WO2005097957A1 - Dishwasher rinse aid - Google Patents

Abstract

The invention relates to dishwasher rinse aid containing between 0.5 and 12 wt. % of a surfactant system comprising c) at least one non-ionic surfactant F of general formula: R1-CH(OH)CH2O-(AO)w (A'O)X (A'O)y-(A '' 0)z,-R 2, wherein R1 represents a linear or branched, saturated or monounsaturated or polyunsaturated C6-24 alkyl or alkenyl radical, R2 represents a linear or branched hydrocarbon radical containing between 2 and 26 carbon atoms, A, A', A' and A' independently represent a radical from the group -CH2CH2, -CH2CH2-CH2, -CH2-CH(CH3), -CH2-CH2-CH2-CH2, -CH2-CH(CH3)-CH2-, -CH2-CH(CH2-CH3), w, x, y and z represent values between 0.5 and 25, and x, y and/or z can also be 0; and d) at least one non-ionic surfactant G of general formula: R1-O-(AO)w (A'O)x (A'O)Y (A'' 0)z,-R 2, wherein R1 represents a linear or branched, saturated or monounsaturated or polyunsaturated C6-24 alkyl or alkenyl radical, R2 represents H or a linear or branch hydrocarbon radical containing between 2 and 26 carbon atoms, A, A', A' and A' independently represent a radical from the group -CH2CH2, -CH2CH2-CH2, -CH2-CH(CH3), -CH2-CH2-CH2-CH2, -CH2-CH(CH3)-CH2-, -CH2-CH(CH2-CH3), w, x, y and z represent values between 0.5 and 25, and y and/or z can also represent 0; said surfactant system containing the non-ionic surfactants F and G in a weight ratio of F:G of between 1:4 and 100:1. The inventive rinse aid is characterised by an improved rinsing performance compared to conventional rinse aid.

Description

Machine dishwashing detergent

This application relates to detergents or cleaners. In particular, this application relates to surfactant-containing detergents or cleaners.

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

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

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

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

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

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

Although a number of different approaches have been described in the prior art for achieving sufficient rinse aid results, there remains a need to improve upon previous means, particularly with regard to improved rinse aid results at low temperatures and use of reduced amounts of automatic dishwashing detergent. It is an object of the present invention to provide machine dishwashing detergents with a rinse aid rinse function which achieve performance advantages with respect to their performance properties compared to commercially available rinse aids. The new dishwashing detergents should unfold their cleaning and rinsing performance independently of the preparation form, in particular without the addition of high-melting additives. Furthermore, the new automatic dishwashing detergents should be distinguished from conventional detergents by improved shelf life and processability.

It has now been found that such automatic dishwashing detergents provide above average cleaning and rinse-aid results which contain as part of a specific surfactant system.

A first subject of the present application is therefore a machine dishwashing detergent comprising from 0.5 to 12% by weight of a surfactant system of a) at least one nonionic surfactant F of the general formula R ^{1 is} -CH (OH) CH ₂ O- (AO) _w - (AO) _x - (A "O) _y - (A" O) _z -R ² in which

R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂ alkyl or alkenyl radical; R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ), w, x, y and z represent values between 0.5 and 25, where x , y and / or z can also be 0; and b) at least one nonionic surfactant G of the general formula

R ¹ -O- (AO) _w - (AO) _x - (A "0) _y - (A '" 0) _z -R ² in which

R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂ alkyl or alkenyl radical; R ^{2 is} H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; - A, A ', A "and A'" independently of one another are radicals from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ - CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ), w, x, y and z represent values between 0.5 and 25, wherein y and / or z can also be 0; wherein the surfactant system comprises the nonionic surfactants F and G in a weight ratio of F: G between 1: 4 and 100: 1.

For the purposes of the present application, solid or liquid additives for machine dishwashing are referred to as "automatic dishwashing detergent." The group of automatic dishwashing detergents therefore includes, for example, the compact automatic dishwashing detergents with combined cleaning and rinsing function ("2 in 1" products) as well as the compact automatic dishwashing detergent with combined cleaning, rinsing and desalting function ("3 in 1" products) or the simple, separately dosed rinse aid.

A first essential constituent of the surfactant systems according to the invention are the hydroxylated nonionic surfactants F of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A "'0) _z -R ² in which R ¹ is a straight or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical; R ² for a linear or branched hydrocarbon residue having 2 to 26 carbon atoms; A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ - CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ); and w, x, y and z are values between 0.5 and 25, where x, y and / or z can also be 0.

Such nonionic surfactants can be prepared, for example, by reacting an epoxide of the general formula R ¹ -CH (O) CH ₂ in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂₄ -alkyl or -Alkenylrest stands with an alcohol of the general formula HO- (AO) _w - (A'0) _x - (A "0) _y - (A '" 0) _z -R ² , in which R ² is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ); and w, x, y and z are values between 0.5 and 25, where x, y and / or z can also be 0, are reacted under the action of a catalyst.

A particularly preferred embodiment of the present application comprises automatic dishwashing agents, characterized in that it comprises, as nonionic surfactant (s) F, a nonionic surfactant of the general formula

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

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

The indicated C chain lengths and degrees of alkoxylation represent statistical averages, which may be an integer or a fractional number for a particular product. Due to the production process, commercial products of the formulas mentioned mostly do not consist of an individual representative but of mixtures, which may result in mean values for the C chain lengths as well as the degrees of alkoxylation and, consequently, fractional numbers. In the table below, particularly preferred nonionic surfactants present in the agents according to the invention are characterized with respect to the radicals R ¹ and R ² and the indices x and y. Preferred agents according to the invention comprise one or more surfactants from the table below or mixtures of these.

In this application, particular preference is given to those nonionic surfactants F of the general formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² , in which R ¹ , for is a saturated, unbranched aliphatic hydrocarbon radical having 8 to 12 carbon atoms, preferably having 8 to 10 carbon atoms, further R ^{2 is} a saturated, linear hydrocarbon radical having 8 to 12 carbon atoms, preferably with 8 hydrocarbon radicals, and in which x is 1 or 2, while y stands for values between 18 and 24, preferably for values from 20 to 24.

Another particularly preferred embodiment of the present application comprises automatic dishwashing agents which contain, as nonionic surfactant (s) F, a nonionic surfactant of the general formula

R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) R ² in which R ^{1 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ² is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably have between 1 and 5 hydroxyl groups and are preferably further functionalized with an ether group, R ^{3 is} H or a methyl, ethyl, n Is propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl and x is between 1 and 40.

In the context of this application, particular preference is furthermore given to automatic dishwasher detergents, characterized in that they contain, as nonionic surfactant (s) F, a nonionic surfactant of the general formula

R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² containing, in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, further a linear or branched, saturated or unsaturated, aliphatic or aromatic Hydrocarbon radical having 1 to 30 carbon atoms R ² , which is a monohydroxylated intermediate group - CH ₂ CH (OH) - adjacent and in which x stands for values between 1 and 90.

With particular preference, the present application claims such automatic dishwashing detergents which nonionic (s) surfactant (s) of the general formula

R ¹ 0 [CH ₂ CH ₂ 0] _x CH ₂ CH (OH) R ² , which in addition to a radical R ¹ , for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably with 4 to 22 carbon atoms, further comprising a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having 1 to 30 carbon atoms, preferably 2 to 22 carbon atoms, which is a monohydroxylated intermediate group -CH ₂ CH (OH) - adjacent and where x is between 40 and 80, preferably between 40 and 60.

The indicated C chain lengths and degrees of alkoxylation represent statistical averages, which may be an integer or a fractional number for a particular product. Due to the production process, commercial products of the formulas mentioned mostly do not consist of an individual representative but of mixtures, which may result in mean values for the C chain lengths as well as the degrees of alkoxylation and, consequently, fractional numbers. In the table below, particular preference is given to nonionic surfactants contained in the agents according to the invention with respect to the radicals R ¹ and R ² and the index x. Preferred agents according to the invention comprise one or more surfactants from the table below or mixtures of these.

Especially those nichtionschen surfactants F of the general formula R are preferred in this application ¹ 0 [CH ₂ CH ₂ 0] _x CH ₂ CH (OH) R ² in which R ^1, a saturated, unbranched aliphatic hydrocarbon radicals having 8 to 12 carbon atoms , preferably having 10 carbon atoms, furthermore R ^{2 stands} for a saturated, linear hydrocarbon radical with 8 to 12 carbon atoms, preferably with 8 hydrocarbon radicals, and in which x stands for values between 14 and 26, preferably for values from 20 to 24.

In the context of the present application, preference is furthermore given to those automatic dishwasher detergents which contain, as nonionic surfactant (s) F, a nonionic surfactant of the general formula

R ¹ 0 [CH ₂ CH ₂ O] _x [CH ₂ CHO] _y CH ₂ CH (OH) R ²

R ³ in which R ¹ and R ² independently of one another are a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ ; -CH ₂ CH ₃ , - CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ , but preferably is -CH ₃ , and x and y are independent CH (CH ₃ ) ₂ , but preferably represents -CH ₃ , and x and y independently of one another represent values between 1 and 32, with nonionic surfactants having values of x of 15 to 32 and y of 0.5 and 1.5 are particularly preferred.

As a further essential constituent, the surfactant systems of the invention comprise a nonionic surfactant G of the general formula R ¹ -O- (AO) _w - (A'O) _x - (A "O) _y - (A '" O) _z -R ² , in the R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂₄ - alkyl or alkenyl radical; R ^{2 is} H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A, A ', A "and A'" independently represent a group from the group

-CH ₂ CH _2, -CH ₂ CH ₂ -CH _2, -CH ₂ -CH (CH 3), -CH ₂ -CH2-CH2-CH2, -CH ₂ -CH (CH 3) -CH ₂ -, -CH ₂ -CH (CH ₂ - CH ₃ ); and w, x, y and z are values between 0.5 and 25, where y and / or z can also be 0.

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

R ¹ -O- (CH ₂ -CH ₂ -O) _w - (CH ₂ -CH-O) _x - (CH ₂ -CH ₂ -O) _y - (CH ₂ -CH-O) _z -HIR ² R ³

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

The preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in the above formula may vary depending on the origin of the alcohol. When native sources are used, the radical R ^{1 has} an even number of carbon atoms and is usually undisplayed, the linear radicals being selected from alcohols of native origin having 12 to 18 C atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred. Alcohols accessible from synthetic sources are, for example, the Guerbet alcohols or methylated in the 2-position. branched or linear and methyl-branched radicals in the mixture, as they are usually present in Oxoal- koholresten. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions according to the invention, automatic dishwasher detergents according to the invention are preferred in which R ¹ in formula I is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.

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

In summary, nonionic surfactants are particularly preferred for use in the inventive compositions, the C ₉ . ₁₅ alkyl having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units. These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.

The stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation represent statistical averages, which may be an integer or a fractional number for a particular product. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers. In the table below, particularly preferred nonionic surfactants present in the agents according to the invention are characterized with respect to the radical R ¹ , the radicals R ² and R ³ and the indices w, x, y and z. Preferred agents according to the invention comprise one or more surfactants from the table below or mixtures of these.

As described above, the surfactant system according to the invention comprises two nonionic surfactants F and G. Of course, however, the automatic dishwashing detergent according to the invention may also contain further nonionic or ionic surfactants.

In the context of this application, particular preference is given to those automatic dishwashing detergents which contain a nonionic surfactant F of the general formula R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² in which R ^{1 is} a saturated, unbranched aliphatic Hydrocarbon radicals having 8 to 12 carbon atoms, preferably having 10 carbon atoms, furthermore R ^{2 stands} for a saturated, linear hydrocarbon radical having 8 to 12 carbon atoms, preferably with 8 hydrocarbon radicals, and in which x for values between 14 and 26, preferably for values of 20 to 24 is in combination with a nichionic surfactant G of the general formula

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

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

In the context of this application, further preference is given to those automatic dishwashing compositions which comprise a nonionic surfactant F of the general formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² in which R ¹ , represents a saturated, unbranched aliphatic hydrocarbon radical having 8 to 12 carbon atoms, preferably having 8 to 10 carbon atoms, further R ^{2 is} a saturated, linear hydrocarbon radical having 8 to 12 carbon atoms, preferably with 8 hydrocarbon radicals, and wherein x stands for values of 1 or 2, while y stands for values between 18 and 24, preferably for Values of 20 to 24 are in combination with a nonionic surfactant G of the general formula

R ¹ -O- (CH ₂ -CH ₂ -O) _w - (CH ₂ -CH-O) _x - (CH ₂ -CH ₂ -O) _y - (CH ₂ -CH-O) _z -HIR ² R ³

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

Preferred automatic dishwashing detergents are characterized in that the surfactant system comprises the nonionic surfactants F and G in a weight ratio of F: G between 2: 9 and 90: 1, preferably between 1: 3 and 80: 1, preferably between 3: 7 and 70: 1, more preferably between 7:13 and 60: 1 and in particular between 2: 3 and 50: 1.

The automatic dishwashing compositions of the invention may contain as optional ingredient a polymer having a molecular weight of 2000 gmol ^-1 or above which has at least one positive charge.

In the context of the present application, preference is given to those automatic dishwashing detergents which, based in each case on the total weight of the automatic dishwashing detergent, are between 0.01 and 10% by weight, preferably 0.01 and 8% by weight, preferably between 0.01 and 6 wt .-%, particularly preferably between 0.01 and 4 wt .-%, most preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, each based on the total weight of the automatic dishwashing detergent, containing a polymer having a molecular weight of 2000 gmol ^-1 or above, which has at least one positive charge.

The above positive charge polymers may in principle be cationic or amphoteric polymers. Preferred machine dishwashing detergents according to the invention are characterized in that the polymer comprising cationic monomer units is a cationic polymer and / or an amphoteric polymer.

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

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

Machine dishwashing detergent, characterized in that it contains a polymer having a molecular weight of 2000 gmol ^-1 or above, which has at least one positive charge, which monomer units of the formula R ¹ R ² C = CR ³ R ⁴ , in which each radical R ¹ , R ² , R ³ , R ^{4 are} independently selected from hydrogen, derivatized hydroxy group, C1 to C30 linear or branched alkyl groups, aryl, aryl substituted C ^ o linear or branched alkyl, polyalkoyxylierte alkyl groups, heteroatomic organic groups at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one amino group with a positive charge in the partial range of the pH range from 2 to 11, or salts thereof, with the proviso that at least one radical R ¹ , R ² , R ³ , R ^{4 is} a heteroatomic organic group having at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one amino group having a positive charge, are particularly preferred in the context of the present application.

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

R ¹ R ² R ⁴ IIIH ₂ C = C- (CH ₂ ) _x -N ⁺ - (CH ₂ ) _y -C = CH ₂ X ^" (I), IR ³

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

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

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

H ₂ C = CH- (CH ₂ ) -N ⁺ (CH ₃ ) ₂ - (CH ₂ ) -CH = CH ₂ X ^"

are referred to in the case of X = ^~ chloride as a DADMAC (diallyldimethylammonium chloride).

Further cationic or amphoteric polymers which are particularly preferred for the purposes of the present application comprise a monomer unit of the general formula (II)

R ¹ HC = CR ² -C (O) -NH- (CH ₂ ) _x -N ⁺ R ³ R ⁴ R ⁵ X ^- (II)

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

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

H ₂ C = C (CH ₃ ) -C (O) -NH- (CH 2) _X -N ⁺ (CH ₃ ) 3 X ^- In the case of X ^" = chloride also referred to as MAPTAC (Methyacrylamidopropyl- trimethylammonium chloride).

Automatic dishwashing detergents which are preferred according to the invention are characterized in that the polymer having a molar mass of 2000 gmol ^-1 or above which has at least one positive charge contains diallyldimethylammonium salts and / or acrylamidopropyltrimethylammonium salts as monomer units.

The aforementioned amphoteric polymers have not only cationic groups but also anionic groups. Such anionic Monomereinheinheiten originate for example from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates or linear or branched, saturated or unsaturated sulfonates. Preferred monomer units are acrylic acid, (meth) acrylic acids, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylessingic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids.

Preferred usable amphoteric polymers are from the group of alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacryla mid / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationic de vatisierten unsaturated carboxylic acids and optionally further ionic or nonionogenic monomers.

Preferably usable zwitterionic polymers are selected from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the methacroylethylbetaine / methacrylate copolymers.

Also preferred are amphoteric polymers which comprise, in addition to one or more anionic monomers as cationic monomers Methacrylamidoalkyl-trialkylammonium chloride and dimethyl (diallyl) -ammonium chloride. Particularly preferred amphoteric polymers are selected from the group of methacrylamidoalkyl trialkyl ammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, methacrylylamidoalkyl trialkyl ammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers and their alkali metal and ammonium salts.

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

In a particularly preferred embodiment of the present invention, the polymers contained in the agents according to the invention have a molecular weight of 2000 gmol ^-1 or above in prefabricated form the encapsulation of the polymers by means of water-insoluble, meltable coating compositions, preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 ° C., the co-granulation of the polymers with inert support materials, preferably with support materials from the group of washing or cleaning-active substances, particularly preferably from the group of builders (builders) or cobuilders.

All of these products contain, as a first essential constituent, one or more polymers having a molecular weight of 2000 gmol ^-1 or more, which have at least one positive charge The compositions according to the invention in this case have a weight fraction of these polymers between 0 However, within the scope of the present application, preference is given to those automatic dishwashing detergents in which the weight fraction of the polymer a) is between 0.01 and 8% by weight, in each case based on the total weight of the automatic dishwashing detergent. preferably between 0.01 and 6 wt .-%, preferably between 0.01 and 4 wt .-%, particularly preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, respectively based on the total weight of the automatic dishwashing detergent. The preferred subject matter of the present application is therefore a machine dishwashing detergent comprising from 0.5 to 12% by weight of a surfactant system of a) at least one nonionic surfactant F of the general formula

R ^{1 is} -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A" O) _z -R ² in which

R ¹ is a straight or branched, saturated or mono- or polyunsaturated C ₆ - ₂ alkyl or alkenyl radical; R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A, A ', A "and A'" independently of one another are radicals from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ "CH (CHs), -CH ₂ -CH ₂ - CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ), w, x, y and z represent values between 0.5 and 25, where x, y and / or z can also be 0, and b) at least one nonionic surfactant G of the general formula

R ¹ -O- (AO) _w - (A'0) _x - (A "0) _y - (A '" 0) _z -R ² in which

R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂₄ alkyl or alkenyl radical; R ^{2 is} H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A, A ', A "and A'" independently of one another are radicals from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CHs), -CH ₂ -CH ₂ - CH ₂ -CH ₂ , -CH ₂ -CH (CHs) - CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ), w, x, y and z represent values between 0.5 and 25, where y and / or z can also be 0; wherein the surfactant system comprises the nonionic surfactants F and G in a weight ratio of F: G between 1: 4 and 100: 1; c) 0.1 to 10 wt .-% of a polymer having a molecular weight of 2000 gmol ^"1 or above, which has at least one positive charge.

As a further optional component, the automatic dishwashing compositions according to the invention may contain one or more complexing agents containing phosphorus, in particular one or more phosphorus-containing complexing agents from the group i) of the phosphonates and / or ii) the condensed phosphates of the general formula (MPO ₃ ) _x , M _{x + 2} P _x θ _{3X + 1} and / or M _x H ₂ P _x 0 _{3x + 1} , in which M is a cation and x is a number greater or equal to 5, included.

The group of phosphonates is one of the complexing agents and comprises a number of different compounds such as 1-hydroxyethane-1, 1-diphosphonic acid (HEDP) or diethylenetriamine penta (methylenephosphonic acid) (DTPMP).

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

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

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

In a preferred embodiment of the present invention, the weight proportion of the phosphonate (s) b) in the total weight of the automatic dishwashing agent is at least equal to the weight proportion of the polymer (s) a). In other words, those agents are particularly preferred in which the ratio of the weight fraction of polymer a) to the weight fraction of phosphonate b) is at least 1: 1, preferably 1: 1 to 200: 1, preferably 2: 1 to 150: 1, particularly preferred 3: 1 to 120: 1, most preferably 4: 1 to 100: 1 and especially 10: 1 to 100: 1 Instead of the abovementioned phosphonates or in combination with these phosphonates, the automatic dishwasher detergents according to the invention may furthermore comprise condensed phosphates. The group of condensed phosphates can be divided into metaphosphates and polyphosphates.

The metaphosphates correspond to compounds of the general formula (MPO ₃ ) _x . In the context of the present application in which M is a cation, preferably an alkali metal, and x is a number greater than or equal to 5. The polyphosphates as well as the aforementioned phosphonates are among the complexing agents. The stated degree of condensation x of the general formula (MPO ₃ ) _x represents a statistical average, which may be an integer or a fractional number for a particular product. Preferred degrees of condensation have a narrow homolog distribution.

The group of polyphosphates includes compounds of the general formula M _{x + 2} P _x 0 _{3x + 1} or M _x H ₂ P _x 0 _{3x +} ι.

The production of these condensed phosphates takes place, for example, by condensation of the NaH ₂ P0 ₄ or of the KH ₂ P0 ₄ . In the resulting polyphosphates can cyclic representatives, the sodium or potassium metaphosphates and chain types, the sodium and potassium polyphosphates, can distinguish. In particular, for the latter are a variety of names in use: melting or annealing phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

In the context of the present application particularly preferred condensed phosphates are the condensed phosphates of the general formula (MP0 ₃ ) _x , M _{x + 2} P _x 0 _3x + ι and / or M _x H ₂ P _x θ3 + ι, in which M for a Cation, preferably an alkali metal, more preferably sodium or potassium, and x is a number greater than or equal to 5, preferably greater than 5, preferably greater than 6, more preferably greater than 8, even more preferably greater than 10 and in particular greater than 12. The particularly preferred condensed phosphates include, for example, the glassy condensed polyphosphate of the general formula (MPO ₃ ) _x , M _{x + 2} P _x 0 _{3x + 1} and / or M _x H ₂ P _x θ _{3X + 1} , where x is a Number between 15 and 20, the condensed polyphosphates of the general formula (MP0 ₃ ) _x , M _{x + 2} P _x 0 _{3x + 1} and / or M _x H ₂ P _x 0 _{3x + 1} , where x is a number between 40 and 50.

Particular preference is given to water-soluble condensed polyphosphates of the general formula (MPO ₃ ) _x , M _{x + 2} P _x 0 ₃ χ _{+ 1} and / or M _x H ₂ P _x 0 _{3x + 1} , where x is a number between 12 and 800, preferably between 12 and 600, more preferably between 12 and 400 and in particular between 12 and 100.

₅₀ and the glassy phosphate with the formula (NaP0 _{3). 15} - the water-insoluble Madrellsche salt, (NaP0 _{3) x} with x> 1000, the water-soluble Graham's salt (NaPO _{3) 0} are particularly preferred in the context of the present application ₂ o, which is known as Calgon ^® .

Of course, the automatic dishwashing compositions according to the invention two or more different condensed phosphates of the general formula (MP0 ₃ ) _x , M _{x + 2} P _x 0 _{3x + 1} and / or M _x H ₂ P _x 0 _{3x + 1} , where M for a Cation and x is a number greater than or equal to 5 included.

In a preferred embodiment of the present invention the weight fraction of / is condensed polyphosphates b _x) of the general formula (MP0 _{3) x} M _{+ 2} P ι _x 0 _{3x +} and / or M _x H ₂ P _{x is} 0 _{to 3x + 1,} wherein M is a cation and x is a number greater than or equal to 5, the total weight of the automatic dishwashing agent is at least equal to the weight fraction of the polymer (s) a). In other words, those agents are particularly preferred in which the ratio of the weight fraction of polymer a) to the weight fraction of the condensed polyphosphate b) is at least 1: 1, preferably 1: 1 to 200: 1, preferably 2: 1 to 150: 1 preferably 3: 1 to 120: 1, very particularly preferably 4: 1 to 100: 1 and in particular 10: 1 to 100: 1

The compositions according to the invention have a proportion by weight of one or more phosphorus-containing complexing agents from the group of the phosphonates and / or the condensed phosphates of the general formula (MPO ₃ ) _x , M _{x + 2} P _x O _{3x +} 1 and / or M _x H ₂ P. _x 0 _{3x + 1} , in which M is a cation, preferably an alkali metal, and x is a number greater than or equal to 5 is between 1, 2 and 10 wt .-%, each based on the total weight of the automatic dishwashing on. In the context of the present application, however, preference is given to those automatic dishwashing detergents in which the weight fraction of the phosphorus-containing complexing agent b) is between 1.5 and 8% by weight, preferably between 1.7 and 7% by weight and in particular between 2, 0 and 6 wt .-%, each based on the total weight of the automatic dishwashing detergent is.

As described above, the phosphonates or the condensed polyphosphates may be contained alone or in admixture with one another in the preferred compositions of the present invention. In other words, the preferred automatic dishwashing compositions of the invention comprise Composition which phosphorus-containing complexing agent from the group of phosphonates in a weight fraction of 1, 2 and 10 wt .-%, preferably between 1, 5 and 8 wt .-%, preferably between 1, 7 and 7 wt .-% and in particular between 2.0 and 6% by weight, based in each case on the total weight of the automatic dishwashing detergent; Means which phosphorus-containing complexing agent from the group of condensed phosphates of the general formula (MP0 ₃ ) _x , M _{x + 2} P _x 0 _{3x + 1} and / or M _x H ₂ P _x 0 _{3x + 1} , in the M for a cation, preferably an alkali metal, and x is a number> 5, in a weight proportion between 1, 2 and 10 wt .-%, preferably between 1, 5 and 8 wt .-%, preferably between 1, 7 and 7 Wt .-% and in particular between 2.0 and 6 wt .-%, each based on the total weight of the automatic dishwashing agent have; and agents which phosphorus-containing complexing agents from the group of phosphonates and phosphorus-containing complexing agents from the group of condensed phosphates of the general formula (MPO ₃ ) _x , M _{x + 2} P _x 0 _{3x + 1} and / or M _x H ₂ P _x O _3x + ι, in which M is a cation, preferably an alkali metal, and x is a number> 5, in a weight proportion of between 1, 2 and 10 wt .-%, preferably between 1, 5 and 8 wt .-%, preferably between 1, 7 and 7 wt .-% and in particular between 2.0 and 6 wt .-%, each based on the total weight of the automatic dishwashing agent have;

The preferred subject matter of the present application is therefore a machine dishwashing detergent comprising from 0.5 to 12% by weight of a surfactant system of a) at least one nonionic surfactant F of the general formula

R ^{1 is} -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A" O) _z -R ² in which

R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂₄ alkyl or alkenyl radical; R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A, AA "and A '" independently of one another are radicals from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ - CH (CHs) - CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ), w, x, y and z are values between 0.5 and 25, where x, y and / or z are also 0 could be; and b) at least one nonionic surfactant G of the general formula

R -0- (AO) _w - (A'0) _x - (A "0) _y - (A '" 0) _z -R ² in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂₄ alkyl or alkenyl radical; R ^{2 is} H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A, A ', A "and A'" are each independently a radical selected from the group -CH ₂ CH _2, -CH ₂ CH ₂ -CH _2, -CH ₂ ^_ CH (CH _3), -CH 2 CH ₂ - CH _{2 is} -CH ₂ , -CH-CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ), w, x, y and z are values between 0.5 and 25, where y and / or z can also be 0; wherein the surfactant system comprises the nonionic surfactants F and G in a weight ratio of F: G between 1: 4 and 100: 1; c) 1, 2 to 10 wt .-% of one or more phosphorus-containing complexing agent from the group of phosphonates.

A further preferred subject matter of the present application is therefore a machine dishwashing detergent comprising 0.5 to 12% by weight of a surfactant system of a) at least one nonionic surfactant F of the general formula

R ^{1 is} -CH (OH) CH ₂ O- (AO) _w - (AO) _x - (A "O) _y - (A '" O) _z -R ² in which

R ¹ is a straight or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical; R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ ^_CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CHs) - CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ), w, x, y and z represent values between 0.5 and 25 where x, y and / or z can also be 0; and b) at least one nonionic surfactant G of the general formula

R ¹ -O- (AO) _w - (A'0) _x - (A "0) _y - (A '" 0) _z -R ² in which

R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂ alkyl or alkenyl radical; R ^{2 is} H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A, A ', A "and A'" are each independently a radical selected from the group -CH ₂ CH _2, -CH2CH2-CH _2, -CH ₂ -CH (CH ₃₎ -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ), w, x, y and z are values between 0.5 and 25, where y and / or z can also be 0; wherein the surfactant system comprises the nonionic surfactants F and G in a weight ratio of F: G between 1: 4 and 100: 1; c) 1, 2 to 10 wt .-% of one or more phosphorus-containing complexing agent from the group of the condensed phosphates of the general formula (MP0 ₃ ) _x , M _{x + 2} P _x 0 _{3x +} ι and / or M _x H ₂ P. _x 0 _{3x + 1} , in which M is a cation, preferably an alkali metal, and x is a number> 5.

If the preferred dishwasher detergents according to the invention contain phosphorus-containing complexing agents as both the abovementioned phosphonates i) and the abovementioned condensed polyphosphates ii), the weight ratio of constituents i) to constituents ii) is preferably between 10: 1 and 1:10, preferably between 7: 1 and 1: 7, more preferably between 6: 1 and 1: 6, even more preferably between 5: 1 and 1: 5 and in particular between 3: 1 and 1: 3.

In addition to the abovementioned polymers, complexing agents and nonionic surfactants, the automatic dishwashing compositions according to the invention preferably comprise further washing and cleaning substances, in particular washing and cleaning substances from the group of bleach activators, builders, surfactants, enzymes, disintegration aids, electrolytes, pH adjusters, fragrances, Perfume carriers, dyes, hydrotropes, foam inhibitors, corrosion inhibitors and glass corrosion inhibitors.

builders

In the context of the present application, the builders include, in particular, the zeolites, silicates, carbonates, organic co-builders and-where there are no ecological prejudices against their use-also the phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x 0 _{2x +} ι Η ₂ 0, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ "yH ₂ Q are preferred. It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates also have a dissolution delay compared with the conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

In the context of the present invention, it is preferred that these silicates, preferably alkali metal silicates, particularly preferably crystalline or amorphous alkali disilicates, be present in detergents or cleaners in amounts of from 10 to 60% by weight, preferably from 15 to 50% by weight .-% and in particular from 20 to 40 wt .-%, each based on the weight of the washing or cleaning agent, are included.

When the silicates are used as part of automatic dishwashing agents, these compositions preferably comprise at least one crystalline, layered silicate of the general formula NaMSi _x 0 _{2x +} ι 'y H ₂ 0 wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1, 9 to 4, and y is a number from 0 to 33. The crystalline layer-form silicates of the formula NaMSi _x 0 _{2x +} 1 H ₂ O are, for example, from the company Clariant GmbH

(Germany) under the trade name Na-SKS, eg Na-SKS-1 (Na ₂ Si ₂₂ θ4 ₅ -χH ₂ O, Kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O _2g -χH ₂ O, magadiite ), Na-SKS-3 (Na ₂ Si ₈ 0 _{17 2} 0 -χH) or Na-SKS-4 (Na ₂ Si ₄ 0 ₉ - ^χ H ₂ 0, makatite).

Particularly suitable for the purposes of the present invention are crystalline phyllosilicates of the formula (I) in which x is 2. Of these, especially Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na are suitable.

SKS-7 (β-Na ₂ Si ₂ O ₅ , natrosilite), Na-SKS-9 (NaHSi ₂ 0 ₅ Η ₂ 0), Na-SKS-10 (NaHSi ₂ O ₅ -3H ₂ O, Kanemite), Na-SKS-11 (t-Na ₂ Si ₂ 0 ₅ ) and Na-SKS-13 (NaHSi ₂ 0 ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ 0 ₅ ).

If the silicates are used as constituents of automatic dishwashing agents, these compositions in the context of the present application contain a proportion by weight of the crystalline layered silicate of the formula NaMSi _x O _{2 + +} Y ₂ O ₂ from 0.1 to 20% by weight, preferably from 0.2 to 15 wt .-% and in particular from 0.4 to 10 wt .-%, each based on the total weight of these agents. It is particularly preferred in particular if such automatic dishwashing agents have a total silicate content of less than 7% by weight, preferably less than 6% by weight, preferably less than 5% by weight, more preferably less than 4% by weight, most preferably less than 3% by weight % and in particular below 2.5 wt .-%, wherein it is in this silicate, based on the total weight of the silicate contained, preferably at least 70 wt .-%, preferably at least 80 wt .-% and in particular to At least 90% by weight of silicate of the general formula NaMSi _x 0 _{2x + 1} 'y H ₂ 0 is.

The finely crystalline, synthetic and bound water-containing zeolite used 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 n Na ₂ 0 ^• (1-n) K ₂ 0 "Al ₂ 0 ₃ ^■ (2 to 2.5) Si0 ₂ ^■ ( 3.5-5.5) H ₂ O

can be described. The zeolite can be used both as a builder in a granular compound, as well as to a kind of "powdering" of the entire mixture to be pressed, usually both ways for incorporating the zeolite are used in the premix. 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.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. This applies in particular to the use of agents according to the invention as automatic dishwasher detergents, which is particularly preferred in the context of the present application. Among the large number of commercially available phosphates, the alkali metal phosphates have been Preference pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphat) in the detergents and cleaning agents industry the greatest importance.

Alkalimetallphosphate is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HP0 ₃ ) _n and orthophosphoric H ₃ P0 _{4 in} addition to high molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts or lime incrustations in fabrics and, moreover, contribute to the cleaning performance.

Suitable phosphates are, for example, the sodium dihydrogen phosphate, NaH ₂ PO ₄ , in the form of the dihydrate (density 1, 91 like ^"3 , melting point 60 °) or in the form of monohydrate (density 2.04 like ^'3 ), the disodium hydrogen phosphate (secondary sodium phosphate) , Na ₂ HP0, which is anhydrous or with 2 moles (density 2.066 like ^"3 , water loss at 95 °), 7 moles (density 1, 68 like ^{" 3} , melting point 48 ° with loss of 5 H ₂ 0) and 12 Mol. Water (density 1, 52 like ^"3 , melting point 35 ° with loss of 5 H ₂ 0) can be used, but in particular the trisodium phosphate (tertiary sodium phosphate) Na ₃ P0 ₄ , which as dodecahydrate, as decahydrate (corresponding to 19- 20% P ₂ 0 ₅ ) and in anhydrous form (corresponding to 39-40% P ₂ 0 ₅ ) can be used.

Another preferred phosphate is the tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ . Also preferred are the tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , which in anhydrous form (density 2.534 like ^"3 , melting point 988 °, also 880 ° indicated) and as decahydrate (density 1, 815-1, 836 like ^"3 , melting point 94 ° with loss of water), as well as the corresponding potassium salt potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ 0 ₇ .

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or with 6 H ₂ 0 crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (0) (ONa) -0] _n -Na with n = 3. The corresponding potassium salt pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is marketed, for example, in the form of a 50% strength by weight solution (> 23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can likewise be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH - Nas ^ O ^ + H ₂ 0 These are used according to the invention exactly as sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.

If phosphates are used as detergents or cleaning agents in the context of the present application, preferred agents comprise this phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate). , in amounts of from 5 to 80% by weight, preferably from 15 to 75% by weight, in particular from 20 to 70% by weight, in each case based on the weight of the washing or cleaning agent.

In particular, it is preferred to use potassium tripolyphosphate and sodium tripolyphosphate in a weight ratio of more than 1: 1, preferably more than 2: 1, preferably more than 5: 1, more preferably more than 10: 1 and in particular more than 20: 1. It is particularly preferred to use exclusively potassium tripolyphosphate without admixtures of other phosphates.

Further builders are the alkali carriers. Suitable alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the alkali silicates mentioned, alkali metal silicates, and mixtures of the abovementioned substances. For the purposes of this invention, preference is given to using the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sumesquicarbonate. Particularly preferred is a builder system comprising a mixture of tripolyphosphate and sodium carbonate. Also particularly preferred is a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate. Because of their low chemical compatibility with the other ingredients of detergents or cleaners compared with other builders, the alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 wt .-% and in particular below 2 wt .-%, each based on the total weight of the detergent or Reinigugnsmittels used. Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.

Particularly preferred is the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of 2 to 50% by weight, preferably from 5 to 40 wt .-% and in particular from 7.5 to 30 wt .-%, each based on the weight of the washing or cleaning agent. Particularly preferred are agents which based on the weight of the washing or cleaning agent (ie the total weight of the combination product without packaging) less than 20 wt .-%, preferably less than 17 wt .-%, preferably less than 13 wt .-% and in particular less than 9 wt. % Carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonates, particularly preferably sodium carbonate.

Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. 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 acid, sugar acids and mixtures thereof.

The acids themselves can also be used. In addition to their builder effect, the acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

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

For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document. Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.

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

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

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

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

Further preferred copolymers are those which have as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

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

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 d with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a customary measure of the reducing action of a polysaccharide compared to dextrose, which is a DE of 100 owns, is. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 to 30,000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide to the carboxylic acid function.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable co-builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates. Suitable amounts are in zeolithhaltigen and / or silicate-containing formulations at 3 to 15 wt .-%.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.

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

Automatic dishwashing agents according to the invention which contain from 10 to 80% by weight, preferably from 15 to 75% by weight, particularly preferably from 20 to 70% by weight and in particular from 25 to 65% by weight, of one or more water-soluble builders are available the present application particularly preferred.

surfactants

The group of surfactants, in addition to the nonionic surfactants described above, further includes the anionic, cationic and amphoteric surfactants. As anionic surfactants, for example, those of the sulfonate type and sulfates are used. As surfactants of the sulfonate type preferably come here C ₉ .ι ₃ -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and Hydroxyalkansulfonaten and disulfonates, as they are for example from C ₁₂ -ι_ monoolefins with terminal or internal double bond by sulfonation with gaseous Sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained. Also suitable are alkanesulfonates, from C ₂ - ₁₈ are obtained, for example, alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. Similarly, the esters of α-sulfo fatty acids (ester sulfonates), for example, the sulfonated methyl esters of hydrogenated coconut, palm kernel or Taigfettsäuren are suitable.

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

Alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical having an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. From washing technical interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₄ -C ₁₅ alkyl sulfates are preferred. Also 2,3-alkyl sulfates, which can be obtained as commercial products of Shell Oil Company under the name DAN ^® , are suitable anionic surfactants.

Also, the sulfuric acid monoesters of straight-chain or branched C ₇ ethoxylated with 1 to 6 moles of ethylene oxide. ₂₁ -AlkohoIe, such as 2-methyl-branched C ₉ _ι _r alcohols having an average of 3.5 moles of ethylene oxide (EO) or C ₁₂ .ι ₈ fatty alcohols having 1 to 4 EO, are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.

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

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

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

If the anionic surfactants are part of automatic dishwasher detergents, their content, based on the total weight of the compositions, is preferably less than 4% by weight, preferably less than 2% by weight and very particularly preferably less than 1% by weight. Machine dishwashing detergents which do not contain anionic surfactants are particularly preferred.

Instead of the surfactants mentioned or in conjunction with them, it is also possible to use cationic and / or amphoteric surfactants.

As cationic active substances, it is possible, for example, to use cationic compounds of the formulas III, IV or V: R ¹

R ¹ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² OH)

(CH ₂ ) _n -TR ²

R ¹ IR ¹ -N ⁽⁺⁾ - (CH ₂ ) _n -CH-CH ₂ (IV) IIIR ¹ TT

R ² R ² R ¹ R ³ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (V) IR ⁴

wherein each group R ^{1 is} independently selected from Cι. ₆ alkyl, alkenyl or hydroxyalkyl groups; each group R ^{2 is} independently selected from C ₈ . ₂₈ alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

In automatic dishwashing detergent, the content of cationic and / or amphoteric surfactants is preferably less than 6% by weight, preferably less than 4% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight. %. Automatic dishwashing detergents containing no cationic or amphoteric surfactants are particularly preferred.

polymers

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

Particularly preferred as Suldonsäuregruppen-containing polymers are copolymers of unsaturated carboxylic acids, sulfonic acid-containing monomers and optionally other ionic or nonionic monomers.

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

R ¹ (R ² ) C = C (R ³ ) COOH (VI),

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

Among the unsaturated carboxylic acids which can be described by the formula VI are in particular acrylic acid (R ¹ = R ² = R ³ = H), methacrylic acid (R ¹ = R ² = H, R ³ = CH ₃ ) and / or maleic acid (R ¹ = COOH; R ² = R ³ = H) is preferred. In the sulfonic acid-containing monomers, those of the formula VII are preferred,

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

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

Preferred among these monomers are those of the formulas VIIa, VIIb and / or VIIc, H ₂ C = CH-X-SO ₃ H (VIIa), H ₂ C = C (CH ₃ ) -X-SO ₃ H (VIIb), H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) - X-S0 ₃ H (Vllc),

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

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₂ CH ₃ ) in formula VIIa), 2-acrylamido-2-propanesulfonic acid (X = -C ( 0) NH-C (CH ₃ ) ₂ in formula VIIa), 2-acrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula VIIa), 2 -Methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula VIIb), 3-methacrylamido-2-hydroxypropanesulfonic acid (X = -C (0) NH-CH ₂ CH (OH) CH ₂ - in formula VIIb), allylsulfonic acid (X = CH ₂ in formula XIIla), methallylsulfonic acid (X = CH ₂ in formula VIIb), allyloxybenzenesulfonic acid (X = - CH ₂ -O-C ₆ H ₄ - in formula VIIa), methallyloxybenzenesulfonic acid (X = -CH ₂ -O-C ₆ H ₄ - in formula XIIIb), 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid (X = CH ₂ in formula VIIb), styrenesulfonic acid (X = C ₆ H in formula VIIa), vinylsulfonic acid (X not present in formula VIIa), 3-sulfopropyl acrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - i n Formula VIIa), 3-sulfopropyl methacrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in formula VIIb), sulfomethacrylamide (X = - C (O) NH- in formula VIIb), sulfomethylmethacrylamide (X = -C (O) NH-CH ₂ - in formula VIIb) and water-soluble salts of said acids.

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

In summary, copolymers are made of

i) unsaturated carboxylic acids of the formula VI.

R ¹ (R ² ) C = C (R ³ ) C 00 H (VI),

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

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

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

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

iii) optionally further ionic or nonionic monomers

particularly preferred.

Further particularly preferred copolymers consist of i) one or more unsaturated carboxylic acids from the group of acrylic acid, methacrylic acid and / or maleic acid ii) one or more monomers containing sulfonic acid groups of the formulas VIIa, VIIb and / or VIIc:

H ₂ C = CH-X-SO ₃ H (VIIa), H ₂ C = C (CH ₃ ) -X-SO ₃ H (VIIb), H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) - X-S0 ₃ H (Vllc),

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

The copolymers may contain the monomers from groups i) and ii) and, if appropriate, iii) in varying amounts, it being possible for all representatives from group i) to be combined with all representatives from group ii) and all representatives from group iii). Particularly preferred polymers have certain structural units, which are described below.

Thus, for example, copolymers are preferred, the structural units of the formula VIII

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

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

These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative. If the sulfonic acid-containing acylic acid derivative is copolymerized with methacrylic acid, another polymer is obtained whose use is also preferred. The corresponding copolymers contain the structural units of the formula IX

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

where m and p are each an integer between 1 and 2,000, and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals containing from 1 to 24 carbon atoms, wherein: Y is -O - (CH ₂ ) _π - where n = 0 to 4, -O- (C ₆ H) -, -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) -, are preferred.

Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Thus, copolymers which are structural units of the formula X.

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (X), in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, as preferred as copolymers, the structural units of the formula XI

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SOsH] _p - (XI),

where m and p are each an integer between 1 and 2,000, and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals containing from 1 to 24 carbon atoms, wherein: Y is -O - (CH ₂ ) _π - where n = 0 to 4, -O- (C ₆ H ₄ ) -, -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - ,

Instead of acrylic acid and / or methacrylic acid or in addition thereto, maleic acid can also be used as a particularly preferred monomer from group i). This gives way to inventively preferred copolymers, the structural units of the formula XII

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

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

- [H00CCH-CHC00H] _m - [CH ₂ -C (CH ₃₎ C (0) 0-Y-S0 ₃ H] _p - (XIII),

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

In summary, such copolymers are preferred according to the invention, the structural units of the formulas VIII and / or IX and / or X and / or XI and / or XII and / or XIII - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (VIII), - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC ( 0) -Y-S0 ₃ H] _p - (IX), - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (X), - [CH ₂ -C (CH ₂₎ C O H] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XI), - [H 00CCH-CHCOH] _m -tCH ₂ - CHC (O) -Y-SO ₃ H] _p - (XII), - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) O-Y-SO ₃ H] _p - (XIII )

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

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

The monomer distribution of the copolymers preferably used according to the invention 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 i) or ii), particularly preferably from 50 to 90% by weight monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case 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 molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use. Preferred washing or cleaning compositions are characterized in that the copolymers have molecular weights of 2000 to 200,000 gmol ^"1 , preferably from 4000 to 25,000 gmol ^{" 1} and in particular from 5000 to 15,000 gmol ^"1 . Bleach activators

Bleach activators are used, for example, in detergents or cleaners to achieve improved bleaching performance when cleaned at temperatures of 60 ° C and below. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylene-diamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5- diacetoxy-2,5-dihydrofuran. Further bleach activators preferably used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula

R ¹

R ^{2 is} -N ⁽⁺⁾ - (CH ₂ ) -CN X ⁽ - ⁾ ,

R ³

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

Particularly preferred is a cationic nitrile of the formula R ⁴

R ^{5 is} -N ⁽⁺⁾ - (CH ₂ ) -CN X ^{ -

R ⁶

in which R ⁴ , R ⁵ and R ^{6 are} independently selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ - CH ₃ , -CH (CH ₃ ) -CH ₃ , wherein R ⁴ additionally can also be -H and X is an anion, wherein preferably R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ and compounds of the formulas (CH ₃ ) ₃ N ^(+> CH ₂ -CN X ^", (CH ₃ CH _{2) 3} N ⁽⁺⁾ CH ₂ -CN ^X" (CHsCHzCHzJsN ^ C ^ -CN X ^", (CH ₃ CH (CH _{3)) 3} N ⁽⁺⁾ CH ₂ -CN X ^" , or (H0-CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^{" are} particularly preferred, wherein from the group of these substances, in turn, the cationic nitrile of the formula (CH ₃ ) ₃ N ^{( +)} CH ₂ - CN X ^" in which X ^{" is} an anion selected from the group consisting of chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate is particularly preferred.

Other suitable bleach activators are 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 isononoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, Ethylene glycol diacetate, 2,5-diacetoxy-2,5-di-hydrofuran, n-methyl-morpholinium acetonitrile-methyl sulfate (MMA) and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG) , Pentaacetylfruktose, tetraacetylxylose and Octaacetyllactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, such as N-benzoyl caprolac tam. Hydrophilic substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used.

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

If, in addition to the nitrile quats, further bleach activators are to be used, preference is given to bleach activators from the group of the polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (US Pat. N- or iso-NOBS), n-methyl-morpholinium acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, especially 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-%, each based on the total weight of the bleach activator-containing agents used.

Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (ammin ) Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate are in conventional amounts, preferably in an amount up to 5 wt .-%, in particular of 0.0025 wt .-% to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the total weight of the bleach activator-containing agents used. But in special cases, more bleach activator can be used.

Glass corrosion inhibitors

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

A preferred class of compounds that can be used to prevent glass corrosion are insoluble zinc salts.

Insoluble zinc salts in the context of this preferred embodiment are zinc salts which have a solubility of a maximum of 10 grams of zinc salt per liter of water at 20 ° C. Examples of particularly preferred insoluble zinc salts according to the invention are zinc silicate, zinc carbonate, zinc oxide, basic zinc carbonate (Zn ₂ (OH) ₂ CO ₃ ), zinc hydroxide, zinc oxalate, zinc monophosphate (Zn ₃ (PO ₄ ) ₂ ), and zinc pyrophosphate (Zn ₂ (P ₂ 0 ₇ )). The zinc compounds mentioned are preferably used in amounts which have a content of the zinc ions of between 0.02 and 10% by weight, preferably between 0.1 and 5.0% by weight and in particular between 0.2 and 1.0 Wt .-%, each based on the total glass corrosion inhibitor-containing agent effect. The exact content of the agent on the zinc salt or zinc salts is naturally dependent on the type of zinc salts - the less soluble the zinc salt used, the higher its concentration should be in the funds.

Since the insoluble zinc salts remain largely unchanged during the Geschirreinigungsvorgangs, the particle size of the salts is a criterion to be observed, so that the salts do not adhere to glassware or machine parts. Here are preferred agents in which the insoluble zinc salts have a particle size below 1, 7 millimeters.

If the maximum particle size of the insoluble zinc salts is below 1.7 mm, insoluble residues in the dishwasher are not to be feared. Preferably, the insoluble zinc salt has an average particle size which is significantly below this value in order to further minimize the risk of insoluble residues, for example an average particle size of less than 250 μm. Again, this is even more true the less the zinc salt is soluble. In addition, the glass corrosion inhibiting effectiveness increases with decreasing particle size. For very poorly soluble zinc salts, the average particle size is preferably below 100 microns. For still less soluble salts, it may be even lower; For example, average particle sizes below 100 μm are preferred for the very poorly soluble zinc oxide.

Another preferred class of compounds are magnesium and / or zinc salt (s) of at least one monomeric and / or polymeric organic acid. The effect of this is that even with repeated use, the surfaces of glassware do not change corrosively, in particular, no turbidity, streaks or scratches, but also iridescence of the glass surfaces are not caused.

Although all magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids can be used, as described above, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids from the groups of unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the amino acids and / or the polymeric carboxylic acids are preferred.

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, and the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.

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

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

corrosion inhibitors

Corrosion inhibitors serve to protect the items to be washed or the machine, with particular silver protectants being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. Examples of the 3-amino-5-alkyl-1, 2,4-triazoles preferably used according to the invention may be: 5-propyl, -butyl, -pentyl, -heptyl, -Octyl, -Nonyl -, - decyl, -nedecyl, -dodecyl, -isononyl, -Versatic-10-alkyl, -phenyl, -p-tolyl, - (4-tert-butylphenyl) -, - ( 4-methoxyphenyl) -, - (2-, -3-, 4-pyridyl) -, - (2-thienyl) -, - (5-methyl-2-furyl) -, - (5-oxo-2- pyrrolidinyl) -, 3-amino-1, 2,4-triazole. In dishwashing agents, the alkylamino-1,2,4-triazoles or their physiologically tolerated salts in a concentration of 0.001 to 10 wt .-%, preferably 0.0025 to 2 wt .-%, particularly preferably 0.01 to 0.04 wt .-% used. Preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulphurous acid, organic carboxylic acids such as acetic, glycolic, citric, succinic acid. Especially effective are 5-pentyl, 5-heptyl, 5-nonyl, 5-undecyl, 5-isononyl, 5-versatic-10-acid-alkyl-3-amino-1,2,4-triazolase and mixtures of these substances. In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface. In chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phlogoglucine, pyrogallol or derivatives of these classes of compounds. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds can be used to prevent corrosion on the items to be washed.

Instead of or in addition to the silver protectants described above, for example the benzotriazoles, redox-active substances can be used. These substances are preferably inorganic redox-active substances from the group of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes, wherein the metals preferably in one of the oxidation states II, III , IV, V or VI.

The metal salts or metal complexes used should be at least partially soluble in water. The counterions suitable for salt formation comprise all customary mono-, di- or tri-positively negatively charged inorganic anions, eg. As oxide, sulfate, nitrate, fluoride, but also organic anions such. Stearate.

Metal complexes in the context of the invention are compounds which consist of a central atom and one or more ligands and optionally additionally one or more of the above-mentioned. Anions exist. The central atom is one of the o.g. Metals in one of the above Oxidation states. The ligands are neutral molecules or anions that are mono- or polydentate; The term "ligand" within the meaning of the invention is e.g. in "Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, page 2507" explained in more detail. If, in a metal complex, the charge of the central atom and the charge of the ligand (s) do not add up to zero, either one or more of the above may be provided, depending on whether there is cationic or anionic charge excess. Anions or one or more cations, e.g. As sodium, potassium, ammonium ions, for the charge balance. Suitable complexing agents are e.g. Citrate, acetylacetonate or 1-hydroxyethane-1, 1-diphosphonate.

The definition of "oxidation state" which is common in chemistry is reproduced, for example, in "Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1991, page 3168". Particularly preferred metal salts and / or metal complexes are selected from the group MnS0 ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1, 1- diphosphonate], V ₂ 0 ₅ , V ₂ 0 ₄ , V0 ₂ , TiOS0 ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , C0SO 4, Co (NO ₃ ) ₂ , Ce (NO ₃ ) ₃ and mixtures thereof in that preferred machine dishwashing detergents according to the invention are characterized in that the metal salts and / or metal complexes are selected from the group consisting of MnS0 ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) [1-hydroxyethane

1, 1-diphosphonate], V ₂ O _δ, V ₂ 0 _4, V0 _2, TiOS0 _4, K ₂ TiF _6, K ₂ ZrF _6, cos 0 _4, Co (N0 _{3) 2,} Ce (N0 _{3). 3}

In these metal salts or metal complexes are generally commercially available substances that can be used for the purpose of silver corrosion protection without prior purification in the compositions of the invention. For example, this is from the S0 ₃ -Herstellung

(Contact method) known mixture of pentavalent and tetravalent vanadium (V ₂ 0 ₅ , V0 ₂ , V ₂ 0 ₄ ) suitable, as well as the resulting by diluting a Ti (S0 ₄ ) ₂ solution titanyl sulfate,

TiOS0 ₄ .

The inorganic redox-active substances, in particular metal salts or metal complexes are preferably coated, i. completely coated with a waterproof, but easily soluble in the cleaning temperatures material to prevent their premature decomposition or oxidation during storage. Preferred coating materials, which are applied by known methods, such as Sandwik from the food industry, are paraffins, microwaxes, waxes of natural origin such as carnauba wax, candellila wax, beeswax, higher melting alcohols such as hexadecanol, soaps or fatty acids. The coating material, which is solid at room temperature, is applied in the molten state to the material to be coated, e.g. in that finely divided material to be coated is spun in continuous stream through a likewise continuously produced spray zone of the molten coating material. The melting point must be chosen so that the coating material easily dissolves or melts during the silver treatment. The melting point should ideally be in the range between 45 ° C and 65 ° C and preferably in the range 50 ° C to 60 ° C.

The metal salts and / or metal complexes mentioned are contained in cleaning agents, preferably in an amount of 0.05 to 6 wt .-%, preferably 0.2 to 2.5 wt .-%, each based on the total corrosion inhibitor-containing agent. enzymes

To increase the washing or cleaning performance of detergents or cleaners enzymes can be used. These include in particular proteases, amylases, lipases, hemicellulases, 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 cleaners, which are preferably used accordingly. Agents according to the invention preferably contain enzymes in total amounts of 1 × 10 ^-6 to 5 weight-percent based on active protein The protein concentration can be determined by known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferable. Examples thereof are the subtilisin 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 which can no longer be assigned to the subtilisins in the narrower sense and the proteases TW3 and TW7. Subtilisin Carlsberg in a developed form under the trade names Alcalase ^® from Novozymes A / S, Bagsvasrd, 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 names Durazym ^®, re lase ^®, Everlase® ^®, Nafizym, Natalase ^®, Kannase® ^® and Ovozymes ^® from Novozymes, which from under the trade names Purafect ^®, Purafect ^® OxP and Properase.RTM ^® Genencor, that under the trade name Protosol® ^® from Advanced Biochemicals Ltd., Thane, India, that of under the trade name Wuxi ^® from Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® ^® and protease P ^® 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 α-amylases from Bacillus licheniformis, from β. amyloliquefaciens or from ß. stearothermophilus and their improved for use in detergents and cleaners further developments. The enzyme from ß. licheniformis is available from Novozymes under the name Termamyl ^® and from Genencor under the name Purastar® ^® ST. Development products of this α-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 α-amylase of β. amyloliquefaciens is sold by Novozymes under the name BAN ^®, and variants derived from the α-amylase from B.. stearothermophilus under the names BSG ^® and Novamyl ^®, likewise from Novozymes.

Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from β. agaradherens (DSM 9948).

In addition, the enhancements available under the trade names Fungamyl.RTM ^® by Novozymes of α-amylase from Aspergillus niger and A. oryzae. Another commercial product is, for example, the amylase ^LT® .

Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are for example marketed by Novozymes under the trade names Lipolase ^®, Lipolase Ultra ^®, LipoPrime® ^®, Lipozyme® ^® and Lipex ^®. Furthermore, for example, the cutinases can be used, which were 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. Genencor can be used, for example, for the lipases or cutinases whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Other important commercial products, the preparations originally sold by Gist-Brocades M1 Lipase ^® and Lipomax® ^® and by the company of opinion to Sangyo KK, Japan under the names Lipase MY-30 ^®, Lipase OF ^® and lipase PL ^® to mention displaced enzymes, and also the product Lumafast ^® from Genencor.

Furthermore, enzymes can be used, which are summarized by the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases. Suitable mannanases are available, 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, USA , The from ß. subtilis .beta.-glucanase obtained is available under the name Cereflo ^® from Novozymes. Oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect. Suitable commercial products Denilite® ^® 1 and 2 from Novozymes should be mentioned. Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.

The enzymes originate, for example, either originally from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by biotechnological methods known per se by suitable microorganisms, such as transgenic expression hosts of the genera Bacillus or filamentous fungi.

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

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

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

One group of stabilizers are reversible protease inhibitors. Frequently, benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are used, including in particular derivatives with aromatic groups, such as ortho-substituted, meta-substituted and para-substituted phenylboronic acids, or their salts or esters. As peptidic protease inhibitors are, inter alia, ovomucoid and leupeptin to mention; An additional option is the formation of fusion proteins from proteases and peptide inhibitors.

Other enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C ₁₂ , such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also suitable. Certain organic acids used as builders are additionally capable of stabilizing a contained enzyme.

Lower aliphatic alcohols, but especially polyols such as glycerol, ethylene glycol, propylene glycol or sorbitol are other frequently used enzyme stabilizers. Also used are calcium salts, such as calcium acetate or calcium formate, and magnesium salts.

Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations. Polyamine N-oxide containing polymers act as enzyme stabilizers. Other polymeric stabilizers are the linear C ₈ -C ₁₈ polyoxyalkylenes. Alkylpolyglycosides can stabilize the enzymatic components of the agent according to the invention and even increase their performance. Crosslinked N-containing compounds also act as enzyme stabilizers. Reducing agents and antioxidants increase the stability of the enzymes to oxidative degradation. A sulfur-containing reducing agent is, for example, sodium sulfite.

Preferably, combinatons of stabilizers are used, for example of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts. The effect of peptide-aldehyde stabilizers is enhanced by the combination with boric acid and / or boric acid derivatives and polyols and further enhanced by the additional use of divalent cations, such as calcium ions.

Preference is given to one or more enzymes and / or enzyme preparations, preferably solid protease preparations and / or amylase preparations, in amounts of from 0.1 to 5% by weight, preferably from 0.2 to 4.5 and in particular from 0, 4 to 4 wt .-%, each based on the total enzyme-containing agent used.

disintegration aid

In order to facilitate the disintegration of preformed molded articles, it is possible to incorporate disintegration aids, so-called disintegrants into these agents in order to shorten the disintegration times. According to Römpp (9th edition, Vol. 6, p. 4440) and Voigt "Textbook of Pharmaceutical Technology" (6th edition, 1987, pp. 182-184), excipients are understood to mean excipients which are suitable for rapid disintegration of tablets in water or gastric juice and for the release of the drugs in resorbable form.

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

Disintegration aids are preferably used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration assistant-containing agent. Preferred disintegrating agents used in the present invention are cellulose-based disintegrating agents, so that preferred washing and cleaning compositions comprise such a cellulose-based disintegrating agent in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular 4 contain up to 6 wt .-%. Pure cellulose has the formal gross composition (C ₆ H ₁₀ θ ₅ ) _n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives.

The cellulose used as disintegration assistant is preferably not used in finely divided form, but converted into a coarser form, for example granulated or konnpaktiert before admixing to be compressed premixes. The particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns. The above and described in more detail in the documents cited coarser disintegration aids, are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ^® TF-30-HG from Rettenmaier available in the present invention.

As a further disintegrating agent based on cellulose or as a component of this component microcrystalline cellulose can be used. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulose mass) of the celluloses, leaving the crystalline regions (about 70%) intact. Subsequent desaggregation of the microfine celluloses resulting from the hydrolysis yields the microcrystalline ones Celluloses which have primary particle sizes of about 5 microns and are compacted, for example, to granules with an average particle size of 200 microns.

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

Furthermore, according to the invention, gas-evolving effervescent systems can furthermore be used as tablet disintegration auxiliaries. The gas-evolving effervescent system may consist of a single substance that releases a gas upon contact with water. Among these compounds, mention should be made in particular of magnesium peroxide, which liberates oxygen on contact with water. Usually, however, the gas-releasing effervescent system in turn consists of at least two constituents which react with one another to form gas. While a variety of systems are conceivable and executable that release, for example, nitrogen, oxygen or hydrogen, the effervescent system used in the detergent and cleaner compositions according to the invention can be selected both on the basis of economic and ecological considerations. Preferred effervescent systems consist of alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution.

In the case of the alkali metal carbonates or bicarbonates, the sodium and potassium salts are clearly preferred over the other salts for reasons of cost. Of course, the relevant pure alkali metal carbonates or bicarbonates do not have to be used; Rather, mixtures of different carbonates and bicarbonates may be preferred.

Preference is given as effervescent 2 to 20 wt .-%, preferably 3 to 15 wt .-% and in particular 5 to 10 wt .-% of an alkali metal carbonate or bicarbonate and 1 to 15, preferably 2 to 12 and especially 3 to 10 wt. % of an acidifying agent, in each case based on the total weight of the agent used.

Suitable acidifying agents which release carbon dioxide from the alkali metal salts in aqueous solution are, for example, boric acid and also alkali metal hydrogensulfates, alkali metal dihydrogenphosphates and other inorganic salts. However, preference is given to using organic acidifying agents, the citric acid being a particularly preferred acidifying agent. However, it is also possible in particular to use the other solid mono-, oligo- and polycarboxylic acids. Again preferred from this group are tartaric acid, succinic acid, malonic acid, Adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. Organic sulfonic acids such as sulfamic acid are also usable. A commercially available as an acidifier in the context of the present invention also preferably be used is Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) and adipic acid ( at most 33% by weight).

Acidifying agents in the effervescent system from the group of organic di-, tri- and oligocarboxylic acids or mixtures are preferred within the scope of the present invention.

fragrances

As perfume oils or fragrances, individual fragrance compounds, e.g. the synthetic products of the type of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons are used. Fragrance compounds of the ester type are known e.g. Benzyl acetate, phenoxyethylisobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalylbenzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styralylpropionate 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, α-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. Also suitable are muscatel, sage, camomile, clove, lemon balm, mint oil, cinnamon leaf oil, linden 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.

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

dyes

Preferred dyestuffs, the choice of which presents no difficulty to a person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, as well as no pronounced substantivity to those with the dye-containing Agents to be treated substrates such as glass, ceramic or plastic dishes, so as not to stain them.

The automatic dishwashing compositions according to the invention can be made available to the consumer in different ready-made forms. In addition to the known powders, granules or extrudates, preference is given in the context of the present application to those automatic dishwashing agents which are made available to the consumer in the form of prefabricated metering units. The automatic dishwashing agent according to the invention is preferably in the form of prefabricated dosage units. Such dosing units can in principle be made up for single or multiple use, but in the context of the present application prefabricated dosing units for single use are preferred.

The aforementioned dosing units can be inserted, for example, in the cutlery box or the dosing compartment of the dishwasher. In the context of this application, preference is given to those metering units which can be inserted into the dispensing compartment of the dishwasher. While the dosing units can in principle have any spatial shape that can be produced by a person skilled in the art, the preferred dosing units provided for the dosing compartment are characterized by certain geometries adapted to the spatial conditions of the commercially available dosing compartments. Preference is therefore given in particular to those dosage units according to the invention which have a volume of between 1 and 35 ml, preferably between 2 and 30 ml, preferably between 4 and 25 ml, more preferably between 8 and 22 ml and in particular between 10 and 20 ml. The maximal

The weight of preferred metering units per metering unit is between 0.5 and 30 g, preferably between 1 and 25 g, preferably between 2 and 24 g, more preferably between 4 and 23 g and in particular between 8 and 22.

A preferred machine dishwashing detergent according to the invention, characterized in that the automatic dishwashing agent is in the form of a prefabricated dosage unit which contains between 0.2 and 2.5 g, preferably between 0.3 and 2.2 g, more preferably between 0.4 and 1 , 9 g and especially between 0.5 and 1.5 g of nonionic surfactant (s).

If, in a preferred embodiment, the machine dishwashing detergents according to the invention also comprise phosphorus-containing complexing agents, particular preference is given to those automatic dishwashing detergents which are in the form of a prefabricated dosage unit and between 0.2 and 4 g, preferably between 0.3 and 3 g between 0.4 and 3.0 g and especially between 0.5 and 3.0 g of the phosphorus-containing complexing agent.

If, in a preferred embodiment, the automatic dishwashing agents according to the invention also contain polymers having a positive charge, those automatic dishwashing agents which are in the form of a prefabricated dosage unit and between 0.001 and 1 g, preferably between 0.01 and 0.1 g, are particularly preferred preferably between 0.01 and 0.07 g and in particular between 0.01 and 0.05 g of the polymer having a molecular weight of 2000 gmol ^-1 or above, which has at least one positive charge.

As ready-made forms for the prefabricated dosing units, in particular the tablet, the extrudate, the casting, the thermoforming body or the injection-molded body or combinations of these dosing units are preferred. Automatic dishwashing detergent in a prefabricated dosing unit, characterized in that the prefabricated dosing unit is a tablet, an extrudate, a filled water-soluble container, preferably a filled injection-molded body, a filled casting body or a filled foil pouch, are particularly suitable within the scope of the present application prefers.

Particular preference is furthermore given to those automatic dishwashing agents which are in the form of a prefabricated dosing unit, this dosing unit having two, three, four or more phases.

A first preferred prefabricated dosage unit is the tablet. To produce tablets, particulate premixes are compacted in a so-called matrix between two punches to form a solid compressed product. This process, hereinafter referred to as tabletting, is divided into four sections: dosing, compaction, plastic deformation and ejection.

First, the premix is introduced into the die, wherein the filling amount and thus the weight and the shape of the resulting shaped body are determined by the position of the lower punch and the shape of the pressing tool. The constant dosage even at high molding throughputs is preferably achieved by a volumetric metering of the premix. As the tableting progresses, the upper punch contacts the pre-mix and continues to descend toward the lower punch. In this compression, the particles of the premix are pressed closer to each other, with the void volume within the filling between the punches decreasing continuously. From a certain position of the upper punch (and thus from a certain pressure on the premix) begins the plastic deformation, in which the particles flow together and it to form the shaped body comes. Depending on the physical properties of the premix, some of the premix particles are also crushed, and at even higher pressures sintering of the premix occurs. With increasing pressing speed, so high throughput amounts, the phase of the elastic deformation is shortened more and more, so that the resulting moldings may have more or less large cavities. In the last step of tableting, the finished molded body is pushed out of the die by the lower punch and carried away by subsequent transport means. At this time, only the weight of the shaped body is finally determined because the compacts due to physical processes (re-expansion, crystallographic effects, cooling, etc.) can change their shape and size.

The tabletting is carried out in commercial tablet presses, which can be equipped in principle with single or double punches. In the latter case, not only the upper punch is used to build up pressure, and the lower punch moves during the pressing on the upper punch, while the upper punch presses down. For small production quantities, eccentric tablet presses are preferably used in which the die or punches are attached to an eccentric disc, which in turn is mounted on an axis at a certain rotational speed. The movement of these punches is comparable to the operation of a conventional four-stroke engine. The compression can be done with a respective upper and lower punch, but it can also be attached more stamp on an eccentric disc, the number of Matrizenbohrungen is extended accordingly. The throughputs of eccentric presses vary depending on the type of a few hundred to a maximum of 3000 tablets per hour.

In eccentric presses, the lower punch is usually not moved during the pressing process. A consequence of this is that the resulting tablet has a hardness gradient, i. harder in the areas closer to the upper punch than in the areas closer to the lower punch.

For larger throughputs, rotary tablet presses are selected in which a larger number of dies are arranged in a circle on a so-called die table. The number of matrices varies between 6 and 55 depending on the model, although larger matrices are commercially available. Each die on the die table is assigned an upper and lower punch, in turn, the pressing pressure can be actively built only by the upper or lower punch, but also by both stamp. The die table and the punches move about a common vertical axis, the punches are brought by means of rail-like cam tracks during the circulation in the positions for filling, compression, plastic deformation and ejection. At the points where a particularly serious increase or decrease of the stamp is required (filling, compaction, ejection), these curved paths are supported by additional low-pressure pieces, Nierderzugschienen and lifting tracks. The Filling of the die takes place via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix. The pressing pressure on the premix is individually adjustable via the compression paths for upper and lower punches, wherein the pressure build-up is done by the Vorbeirollen the stamp shank heads on adjustable pressure rollers.

Concentric presses can be provided with two Füllschuhen to increase the throughput, with the production of a tablet only a semicircle must be traversed. To produce two-layered and multi-layered shaped bodies, several filling shoes are arranged one after the other without the slightly pressed-on first layer being ejected before further filling. By suitable process control coat and point tablets can be produced in this way, which have a zwiebelschalenartigen structure, wherein in the case of the point tablets, the top of the core or the core layers is not covered and thus remains visible. Even rotary tablet presses can be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes are used simultaneously for pressing. The throughputs of modern rotary tablet presses amount to over one million moldings per hour.

Of course, the tablets can also in the context of the present invention, multi-phase, in particular multi-layered, ausgestalten. The moldings can be made in a predetermined spatial form and predetermined size. As a form of space practically all useful manageable configurations come into consideration, for example, the training as a blackboard, the bar or bar shape, cubes, cuboids and corresponding space elements with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section. This last embodiment covers the presentation form of the tablet up to compact cylinder pieces with a ratio of height to diameter above 1.

The spatial form of another embodiment of the moldings is adapted in their dimensions of Einspülkammer of commercial household washing machines or the dosing of commercial dishwashers, so that the moldings can be metered without dosing directly into the dispenser, where they dissolve during the Einspülvorgangs, or from where they are released during the cleaning process. Of course, however, it is also possible to use the washing and cleaning agent tablets via dosing aids without problems.

After pressing, the detergent tablets have a high stability. The breaking strength of cylindrical shaped bodies can be detected by the measurand of the diametric breaking load. This is determinable 2P σ = πDt

Herein, σ is the diametrical fracture stress (DFS) in Pa, P is the force in N which results in the pressure applied to the molded article causing the breakage of the molded article, D is the molded article diameter in meters and t the height of the moldings.

A further preferred embodiment of the present application relates to automatic dishwashing compositions according to the invention, which are in the form of a prefabricated dosage unit, characterized in that the prefabricated dosage unit is a shaped body, preferably a multi-phase shaped body, preferably a multi-phase tablet and in particular a multi-phase Tablet with a trough, preferably with a filled trough, acts.

For the purposes of the present application, "deep-drawing body" refers to those containers which are obtained by deep-drawing a first film-like wrapping material, preferably by bringing the wrapping material over a receiving trough located in a die forming the deep-drawing mold and molding the wrapping material into it The shell material can be pretreated before or during the molding by the action of heat and / or solvent and / or conditioning by relative humidity and / or temperatures changed relative to ambient conditions can be done by two parts of a tool, which behave as positive and negative to each other and deform a film placed between these tools when pressed together.As pressure forces, however, the effect of pressure is also suitable air and / or the weight of the film and / or the weight of a spent on the top of the film active substance.

The deep-drawn shell materials are preferably fixed after deep drawing by using a vacuum within the receiving wells and in their achieved by the deep-drawing process space shape. The vacuum is preferably applied continuously from deep drawing to filling until sealing and in particular until the separation of the receiving chambers. With comparable results, however, the use of a discontinuous vacuum, for example, for deep drawing of the receiving chambers and (after an interruption) before and during the filling of the receiving chambers, possible. Also, the continuous or discontinuous vacuum may vary in strength and, for example, at the beginning of the process (during thermoforming of the film) assume higher values than at the end (when filling or sealing or separating).

As already mentioned, the shell material can be pre-treated by the action of heat before or during the molding into the receiving troughs of the matrices. The shell material, preferably a water-soluble or water-dispersible polymer film, is heated to temperatures above 60 ° C. for up to 5 seconds, preferably for 0.1 to 4 seconds, particularly preferably for 0.2 to 3 seconds and in particular for 0.4 to 2 seconds. preferably above 80 ° C, more preferably between 100 and 120 ° C and in particular heated to temperatures between 105 and 115 ° C. To dissipate this heat, but in particular also to dissipate the heat introduced by the means filled in the deep-drawn receiving chambers (for example melting), it is preferable to cool the dies used and the receiving cavities located in these dies. The cooling is preferably carried out at temperatures below 20 ° C, preferably below 15 ° C, more preferably at temperatures between 2 and 14 ° C and in particular at temperatures between 4 and 12 ° C. Preferably, the cooling takes place continuously from the beginning of the deep-drawing process to the sealing and separation of the receiving chambers. Cooling fluids, preferably water, which are circulated in special cooling lines within the matrix, are particularly suitable for cooling.

This cooling, as well as the previously described continuous or discontinuous application of a vacuum has the advantage of preventing shrinkage of the deep-drawn containers after deep drawing, whereby not only the appearance of the process product is improved, but also at the same time the discharge of the filled into the receiving chambers means the edge of the receiving chamber, for example in the sealing areas of the chamber, is avoided. Problems with the sealing of the filled chambers are thus avoided.

In the deep-drawing process can be between methods in which the shell material is guided horizontally in a forming station and from there in a horizontal manner for filling and / or sealing and / or separating and methods in which the shell material via a continuously rotating Matrizenformwalze (optionally optionally with a counter-guided Patrizenform- roller, which lead the forming upper punch to the cavities of the Matrizenformwalze), different. The first-mentioned process variant of the flat bed process is to operate both continuously and discontinuously, the process variant using a molding roll is usually continuous. All of the mentioned deep drawing methods are suitable for the production of the inventively preferred means. The receiving troughs located in the matrices can be arranged "in series" or staggered. The thermoforming bodies can have one, two, three or more receiving chambers. These receiving chambers can be arranged side by side and / or one above the other in the deep-drawn part. In a preferred embodiment of the present application, the machine dishwashing detergent according to the invention is packaged in a water-soluble or water-dispersible thermoforming body, which in addition to the solid automatic dishwasher according to the invention in a separate receiving chamber further contains a liquid or gel detergent or detergent mixture.

A further preferred embodiment of the present application relates to automatic dishwashing agents according to the invention, which are in the form of a prefabricated dosing unit, characterized in that the prefabricated dosing unit is a thermoformed body, preferably a thermoformed body with two or more receiving chambers, in particular a thermoformed body with one above the other arranged receiving chambers acts.

The water-soluble or wasseridispergierbaren container can be prepared by injection molding in addition to deep drawing. Injection molding refers to the forming of a molding material such that the mass contained in a mass cylinder for more than one injection molding plastically softens under heat and flows under pressure through a nozzle into the cavity of a previously closed tool. The method is mainly applied to non-hardenable molding compounds which solidify in the tool by cooling. Injection molding is a very economical modern process for producing non-cutting shaped articles and is particularly suitable for automated mass production. In practical operation, the thermoplastic molding compounds (powders, granules, cubes, pastes, etc.) are heated to liquefaction (up to 180 ° C) and injected under high pressure (up to 140 MPa) in closed, two-piece, that is from Gesenk (earlier Die) and core (formerly male) existing, preferably water-cooled molds, where they cool and solidify. Can be used piston and screw injection molding machines. Suitable molding compounds (injection molding compounds) are water-soluble polymers, for example the abovementioned cellulose ethers, pectins, polyethylene glycols, polyvinyl alcohols, polyvinylpyrrolidones, alginates, gelatin or starch.

A further preferred embodiment of the present application relates to automatic dishwashing agents according to the invention, which are in the form of a prefabricated dosing unit, characterized in that the prefabricated dosing unit is an injection-molded body, preferably an injection-molded body with two or more receiving chambers.

However, the shell materials can also be cast into molds. The hollow form of the resulting inventively preferred water-soluble or water-dispersible portioned agent comprises at least one solidified melt. This melt can be an be molten pure substance or a mixture of several substances. It is of course possible to mix the individual substances of a multi-substance melt before melting or to produce separate melts, which are then combined. Mixtures of mixtures of substances may be advantageous, for example, when eutectic mixtures are formed which melt significantly lower and thus lower the process costs.

In a preferred embodiment of the present invention, the shell material poured into the mold comprises at least partially a washing or cleaning agent according to the invention. Particular preference is given to the production of cast hollow molds which consist entirely of a washing or cleaning agent according to the invention.

A further preferred embodiment of the present application relates to automatic dishwashing agents according to the invention which are in the form of a prefabricated dosing unit, characterized in that the prefabricated dosing unit is a casting body, preferably a casting body having at least one depression.

The automatic dishwashing compositions according to the invention, in particular the automatic dishwashing compositions according to the invention in the form of prefabricated metering units, preferably have a water-soluble coating. Such a water-soluble casing is, for example, a water-soluble or water-dispersible deep-drawn or injection-molded body described above. Further preferred water-soluble coatings are water-soluble coatings of tablets, castings or extrudates, in particular in the form of a spray or dip coating or in the form of a water-soluble or water-dispersible outer packaging. The water-soluble coating preferably contains organic polymers or organic salts, in particular salts of carboxylic acids.

A further subject matter of the present application Method for automatic dishwashing, in which a machine dishwashing detergent according to one of claims 1 to 20 is introduced into the interior of a dishwasher before or while the dishwasher is running through a cleaning program.

Another object of the present application is a method for automatic dishwashing, wherein a surfactant system of a) at least one nonionic surfactant F of the general formula

R ^{1 is} -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A" O) _z -R ² in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂ alkyl or alkenyl radical; R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH., -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH _2, -CH ₂ ^_ CH (CH3) - CH ₂ -, -CH 2 -CH (CH ₂ -CH _3), w, x, y and z are values between 0.5 and 25 are, where x, y and / or z can also be 0; and b) at least one nonionic surfactant G of the general formula

R ¹ -O- (AO) _w - (AO) _x - (A "0) _y - (A '" 0) _z -R ² in which

R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂₄ alkyl or alkenyl radical; R ^{2 is} H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) - CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ), w, x, y and z represent values between 0.5 and 25 where y and / or z can also be 0; wherein the surfactant system comprises the nonionic surfactants F and G in a weight ratio of F: G between 1: 4 and 100: 1 for automatic dishwashing, characterized in that the surfactant system is released in the main cleaning cycle and / or in the final rinse cycle.

Claims

- HO claims:

A machine dishwashing detergent comprising 0.5 to 12% by weight of a surfactant system of a) at least one nonionic surfactant F of the general formula

R ¹ -CH (OH) CH ₂ O- (AO) _w - (AO) _x - (A "0) _y - (A"'O) _z -R ² , in which

R ¹ is a straight or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical; R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A, A \ A "and A"'independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH, -CH ₂ -CH (CHs), -CH ₂ -CHO. -CH ₂ -CH ₂ , -CH ₂ -CH (CHs) - CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ), w, x, y and z are values between 0.5 and 25, where x, y and / or z can also be 0; and b) at least one nonionic surfactant G of the general formula

R ¹ -O- (AO) _w - (AO) _x - (A "O) _y - (A" O) _z -R ² in which

R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂₄ alkyl or alkenyl radical; R ^{2 is} H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; - A, A ', A "and A'" independently of one another are radicals from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH _{3 )} , -CH ₂ -CH ₂ - CH ₂ -CH ₂ , -CH ₂ -CH (CHs) - CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ), w, x, y and z represent values between 0.5 and 25, where y and / or z can also be 0; wherein the surfactant system comprises the nonionic surfactants F and G in a weight ratio of F: G between 1: 4 and 100: 1.

2. Machine dishwashing detergent according to claim 1, characterized in that it is a nonionic surfactant (s) F as a nonionic surfactant of the general formula

R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y is a value of at least 15.

3. Machine dishwashing detergent according to one of claims 1 or 2, characterized in that it is a nonionic (s) surfactant (s) F is a nonionic surfactant of the general formula

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x R ² in which R ^{1 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{2 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which have between 1 and 5 hydroxy groups and are preferably further functionalized with an ether group, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl , n-butyl, 2-butyl or 2-methyl-2-butyl and x is between 1 and 40.

4. Machine dishwashing detergent according to one of claims 1 to 3, characterized in that it is a nonionic (s) surfactant (s) F is a nonionic surfactant of the general formula

R ¹ 0 [CH ₂ CH ₂ 0] _x CH ₂ CH (OH) R ² , which in addition to a radical R ¹ , for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably with 4 to 20 carbon atoms, further having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30 carbon atoms R ² , which is a monohydroxylated intermediate group -CH ₂ CH (OH) - adjacent and in which x for values between 1 and 40 stands.

5. Machine dishwashing detergent according to one of claims 1 to 4, characterized in that it nonionic (s) surfactant (s) F is a nonionic surfactant of the general formula

R ¹ 0 [CH ₂ CH ₂ O] _x [CH ₂ CHO] _y CH ₂ CH (OH) R ² IR ³ contains, in which R ¹ and R ² independently of one another is a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ ; -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ , but preferably -CH ₃ , and x and y are independently from each other values between 1 and 32, wherein nonionic surfactants with values for x from 15 to 32 and y of 0.5 and 1.5 are most preferred.

6. Machine dishwashing detergent according to one of claims 1 to 5, characterized in that it is a nonionic surfactant (s) G as a nonionic surfactant of the general formula

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

7. A machine dishwashing detergent according to any one of claims 1 to 6, characterized in that the surfactant system, the nonionic surfactants F and G in a weight ratio of F: G between 2: 9 and 90: 1, preferably between 1: 3 and 80: 1, preferably between 3: 7 and 70: 1, more preferably between 7:13 and 60: 1 and in particular between 2: 3 and 50: 1.

8. Machine dishwashing detergent according to one of claims 1 to 7, characterized in that the automatic dishwashing agent is in the form of a prefabricated dosage unit, which is between 0.2 and 2.5 g, preferably between 0.3 and 2.2 g, particularly preferred between 0.4 and 1, 9 g and in particular between 0.5 and 1, 5 g of nonionic (s) surfactant (s).

Machine dishwashing detergent according to any one of Claims 1 to 8, characterized in that it additionally comprises at least one polymer having a molecular weight of 2000 gmol ^-1 or above and containing at least one positive charge.

10. A machine dishwashing detergent according to claim 9, characterized in that it contains the polymer in a weight proportion of the polymer having a molecular weight of 2000 gmol ^"1 or above, which has at least one positive charge in a weight fraction between 0.01 and 10 wt .-%, preferably between 0.01 and 8 wt .-%, preferably between 0.01 and 6 wt .-%, particularly preferably between 0 , 01 and 4 wt .-%, most preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, each based on the total weight of the automatic dishwashing detergent contains.

11. A machine dishwashing detergent according to any one of claims 9 or 10, characterized in that the automatic dishwashing agent is in the form of a prefabricated dosage unit, which is between 0.001 and 1 g, preferably between 0.01 and 0.1 g, more preferably between 0.01 and 0.07 g and especially between 0.01 and 0.05 g of the polymer having a molecular weight of 2000 gmol ^-1 or above and having at least one positive charge.

12. A machine dishwashing detergent according to any one of claims 9 to 11, characterized in that the polymer having a molecular weight of 2000 gmol ^"1 or above, which has at least one positive charge, monomer units of the formula R ¹ R ² C = CR ³ R ⁴ in which each radical R ¹ , R ² , R ³ , R ^{4 is} independently selected from i) hydrogen, ii) derivatized hydroxy group, iii) C 1 to C ₃₀ linear or branched alkyl groups, aryl, aryl substituted C 1-10 linear or branched alkyl groups; iv) polyalkoxylated alkyl groups;

13. A machine dishwashing detergent according to any one of claims 9 to 12, characterized in that the polymer having a molecular weight of 2000 gmol ^"1 or above, which has at least one positive charge, as monomer units diallyldimethylammonium salts and / or acrylamidopropyltrimethylammonium salts.

14. Machine dishwashing detergent according to one of claims 1 to 13, characterized in that it contains one or more phosphorus-containing complexing agents from the group i) of the phosphonates and / or ii) the condensed phosphates of the general formula (MPO ₃ ) _x , M _{x +2} P _x 0 _{3x + 1} and / or M _x H ₂ P _x 0 _{3x + 1} , where M is a cation and x is a number greater than or equal to 5.

15. Machine dishwashing detergent according to claim 14, characterized in that the weight fraction of the phosphorus-containing complexing agent between 1, 2 and 10 wt .-%, preferably between 1.5 and 8 wt .-%, preferably between 1, 7 and 7 wt .-% and particularly - In¬

between 2.0 and 6% by weight, based in each case on the total weight of the automatic dishwashing detergent.

16. Machine dishwashing detergent according to claim 15, characterized in that the automatic dishwashing agent is in the form of a prefabricated dosage unit which contains between 0.2 and 4 g, preferably between 0.3 and 3 g, particularly preferably between 0.4 and 3.0 g and in particular between 0.5 and 3.0 g of the phosphorus-containing complexing agent

17. A machine dishwashing detergent according to any one of claims 14 to 16, characterized in that it contains one or more phosphonate (s) from the group i) aminotrimethylenephosphonic acid (ATMP); ii) ethylenediaminetetra (methylenephosphonic acid) (EDTMP); iii) diethylenetriamine penta (methylenephosphonic acid) (DTPMP); iv) 1-hydroxyethane-1, 1-diphosphonic acid (HEDP); vi) 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC); vii) hexamethylenediaminetetra (methylenephosphonic acid) (HDTMP); a. Nitrilotri (methylenephosphonic acid) (NTMP).

18. A machine dishwashing detergent according to any one of claims 14 to 17, characterized in that it contains as phosphonates both 1-hydroxyethane-1, 1-diphosphonic acid (HEDP) and Diethylentriaminpenta (methylenephosphonic acid) (DTPMP), wherein the weight ratio of HEDP to DTPMP between 20: 1 and 1:20, preferably between 15: 1 and 1:15 and in particular between 10: 1 and 1:10.

19. A machine dishwashing detergent according to any one of claims 14 to 18, characterized in that it contains as phosphorus-containing complexing agent is a condensed phosphate of the general formula (MP0 ₃ ) _x , M _{x + 2} P _x 0 _{3x + 1} and / or M _x H ₂ P _x 0 _{3x + 1} , in which M is a cation, preferably an alkali metal, more preferably sodium or potassium, where x is a number greater than 6, more preferably greater than 8, most preferably greater than 10 and especially greater than 12 stands.

20. Machine dishwashing detergent according to one of claims 1 to 19, characterized in that it is in the form of a prefabricated dosing unit with two or more phases.

21. Machine dishwashing detergent according to one of claims 1 to 20, characterized in that it comprises a water-soluble casing.

22. A method for automatic dishwashing, in which a machine dishwashing detergent according to any one of claims 1 to 20 is introduced into the interior of a dishwasher before or while the dishwasher passes through a cleaning program.

23. The method of claim 22, wherein a surfactant system of a) at least one nonionic surfactant F of the general formula

R ¹ -CH (OH) CH ₂ O- (AO) _w - (AO) _x - (A "0) _y - (A"'O) _z -R ² , in which

R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . Alkyl or alkenyl radical; R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A, A ', A "and A'" independently of one another are radicals from the group -CH ₂ CH., -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CHs), -CH ₂ -CH ₂ - CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ), w, x, y and z are values between 0.5 and 25 where x, y and / or z can also be 0; and b) at least one nonionic surfactant G of the general formula

R ¹ -O- (AO) _w - (AO) _x - (A "0) _y - (A '" 0) _z -R ² in which

R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂₄ alkyl or alkenyl radical; R ^{2 is} H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A, A ', A "and A''independently of one another represent a radical from the group CH 2 -CH _2, -CH ₂ CH ₂ -CH _2, -CH ₂ -CH (CH ₃₎ -CH ₂ -CH ₂ - CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ), - w, x, y and z represent values between 0.5 and 25 where y and / or z can also be 0; wherein the surfactant system comprises the nonionic surfactants F and G in a weight ratio of F: G between 1: 4 and 100: 1 for automatic dishwashing, characterized in that the surfactant system is released in the main cleaning cycle and / or in the final rinse cycle.