EP1711589A1

EP1711589A1 - Dishwasher detergent

Info

Publication number: EP1711589A1
Application number: EP05700758A
Authority: EP
Inventors: Ulrich Pegelow; Maren Jekel; Christian Nitsch; Arnd Kessler
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2004-02-04
Filing date: 2005-01-08
Publication date: 2006-10-18
Anticipated expiration: 2025-01-08
Also published as: WO2005075621A1; PL1711589T3; ES2513090T3; DE102004005344A1; US20070203047A1; EP1711589B1

Abstract

The invention relates to a solid dishwasher detergent which comprises a) 1 to 40 wt.- % of a bleaching agent, b) 0.25 to 20 wt.- % of niotenside(s); c) 0.01 to 10 wt.- % of at least one polymer having a molar mass of 2000 gmol-1 or more and having at least one positive charge. The detergent is characterized in that the weight ratio of component b) to component c) ranges between 25:1 and 100:1, preferably between 30:1 and 80:1, and specifically between 35:1 and 75:1. The inventive dishwasher detergent is characterized by an improved cleaning and rinsing power and improved processability and shelf life.

Description

Machine dishwashing detergent

This application relates to detergents or cleaners. In particular, this application relates to polymer- and 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 washing 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 washing 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 to a small extent, 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. By . the refractory continuous medium should release the acid (s) and scale inhibitor (s) with a delay and cause a clear rinse effect. Powdered automatic dishwashing or surfactant-containing rinse systems are not mentioned in this document.

It is an object of the present invention to provide bleach-containing automatic dishwashing detergents having a rinse-aid function which provide at least the same results in terms of performance properties as commercially available rinse aids and which, moreover, provide further performance advantages. 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 bleach-containing detergents provide above average cleaning and rinsing results, which are contained as further constituents of nonionic surfactants and polymers with positively charged monomer units, wherein the nonionic surfactants and said polymers are present in a certain weight ratio in these agents.

The present application therefore relates to a solid machine dishwashing detergent comprising a) from 1 to 40% by weight of bleaching agent, b) from 0.25 to 20% by weight of nonionic surfactant (s); c) from 0.01 to 10% by weight of at least one polymer having a molecular weight of 2000 gmol ^-1 or above and having at least one positive charge, characterized in that the weight ratio of component b) to component c) is between 25: 1 and 100: 1, preferably between 30: 1 and 80: 1 and in particular between 35: 1 and 75: 1.

A first essential ingredient of the solid automatic dishwashing compositions of the invention is the bleaching agent. Among the compounds which serve as bleaches and deliver in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids which yield H ₂ O ₂ , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Cleaning agents according to the invention may also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid

[Phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1, 12-diperoxycarboxylic acid, 1, 9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2- Decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronate) can be used.

As bleaching agents in the dispersions of the invention it is also possible to use chlorine or bromine-releasing substances. Among the suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or

Dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

Machine dishwashing detergent according to the invention, characterized in that it contains from 1 to 35% by weight, preferably from 2.5 to 30% by weight, particularly preferably from 3.5 to 20% by weight and in particular from 5 to 15% by weight of bleaching agent, Preferably, sodium percarbonate, are particularly preferred in the context of the present application.

The active oxygen content of the automatic dishwasher detergents according to the invention, in each case based on the total weight of the dishwashing detergent, is preferably between 0.4 and 10 wt .-%, more preferably between 0.5 and 8 wt .-% and in particular between 0.6 and 5 wt .-%. Particularly preferably processed solid dishwashing agents have an active oxygen content above 0.3 wt .-%, preferably above 0.7 wt .-%, more preferably above 0.8 wt .-% and in particular above 1, 0 wt .-% to.

A second essential ingredient of the automatic dishwashing compositions of the invention is the nonionic surfactant. As described above, agents according to the invention contain between 0.25 and 20% by weight of nonionic surfactant (s). In the context of the present application, however, preference is given to agents which contain from 0.5 to 15% by weight, preferably from 1 to 12.5% by weight, more preferably from 1.5 to 10% by weight and in particular from 2 to 8 Wt% nonionic surfactant (s). However, the compositions according to the invention preferably contain more than 2.0% by weight of nonionic surfactant (s), in particular between 2.5 and 7% by weight, preferably between 3.0 and 6% by weight, very particularly preferably between 3, 0 and 6.0 wt .-% and in particular between 3.0 and 5.5 wt .-%.

In the context of the present application, all nonionic surfactants known to the person skilled in the art can be used as nonionic surfactants, provided that they are generally suitable for compounding with bleaching agents. Preference is given to alkoxylated, advantageously ethoxylated, especially primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol used in which the alcohol radical may be linear or methyl branched preferably in the 2-position or linear and methyl-branched radicals may be present in the mixture as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. Preferred ethoxylated alcohols include, for example, C _12- ι ₄ alcohols containing 3 EO or 4 EO, C ₉ n-alcohol with 7 EO, C ₃ -i ₅ alcohols containing 3 EO, 5 EO, 7 EO or 8 EO , C _12- ι ₈ alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12- ι ₄ alcohol containing 3 EO and C _12-i ₈ alcohol containing 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) _x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol used for a glycose unit with 5 or 6 C atoms. men, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number between 1 and 10; preferably x is 1, 2 to 1, 4.

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

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

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

R '

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

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

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

R ¹ -0-R ²

R-CO-N- [Z j

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

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Low-foaming nonionic surfactants are used as preferred surfactants. With particular preference, the machine dishwashing detergents according to the invention contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example C ₁₂ -ι ₄ -alcohols with 3 EO or 4 EO, Cg-n-alcohol with 7 EO, Cιs- ₁₅ -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ ₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _2- ι ₄ -alcohol with 3 EO and C ₁₂ . _18- alcohol with 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Nonionic surfactants from the group of alkoxylated alcohols, particularly preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO-nonionic surfactants, are used with particular preference in the context of the present application.

Particular preference is given to compositions according to the invention which comprise a nonionic surfactant which has a melting point above room temperature. Accordingly, preferred dishwashing detergents are characterized by containing nonionic surfactant (s) with a Melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and in particular between 26.6 and 43.3 ° C.

Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If highly viscous nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have waxy consistency at room temperature are also preferred.

Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols, and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

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

A particularly preferred solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C _{_16-2} alcohol), a C preferably ₁₈ alcohol and at least 12 mole, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide won. Of these, the so-called "narrow rank ethoxylates" (see above) are particularly preferred.

Accordingly, particularly preferred dishwashing agents of the invention contain ethoxylated nonionic surfactant (s) consisting of C _6-20 monohydroxyalkanols or C ₆ . _20- alkylphenols or C _16-2 o-fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol was won (n).

The nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule. Preferably, such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from. Particularly preferred nonionic surfactants are ethoxylated Monohydroxyalkanols or alkylphenols additionally having polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants. Preferred dishwashing detergents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule contain up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic Surfactants are included.

Further particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

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

Another preferred dishwashing detergent according to the invention contains nonionic surfactant (s) of the formula (I)

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The preferred nonionic surfactants of formula II can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in formula II above 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 which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions according to the invention, automatic dishwasher detergents according to the invention are preferred in which R ¹ in formula VII is an alkyl radical having from 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 having a C _9-15 -alkyl radical with 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 are particularly preferred for use in the compositions according to the invention. These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.

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

R ¹ O [CH ₂ CH (R ³ ) O] _x R ² (III)

in which R ^{1 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{2 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably between 1 and have 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- ButyIrest stands, x for values between 1 and 40.

Automatic dishwashing detergents containing nonionic surfactant (s) of the general formula

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

In particularly preferred nonionic surfactants of the above formula (III), R ^{3 is} H. In the resulting end-capped poly (oxyalkylated) nonionic surfactants of the formula (IV)

R ¹ 0fCH ₂ CH ₂ 0] _x R ² (IV)

In particular those nonionic surfactants are preferred in which R ^{1 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, 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 x stands for values between 1 and 40.

Particular preference is given to those end-capped poly (oxyalkylated) nonionic surfactants which, according to the formula (V) R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² (V)

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, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical with 1 have up to 30 carbon atoms R ² , which is a monohydroxylated intermediate group - CH ₂ CH (OH) - adjacent. x in this formula stands for values between 1 and 40.

In particular, in the context of the present application, preference is given to those automatic dishwashing agents which contain nonionic surfactant (s) 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 40. The corresponding end-capped poly (oxyalkylated) nonionic surfactants of the above formula can be prepared, for example, by reacting a terminal epoxide of the formula R ² CH (O) CH ₂ with an ethoxylated alcohol of the formula R ¹ O [CH ₂ CH ₂ O] _x-1 CH ₂ Obtained CH ₂ OH.

Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula (VI)

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

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 -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.

Machine dishwashing detergent according to one of claims 1 to 7, characterized in that it contains nonionic surfactant (s) of the general formula

R ¹ 0 [CH ₂ CH ₂ Oj _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.

The stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers. Of course, the dishwasher detergents according to the invention may contain the aforementioned nonionic surfactants not only as individual substances but also as surfactant mixtures of two, three, four or more surfactants. Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas ,

If the machine dishwashing detergent according to the invention contains two, three, four or more nonionic surfactants, the proportion of the nonionic surfactants present in the detergent is preferably within narrow limits. If a mixture of two nonionic surfactants (surfactant 1 and surfactant 2) is used, the weight ratio of the nonionic surfactants used (weight ratio of surfactant 1 to surfactant 2) is preferably between 10: 1 and 1:10, preferably between 8: 1 and 1 : 8, more preferably between 6: 1 and 1: 6 and especially between 4: 1 and 1: 4.

If the machine dishwashing detergent according to the invention contains a surfactant mixture of two, three, four or more surfactants, it is preferred if at least one of the surfactants has a weight fraction of above 2.0% by weight, preferably above 3.0% by weight and in particular above 4 , 0 wt .-%.

As a third essential ingredient, the compositions of the invention contain from 0.01% to 10% by weight of at least one polymer having a molecular weight of 2000 gmol ^-1 or greater having at least one positive charge, with automatic dishwashing agents ranging from 0.02 to 7.5% % By weight, preferably 0.05 to 5 wt .-%, particularly preferably 0.07 to 2.5 wt .-% and in particular 0.1 to 1 wt .-% of at least one polymer having a molecular weight of 2000 gmol ^{" 1} or more, which has at least one positive charge, are particularly preferred.

The aforementioned polymers with cationic charge 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" for the purposes 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 become. Particularly preferred cationic polymers are selected from the groups of quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylates, 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 negatively charged groups or monomer units in addition to a positively charged group in the polymer chain.

Machine dishwashing detergent, characterized in that they contain a polymer c) which has monomer units of the formula R ¹ R ² C =CR ³ R ⁴ , in which each R ¹ , R ² , R ³ , R ^{4 is} selected independently of one another Hydrogen, derivatized hydroxy group, C1 to C30 linear or branched alkyl groups, aryl, aryl-substituted C _1-30 linear or branched alkyl groups, polyalkoyxylierte alkyl groups, heteroatomic organic groups 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 in the partial range of the pH range of 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 within the scope of the present invention en Registration particularly preferred.

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

R ¹ R ² R ⁴ IIIH ₂ C = C- (CH ₂ ) _x -N ⁺ - (CH ₂ ) _y -C = CH ₂ X ^" (VII), IR ³ in which R and R ⁴ are each independently H or a linear or branched one

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

Preferred radicals R ¹ and R ⁴ in the above formula (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 (VII) 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 units of the formula

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

in the case of X ^" = chloride also referred to as 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

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

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.

For the purposes of the present application, very particular preference is given to polymers which have a cationic monomer unit of the general formula (VIII) 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).

Automated dishwashing agents which are preferred according to the invention are characterized in that the polymer c) 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 useful amphoteric polymers are from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the

Alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the

Alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic 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, methacrylamidoalkyltrialkylammonium chloride and dimethyl (diallyl) ammonium chloride. Particularly preferred amphoteric polymers come from the group of Methacrylamidoalkyl- trialkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the

Methacryl-amidoalkyltrialkylammoniumchlorid / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the

Methacrylamidoalkyltrialkylammoniumchlorid / 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 the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers and the 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 μmol ^"1 or more in prefabricated form For the preparation of the polymers, the encapsulation of the polymers by means of water-soluble or water-dispersible coating agents is preferred by means of water-soluble or water-dispersible natural or synthetic polymers; the encapsulation of the polymers by means of water-insoluble, meltable coating compositions, preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 ° C. Cogranulation of the polymers with inert support materials, preferably with support materials the group of washing or cleaning substances, particularly preferably from the group of builders or cobuilders.

Machine dishwashing detergent according to one of Claims 1 to 12, characterized in that the weight ratio of component b) to component c) is between 25: 1 and 100: 1, preferably between 28: 1 and 90: 1, particularly preferably between 33: 1 and 80: 1 and especially between 35: 1 and 70: 1.

The solid automatic dishwashing compositions according to the invention can be made available to the consumer in various 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 dishwasher detergents which are made available to the consumer in the form of prefabricated metering units. The group of these prefabricated metering units include, for example, the single- or multi-phase compactates (preferably single-phase or multi-phase tablets), single-phase or multi-phase casting bodies or to filled water-soluble or water-dispersible container, preferably filled water-soluble or water-dispersible injection molded body, thermoformed body or filled foil bag.

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, in particular a multi-phase tablet with a filled well ,

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 may be pretreated before or during shaping by the action of heat and / or solvent and / or conditioning by relative humidity and / or temperature changes 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 can vary in its thickness and, for example, take higher values at the beginning of the process (during deep drawing of the film) than at its end (during filling or sealing or singulation).

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, becomes thereby for up to 5 seconds, preferably for 0.1 to 4 seconds, more preferably for 0.2 to 3 seconds and especially for 0.4 to 2 seconds at temperatures above 60 ° C, preferably above 80 ° C, particularly preferably between 100 and Heated to 120 ° C and in particular to temperatures between 105 and 115 ° C. In order to dissipate this heat, but in particular also to dissipate the heat introduced by the means filled into the deep-drawn receiving chambers (eg melting), it is preferable to cool the dies used and the receiving troughs located in these dies. The cooling is preferably carried out at temperatures below 20 ^C C, preferably below 15 ° C, more preferably at temperatures between 2 and 14 ° C and in particular at temperatures between 4 and 12 ^C C. Preferably, the cooling is carried out continuously from the beginning of the deep-drawing process to 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 Patrizenformwalze, which lead the forming upper punch to the cavities of the Matrizenformwalze) is 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 formulated in a water-soluble or water-dispersible thermoformed body, which in addition to the inventive solid machine dishwasher detergent in a separate receiving chamber further contains a liquid or gel detergent or detergent mixture.

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 compositions (injection molding compounds) are water-soluble polymers, for example the abovementioned cellulose ethers, pectins, polyethylene glycols, polyvinyl alcohols, polyvinylpyrrolidones, alginates, gelatin or starch.

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 may be a melted 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. Melt mixtures of substance mixtures can e.g. be beneficial when forming eutectic mixtures that melt significantly lower and thus reduce 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.

Automatic dishwashing detergent in a prefabricated metering unit, characterized in that the prefabricated metering unit is a filled water-soluble container, preferably a filled injection molding body, a filled casting body or a filled foil bag, are particularly preferred within the scope of the present application. The prefabricated dosing units described above are preferably dosing units for simple application. In order to be able to be used also via the dosing boxes of the dishwashers, such dosing units preferably have a volume below 25 ml, preferably between 10 and 25 ml, more preferably between 12 and 23 and in particular between 15 and 21 ml. The weight of these prefabricated metering units is preferably between 10 and 30 g, more preferably between 13 and 27 g and in particular between 16 and 24 g. Machine dishwashing detergent, characterized in that the automatic dishwashing detergent is in the form of a prefabricated metering unit which contains between 0.5 and 4 g, preferably between 0.8 and 3.5 g, particularly preferably between 1, 0 and 3.0 g and in particular contains between 1, 5 and 2.5 g of nonionic surfactants are particularly preferred in the context of the present application.

The solid dishwashing detergents according to the invention are particularly suitable for cleaning glassware. A further subject of the present application is therefore the use of the automatic dishwasher detergents according to the invention for the cleaning and rinsing of glassware.

In addition to the abovementioned bleaching agents, nonionic surfactants and polymers, the dishwasher detergents according to the invention preferably comprise further washing and cleaning substances, in particular washing and cleaning substances from the group of bleach activators, polymers, builders, surfactants, enzymes, disintegration aids, electrolytes, pH adjusters, Perfumes, perfume carriers, dyes, hydrotropes, foam inhibitors, corrosion inhibitors and gaseous 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 +} 1 'H ₂ O, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both ß- and δ-sodium disilicates Na ₂ Si ₂ 0 ₅ 'yH ₂ 0 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 sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS, eg Na-SKS-1

(Na ₂ Si ₂₂ O ₄₅ -H ₂ 0, Kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O _2g- H ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ O ₁₇ -H ₂ O) or Na-SKS-4 (Na ₂ Si ₄ Og-χH ₂ O, Makatit).

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 ).

When the silicates are used as a constituent of machine dishwashing detergents, such funds included in the present application, a proportion by weight of the crystalline layered silicate of the formula NaMSi _x 0 _{2x + 1} 'y H ₂ 0 of 0.1 to 20 wt .-%, 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 wt .-% to silicate of the general formula NaMSi _x 0 _{2x +} ι ^• 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 machine Dishwashing detergent, which is particularly preferred in the context of the present application. Among the large number of commercially available phosphates, the alkali metal phosphates, with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.

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 höhermölekularen representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also 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 the 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 P0. 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 indicated 880 °) and as decahydrate (density 1, 815-1, 836 like ^{" 3} , melting point 94 ° with loss of water), and the corresponding potassium salt potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ 0 ₇ .

Condensation of the NaH ₂ P0 ₄ or the KH ₂ P0 ₄ gives higher mol. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: hot or cold phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ 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] _π -Na with n = 3. The corresponding potassium salt Pentakaliumtriphosphat, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P ₂ 0 ₅ , 25% K ₂ 0) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH -> Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

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

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.

It is preferred in particular 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, alkali metal silicates and mixtures of the abovementioned substances, preference being given to using alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium metabicarbonate, for the purposes of this invention. 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. Due to their low chemical compatibility with the other ingredients of detergents or cleaners compared to other builders, the Alkali metal hydroxides are preferred 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 washing 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 wt .-%, 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% by weight of 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 action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

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 cleaners to (co) polymeric polycarboxylates is preferably 0.5 to 20 wt .-%, in particular 3 to 10 wt .-%.

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

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

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

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

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

In addition to the nonionic surfactants described at the outset, the anionic, cationic and amphoteric surfactants are also counted among the group of surfactants.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. The surfactants of the sulfonate type are preferably C ₉ . _13- Alkylbenzolsul- fonate, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained for example from C _12-18 monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation, into consideration. Also suitable are alkanesulfonates, which are for example derived from C _{12 8} alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. Similarly, the esters of α-sulfo fatty acids (ester sulfonates), for example, the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or Taigfettsäuren are suitable. Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 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. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ - alkyl sulfates and C ₁₄ -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 the straight-chain or branched C _7-21 -alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ . ₁ alcohols with an average of 3.5 moles of ethylene oxide (EO) or C ₁₂ . ₁₈ fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ .ι ₈ fatty alcohol radicals 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, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.

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 IX, X or XI: R ¹

R ¹ -N ⁽⁺⁾ - (CH ₂ ) _π -TR ² (IX)

(CH ₂ ) _n -TR ²

R ¹ IR ¹ -N ⁽⁺⁾ - (CH ₂ ) _n -CH-CH ₂ (X) II IR ¹ TT

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

R ⁴ wherein each R ^{1 group is} independently selected from C _1-6 alkyl, alkenyl or hydroxyalkyl groups; each R ^{2 group 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 X are preferred as the monomer,

R ¹ (R ² ) C = C (R ³ ) COOH (XII),

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 XII 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 XIII are preferred,

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

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 XIIIa, XIIIb and / or XIIIc,

H ₂ C = CH-X-SO ₃ H (XIIIa), H ₂ C = C (CH ₃ ) -X-SO ₃ H (XIIIb), H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) - X-S0 ₃ H (XIIIc),

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 Xla), 2-acrylamido-2-propanesulfonic acid (X = -C ( 0) NH-C (CH ₃ ) ₂ in formula XIIla), 2-acrylamido-2-methyl-1-propanesulfonic acid (X = - C (O) NH-CH (CH ₃ ) CH ₂ - in formula XIIla), 2 -Methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula XIIIb), 3-methacrylamido-2-hydroxypropanesulfonic acid (X = -C (0) NH-CH ₂ CH (OH) CH ₂ - in formula XIIIb), allylsulfonic acid (X = CH ₂ in formula XIIIa), methallylsulfonic acid (X = CH ₂ in formula XIIIb), allyloxybenzenesulfonic acid (X = -CH ₂ -O-C ₆ H ₄ - in formula XIIla), methallyloxybenzenesulfonic acid (X = -CH ₂ -O-C ₆ H ₄ - in formula XIIIb), 2-hydroxy-3- (2-propenyloxy) propanoic acid, 2-methyl-2-propene1 sulfonic acid (X = CH ₂ in formula XIIIb), styrenesulfonic acid (X = C ₆ H ₄ in formula XIIIa), vinylsulfonic acid (X not present in formula Xllla), 3-sulfopropyl acrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in formula XIIla), 3-sulfopropyl methacrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in formula XIIIb), sulfomethacrylamide (X = -C (O) NH- in formula XIIIb), sulfomethylmethacrylamide (X = -C (O) NH-CH ₂ - in formula XIIIb) and water-soluble salts of said acids.

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

In summary, copolymers are made of

i) unsaturated carboxylic acids of the formula XII.

R ¹ (R ² ) C = C (R ³ ) COOH (XII),

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 XIII

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

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 sulfonic acid-containing monomers of the formulas XIIIa, XIIIb and / or XIIIc:

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

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

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

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

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. When the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained whose use is likewise preferred. The corresponding copolymers contain the structural units of the formula XV

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

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 ) _n - where n = 0 to 4, -O- (C ₆ H ₄ ) -, -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 XVI

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

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) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is, as preferred as copolymers, the structural units of the formula XVII

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

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 ) _n - 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). you arrives in this way to inventively preferred copolymers, the structural units of the formula XVIII

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

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 XIX

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

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 XIV and / or XV and / or XVI and / or XVII and / or XVIII and / or XIX

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XIV), - [CH ₂ -C (CH ₃ ) C O H] _m - [CH ₂ -CHC ( 0) -Y-S0 ₃ H] _p - (XV), - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XVI), - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XVII), - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XVIII), - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) O-Y-SO ₃ H] _p - (XIX)

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, ie, the acidic acid of the sulfonic acid group in some or all of the sulfonic acid groups may be exchanged for metal ions, preferably alkali metal ions and especially sodium ions. The use of partially or fully neutralized sulfonic acid-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, especially 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 IR ² -N ⁽⁺⁾ - (CH ₂ ) -CN X ^H ,

R ³

in the R ^{1 is} -H, -CH ₃ , a C _2-24 alkyl or alkenyl radical, a substituted C _2-2 alkyl or alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical having a C _1-2 alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C _1-24 alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ - OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH _3, -CH ₂ - CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH _3, -CH (OH) - CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _π 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 ^H ,

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 also -H may be and X is an anion, preferably R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ and compounds of formein (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ( CH ₃ )) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , or (HO-CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^{" are} particularly preferred, wherein from the group of these substances turn the cationic Nitrile of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" in which X ^{" represents} 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 the O- and / or N-acyl groups of the mentioned 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, especially tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5- Diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA) and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfruktose, tetraacetylxylose and octaacetyllactose as well as acetylated, if appropriate N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam. 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, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.

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 having 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, particularly preferably the cobalt (ammine) Complexes of the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate are used 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 bleach activator-containing agent 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) ₂ ), and zinc pyrophosphate (Zn ₂ (P ₂ O 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 % By weight, based in each case on the entire glass corrosion inhibitor-containing agent. 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 it may be even lower in soluble salts; 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, of the branched saturated or unsaturated monocarboxylic acids, of saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, ^'preferably, the sugar acids, of the hydroxy acids, of the oxo acids, of the amino acids and / or polymeric carboxylic acids.

The spectrum of the inventively preferred zinc salts of organic acids, preferably organic carboxylic acids, ranging from salts which are difficult or insoluble in water, ie a solubility below 100 mg / L, preferably below 10 mg / L, in particular have no solubility, to such Salts 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, zinc citrate, zinc oleate and zinc stearate, and the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.

With particular preference, the glass corrosion inhibitor used is 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 zinc citrate. 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 are used to protect the items to be washed or the machine, and in the field of automatic dishwashing, especially anti-soiling agents are of particular importance. 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, undecyl, 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 detergents, the alkylamino-1,2,4-triazoles or their physiologically tolerated salts are present in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2% by weight, 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-alkyl-3-amino-1, 2,4-triazoles 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, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (amine) complexes, the cobalt (acetate) complex, 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" common in chemistry is e.g. in "Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart New York, 9th edition, 1991, page 3168" reproduced.

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 , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) ₃ and mixtures thereof. so that preferred automatic dishwasher detergents according to the invention are characterized in that the 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-hydroxy-ethane

1, 1-diphosphonate], V ₂ 0 ₅ , V ₂ 0 ₄ , V0 ₂ , TiOS0 ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO 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, e.g. that from the S0-production

(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, ie completely coated with a waterproof material which is readily soluble in the cleaning temperatures, in order 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, for example by spinning finely divided material to be coated in a 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, subtilisin type ones are preferred. Examples thereof are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg in a developed form under the trade names Alcalase ^® from Novozymes A / S, Bagsvaard, Denmark. The subtilisins 147 and 309 are under the trade names Esperase ^®, respectively Sold 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 ^®, relase ^®, Everlase® ^®, Nafizym, Natalase ^®, Kannase® ^® and Ovozymes ^® from Novozymes, under the trade names Purafect ^®, Purafect ^® OxP and Properase.RTM ^® by the company Genencor, under .the trade name Protosol® ^® from Advanced Biochemicals Ltd., Thane, India, that under the trade name Wuxi ^® from Wuxi Snyder Bioproducts Ltd., China, from 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 ^®. The α-amylase of β. amyloliquefaciens is sold by Novozymes under the name BAN ^®, and derived variants from the α- amylase from ß. 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, by Novozymes under the trade names Lipolase ^®, Lipolase ^® UItra, LipoPrime® ^®, ^® Lipozyme® and Lipex ^® marketed. 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. From the company Genencor, for example, the lipases, or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Other important commercial products, the preparations originally sold by Gist-Brocades M1 Lipase ^® and Lipomax® ^® and the enzymes marketed by Meito Sangyo KK, Japan under the names Lipase MY-30 ^®, Lipase OF ^® and lipase PL ^® to mention 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 biotechnoiogic 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 a peptidic Protease inhibitors include ovomucoid and leupeptin; 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 moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, into these compositions 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. Well-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 O 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 cellulosic disintegrating agents used but used in mixture 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 a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted. The particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns. 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 deaggregation of the microfine celluloses produced by the hydrolysis yields the microcrystalline celluloses which have primary particle sizes of about 5 μm and can be compacted, for example, into granules having an average particle size of 200 μm.

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 thinkable and executable, such as nitrogen, Release oxygen or hydrogen, the effervescent system used in the detergent and cleaning compositions of the invention will be selected both on the basis of economic and environmental 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.

Acidifying agents that release carbon dioxide from the alkali salts in aqueous solution include, for example, boric acid and alkali metal hydrogen sulfates,

Alkali metal dihydrogen phosphates 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. Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are again preferred from this group. 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 perfumes, individual fragrance compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenylglycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals with 8-18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the ionone, α-lsomethylionon and Methylcedrylketon to the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol; the hydrocarbons mainly include the terpenes such as limonene and pinene. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures as are available from vegetable sources, eg pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint oil, cinnamon oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil, 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 dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to the dye-containing agents to be treated substrates such as glass, ceramic or plastic tableware, not these to stain.

Claims

claims:

A solid machine dishwashing detergent comprising a) from 1 to 40% by weight of bleaching agent, b) from 0.25 to 20% by weight of nonionic surfactant (s); c) 0.01 to 10 wt .-% of at least one polymer having a molecular weight of 2000 gmol ^'1 or above, which has at least one positive charge, characterized in that the weight ratio of component b) to component c) is between 25: 1 and 100: 1 is preferably between 30: 1 and 80: 1, and more preferably between 35: 1 and 75: 1.

2. Machine dishwashing detergent according to claim 1, characterized in that it contains 1 to 35 wt .-%, preferably 2.5 to 30 wt .-%, particularly preferably 3.5 to 20 wt .-% and in particular 5 to 15 wt. % Bleaching agent, preferably sodium percarbonate.

3. Machine dishwashing detergent according to one of claims 1 or 2, characterized in that it 0.5 to 15 wt .-%, preferably 1 to 12.5 wt .-%, particularly preferably 1, 5 to 10 wt .-% and in particular 2 to 8 wt .-% of nonionic surfactant (s).

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

R ¹ 0 [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² contains, in the R ¹ for a linear or branched aliphatic hydrocarbon remainder with 4 to 18 carbon atoms or mixtures from this, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x represents values between 0.5 and 1, 5 and y represents a value of at least 15.

5. Machine dishwashing detergent according to one of claims 1 to 4, characterized in that it nonionic (s) surfactant (s) 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 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.

6. Machine dishwashing detergent according to one of claims 1 to 5, characterized in that it nonionic (s) surfactant (s) 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 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-propyl, iso Propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical and x stands for values between 1 and 40.

7. Machine dishwashing detergent according to one of claims 1 to 6, characterized in that it 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 20 carbon atoms, further comprising 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 CH (OH) - adjacent and in which x for values between 1 and 40 stands.

8. Machine dishwashing detergent according to one of claims 1 to 7, characterized in that it nonionic (s) surfactant (s) of the general formula

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

^RJ 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 is -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 very particularly preferred.

9. Machine dishwashing detergent according to one of claims 1 to 8, characterized in that the automatic dishwashing agent is in the form of a prefabricated dosing unit which is between 0.5 and 4 g, preferably between 0.8 and 3.5 g, particularly preferably between 1 , 0 and 3.0 g and especially between 1.5 and 2.5 g of nonionic surfactants.

10. Machine dishwashing detergent according to one of claims 1 to 9, characterized in that the automatic dishwashing agent is in the form of a prefabricated metering unit, wherein the prefabricated metering unit is a shaped body, preferably a multi-phase shaped body, in particular a mono- or multi-phase Tablet with a filled trough.

11. Machine dishwashing detergent according to one of claims 1 to 9, characterized in that the automatic dishwashing agent is in the form of a prefabricated metering unit, wherein it is in the prefabricated metering unit to a filled water-soluble container, preferably a filled injection molding, a filled casting or a filled foil bag is.

12. Machine dishwashing detergent according to one of claims 1 to 11, characterized in that it 0.02 to 7.5 wt .-%, preferably 0.05 to 5 wt .-%, particularly preferably 0.07 to 2.5 wt and more preferably 0.1 to 1% by weight of at least one polymer having a molecular weight of 2000 gmol ^-1 or above and having at least one positive charge.

13. Machine dishwashing detergent according to one of claims 1 to 12, characterized in that the polymer c) 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 hydrogen, derivatized hydroxy, C1 to C30 linear or branched alkyl groups, aryl, aryl substituted C1-30 linear or branched alkyl groups, polyalkoxylated alkyl groups, heteroatomic organic groups having at least one positive charge without charged nitrogen, at least one quaternized N- Atom or at least one Amino group with a postitive charge in the partial range of the pH range of 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 , is at least one quaternized N atom or at least one amino group with a positive charge.

14. Machine dishwashing detergent according to any one of claims 1 to 13, characterized in that the polymer c) contains as monomer units diallyldimethylammonium salts and / or acrylamidopropyltrimethylammonium salts.

15. Machine dishwashing detergent according to one of claims 1 to 14, characterized in that the weight ratio of component b) to component c) is between 25: 1 and 100: 1, preferably between 28: 1 and 90: 1, particularly preferably between 33 : 1 and 80: 1 and especially between 35: 1 and 70: 1.

16. Machine dishwashing detergent according to one of claims 1 to 15, characterized in that it contains 10 to 80 wt .-%, preferably 15 to 75 wt .-%, particularly preferably 20 to 70 wt .-% and in particular 25 to 65 wt. - contains% of one or more water-soluble builders.

17. Use of automatic dishwasher detergents according to one of claims 1 to 16 for cleaning and rinsing glassware.