DE102012222268A1 - Low-water to anhydrous liquid detergents - Google Patents

Abstract

The present invention relates to liquid, phosphate-containing, low-water to water-free cleaning agents, in particular an automatic dishwashing detergent which contains at least one phosphate-containing builder component, preferably a polyphosphate, potassium and sodium ions and at least one polyhydric alcohol selected from glycerol and mixtures of glycerol and 1,2-propylene glycol and has a water content of less than 25% by weight, characterized in that the mass ratio of glycerol to 1,2-propylene glycol is 1: 1 or greater, preferably 2: 1 or greater, and the mass ratio of potassium to sodium ions in the cleaning agent is either 2: 1 or more, or 1.5: 1 or less, and a method for producing and using them.

Description

The present invention relates to liquid, phosphate-containing, low-water to anhydrous detergents, in particular automatic dishwashing detergents which comprise at least one phosphate-containing builder component and at least one polyhydric alcohol, 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 here. 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. The European patent EP 1311654 B1 describes the preparation of aqueous liquid compositions having water contents of from 20 to 50% by weight, sodium salts being exchanged for potassium salts for improved solubility of the ingredients such that the molar ratio of potassium ions to sodium ions 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 rinsing performance of low-water to anhydrous, phosphate-containing, liquid detergent compositions containing less than 25 wt .-%, preferably less than 20 wt .-% water, sodium and potassium ions and glycerol or a mixture of glycerol and 1 , 2-propylene glycol, especially on the substrates glass and porcelain, can be optimized for the same amount of rinse aid by the choice of a suitable ratio of glycerol to 1,2-propylene glycol. It has also been found that the rinse performance can be further optimized by varying the ratios of sodium ions to potassium ions.

In a first aspect, therefore, the invention is directed to a liquid, phosphate-containing, low-water to anhydrous detergent containing at least one phosphate-containing builder component, preferably a polyphosphate, sodium and potassium ions and at least one polyhydric alcohol selected from glycerol and mixtures of glycerol and 1,2- Contains propylene glycol and has a water content less than 25 wt .-%, characterized in that the mass ratio of glycerol to 1,2-propylene glycol 1: 1 or greater, preferably 2: 1 or greater and the mass ratio of potassium to sodium ions in the Detergent is either (1) 2: 1 or more or (2) 1.5: 1 or less.

The term "low in water" as used herein means that the composition thus characterized contains less than 25% by weight of water, preferably less than 20% by weight of water. In particular, this term covers compositions which contain 1 to 20% by weight of water, 1 to 15% by weight of water, 5 to 15% by weight of water or 10 to less than 20% by weight of 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.

The polyhydric alcohols present in the detergents according to the invention make it possible to incorporate other constituents into the detergent formulation even if the amount of water is small, in particular if the amount of water is limited to 20% by weight.

The total amount of polyhydric alcohol or mixtures of alcohols used in detergents according to the invention is preferably at least 20% by weight, in particular at least 25% by weight, more preferably at least 28% by weight, especially at least 30% by weight. 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 selected from glycerine and mixtures of glycerol with 1,2-propylene glycol. Glycerol is used in inventive compositions preferably in an amount of 1 to 50 wt .-%, in particular in an amount of 10 to 45 wt .-%, particularly preferably in an amount of 20 to 40 wt .-%.

Alternatively, a mixture of glycerol and 1,2-propylene glycol is used. The glycerol is preferably used here in an amount of 0.1 to 50 wt .-%, in particular in an amount of 15 to 45 wt .-%, particularly preferably in an amount of 20 to 40 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 detergent used, 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 .-% in each case based on the total mass of the cleaning agent is.

In various embodiments of the invention, the cleaning agents are characterized in that the mass ratio of glycerol to 1,2-propylene glycol is greater than 2: 1, preferably greater than 3: 1, more preferably greater than 4: 1, most preferably 5: 1 until 1: 0.

The detergent further contains potassium and sodium ions, the mass ratio of potassium to sodium ions in the detergent being either 2: 1 or more or 1.5: 1 or less, preferably 3: 1 or more or 1: 1 or less. Alternatively, the mass ratio of potassium to sodium ions in the detergent is selected so that it does not fall in the range of 1.5: 1 to 2: 1, preferably not in the range of 1.1: 1 to 2.9: 1 ,

In various embodiments, the mass ratio of potassium to sodium ions in the detergent is either (1) 3: 1 to 85: 1, preferably 4: 1 to 30: 1, more preferably about 5: 1; or (2) 1.5: 1 to 0.25: 1, preferably 1.25: 1 to 0.5: 1, more preferably about 1: 1 to 0.7: 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 containing a disposable portion.

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

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

Nowadays commercially available automatic dishwashing agents generally contain as builder component 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 condensation products of ortho-phosphoric acid (H ₃ PO ₄ ) with the empirical formula P ₃ O ₁₀ ^5- usually in the form of their salts, preferably the alkali metal or alkaline earth metal, more preferably in the form of their salts Alkali metal salts are used. Tripolyphosphate salts are generally hygroscopic, white, odorless, nonflammable solids that are readily soluble in water. According to the invention, especially the potassium salt of tripolyphosphate (K ₅ P ₃ O ₁₀ ) or a mixture of the potassium salt of the tripolyphosphate and the sodium salt of the tripolyphosphate (Na ₅ P ₃ O ₁₀ ) are used. The mass ratio of potassium and sodium ions is chosen so that the mass ratio of potassium to sodium ions in the final detergent product is either 2: 1 or more or 1.5: 1 or less. For this purpose, the potassium and sodium salt are used in a corresponding mass ratio in a mixture of the potassium salt and the sodium salt of the tripolyphosphate. 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 .-%.

As a further constituent, the cleaning agents preferably contain one or more builder (s) (builders / cobuilders) in addition to the at least one phosphate-containing builder component. 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 other than the at least one phosphate-containing builder component 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 their salts, 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 action, the free acids typically also 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 potassium and / or potassium in the detergent Be sodium ions. Detergents containing from 1 to 10% by weight, preferably from 2 to 5% by weight, of citrate are preferred according to the invention.

Other suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of 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.

The cleaning agents may contain, in particular, phosphonates as further builder other than the at least one phosphate-containing builder component. 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 ethylenediamine tetramethylenephosphonate (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 cleaning agents may further comprise crystalline layered silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1, as a builder different from the at least one phosphate-containing builder component , 9 to 4, with particularly preferred values for x being 2, 3 or 4, and y being 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 sulfopolymer (s).

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 not only sulfonic acid group-containing monomer (s) but also at least one monomer selected from the group consisting of unsaturated carboxylic acids.

Unsaturated carboxylic acid (s) used are, with particular preference, unsaturated carboxylic acids of the formula R ¹ (R ² ) C =C (R ³ ) COOH, in which 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, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH as defined above 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.

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 or mixtures thereof. It goes without saying that it is also possible to use the unsaturated dicarboxylic acids.

In the sulfonic acid-containing monomers are 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 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, NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals 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 HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO 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, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble salts.

In the polymers, the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or fully neutralized sulfonic acid-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 the sulfonic acid group, the copolymers further 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.

The nonionic monomers used are preferably monomers of the general formula R ¹ (R ² ) C =C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another are -H, -CH ₃ or -C ₂ H ₅ , X for an optional is present spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 is} a straight-chain or branched 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, ethylcyclohexyn, 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, pentyl acrylate, hexyl acrylate, methyl methacrylate, N - (methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N- (2-ethylhexyl) acrylamide, octyl acrylate octyl acrylate, N- (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N- (lauryl) acrylamide, stearyl acrylate, methacrylic acid stearyl ester, N- (stearyl) acrylamide, behenyl acrylate, behenyl methacrylate and N- (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 aforementioned builders other than the at least one phosphate-containing builder component, the detergents may contain 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 surfactant (s) 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 come from the groups of 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.

bevorzugt, in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht; jede Gruppe R² bzw. R³ unabhängig voneinander ausgewählt ist aus -CH₃, -CH₂CH₃, -CH₂CH₂-CH₃, CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen. 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

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 stand for integers from 1 to 6.

Thus, particularly preferred are nonionic surfactants having a C _9-15 alkyl group 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.

• – R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht;
• – R² für H oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• – A, A’, A’’ und A’’’ unabhängig voneinander für einen Rest aus der Gruppe -CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃), -CH₂-CH₂-CH₂-CH₂, -CH₂-CH(CH₃)-CH₂-, -CH₂-CH(CH₂-CH₃) stehen,
• – w, x, y und z für Werte zwischen 0,5 und 120 stehen, wobei x, y und/oder z auch 0 sein können.

Preferred nonionic surfactants here are those of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A''O) _y - (A '''O) _z -R ² , in the

• R ^{1 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ^{2 is} H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• - A, A ', A''andA''' are independently 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 abovementioned nonionic surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _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 ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² , in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 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 30 carbon atoms and 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 ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² , in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical with 4 R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1.5 and y is a value of at least 15. The group of these nonionic surfactants includes, for example, the C _2-26 fatty alcohol (PO) ₁ - (EO) _15-40 -2-hydroxyalkyl ethers, in particular also the C _8-10 fatty alcohol (PO) ₁ - (EO) ₂₂ -2 -hydroxydecylether.

Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² , 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 R ³ = -CH ₃ and values of x from 15 to 32 and y of 0.5 and 1.5 are very particularly preferred.

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 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 ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ^{2 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, 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 such that the above formula is R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH ) CH ₂ OR ² simplified. In the latter 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.

• – R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht;
• – R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• – A für einen Rest aus der Gruppe CH₂CH₂, CH₂CH₂CH₂, CH₂CH(CH₃), vorzugsweise für CH₂CH₂ steht, und
• – w für Werte zwischen 1 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht

Finally, the nonionic surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w -R ^{2 have} proved to be particularly effective, in which

• R ^{1 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• A 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) _10-80 -2-hydroxyalkyl ethers, in particular also the C _8-12 fatty alcohol (EO) ₂₂ -2-hydroxydecyl ethers and the C _4-22 fatty alcohol (EO) _40-80 -2-hydroxyalkyl ether.

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 ¹ , R ³ , A, A ', 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 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 buffer substances are the citric acid or the citrates, in particular the sodium and potassium citrates, for example trisodium citrate.2H ₂ O and tripotassium citrate H ₂ O.

The agents according to the invention preferably comprise at least one further constituent, preferably selected from the group consisting of anionic, cationic and amphoteric surfactants, bleaches, 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. Also usable in the context of the present invention are fatty acid cyanamides, sulfosuccinates (sulfosuccinic esters), in particular sulfosuccinic mono- and di-C ₈ -C ₁₈ -alkyl esters, sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates and α-sulfofatty acid salts, acylglutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.

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

Suitable amphoteric surfactants are, for example, betaines of the formula (R ⁱⁱⁱ ) (R ^iv ) (R ^v ) N ⁺ CH ₂ COO ^- , in which R ^{iii 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 ₁₈ -Alkyldimethylcarboxymethylbetain and C ₁₁ -C ₁₇ -Alkylamidopropyl-dimethylcarboxymethylbetain.

Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R ^vi ) (R ^vii ) (R ^viii ) (R ^ix ) N ⁺ X ^- , in which R ^vi to R ^{ix are} four identical or different, in particular two long and two short-chain, alkyl radicals and X ^{- are} 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 having 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 preferably contain enzymes in total amounts of 1 × 10 ^-6 to 5% by weight, based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferable. Examples of these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as the further developments of the aforementioned amylases which are improved for use in cleaning agents. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

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.

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.

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. 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.

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. Such prefabricated preparations 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, low in water and / or added with stabilizers or further auxiliaries.

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 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, particularly 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 10,000 mPas, for example in the range 10000-50000 mPas, preferably around 35000 mPas (Brookfield Viscometer DV-II + Pro, spindle 25, 5 rpm, 20 ° C).

The cleaning agent can be in a water-insoluble, water-soluble or water-dispersible packaging. The invention therefore also relates to kits containing 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 preferable that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer have a good stability with a sufficiently high water solubility, in particular cold water solubility on.

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 of 10,000 to 1,000,000 gmol ^-1 , preferably 20,000 to 500,000 gmol ^-1 , more preferably 30,000 to 100,000 gmol ^-1 and especially 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 consisting of (meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyethers, polylactic acid, or mixtures of the above can be additionally used in a polyvinyl alcohol-containing film material suitable for producing the water-soluble coating Be added polymers. 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, methacrylates 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 with the label Solublon ^® PT, Solublon ^® GA, Solublon KC ^® or Solublon ^® KL by Aicello Chemical Europe GmbH, or VF-HP film available from Kuraray.

The cleaning agents according to the invention can be used as dishwashing agents, in particular automatic dishwasher detergents. The corresponding use is also the subject of the invention. The invention likewise relates to a dishwashing process, in particular a machine dishwashing process, in which a cleaning agent according to the invention is used.

Finally, the invention also relates to processes for the preparation of a cleaning agent, in particular a dishwasher detergent, according to the invention, characterized in that 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-containing 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 ( n) builder component (s). Suitable methods are known to those skilled in the art.

• (1) Vorlegen der wässrigen Lösung mindestens eines Bestandteils des Reinigungsmittels, beispielsweise des Sulfopolymers, insbesondere zusammen mit mindestens einem organischen Lösungsmittel, beispielsweise dem Glycerin oder der Glycerin/1,2-Propylenglykol-Mischung;
• (2) Zugabe der mindestens einen phosphathaltigen Builderkomponente, vorzugsweise des Tripolyphosphats, in fester Form; und
• (3) Rühren der Mischung bis sich die mindestens eine phosphathaltige Builderkomponente gelöst hat.

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

• (1) presenting the aqueous solution of at least one constituent of the cleaning agent, for example 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 surfactant (s), pH adjuster. 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 cleaning agents M11, M12, M21, M22, M31 and M32 (according to the invention) as well as V1, V2 and V3 (comparative examples not according to the invention) were produced. The compositions are shown in Tables 1-3 below, the quantities are in wt .-% active ingredient. 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, 3 pieces, porcelain (black) 3 pieces) with 20 g of the respective recipe and 100 g of soiling ("Steel Care": 4g Magarine / 4g potato starch / 1.6g NaCl / 16g whole egg and 74.4g water) rinsed 3x and visually peeled off 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 painted or lined and light-tight shielded and equipped with artificial lighting with 2 fluorescent tubes (Philips TLD 36W / 965 Natural Daylight 6500) Rinse scores were determined on the basis of the visual appearance of the dry dishes as indicated in Table 4. The results for the recipes tested are listed as arithmetic mean values in Tables 1-3. Higher values mean less spotting. ie a better rinse performance Table 1: Formulations with glycerol: propylene glycol ratio 1: 1 M11 V1 M21 potassium 20 15 10 sodium tripolyphosphate - 5 10 Sulfopolymer, Na salt 9 9 9 Sodium citrate dihydrate 4 4 4 HEDP 2.5 2.5 2.5 glycerin 18.5 18.5 18.5 1,2-propylene glycol 18.5 18.5 18.5 hydroxy mixed 2 2 2 Acrylic acid polymer, Na salt 0.2 0.2 0.2 ethanolamine 3.5 3.5 3.5 enzymes 4 4 4 zinc acetate 0.2 0.2 0.2 Perfume, dye, auxiliaries Ad 100 Ad 100 Ad 100 Mass ratio glycerol: propylene glycol 1: 1 1: 1 1: 1 Mass ratio K ⁺ : Na ⁺ 5: 1 1.7: 1 0.7: 1 Rinse power (porcelain (black)) 7.3 5.6 6.0 Table 2: Formulations with glycerol: propylene glycol ratio 3.1: 1 109 110 111 potassium 20 15 10 sodium tripolyphosphate - 5 10 sulfopolymer 9 9 9 Sodium citrate dihydrate 4 4 4 HEDP 2.5 2.5 2.5 glycerin 28 28 28 1,2-propylene glycol 9 9 9 hydroxy mixed 2 2 2 acrylic polymer 0.2 0.2 0.2 ethanolamine 3.5 3.5 3.5 enzymes 4 4 4 zinc acetate 0.2 0.2 0.2 Perfume, dye, auxiliaries Ad 100 Ad 100 Ad 100 Mass ratio glycerol: propylene glycol 3.1: 1 3.1: 1 3.1: 1 Mass ratio K ⁺ : Na ⁺ 5: 1 1.7: 1 0.7: 1 Rinse power (glass) 6.6 3.8 6.5 Rinse power (porcelain (black)) 8.3 6.0 8.3 Table 3: Formulations with glycerol: propylene glycol ratio 1: 0 112 113 114 potassium 20 15 10 sodium tripolyphosphate - 5 10 sulfopolymer 9 9 9 Sodium citrate dihydrate 4 4 4 HEDP 2.5 2.5 2.5 glycerin 37 37 37 1,2-propylene glycol - - - hydroxy mixed 2 2 2 acrylic polymer 0.2 0.2 0.2 ethanolamine 3.5 3.5 3.5 enzymes 4 4 4 zinc acetate 0.2 0.2 0.2 Perfume, dye, auxiliaries Ad 100 Ad 100 Ad 100 Mass ratio glycerol: propylene glycol 1: 0 1: 0 1: 0 Mass ratio K ⁺ : Na ⁺ 5: 1 1.7: 1 0.7: 1 Rinse power (glass) 7.1 6.2 7.6 Rinse power (porcelain (black)) 9.2 7.8 8.9

The results clearly show that the formulations of the invention compared to the non-inventive formulations give a significantly better rinse results on porcelain and glass. Table 4: Evaluation table rinse performance grade Intensity of the drops Number of drops 10 None None 9 Very low Very low 8th Low Very low 8th 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

QUOTES INCLUDE IN THE DESCRIPTION

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Cited patent literature

• EP 1311654 B1 [0006]

Claims (12)

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 at least one polyhydric alcohol selected from glycerol and mixtures of glycerol and 1,2-propylene glycol, and a water content of less than 25% by weight. characterized in that the mass ratio of glycerol to 1,2-propylene glycol is 1: 1 or greater, preferably 2: 1 or greater, and the mass ratio of potassium to sodium ions in the detergent is either (1) 2: 1 or greater, preferably 3: 1 or more, or (2) 1.5: 1 or less, preferably 1: 1 or less. Detergent according to claim 1, characterized in that the mass ratio of potassium to sodium ions in the detergent (1) is in the range 3: 1 to 85: 1, preferably 4: 1 to 30: 1, more preferably about 5: 1; or (2) is in the range 1.5: 1 to 0.25: 1, preferably 1.25: 1 to 0.5: 1, more preferably about 1: 1 to 0.7: 1. Detergent according to Claim 1 or 2, characterized in that the mass ratio of glycerol to 1,2-propylene glycol is greater than 2: 1, preferably greater than 3: 1, more preferably greater than 4: 1, most preferably 5: 1 to 1 : 0 is. Cleaning agent according to one of claims 1 to 3, 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. Cleaning agent according to claim 4, characterized in that the polyphosphate contains a potassium polyphosphate, in particular potassium tripolyphosphate. Cleaning agent according to one of claims 1 to 5, 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. Cleaning agent according to one of claims 1 to 6, characterized in that the cleaning agent contains at least one sulfopolymer. Cleaning agent according to one of claims 1 to 7, characterized in that the cleaning agent further comprises one or more of the substances selected from the group consisting of complexing agents, pH adjusters, nonionic, anionic, cationic and amphoteric surfactants, bleaching agents, bleach activators, bleach catalysts, enzymes, Thickeners, sequestering agents, electrolytes, corrosion inhibitors, especially silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances, bittering agents, and antimicrobial agents. Detergent according to one of claims 1 to 8, characterized in that it is in a water-insoluble, water-soluble or water-dispersible packaging, in particular in a polyvinyl alcohol-containing film. Use of the cleaning agent according to one of claims 1 to 9 as dishwashing detergent, in particular automatic dishwashing detergent. Machine dishwashing process, characterized in that a cleaning agent according to any one of claims 1 to 9 is used. A process for producing a detergent, in particular a dishwasher, according to one of claims 1 to 9, characterized in that presented in a first step, the sodium-containing ingredients dissolved in water and / or organic solvents and then the potassium-containing ingredients are added in a second step ,