EP2148918A1

EP2148918A1 - Phosphate-free dishwasher detergent with excellent rinsing power

Info

Publication number: EP2148918A1
Application number: EP08736539A
Authority: EP
Inventors: Jürgen Tropsch
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2007-04-25
Filing date: 2008-04-24
Publication date: 2010-02-03
Also published as: CN101688155B; CN101688155A; JP2010525128A; CA2684533A1; US20100294309A1; KR101445421B1; KR20100016623A; DE102007019458A1; WO2008132133A1; US8123867B2; JP5595263B2

Abstract

The invention relates to a phosphate-free dishwasher detergent, containing 0.01 - 20% by weight of at least one alcohol alkoxylate, 0.01 - 10% by weight of at least one alcohol ethoxylate, 0 - 15% by weight of at least one sulfonate group-containing polymer, 0 - 15% by weight of at least one hydrophilically modified polycarboxylate, 0 - 8% by weight of at least one polycarboxylate, 1 - 50% by weight of at least one complexing agent and 0.1 - 60% by weight of at least one further additive, components (A), (B), (C), (D), (E), (F) and (G) adding up to 100%. The invention also relates to a method for washing the surfaces of articles by treating said surfaces with the agent and to the use of the agent for increasing the rinsing power when articles are cleaned in a dishwasher.

Description

Phosphate-free machine dishwashing detergent with excellent rinse performance

description

The present invention relates to a phosphate-free machine dishwashing detergent containing an alcohol alkoxylate, an alcohol ethoxylate, at least one polymer, at least one complexing agent and other additives, a method for rinsing surfaces, and the use of the phosphate-free dishwasher detergent to increase the rinsing performance in the machine rinsing of objects, in particular special dishes, glasses, cutlery and kitchen accessories.

At present, 3-in-1 dishwashing detergents have a market share of around 60% for machine dishwashing detergents in Europe. They combine the three functions of cleaning, rinsing and softening in a dishwashing detergent. Machine dishwashing detergents are already known from the prior art.

EP 0 877 002 B1 discloses a process for controlling the amount of (poly) phosphates by treating aqueous systems with at least one copolymer containing as monomers at least one weak acid, at least one unsaturated sulfonic acid, optionally at least one monoethylenically unsaturated C ₄ -C 8 -dicarboxylic acid and optionally at least one unsaturated monomer which is polymerizable with the aforementioned compounds.

WO 00/50551 discloses a dishwashing composition comprising a binder, a non-ionic surfactant, bleaching compounds and other additives selected from enzymes, surfactants or gelatinizing compounds.

DE 102 33 834 A1 discloses dishwashing compositions for automated cleaning of dishes containing builders, polymers and surfactants. Non-ionic surfactants which can be used with propylene oxide and ethylene oxide alkoxylated primary alcohols, such as trimethylolpropane.

While the cleaning performance of known 3-in-1 dishwashing detergents is adequate, the rinse performance is an unsolved problem, especially at hardness levels above 14 ° dH. Moreover, adequate rinse performance is difficult to achieve if the dishwashing detergent is phosphate-free.

It has surprisingly been found that by using a combination of various components containing at least one alcohol alkoxylate, at least one short-chain alcohol ethoxylate, at least one polymer containing sulfonate groups and / or at least one hydrophilically modified polycarboxylate, optionally a polycarboxylate, and at least one complexing agent together with generally customary other constituents, the rinse aid performance can be greatly improved even at significantly higher water hardness and in the absence of phosphates.

The object of the present invention is to increase the rinse performance of phosphate-free 3-in-1 dishwashing detergents during dishwashing.

Another object of the present invention is to increase the rinse performance of phosphate-free 3-in-1 dishwashing detergents at water hardnesses above 14 ° dH.

This object is achieved by a phosphate-free machine dishwashing detergent containing

(A) 0.01-20% by weight of at least one alcohol alkoxylate of the general formula (I)

R ¹ - (OCH ₂ CHR ² ) _x (OCH ₂ CHR ³ ) _y -OR ⁴ (I)

With

R ¹ : linear or branched C ₆ -C ₂₄ -alkyl radical,

R ² , R ³ : independently of one another, different hydrogen, linear or branched C ₁ -C ₆ -alkyl radical, R ⁴ : hydrogen, linear or branched C ₁ -C ₈ -alkyl radical. x, y: independently mean value in the range of 0.5-80,

wherein the individual alkylene oxide units can be present as a block or randomly distributed,

(B) 0.01-10% by weight of at least one alcohol ethoxylate of the general formula (H)

R ⁵ - (OCH ₂ CH ₂ ) _Z OH (II)

With

R ⁵ : linear or branched C ₄ -C ₈ -alkyl radical and z: average value of 2 to 10, the content of residual alcohol R ⁵ -OH being less than 1% by weight, (C) 0-15% by weight of at least one sulfonate group-containing polymer,

(D) 0-15% by weight of at least one hydrophilic modified polycarboxylate,

(E) 0-8% by weight of at least one polycarboxylate,

(F) 1 - 40 wt .-% of at least one complexing agent and

(G) 0.1-60% by weight of at least one further additive,

wherein the sum of components (A), (B), (C), (D), (E), (F) and (G) is 100% by weight.

In a preferred embodiment, the inventive phosphate-free dishwashing detergent consists of the components (A), (B), (F), (G) and optionally (C), (D) and (E).

By the use of components selected from at least one alcohol alkoxylate (A), at least one short-chain alcohol ethoxylate (B), at least one sulfonate group-containing polymer (C) and / or a hydrophilically modified polycarboxylate (D) which causes the formation of calcium phosphate coatings and optionally a polycarboxylate which inhibits the formation of calcium carbonate coatings, in combination with at least one complexing agent and at least one further additive, the rinse aid performance of the dishwashing compositions according to the invention can be greatly improved even at significantly higher water hardness and in the absence of phosphates.

In the context of the present invention, the term "phosphate-free" means that less than 0.1%, preferably less than 0.01%, particularly preferably 0% phosphates are present in the dishwashing detergent according to the invention.

According to the invention, the term "phosphates" refers to compounds which have the anion PO ₄ ^{3 "} individually or as a higher-order structural unit, so-called polyphosphates, and in which the phosphorus atom is bound exclusively to oxygen atoms and is present in the + V oxidation state ,

In addition to the excellent rinse performance of the dishwasher according to the invention this is characterized by the absence of phosphates also by its very good biocompatibility. The ingredients (A), (B), (C), (D), (E), (F) and (G) of the phosphate-free machine dishwashing detergent are explained in more detail below.

Component (A)

The phosphate-free machine dishwashing detergent contains as component (A) 0.01 to 20 wt .-%, preferably 0.5 to 15 wt .-%, particularly preferably 1 to 10 wt .-% of at least one alcohol alkoxylate of the general formula (I)

R ¹ - (OCH ₂ CHR ² ) _x (OCH ₂ CHR ³ ) _y -OR ⁴ (I)

With

R ¹ : linear or branched C ₆ -C ₂₄ -alkyl radical,

R ² , R ³ : independently of one another, different hydrogen, linear or branched dC ₆ alkyl radical,

R ⁴ : hydrogen, linear or branched C 1 -C 6 -alkyl radical and x, y: independently of one another mean value in the range from 0.5 to 80,

wherein the individual alkylene oxide units may be present as a block or randomly distributed.

The radical R ¹ in the alcohol alkoxylate of the general formula (I) is generally a linear or branched C ₆ - to C ₂₄ -alkyl radical, preferably a linear or branched C ₈ - to C 16 -alkyl radical, more preferably a linear or branched C ₉ - to Ci ₅ - alkyl radical.

The alkylene oxide blocks (OCH ₂ CHR ² ) and (OCH ₂ CHR ³ ) represent structural units obtained by alkoxylation of the alcohols R ¹ -OH with a compound selected from among

Group consisting of ethylene oxide, propylene oxide, butylene oxide, pentenoxide, hexylene oxide, heptylene oxide, octylene oxide, nonylene oxide, decylene oxide and mixtures thereof, preferably selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, pentenoxide and mixtures thereof. The reaction with the different alkylene oxides can be carried out in blocks (successively or alternately) or simultaneously (random or mixed procedure). Thus, the radicals R ² and R ³ in the general formula (I) independently of one another, different hydrogen or a C ₁ to C ₆ alkyl, preferably hydrogen or a C ₁ to C ₃ alkyl, ie independently of one another hydrogen, methyl , Ethyl or propyl. R ³ in the general formula (I) is hydrogen, linear or branched C ₁ - to C ₆ -alkyl radical, preferably hydrogen or linear or branched C ₁ - to C ₄ -alkyl radical, particularly preferably hydrogen, methyl or ethyl.

In the general formula (I), x describes the number of units (OCH ₂ CHR ² ), and y describes the number of units (OCH ₂ CHR ³ ). In the compounds of the general formula (I), x and y independently of one another have an average value of 0.5 to 80, preferably 0.5 to 40, particularly preferably 0.5 to 20. Describes x the number of ethylene oxide present in the alcohol alkoxylate of the general formula (I) In the case of units, x has an average value of from 2 to 20, preferably from 2 to 15. If y in the alcohol alkoxylate of the general formula (I) describes the number of propylene oxide, butylene oxide or pentenoxide units, then y has a mean value Value of 0.5 to 20, preferably 0.5 to 10, particularly preferably 0.5 to 6.

The values x and y in the general formula (I) represent average values, since in the alkoxylation of alcohols a distribution of the degree of alkoxylation is generally obtained. Therefore, x and y may differ from integer values. The distribution of the degree of alkoxylation can be adjusted to some extent by using different alkoxylation catalysts. Since at least one longer-chain alkylene oxide is used in addition to ethylene oxide, the different alkylene oxide structural units can be randomly distributed, alternating or in the form of two or more blocks in any order. The mean of the homolog distribution is represented by the given numbers x and y.

In a preferred embodiment, in component (A) R ¹ is a linear or branched C ₈ -C ₈ alkyl, R ² and R ³ independently of one another hydrogen, methyl, ethyl or propyl and x and y have independent of one another an average value from 0.5 to 20.

Very particular preference is given to using the following compounds of the general formula (I):

Ci3- to Ci ₅ -Oxoalkohol + 10 units of ethylene oxide + 2 units of butylene oxide, iso-Cio-alcohol + 10 units of ethylene oxide + 1, 5 units of pentenoxide, - Ci to Ci ₂ -fatty alcohol + 9 units of ethylene oxide + 5 units of propylene oxide,

_I C 3 to C ₅ -oxo alcohol + 4.46 + 0.86 units of ethylene oxide units of butylene oxide, end-capped with a methyl group,

2-propylheptanol + 6 units of ethylene oxide + 4.5 units of propylene oxide or mixtures thereof. The compounds of the general formula (I) according to the invention are prepared, for example, by alkoxylation of alcohols of the general formula R ¹ -OH with alkylene oxides which contain the units (OCH ₂ CHR ² ) and (OCH ₂ CHR ³ ) in the general formula (I) yield, received. In this case, if the radical R ^{4 is} not hydrogen, an etherification, for example with dimethyl sulfate, can follow the alkoxylation.

The alkoxylation can be carried out, for example, using alkaline catalysts such as alkali metal hydroxides or alkali metal alkoxides. The use of these catalysts results in special properties, in particular the homolog distribution of the alkylene oxides.

The alkoxylation can also be carried out using Lewis acid catalysis with the special properties resulting therefrom, in particular in the presence of BF ₃ × H ₃ PO ₄ , BF ₃ × dietherate, BF ₃ , SbCl ₅ , SnCl ₄ × 2 H ₂ O , Hydrotalcite. Suitable catalysts are also double metal cyanide (DMC) compounds.

In this case, the excess alcohol can be distilled off, or the alkoxylate can be obtained by a 2-step process. It is also possible to prepare mixed alkoxylates of, for example, ethylene oxide (EO) and propylene oxide (PO), it being possible first to attach a propylene oxide block and then an ethylene oxide block to the alcohol radical, or first an ethylene oxide block and then a propylene oxide block , Statistical (random) distributions are also possible. Preferred reaction conditions are given below.

The alkoxylation is preferably catalyzed by strong bases, which are expediently added in the form of an alkali metal hydroxide or alkaline earth metal hydroxide, generally in an amount of from 0.1 to 1% by weight, based on the amount of the alcohol R ¹ -OH (cf. Gee et al., J. Chem. Soc. (1961), p 1345, B. Wojtech, Makromol Chem 66 (1966), p 180).

Acid catalysis of the addition reaction is also possible. In addition to Bronsted acids, Lewis acids such as aluminum trichloride or BF ₃ are also suitable (compare PH Plesch, The Chemistry of Cationic Polymerization, Pergamon Press, New York (1963)).

The alkoxylation can also be carried out by double metal cyanide catalysts by methods known to the person skilled in the art. As a double metal cyanide compound, it is possible in principle to use all suitable compounds known to the person skilled in the art. DMC compounds suitable as catalyst are described, for example, in WO 99/16775 and in DE-A-101 17273. The addition reaction is carried out at temperatures of about 90 to about 240 ⁰ C, preferably from 120 to 180 ⁰ C, in a closed vessel. The alkylene oxide or the mixture of different alkylene oxides are fed to the mixture of alcohol or mixture according to the invention and alkali under the vapor pressure of the alkylene oxide mixture prevailing at the selected reaction temperature. If desired, the alkylene oxide may be diluted with up to about 30 to 60% of an inert gas. This provides additional security against explosive polyaddition or decomposition of the alkylene oxide. If an alkylene oxide mixture is used, polyether chains are formed in which the various alkylene oxide building blocks are virtually randomly distributed. Variations in the distribution of building blocks along the polyether chain arise due to different reaction rates of the components and can also be arbitrarily submitted by continuous supply of an alkylene oxide mixture of programmable composition. If the various alkylene oxides are reacted successively, polyether chains are obtained with a block-like distribution of the alkylene oxide units.

Component (B)

The phosphate-free machine dishwashing detergent contains as component (B) 0.01 to 10 wt .-%, preferably 0.1 to 5 wt .-%, particularly preferably 0.1 to 2 wt .-% of an alcohol ethoxylate of the general formula (II)

R ⁵ - (OCH ₂ CH ₂ ) _Z OH (II)

With

R ⁵ : linear or branched C ₂ -C 10 -alkyl radical and z: average value of 2-10,

wherein the content of residual alcohol R ⁵ -OH less than 1 wt .-%, preferably less than 0.5 wt .-%, more preferably less than 0.2 wt .-% is.

In the alcohol ethoxylate of the general formula (II) R ⁵ is linear or branched C ₂ -C comparable ₀ alkyl, preferably C ₄ -C ₈ alkyl radical.

In the general formula (II), z means a mean value of 2 to 10, preferably 3 to 8, particularly preferably 4 to 6. With regard to the mean value of z, what has already been said about x and y in component (A) applies. Component (B) is a linear or branched C ₄ -C 8 alcohol which has been alkoxylated with 2 to 10 units of ethylene oxide. The preparation of the alcohol ethoxylate of the general formula (II) can be carried out according to the preparation of the alcohol alkoxylate of the general formula (I), it being noted that exclusively ethylene oxide is used as the alkylene oxide. With regard to catalysis, what has been said for the alcohol alkoxylate of general formula (I) also applies.

For the preparation of the alcohol ethoxylates of the general formula (II) it is also possible to use alkyl glycol alkoxylates or dialklycol alkoxylates obtainable by alkoxylation of corresponding C ₄ -C ₈ -alkyl glycols or diglycols with ethylene oxide, preferably to a moderate degree of alkoxylation, which comprises previously mentioned compounds of the general formula (II).

The preparation takes place starting from the corresponding alcohol-free, preferably pure, alkyl glycols and alkyl diglycols and not, as described above, starting from alcohols, by alkoxylation. Therefore, the product mixtures also contain no remaining alcohols, but at most Alkylglykole. The result is a specific for alkyl glycol distribution of the degree of alkoxylation. This preparation process makes it possible for the alcohol ethoxylates of the general formula (II) to have a residual alcohol R ⁵ -OH content of less than 1% by weight, preferably less than 0.5% by weight, particularly preferably less than 0.2% by weight. exhibit.

If the alcohol ethoxylates of the general formula (II) are prepared by ethoxylation of the corresponding alcohols R ⁵ -OH, the residual alcohol R ⁵ -OH present in the mixture after ethoxylation can be removed by methods known to the person skilled in the art, for example distillation.

Precisely because of the presence of component (B) in the machine dishwashing detergent according to the invention, the rinse-aid performance is markedly increased at elevated water hardness above 14 ° dH.

Component (C)

The phosphate-free machine dishwashing detergent contains as component (C) 0 to 15 wt .-%, preferably 0.5 to 12 wt .-%, particularly preferably 1 to 10 wt .-% of at least one sulfonate polymer / copolymer. This at least one sulfonate group-containing polymer / copolymer prevents the formation of deposits, which consist of calcium phosphate. In a preferred embodiment, the dishwashing agent according to the invention comprises at least one copolymer C comprising the following monomers

(I) 50-98% by weight of one or more weak acids,

(II) 2-50% by weight of one or more unsaturated sulfonic acid monomers selected from the group consisting of 2-acrylamidomethyl-1-propanesulfonic acid, 2-methacrylic acid amido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2 -hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-

(2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethylacrylamide, sulfomethylmethacrylamide, and water-soluble salts thereof,

(III) 0-30% by weight of one or more monoethylenically unsaturated C ₄ -C ₈ dicarboxylic acids and

(IV) 0-30% by weight of one or more monoethylenically unsaturated monomers polymerizable with (I), (II) and (III), the totality of monomers (I), (II) being , (III) and (IV) corresponds to 100% by weight of the copolymer.

In a particularly preferred embodiment, the copolymer C comprises the following monomers in polymerized form:

(I) 50-98% by weight of one or more ethylenically unsaturated C ₃ -C ₆ monocarboxylic acids, (II) 2-50% by weight of one or more unsaturated sulfonic acids,

(III) 0-30% by weight of one or more monoethylenically unsaturated C ₄ to C ₈ dicarboxylic acids and

(IV) 0-30% by weight of one or more monoethylenically unsaturated monomers which are / can be polymerized with (I), (II) and (III), the total of monomers (I), ( II); (III) and (IV) corresponds to 100% by weight of the copolymer.

In a particularly preferred embodiment, the copolymer C comprises polymerized units of the following units:

(I) 50-90% by weight of one or more ethylenically unsaturated C ₃ -C ₆ monocarboxylic acids,

(II) 10-50% by weight of unsaturated sulfonic acid,

(IV) 0-30% by weight of one or more monethylenically unsaturated monomers which is / are polymerisable with (I), (II) and (III), the totality of monomers (I), ( II); (III) and (IV) corresponds to 100% by weight of the copolymer. In a very particularly preferred embodiment, the copolymer (C) comprises polymerized units of the following monomers:

(I) 60-90% by weight of one or more ethylenically unsaturated C ₃ -C ₆ -

Monocarboxylic acids, (II) 10-40% by weight of the unsaturated sulfonic acid,

A copolymer C with particularly good properties for use in dishwashing detergents comprises polymerized units of the following monomers:

(I) 77% by weight of one or more ethylenically unsaturated C ₃ -C ₆ monocarboxylic acids,

(II) 23 wt .-% of the unsaturated sulfonic acid, wherein the unsaturated C ₃ -C ₆ monocarboxylic acid is preferably (meth) acrylic acid.

The monoethylenically unsaturated C ₄ -C 8 -dicarboxylic acid is preferably maleic acid and the monoethylenically unsaturated monomer polymerizable with (I), (II) and (III) is preferably selected from one or more of C 1 -C ₄ -alkyl esters of (meth ) Acrylic acid, C 1 -C ₄ -hydroxyalkyl esters of (meth) acrylic acid, acrylamide, alkyl-substituted acrylamide, N, N-dialkyl-substituted acrylamides, sulfonated alkylacrylamides, vinylphosphonic acids, vinyl acetate, allyl alcohols, sulfonated allyl alcohols, styrene and similar monomers, acrylonitrile, N-vinylpyrrolidone, N-vinylformamide, N-vinylimidazole and N-vinylpyridine.

Further sulfone-group-containing copolymers suitable as component C are copolymers of i) unsaturated carboxylic acids ii) monomers containing sulfonic acid groups and iii) optionally further ionic or nonionic monomers.

In the context of the present invention, unsaturated carboxylic acids i) of the formula (III) are preferred as the monomer,

R ⁶ (R ⁷ ) C = C (R ⁸ ) COOH (III),

in the R ⁶ to R ⁸ independently of one another represent hydrogen, methyl, a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms alkyl, or alkenyl radicals substituted by -NH ₂ , -OH or -COOH as defined above or -COOH or -COOR ⁹ , where R ^{9 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 (III) are in particular acrylic acid (R ⁶ = R ⁷ = R ⁸ = H), methacrylic acid (R ⁶ = R ⁷ = H, R ⁸ = CH ₃ ) and / or maleic acid (R ⁶ = COOH, R ⁷ = R ⁸ = H) is preferred.

In the sulfonic acid-containing monomers, those of the formula (IV) are preferred,

R ¹⁰ (R ¹¹ ) C = C (R ¹² ) -X-SO ₃ H (IV),

in the R ¹⁰ to R ¹² independently of one another are hydrogen, methyl, 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 ⁹ , wherein R ^{9 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 ) ,, - with n = O to 4, -C00- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CN (CH ₂ CH ₃ ) -.

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

H ₂ C = CH-X-SO ₃ H (IVa),

H ₂ C = C (CH ₃ ) -X-SO ₃ H (IVb),

HO ₃ SX- (R ¹¹ ) C = C (R ¹² ) -X-SO ₃ H (IVc),

in which R ¹¹ and R ^{12 are} independently selected from hydrogen, methyl, ethyl, propyl, iso-propyl and X is an optionally present spacer group which is selected from - (CH 2) n - where n = 0 to 4, - C00- (CH 2) k- with k = 1 to 6, -C (O) -NH-C (CH ₃ ), - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₂ CH ₃ ) in formula IVa), 2-acrylamido-2-propanesulfonic acid (X = -C ( O) NH-C (CH ₃ ) ₂ in formula IVa), 2-acrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula IVa), 2 - Methacrylamido-2-methyl-i-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula IVb), S-methacrylamido-hydroxypropanesulfonic acid (X = -C (O) NH- CH ₂ CH (OH) CH ₂ - in formula IVb), allyl sulfonic acid (X = CH ₂ in formula (IVa), methallylsulfonic X = CH ₂ in the formula (IIIb), allyloxybenzenesulfonic X = -CH ₂ -O-C _O H ₄ - in Formula IVa), methallyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula IVb), 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid (X = CH ₂ in formula IVb), styrenesulfonic acid (X = CβH ₄ in formula IVa), vinylsulfonic acid (X not present in formula IVa), 3-sulfopropyl acrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in formula IVa ), 3-sulfopropyl methacrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in formula IVb), sulfomethacrylamide (X = -C (O) NH- in formula IVb), sulfomethylmethacrylamide (X = -C ( O) NH-CH ₂ - in formula IVb) and water-soluble salts of said acids.

Suitable further ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds. A nonionic monomer of the formula V is preferably used

H ₂ C = C (R ¹³ ) C (= O) -OR ¹⁴ - [R ¹⁵ -O] _O -R ¹⁵ (V),

in the R ^{13 is} hydrogen or methyl, R ^{14 is} a chemical bond or a straight-chain or branched C ₁ -C ₆ -alkyl radical, R ^{15 is} in each case identical or different, straight-chain or branched C ₁ -C ₆ -alkyl radicals and o is one course number from 3 to 50, randomly or blockwise polymerized contains.

The content of the abovementioned sulfonic acid group-containing polymers to monomers of group iii) is preferably less than 20% by weight, based on the polymer. Particularly preferred sulfonic acid-containing polymers consist only of monomers of groups i) and ii).

The copolymers described above optionally contained in the dishwasher detergents according to the invention may contain the monomers from groups i) and ii) and optionally iii) in varying amounts, all representatives from group i) with all representatives from group ii) and all Representatives from group iii) can be combined.

In the copolymers C, the sulfonic acid groups may be completely or partially in neutralized form, ie that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups may be exchanged for metal ions, preferably alkali metal ions and especially sodium ions. Corresponding agents according to the invention, wherein the sulfonic acid groups are partially or completely neutralized in the copolymer, are preferred according to the invention. 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 5 to 95 wt .-%, particularly preferably 10 to 50 wt .-% of monomer from the 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 above-described copolymers contained in the dishwashing compositions according to the invention can be varied in order to adapt the properties of the polymers to the desired use. Preferred uses are characterized in that the copolymers have molar masses of from 2000 to 200,000 g / mol, preferably from 4000 to 25,000 g / mol and in particular from 5000 to 15,000 g / mol.

In a preferred embodiment, copolymers which contain a) from 30 to 95 mol% of acrylic acid and / or methacrylic acid and / or of a water-soluble salt of acrylic acid and / or a water-soluble salt of methacrylic acid, b) 3, can be used as component C in the dishwashing composition according to the invention to 35 mole% of at least one sulfonic acid group-containing monomer of the formula III c) 2 to 35 mole% of at least one nonionic monomer of the formula V

H ₂ C = C (R ¹³ ) C (= O) -OR ¹⁴ - [R ¹⁵ -O] OR ¹⁵ (V),

in the R ^{13 is} hydrogen or methyl, R ^{14 is} a chemical bond or a straight-chain or branched C 1 -C ₆ -alkyl radical, R ^{15 is} in each case identical or different, straight-chain or branched C 1 -C ₆ -alkyl radicals and o is a natural number from 3 to 50, randomly or in block polymerized contains.

Preferably, the proportion a) of copolymerized acrylic acid and / or methacrylic acid and / or a water-soluble salt of these acids is 50 to 90 mol%, preferably 55 to 85 mol% and particularly preferably 60 to 90 mol%. The proportion b) of copolymerized sulfonic acid group-containing monomers of the formula (IV) is preferably from 4 to 30 mol%, preferably from 5 to 25 mol% and particularly preferably from 5 to 20 mol%. The proportion c) of monomer units of the formula (V) is preferably from 3 to 30 mol%, particularly preferably from 4 to 25 mol%, and in particular at 5 to 20 mol%. All the abovementioned mol% data relate to the polymer contained in the agents according to the invention.

The K value of the copolymers is preferably from 15 to 35, in particular from 20 to 32, especially from 27 to 30 (measured in 1 wt .-% aqueous solution at 25 ⁰ C).

Component (D)

The phosphate-free machine dishwashing detergent contains as component D 0 to 15 wt .-%, preferably 0.5 to 12 wt .-%, particularly preferably 1 to 10 wt .-% of at least one hydrophilic modified polycarboxylate, which is the formation of deposits of calcium phosphate exist, inhibited.

In a preferred embodiment, copolymers containing hydrophilic modified polycarboxylate-containing alkylene oxide units are used, built up from

(1) 50 to 93 mol% of acrylic acid and / or a water-soluble salt of acrylic acid,

(2) 5 to 30 mol% of methacrylic acid and / or a water-soluble salt of methacrylic acid and

(3) 2 to 20 mol% of at least one nonionic monomer of formula VI

H ₂ C = C (R ¹⁶ ) -C (= O) -OR ¹⁷ - [- R ¹⁸ -O-] _s -R ¹⁹ (VI),

in which the variables have the following meaning:

R ^{16 is} hydrogen or methyl;

R ^{17 is} a chemical bond or unbranched or branched C ₁ -C ₆ -alkylene; R ¹⁸ identical or different unbranched or branched C ₂ -C ₄ -alkylene radicals;

R ^{19 is} unbranched or branched C 1 -C 6 -alkyl; s 3 to 50,

wherein the components (1), (2) and (3) are copolymerized randomly or in blocks.

These copolymers containing alkylene oxide units contain as copolymerized components (1) and (2) acrylic acid or methacrylic acid and / or water-soluble salts of these acids, in particular the alkali metal salts, such as potassium and especially sodium salts, and ammonium salts. The proportion of acrylic acid (1) in the copolymers to be used according to the invention is 50 to 93 mol%, preferably 65 to 85 mol% and particularly preferably 65 to 75 mol%.

Methacrylic acid (2) is contained in the copolymers to be used according to the invention to 5 to 30 mol%, preferably to 10 to 25 mol% and especially to 15 to 25 mol%.

The copolymers contain as component (3) nonionic monomers of the formula VI

H ₂ C = C (R ¹⁶ ) -C (= O) -OR ¹⁷ - [- R ¹⁸ -O-] _s -R ¹⁹ (VI),

With

R ^{16 is} hydrogen or preferably methyl;

R ^{17 is} unbranched or branched C ₁ -C ₆ -alkylene or preferably a chemical bond;

R ^{18 are} identical or different unbranched or branched C ₂ -C ₄ -alkylene radicals, especially C ₂ -C ₃ -alkylene radicals, in particular ethylene;

R ^{19 is} unbranched or branched C ₁ -C ₆ -alkyl, preferably C ₁ -C ₂ -alkyl; s 3 to 50, preferably 5 to 40, particularly preferably 10 to 30.

Particularly suitable examples of the monomers of the formula (VI) are: methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, methoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, ethoxypolyethylene glycol ( meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, ethoxypolybutylene glycol (meth) acrylate and ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, with methoxypolyethylene glycol (meth) acrylate and methoxypolypropylene glycol (meth) acrylate being preferred and Methoxypolyethylenglykolmethacrylat is particularly preferred.

The polyalkylene glycols contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units.

The proportion of nonionic monomers (3) in the copolymers D to be used according to the invention is 2 to 20 mol%, preferably 5 to 15 mol% and especially 5 to 10 mol%.

The copolymers D to be used according to the invention generally have a medium Res molecular weight M _w from 3,000 to 50,000 g / mol, preferably from 10,000 to 30,000 g / mol and particularly preferably from 15,000 to 25,000 g / mol.

The K value of the copolymers D is usually from 15 to 40, in particular from 20 to 35, especially from 27 to 30 (measured in 1 wt .-% aqueous solution at 25 ° C, according to H. Fikentscher, cellulose chemistry 13, pp. 58-64 and 71-74 (1932)).

The copolymers C and D to be used according to the invention can be prepared by free-radical polymerization of the monomers. In this case, it is possible to work according to all the radical polymerization processes known to the person skilled in the art. In addition to the bulk polymerization, the methods of solution polymerization and emulsion polymerization should be mentioned in particular, with the solution polymerization being preferred.

The polymerization is preferably carried out in water as a solvent. However, it can also be carried out in alcoholic solvents, in particular C ₄ -alcohols, such as methanol, ethanol and isopropanol, or mixtures of these solvents with water.

Suitable polymerization initiators are both thermally and photochemically (photoinitiators) decomposing and thereby radical-forming compounds.

Among the thermally activatable polymerization initiators whose decomposition temperature in the range from 20 to 180 ⁰ C, in particular from 50 to 90 ⁰ C, aeration vorzugt. Examples of suitable thermal initiators are inorganic peroxo compounds, such as peroxodisulfates (ammonium and preferably sodium peroxodisulfate), peroxosulfates, percarbonates and hydrogen peroxide; organic peroxo compounds, such as diacetyl peroxide, di-tert-butyl peroxide, diamyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, bis (o-toloyl) peroxide, succinyl peroxide, tert-butyl peracetate, tert-butyl permalate, tert. Butyl perisobutyrate, tertiary

Butyl perpivalate, tert-butyl peroctoate, tert-butyl perodecanoate, tert-butyl perbenzoate, tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxy-2-ethylhexanoate and diisopropyl peroxydicarbamate; Azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile) and azobis (2-amidopropane) dihydrochloride.

These initiators can be used in combination with reducing compounds as starter / regulator systems. Examples of such reducing compounds include phosphorus-containing compounds such as phosphorous acid, hypophosphites and phosphinates, sulfur-containing compounds such as sodium hydrogen sulfite, sodium sulfite and sodium formaldehyde sulfoxilate, and hydrazine. Examples of suitable photoinitiators are benzophenone, acetophenone, benzoin ethers, benzyl dialkyl ketones and their derivatives.

Preferably, thermal initiators are used, with inorganic peroxo compounds, in particular sodium peroxodisulfate (sodium persulfate), being preferred. The peroxo compounds are particularly advantageously used in combination with sulfur-containing reducing agents, in particular sodium hydrogen sulfite, as the redox initiator system. When using this starter / regulator system copolymers are obtained, which contain as end groups -SO ₃ ^" Na ⁺ and / or -SO ₄ ^" Na ⁺ and are characterized by special cleaning power and deposit-inhibiting effect.

Alternatively, phosphorus-containing starter / regulator systems may also be used, e.g. Hypophosphites / phosphinates.

The amounts of photoinitiator or starter / regulator system are to be matched to the substances used in each case. If, for example, the preferred system peroxodisulfate / hydrogen sulfite is used, then usually 2 to 6% by weight, preferably 3 to 5% by weight, of peroxodisulfate and generally 5 to 30% by weight, preferably 5 to 10% by weight .-%, hydrogen sulfite, in each case based on the total amount of monomers to be polymerized used.

If desired, polymerization regulators can also be used. Suitable compounds known to those skilled in the art, e.g. Sulfur compounds such as mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid and dodecylmercaptan. When polymerization regulators are used, their amount used is usually 0.1 to 15 wt .-%, preferably 0.1 to 5 wt .-% and particularly preferably 0.1 to 2.5 wt .-%, based on the total amount the monomers to be polymerized.

The temperature in the preparation of the polymers which can be used according to the invention is generally from 30 to 200 ^° C., preferably from 50 to 150 ^° C. and more preferably from 80 to 120 ^° C.

The polymerization may be carried out under atmospheric pressure, but is preferably carried out in a closed system under the evolving autogenous pressure.

In the preparation of the copolymers D to be used according to the invention, the monomers (1), (2) and (3) can be used as such, although it is also possible to use reaction mixtures which are obtained in the preparation of the monomers (3). For example, instead of methoxypolyethylene glycol methacrylate used in the esterification of polyethylene glycol monomethyl ether with an excess of methacrylic acid resulting monomer mixture. Advantageously, the esterification can also be carried out in situ in the polymerization mixture by adding acrylic acid, a mixture of methacrylic acid and polyethylene glycol monomethyl ether and free-radical initiator in parallel. If appropriate, a catalyst necessary for the esterification, such as methanesulfonic acid or p-toluenesulfonic acid, may additionally be used.

The copolymers D to be used according to the invention can also be obtained by polymer-analogous reaction, e.g. by reacting an acrylic acid / methacrylic acid copolymer with polyalkylene glycol monoalkyl ether. However, preferred is the radical copolymerization of the monomers.

If desired for the application, the aqueous solutions obtained in the preparation of the carboxylic acid group-containing copolymers to be used according to the invention can be neutralized or partially neutralized by adding base, in particular sodium hydroxide solution, i. adjusted to a pH in the range of 4-8, preferably 4.5-7.5.

The copolymers C and D used according to the invention are outstandingly suitable as an additive to dishwasher detergents. They are characterized mainly by their deposit-inhibiting effect against both inorganic and organic coatings. In particular, deposits which are caused by the other constituents of the cleaner formulation, such as deposits of calcium and magnesium phosphate, calcium and magnesium silicate, calcium and magnesium phosphonate, calcium and magnesium carbonate and deposits derived from the contaminants of the rinse, such as Fat, protein and starch deposits, called.

The copolymers used according to the invention thereby also increase the cleaning power of the dishwashing detergent. In addition, even at low concentrations, they facilitate the drainage of the water from the items to be washed, so that the proportion of rinse aid surfactants in the dishwashing detergent can be reduced.

The copolymers C and D used according to the invention can be used directly in the form of the aqueous solutions obtained in the preparation and in dried form obtained, for example, by spray drying, fluidized spray drying, drum drying or freeze drying. Component (E)

As component E, from 0 to 8% by weight, preferably from 0 to 7% by weight, more preferably from 0 to 6% by weight, of at least one polycarboxylate is present in the dishwashing detergent according to the invention. Suitable are homo- and copolymers of acrylic acid or methacrylic acid with monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid. A suitable polymer is in particular polyacrylic acid, which preferably has a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylic acid, which has molar masses of 2000 to 10,000 g / mol, in particular 3000 to 5000 g / mol, may be preferred from this group. Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and / or fumaric acid. Copolymers of acrylic acid with maleic acid, which contain 30 to 90% by weight of acrylic acid and 70 to 10% by weight of maleic acid, have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 1000 to 150000 g / mol, preferably from 1500 to 100000 g / mol and in particular from 2500 to 80 000 g / mol. The polycarboxylate present in the mixture according to the invention prevents the formation of calcium carbonate coatings.

Component (F)

The machine dishwashing detergent according to the invention contains as component (F) 1 to 50 wt .-%, preferably 2 to 45 wt .-%, particularly preferably 5 to 40 wt .-% of at least one complexing agent, preferably a chelating agent.

Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination site on a central atom, i. at least "bidentate". In this case, normally stretched compounds are closed by complex formation via an ion into rings. The number of bound ligands depends on the coordination number of the central ion.

Common and preferred chelating agents in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), methyleneglycinediacetic acid (MGDA) and glutamic diacetic acid (GLDA). It can also be used mixtures. Also, complex-forming polymers, ie polymers which carry functional groups either in the main chain themselves or laterally thereto, which can act as ligands and generally react with suitable metal atoms to form chelate complexes, can be used according to the invention , The polymer-bound Ligands of the resulting metal complexes can originate from only one macromolecule or belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.

Complexing groups (ligands) of conventional complex-forming polymers are imino-diacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, amidoxime, aminophosphoric acid, (cyclic) polyamino, mercapto, 1 , 3-dicarbonyl and crown ether radicals with sometimes very specific activities against ions of different metals. Base polymers of many also commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinylpyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided by polymer-analogous transformations with further ligand functionalities.

In the context of the present invention, all complexing agents of the prior art can be used. These can belong to different chemical groups. Preferably, used individually or in admixture with each other:

i) polycarboxylic acids in which the sum of the carboxyl and optionally

Hydroxyl groups is at least 5, such as gluconic acid, ii) nitrogen-containing monocarboxylic or polycarboxylic acids, such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriamine pentaacetic acid, hydroxyethyliminodiacetic acid, nitridodiacetic acid-3-propionic acid, isoindiniacetic acid, N, N-di ([beta] -hydroxyethyl) glycine, N- (1, 2-dicarboxy-2-hydroxyethyl) glycine, N- (1, 2-dicarboxy-2-hydroxyethyl) aspartic acid, nitrilotriacetic acid (NTA), methylene glycol diacetic acid (MGDA) or Glutamic diacetic acid (GLDA) iii) geminal diphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), the higher homologues of which have up to 8 carbon atoms and hydroxy- or amino-containing derivatives thereof and 1-aminoethane-1, 1- diphosphonic acid, the higher homologs of which have up to 8 carbon atoms, and hydroxy- or amino-containing derivatives thereof, iv) aminophosphonic acids, such as ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (m ethylenephosphonic acid) or nitrilotri (methylenephosphonic acid), v) phosphonopolycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid and also vi) cyclodextrins. At the alkaline pH values of the treatment solutions required according to the invention, the complexing agents are at least partially present as anions. It is irrelevant whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali metal, ammonium or alkylammonium salts, in particular sodium salts, are preferred.

In a particularly preferred embodiment, component (F) used is a complexing agent selected from the group consisting of nitrilotriacetic acid (NTA), methylene glycol diacetic acid (MGDA), glutamine diacetic acid (GLDA) and mixtures thereof.

Component (G)

The phosphate-free machine dishwashing detergent contains as component (G) 0.01 to 60 wt .-%, preferably 0.05 to 50 wt .-%, particularly preferably 0.1 to 40 wt .-% of at least one other additive. Suitable additives are selected from the group consisting of builders, enzymes, bleaches, bleach activators, dyes and fragrances, corrosion inhibitors, stabilizers such as antioxidants or UV absorbers, fillers, other surfactants and polymers, setting agents and tablet binders.

Builder

The automatic dishwashing detergents according to the invention contain builders. They may contain all builders commonly used in detergents and cleaners, in particular silicates, carbonates, zeolites, organic builders and co-builders such as citrates or polycarboxylates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + I} ^* y H ₂ O, wherein 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 are 2, 3 or 4. 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 [beta] - and [delta] sodium disilicates Na ₂ Si ₂ O ₅ ^* y H 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 are delay-delayed and have secondary washing properties. The dissolution delay compared to conventional amorphous sodium silicates can be achieved in various ways, for example by surface treatment, compounding, compacting or caused by overdrying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that the silicates in X-ray diffraction experiments do not give sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-radiation, which have a width of several degrees of the 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 of up to max. 50 nm and in particular up to max. 20 nm are preferred. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

The optionally usable finely crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P. As zeolite P zeolite MAP ^® (commercial product from Crosfield) is particularly preferred. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is marketed by CONDEA Augusta SpA under the trade name AX VEGOBOND ^® and by the formula (VII)

n Na ₂ O ^* (1-n) K ₂ O ^* .Al ₂ O ₃ ^* (2-2.5) SiO ₂ ^* (3.5-5.5) H ₂ O (VII)

can be described. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

The compositions according to the invention can furthermore contain carbonates and / or bicarbonates as builders. Among them, the alkali metal salts, especially sodium carbonate, are particularly preferred.

As organic cobuilders, it is possible in particular to use polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and phosphonates in the dishwasher detergents according to the invention. These 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 acids, 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 to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Likewise, further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives which, in addition to co-builder properties, also have a bleach-stabilizing effect.

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. Both maltodextrins with a DE of between 3 and 20 and dry glucose syrups with a DE of between 20 and 37 and also so-called yellow dextrins and white dextrins with molar masses in the range from 2000 to 30 000 g / mol are useful. 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 at C6 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.

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 ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral reacting sodium salts, e.g. as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP. 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 that are capable of forming complexes with alkaline earth ions can be used as co-builders.

enzymes

Agents according to the invention may contain enzymes to increase the washing or cleaning performance, and in principle all of them in the prior art for these

Purposes established enzymes can be used. These include in particular enzymes selected from the group consisting of proteases, amylases, lipases, hemicellulose lases, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin. Starting from the natural molecules, improved variants are available for use in detergents and cleaning agents, which are preferably used accordingly. Agents according to the invention preferably contain enzymes in total amounts of 1 ^× 10 ^-6 to 5% by weight, based on active protein The protein concentration can be determined by means of known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferable. Examples thereof are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg in a developed form under the trade names Alcalase ^® from Novozymes A / S, Bagsvaerd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase ^®, or Savinase ^® from Novozymes. From the protease from Bacillus lentus DSM 5483 derived under the name BLAP ^® variants are derived.

Other usable proteases are, for example, under the trade name Dura-zyme ^®, relase ^®, Everlase® ^®, Nafizym, Natalase ^®, Kannase® ^® and Ovozymes ^® from Novozymes, the rase under the trade names Purafect ^®, Purafect ^® OxP and Prope- ^® from Genencor, that under the trade name Wuxi ^® from Wuxi Snyder Bioproducts Ltd., China, under the trade name Protosol® ^® from Advanced Biochemicals Ltd., Thane, India, that under the trade name product leather ^® and Protease ^P® from Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.

Examples of amylases which can be used according to the invention are the amylases from Bacillus licheniformis, B. amyloliquefaciens or B. stearothermophilus and their further developments which are improved for use in detergents and cleaners. The enzyme from B. licheniformis is available from Novozymes under the name terma myl ^® and from Genencor under the name Purastar® ^® ST. Further development of these products amylase are available from Novozymes under the trade names Duramyl ^® and Termamyl ^® ultra, from Genencor under the name Purastar® ^® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ^® available. The alpha-amylase from B. amyloliquefaciens is marketed by Novozymes under the name BAN ^®, and variants derived from the amylase from B. stearothermophilus under the names BSG ^® and Novamyl ^®, likewise from Novozymes. Furthermore, for this purpose, the alpha-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948). In addition, the enhancements available under the trade names Fungamyl.RTM ^® by Novozymes of amylase from Aspergillus niger and A. oryzae, which are. Another commercial product is, for example, the amylase ^LT® .

Compositions according to the invention may contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases which were originally obtainable from Hupiculola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ^®, Lipolase Ultra ^®, LipoPrime® ^®, Lipozyme® ^® and Lipex ^®. Furthermore, for example, the cutinases can be used, which have been originally isolated from Fusarium solani pisi and Humicola insolens. Likewise useable lipases are available from Amano under the designations Lipase CE ^®, Lipase P ^®, Lipase B ^®, or lipase CES ^®, Lipase AKG ^®, Bacillis sp. ^Lipase® , Lipase ^AP® , Lipase M- ^AP® and Lipase ^{AML® are} available. From the company Genencor, for example, the lipases, or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Other important commercial products are the originally marketed by Gist-Brocades preparations M1 Lipase ^® and Lipomax® ^® and sold by the company Meito Sangyo KK, Japan, un- ter the names Lipase MY-30 ^®, Lipase OF ^® and lipase PL ^® to mention displaced enzymes, and also the product Lumafast ^® from Genencor.

Compositions according to the invention may contain further enzymes, which are summarized by the term hemicellulases. These include, for example, mannanose, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and [beta] -glucanases. Suitable mannanases, for example, under the name Gamanase ^® and Pektinex AR ^® from Novozymes, under the name Rohapec ^® B1 L from AB Enzymes and under the name Pyrolase® ^® from Diversa Corp., San Diego, CA, United States receives - lent. The obtained from B. subtilis [beta] -glucanase is available under the name Cereflo ^® from Novozymes.

To increase the bleaching effect, dishwashing agents according to the invention may contain oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases). Suitable commercial products Denilite® ^® 1 and 2 from Novozymes should be mentioned. Vorteilhafterwei- In addition, it is preferable to add organic, particularly preferably aromatic, compounds which interact with the enzymes, in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly differing redox potentials between the oxidizing enzymes and the soiling.

The enzymes used in agents according to the invention are either originally derived from microorganisms, such as the genera Bacillus, Streptomyces, Humicola or Pseudomonas, and / or are produced according to biotechnological processes known per se by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or filamentous fungi.

The purification of the relevant enzymes is carried out by conventional methods, for example by precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.

The agents of the invention may be added to the enzymes in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-form detergents, solutions of the enzymes, preferably as concentrated as possible, sparing in water and / or added with stabilizers. Alternatively, the enzymes can be used both for the solid and for encapsulating the liquid dosage form, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer. In deposited layers, it is additionally possible to apply further active compounds, for example stabilizers, emulsifiers, pigments, bleaches or dyes. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.

Furthermore, it is possible to assemble two or more enzymes together so that a single granule has several enzyme activities. A protein and / or enzyme contained in an agent according to the invention can be protected against damage, for example inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage, in particular during storage. In microbial recovery of proteins and / or enzymes is a Inhibition of proteolysis particularly preferred, especially if the agents contain proteases. Compositions according to the invention may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.

bleach

Among the compounds serving as bleaches in water H ₂ O ₂ , sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Detergents according to the invention may also contain bleaches from the group of organic bleaches. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaching agents are the peroxyacids, examples of which include the alkylpolyacids and the aryl peroxyacids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- [alpha] -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, [epsilon] -phthalimidoperoxycaproic acid [Phthaloiminoperoxyhexylic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamide-operadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1, 12-diperoxycarboxylic acid, 1, 9-

Diperoxyazelaic acid, diperocysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercaponic acid) can be used.

Chlorine or bromine-releasing substances can also be used as bleaching agents in the machine dishwashing detergents according to the invention. Examples of suitable chlorine or bromine-releasing materials are heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tiibromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium , Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable. Bleach activators

Bleach activators which aid in the action of bleaches may also be included in the compositions of this invention. Known bleach activators are compounds which contain one or more N- or O-acyl groups, such as substances from the class of the anhydrides, the esters, the imides and the acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.

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, 2,5-diacetoxy- 2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methylsulfate (MMA), and enol esters and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and Octaacetyllactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N- B. enzoylcaprolactam. Hydrophilically substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used.

In addition to or in place of the conventional bleach activators, so-called bleach catalysts can also be incorporated into the rinse aid particles. These substances are bleach-enhancing transition metal salts or transition-metal complexes such as manganese, iron, cobalt, ruthenium or molybdenum-salene complexes or carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanandium and copper complexes with nitrogen-containing tripod ligands and cobalt, iron, copper and ruthenium-amine complexes can also be used as bleach catalysts. Bleach activators from the group of the multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), are preferred. , n-methyl-morpholinium acetonitrile methyl sulfate (MMA).

Dyes and perfumes

Dyes and fragrances can be added to the machine dishwasher detergents according to the invention in order to improve the aesthetic impression of the resulting products and to provide the consumer, in addition to the performance, a visually and sensory "typical and unmistakable" product. As perfume oils or fragrances, 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, phenylethyl acetate, linalylbenzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes e.g. the linear alkanals having 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the ionones, isomethylionone and methyl cedryl ketone, the alcohols 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 such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. 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 as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil are also suitable.

The fragrances can be incorporated directly into the detergents according to the invention, but it can also be advantageous to apply the fragrances to carriers, which ensure a long-lasting fragrance by a slower release of fragrance. Cyclodextrins, for example, have proven useful as such carrier materials, with the cyclodextrin-perfume complexes additionally being able to be coated with further auxiliaries. In order to improve the aesthetic impression of the agents according to the invention, it (or parts thereof) can be dyed with suitable dyes. Preferred dyes have a high storage stability and insensitivity to the other ingredients of the agents and against light as well as no pronounced substantivity to the substrates to be treated with the agents such as glass, ceramic or plastic crockery, so as not to stain them.

corrosion inhibitors

The cleaning agents according to the invention may contain corrosion inhibitors for protecting 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, it is possible above all to use silver protectants selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes. Particular preference is given to using benzotriazole and / or alkylaminotriazole. In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface. In chlorine-free cleaners, especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. Hydroquinone, catechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogalol or derivatives of these classes of compounds. Also, salt and complex inorganic compounds, such as salts of the metals manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium 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, particularly preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt ( Carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds can be used to prevent corrosion on the items to be washed.

Preferred agents which are able to provide corrosion protection for glassware in the case of cleaning and / or rinsing processes of a dishwashing machine are selected from the group consisting of the compounds of zinc, aluminum, silicon, tin, magnesium, calcium, strontium, titanium, zirconium, Manganese and / or lanthanum. Of the compounds mentioned, the oxides are particularly preferred.

A preferred agent for providing corrosion protection for glassware during dishwashing and / or rinsing operations of a dishwashing machine is zinc in oxidized form, ie zinc compounds in which zinc is cationic. Similarly, magnesium salts are also preferred. This can be both soluble and bad or not soluble zinc or magnesium compounds are incorporated in the compositions of the invention. Preferred agents according to the invention comprise one or more magnesium and / or zinc salts of at least one monomeric and / or polymeric organic acid. The acids concerned 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 salts of monomeric and / or polymeric organic acids may be present in the polymer matrix according to the invention, as described above, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids are selected from the groups of unbranched saturated ones or unsaturated monocarboxylic acids, branched saturated or unsaturated monocarboxylic acids, saturated and unsaturated dicarboxylic acids, aromatic mono-, di- and tricarboxylic acids, sugar acids, hydroxy acids, oxo acids, amino acids and / or polymeric carboxylic acids. 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 (oenanthic 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), docanoic acid (behenic acid), tetracosanic acid (lignoceric acid), hexacosanoic acid (cerotic acid), triacotanoic acid (melissic acid), 9c-hexadecenoic acid (palmitoleic acid), 6c

Octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidinic 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 octadecatreic 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), 2-butenedioic acid (maleic acid), 2-t-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-carboxyphenylbenzoic 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-dihydroxybutanedioic 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, VaNn, 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 / inyl acrylate copolymers.

The spectrum of the inventively preferred zinc salts of organic acids, preferably organic carboxylic acids, ranges 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 those salts which have a solubility in water above 100 mg / L, preferably above 500 mg / L, more preferably above 1 g / L and in particular above 5 g / L (all Solubilities at 20 ^° C. water temperature). The first group of zinc salts includes, for example, 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 agents according to the invention comprise 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 benzoate and zinc oxalate are preferably used. To summarize, preferred automatic dishwashing agents additionally comprise one or more magnesium and / or zinc salts and / or magnesium and / or zinc complexes, preferably one or more magnesium and / or zinc salts of at least one monomer and / or polymeric organic acid.

The automatic dishwashing detergents according to the invention can be provided in all forms of supply known from the prior art, for example as powdered or granular detergents, as extrudates, pellets, flakes or tablets, preferably as tablets.

A further possibility of providing pre-portioned means is the packaging in water-soluble containers. The compositions according to the invention can be packaged in water-soluble packaging, for example pouches, deep-drawn parts, injection-molded parts, bottle-blowing parts, etc. Preferred automatic dishwasher detergents according to the invention are characterized in that they are packed in portions in a water-soluble casing, wherein the casing preferably contains one or more materials from the group of acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters and polyethers and mixtures thereof and preferably has a wall thickness of 10 to 5000 .mu.m, preferably from 20 to 3000 .mu.m, more preferably from 25 to 2000 .mu.m and in particular from 100 to 1500 .mu.m.

Particularly preferred automatic dishwashing detergents are characterized in that the water-soluble casing comprises a bag of water-soluble film and / or an injection molded part and / or a blow-molded part and / or a deep-drawn part, wherein the casing preferably contains one or more water-soluble polymer (s), preferably a material from the group (optionally acetalized) polyvinylalcohol poly (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and derivatives thereof and mixtures thereof, more preferably (optionally acetalized) polyvinyl alcohol (PVAL).

The above-mentioned polyvinyl alcohols are widely available commercially, for example, under the trademark Mowiol (Clariant).

Also preferred in the context of the present invention are agents whose packaging consists of at least partially water-soluble film of at least one polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose and mixtures thereof.

Particulate detergents according to the invention, preferably those packaged in transparent sachets, may contain a stabilizing agent as further constituent. Stabilizing agents in the context of the invention are materials which protect the detergent components in their water-soluble, transparent bags against decomposition or deactivation by light irradiation. Antioxidants, UV absorbers and fluorescent dyes have proven to be particularly suitable here.

Particularly suitable stabilizing agents in the context of the invention are the antioxidants. In order to prevent undesirable changes in the formulations caused by light irradiation and thus radical decomposition, the formulations may contain antioxidants.

Examples of antioxidants which may be used here are sterically hindered groups, substituted phenols, bisphenols and thiobisphenols. Further examples are propyl gallate, butylated hydroxytoluene (BHT), butylhydroxyanisole (BHA), t-butylhydroquinone (TBHQ), tocopherol and the long chain (C8-C ₂₂₎ esters of gallic acid such as dodecyl gallate. Other classes of compounds are aromatic amines, preferably secondary aromatic amines and substituted p-phenylenediamines, phosphorus compounds with trivalent phosphorus such as phosphines, phosphites and phosphonites, citric acids and citric acid derivatives such as isopropyl citrate, endiol group-containing compounds, so-called reductones, such as ascorbic acid and its derivatives , such as ascorbic palmitate, organosulfur compounds, such as the esters of 3,3 "-thiodipropionic acid with ds-alkanols, especially ci- ₁₈ -alkanols, metal ion deactivators capable of auto-oxidation catalyzing metal ions, such as copper complex, such as nitrilotriacetic acid and its derivatives and their mixtures.

Another class of preferably usable stabilizers are the UV absorbers. UV absorbers can improve the light stability of the formulation ingredients. representation Under are organic substances (sunscreen) to understand, which are able to absorb ultraviolet rays and the absorbed energy in the form of longer-wave radiation, eg heat to give back. Compounds which have these desired properties are, for example, the compounds which are active by radiationless deactivation and derivatives of benzophenone having substituents in the 2- and / or 4-position. In addition, substituted benzotriazoles, such as the water-soluble sodium salt of 3- (2N-benzotriazol-2-yl) -4-hydroxy-5- (methylpropyl) monosodium salt (Ciba ^® Fast H), phenyl-substituted in the 3-position acrylamide te ( Cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the endogenous uronic acid. The biphenyl and especially stilbene derivatives which are available commercially as Tinosorb ^® FD or Tinosorb ^® FR available ex Ciba. As UV-B absorber are to call 3-Benzylidencampher or 3-Benzylidennorcampher and its derivatives, eg. B. 3- (4-methylbenzylidene) camphor; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and 4- (dimethylamino) benzoic acid amyl ester; Esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester, 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene); Esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomenthyl salicylate; Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate; Triazine derivatives such as 2,4,6-trianilino (p-carbo-2'-ethyl-1 '-hexyloxy) -1, 3,5-triazine and octyl triazone or dioctyl butamido triazone (Uvasorb (R) HEB); Propane-1,3-diones such as 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione; Ketotricyclo (5.2.1.0) decane-Dervate. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts; Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts; Sulfonic acid derivatives of 3-Benzylidencamphers, such as 4- (2-oxo-3-bomylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and salts thereof.

As a typical UV-A filter in particular derivatives of benzoylmethane come into question, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1, 3-dione, 4-tert-butyl 4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione and enamine compounds. Of course, the UV-A and UV-B filters can also be used in mixtures. In addition to the soluble substances mentioned, insoluble photoprotective pigments, namely finely dispersed, preferably nano-metal oxides or salts, are also suitable for this purpose. Examples of In particular, metal oxides are zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium, and mixtures thereof. As salts silicates (talc), barium sulfate or zinc stearate can be used. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They may have a spherical shape, but it is also possible to use those particles which have an ellipsoidal or otherwise deviating shape from the spherical shape. The pigments can also be surface-treated, ie hydrophilized or hydrophobized. Typical examples are coated titanium dioxides, for example Titandioxid T 805 (Degussa) or Eusolex ^® T2000 (Merck). Suitable hydrophobic coating agents are in particular silicones and in particular trialkoxyoctylsilanes or simethicones. Preferably, micronized zinc oxide is used.

Another preferred class of stabilizers to be used are the fluorescent dyes. These include the 4,4 "diamino-2,2" -stilbene disulfonic acids (fumaric acids), 4,4'-distyrylbiphenyls, methyl umbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic imides, benzoxazole- , Benzisoxazole and benzimidazole systems as well as heterocyclic substituted pyrene derivatives. Of particular importance are the sulfonic acid salts of diaminostilbene derivatives, as well as polymeric fluorescers.

In a preferred embodiment, the abovementioned stabilizers are used in any mixtures.

fillers

The storage density of the composition according to the invention can be adapted to the specific uses by adding fillers. Suitable fillers are selected from the group consisting of sucrose, sucrose esters, sodium sulfate and potassium sulfate. A preferred filler is sodium sulfate.

In a preferred embodiment, the dishwashing detergent according to the invention contains 2-10% by weight of component (A), 0.1-5% by weight of component (B), if present, 2-10% by weight of component (C), if 2 to 10% by weight of component (D), if present, 2 to 10% by weight of a polycarboxylate (E), 5 to 40% by weight of component (F) and 1 to 40% by weight of component ( G), wherein the sums of the components (A), (B), (C), (D), (E), (F) and (G) gives 100 wt .-%. The present invention also relates to a method for rinsing surfaces, preferably hard surfaces, in particular cutlery, glasses, dishes and kitchen accessories, by treating these surfaces with the dishwashing agent according to the invention.

The surfaces to be treated are made of at least one material selected from the group consisting of ceramics, stoneware, porcelain, wood, plastic, glass and a metal or a metal alloy, such as silver, metal, copper, bronze and / or brass.

The present invention also relates to the use of the dishwashing agent according to the invention for increasing the rinsing performance in the machine rinsing of objects.

Examples:

All examples are carried out with a basic formulation of the following compositions:

20% by weight of methylglycinediacetic acid trisodium salt

30% by weight sodium citrate + 5.5% water

25% by weight of sodium carbonate

6 wt .-% sodium disilicate

15% by weight of sodium percarbonate

4% by weight of tetraacetylethylenediamine

Inventive surfactants

Example 1: Hexanol + 5 EO

408 g of n-hexanol are charged with 1.5 g of NaOH in a dry 2 l autoclave. The autoclave contents are heated to 150 ^° C. and 880 g of ethylene oxide are pressed under pressure into the autoclave. After the total amount of ethylene oxide is in the autoclave, the autoclave for 30 minutes at 150 ⁰ C is maintained. After cooling, the catalyst is neutralized with acetic acid. The unreacted n-hexanol is distilled off.

The surfactant obtained has a cloud point of 72 ⁰ C, measured 1% in 5% saline solution according to EN 1890, method B on. The surface tension at a concentration of 1 g / l and a temperature of 23 ⁰ C is 52.3 mN / m, measured according to DIN 53914. The residual content of n-hexanol is 0.1 wt .-%.

Example 2: i-C10 oxoalcohol + 10 EO + 1.5 PeO

395 g of i-Cio-oxo-alcohol are charged with 1, 8 g of NaOH in a dry 2 l autoclave. The autoclave contents are heated to 150 ^° C. and 1 100 g of ethylene oxide are pressed under pressure into the autoclave. After the total amount of ethylene oxide is in the autoclave, the autoclave for 30 minutes at 150 ⁰ C is maintained. Subsequently, 322 g of pentenoxide are pressed under pressure into the autoclave. After the entire Pentenoxidmenge is in the autoclave, the autoclave for 180 minutes at 150 ⁰ C. After cooling, the catalyst is neutralized with acetic acid.

The surfactant obtained has a cloud point of 38 ⁰ C, measured 1% in 10% butyl diglycol solution according to EN 1890, method E on. The surface tension at a concentration of 1 g / l and a temperature of 23 ⁰ C is 30.7 mN / m, measured according to DIN 53914.

Example 3: C10-C12 fatty alcohol + 9 EO + 5 PO

344 g of C10-C12 fatty alcohol are charged with 1.5 g of NaOH in a dry 2 l autoclave. The autoclave contents are heated to 150 ^° C. and 580 g of propylene oxide are pressed under pressure into the autoclave. After the entire amount of propylene oxide is in the autoclave, the autoclave is kept at 150 ^° C. for 30 minutes. Subsequently, 792 g of ethylene oxide are pressed under pressure into the autoclave. After the total amount of ethylene oxide is in the autoclave, the autoclave for 180 minutes at 150 ⁰ C is maintained. After cooling, the catalyst is neutralized with acetic acid.

The surfactant obtained has a cloud point of 70 ^° C., measured at 1% strength in 10% strength butyl diglycol solution according to EN 1890, Method E. The surface tension at a concentration of 1 g / l and a temperature of 23 ⁰ C is 29.5 mN / m, measured according to DIN 53914.

Example 4

In a reactor with nitrogen feed, reflux condenser and metering device, a mixture of 612 g of distilled water and 2.2 g of phosphorous acid is heated under nitrogen and stirring from 100 ⁰ C internal temperature. Then were parallel

(1) a mixture of 123.3 g of acrylic acid and 368.5 g of distilled water, (2) a mixture of of 18.4 g of sodium peroxodisulfate and 164.6 g of distilled water, (3) a mixture of 72.0 g of water, 49.1 g of methacrylic acid and 166.9 g of methoxypolyethylene glycol methacrylate (Mw = 1100) and (4) 46 g of a 40% strength by weight aqueous solution Sodium bisulfite solution added continuously in 5 h. After two hours of stirring at 100 ⁰ C, the reaction mixture was cooled to room temperature and adjusted by the addition of 190 g of 50 wt .-% sodium hydroxide solution from a pH of 7.2.

There is obtained a slightly yellowish, clear solution of a copolymer having a solids content of 25.7 wt .-% and a K value of 27.2 (1 wt .-% aqueous solution, 25 ⁰ C).

Example 5

In a reactor with nitrogen supply, reflux condenser and metering device, a mixture of 2248 g of distilled water is heated under nitrogen and stirring to 100 ⁰ C internal temperature. Then, in parallel, (1) a mixture of 767 g of acrylic acid and 1100 g of distilled water, (2) a mixture of 82.2 g of sodium peroxodisulfate and 1092 g of distilled water and (3) 1680 g of methacrylic acid are added continuously in 2.5 hours , After two hours of stirring at 100 ⁰ C the reaction is onsgemisch cooled to 60 ⁰ C and adjusted by the addition of 2400 g of distilled water to a solids content of 25%. The product has a viscosity (Brookfield LVT, spindle 2, 30 s-1) of 65 mPas.

All Klarspülversuche be in a dishwasher of the Fa. Miele (Type G 670) at 55 ⁰ C in the saving program with synthetic Ca-hardness of 21 ° dH water. No separate rinse aid is added and the built-in water softener (ion exchanger) is not regenerated with regenerating salt. The test dishes used in each cleaning cycle are knives made of Cromargan, black plastic plates made of ASA material), drinking glasses and lids of freezer boxes (EMSA) made of polyethylene.

After completion of the Spülzyklusses this crockery is visually graded and assessed on a scale from 1 (= strong residues) to 5 (= no residue) in terms of stains, stripes and film-like coverings. Inventive Experiments 1 to 4; Experiments V1, V2 and V3 are comparative experiments

Weighed in g per cleaning cycle

Claims

claims

1. Phosphate-free machine dishwashing detergent containing

R ¹ - (OCH ₂ CHR ² ) _x (OCH ₂ CHR ³ ) _y -OR ⁴ (I)

With

R ¹ : linear or branched C ₆ -C ₂₄ -alkyl radical,

R ² , R ³ : independently of one another, different hydrogen, linear or branched C 1 -C 6 -alkyl radical,

R ⁴ : hydrogen, linear or branched Ci-Cβ-alkyl radical. x, y: independently mean value in the range of 0.5-80,

(B) 0.01-10% by weight of at least one alcohol ethoxylate of the general formula (II)

R ⁵ - (OCH ₂ CH ₂ ) _Z OH (II)

With

R ⁵ : linear or branched C ₄ -Cs-Al ky I rest and z: average value of 2 - 10, wherein the content of residual alcohol

R ⁵ is -OH less than 1 wt .-% by weight,

(C) 0-15% by weight of at least one sulfonate group-containing polymer,

(D) 0-15% by weight of at least one hydrophilic modified polycarboxylate,

(E) 0-8% by weight of at least one polycarboxylate,

(F) 1 - 50 wt .-% of at least one complexing agent and

(G) 0.01-60% by weight of at least one further additive,

2. Composition according to claim 1, characterized in that in component (A) R ^{1 is} a linear or branched C ₈ -C ₈ -alkyl radical, R ² and R ^{3 are} independently hydrogen, methyl, ethyl or propyl and x and y independently from each other have a mean value of 0.5 to 20.

3. Composition according to claim 1 or 2, characterized in that component (C) is a copolymer comprising the following monomers

(I) 50-98% by weight of one or more weak acids,

(II) 2-50% by weight of one or more unsaturated sulfonic acid monomers selected from the group consisting of 2-acrylamidomethyl-1-propane-sulfonic acid, 2-methacrylic acid-2-methyl-1-propanesulfonic acid, 3-methacrylamido 2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid,

2-Hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethylacrylamide, sulfomethylmethacrylamide, and water-soluble salts thereof, (III) -30% by weight of one or more monoethylenically unsaturated C ₄ -

C ₈ dicarboxylic acids and

(IV) 0-30% by weight of one or more monoethylenically unsaturated monomers polymerizable with (I), (II) and (III),

wherein the total of monomers (I), (II), (III) and (IV) corresponds to 100% by weight of the copolymer.

4. Composition according to one of claims 1 to 3, characterized in that as component (D) alkylene oxide units containing copolymers are used, composed of (1) 50 to 93 mol% of acrylic acid and / or a water-soluble salt of acrylic acid, ( 2) 5 to 30 mol% of methacrylic acid and / or a water-soluble salt of methacrylic acid and (3) 2 to 20 mol% of at least one nonionic monomer of formula VI

H ₂ C = C (R ¹⁶ ) -C (= O) -OR ¹⁷ - [- R ¹⁸ -O-] _s -R ¹⁹ (VI),

in which the variables have the following meaning: R ^{16 is} hydrogen or methyl,

R ^{17 is} a chemical bond or unbranched or branched C 1 -C 6 -alkylene, R ¹⁸ identical or different unbranched or branched C ₂ -C ₄ -

alkylene

R ^{19 is} unbranched or branched C ₁ -C ₆ -alkyl; s 3 to 50, wherein components (1), (2) and (3) are randomly or blockwise copolymerized.

5. Composition according to one of claims 1 to 4, characterized in that as component (F) a complexing agent selected from the group consisting of nitrilotriacetic acid (NTA), Methylenglycindiessigsäure (MGDA), Glutamindiessig- acid (GLDA) and mixtures thereof, used becomes.

6. Composition according to one of claims 1 to 5, characterized in that the additive is selected from the group consisting of builders, enzymes, bleaches, bleach activators, dyes and fragrances, corrosion inhibitors, stabilizers such as antioxidants or UV absorbers, Fillers, other tensides and polymers, setting agents and tablet binders.

7. Composition according to one of claims 1 to 6, characterized in that it contains 2 - 10 wt .-% component (A), 0.1 - 5 wt .-% component (B), if present, 2-10

% By weight of component (C), if present, 2-10% by weight of component (D), if present, 2 to 10% by weight of a polycarboxylate (E), 20 to 55% by weight of component (F) and 1 to 40 wt .-% component (G), wherein the sums of the components (A), (B), (C), (D), (E), (F) and (G) 100 wt. -% results.

8. A method for rinsing hard surfaces of articles by treating these surfaces with the agent according to one of claims 1 to 7.

9. The method according to claim 8, characterized in that the surfaces of at least one material selected from the group consisting of ceramic,

Earthenware, porcelain, wood, plastic, glass, metal and a metal alloy exist.

10. Use of the agent according to one of claims 1 to 7 for increasing the rinsing performance in the machine rinsing of objects.