EP3080242B1 - Phosphate-free liquid dish soap - Google Patents

Description

The present invention relates to a phosphate-free, liquid dishwashing detergent which exhibits improved stability and cleaning performance, in particular of enzyme-sensitive soiling, the use of this dishwashing detergent and a method for automatic dishwashing using this dishwashing detergent.

The most important criterion in automatic dishwashing is the cleaning performance on a wide variety of soiling, which are introduced into the dishwasher in the form of food residues. In this respect, there is generally a need for dishwashing detergents with increased cleaning performance. In addition, a general trend for reasons of environmental protection in machine dishwashing to dispense with phosphates is observed. Thus, there is the problem of providing phosphate-free automatic dishwashing detergents without compromising cleaning performance or stability.

In order to be able to effectively remove baked stains, a dishwashing detergent requires alkalinity. Many other dried-on food residues require enzymes, such as amylases and proteases. However, there is the problem that alkalinity and enzymes together can not be stably formulated. That's how it describes WO 2007/025665 A2 For example, multi-component detergents in which the alkalinity is preferably formulated separately from the enzymes.

Liquid dishwashing detergents also require special stabilizers to stabilize the enzymes. These include, inter alia, calcium salts and especially for proteases additionally polyols and / or boric acid. The use of calcium salts to stabilize enzymes against the influence of builders based on amino acids or succinates is disclosed, for example, in International Patent Publication WO 2007/141527 A1 described.

Finally, builders, such as glutamic diacetic acid (GLDA), and complexing agents are required to optimize the performance of the dishwashing detergent. In particular, phosphonates, such as, for example, 1-hydroxyethane- (1,1-diphosphonic acid) (HEDP), are suitable as complexing agents. The GB 2 355 269 A describes such liquid detergent compositions containing both HEDP and enzymes and calcium chloride.

However, if HEPP is formulated with a calcium salt in a phosphate-free formulation, calcium phosphonate may precipitate. This is undesirable on the one hand for aesthetic reasons, because the appearance of the product suffers from the white precipitates and, on the other hand, the enzyme performance is reduced by the loss of enzyme stabilizer.

The object of the present invention was therefore to provide a phosphate-free, liquid dishwashing detergent which overcomes the stated stability problems and has a good cleaning performance.

It has now been found that in order to ensure a stable and thus visually appealing dishwasher detergent formulation, the phosphonate used as a complexing agent must be formulated spatially separated from enzymes and enzyme stabilizers, especially calcium salts.

1. (a) Zusammensetzung A phosphonatfrei ist und mindestens ein Enzym, vorzugsweise eine Protease und/oder Amylase, und mindestens ein zur Stabilisierung des mindestens einen Enzyms geeignetes Calciumsalz umfasst und einen pH-Wert kleiner als 8,5, vorzugsweise von 8, insbesondere von 7,5 oder weniger, aufweist, und
2. (b) Zusammensetzung B enzym- und calciumfrei ist und mindestens ein Phosphonat, insbesondere 1-Hydroxyethan-(1,1-diphosphonsäure) (HEDP), umfasst und einen pH-Wert größer als 9, vorzugsweise größer als 10, aufweist.

A first subject of the present invention is therefore a phosphate-free, liquid dishwashing detergent, in particular a machine dishwashing detergent, comprising two spatially separate liquid compositions A and B, wherein

1. (a) Composition A is phosphonate-free and comprises at least one enzyme, preferably a protease and / or amylase, and at least one calcium salt suitable for stabilizing the at least one enzyme and having a pH of less than 8.5, preferably 8, in particular 7 , 5 or less, and, and
2. (b) Composition B is enzyme- and calcium-free and comprises at least one phosphonate, in particular 1-hydroxyethane- (1,1-diphosphonic acid) (HEDP), and has a pH greater than 9, preferably greater than 10.

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

Likewise provided by the present invention is the use of a dishwashing agent according to the invention in a machine dishwashing process, in particular the use for improving the cleaning performance of enzyme-sensitive soiling on dishes during its cleaning in an automatic dishwashing machine.

Finally, the present invention is also directed to a machine dishwashing process in which a dishwasher detergent according to the invention is used in particular for the purpose of improving the cleaning performance of enzyme-sensitive soiling.

These and other aspects, features, and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Any feature of one aspect of the invention may be employed in any other aspect of the invention. Furthermore, it is to be understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular those Invention is not limited to these examples. All percentages are by weight unless otherwise specified. Numeric ranges indicated in the format "from x to y" include the above values. If multiple preferred numeric ranges are specified in this format, it is understood that all ranges resulting from the combination of the various endpoints are also captured.

"Phosphate-free" and "phosphonate-free" as used herein means that the subject composition is substantially free of phosphates or phosphonates, i. in particular phosphates or phosphonates in amounts less than 0.1 wt .-%, preferably less than 0.01 wt .-%, based on the composition A contains.

"Calcium free" as used herein means that the subject composition is substantially free of calcium salts, i. in particular calcium salts in amounts less than 0.1 wt .-%, preferably less than 0.07 wt .-%, more preferably less than 0.05 wt .-%, preferably less than 0.03 wt .-%, particularly preferably less than 0.01 wt .-%, based on the composition B contains.

"Enzyme-free" as used herein means that the subject composition is substantially free of enzymes, i. in particular enzymes or enzyme preparations or preparations in amounts of less than 0.1% by weight, preferably less than 0.05% by weight, preferably less than 0.01% by weight, in particular less than 0.001% by weight based on the composition B contains.

"Liquid" as used herein includes liquids and gels.

The term "spatially separated" with respect to the compositions as used herein means that the compositions can not come into contact with each other prior to use. Typically, the dishwashing detergent is provided in a multi-compartment package, such as a bottle or pouch, in particular a two-chamber bottle or a two-chamber bag, the respective composition being separate from the other composition (s) in a separate chamber.

Preferably, composition A contains at least one further enzyme. Suitable enzymes include, but are not limited to, proteases, lipases, hemicellulases, particularly pectinases and / or mannanases, 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 by known methods, for example the BCA method or the biuret method.

Proteases are among the most technically important enzymes of all. For detergents and dishwashing detergents, they are the longest established enzymes and 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, in turn, proteases of the subtilisin type (subtilases, subtilopeptidases, EC 3.4.21.62) are particularly important, which are due to the catalytically active amino acids 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, for example, 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 produced 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 the subtilases, but not the subtilisins in the narrower sense attributable enzyme thermitase, proteinase K and the proteases TW3 and TW7, as well as variants of said proteases, which have a relation to the parent protease modified amino acid sequence. 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 the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases which are obtainable or further developed from Humicola lanuginosa (Thermomyces lanuginosus), in particular those having 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 summarized by the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

Oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect. Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.

A protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage. In microbial recovery of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. For this purpose, the dishwashing agents may contain, in addition to the calcium salts, further stabilizers, in particular polyols, in particular glycerol, propylene glycol and / or boron-containing compounds, such as boric acid and salts thereof. Preferred boron-containing compounds are phenylboronic acid derivatives, in particular the phenylboronic acid derivative 4-formyl-phenylboronic acid (4-FPBA). Further preferred phenylboronic acid derivatives may also have further 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 is coated with a water, air and / or chemical impermeable protective layer. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.

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

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

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

Water-soluble calcium salts useful as enzyme stabilizers include, but are not limited to, calcium chloride (CaCl ₂ , calcium lactate or calcium acetate.) Also suitable are other salts of calcium with alpha-hydroxycarboxylic acids or alpha-amino acids.

The at least one calcium salt suitable for the stabilization of enzymes is contained in various embodiments in an amount of 0.05 to 2 wt .-%, in particular 0.1 to 0.6 wt .-%, based on composition A.

As phosphonate, it is generally possible to use all phosphonates which are suitable as complexing agents for dishwashing detergents. The phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. Phosphonates are present in the compositions preferably in amounts of from 0.5 to 5% by weight, in particular in amounts of from 1 to 3% by weight, in each case based on the total weight of the composition B.

The dishwashing agents described herein are of a liquid nature and may, in particular, be present as homogeneous solutions or suspensions. In a further preferred embodiment of the invention, the dishwashing detergent is present in a pre-portioned form. The automatic dishwashing detergent has several spatially separate compositions, making it possible, on the one hand, to separate incompatible ingredients from one another, and, on the other hand, to offer compositions in combination which are used at different times in the dishwasher.

The dishwashing agents preferably also contain builders and surfactants. Unless otherwise specified, the percentages by weight are based on the total weight of the total dishwashing detergent composition.

The builders which can be used include, in particular, carbonates, citrates, MGDA (methylglycinediacetic acid) or its salts, GLDA (glutamic acid-N, N-diacetic acid) or its salts, EDDS (ethylenediamine-N, N'-disuccinic acid) or its salts, organic cobuilders and silicates. Particularly preferred are GLDA (glutamic acid-N, N-diacetic acid) or salts thereof.

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 and dextrins.

Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these. In addition to their builder effect, the free acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of dishwashing detergents. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Particularly preferred dishwashing detergent compositions contain as builders citrate, for example sodium or potassium citrate. Compositions containing from 1 to 15% by weight, preferably from 2 to 12% by weight of citrate are preferred according to the invention.

Other suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol.

Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.

The dishwashing detergents can also be builders of crystalline layered silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, where Particularly preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.

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

The dishwashing compositions of the invention may further comprise a sulfopolymer. The proportion by weight of the sulfopolymer in the total weight of the dishwashing agent according to the invention is preferably from 0.1 to 20 wt .-%, in particular from 0.5 to 18 wt .-%, particularly preferably 1.0 to 15 wt .-%, in particular from 4 to 14 wt .-%, especially from 6 to 12 wt .-%. The sulfopolymer is usually used in the form of an aqueous solution, the aqueous solutions typically containing 20 to 70 wt .-%, in particular 30 to 50 wt .-%, preferably about 35 to 40 wt .-% sulfopolymers.

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

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

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

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

Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. It goes without saying that it is also possible to use the unsaturated dicarboxylic acids.

In the sulfonic acid-containing monomers are those of the formula

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H

in which R ⁵ to R ⁷ are each independently -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - , -C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -NH-CH (CH ₃ ) -CH ₂ -.

Preferred among these monomers are those of the formulas

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH ₃ ) -X-SO ₃ H

HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H,

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

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

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

The monomer distribution of the copolymers preferably used according to the invention in the case of copolymers containing only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably in each case from 5 to 95% by weight, particularly preferably Proportion of the sulfonic acid group-containing monomer 50 to 90 wt .-% 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 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 ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

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

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

The nonionic monomers used are preferably monomers of the general formula R ¹ (R ² ) C =C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another are -H, -CH ₃ or -C ₂ H ₅ , X represents an optionally present spacer group selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 represents} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or represents 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, ethylcyclohexyne, 1-octene, alpha-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22-alpha-olefin, 2-styrene, alpha Methylstyrene, 3-methylstyrene, 4-propylstryol, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2, vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methyl methacrylate, N - (methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N- (2-ethylhexyl) acrylamide, acrylic acid reoctylester, Octyl methacrylate, N- (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N- (lauryl) acrylamide, stearyl acrylate, methacrylic acid stearyl ester, N- (stearyl) acrylamide, behenyl acrylate, behenyl methacrylate and N- (behenyl) acrylamide or mixtures thereof.

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

In addition to the aforementioned builders, the dishwashing detergents may contain alkali metal hydroxides. These alkali carriers are preferred in dishwashing detergents only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below 5% by weight, particularly preferably between 0.1 and 5% by weight. and in particular between 0.5 and 5 wt .-%, each based on the total weight of the dishwashing detergent composition. In particular, the alkali metal hydroxides are used in amounts such that the pH values according to the invention are achieved.

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

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

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

bevorzugt, in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht; jede Gruppe R² bzw. R³ unabhängig voneinander ausgewählt ist aus -CH₃, -CH₂CH₃, -CH₂CH₂-CH₃, CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.In the context of the present invention, particularly preferred nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here are nonionic surfactants of the general formula

in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical; each group R ² or R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently stand for integers from 1 to 6.

Thus, particularly preferred are nonionic surfactants having a C _9-15 alkyl group having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units.

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

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

• R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ^{2 is} H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• A, A ', 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 ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A '''O) _z -R ² , hereinafter also referred to as "hydroxy mixed ethers", the cleaning performance of the preparations according to the invention can be significantly improved both in comparison to surfactant-free system and in comparison to systems containing alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.

Preference is given in particular to those end-capped, poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² , in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having 1 to 30 carbon atoms, where x is from 1 to 30 carbon atoms and 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.

Particularly preferred are surfactants of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² , in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical with 4 R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1.5 and y is a value of at least 15.
The group of these nonionic surfactants includes, for example, the C _2-26 fatty alcohol (PO) ₁ - (EO) _15-40 -2-hydroxyalkyl ethers, in particular also the C _8-10 fatty alcohol (PO) ₁ - (EO) ₂₂ -2 -hydroxydecylether.

Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² , in which R ¹ and R ² independently of one another is a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ , but preferably -CH ₃ , and x and y are independently from each other values between 1 and 32, wherein nonionic surfactants with R ³ = -CH ₃ and values of x from 15 to 32 and y of 0.5 and 1.5 are very particularly preferred.

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2 Butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. When the value x ≥ 2, each R ³ in the above formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ^{2 may be} different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

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

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1 such that the above formula is R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH ) CH ₂ OR ² simplified. In the latter formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

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

Zur Gruppe dieser nichtionischen Tenside zählen beispielsweise die C_4-22 Fettalkohol-(EO)_10-80-2-hydroxyalkylether, insbesondere auch die C_8-12 Fettalkohol-(EO)₂₂-2-hydroxydecylether und die C_4-22 Fettalkohol-(EO)_40-80-2-hydroxyalkylether.Finally, the nonionic surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w -R ^{2 have} proved to be particularly effective, in which

• R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• A is a radical from the group CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ , CH ₂ CH (CH ₃ ), preferably CH ₂ CH ₂ , and
• w stands for values between 1 and 120, preferably 10 to 80, in particular 20 to 40

The group of these nonionic surfactants include, for example, the C _4-22 fatty alcohol (EO) _10-80 -2-hydroxyalkyl ethers, in particular also the C _8-12 fatty alcohol (EO) ₂₂ -2-hydroxydecyl ethers and the C _4-22 fatty alcohol (EO) _40-80 -2-hydroxyalkyl ether.

In various embodiments of the invention, instead of the above-defined end-capped hydroxy mixed ethers, it is also possible to use the corresponding non-end-capped hydroxy mixed ethers. These may satisfy the above formulas, but R ² is hydrogen and R ¹ , R ³ , A, A ', A ", A'", w, x, y and z are as defined above.

Preferred liquid dishwashing detergents are characterized in that the dishwashing detergent 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 dishwashing agent is preferably 0.1 to 10 wt.%, Preferably 0 , 5 to 8.0 wt .-% and in particular 1.0 to 4.0 wt .-% is.

In general, the pH of the dishwashing detergent can be adjusted by means of customary pH regulators. In various embodiments, the pH of Composition A is in the range of 5.5 to 8.5, preferably 6.5 to 8.0, more preferably 6.8 to 7.5, and the pH of Composition B is in a range from 9.0 to 12, preferably 10.0 to 11.5, preferably greater than 10, in particular 10.5 to 11.5. 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. Also preferred is volatile alkali, for example in the form of ammonia and / or alkanolamines, which may contain up to 9 carbon atoms in the molecule. The alkanolamine here is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof. The alkanolamine is preferably contained in agents according to the invention in an amount of from 0.5 to 10% by weight, in particular in an amount of from 1 to 6% by weight.

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

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

Preferred anionic surfactants are fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, alkylbenzenesulfonates, olefinsulfonates, alkanesulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignosulfonates. Also usable in the context of the present invention are fatty acid cyanamides, sulfosuccinates (sulfosuccinic esters), in particular sulfosuccinic mono- and di-C ₈ -C ₁₈ -alkyl esters, sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates and α-sulfofatty acid salts, acylglutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.
The anionic surfactants are preferably used as sodium salts, but may also be present as other alkali or alkaline earth metal salts, for example potassium or magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, in the case of the sulfonates also in the form of their corresponding acid, eg dodecylbenzenesulfonic acid.

Suitable amphoteric surfactants are, for example, betaines of the formula (R ⁱⁱⁱ ) (R ^iv ) (R ^v ) N ⁺ CH ₂ COO ^- , in which R ^{iii is} an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R ^iv and R ^{v are} identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C ₁₀ -C ₁₈ -alkyl-dimethylcarboxymethylbetain and C ₁₁ -C ₁₇ -alkylamidopropyl-dimethylcarboxymethylbetain.

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

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 dishwashing detergents is preferably between 0.1 and 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 to 1% by weight, preferably between 0.02 to 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.

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 dishwashing agents described herein can be done in different ways. The liquid supply forms based on water and / or organic solvents may be thickened, in the form of gels.

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

The dishwashing agents described herein are preferably prefabricated into dosage units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 16 and 22 g. In order to achieve an optimum cleaning and rinse-aid result, preference is given to those automatic dishwashing agents which are present in the form of a prefabricated dosing unit and between 0.001 and 1 g, preferably between 0.01 and 0.1 g, particularly preferably between 0.01 and 0, 07 g and in particular between 0.01 and 0.05 g of the polymer a) or between 0.1 and 2.5 g, preferably between 0.2 and 2.2 g, particularly preferably between 0.3 and 1.9 g and in particular between 0.4 and 1.5 g of nonionic (s) surfactant (s) b). 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.

The dishwashing agents, in particular the prefabricated metering units, with particular preference have a water-soluble coating.

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

It is preferable that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer have a good stability with a sufficiently high water solubility, in particular cold water solubility on.

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

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

In addition, a polymer selected from the group consisting of (meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyethers, polylactic acid, or mixtures of the above may be additionally used in a polyvinyl alcohol-containing film material suitable for producing the water-soluble coating Be added polymers. A preferred additional polymer is polylactic acids.

Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.

Likewise preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters. Particularly preferably contain such Polyvinyl alcohol copolymers in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof.

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

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

The corresponding use of the automatic dishwasher detergents according to the invention is likewise an object of the invention. The invention likewise relates to a dishwashing process, in particular a machine dishwashing process, in which a dishwashing detergent according to the invention is used. The subject matter of the present application is therefore furthermore a process for the cleaning of dishes in a dishwashing machine, in which the agent according to the invention 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 according to the invention into the interior of the dishwasher can be done manually, but preferably the agent is metered by means of the metering chamber into the interior of the dishwasher.

Examples Example 1: Liquid Machine Dishwashing Formulations

The dishwashing compositions according to the invention comprise an enzyme phase which corresponds to Formulation A and an alkali phase which corresponds to Formulation B. Formulation 1 corresponds to the formulation according to the invention, Formulation 2 is a comparison formulation showing precipitations of calcium phosphonate. Table 1: Composition of the automatic dishwashing agent (% by weight) Enzyme Phase (EP) Preparation A Rez. 1 Rez. 1 Rez. 2 (V) Rez. 2 (V) active content active content water 28.72 28.72 25,00 25,00 HEDP 0.00 0.00 2.00 1.20 CaCl ₂ 0.27 0.27 0.27 0.27 Amylase-containing enzyme composition 1.50 0.04 1.50 0.04 Protease-containing enzyme composition 3.00 0.14 3.00 0.14 boric acid 3.00 3.00 3.00 3.00 sorbitol 12,00 8.40 12,00 8.40 Sulfonic acid group-containing polymer 15.00 5.70 15.00 5.70 Thickener (acrylate) 4.60 1.75 4.60 1.75 GLDA 20.00 9.40 20.00 9.40 KOH (50%) 4.85 2.43 4.85 2.43 Nonionic surfactants 3.50 3.50 3.50 3.50 Sodium Citrate x 2H ₂ O 3.00 3.00 3.00 3.00 Zinc acetate (wt%) 0.19 0.19 0.19 0.19 Residues (perfume, dyes, preservatives) (% by weight) ad 100 ad 100 ad 100 ad 100 PH value 7.5 7.5 Alkaline phase (AP) Preparation B Rez. 1 Rez. 1 Rez. 2 (V) Rez. 2 (V) active content active content water 31,56 31,56 35.76 35.76 HEDP 4.30 2.58 2.30 1.38 Thickener (acrylate) 5.20 1.98 5.20 1.98 GLDA 30.00 14.10 30.00 14.10 KOH (50%) 4.70 2.35 2.50 1.25 soda 9.00 9.00 9.00 9.00 Monoethanolamine 2.75 2.75 2.75 2.75 Aqueous acrylate polymer solution 1.00 1.00 1.00 1.00 Sodium Citrate x 2H ₂ O 11.40 11.40 11.40 11.40 Residues (perfume, dyes, preservatives, water, etc.) (% by weight) ad 100 ad 100 ad 100 ad 100 PH value 11.4 11.4

Example 2: Cleaning performance in automatic dishwashing

In a Miele G698SC dishwasher at 50 ° C ("Normal" program) and 21 ° dH dishes with various soils were mixed with a 1: 1 mixture of the enzyme and alkaline phases (19.3 g / job each; 40 ° C stored) and after each rinsing cycle visually determines the cleaning performance according to IKW (evaluation of 1-10, the higher the value, the better the performance, differences of at least 1 are significant). The results for the tested formulations are listed in Table 2 as arithmetic mean values. Higher values mean better cleaning performance. Table 2: Cleaning performance on enzyme-sensitive soiling minced meat egg yolk Recipe 1 4.2 3.4 Recipe 2 (comparison) 2.1 2.1

It can be clearly seen from the table that the formulation according to the invention performs better on protease-sensitive stains.

Claims (10)

1. A phosphate-free liquid dishwashing detergent, preferably an automatic dishwashing detergent, characterized in that the dishwashing detergent comprises two mutually spatially separated liquid compositions A and B,

   (a) composition A being phosphonate-free and comprising at least one enzyme, preferably a protease and/or amylase, and at least one calcium salt that is suitable for stabilizing the at least one enzyme, and having a pH that is less than 8.5, preferably of 8, in particular of 7.5 or less, and

   (b) composition B being enzyme-free and calcium-free and comprising at least one phosphonate, in particular 1-hydroxyethane-(1,1-diphosphonic acid) (HEDP), and having a pH that is greater than 9, preferably greater than 10.
2. The dishwashing detergent according to claim 1, characterized in that composition A contains the at least one calcium salt, in particular calcium chloride (CaCl₂), in an amount of 0.05 to 2 wt.%, in particular 0.1 to 0.6 wt.%, with respect to composition A.
3. The dishwashing detergent according to claim 1 or 2, characterized in that composition B contains the at least one phosphonate, in particular HEDP, in an amount of 0.5 to 5 wt.%, in particular 1 to 3 wt.%, with respect to composition B.
4. The dishwashing detergent according to one of claims 1 to 3, characterized in that composition A contains at least one amylase and at least one protease and optionally at least one further enzyme selected from the group consisting of lipases, hemicellulases, in particular pectinases and/or mannanases, cellulases, perhydrolases and oxidoreductases.
5. The dishwashing detergent according to one of claims 1 to 4, characterized in that composition A contains further enzyme stabilizers, in particular polyols and/or boric acid.
6. The dishwashing detergent according to one of claims 1 to 5, characterized in that compositions A and/or B further contain at least one builder selected from the group of glutamic diacetic acid (GLDA), methylglycinediacetic acid (MGDA) and ethylenediamine diacetic acid (EDDA) or the salts thereof.
7. The dishwashing detergent according to one of claims 1 to 6, characterized in that compositions A and/or B further contain citrate.
8. The dishwashing detergent according to one of claims 1 to 7, characterized in that the dishwashing detergent contains at least one further component, preferably at least two further components, selected from the group consisting of surfactants, polymers, corrosion inhibitors, glass corrosion inhibitors, odorants and perfume carriers.
9. The use of a dishwashing detergent according to one of claims 1 to 8 in an automatic dishwashing method.
10. An automatic dishwashing method, characterized in that a dishwashing detergent according to one of claims 1 to 8 is used.