. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. For highly soluble dyes, for example, the above-mentioned Basacid ^® Green or the above-mentioned Sandolan Blue ^®, are typically selected dye concentrations in the range of some 10 ^"2 to ^{10" 3} wt .-%. In the due to their brilliance, particularly preferred, but are less readily water-soluble pigment dyes, for example the above-mentioned Pigmosol ^® - dyes, the appropriate concentration of the colorant is in washing or cleaning agents, however, typically a few 10 ^"3 to ^{10" 4} wt .-% ,

fragrances

As perfume oils or fragrances according to the invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are known e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate,

Dimethylbenzylcarbinylacetate (DMBCA), phenylethylacetate, benzylacetate,

Ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate, benzylsalicylate, cyclohexylsalicylate, floramate, melusate and jasmecyclate. The ethers include, for example, benzyl ethyl ether and ambroxane, to the aldehydes e.g. the linear alkanals having 8-18 C atoms, citral, citronellal, citronellyloxy-acetaldehyde, cyclamen aldehyde, lilial and bourgeonal, to the ketones e.g. the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol; the hydrocarbons mainly include the terpenes such as limonene and pinene. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance.

Such perfume oils may also contain natural fragrance mixtures as are available from vegetable sources, eg pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are Muskateller sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, Cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil, and orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The general description of the perfumes that can be used (see above) generally represents the different substance classes of fragrances. To be perceptible, a fragrance must be volatile, whereby besides the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role , For example, most odorants have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception. Due to the different volatility of fragrances, the smell of a perfume or fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note", "middle note or body" As the smell perception is based to a large extent on the odor intensity, the top note of a perfume or fragrance consists not only of volatile compounds, while the base note for the most part from less volatile In the composition of perfumes, for example, more volatile fragrances may be bound to certain fixatives, thereby preventing them from evaporating too quickly The embodiment of the present invention described above in which the more volatile fragrances are based on the water-insoluble fragrances support material low density is one such method of fragrance fixation. In the subsequent classification of the fragrances in "more volatile" or "adherent" fragrances so nothing about the olfactory impression and whether the corresponding fragrance is perceived as a head or middle note, nothing said.

Adhesive-resistant fragrances which can be used in the context of the present invention are, for example, the essential oils such as angelica root oil, aniseed oil, amicaceous oil, basil oil, bay oil, bergamot oil, Champacablütenöl, Edeltannöl, Edeltannenzapfenapfen, Elemiöl, eucalyptus oil, fennel oil, spruce algae oil, galbanum oil, geranium oil, gingergrass oil, Guaiac wood oil, gurdy balm oil, helichrysum oil, ho oil, ginger oil, iris oil, cajeput oil, calamus oil, chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine oil, copaϊva balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, tangerine oil, lemon balm oil, Moisturizer Oil, Myrrh Oil, Clove Oil, Neroliol, Niaouli Oil, Olibanum Oil, Orange Oil, Origanum Oil, Palmarosa Oil, Patchouli Oil, Peru Balsam Oil, Petitgrain Oil, Pepper Oil, Peppermint Oil, Pimento Oil, Pine Oil, Rose Oil, Rosemary Oil, Sandalwood Oil, Celery Oil, Spik Oil, Stem Oil, Turpentine Oil, Thuja Oil, Thyme oil, Verbena oil, vetiver oil, juniper berry oil, wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon oil, citronella oil, lemon oil and cypress oil. But also the higher-boiling or solid fragrances of natural or synthetic origin can be used in the context of the present invention as adherent fragrances or fragrance mixtures, ie fragrances. These compounds include the following compounds and mixtures thereof: ambrettolide, α-amyl cinnamic aldehyde, anethole, anisaldehyde, anisalcohol, anisole, methyl anthranilate, acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, Benzyl valerate, borneol, bornyl acetate, α-bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin, hepticarboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamyl alcohol, indole, Iran, isoeugenol, isoeugenol methyl ether, isosafrole, jasmon, camphor, karvakrol, karvon, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl n-amyl ketone, methyl anthranilate, p-methylacetophenone, methylchavikole, p-methylquinoline, methyl-naphthyl ketone, Methyl-n-nonylacetaldehyde, methyl n-nonyl ketone, Muskon, β-naphthol ethyl ether, β-naphthol methyl ether, nerol, nitrobenzene, n-nonylaldehyde, nonyl alcohol, n-octylaldehyde, p-oxyacetophenone, pentadecanolide, β-phenylethyl alcohol, phenylacetaldehyde dimethyacetal, phenylacetic acid, pulegone, safrole, salicylic acid isoamyl ester, methyl salicylate, salicylic acid hexyl ester, Salicylic acid cyclohexyl esters, santalol, skatole, terpineol, thymes, thymol, γ-undelactone, vaniline, veratrum aldehyde, cinnamaldehyde, cimat alcohol, cinnamic acid, cinnamic acid ethyl ester, cinnamic acid benzyl ester.

The more volatile fragrances include in particular the lower-boiling fragrances natural or synthetic origin, which can be used alone or in mixtures. Examples of more readily volatile fragrances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linayl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral, citronellal.

Corrosion protection

Detergents for automatic dishwashing may contain corrosion inhibitors to protect the items to be washed or the machine, with silver protectants in particular 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. In addition, cleaner formulations often contain active chlorine-containing agents which corrode the Silver surface can significantly reduce. In chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate and the manganese complexes tMe-TACN) Mn ^{, V} (m-0) ₃ Mn ^JV (Me-TACN)] ²⁺ (PF ₆ -) ₂ >

[Me-MeTACN) Mn ^{, v} (m-0) ₃ Mn ^lv (Me-MeTACN)] ²⁺ (PF ₆ ^" ) ₂ .

[Me-TACN] Mn ^III (m-0) (m-0Ac) ₂ Mn ^{, II} (Me-TACN)] ²⁺ (PF ₆ -) ₂ and

[Me-MeTACN) Mn ^{I, I} (m-O) (m-OAc) ₂ Mn ^{, II} (Me-MeTACN)] ²⁺ (PF ₆ ^" ) ₂ , wherein Me-TACN is 1,4,7-trimethyl 1, 4,7-triazacyclononane and Me-MeTACN are 1, 2,4,7-tetramethyl-1, 4,7-triazacyclononane. Also, zinc compounds can be used to prevent corrosion on the dishes.

A preferred agent for providing anticorrosive protection to glassware during dishwashing and / or rinsing operations of a dishwashing machine is zinc in oxidized form, i. Zinc compounds in which zinc is cationic. Similarly, magnesium salts are also preferred. Both soluble and non-soluble zinc or magnesium compounds can be used here. Preferred inventive

Compositions contain one or more magnesium and / or zinc salt (s) of at least one monomeric and / or polymeric organic acid.

The acids in question preferably originate from the group of unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the Amino acids and / or the polymeric carboxylic acids, the unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acids having at least 8 carbon atoms and / or resin acids.

Although all magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids may be present according to the invention, as described above, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids from the Groups of unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the amino acids and / or the polymeric carboxylic acids are preferred. Within these groups, the acids mentioned below are again preferred in the context of the present invention:

From the group of unbranched saturated or unsaturated monocarboxylic acids: methanoic acid (formic acid), ethanoic acid (acetic acid), propionic acid (propionic acid), pentanoic acid (valeric acid), hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), Decanoic acid (capric acid), undecanoic acid, dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid (myristic acid), pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid (margaric acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid) , Hexacosanoic acid (cerotic acid), triacotinic acid (melissic acid), 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselenic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid (elaidic acid), 9c, 12c Octadecadienoic acid (linoleic acid), 9t, 12t-octadecadienoic acid

(Linolaidic acid) and 9c, 12c, 15c-octadecatenic acid (linolenic acid).

From the group of branched saturated or unsaturated monocarboxylic acids: 2-methylpentanoic acid, 2-ethylhexanoic acid, 2-propylheptanoic acid, 2-butyloctanoic acid, 2-pentylnonanoic acid, 2-hexyldecanoic acid, 2-heptylundecanoic acid, 2-octyldodecanoic acid, 2-nonyltridecanoic acid, 2-decyltetradecanoic acid, 2-undecylpentadecanoic acid, 2-dodecylhexadecanoic acid, 2-tridecylheptadecanoic acid, 2-tetradecyloctadecanoic acid, 2-pentadecylnonadecanoic acid, 2-hexadecyleicosanoic acid, 2-heptadecylheneicosanoic acid.

From the group of unbranched saturated or unsaturated di- or tricarboxylic acids: propanedioic acid (malonic acid), butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), octanedioic acid (suberic acid), nonanedioic acid (azelaic acid), decanedioic acid ( Sebacic acid), 2c-butenedioic acid (maleic acid), 2t-butenedioic acid (fumaric acid), 2-butynedicarboxylic acid (acetylenedicarboxylic acid).

From the group of aromatic mono-, di- and tricarboxylic acids: benzoic acid, 2-carboxybenzoic acid (phthalic acid), 3-carboxybenzoic acid (isophthalic acid), 4-carboxybenzoic acid (terephthalic acid), 3,4-dicarboxybenzoic acid (trimellitic acid), 3,5-dicarboxybenzoic acid (Trimesionsäure). From the group of sugar acids: galactonic acid, mannonic acid, fructonic acid, arabinonic acid, xylonic acid, ribonic acid, 2-deoxy-ribonic acid, alginic acid.

From the group of hydroxy acids: hydroxyphenylacetic acid (mandelic acid), 2-hydroxypropionic acid (lactic acid), malic acid (malic acid), 2,3-

Dihydorxybutanedioic acid (tartaric acid), 2-hydroxy-1,2,3-propanetricarboxylic acid (citric acid), ascorbic acid, 2-hydroxybenzoic acid (salicylic acid), 3,4,5-trihydroxybenzoic acid (gallic acid).

From the group of oxo acids: 2-oxopropionic acid (pyruvic acid), 4-oxopentanoic acid (levulinic acid).

From the group of amino acids: alanine, valine, leucine, isoleucine, proline, tryptophan, phenylalanine, methionine, glycine, serine, tyrosine; Threonine, cysteine, asparagine, glutamine, aspartic acid, glutamic acid, lysine, arginine, histidine.

From the group of polymeric carboxylic acids: polyacrylic acid, polymethacrylic acid, alkylacrylamide / acrylic acid copolymers, alkylacrylamide / methacrylic acid copolymers,

Alkylacrylamide / methylmethacrylic acid copolymers, copolymers of unsaturated carboxylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers.

The spectrum of the inventively preferred zinc salts of organic acids, 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 have no solubility, to such salts having a solubility in water above 100 mg / L, preferably above 500 mg / L, more preferably above 1 g / L and in particular above 5 g / L (all solubilities at 20 ° C water temperature). The first group of zinc salts includes, for example, the zinc nitrate, the zinc oleate and the zinc stearate; the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate:

In a further preferred embodiment of the present invention, the compositions according to the invention contain at least one zinc salt but no magnesium salt of an organic acid, which is preferably at least one zinc salt of an organic carboxylic acid, more preferably a zinc salt selected from zinc stearate, zinc oleate, zinc gluconate, zinc acetate , Zinc lactate and / or Zinkeitrat acts. Furthermore, zinc ricinoleate, zinc abietate and zinc oxalate are also preferably used.

Claims

claims:

1. Machine dishwashing detergent, comprising at least one polymer which is modified with phosphorus-containing groups, characterized in that the polymer in 1 wt .-% solution in distilled water at 20 ° C has a pH below 6.

2. Machine dishwashing detergent according to claim 1, characterized in that it comprises a polymer of i) unsaturated carboxylic acids ii) phosphate group-containing monomers iii) optionally further ionic or nonionic monomers.

3. Machine dishwashing detergent according to one of claims 1 or 2, characterized in that it comprises a polymer of i) unsaturated carboxylic acids ii) phosphonate group-containing monomers iii) optionally further ionic or nonionic monomers.

4. Machine dishwashing detergent according to one of claims 1 to 3, characterized in that it comprises a polymer of i) unsaturated carboxylic acids ii) phosphite-containing monomers iii) optionally further ionic or nonionic monomers.

5. Machine dishwashing detergent according to one of claims 1 to 4, characterized in that it comprises a polymer of i) unsaturated carboxylic acids ii) phosphine oxide group-containing monomers iii) optionally further ionic or nonionic monomers.

6. Machine dishwashing detergent according to one of claims 1 to 5, characterized in that the polymer modified with phosphorus-containing groups has at least partially terminal phosphorus-containing groups.

7. A machine dishwashing detergent according to any one of claims 1 to 6, characterized in that it is the (s) containing Phόsphor-containing polymer (s) polymer (s) preferably in amounts of 0.1 to 20 wt .-%, particularly preferably of 0.2 to 10 wt .-% and in particular from 0.5 to 7.5 wt .-%, each based on the total agent contains.

8. A machine dishwashing detergent according to any one of claims 1 to 7, characterized in that the / the (s) containing phosphorus-containing polymer (s) average molecular weights of 1000 to 10,000,000 gmol ^"1 , preferably from 1500 to 1,000. 000 gmol ^"1 , more preferably from 2000 to 100,000 gmol ^{" 1} and in particular from 2500 to 50,000 gmol ^"1 .

9. Machine dishwashing detergent according to one of claims 1 to 8, characterized in that the (s) containing phosphorus-containing (s) polymer (s) has a degree of polymerization of 10 to 10,000, preferably from 20 to 5000, particularly preferably from 40 to 2000 and in particular from 80 to 1000 have.

10. Machine dishwashing detergent according to one of claims 2 to 9, characterized in that the molar ratio of the monomers i) to ii) 1: 1 to 200: 1, preferably 1: 1 to 100: 1 and in particular 1: 1 to 10: 1 amounts to.

11. A machine dishwashing detergent according to any one of claims 2 to 10, characterized in that the (s) containing phosphorus-containing (s) polymer (s) has a phosphorus content of 0.5 to 5.0 wt .-%, preferably from 0 , 7 to 4.0 wt .-% and in particular from 0.9 to 3.0 wt .-%, each based on the total weight of the / the phosphorus-containing polymer (s) s, have.

12. Machine dishwashing detergent according to one of claims 2 to 11, characterized in that the content of the polymers of monomers iii) is not more than 20 mol%, preferably not more than 10 mol% and in particular not more than 5 mol%.

13. Machine dishwashing detergent according to one of claims 1 to 12, characterized in that it additionally contains one or more cationic and / or amphoteric polymer (s), preferably in amounts of from 0.1 to 20% by weight. , particularly preferably from 0.2 to 10 wt .-% and in particular from 0.5 to 7.5 wt .-%, each based on the total agent contains.

14. Machine dishwashing detergent according to one of claims 1 to 13, characterized in that it additionally comprises one or more polymer (s) i) unsaturated carboxylic acids ii) monomers containing sulfonic acid groups iii) optionally further ionic or nonionic monomers, preferably in amounts of from 0.1 to 20% by weight, particularly preferably from 0.2 to 10% by weight and in particular of 0.5 to 7.5 wt .-%, each based on the total agent contains.

15. Machine dishwashing detergent according to one of claims 1 to 14, characterized in that it additionally comprises one or more surfactants, preferably nonionic (s) surfactant (s), preferably in amounts of 0.1 to 20 wt .-%, particularly preferably of 0.2 to 15 wt .-% and in particular from 0.5 to 12 wt .-%, each based on the total agent contains.