EP2929000A1

EP2929000A1 - Low-in-water to water-free liquid cleaning agents

Info

Publication number: EP2929000A1
Application number: EP13732545.2A
Authority: EP
Inventors: Konstantin Benda; Thomas Eiting; Nina Mussmann; Thorsten Bastigkeit; Volker Blank; Noelle Wrubbel; Peter Schmiedel
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2012-12-05
Filing date: 2013-07-01
Publication date: 2015-10-14
Also published as: DE102012222267A1; WO2014086506A1

Abstract

The invention relates to liquid, phosphate-containing, low-in-water to water-free cleaning agents, in particular a machine dishwashing detergent, which contains at least one phosphate-containing builder component, preferably a polyphosphate, potassium ions and sodium ions and has a water content of less than 20% by weight, characterized in that the mass ratio of potassium to sodium ions in the cleaning agent is at least 1:1 or more. The invention further relates to processes for the production and use of said cleaning agents.

Description

Low-water to anhydrous liquid detergents

The present invention relates to liquid, phosphate-containing, low-water to anhydrous detergents, in particular automatic dishwasher detergents which contain at least one phosphate-containing builder component and sodium and potassium ions, a process for their preparation and their use.

Hard surface cleaners, such as dishwashing detergents, are available to the consumer in a variety of forms. In addition to the traditional solid agents are gaining increasingly increasingly flowable and especially liquid to gel detergent in importance. The consumer particularly appreciates the rapid solubility and the associated rapid availability of the ingredients in the cleaning liquor, especially in short-dishwashing programs and at low temperatures.

The importance of concentrated compositions, in which in particular the water content is reduced compared to conventional compositions, increases. For the consumer, therefore, compositions whose water content is as low as possible, for example less than 20% by weight, are particularly desirable.

Further, consumers have become accustomed to conveniently dosing pre-portioned automatic dishwashing detergents and have been using these products primarily in the form of tablets. In order to put a liquid dishwashing detergent offering the above-mentioned advantages over solid compositions in a pre-portioned form, the use of cold water-soluble films in the form of sachets is common. However, there are limits to the development of the formula since only a limited amount of water can be incorporated into the product. Exceeding the tolerable amount of water leads to premature dissolution of the enveloping water-soluble film. In order to ensure good storage stability of these water-soluble containers, water contents of less than 20 wt .-% are also desirable.

In order to ensure adequate flowability of the formulation, organic solvents, in particular polyhydric alcohols, are therefore used instead of water. In particular, 1,2-propylene glycol and glycerol and mixtures thereof have proved to be advantageous. However, a matrix of these solvents is only able to absorb sufficient quantities of rinse aid surfactant to a limited extent, which may adversely affect the rinse performance of the product.

Known formulations usually contain a large part of the ingredients in the form of Sodium salts. European Patent EP 131 1654 B1 describes the preparation of aqueous liquid compositions with water contents of 20 to 50% by weight, sodium salts being exchanged for potassium salts for improved solubility of the ingredients, so that the molar ratio of the potassium ions to the sodium Ion in the total composition is between 0.55: 1 and 20: 1. In the process described, sodium salts are first dissolved in water, preferably even the entire amount of sodium salts, while in a further step, the potassium salts and in particular potassium tripolyphosphate are added.

Surprisingly, it has now been found that the replacement of sodium ions by potassium ions in low-water to anhydrous, phosphate-containing, liquid detergent compositions containing less than 20 wt .-% water, to improve the rinse performance with the same amount of rinse aid, especially on plastic articles such as melamine or Tupperware.

In a first aspect, the invention is therefore directed to a liquid, phosphate-containing, water-poor to anhydrous cleaning agent which contains at least one phosphate-containing builder component, preferably a polyphosphate, potassium and sodium ions and has a water content of less than 20% by weight, characterized the mass ratio of potassium to sodium ions in the detergent is 1: 1 or more.

The term "low in water" as used herein means that the composition so characterized contains less than 20% by weight of water, preferably less than 15% by weight of water. -% water, 1 to 15 wt .-% water, 5-15 wt .-% water or 10 to less than 20 wt .-% water.

"Anhydrous" as used herein means that a composition contains less than 5% by weight, more preferably less than 3% by weight, preferably less than 1% by weight of water.

The water content as defined herein refers to the water content determined by Karl Fischer titration.

"Liquid" as used herein with respect to the cleaning agent of the present invention includes all flowable compositions and, in particular, also encompasses gels and pasty compositions.

"At least one" as used herein means 1 or more, for example, 1, 2, 3, 4, 5, or more. In preferred embodiments of the invention, the water activity is a _w , which is a measure of freely available water in a material and is defined as the quotient of the water vapor pressure over a material to the water vapor pressure over pure water at room temperature (23 ° C), at most 0.6 and preferably 0.3 to 0.6.

The mass ratio of potassium and sodium ions in the cleaning agent according to the invention is preferably in the range 1: 1 to 85: 1 (corresponds to a molar ratio of about 0.55: 1 to 50: 1), preferably 1, 5: 1 to 30: 1 more preferably 2: 1 to 15: 1, most preferably 3: 1 to 10: 1 or about 5: 1. The sodium and potassium ions can originate from the various ingredients of the cleaning agent, in particular the builder components and anionic surfactants, but also from all other optionally contained constituents, in particular those which are described below.

The cleaning agents according to the invention are preferably a dishwasher detergent, in particular a machine dishwashing detergent.

In a further aspect, the invention relates to such cleaning agents, which may be present in a water-insoluble, water-soluble or water-dispersible packaging, for example a film. The cleaning agent according to the invention is preferably contained in a water-soluble packaging. The water-soluble packaging in particular allows a one-time portioning of the cleaning agent. The invention therefore also relates to kits which contain the cleaning agent in such a water-soluble package in the form of a bag. The cleaning agent can be made up so that disposable portions are each packed separately.

A further subject of the present invention is also a machine dishwashing process in which a cleaning agent according to the invention or a cleaning agent according to the invention is used in a water-soluble packaging.

In yet another aspect, the invention also relates to the use of the cleaning agent according to the invention or of the cleaning agent according to the invention in a water-soluble packaging as dishwashing detergent, in particular automatic dishwashing detergent.

Commercially available dishwashing detergents which are commercially available as a rule contain as builders phosphates in the form of polyphosphates. Polyphosphates which can be used according to the invention are, for example, tripolyphosphates, pyrophosphates and metaphosphates and, in particular, their sodium or potassium salts. Preference is given to using tripolyphosphates.

The tripolyphosphates (or else triphosphates) which can be used according to the invention are condensates. ortho-phosphoric acid (H ₃ PO ₄ ) having the empirical formula P ³ O 10 ^{5 "} , which are usually used in the form of their salts, preferably the alkali metal or alkaline earth metal, more preferably in the form of their alkali metal salts Tripolyphosphate salts are generally hygroscopic, white, odorless , non-combustible solids which are readily soluble in water According to the invention, the potassium salt of tripolyphosphate (K ₅ P ₃ Oi ₀ ) or a mixture of the potassium salt of tripolyphosphate and the sodium salt of tripolyphosphate (Na ₅ P ₃ Oi ₀ ) are used. The mass ratio of the salts used, ie between potassium and sodium ions, is chosen so that the mass ratio of potassium to sodium ions in the final detergent product is more than 1: 1, preferably between 1: 1 and 85: 1 the potassium salt and the sodium salt of the tripolyphosphate, the potassium and sodium salt in a mass ratio of min at least 1, 5: 1, preferably 1, 8: 1 or more, more preferably 2: 1 or more, for example in the range of 2: 1 to 100: 1 used. Most preferably, only the potassium salt of the tripolyphosphate is used.

The proportion by weight of the polyphosphates, in particular the tripolyphosphate, in the total weight of the cleaning agent according to the invention is preferably 0.1 to 30 wt .-%, in particular from 1 to 28 wt .-%, particularly preferably from 5 to 25 wt .-%, more preferably from 10 to 23 wt .-%.

The cleaning agents according to the invention may further comprise at least one polyhydric alcohol. Such polyhydric alcohols may allow incorporation of other ingredients in a detergent formulation with a small amount of water, especially with a limitation of the amount of water to less than 20% by weight.

The amount of polyhydric alcohol used in detergents according to the invention is preferably at least 20 wt .-%, in particular at least 25 wt .-%, particularly preferably at least 28 wt .-%, especially at least 30 wt .-%. Preferred quantitative ranges are in this case from 20 to 50% by weight, in particular from 25 to 45% by weight, in particular from 28 to 40% by weight.

The polyhydric alcohol is preferably selected from glycerol, ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 2-methyl-1, 3-propanediol and mixtures thereof.

In a preferred embodiment, a mixture of at least two polyhydric alcohols is used.

A polyhydric alcohol which is particularly preferably used according to the invention is glycerol. Glycerol is preferably used in agents according to the invention in an amount of from 1 to 40% by weight, in particular in an amount of 10 to 35 wt .-%, particularly preferably in an amount of 20 to 30 wt .-%, used.

Another polyhydric alcohol which is particularly preferably used according to the invention is 1,2-propylene glycol. 1,2-Propylene glycol is preferably present in agents according to the invention in an amount of 1 to 40% by weight, in particular in an amount of 2 to 35% by weight, more preferably in an amount of 5 to 30% by weight all used 10 to 25 wt .-%.

In a particularly preferred embodiment, a mixture of glycerol and 1, 2-propylene glycol is used.

The glycerol is preferably used in an amount of 0, 1 to 40 wt .-%, in particular in an amount of 15 to 35 wt .-%, particularly preferably in an amount of 20 to 30 wt .-%. The 1, 2-propylene glycol is in this case preferably in an amount of 1 to 20 wt .-%, in particular in an amount of 5 to 15 wt .-%, particularly preferably in an amount of 8 to 12 wt .-%, respectively to the total mass of the cleaning agent, wherein the total amount of glycerol and 1, 2-propylene glycol preferably at least 20 wt .-%, in particular at least 25 wt .-%, especially at least 30 wt .-%, particularly preferably 25 to 45 wt .-%, in particular 30 to 42 wt .-%, especially 35 to 40 wt .-%, is. The mass ratios of glycerol: 1,2-propylene glycol are preferably at least 1: 1, in particular 1: 1 to 4: 1, particularly preferably 2: 1 to 3: 1.

As a further constituent, the cleaning agents preferably contain one or more builders (builders / cobuilders) in addition to the polyphosphate. The proportion by weight of these additional builders differing from the at least one phosphate-containing builder component in the total weight of the compositions according to the invention is preferably from 0.1 to 10% by weight and in particular from 2 to 7% by weight. These builders include, in particular, carbonates, citrates, phosphonates, MGDA (methylglycinediacetic acid) or its salts, GLDA (glutamic acid-N, N-diacetic acid) or its salts, EDDS (ethylenediamine-N, N'-disuccinic acid) or salts thereof, organic cobuilders and silicates.

For example, it is possible to use carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate.

Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and organic cobuilders. These classes of substances are described below. Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. 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. In addition to their builder effect, the free acids also typically have the property of an acidifying component and thus also serve for setting a lower and milder pH of cleaning agents. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Particularly preferred cleaning agents contain citrates, for example sodium or potassium citrate, as one of their essential builders, which differ from the at least one phosphate-containing builder component. The citrate may be a source of the potassium and / or sodium ions contained in the detergent. Detergents containing from 1 to 10% by weight, preferably from 2 to 5% by weight, of citrate are preferred according to the invention.

Polymeric polycarboxylates which are furthermore suitable as builders which differ from the at least one phosphate-containing builder component are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.

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.

In particular, the cleaning agents may contain, as further builders differing from the at least one phosphate-containing builder component, phosphonates. The phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Preferred aminoalkanephosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. Phosphonates are contained in the compositions preferably in amounts of 0.1 to 10 wt .-%, in particular in amounts of 0.5 to 8 wt .-%, each based on the total weight of the cleaning agent.

The detergents may further comprise, as builders differing from the at least one phosphate-containing builder component, crystalline layered silicates of the general formula NaMSi _x 0 ₂ x ₊ i ^■ y H ₂ O, where M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1, 9 to 4, with particularly preferred values for x being 2, 3 or 4 , and y is a number from 0 to 33, preferably from 0 to 20. It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.

In preferred cleaning agents, the content of silicates, based on the total weight of the cleaning agent, is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight. Particularly preferred cleaning agents are silicate-free.

The cleaning agents of the invention may further contain a sulfopolymer. The proportion by weight of the sulfopolymer in the total weight of the cleaning agent according to the invention is preferably from 0.1 to 20 wt .-%, in particular from 0.5 to 18 wt .-%, particularly preferably 1, 0 to 15 wt .-%, in particular from 4 to 14 wt .-%, especially from 6 to 12 wt .-%. The sulfopolymer is typically employed in the form of an aqueous solution, with the aqueous solutions typically containing from 20 to 70 weight percent, more preferably from 30 to 50 weight percent, preferably from about 35 to 40 weight percent sulfopolymers.

The sulfopolymer used is preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate.

The copolymers may have two, three, four or more different monomer units.

Preferred copolymeric polysulfonates contain, in addition to sulfonic acid-containing monomers, at least one monomer selected from the group consisting of unsaturated carboxylic acids.

As unsaturated carboxylic acid (s) is / are used with particular preference unsaturated carboxylic acids of the formula R (R ² ) C = C (R ³ ) COOH, in which R to R ³ independently of -H, - CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH as defined above or -COOH or - COOR ⁴ is where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid. acid or mixtures thereof. Naturally, it is also possible to use the unsaturated dicarboxylic acids.

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

Preferred among these monomers are those of the formulas

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH ₃ ) -X-SO ₃ H

H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H, in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , - CH ₂ CH ₂ CH ₃ and -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 (O) -NH-C (CH ₃ ) ₂ -, -C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -NH-CH ( CH ₃ ) -CH ₂ -.

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

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

The monomer distribution of the copolymers preferably used according to the invention in the case of copolymers containing only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably from 5 to 95% by weight, more preferably from 50 to 90% by weight of the sulfonic acid group-containing monomer. % and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are hereby preferably selected from the aforementioned.

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 cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol ¹ , preferably from 4000 to 25,000 gmol ¹ and in particular from 5000 to 15,000 gmol ^"1 .

In a further preferred embodiment, in addition to the carboxyl group-containing monomer and the monomer containing sulfonic acid groups, the copolymers furthermore comprise at least one nonionic, preferably hydrophobic monomer. The use of these hydrophobically modified polymers has made it possible in particular to improve the rinse aid performance of automatic dishwashing detergents according to the invention.

Anionic copolymers comprising monomers containing carboxylic acid groups, monomers containing sulfonic acid groups and nonionic monomers, in particular hydrophobic monomers, are therefore preferred according to the invention.

As nonionic monomers are preferably monomers of the general formula

R (R ² ) C = C (R ³ ) -XR ⁴ used, in which R to R ^{3 are} independently -H, -CH ₃ or -C ₂ H ₅ , X is an optional spacer group selected is from -CH ₂ -, -C (0) 0- and -C (0) -NH-, and R ^{4 is} a straight or branched chain saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.

Particularly preferred nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexene, 1-octene, α-olefins having 10 or more carbon atoms, such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22- α-olefin, 2-styrene, α-methylstyrene, 3-methylstyrene, 4-propylstryol, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2, vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, Butyl acrylate, acrylic acid pentyl ester, acrylic acid hexyl ester, methyl methacrylate, N- (methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, A / - (2-ethylhexyl) acrylamide, octyl acrylate, octyl methacrylate, A / (Octyl) acrylamide, lauryl acrylate, lauryl methacrylate, A / - (lauryl) acrylamide, stearyl acrylate, stearyl methacrylate, A / - (stearyl) acrylamide, behenyl acrylate, behenyl methacrylate and A / - (behenyl) acrylamide or mixtures thereof.

The monomer distribution of the hydrophobically modified copolymers preferably used according to the invention is preferably in each case from 5 to 80% by weight, with respect to the sulfonic acid group-containing monomer, the hydrophobic monomer and the carboxylic acid group-containing monomer, the proportion of the sulfonic acid group-containing monomer and of the each hydrophobic monomer 5 to 30 wt .-% and the proportion of the carboxylic acid group-containing monomer 60 to 80 wt .-%, the monomers are in this case preferably selected from the aforementioned.

In addition to the abovementioned builders which differ from the at least one phosphate-containing builder component, the cleaning agents may comprise alkali metal hydroxides. These alkali carriers are preferred in the cleaning agents only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, preferably below 5 wt .-%, particularly preferably between 0, 1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of the cleaning agent used. Alternative cleaning agents according to the invention are free of alkali metal hydroxides.

The cleaning agents according to the invention preferably also contain at least one nonionic surfactant. As nonionic surfactants, it is possible to use all nonionic surfactants known to the person skilled in the art. Low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants. With particular preference, the automatic dishwashing detergents contain nonionic surfactants from the group of the alkoxylated alcohols.

Particular preference is given to nonionic surfactants which have a melting point above room temperature. Nonionic (s) surfactants having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, is / are particularly preferred.

Preferably used surfactants are derived from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally compatible of compounded surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

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. Here are nonionic surfactants of the general formula

R -0- (CH ₂ -CH ₂ -0) - (CH ₂ -C H-0) - (CH ₂ -CH ₂ -0) _r (CH ₂ -C HO) - H

R2 R3

preferred, in which R stands for a straight-chain or branched, saturated or mono- or polyunsaturated _C6 -24 alkyl or alkenyl group; 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 stand for integers from 1 to 6.

Thus, in particular nonionic surfactants are preferred which have a C ₉ . ₁₅ alkyl having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units.

Preferred nonionic surfactants here are those of the general formula R -CH (OH) CH ₂ O-

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

R is a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ _24 -alkyl or -alkenyl radical;

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

A, Α ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ "CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, - CH ₂ -CH (CH ₂ -CH ₃ ),

w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0.

By the addition of the aforementioned nonionic surfactants of the general formula R - CH (OH) CH ₂ O- (AO) w - (AO) _x - (A "O) _y - (A '" O) _z -R ² , hereinafter also referred to as "hydroxy mixed ethers", the cleaning performance of the preparations according to the invention can be significantly improved both in comparison to surfactant-free system as well as in comparison to systems containing alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols. Preference is given in particular to those end-capped, poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R 0 [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² , in addition to a radical R, which is linear or branched, saturated or unsaturated , aliphatic or aromatic hydrocarbon radicals having from 2 to 30 carbon atoms, preferably having from 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having 1 to 30 carbon atoms, where x is from 1 to 90 , preferably for values between 30 and 80 and in particular for values between 30 and 60.

Particularly preferred are surfactants of the formula R 0 [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ Cl-1 (OI-l) R ² , in which R is a linear or branched aliphatic hydrocarbon radical with 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 represents values between 0.5 and 1, 5 and y represents a value of at least 15.

The group of these nonionic surfactants include, for example, the C ₂ -26 fatty alcohol (PO) i (EO) i ₅ . 4o-2-hydroxyalkyl ethers, in particular also the C ₈ . ₁₀ fatty alcohol (PO) - | - (EO) ₂ 2-2-hydroxydecyl ethers.

Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula R 0 [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² , in which R and R ^{2 are} independent each represent 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 independently of one another are values between 1 and 32, where nonionic surfactants with R ³ = -CH ³ and values for x of 15 to 32 and y of 0.5 and 1, 5 are very particularly preferred.

Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 0 [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² in which R and R ² R ^{1 is} H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2 Butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. When the value x> 2, each R ³ in the above formula R 0 [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ^{2 may be} different. R 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 may be} selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO ) (PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO ) (PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, with the variation width 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 zu

R 0 [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² simplified. In the latter formula, R, 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 and R ² Have 9 to 14 carbon atoms, R ^{3 is} H and x assumes values of 6 to 15.

Finally, the nonionic surfactants of the general formula R -CH (OH) CH ₂ O- (AO) wR ^{2 have} proven to be particularly effective, in which

R stands for a straight-chain or branched, saturated or mono- or polyunsaturated _C6 -24 alkyl or alkenyl group;

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

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

w stands for values between 1 and 120, preferably 10 to 80, in particular 20 to 40

The group of these nonionic surfactants include, for example, the C ₄ . ₂₂ fatty alcohol (EO) i ₀ -8o-2-hydroxyalkyl ethers, in particular also the C ₈ -i ₂ fatty alcohol (EO) ₂₂ -2-hydroxydecyl ethers and the C ₄ . ₂₂ fatty alcohol (EO) ₄₀ -8o-2-hydroxyalkyl ethers.

In various embodiments of the invention, instead of the above-defined end-capped hydroxy mixed ethers, it is also possible to use the corresponding non-end-capped hydroxy mixed ethers. These may satisfy the above formulas, but R ² is hydrogen and R, R ³ , A, Α ', A ", A", w, x, y and z are as defined above.

Preferred liquid cleaning agents are characterized in that the cleaning agent contains at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, wherein the weight fraction of the nonionic surfactant in the total weight of the cleaning agent is preferably 0, 1 to 10 wt .-%, preferably 0.5 to 8.0 wt .-% and in particular 1, 0 to 4.0 wt .-% is.

In general, the pH of the cleaning agent can be adjusted by means of customary pH regulators, the pH value being selected depending on the desired application. In various embodiments, the pH is in a range of 5.5 to 10.5, preferably 5.5 to 9.5, more preferably 7 to 9, especially greater than 7, especially in the range 7.5 to 8.5 , The pH adjusting agents are acids and / or alkalis, preferably alkalis. Suitable acids are in particular organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid. In addition, however, it is also possible to use the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof. Suitable bases are selected from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular the alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide is preferred. However, particularly preferred is volatile alkali, for example in the form of ammonia and / or alkanolamines, which may contain up to 9 carbon atoms in the molecule. The alkanolamine here is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof. The alkanolamine is preferably contained in agents according to the invention in an amount of from 0.5 to 10% by weight, in particular in an amount of from 1 to 6% by weight.

To adjust and / or stabilize the pH, the composition according to the invention may contain one or more buffer substances (INCI Buffering Agents), usually in amounts of from 0.001 to 5% by weight. Preference is given to buffer substances which are at the same time complexing agents or even chelating agents (chelating agents, INCI chelating agents). Particularly preferred buffers are citric acid or citrates, in particular the sodium and Kaliumeitrate, for example, tri- sodium citrate 2H ₂ 0 and H ₂ tripotassium 0th

The compositions according to the invention preferably comprise at least one further constituent, preferably selected from the group consisting of anionic, cationic and amphoteric surfactants, bleaching agents, bleach activators, bleach catalysts, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances , Bitter substances, and antimicrobial agents.

Preferred anionic surfactants are fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, alkylbenzenesulfonates, olefinsulfonates, alkanesulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignosulfonates.

The anionic surfactants are preferably used as sodium salts, but can also be used as other alkali or alkaline earth metal salts, for example potassium or magnesium salts, and in Form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, in the case of the sulfonates also in the form of their corresponding acid, for example dodecylbenzenesulfonic acid.

Suitable amphoteric surfactants are, for example, betaines of the formula (R " ¹ ) (R ^lv ) (R ^v ) N ⁺ CH ₂ COO ^" , in which R '"is an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R ^IV and R ^v are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C ₁₀ -C ₈ alkyl dimethylcarboxymethylbetain and Cn-Ci7-Alkylamidopropyl-dimethylcarboxymethylbetain.

Suitable cationic surfactants are i.a. the quaternary ammonium compounds of the formula

(R ^VI ) (R ^vii ) (R ^viii ) (R ^ix ) N ⁺ X ^" , in which R ^vi to R ^ix for four identical or different, in particular two long and two short-chain, alkyl radicals and X ^" for an anion , in particular a halide ion, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof. Further suitable cationic surfactants are the quaternary surface-active compounds, in particular with a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents. Through the use of quaternary surface-active compounds with antimicrobial action, the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.

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

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

Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storage and transportable preparations. To These ready-to-use preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in the case of liquid or gelated agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.

Alternatively, the enzymes can be encapsulated for both the solid and liquid dosage forms.

Furthermore, it is possible to assemble two or more enzymes together so that a single granule has several enzyme activities.

As can be seen from the previous comments, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, more preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10 wt .-% of the enzyme protein.

Particular preference is given to detergents which, based in each case on their total weight, contain 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight, of enzyme preparations.

The glass corrosion inhibitors used are preferably zinc salts, in particular zinc acetate. Glass corrosion inhibitors are preferably present in compositions according to the invention in an amount of from 0.05 to 5% by weight, in particular in an amount of from 0.1 to 2% by weight.

In various embodiments, the detergent immediately after production has a viscosity above 2000 mPas (Brookfield Viscometer DV-II + Pro, spindle 25, 30 rpm, 20 ° C), in particular between 2000 and 10,000 mPas. After storage, the viscosity may be higher, for example greater than 10000 mPas, such as in the range 10000-50000 mPas, preferably around 35000 mPas (Brookfield Viscometer DV-II + Pro, spindle 25, 5 rpm, 20 ° C).

The cleaning agent may be in a water-insoluble, water-soluble or water-dispersible packaging. The invention therefore also relates to kits which contain the cleaning agent together with such a package. The cleaning agent can be made up so that disposable portions are each packed separately.

The cleaning agent according to the invention is preferably contained in a water-soluble packaging. The water-soluble packaging allows a portioning of the cleaning agent. The Amount of detergent in the sachet is preferably 5 to 50 g, more preferably 10 to 30 g, especially 15 to 25 g.

The water-soluble coating is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends. The wrapper may be formed of one or two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if present, may be the same or different. Particularly preferred are films which, for example, can be glued and / or sealed to packages such as hoses or cushions after being filled with an agent.

It is preferred that the water-soluble casing contain polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer exhibit good stability with sufficiently high water solubility, in particular cold water solubility.

Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range from 10,000 to 1,000,000 gimol ^" , preferably from 20,000 to 500,000 gimol ^{" 1} , more preferably from 30,000 to 100,000 gmol ^"1 and in particular from 40,000 to 80,000 gmol ^"1 .

The production of polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.

In addition, a polymer selected from the group comprising a polyvinyl alcohol-containing sheet material suitable for producing the water-soluble sheath

(Meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above polymers may be added. A preferred additional polymer is polylactic acids.

Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred. Likewise preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylic esters or mixtures thereof.

It may be preferred that the film material contains further additives. The film material may contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, sorbitol, mannitol or mixtures thereof. Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-sticking agents or mixtures thereof.

Suitable water-soluble films for use in the water-soluble casings of the water-soluble packaging according to the invention are films sold by the company MonoSol LLC, for example under the designation M8630, C8400 or M8900. Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.

The dimensions of the disposable portions in the form of water-soluble bags should be designed so that the bags can not be swallowed by children.

In order to ensure the child safety of the disposable portions in the form of water-soluble bags, the standard gull test is used based on the European Standard 71-1 standard (modified version of the ISO 8124.1 standard). The standard gullet is a test cylinder, which has the size of a Kinderschlundes. The Standard Maw is usually used to test whether toys or small parts can be swallowed on toys of infants under the age of 3 years. The dimensions of the standard throat (in mm) are as follows:

If the examined part fits completely into the cylinder, it is considered as swallowable and therefore not allowed for toys of the mentioned age group. It can be seen that parts with a width of 31, 7 mm and a length of at least 31, 7 mm must have a height (thickness) of 25.4 mm in order to pass the standard gullet test. With a larger width, the height (thickness) can also be slightly smaller.

Preferably, therefore, disposable portions are provided in the form of water-soluble bags having a width of at least 32 mm, in particular from 32 to 40 mm and more preferably from 33 to 38 mm and a height (thickness) of at least 25 to 30 mm and in particular from 25 to 27 mm have. The length of the disposable portions can be flexibly designed; By definition (and for safety reasons) the length should be at least equal to the width. The maximum length is determined by the size of the dosing chambers in automatic dishwashers and should therefore not exceed 50 mm.

Disposable portions in the form of water-soluble pouches which contain cleaning agents according to the invention are distinguished by dimensional stability. The dimensional stability of the disposable portion can be defined by the weight constancy during storage of the detergent contained in the water-soluble bag. The highest possible weight constancy during storage of the detergent contained in the water-soluble bag is given when the pure agent (without the bag packaging) as high a constant weight in the test described below has 50 mg of the detergent (without bag packaging) in an open Aluminum crucible under isothermal conditions (40 ° C) for several hours under purge gas (air, 3 l / h) kept. At intervals of 30 minutes, the weight of the filled crucible is checked and the residue of the dishwashing detergent or the weight loss of dishwashing detergent is determined.

Usually, weight loss is highest in the first two hours of the given test. In the context of the present invention, dimensional stability of the disposable portions in the form of water-soluble pouches is understood to mean that the detergent in the specified test has a weight loss of not more than 15% by weight after 2 hours, preferably after 4 hours. In particular, it is preferred that the weight loss after one hour is not above 10% by weight. It is even more advantageous if the weight loss after 2 hours is not above 10% by weight.

The cleaning agents according to the invention or the kits which contain the cleaning agents according to the invention in a water-soluble packaging can be used as dishwashing detergents, in particular automatic dishwasher detergents. The corresponding use is also the subject of the invention. The invention likewise relates to a dishwashing method, in particular a machine dishwashing method, in which a cleaning agent according to the invention is used. or a kit which contains a detergent according to the invention in a water-soluble packaging is used.

Finally, the invention also relates to processes for the preparation of a cleaning agent, in particular a machine dishwashing agent, wherein presented in a first step, water, aqueous solutions and organic solvents and then added in a second step, the solid components. In particular, in the second step, solid sodium-containing constituents, in particular the phosphate- and sodium-containing builder component (s), may be dissolved in water and / or organic solvents and then in a second step solid potassium-containing constituents, in particular the phosphate and potassium containing builder component). Suitable methods are known to those skilled in the art.

In various embodiments of the invention, the method comprises the following steps:

(1) presentation of the aqueous solution of at least one constituent of the cleaning agent, for example of the sulfopolymer, in particular together with at least one organic solvent, for example the glycerol or the glycerol / 1, 2-propylene glycol mixture;

(2) adding the at least one phosphate-containing builder component, preferably the tripolyphosphate, in solid form; and

(3) Stir the mixture until the at least one phosphate-containing builder component has dissolved.

In step (1), either the solvent can be initially introduced and the aqueous solution of the at least one sulfo polymer added, or conversely the solution of the sulfo polymer can be initially charged and the organic solvent added. The at least one sulfopolymer or its aqueous solution is preferably as defined above.

The at least one phosphate-containing builder component, in particular tripolyphosphate, is preferably added in the form of a powder or granules. In various embodiments, the at least one phosphate-containing builder component is a tripolyphosphate, especially a tripolyphosphate salt, as defined above.

When mixtures of potassium and sodium salts of the tripolyphosphate are used in the process, it is preferred that the addition of the sodium salt be due to its poorer solubility prior to the addition of the potassium salt.

The addition of builders differing from the at least one phosphate-containing builder component, in particular citrate and / or phosphonate, can be carried out before step (2) or before step (3). In one embodiment, the method according to the invention comprises the addition of citrate before step (2) or step (3). Alternatively, the builders may also be added after stirring in step (3). For example, in one embodiment of the invention, phosphonate is added after stirring in step (3). All builders other than the at least one phosphate-containing builder component can be used as solids or in the form of their aqueous solutions in the preparation of the formulations according to the invention.

It is generally preferred that when potassium salts of the tripolyphosphate are used, the sodium containing ingredients, such as sodium citrate, are added prior to step (2).

After stirring the mixture in step (3), one or more further constituents of the cleaning agent can then be added. These may, for example, without limitation, be selected from nonionic surfactants, for example hydroxy mixed ethers, and pH adjusters. The addition can be carried out, for example, in the order: nonionic surfactants, pH adjusters. Since an exothermic neutralization reaction takes place when the pH-adjusting agent is added, the reaction mixture is preferably cooled. In general, it is preferred that during the addition of ingredients, the mixture is stirred continuously.

The said additional ingredients are preferably after the neutralization reaction, i. the pH adjustment and optionally added to a stirring step carried out during the pH adjustment or thereafter. In particular, after the pH adjustment in any order, one or more of the substances selected from the group consisting of cationic surfactants, amphoteric surfactants, zinc acetate, dyes, fragrances, bittering agents, enzymes, and preservatives are added.

In the method according to the invention, the necessary stirring steps, for example after the addition of the tripolyphosphate to dissolve the same, and at the pH adjustment and the necessary neutralization, preferably in a mixer with Wandgängigem stirring, in particular an anchor or helical stirrer performed. This preferably has a geometry which ensures complete mixing of the entire reaction mixture. In various embodiments, therefore, the agitator has a stirrer geometry d / D of at least 0.9, preferably greater than 0.9 to 0.99, where d is the diameter of the agitating tool and D is the diameter of the mixer.

The detergents prepared by the process according to the invention are distinguished on the one hand by their composition and on the other hand by the fact that they are stable on storage and even after a prolonged period no phase separation occurs. embodiments

The detergents E1 and E2 were prepared. The compositions are shown in the following Table 1, the quantities are in wt .-% active substance.

Table 1: Recipes

In the following, the rinse performance of the formulations was tested. For this purpose, in a Miele G 968 SC dishwasher at 50 ° C and 21 ° dH different materials (glass cups, 3 pieces, porcelain plate (black), 3 pieces, stainless steel cutlery, 3 pieces, melamine plates (blue), 3 pieces, Tupperdose (yellow) , 2 pieces) with 20 g of the respective recipe and 100 g of soiling ("Steel Cerare": 4g margarine / 4g potato starch / 1, 6 g NaCl / 16 g whole egg and 74.4 g water) rinsed 3 times and after each rinse cycle For this purpose, the machine was fully opened for 30 minutes after the rinse cycle and then in the black box (evaluation room, which is matte black coated or lined and light-tight shielded and with artificial lighting with 2 fluorescent tubes (Philips TLD 36W / 965 Natural Daylight 6500) are determined as visual characteristics, rinse notes are given on the basis of the visual appearance of the dry items as shown in Table 3. The results for the recipes tested, Table 2 is listed as arithmetic mean. Higher values mean less spotting, ie better rinse performance. Table 2: Rinse performance

Table 3: Evaluation table rinse performance

Note Intensity of the drops Number of drops

10 None None

9 Very low Very low

8 Low Very low

8 Very low Low

7 Average Very low

7 Low Low

7 Very low Average

6 High Very low

6 Average Low

6 Low Average

6 Very low high

5 Very high Very low

5 High Low

5 Average Average

5 Low High

5 Very low Very high

4 Very high Low

4 High Average

4 Average high

4 Low Very high

3 Very high Average

3 high high

3 Average Very high

2 Very high high

2 high Very high

1 Very high Very high

Claims

claims

1. Liquid, phosphate-containing, water-poor to anhydrous detergent containing at least one phosphate-containing builder component, preferably a polyphosphate, potassium and sodium ions and having a water content less than 20 wt .-%, characterized in that the mass ratio of potassium to sodium ions in the detergent 1: 1 or more.

2. Cleaning agent according to claim 1, characterized in that the mass ratio of potassium to sodium ions in the range 1: 1 to 85: 1, preferably 1, 5: 1 to 30: 1, more preferably 2: 1 to 15: 1, on most preferably 3: 1 to 10: 1 or about 5: 1.

3. Cleaning agent according to claim 1 or 2, characterized in that the at least one phosphate-containing builder component is a polyphosphate selected from the group of tripolyphosphates, pyrophosphates and metaphosphates, in particular a tripolyphosphate.

4. Cleaning agent according to claim 3, characterized in that the polyphosphate contains a potassium polyphosphate, in particular potassium tripolyphosphate.

5. Cleaning agent according to one of claims 1 to 4, characterized in that the cleaning agent further contains at least one further builder or co-builder, in particular citrate and / or phosphonate, preferably in the form of the sodium salt.

6. Cleaning agent according to one of claims 1 to 5, characterized in that the cleaning agent contains at least one sulfopolymer.

7. Cleaning agent according to one of claims 1 to 6, characterized in that the cleaning agent further comprises a polyhydric alcohol, in particular selected from the group glycerol, ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 2-methyl-1, 3 - Propandiol and mixtures thereof, contains.

8. Cleaning agent according to claim 7, characterized in that the cleaning agent glycerol and 1, 2-propylene glycol in a mass ratio of glycerol: 1, 2-propylene glycol of at least 1: 1, in particular 1: 1 to 4: 1, particularly preferably 2: 1 to 3: 1 contains.

9. Cleaning agent according to one of claims 1 to 8, characterized in that it has a water activity a _w , measured at 23 ° C, of at most 0.6 and preferably 0.3 to 0.6.

10. Kit, containing a cleaning agent according to any one of claims 1 to 9, characterized in that the cleaning agent is in a water-insoluble, water-soluble or water-dispersible packaging, in particular in a polyvinyl alcohol-containing film.

1 1. A kit according to claim 10, characterized in that it is a disposable portion in the form of a water-soluble bag, in particular of a polyvinyl alcohol-containing film, which contains the liquid detergent, wherein the detergent has a water activity a _w , measured at 23 ° C, of not more than 0.6, and preferably from 0.3 to 0.6.

12. Kit according to claim 10 or 1 1, characterized in that the filled with the detergent disposable portion in the form of a water-soluble bag has dimensional stability, wherein the detergent when stored under flushing gas (air, 3 l / h) at an isothermal temperature of 40 ° C after 2 hours has a maximum weight loss of 15 wt .-%.

13. Use of the cleaning agent according to any one of claims 1 to 1 to 9 or a kit according to any one of claims 1 1 to 12 as a dishwashing detergent, in particular as machine dishwashing detergent.

14. A machine dishwashing process, characterized in that a cleaning agent according to any one of claims 1 to 9 or a kit according to any one of claims 1 1 to 12 is used.

15. A process for the preparation of a cleaning agent, in particular a machine dishwashing agent, according to any one of claims 1 to 9, characterized in that presented in a first step solid sodium-containing components, in particular solid sodium and phosphate-containing builder components dissolved in water and / or organic solvents and then, in a second step, solid potassium-containing constituents, in particular solid potassium and phosphate-containing builder components, are added.