EP3083927A1

EP3083927A1 - Liquid dishwashing detergents having optimized viscosity

Info

Publication number: EP3083927A1
Application number: EP14820769.9A
Authority: EP
Inventors: Nina Mussmann; Thomas Eiting; Noelle Wrubbel; Thorsten Bastigkeit; Hans Hartmut Janke
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2013-12-17
Filing date: 2014-12-10
Publication date: 2016-10-26
Also published as: WO2015091147A1; DE102013226301A1

Abstract

The present invention relates to liquid dishwashing detergents, in particular machine dishwashing detergents, which contain at least one sulfopolymer, at least one citrate, at least one organic builder selected from the class of nitrogen-containing polycarboxylates, and a thickener, and to the use of said dishwashing detergents in a dishwashing method and a corresponding method for dishwashing.

Description

Liquid dishwashing detergent with optimized viscosity

The present invention relates to liquid dishwashing detergents, in particular mechanical

Dishwashing compositions containing at least one sulfopolymer, a citrate, an organic builder and a thickener, and their use in a dishwashing process and a corresponding process for dishwashing.

Since insufficient viscosity in liquid dishwashing products leads to consumer dissatisfaction, it is a general effort to optimize the viscosity of liquid dishwashing detergents. For this purpose, thickeners are usually used in liquid dishwashing detergents. The use of such thickeners, however, has the disadvantage that in modern

Dishwashing detergents, which are highly complex blends that thickeners must be carefully selected to be compatible with the remaining ingredients. In addition, even these special thickeners can affect the viscosity of liquid dishwashing detergents only to a certain extent positive, as they cause negative effects in large quantities, such as threading, which lead to contamination and complicate the dosing. For these reasons, the selection of possible thickeners and their amount used is subject to a number of limitations. In addition, it is also desirable to use thickeners

To limit costs as much as possible.

It has now surprisingly been found that can be adjusted by the selection of the active ingredients of the dishwashing detergent and their amounts, the viscosity such that the amount of thickener required can be minimized. In particular, the present invention has for its object to provide a dishwashing detergent in which the conditions or the concentrations of the components sulfopolymer, citrate and organic builders can be varied so that a viscosity of about 230 mPa ^* s-1 at the same time minimizing the amount achieved thickener used, without causing negative effects.

In a first aspect, this object is achieved by a liquid dishwashing detergent, characterized in that it contains at least one sulfopolymer in a concentration between 2 and 8 wt.%, At least one citrate in a concentration between 0.25 and 15 wt.%, At least one organic builder from the class of nitrogen-containing polycarboxylates in one Concentration between 2 and 20 wt.% In each case based on the liquid dishwashing detergent, and a thickener contains.

"Liquid" as used herein in reference to the dishwashing detergent includes all principally flowable compositions and more particularly includes gels and pastes

Compositions. In particular, the term also includes non-Newtonian fluids having a yield point.

"At least one" as used herein includes, but is not limited to, 1, 2, 3, 4, 5, 6 and more.

Unless indicated otherwise, all amounts in this table refer to% by weight, in each case based on the total formulation of the dishwashing detergent.

The liquid dishwashing detergent contains at least one organic builder (builder) from the group of nitrogen-containing polycarboxylate builders, in particular the aminocarboxylic acids and / or their salts. Particularly preferred representatives of this class are methylglycinediacetic acid (MGDA) and its salts, glutamic diacetic acid (GLDA) and its salts and

Ethylenediamine diacetic acid and its salts (EDDA).

The liquid dishwashing detergent also contains at least one citrate - a salt of citric acid (ΟβΗβΟ). Suitable salts include, but are not limited to, the alkali metal salts, and especially the sodium and potassium salts of citric acid.

Moreover, the liquid dishwashing detergent contains at least one sulfopolymer. As the sulfopolymer, for example, a copolymeric polysulfonate such as hydrophobically modified copolymeric polysulfonate is used. Such copolymers may have two, three, four or more different monomer units.

Copolymers Polysulfonate can contain in addition to sulfonic acid-containing (s) monomer (s) at least one monomer from the group of unsaturated carboxylic acids.

Unsaturated carboxylic acid (s) used are, with particular preference, unsaturated carboxylic acids of the formula R (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ³ independently of one another represent -H, -Chta, a straight-chain or branched one saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12

Carbon atoms, with -NH2, -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, 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 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, with --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

H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H in which R ⁶ and R ^{7 are} independently selected

from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ and -CH (CH ₃ ) ₂ and X is an optional

Spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) k- with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ -, -C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -NH-CH (CH ₃ ) -CH ₂ -.

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

In particularly preferred embodiments, these are the sulfopolymers, the mixed polymer (copolymers, terpolymers) of acrylic acid and acrylamido-propanesulfonic acid (as monomers) with optionally other monomers, in particular as described above, are selected. Such polymers are, for example, under the trade name Acusol 590 ^® or Acusol® 588 from Dow Chemical, is.

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 monomer distribution of the copolymers preferably used in the case of copolymers which contain only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably in each case from 5 to 95% by weight, with the proportion of

Sulfonic acid group-containing monomers 50 to 90 wt .-% and the proportion of

Carboxylic acid-containing monomers 10 to 50 wt .-%, the monomers are hereby preferably selected from the aforementioned.

The molecular weight of the sulfo copolymers preferably used can be varied in order to adapt the properties of the polymers to the desired end use. Preferred liquid dishwashing detergents are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol and in particular from 5000 to 15,000 gmol ^-1 .

In addition, the liquid dishwashing detergent contains a thickener. In one embodiment, the liquid dishwashing detergent contains acrylic acid copolymers which are suitable as thickeners. As such acrylic acid copolymers are particularly suitable: (i) copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably formed with C1-4-alkanols, esters (INCI acrylates copolymer), such as the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS designation according to Chemical Abstracts Service: 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) belong and which, for example, under the names Aculyn 22, Aculyn 28, Aculyn 33 ( cross-linked), Acusol 810, Acusol 820, Acusol 823 and Acusol 830 (CAS 25852-37-3); (ii) crosslinked high molecular weight acrylic acid copolymers, such as those crosslinked with an allyl ether of sucrose or pentaerythritol copolymers of C10-30-alkyl acrylates with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably formed with C14-alkanols, Ester (INCI Acrylates / C 10-30 Alkyl Acrylates

Crosspolymer) and which are available, for example, from B.F. Goodrich available, e.g. the hydrophobized Carbopol ETD 2623 and Carbopol 1382 (INCI acrylates / C 10-30 alkyl acrylate crosspolymer) and Carbopol Aqua 30 (formerly Carbopol EX 473). Particularly preferred is Acusol 810.

Furthermore, in one embodiment, the liquid dishwashing detergent is characterized in that the thickener, for example an acrylic acid-based copolymer, in particular Acusol® 810 (available from DOW CHEMICAL, active substance content 18%) in a concentration between 0.1 and 5% by weight, preferably between 0.2 and 2% by weight, more preferably between 0.3 and 1.5% by weight, in particular between 0.35 and 1.3% by weight, most preferably between 0.6 and 0.9 Wt.% Active ingredient based on the liquid dishwashing detergent is present.

Particularly preferred are combinations of a sulfopolymer, and a thickener, preferably based on an acrylic acid polymer, in particular acrylic acid copolymer, in particular Acusol® 810. In particular, the sulfo-polymer is selected from a

Mixed polymer (copolymers, terpolymers) of acrylic acid and acrylamido-propanesulfonic acid (as monomers) with possibly other monomers, in particular those as described above (for example, ethacrylic acid) are selected. Such polymers are, for example, Acusol 588® or Acusol® 590,

In particular, the sulfopolymer becomes 4.0 to 7% by weight, preferably between 4.5 and 6% by weight, for example 5.0 to 5.8% by weight, and the thickener is 0.1 to 2, preferably 0 , 3 to 1, 5 wt .-%, in particular 0.5 to 1, 0, for example, 0.7 to 0.9 wt .-% (in each case based on the amount of active substances) used.

For example, the sulfopolymer between 4.5 and 6 wt.% And the thickener to 0.5 to 1, 0, for example 0.7 to 0.9 wt .-% (in each case based on the amount of the active substances).

In a further aspect, the present invention relates to the use of the liquid

Dishwashing agent, preferably as machine dishwashing detergent. Another object of the present invention is also a dishwashing process, in particular a machine dishwashing process, in which the liquid dishwashing detergent is used.

As already described, it has surprisingly been found that the use of certain concentrations and ratios of sulfopolymer, citrate, organic builder and thickener can increase the viscosity of a liquid dishwashing detergent without causing negative effects, such as, for example, stringing, which occurs. when the amount of thickener, for example, an acrylic acid copolymer thickener, is increased.

In addition, the agent described has the advantage that it is cheaper to manufacture than comparable dishwashing detergents containing a larger amount of thickener.

In one embodiment of the invention, the viscosity of the liquid dishwashing detergent is above 230 mPa ^* s-1 (Brookfield instrument LVDV II +, spindle 31, 30 rpm, 20 ° C.), in particular between 240 mPa ^* s-1 and 1000 mPa ^* s-1, preferably between 250 mPa ^* s-1 and 1000 mPa ^* s-1 and between 250 mPa ^* s-1 and 350 mPa ^* s-1.

In various embodiments, the liquid dishwashing detergent comprises

(I) the at least one sulfopolymer in a concentration between 4.0 and 7.5 wt.%, Preferably between 4.5 and 6 wt.%, For example, 5.0 to 5.8 wt .-% based on the liquid dishwashing detergent , and or

(Ii) the at least one citrate in a concentration between 1 and 6 wt.%, Preferably 2 and 5 wt .-%, particularly preferably 2.5 to 3.5 wt .-%, for example 3 wt.% Based on the liquid Dishwashing detergent, and / or

(iii) the at least one organic builder, preferably a nitrogen-containing one

Polycarboxylate builder, preferably an aminocarboxylic acid, more preferably

Methylglycinediacetic acid (MGDA) or its salts and / or glutamic diacetic acid (GLDA) or its salts and / or ethylenediaminediacetic acid or its salts (EDDS), in a concentration between 5 and 20 wt.%, In particular between 7 and 18 wt .-% based on the liquid dishwashing detergent.

In a preferred embodiment, the liquid dishwashing detergent comprises

(I) the at least one sulfopolymer in a concentration of 5.0 to 5.8 wt .-% based on the liquid dishwashing detergent, and / or (Ii) the at least one citrate in a concentration between 2.5 to 3.5 wt .-%, for example 3 wt.% Based on the liquid dishwashing detergent, and / or

(iii) the at least one organic builder, preferably a nitrogen-containing one

Polycarboxylate builder, preferably an aminocarboxylic acid, more preferably

Methylglycinediacetic acid (MGDA) or its salts and / or glutamic diacetic acid (GLDA) or its salts and / or ethylenediaminediacetic acid or its salts (EDDS), in a concentration between 7 and 18% by weight, based on the liquid dishwashing detergent.

The abovementioned concentrations in each case relate to the total amount of sulfopolymer, citrate or builder in the dishwashing detergent.

The liquid dishwashing detergent in a preferred embodiment has the advantage that it contains no phosphates and is therefore more compatible with the environment.

In addition, the liquid dishwashing detergent may comprise one or more of the substances selected from the group consisting of further builders, alcohols, pH adjusters, nonionic, anionic, cationic and amphoteric surfactants, bleaches, bleach activators,

Bleach catalysts, enzymes, polymers, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors,

Disintegration aids, fragrances, perfume carriers. Foam inhibitors, dyes,

Bitter substances, and antimicrobial agents.

Suitable enzymes include, but are not limited to, proteases, lipases,

Hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof.

These enzymes and the amylases used are in principle of natural origin; Based on the natural molecules, improved variants are available for use in dishwashing detergents, which are preferably used accordingly. Dishwashing agents according to the invention contain enzymes, including amylase, preferably in total amounts of from 1 × 10 ^-6 to 5% by weight, based on active protein. The protein concentration can be determined using known

Methods, for example, the BCA method or the biuret method can be determined.

Proteases are among the most technically important enzymes of all. For washing and

Dishwashing detergents are the longest-established enzymes contained in virtually all modern, powerful detergents and dishwashing detergents. They cause the degradation of protein-containing stains on the items to be cleaned. Of these, proteases of the subtilisin type (subtilases, subtilopeptidases, EC 3.4.21.62) are again particularly important, which due to of the catalytically active amino acids are serine proteases. They act as nonspecific endopeptidases and hydrolyze any acid amide linkages that are internal to peptides or proteins. Their pH optimum is usually in the clearly alkaline range. An overview of this family is provided, for example, by the article "Subtilases: Subtilisin-like Proteases" by R. Siezen, pages 75-95 in "Subtilisin enzymes", edited by R. Bott and C. Betzel, New York, 1996. Subtilases are naturally occurring formed by microorganisms. Of these, in particular, the subtilisins formed and secreted by Bacillus species are to be mentioned as the most important group within the subtilases.

Examples of the subtilisin-type proteases preferably used in washing and dishwashing detergents are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the protease from Bacillus lentus, in particular from Bacillus lentus DSM 5483,

Subtilisin DY and the enzymes thermitase, proteinase K and the proteases TW3 and TW7 attributable to the subtilases, but no longer to the subtilisins in the narrower sense, as well as variants of said proteases which have an altered amino acid sequence compared to the starting protease. Proteases are selectively or randomly modified by methods known from the prior art and thus optimized, for example, for use in detergents and dishwashing detergents. These include point mutagenesis, deletion or insertion mutagenesis or fusion with other proteins or protein parts. Thus, correspondingly optimized variants are known for most proteases known from the prior art.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, B. amyloliquefaciens, B. stearothermophilus, Aspergillus niger and A. oryzae and the further developments of the aforementioned amylases which are improved for use in dishwashing detergents. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and 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, those originally from Humicola lanuginosa

(Thermomyces lanuginosus) available, or further developed lipases, in particular those with one or more of the following amino acid substitutions starting from said lipase in positions D96L, T213R and / or N233R., Particularly preferably T213R and N233R.

Furthermore, enzymes can be used which are termed hemicellulases

be summarized. These include, for example, mannanases, xanthanlyases, Pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and ß-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 preferable to add organic, more preferably aromatic, enzyme-interacting compounds to enhance the activity of the respective oxidoreductases (enhancers) or to react at greatly varying redox potentials between the oxidizing enzymes and the

Stains to ensure the flow of electrons (mediators).

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. For this purpose, the dishwashing agents may contain calcium salts and / or further stabilizers, in particular polyols and / or boron-containing

Compounds such as boric acid and its salts. Preferred boron-containing compounds are substituted phenylboronic acid / phenylboronic acid derivatives, in particular the

Phenylboronic acid derivative 4-formyl-phenylboronic acid (4-FPBA). Further preferred

Phenylboronic acid derivatives may also have other chemical modifications on the phenyl ring, in particular they may contain one or more methyl, amino, nitro, chloro, fluoro, bromo, hydroxyl, formyl, ethyl, acetyl, t Butyl, anisyl, benzyl, trifluoroacetyl, N-hydroxysuccinimide, t-butyloxycarbonyl, benzoyl, 4-methylbenzyl, thioanizyl, thiocresyl, benzyloxymethyl, 4-nitrophenyl, benzyloxycarbonyl, 2-nitrobenzoyl -, 2-Nitrophenylsulphenyl-, 4-Toluenesulphonyl, pentafluorophenyl, diphenylmethyl, 2-chlorobenzyloxycarbonyl, 2,4,5-trichlorophenyl, 2-bromobenzyloxycarbonyl, 9-fluorenylmethyloxycarbonyl, triphenylmethyl, 2,2,5 , 7,8-pentamethylchroman-6-sulphonyl radicals or groups or combinations thereof.

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 with a water, air and / or

Chemical-impermeable protective layer is coated. 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.

Besides the organic builder described above, the liquid dishwashing detergent may comprise further builders. The additionally usable builders include, in particular, the zeolites, silicates, carbonates, in particular the alkali metal carbonates, for example sodium carbonate,

Sodium hydrogen carbonate or sodium sesquicarbonate, and phosphonates and - where there are no ecological prejudices against their use - also the phosphates. Preferably, however, the agents are phosphate-free. "Phosphate-free" means that the amount of phosphates in the dishwashing detergent is less than 0.1% by weight, preferably less than 0.01% by weight, more preferably less than 0.001% by weight.

When silicates are, in particular crystalline layered silicates of general formula NaMSix02x + i ^■ y H2O wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1: 9 to 4, particularly preferred values for x being 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20, into consideration. It is also possible to use amorphous sodium silicates having a modulus Na 2 O: SiO 2 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 are preferably delayed in dissolution and secondary wash properties.

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

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Among the large number of commercially available phosphates, the alkali metal phosphates have particular preference of pentasodium or Pentakaliumtriphosphat (sodium or

Potassium tripolyphosphate) is the most important in the dishwashing industry.

Other builders that can be used are the alkali carriers. Examples of alkali carriers are alkali metal hydroxides, the alkali metal carbonates mentioned, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the alkali metal silicates mentioned, alkali metal silicates, and mixtures of the abovementioned substances. Because of her in comparison with others

Builders low chemical compatibility with the other ingredients of dishwashing detergents, the optional alkali metal hydroxides are preferably used only in small amounts, preferably in amounts below 10 wt .-% based on the total weight of the automatic dishwashing detergent.

Other builders are in particular all polycarboxylates / polycarboxylic acids with the exception of citrate, which are not already covered by the abovementioned definition of the organic builder, and polymeric polycarboxylates, aspartic acid, polyacetals and dextrins.

Thus, further builder substances 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 adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these. In addition to their builder effect, the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of the machine

Dishwashing liquid. In particular, succinic acid, glutaric acid, adipic acid,

Gluconic acid and any mixtures of these.

Furthermore, polymeric polycarboxylates are suitable, these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a molecular weight of 500 to 70000 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.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. As especially suitable have proven copolymers of acrylic acid with maleic acid containing 50 to 90 wt .-% of acrylic acid and 50 to 10 wt .-% maleic acid. Their relative molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of automatic dishwashing detergents on (co) polymers

Polycarboxylates is preferably 0.5 to 20 wt .-% and in particular 3 to 10 wt .-%.

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

Further preferred copolymers are those which are used as monomers acrolein and

Acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

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

The liquid dishwashing detergent may contain at least one alcohol, in particular a polyhydric alcohol. Such polyhydric alcohols can be used with a small amount of water,

especially with a limitation of the amount of water to 20 wt .-%, allow the incorporation of other ingredients in a liquid dishwashing detergent formulation.

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

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

In general, the pH of the liquid dishwashing detergent can be adjusted by means of customary pH regulators, the pH value being chosen 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, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or else Sulfamic 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 described agents in an amount of 0.5 to 10 wt .-%, in particular in an amount of 1 to 6 wt .-%.

To stabilize the pH, the liquid dishwashing detergent may one or more

Buffer substances (INCI Buffering Agents), usually in amounts of 0.001 to 5 wt .-%.

Preferably, the liquid dishwashing detergent contains at least one enzyme preparation or enzyme composition containing one or more enzymes. In principle, all the enzymes established in the prior art for this purpose can be used in this regard. Preferably, it is one or more enzymes capable of exhibiting catalytic activity in a liquid dishwashing detergent, in particular a protease, amylase, lipase, cellulase, hemicellulase, mannanase, pectin-splitting enzyme, tannase, xylanase, xanthanase, β-glucosidase, Carrageenase, perhydrolase, oxidase, oxidoreductase and mixtures thereof. Preferred hydrolytic enzymes include in particular proteases, amylases, in particular α-amylases, cellulases, lipases, hemicellulases, in particular pectinases, mannanases, β-glucanases, and mixtures thereof. Proteases, amylases and / or lipases and mixtures thereof are particularly preferred, and proteases are particularly preferred. These enzymes are basically of natural origin; Based on the natural molecules, improved variants are available for use in dishwashing detergents, which are preferably used accordingly.

The enzymes to be used can also be used together with accompanying substances, such as from

Fermentation, or be prepared with stabilizers.

The liquid dishwashing detergent may contain surfactants, the nonionic, the anionic, the cationic and the amphoteric surfactants being counted among the group of surfactants.

As nonionic surfactants, it is possible to use all nonionic surfactants known to the person skilled in the art. Examples of suitable nonionic surfactants are alkyl glycosides of general mean formula RO (G) x, in which R corresponds to a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glykoseeinheit with 5 or 6 C-atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number between 1 and 10; preferably x is 1, 2 to 1, 4.

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

Further suitable surfactants are the polyhydroxy fatty acid amides known as PHFA.

Particular preference is given to nonionic surfactants which have a melting point above

Have 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, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain 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.

Particularly preferred nonionic surfactants used are low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here are nonionic surfactants of the general formula

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

R2 R3

in which R 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 are independently integers from 1 to 6. Thus, particularly preferred are nonionic surfactants having a C9-alkyl group with 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units, followed by 1 to 4

Ethylene oxide units followed by 1 to 4 propylene oxide units.

Preferred nonionic surfactants are also those of the general formula R -CH (OH) CH 2 O- (AO) w- (AO) x- (A "0) _y - (A"'0) z R ² , in which

R is a straight-chain or branched, saturated or mono- or polysubstituted

unsaturated C6-24 alkyl or alkenyl radical;

R ^{2 is} H or a linear or branched hydrocarbon radical of 2 to 26

Carbon atoms;

- A, Α ', A "and A" independently represent a residue 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) CH20 - (AO) w - (AO) x - (A "0) y - (A '" 0) zR ² , hereinafter also referred to as

"Hydroxymix ethers" referred to, the cleaning performance of the described agents can be significantly improved both compared to surfactant-free system as well as compared 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 of the formula R 0 [CH ₂ CH (R ³ ) O] x [CH ₂ ] k CH (OH) [CH ² ] jOR ² in which R 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 0 [CH ₂ CH (R ³ ) O] x [CH ₂ ] k CH (OH) [CH ² ] jOR ^{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 -ChhCl-ta 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. Stands For example, for 3, the radical R ^{3 may be} selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = Chta) units which may be joined together in any order, for example (EO) (PO). (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO),

(PO) (PO) (EO) and (PO) (PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

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

RO [CH ₂ CH (R ³ ) O] x CH ₂ CH (OH) CH ₂ OR ² simplified. In the last-mentioned formula R 1, R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R 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 is a straight-chain or branched, saturated or mono- or polysubstituted

unsaturated Ce-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

The group of these nonionic surfactants includes, for example, the C4-22 fatty alcohol (EO) 10-so-2-hydroxyalkyl ethers, in particular also the C8-12 fatty alcohol - (EO) 22-2-Hydroxydecylether and the C4-22 fatty alcohol (EO) 4o-8o-2-hydroxyalkyl ether.

In various embodiments of the invention, instead of the above-defined end-capped hydroxy mixed ethers, the corresponding ones can not

end-capped hydroxy mixed ethers. These may satisfy the above formulas, but R ² is hydrogen and R, R ³ , A, Α ', A ", A'", w, x, y and z are as defined above.

The liquid dishwashing detergent preferably contains a nonionic surfactant, wherein the weight fraction of the nonionic surfactant in the total weight of the liquid dishwashing detergent is preferably 0.1 to 10, preferably 0.5 to 5, more preferably 1.0 to 4.0 wt%. Anionic surfactants can also be used as part of liquid dishwashing detergents. These include in particular alkylbenzenesulfonates, (fatty) alkyl sulfates, (fatty) alkyl ether sulfates and alkanesulfonates. The content of the anionic surfactant is usually 0 to 10% by weight.

Instead of the surfactants mentioned or in combination with them, it is also possible to use cationic and / or amphoteric surfactants. Dishwashing agents which do not contain cationic or amphoteric surfactants, however, are preferred.

The group of polymers includes, in particular, the cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners. Generally are in liquid

Dishwashing agents in addition to nonionic polymers and cationic, anionic and amphoteric polymers used.

"Cationic polymers" for the purposes of the present invention are polymers which carry a positive charge in the polymer molecule, which can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, the vinylpyrrolidone-methoimidazolinium chloride Copolymers, the quaternized polyvinyl alcohols or the INCI names

Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 indicated polymers.

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

Preferred usable amphoteric polymers are from the group of

Alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers , the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic monomers.

Preferred zwitterionic polymers are from the group of acrylamidoalkyl trialkyl ammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the Methacroylethylbetain / methacrylate copolymers.

In a particularly preferred embodiment, the polymers are present in prefabricated form. To prepare the polymers u.a.

the encapsulation of the polymers by means of water-soluble or water-dispersible coating compositions, preferably by means of water-soluble or water-dispersible natural or synthetic polymers;

the encapsulation of the polymers by means of water-insoluble, fusible

Coating compositions, preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 ° C;

the co-granulation of the polymers with inert support materials, preferably with

Support materials from the group of cleaning-active substances.

Liquid dishwashing detergents preferably contain the abovementioned cationic and / or amphoteric polymers in amounts of from 0.01 to 10% by weight, based in each case on the total weight of the liquid dishwashing detergent.

The dishwashing detergents may additionally contain bleaches. enzyme-containing

However, dishwashing agents are preferably free of non-enzymatic bleaches. Among the compounds serving as bleaches in water H2O2 have the

Sodium percarbonate, the sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaches which can be used are, for example, peroxypyrophosphates, citrate perhydrates and peroxygenic salts or peracids yielding H2O2, such as perbenzoates.

Peroxophthalates, diperazelaic acid, phthaloimino peracids, in particular ε-phthalimidoperoxycaproic acid (phthalimidoperoxyhexanoic acid, PAP), or diperdodecanedioic acid. In addition, all other known to the expert from the prior art can be used

inorganic or organic peroxy bleach.

As a bleaching agent and chlorine or bromine releasing substances can be used. Examples of suitable chlorine or bromine releasing materials

heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid,

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

If bleaches are contained, the liquid dishwashing agents preferably contain from 1 to 35% by weight, preferably from 2.5 to 30% by weight, particularly preferably from 3.5 to 20% by weight and in particular from 5 to 15% by weight of bleaching agent , preferably sodium percarbonate, wherein the

Quantities are each based on the dishwashing detergent.

As bleach catalysts are bleach-enhancing transition metal salts and transition metal complexes, preferably the Mn, Fe, Co, Ru or Mo complexes, particularly preferably from the group of manganese and / or cobalt salts and / or complexes, in particular

Cobalt (ammin) complexes, cobalt (acetate) complexes, cobalt (carbonyl) complexes, chlorides of cobalt or manganese, manganese sulfate and complexes of manganese with 1, 4,7-trimethyl-1, 4, 7-triazacyclononane (Mm-TACN) or 1, 2,4,7-tetramethyl-1, 4,7-triazacyclononane (Mm-TACN) in question.

In various embodiments, the liquid dishwashing detergent additionally contains at least one bleach activator. As bleach activators, compounds mentioned in U.S. Pat

Perhydrolysis aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid, can be used. Of all those skilled in the art known from the prior art

Bleach activators are polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) are particularly preferably used. Combinations of conventional bleach activators can also be used. These

Bleach activators are preferably used in amounts of up to 10% by weight, in particular from 0.1% by weight to 8% by weight, especially from 2 to 8% by weight and more preferably from 2 to 6% by weight, based in each case on Total weight of bleach activator-containing agents used.

Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group of magnesium and zinc salts and magnesium and zinc complexes. In the context of the present invention, the content of zinc salt in liquid dishwashing detergents is preferably between 0.1 to 5 wt.%, Preferably between 0.2 and 4 wt.% And in particular between 0.4 and 3 wt the content of zinc in oxidized form (calculated as Zn ²⁺ ) is between 0.01 and 1% by weight, preferably between 0.02 and 0.5% by weight. % and in particular between 0.04 to 0.2 wt .-%, each based on the total weight of the glass corrosion inhibitor-containing agent.

In order to facilitate the disintegration of preformed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, into these compositions in order to shorten the disintegration times. Among tablet disintegrants and disintegrants are adjuvants

understood that provide for the rapid disintegration of tablets in water or other media and for the rapid release of the active ingredients. Desintegration aids may preferably be used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration assistant-containing agent.

As perfume oils or perfumes, within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.

The formulation of liquid dishwashing detergent described herein can be done in different ways. The agents may be formulated in the form of single-phase or multi-phase products. In particular, liquid dishwashing detergents with one, two, three or four phases are preferred. Unless otherwise specified, the quantities are also based on the entire amount of the liquid, even in the case of multiphase dishwashing detergents

Dishwashing detergent.

The liquid dishwashing agents described herein are preferably preformed into dosage units. These metering units preferably comprise the amount of cleaning-active substances necessary for a cleaning cycle. Preferred metering units have a weight between 10 and 40 g, in particular between 12 and 30 g, more preferably between 14 and 26 g and in particular between 16 and 22 g. In order to achieve an optimum cleaning and rinse-off result, preference is given to those liquid dishwashing detergents which are in the form of a prefabricated dosing unit. The volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher. The volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml, for example 15 to 22 ml. Preferably, the liquid dishwashing detergent is contained in a water-soluble packaging. The water-soluble packaging allows portioning of the liquid dishwashing detergent. The amount of liquid dishwashing 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 coating be polyvinyl alcohol or a

Contains 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 in the range of 10,000 to 1,000,000 gmol ^"1 , preferably from 20,000 to 500,000 gmol, more preferably from 30,000 to 100,000 gmol ^{" 1} and in particular from 40,000 to 80,000 gmol.

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

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

(Meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above polymers may be added. A preferred additional polymer is polylactic acids. Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and

Mixtures thereof, with itaconic acid being preferred.

Likewise preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof.

It may be preferred that the film material contains further additives. The film material may include, 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, detackifiers, or mixtures thereof.

Suitable water-soluble films for use in the water-soluble sheaths of

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

The corresponding use of the liquid dishwashing detergent is also the subject of the invention as mentioned above. Likewise, the invention relates to a dishwashing process, in particular a machine dishwashing process, in which the liquid dishwashing detergent is used. The subject matter of the present application is therefore furthermore a process for cleaning dishes in a dishwasher, in which the described agent is metered into the interior of a dishwasher during the passage of a dishwashing program before the main wash cycle or during the main wash cycle. The metering or the entry of the agent in the interior of the dishwasher can be done manually, but preferably the means by means of the metering chamber in the interior of the

Dishwasher dosed. Example:

There were the liquid dishwashing detergent formulations M1 and M2 and the

Comparative formulations prepared V1-V7. The compositions are shown in the following Table 1, the quantities are in wt .-%.

The viscosity of the dishwashing detergent was measured using a Brookfield instrument LVDV II +, 20 ° C, spindle 31, 30 rpm.

Table 1 :

Recipe V1 V2 V3 V4 V5 V6 M1 M2 V7

Phosphonate 1, 2 1, 2 1, 2 1, 2 1, 2 1, 2 1, 2 1, 2 1, 2

Dye 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02

Sorbitol 8.4 8.4 8.4 8.4 8.4 8.4 8.4 8.4 8.4

Sodium citrate 0.00 3.00 0.00 3.00 3.00 3.00 3.00 3.00 3.00 Anhydrous

Calcium chloride 0.27 0.27 0.27 0.27 0.27 0.27 0.27 0.27 0.27

Zn acetate 0, 19 0.19 0, 19 0, 19 0.19 0, 19 0, 19 0.19 0, 19

Boric acid 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00

Acusol® 590 14.00 14.00 14.00 0.00 3.50 7.00 14.00 14.00 14.00 (Sulfopolymer, AS

38%, Dow Chemical)

Acusol® 810 4,60 0,00 5,20 4,60 4,60 4,60 4,60 4,60 4,60 (thickener, AS 18%,

Dow Chemical)

GLDA 9.4 9.4 9.4 9.4 9.4 9.4 9.4 7.05 4.7

KOH 50% 7,00 5,95 7.01 3, 1 3,97 4,87 6,57 7,48 8,38

Parmetol 0, 15 0.15 0, 15 0, 15 0.15 0, 15 0, 15 0.15 0, 15

Nonionic surfactant 3.50 3.50 3.50 3.50 3.50 3.50 3.50 3.50 3.50

Amylase (based on 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 the amount of active

Protein)

Protease (based 0, 14 0.14 0, 14 0, 14 0.14 0, 14 0, 14 0.14 0, 14 on the amount of active

Protein)

Perfume 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20

Water Ad Ad Ad 100 Ad Ad Ad Ad Ad

100 100 100 100 100 100 100 100 Viscosity 229 Separates 277 178 198 228 300 258 187 [mPas ^* s] itself

Negative thread

Pull effect

The results clearly show that only the liquid dishwashing detergents M1 and M2 according to the invention have a high viscosity of more than 230 mPas ^* s without negative effects.

Claims

claims

Liquid dishwashing detergent, characterized in that it comprises at least one sulfopolymer in a concentration between 2 and 8 wt.%, At least one citrate in a concentration between 0.25 and 15 wt.%, At least one organic builder from the class of nitrogen-containing polycarboxylates in a concentration between 2 and 20 wt.%, Based in each case on the liquid dishwashing detergent, and a thickener.

2. Liquid dishwashing detergent according to claim 1, characterized in that the

Dishwashing agent has a viscosity of more than 230 mPa ^* s-1, in particular between 240 mPa ^* s-1 and 1000 mPa ^* s-1, preferably between 250 mPa ^* s-1 and 1000 mPa ^* s-1, particularly preferably between 250 mPa ^* s-1 and 400 mPa ^* s-1, in particular between 250 mPa ^* s-1 and 350 mPa ^* s-1, (measured with Brookfield LVDV II + viscometer, at 20 ° C, 30 rpm and Spindle No. 31).

3. Liquid dishwashing detergent according to one of claims 1 or 2, characterized in that

(i) the at least one sulfopolymer is present in a concentration of between 4.0 and 7.5% by weight, preferably between 4.5 and 6% by weight, based on the liquid dishwashing detergent, and / or

(ii) the at least one citrate is present in a concentration of between 1 and 6% by weight, preferably 3% by weight, based on the liquid dishwashing detergent, and / or

(Iii) the at least one organic builder in a concentration between 5 and 20, preferably between 7 and 18 wt.% Based on the liquid dishwashing detergent, is present.

4. Liquid dishwashing detergent according to any one of claims 1-3, characterized in that it is the organic builder is an amino carboxylic acid, more preferably methylglycinediacetic acid (MGDA) or its salts and / or glutamic diacetic acid (GLDA) or its salts and / or ethylenediaminediacetic or their salts (EDDS).

5. Liquid dishwashing detergent according to any one of claims 1-4, characterized in that it is the thickener is an acrylic acid copolymer and this thickener in a concentration between 0, 1 and 5 wt .-%, preferably between 0.2 and More preferably between 0.3 and 1.5% by weight, in particular between 0.35 and 1.3% by weight, most preferably between 0.6 and 0.9% by weight of active substance, based on the liquid dishwashing detergent is present.

6. Liquid dishwashing detergent according to any one of claims 1-5, characterized in that the liquid dishwashing agent further comprises one or more of the substances selected from the group consisting of other builders, pH adjusters, nonionic, anionic, cationic and amphoteric surfactants, bleaching agents, bleach activators .

Disintegration aids, fragrances, perfume carriers. Foam inhibitors, dyes, bittering agents, and antimicrobial agents.

7. Liquid dishwashing detergent according to one of claims 1-6, characterized in that the dishwashing agent is phosphate-free.

8. Use of the liquid dishwashing detergent according to one of claims 1 to 7 as

machine dishwashing detergent.

9. Machine dishwashing process, characterized in that a liquid

Dishwashing composition according to one of claims 1 to 7 is used.