EP2929001A1

EP2929001A1 - Process for producing low-in-water to water-free liquid detergent or cleaning agents

Info

Publication number: EP2929001A1
Application number: EP13732542.9A
Authority: EP
Inventors: Konstantin Benda; Thomas Eiting; Nina Mussmann; Volker Blank; Noelle Wrubbel; Thorsten Bastigkeit; Oliver Kurth; von den Karl-Josef DRIESCH; Matthias Sunder
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
Anticipated expiration: 2033-07-01
Also published as: DE102012222266A1; EP2929001B2; WO2014086504A1; PL2929001T5; ES2660245T3; PL2929001T3; EP2929001B1; ES2660245T5; KR20150096434A; US20150267153A1

Abstract

The invention relates to a process for producing liquid, low-in-water to water-free detergents or cleaning agents, in particular a machine dishwashing detergent, which contain at least one sulfopolymer and at least one builder component, wherein, during the production, the at least one sulfopolymer is used in the form of an aqueous solution and the at least one builder component is used in solid form. The invention further relates to detergents and cleaning agents produced using said process and the use thereof.

Description

Process for the preparation of low-water to anhydrous liquid washing or cleaning agents

The present invention relates to a process for the preparation of liquid, water-poor to anhydrous detergents or cleaners, in particular a machine dishwashing detergent containing at least one sulfopolymer and at least one builder component, and the detergents and cleaning agents thus prepared and their use.

Detergents and cleaners for hard surfaces as well as dishwashing detergents are available to the consumer in a variety of forms. In addition to the traditional solid means increasingly lately increasingly flowable and especially liquid to gel detergent or cleaning agents gain in importance. The consumer particularly appreciates the rapid solubility and the associated rapid availability of the ingredients in the washing or cleaning liquor, in particular also in short wash 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.

The problem with such formulations, however, is that some raw materials are either in the form of aqueous solutions, so that either the amount of these raw materials must be limited in order not to increase the water content of the composition unintentionally, or the raw materials if chemically possible dried or used in solid form Need to become. In the latter approach, the problem often arises of dissolving the required amount of solids in the small amount of water available.

Such a problem may occur even at water contents of 20% by weight and more. So European Patent EP 131 1654 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, 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.

Nowadays commercially available automatic dishwashing agents generally contain phosphates in the form of tripolyphosphates and so-called sulfopolymers. Tripolyphosphates are usually offered in a 50 to 60 wt .-% aqueous solution, sulfopolymers in solid form or as about 30 to 40 wt .-% aqueous solution. If both raw materials are to be contained in the product in essential amounts, water contents of less than 20% by weight in the overall composition can generally not be achieved by using the raw materials in liquid form.

The Applicant has now found that in the preparation of builder-containing, in particular phosphate-containing, low-water compositions, the use of an aqueous builder component, especially of aqueous tripolyphosphate, in particular of potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium tripolyphosphate, and adding In the form of granules, sulfopoly- mer leads to compositions which undergo phase separation after storage for several weeks at room temperature. Such compositions are therefore not sufficiently stable on storage. Furthermore, it is disadvantageous in such compositions that the dissolution time of the sulfopolymer in the TPP solution is very long and therefore also requires very long preparation times.

In order to overcome these problems, Applicants have made further experiments and found that such phase separation can be avoided by using the reverse approach instead of aqueous tripolyphosphate and solid sulfopolymer and using an aqueous sulfopolymer solution together with a solid tripolyphosphate (TPP) , Such an approach also has the advantage that the dissolution time of solid TPP granules in aqueous sulfopolymer solution is significantly shorter than in the reverse approach, resulting in a favorable shortening of the preparation times.

In a first aspect, the invention is therefore directed to a process for the preparation of liquid, water-poor to anhydrous detergents or cleaners containing at least one sulfopolymer and at least one builder component, wherein the method is characterized in that in the preparation of at least one sulfopolymer in Form of an aqueous solution and the at least one builder component are used in solid form. The term "low in water" as used herein means that the composition so characterized contains less than 25% by weight of water, preferably at most 20% by weight of water or less, more preferably less than 15% by weight of water fall under this term compositions containing 1 to 20 wt .-% 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, especially less than 3% by weight, preferably <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 manufactured detergent or cleaning agent includes all flowable compositions and more particularly includes gels and pasty compositions.

In "solid form" as used herein refers to solids and includes, for example, forms such as powders and granules.

"At least one" as used herein means 1 or more, for example, 1, 2, 3, 4, 5, or more.

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

In a further aspect, the invention relates to the detergents or cleaners prepared in this way, which may optionally be present in a water-insoluble, water-soluble or water-dispersible packaging, for example a film which contains 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 washing or cleaning agent according to the invention as a dishwashing detergent, in particular automatic dishwashing detergent.

The at least one builder component in solid form used in the process according to the invention is selected from tripolyphosphates (TPP), methylglycinediacetic acid or a salt thereof (MGDA), glutamic acid diacetic acid or a salt thereof (GLDA) and combinations thereof. In preferred embodiments, the at least one builder component is tripolyphosphate.

Tripolyphosphates (or else triphosphates) are condensation products of ortho-phosphoric acid (H 3 PO 4) with the empirical formula P ³ O 10 ^{5 "} , which are used in the novel processes, in particular in the form of their salts, preferably the alkali metal or alkaline earth metal, more preferably in the form of their alkali metal salts are generally hygroscopic, white, odorless, nonflammable solids which are readily soluble in water According to the invention, the potassium salt of tripolyphosphate (K5P3O-10) or a mixture of the potassium salt of the tripolyphosphate and the sodium salt of the tripolyphosphate are particularly preferred because of their solubility (Na ₅ P ₃ Oi ₀ ) The mass ratio between potassium and sodium salt may be between 20: 1 and 1:20, preferably between 20: 1 and 1: 1.

Methylglycine-N, N-diacetic acid and glutamic acid-N, N-diacetic acid are used in the inventive method, in particular in the form of their salts, preferably the alkali metal or alkaline earth metal, more preferably in the form of their alkali metal salts. In particular, the trisodium or tripotassium salt of MGDA and GLDA or a mixture of the sodium and potassium salts are used according to the invention. In the context of the present invention, the term MGDA or GLDA is used synonymously for the acid and also for the corresponding salts.

The proportion by weight of the builder component in solid form relative to the total weight of the washing or cleaning agent prepared according to the invention is preferably 0.1 to 30% by weight, in particular 1 to 28% by weight, particularly preferably 5 to 25% by weight more preferably from 10 to 20% by weight.

The proportion by weight of the sulfopolymer in the total weight of the washing or cleaning agent produced according to the invention is preferably from 0.1 to 20% by weight, in particular from 0.5 to 18% by weight, particularly preferably from 0.1 to 15% by weight. in particular from 4 to 14% by weight, especially from 6 to 12% by weight.

The aqueous solutions of the at least one sulfopolymer typically contain 20 to 70% by weight, in particular 30 to 50% by weight, preferably about 35 to 40% by weight of 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, 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 , 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 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, the is selected from - (CH ₂ ) _n - where 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 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 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, 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, a 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 acrylate, 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 their mixtures.

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 detergents or cleaning agents prepared by the process according to the invention may further contain 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 when limiting the amount of water to 20% by weight. The amount of polyhydric alcohol used in detergents or cleaners 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 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 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 .-%.

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

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 3: 1.

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

(1) presentation of the aqueous solution of at least one sulfopolymer, in particular together with at least one organic solvent; (2) adding the at least one builder component in solid form; and

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

The organic solvent is preferably the polyhydric alcohols described above, in particular selected from glycerol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2-methyl-1,3-propanediol and mixtures thereof. 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 builder component in solid form is preferably added in the form of a powder or granules. In various embodiments, this builder component is a salt as defined above, in particular 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.

As a further constituent, the detergents or cleaning agents may contain one or more builders (builders / cobuilders) in addition to the builders listed in solid form as builders. The proportion by weight of these additional builders in the total weight of the compositions prepared according to the invention is preferably from 0.1 to 10% by weight and in particular from 2 to 7% by weight. These builders, which differ from the at least one builder component in solid form, include, in particular, carbonates, citrates, phosphonates, 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 builder substances which differ from the at least one builder component in solid form 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. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such use is not objectionable for environmental reasons, and mixtures thereof. 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 detergents or cleaners contain citrate, for example sodium citrate, as one of their essential builders which differ from the at least one builder component in solid form. Detergents containing from 1 to 10% by weight, preferably from 2 to 5% by weight, of citrate are preferred according to the invention. The citrate in these embodiments is in addition to the at least one solid builder component selected from TPP, MGDA and GLDA as described above. Citrates are preferably used in the processes according to the invention in the form of their salts, preferably the alkali metal or alkaline earth metal, more preferably in the form of their alkali metal salts. In particular, the trisodium or tripotassium salt of citric acid or a mixture of the sodium and potassium salts are used according to the invention.

Polymeric polycarboxylates are furthermore suitable as builders which differ from the at least one builder component in solid form; these 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.

The detergents or cleaning agents may in particular contain phosphonates as further builders differing from the at least one builder component in solid form. 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 aminoalkane phosphonates are ethylene diaminedetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (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 detergent or cleaning agent. The washing or cleaning agent can be used as different from the at least one builder component in solid form builder also crystalline layered silicates of general formula NaMSi _x 0 _{2x +} i ^■ y H ₂ 0 wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1, 9 to 4, 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 washing or 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 detergents or cleaners are silicate-free.

The further builders added in addition to the at least one builder component in solid form are likewise preferably used in solid form or at least predominantly in solid form. Aqueous solutions are used only in the context that the desired low-water content of the agent is not exceeded. However, it is essential for the invention that the builders listed as at least one builder component to be used in solid form, selected from tripolyphosphate, MGDA, GLDA and mixtures thereof, are not introduced into the process in liquid form.

In addition to the abovementioned builders, the detergents or cleaners 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 other builders listed above, which are not included in the builder component in solid form, ie, are not TPP, MGDA, or GLDA, can be incorporated into the process either in solid form or in liquid form. It is preferred that these other builders differing from the at least one builder component in solid form are introduced predominantly in solid form. In a very particularly preferred embodiment of the invention, all builders / builders used are used in solid form. In one embodiment of the invention, the at least one builder component in solid form is tripolyphosphate and the builder (s) other than the at least one builder component is / are citrate and / or phosphonate.

The addition of the at least one builder component in solid form different builders, in particular citrate and / or phosphonate, before step (2) or before step (3) take place. In an embodiment, the method comprises adding citrate before step (2) or step (3). Alternatively, builders other than the at least one builder component in solid form may also be added after stirring in step (3). For example, in one embodiment, phosphonate is added after stirring in step (3).

After stirring the mixture in step (3), one or more further constituents of the washing or 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 of 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 detergents or cleaners 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.

In the context of the present invention, particularly preferred nonionic surfactants have been low-foaming nonionic surfactants which comprise alternating ethylene oxide and alkylene oxide units exhibit. 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 ^ 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, nonionic surfactants are particularly preferable, ₉ have a C .i ₅ alkyl radical 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 stands for a straight-chain or branched, saturated or mono- or polyunsaturated _C6 -24 alkyl or alkenyl group;

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 "hydroxymix ether", 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 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic Hydrocarbon radical R ² having 1 to 30 carbon atoms, wherein x stands for values between 1 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 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 includes, for example, the C ₂ _26 fatty alcohol (PO) - | (EO) ₁₅ . 4o-2-hydroxyalkyl ethers, in particular also the C ₈ -io-fatty alcohol (PO) i- (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 chosen here by way of example and may well be greater, the variation width increasing with increasing x-values and, 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 ^{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, A ', A ", A", w, x, y and z are as defined above.

Preferred liquid cleaning agents which are prepared according to the invention 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 washing or 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> 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 compositions according to the invention in an amount of 0.5 to 10 wt .-%, in particular in an amount of 1 to 6 wt .-%.

For adjusting and / or stabilizing the pH, the composition prepared according to the invention may contain one or more buffer substances (INCI Buffering Agents), usually in amounts of 0.001 to 5 wt .-%. 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 lead, for example trisodium citrate 2H ₂ 0 and tripotassium citrate H ₂ 0.

The compositions according to the invention preferably contain 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 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 '") (R ^IV ) (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 the} same or different represent different alkyl radicals having 1 to 3 carbon atoms, in particular C ₁₀ -C ₈ alkyl dimethylcarboxymethylbetain and Cn-Ciz-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.

The glass corrosion inhibitors used are preferably zinc salts, in particular zinc acetate. Glaskorrosioninhibitoren are in inventively prepared compositions preferably in an amount of 0.05 to 5 wt .-%, in particular in an amount of 0, 1 to 2 wt .-%, included.

The said additional ingredients are preferably added after the neutralization reaction, ie the pH adjustment and optionally a stirring step carried out during the pH adjustment or thereafter. In particular, after the pH value adjustment in any series Follow 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 added.

In the method according to the invention, the necessary stirring steps, for example after the addition of the builder, such as. B. the Tripolyphosphates, for dissolving the same, and in 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> 0.9 to 0.99, where d is the diameter of the agitating tool and D is the diameter of the mixer.

The invention also relates to the detergents or cleaning agents prepared by the process according to the invention. These are characterized on the one hand by their ingredients and on the other hand by the fact that they are stable in storage and even after a prolonged period no phase separation occurs.

In various embodiments, the washing or cleaning agent has a viscosity above 2000 mPas directly after preparation (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> 10000 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 washing or cleaning agent may be in a water-insoluble, water-soluble or water-dispersible packaging. The invention therefore also relates to kits containing the detergent or cleaning agent together with such a package. The washing or cleaning agent can be made up in such a way 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.

Also 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, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol glycol, glycerin, 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.

embodiments

The cleaning agents V1 and E1 and E2 were prepared. The compositions are shown in the table below, the quantities are in wt .-% active ingredient.

Composition V1, which is not according to the invention, was prepared by mixing the ingredients in the following order: mixed 1/4/5 and charged - 2 - 3 - stirring - 9 - 6 - 8 - stirring - 7/10/12. After four weeks storage at room temperature, phase separation occurred in this composition.

Compositions E1 / E2 which are in accordance with the invention were prepared by mixing the ingredients in the following order: 2/4/5 mixed and charged - 1-3 stirring - 9 - 6 - 8 - stirring - 7/10/1 1/12 , After storage for more than four weeks at room temperature, phase separation did not occur in these compositions, unlike Composition V1.

Claims

claims

1. A process for the preparation of liquid, water-poor to anhydrous detergents or cleaners containing at least one sulfopolymer and at least one builder component, characterized in that used in the preparation of at least one sulfopolymer in the form of an aqueous solution and the at least one builder component in solid form wherein the builder component in solid form is selected from tripolyphosphate, methylglycinediacetic acid or a salt thereof (MGDA), glutamic acid diacetic acid or a salt thereof (GLDA) and combinations thereof.

2. The method according to claim 1, characterized in that the washing or cleaning agent has a water content of less than 20 wt .-%.

3. The method according to claim 1 or 2, characterized in that the washing or cleaning agent further comprises at least one polyhydric alcohol, in particular selected from the group glycerol, ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 2-methyl-1 , 3-propanediol and mixtures thereof.

4. The method according to any one of claims 1 to 3, characterized in that it comprises the following steps:

(1) presentation of the aqueous solution of at least one sulfopolymer, in particular together with at least one organic solvent, in particular a polyhydric alcohol according to claim 3;

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

(3) Stir the mixture until the at least one builder component has dissolved in solid form.

5. The method according to claim 4, characterized in that if in step (2) the at least one builder component in solid form is tripolyphosphate comprising potassium and sodium tripolyphosphate, the addition of the sodium salt takes place before the addition of the potassium salt.

6. The method according to claim 4 or 5, characterized in that before step (2) or before step (3) at least one further, of the at least one builder component in solid form different builder, in particular citrate and / or phosphonate, is added.

7. The method according to any one of claims 4 to 6, characterized in that after step (3) in any order one or more of the substances selected from the group consisting of nonionic surfactants and pH adjusters are added and the mixture is stirred and, if pH Adjusting agent are added, optionally cooled.

8. The method according to any one of claims 4 to 7, characterized in that for stirring the mixture, a mixer with Wandgängigem stirring, in particular an anchor or helical stirrer, with a stirrer geometry d / D of at least 0.9 is used, where d is the diameter of Stirring tool and D is the diameter of the mixer.

9. washing or cleaning agent, in particular automatic dishwashing detergent, prepared by a process according to any one of the preceding claims, characterized in that it is in a water-insoluble, water-soluble or water-dispersible packaging, in particular in a polyvinyl alcohol-containing film.

10. Use of the washing or cleaning agent according to claim 9 as a dishwashing detergent, in particular automatic dishwashing detergent.

1 1. A machine dishwashing process, characterized in that a washing or cleaning agent prepared according to any one of claims 1 to 8 or used according to claim 9.