EP3498810A1 - Machine dishwashing detergent with improved rinsing and cleaning power, method using said agent as well as its utilization - Google Patents

Abstract

The present invention relates to a phosphate-free dishwashing detergent, in particular machine dishwashing detergent, comprising at least one surfactant and at least one protease, characterized in that the surfactant is an anionic surfactant from the group of sulfated or sulfonated triglycerides. Furthermore, a machine dishwashing process, in which this dishwashing detergent is used, the subject of the invention. Likewise provided by the invention is the use of at least one sulfated or sulfonated triglyceride as enzyme-enhancing agent and / or for improving the rinsing performance, preferably in these automatic dishwashing detergents and / or in these automatic dishwashing processes.

Description

"Machine dishwashing detergent with improved rinsing and cleaning performance, method using this agent and use of the agent"

The present invention relates to a non-phosphate machine dishwashing detergent which exhibits improved cleaning performance and rinse performance, the use of this dishwashing detergent and a machine dishwashing method using this dishwashing detergent.

Machine-washed dishes are often subject to more stringent requirements today than manually-washed dishes. So the dishes after machine cleaning should not only be free from food debris, but also, for example, have no whitish, based on water hardness or other mineral salts stains that come from lack of wetting agent from dried water droplets. Such staining and streaking is in principle observable on surfaces of all kinds (porcelain, glass, plastic, stainless steel). This harness is the consumer - often by hand - post-treated, which is not very user-friendly. Therefore, there is a need for automatic dishwashing agents that reduce the formation of so-called spotting and / or filming stains and / or deposits.

To obtain glossy and spotless dishes, rinse aids are used in dishwashing formulations. Through a mediated by these agents film formation on the dishes, the water should run as completely as possible from the dishes, so that the surfaces are residue-free and flawless gloss at the end of the wash program. Although the use of such rinse aids is known in the art, there continues to be a need for dishwashing detergents which exhibit improved rinse performance.

In view of this initial situation, therefore, the object of the present application was to provide a dishwasher detergent, which shows both in terms of its cleaning performance and with respect to its rinse results improved performance over conventional detergents.

Enzymes in automatic dishwashing detergents have the important function of enzymatically removing food residues. In many cases, they enable automatic dishwashing to produce clean dishes even at low temperatures. The enzymes most commonly used in dishwashing detergents are of the protease type. Often it turns out that the cleaning performance of the enzymes can be increased by the presence of other substances.

It has surprisingly been found that the use of sulfated or sulfonated triglycerides leads both to an increase in the cleaning performance of persistent enzyme-sensitive soiling and to an increase in the final rinse performance. With the simultaneous presence of protease improved cleaning performance and rinse performance over conventional dishwashing detergents could be observed.

The object underlying the present invention is therefore achieved by a phosphate-free dishwashing detergent, in particular machine dishwashing detergent, comprising at least one surfactant and at least one protease, wherein the surfactant is an anionic surfactant from the group of sulfated or sulfonated triglycerides.

A first subject of the present application is therefore a phosphate-free dishwashing detergent, in particular automatic dishwashing detergent, comprising at least one surfactant and at least one protease, wherein the surfactant is an anionic surfactant from the group of sulfated or sulfonated triglycerides.

Likewise provided by the present invention is a machine dishwashing process for the cleaning of dishes, using a dishwashing detergent according to the invention.

Yet another object of the invention is the use of at least one sulfated or sulfonated triglyceride as enzyme-enhancing agent and / or to improve the rinse aid performance, preferably in automatic dishwashing detergents according to the invention and / or in automatic dishwashing processes according to the invention.

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. Further, 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 that the 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.

"At least one" as used herein means 1 or more, ie 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. With respect to an ingredient, the indication refers to the type of ingredient, not the absolute number of molecules. "At least one surfactant" thus means, for example at least one type of surfactant, ie, one type of surfactant or a mixture of several different surfactants may be meant. The term "weight information" refers to all compounds of the specified type which are contained in the composition / mixture, ie that the composition does not contain any further compounds of this type beyond the stated amount of the corresponding compounds.

All percentages given in connection with the compositions described herein, unless explicitly stated otherwise, relate to% by weight, in each case based on the mixture in question.

In the context of the present invention are fatty acids or fatty alcohols or their derivatives - unless otherwise stated - representative of branched or unbranched carboxylic acids or alcohols or their derivatives having preferably 6 to 22 carbon atoms. In particular, the oxo alcohols or their derivatives which are obtainable, for example, by the ROELEN's oxo synthesis can also be used correspondingly.

Whenever alkaline earth metals are referred to below as counterions for monovalent anions, this means that the alkaline earth metal is present only in half - as sufficient to charge balance - amount of substance as the anion.

The agent is phosphate-free; this means that the dishwashing agents according to the invention are essentially phosphate-free, i. Phosphate in amounts less than 1 wt .-%, preferably less 0.1 wt .-%, and / or contain no deliberately added phosphate.

The dishwashing agent according to the invention contains at least one protease. Proteases are among the most technically important enzymes of all. 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. 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 enzymes Thermitase, proteinase K and the proteases TW3 and TW7, and Variants of the mentioned proteases which have an amino acid sequence which is altered in relation 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.

Preference is given in particular to dishwashing agents which, based in each case on their total weight, contain 0.1 to 9% by weight, preferably 0.5 to 7% by weight and in particular 1.5 to 5% by weight, of protease preparations.

The dishwasher according to the invention further contains at least one anionic surfactant from the group of sulfated or sulfonated triglycerides. Triglycerides are also referred to as triacylglycerols and are compounds of the trihydric alcohol glycerol (propane-1,2,3-triol), in which the three OH groups of the molecule are esterified with carboxylic acids. The triglycerides include animal and vegetable fats and oils. These usually contain several different fatty acid residues in the molecule.

The sulfated or sulfonated triglyceride preferably contains saturated or unsaturated, linear or branched, substituted or unsubstituted hydrocarbon chains having a chain length of 3 to 25 carbon atoms, preferably 11 to 21 carbon atoms, more preferably 13 to 19 carbon atoms, wherein at least one of the chains is sulfated or sulfonated ,

In particular, the sulphate or sulphonate substitution may have been introduced at certain functionalities previously present in the triglycerides, such as double bonds or hydroxy groups. For this reason, these substitutions can occur at different sites of the hydrocarbon chains of the triglycerides.

mit R¹, R², R³ welche unabhängig voneinander eine gesättigte oder ungesättigte, lineare oder verzweigte, substituierte oder unsubstituierte Kohlenwasserstoffkette mit einer Kettenlänge von 3 bis 25 Kohlenstoffatomen, bevorzugt 11 bis 21 Kohlenstoffatomen, besonders bevorzugt 13 bis 19 Kohlenstoffatomen darstellen, wobei mindestens eine der Ketten sulfatiert oder sulfoniert ist.The sulfated or sulfonated triglyceride has the general formula

with R ¹ , R ² , R ³ independently of one another a saturated or unsaturated, linear or branched, substituted or unsubstituted hydrocarbon chain having a chain length of 3 to 25 carbon atoms, preferably 11 to 21 carbon atoms, more preferably 13 to 19 carbon atoms, wherein at least one of the chains is sulfated or sulfonated.

R ¹ , R ² and R ³ may be different. Two or three of the groups R ¹ , R ² and R ³ may be identical. Preferably, two of the groups are identical. Particularly preferably, the groups R ¹ , R ² and R ^{3 are} identical.

These are the hydrocarbon chains of saturated or unsaturated, linear or branched and substituted or unsubstituted carboxylic acids, wherein the carboxylic acids have a total chain length of 4 to 26 carbon atoms, preferably 12 to 22 carbon atoms, particularly preferably 14 to 20 carbon atoms. The hydrocarbon chains can be mono- or polyunsaturated, that is, they can have both one or more double bonds. Both the cis and the trans configuration of the double bonds are possible. Preferably, the triglyceride contains at least one hydrocarbon chain having at least one double bond. Particularly preferably, the triglyceride contains at least two hydrocarbon chains each having at least one double bond. Most preferably, the triglyceride contains three hydrocarbon chains each having at least one double bond. The hydrocarbon chains of the triglyceride may be linear or branched. Branched hydrocarbon chains can be single or multiple branched, furthermore, the branches can occur at different positions of the chain. They are preferably linear hydrocarbon chains. The hydrocarbon chains may have, in addition to the sulfonation or sulfation, one or more further substitutions. These may be, for example, keto or hydroxy substitutions. Preferably, at least one of the chains has no further substitution. Particularly preferably, none of the chains has a further substitution.

The hydrocarbon chains may have a chain length of from 3 to 25 carbon atoms, preferably from 11 to 21 carbon atoms, more preferably from 13 to 19 carbon atoms. Very particular preference is given to hydrocarbon chains having 17 carbon atoms or the corresponding fatty acids having 18 carbon atoms.

In a preferred embodiment, the sulfated or sulfonated triglyceride contains at least one monounsaturated linear fatty acid residue having a chain length of 18 carbon atoms, more preferably the sulfated or sulfonated triglyceride contains at least two monounsaturated linear fatty acid residues having a chain length of 18 carbon atoms, most preferably the sulfated one or sulfonated triglyceride three monounsaturated linear fatty acid residues having a chain length of 18 carbon atoms, wherein at least one of these fatty acid residues is sulfated or sulfonated.

In another preferred embodiment, the sulfated or sulfonated triglyceride contains two monounsaturated linear fatty acid residues having a chain length of 18 carbon atoms, wherein the third fatty acid residue is a saturated or diunsaturated linear fatty acid residue having a chain length of 18 carbon atoms, at least one of them Fatty acid residues is sulfated or sulfonated.

In another preferred embodiment, the sulfated or sulfonated triglyceride contains two ricinoleic acid groups, wherein the third fatty acid residue is selected from the group consisting of residues of linoleic acid, oleic acid and stearic acid, wherein at least one of these fatty acid residues of the triglyceride is sulfated or sulfonated.

The sulfated or sulfonated triglyceride preferably contains at least one ricinoleic acid group, more preferably it contains at least two ricinolic acid groups, most preferably it contains three ricinolic acid groups, wherein at least one ricinoleic acid group is sulfated or sulfonated.

In a preferred embodiment, the triglyceride contains on average 1 to 6 sulfate or sulfonate groups per molecule, more preferably an average number of 1 to 3 sulfate or sulfonate groups per triglyceride molecule, most preferably an average number of 1 to 2 sulfate or sulfonate groups per triglyceride molecule.

Turkish red oil comprising a mixture of castor oil and sulfated and / or sulfonated castor oil is contained in a further preferred embodiment in the inventive compositions. Turkish red oil is particularly preferred in an amount of 0.3 to 30% by weight, more preferably in an amount of 0.5 to 10% by weight, and most preferably in an amount of 0.7 to 3% by weight. , based on the total weight of the dishwashing agent, in the inventive compositions.

The agents according to the invention preferably contain the sulfated or sulfonated triglyceride in an amount of from 0.1 to 25% by weight, preferably in an amount of from 0.2 to 10% by weight, more preferably in an amount of from 0.5 to 5 Wt .-% and most preferably in an amount of 0.7 to 1.5 wt .-%, based on the total weight of the dishwashing detergent.

In a preferred embodiment, the agent according to the invention contains 1% by weight of the sulfated or sulfonated triglyceride, based on the total weight of the dishwashing detergent.

The agent according to the invention preferably contains at least one further surfactant, preferably selected from the group of anionic, nonionic, amphoteric and cationic surfactants, more preferably from the group of nonionic surfactants.

As anionic, cationic, amphoteric or nonionic surfactants it is possible to use all surfactants of these types known to the person skilled in the art.

Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) _x in which R is 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 is a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any 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.

In various embodiments, aminal alkoxylates or sorbitan esters can also be present in the compositions according to the invention.

However, 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.

A class of useful nonionic surfactants which can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants are accordingly alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.

Preferably used surfactants come from the groups of 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 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.Particularly preferred nonionic surfactants are those 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 is} -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.

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 a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having 1 to 30 Have carbon atoms, wherein x stands for values between 1 and 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.

Particularly preferred are surfactants of the formula R 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 include, for example, the C _2-26 fatty alcohol (PO) i (EO) _15-40 -2-hydroxyalkyl ethers, in particular also the C _8-10 fatty alcohol (PO) ₁ - (EO) ₂₂ -2 -hydroxydecylether.

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

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

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

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

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

Finally, the nonionic surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w -R ^{2 have} proven 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.

The compositions described herein, which preferably comprise at least one nonionic surfactant, more preferably a nonionic surfactant from the group of hydroxy mixed ethers, contain the surfactant in various embodiments in an amount based on the total weight of the composition of at least 1 wt .-%, preferably at least 2.5% by weight.

Dishwasher detergents which are suitable as further anionic surfactants are all anionic surface-active substances. These are characterized by a water-solubilizing, anionic group such as. Example, a carboxylate, sulfate or sulfonate group and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Suitable anionic surfactants are preferably present in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts having 2 to 4 carbon atoms in the alkanol group.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule.

The dishwashing detergents can therefore, in various embodiments, contain at least one surfactant of the formula R ⁴ -O- (AO) _n -SO ₃ ^- X ⁺ .

In this formula, R ^{4 is} a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical, preferably a linear, unsubstituted alkyl radical, more preferably a fatty alcohol radical. Preferred radicals R ¹ are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, where the representatives with an even number of carbon atoms Atoms are preferred. Particularly preferred radicals R ¹ are derived from C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C ₁₀ -C ₂₀ oxo alcohols.

AO represents an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety. The index n stands for an integer from 1 to 50, preferably from 1 to 20 and especially from 2 to 10. Most preferably, n stands for the numbers 2, 3, 4, 5, 6, 7 or 8. X stands for a monovalent cation or the nth part of an n-valent cation, the alkali metal ions are preferred, and Na ⁺ or K ⁺ including Na, with Na ^{+ being} extremely preferred. Other cations X ⁺ may be selected from NH ₄ ⁺ , ½Zn ²⁺ , ½Mg ²⁺ , ½Ca ²⁺ , ½Mn ²⁺ , and mixtures thereof.

mit k = 11 bis 19, n = 2, 3, 4, 5, 6, 7 oder 8. Ganz besonders bevorzugte Vertreter sind Na-C_12-14 Fettalkoholethersulfate mit 2 EO (k = 11-13, n = 2).Particularly preferred anionic surfactants are selected from fatty alcohol ether sulfates of the formula

with k = 11 to 19, n = 2, 3, 4, 5, 6, 7 or 8. Very particularly preferred representatives are Na-C _12-14 fatty alcohol _ether sulfates with 2 EO (k = 11-13, n = 2).

The agents may additionally or alternatively contain at least one surfactant of the formula R ⁵ -A-SO ₃ ^- Y ⁺ .

In this formula, R ^{5 is} a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical and the grouping -A- for -O- or a chemical bond. In other words, sulfate (A = O) or sulfonate (A = chemical bond) surfactants can be described by the above formula. Depending on the choice of the group A, certain radicals R ^{5 are} preferred. In the case of the sulfate surfactants (A = O), R ⁵ preferably represents a linear, unsubstituted alkyl radical, more preferably a fatty alcohol radical. Preferred radicals R ⁵ are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, where the representatives with an even number of carbon atoms Atoms are preferred. Particularly preferred radicals R ⁵ are derived from C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C ₁₀ -C ₂₀ oxo alcohols. Y stands for a monovalent cation or the n-th part of an n-valent cation, the alkali metal ions being preferred, and Na ⁺ or K ⁺ being preferred, Na ^{+ being} extremely preferred. Other cations Y + may be selected from NH ₄ ⁺ , ½Zn ²⁺ , ½Mg ²⁺ , ½Ca ²⁺ , ½Mn ²⁺ , and mixtures thereof.

mit k = 11 bis 19. Ganz besonders bevorzugte Vertreter sind Na-C_12-14 Fettalkoholsulfate (k = 11-13).Such particularly preferred surfactants are selected from fatty alcohol sulfates of the formula

with k = 11 to 19. Very particularly preferred representatives are Na-C _12-14 fatty alcohol sulfates (k = 11-13).

In the case of the sulfonate surfactants (A = chemical bond) R ⁵ preferably represents a linear or branched unsubstituted alkylaryl radical. Here, too, X is a monovalent cation or the nth part of an n-valent cation, the alkali metal ions being preferred, and Na ⁺ or K ⁺ being preferred, Na ^{+ being} extremely preferred. Other cations X + may be selected from NH ₄ ^+, ½ Zn ^2+, ½Mg ^2+, ½Ca ^2+, ½Mn ^2+, and mixtures thereof. Such surfactants may be selected from linear or branched alkyl benzene sulfonates.

In the compositions according to the invention, the content of further anionic surfactants is preferably less than 4% by weight, more preferably less than 2% by weight and in particular less than 1% by weight. Dishwashing detergents which are not further anionic Containing surfactants are particularly preferred. No further surfactant means that less than a further 0.5% by weight of said surfactant, preferably less than a further 0.2% by weight of said surfactant, are contained, more preferably no further surfactant has been added to this group.

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.

In dishwashing compositions, the content of cationic and / or amphoteric surfactants is preferably less than 4% by weight, more preferably less than 2% by weight and in particular less than 1% by weight. Dishwashing detergents containing no cationic or amphoteric surfactants are particularly preferred.

In various embodiments, silicone surfactants can also be present in the compositions according to the invention, which, depending on their structure, can be assigned to different classes of surfactants.

In various embodiments, amphiphilic carboxyalkylated polyamines can also be present in the agents according to the invention.

The agents according to the invention preferably contain at least one builder. Builders which may be present in the dishwashing detergent are, in particular, silicates, aluminum silicates (in particular zeolites), carbonates, phosphonates, organic (co) builders, for example salts of organic di- and polycarboxylic acids, and mixtures of these substances.

It is possible, for example, to use crystalline layer-form silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, in which M represents sodium or hydrogen, x a number from 1.9 to 22, preferably from 1.9 to 4, where especially preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. The crystalline layer-form silicates of the formula NaMSi _x O _{2x + 1} .yH ₂ O are for example sold by Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ .xH ₂ O, Kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ .xH ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ O ₁₇ · x H ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ · xH ₂ O, makatite). Particularly suitable for the purposes of the present invention are crystalline phyllosilicates of the formula NaMSi _x O _{2x + 1} .yH ₂ O, in which x is 2. In particular, both β- and δ-sodium disilicates are Na ₂ Si ₂ O ₅ .yH ₂ O and furthermore especially Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O _5, natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ · H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ · 3H ₂ O, kanemite), Na-SKS-11 (t- Na ₂ Si ₂ O ₅ ) and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ).

The dishwashing detergents in various embodiments contain a weight fraction of the crystalline layered silicate of the formula NaMSi _x O _{2x + 1} .yH ₂ O of from 0.1 to 45% by weight, preferably from 1 to 40% by weight and in particular from 5 to 35 Wt .-%, each based on the total weight of these agents. In various embodiments, the agents are free of such silicates.

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. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is understood to mean that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle , cause.

In various embodiments, these silicate (s), preferably alkali metal silicates, more preferably crystalline or amorphous Alkalidisilikate, in the compositions in amounts of from 3 to 60 wt .-%, preferably from 8 to 50 wt .-% and in particular from 20 to 40 wt .-%, each based on the weight of the dishwashing detergent to be included. In other embodiments, the agents are free of these silicates.

Further builders are the alkali carriers. Suitable alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the cited alkali metal silicates, alkali metal silicates, and mixtures of the abovementioned substances, it being possible to use the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate, for the purposes of this invention. Because of their low chemical compatibility with the other ingredients of dishwasher detergents in comparison with other builders, the optional alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 Wt .-% and in particular below 2 wt .-%, in each case based on the total weight of the dishwashing detergent used. Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.

In various embodiments, carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of 2 to 50 wt .-%, preferably from 5 to 40 wt .-% and in particular from 7 , 5 to 30 wt .-%, each based on the weight of the dishwashing detergent are used.

The dishwashing detergents can contain as further builders in particular also phosphonates, which according to the invention are not subsumed under the phosphates. The phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. Phosphonates are contained in the compositions preferably in amounts of 0.1 to 10 wt .-%, in particular in amounts of 0.3 to 8 wt .-%, each based on the total weight of the dishwashing detergent.

Particularly suitable organic (co) builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders and the phosphonates already mentioned above as builders. These classes of substances are described below.

Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. For example, these are citric acid, 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 thereof. The free In addition to their builder effect, acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of the dishwasher detergent. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

The use of citric acid and / or citrates has proved to be particularly advantageous for the cleaning and rinsing performance. Therefore, machine dishwashing detergents are preferred according to the invention in that the dishwashing detergent contains citric acid or a salt of citric acid and the weight fraction of citric acid or the salt of citric acid is preferably 1 to 40 wt.%, Preferably 10 to 25 wt between 15 and 22 wt .-% is.

Another important class of phosphate-free builders are aminocarboxylic acids and / or their salts. Particularly preferred members of this class are methylglycinediacetic acid (MGDA) or its salts, and glutamic diacetic acid (GLDA) or its salts or ethylenediaminediacetic acid (EDDS) or its salts. Very particular preference is GLDA or its salts. The content of these aminocarboxylic acids or their salts, in particular GLDA sodium salt, may for example be between 0.1 and 25% by weight, preferably between 5 and 25% by weight and in particular between 15 and 25% by weight. Aminocarboxylic acids and their salts can be used, for example, together with the abovementioned builders, in particular together with citrate and the abovementioned phosphonates.

The compositions according to the invention preferably comprise at least one builder selected from the group comprising silicates, aluminum silicates, carbonates, phosphonates, organic di- and polycarboxylic acids or salts thereof and mixtures thereof.

The agent according to the invention preferably comprises at least one further constituent, preferably at least two further constituents selected from the group comprising further builders, further enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, polymers, bleaches, bleach catalysts, bleach activators, foam inhibitors, Dyes, fragrances, bitter substances, antimicrobial agents and disintegration aids.

The dishwashing agents according to the invention may further comprise a sulfopolymer as further builder. 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 in the form of an aqueous solution used, wherein the aqueous solutions typically contain 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.

As unsaturated carboxylic acid (s) is / are used 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 each other is -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH as defined above or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

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

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

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H

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

Preferred among these monomers are those of the formulas

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH ₃ ) -X-SO ₃ H

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

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

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

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

The monomer distribution of the copolymers preferably used in the case of copolymers containing only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably from 5 to 95% by weight, more preferably the proportion of the sulfonic acid group-containing monomer is from 50 to 90% by weight. and the proportion of the carboxylic acid group-containing monomer 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 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 various embodiments, other polymers can be used in the compositions of the invention. The group of suitable polymers includes, in particular, the washing or cleaning-active polymers, for example the rinse aid polymers and / or as softeners Polymers. In general, cationic, anionic and amphoteric polymers can be used in automatic dishwashing detergents in addition to nonionic polymers. The sulfo (co) polymers described above are, for example, anionic polymers.

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

Preferred polymers which can be used are from the group of the 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.

Other usable polymers come from the group of acrylamidoalkyltrialkylammonium 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.

"Cationic polymers" are polymers which carry a positive charge in the polymer molecule. This can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain. Particularly preferred cationic polymers come from the groups of 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 dialkylamino and methacrylates, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

The amounts given above for the described surfactants and builders usually refer to the amounts that are used when the particular surfactant or the respective builder is used alone, unless explicitly stated otherwise. It is therefore of course, that when using multiple surfactants or builders, the quantities are adjusted accordingly.

The agents of the present invention contain at least one protease but may also contain other enzymes. The agent according to the invention preferably has further enzymes. The enzyme or enzymes used may be present in one or more enzyme preparations or enzyme compositions. Other suitable enzymes include, but are not limited to, other proteases, amylases, lipases, hemicellulases, cellulases, β-glucanases, perhydrolases or oxidoreductases, and preferably mixtures thereof. 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 agents contain enzymes preferably in total amounts of 1 × 10 ^-6 to 5 wt .-% based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.

Examples of usable amylases are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as the further developments of the aforementioned amylases which are improved for use in 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).

It is also possible to use lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L.

Furthermore, enzymes can be used, which are summarized by the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases. Among the latter, the licheninases in particular should be mentioned.

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 to increase the bleaching effect. Advantageously, organic compounds are additionally preferably used aromatic, interacting with the enzymes compounds added to enhance the activity of the respective oxidoreductases (enhancer) or to ensure the electron flow at greatly varying redox potentials between the oxidizing enzymes and the stains (mediators).

An enzyme can be particularly protected during storage against damage such as inactivation, denaturation or disintegration 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. Dishwashing agents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.

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

Alternatively, the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.

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

As can be seen from the previous comments, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Preferably used protease and amylase preparations contain between 0.1 and 40 wt .-%, preferably between 0.2 and 30 wt .-%, particularly preferably between 0.4 and 20% by weight and in particular between 0.8 and 10% by weight 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.

The compositions described herein may also include enzyme stabilizers. One group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used for this purpose, including, in particular, derivatives with aromatic groups, for example ortho, meta or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or the salts or Esters of the compounds mentioned. Also, peptide aldehydes, that is oligopeptides with a reduced C-terminus, especially those of 2 to 50 monomers are used for this purpose. Among the peptidic reversible protease inhibitors include ovomucoid and leupeptin. Also, specific, reversible peptide inhibitors for the protease subtilisin and fusion proteins from proteases and specific peptide inhibitors are suitable.

Other enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C ₁₂ , such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Other enzyme stabilizers are known to those skilled in the art.

Machine dishwashing detergents according to the invention may contain a bleaching agent as further constituent, with oxygen bleaches being preferred. Among the compounds serving as bleaches in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
Furthermore, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. It is also possible to use all other inorganic or organic peroxy bleaches known to the person skilled in the art. As a bleaching agent, the percarbonates and in particular sodium percarbonate are particularly preferred.

Preferred automatic dishwashing agents according to the invention are characterized in that they contain an oxygen bleaching agent, preferably sodium percarbonate, more preferably a coated sodium percarbonate. The proportion by weight of the bleaching agent, based on the total weight of the washing or cleaning agent, in preferred embodiments is between 1 and 35% by weight, preferably between 2.5 and 30% by weight, more preferably between 5 and 20% by weight in particular between 10 and 15 wt .-%.

In various embodiments of the invention, the automatic dishwashing agents additionally contain at least one bleach activator. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Of all the bleach activators known to the person skilled in the art, polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), are 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. As a bleach activator, TAED, especially in combination with a percarbonate bleach, preferably sodium percarbonate, is most preferred.

These bleach activators are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, especially 2 to 8% by weight and more preferably 2 to 6% by weight or 2 to 3 % By weight, based in each case on the total weight of the agent.

In addition or as an alternative to the conventional bleach activators, the automatic dishwasher detergents according to the invention preferably contain at least one bleach catalyst. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.

It is particularly preferred to use complexes of manganese in the oxidation state II, III, IV or IV, which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S. Preferably, ligands are used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononan (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and / or 2-methyl-1,4,7-triazacyclononane (Me / TACN ) contain. Suitable manganese complexes are, for example, [Mn ^III ₂ (μ-O) ₁ (μ-OAc) ₂ (TACN) ₂ ] (ClO ₄ ) ₂ , [Mn ^III Mn ^IV (μ-O) ₂ (μ-OAc) ₁ (TACN ) ₂ ] (BPh ₄ ) ₂ , [Mn ^IV ₄ (μ-O) ₆ (TACN) ₄ ] (ClO ₄ ) ₄ , [Mn ^III ₂ (μ-O) ₁ (μ-OAc) ₂ (Me-TACN ) ₂ ] (ClO ₄ ) ₂ , [Mn ^III Mn ^IV (μ-O) ₁ (μ-OAc) ₂ (Me-TACN) ₂ ] (ClO ₄ ) ₃ , [Mn ^IV ₂ (μ-O) ₃ ( Me-TACN) ₂ ] (PF ₆ ) ₂ and [Mn ^IV ₂ (μ-O) ₃ (Me / Me-TACN) ₂ ] (PF ₆ ) ₂ (OAc = OC (O) CH ₃ ).

Machine dishwashing detergent, characterized in that it further comprises a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me ₃ -TACN ) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me ₄ -TACN), are preferred according to the invention, since in particular the cleaning result can be significantly improved by the aforementioned bleach catalysts.

The aforementioned bleach-enhancing transition metal complexes, in particular with the central atoms Mn and Co, are used in customary amounts, preferably in an amount of up to 5% by weight, in particular of 0.0025% by weight to 1% by weight and more preferably of 0 , 01 wt .-% to 0.30 wt .-% or 0.02 wt .-% to 0.5 wt .-%, each based on the total weight of the bleach catalyst-containing agents used. In special cases, however, more bleach catalyst can be used.

In general, the pH of the dishwashing detergent can be adjusted by means of customary pH regulators, the pH value being chosen as a function of the desired intended use. In various embodiments, the pH is in a range of 5.5 to 10.5, preferably 5.5 to 9.5, more preferably greater than 7, even more preferably greater than 7.5 and in particular greater than 8, 5. Usually a dishwasher detergent, for example a tablet, while a pH greater than 10, and the rinse liquor receives in a preferred embodiment when using the dishwashing a pH value between 9 and 10, for example 9.5.
The pH adjusting agents are acids and / or alkalis, preferably alkalis. Suitable acids are in particular organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid. In addition, however, it is also possible to use the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof. Suitable bases are selected from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular the alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide is preferred. However, particularly preferred is volatile alkali, for example in the form of ammonia and / or alkanolamines, which may contain up to 9 carbon atoms in the molecule. The alkanolamine is in this case preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof.

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

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 as well as 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 and 1% by weight, preferably between 0.02 and 0.5% by weight and in particular between 0.04 and 0.2% by weight. -%, in each case 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.

Furthermore, preservatives may be included in the compositions. Suitable examples are preservatives from the groups of alcohols, aldehydes, antimicrobial acids and / or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazoles and derivatives thereof such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores and peroxides. Preferred antimicrobial agents are preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2 Benzyl 4-chlorophenol, 2,2'-methylenebis (6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N- (4-chlorophenyl) -N- ( 3,4-dichlorophenyl) urea, N, N '- (1,10-decanediyldi-1-pyridinyl-4-ylidene) bis (1-octanamine) dihydrochloride, N, N'-bis (4-chlorophenyl) -3,12-diimino 2,4,11,13-tetraazatetradecandiimidamide, antimicrobial quaternary surface active compounds, guanidines. However, particularly preferred preservatives are selected from the group comprising salicylic acid, quaternary surfactants, in particular benzalkonium chloride and isothiazoles and their derivatives such as isothiazolines and isothiazolinones.

Solvents which are suitable for the compositions used according to the invention are, in addition to water as the preferred solvent, generally water-miscible organic solvents, such as, without limitation, ethanol, propanol, 1,2-propanediol and glycerol. In various embodiments, the dishwashing detergent may be a low-water, liquid dishwashing detergent containing water in amounts up to a maximum of 25% by weight, preferably up to 20% by weight, based on the total weight of the composition.

The term "low in water" as used herein means that the composition thus characterized contains less than 25% by weight of water, preferably less than 20% by weight of water. In particular, this term covers compositions which contain from 1 to 20% by weight of water. The water content as defined herein refers to the water content determined by Karl Fischer titration.

In general, the formulation of automatic dishwashing agents described herein can be carried out in different ways. The agents may be in solid or liquid form as well as in a combination of solid and liquid forms. Powder, granules, extrudates, compacts, in particular tablets, are particularly suitable as firm supply forms. The liquid supply forms based on water and / or organic solvents may be thickened, in the form of gels. The agents can be formulated in the form of single-phase or multi-phase products. The individual phases of multiphase agents may have the same or different states of matter.

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

The dishwashing agents described herein are preferably automatic dishwashing agents, which may be in solid or liquid form. However, the solid moldings described below are particularly preferably also liquid agents, in particular in the form of gels.

The dishwashing detergents can be present as shaped bodies. In order to facilitate the disintegration of such prefabricated moldings, it is possible Disintegrationshilfsmittel, so-called Tablet disintegrants to incorporate into these agents to shorten the disintegration times. By tablet disintegrants or disintegrants are meant excipients which ensure 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.

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. 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, may 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.

The water soluble package may have one or more chambers. The agent may be contained in one or more chambers, if any, of the water soluble envelope. The amount of agent preferably corresponds to the full or half dose needed for a rinse.
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 , particularly preferably from 30,000 to 100,000 gmol ^-1 and in particular from 40,000 to 80,000 gmol ^-1 .

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

In addition, a polymer selected from the group 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.

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

It may be preferred that the film material contains further additives. The film material may 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.

A further subject of this application is a machine dishwashing process for the cleaning of dishes, characterized in that a dishwasher detergent according to the invention is used.

In this method, the agent according to the invention is metered into the interior of a dishwasher during the passage of a dishwashing program before the start of 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.

Preference is given to automatic dishwashing processes in which the cleaning takes place at a temperature in the range from 30 ° C to 70 ° C, preferably from 35 ° C to 60 ° C, more preferably from 35 ° C to 50 ° C, particularly preferably from 40 to 45 ° C takes place.

Another object of the invention is the use of at least one sulfated or sulfonated triglyceride as an enzyme-enhancing agent and / or to improve the rinsing performance, preferably in automatic dishwashing detergents according to the invention and / or automatic dishwashing process according to the invention.

The embodiments described in context with the agents according to the invention are readily transferable to the methods and uses of the invention and vice versa.

embodiment Example 1: Composition

A solid detergent having the following composition was prepared: raw material Amount (wt%) Na citrate 15.00 to 20.00 Phosphonate (HEDP) 2.50 to 7.50 MGDA 0.00 to 25.00 Na disilicate 5.00 to 35.00 soda 12.50 to 25.00 Na Percarbonate 10.00 to 15.00 Bleach catalyst (Mn-based) 0.02-0.50 TAED 2.00-3.00 Nonionic surfactant 20-40 EO end-cap mgl. 2.50 to 10.00 polycarboxylate 5.00 to 10.00 Cationic copolymer 0.25-0.75 PVP (cross-linked) 0.00 to 1.50 protease 1.50 to 5.00 amylase 0.50 to 3.00 Benzotriazole (silver protection) 0.00 to 0.50 Perfume 0.05-0.15 dye 0.00-1.00 Zn acetate 0.10-0.30 Na sulfate 0.00 to 25.00 water 0.00 to 1.50 pH adjusters 1.00-1.50 processing aids 0.00 to 5.00 TAED: tetraacetylethylenediamine

Example 2: Cleaning Performance:

The dishwashing process was carried out in a dishwasher Bosch® SMS68m62 (program: 40 ° C, 8 min holding time, program duration 57 min) with a water hardness of 21 ° German hardness according to the IKW method.

These Method of the industry association body care and detergent registered association (IKW) becomes in the SÖFW journal, 142. year, 6/2016 (pages 34 to 48 ).

The evaluation of the cleaning performance was carried out visually according to a scale of 1 to 10, with the value 10 being the best grade (no discernible residue). There were repetitions with 6 internal replicates per machine. The results given are the means of multiple determinations

The detergent 1 corresponded to the above-mentioned composition. Experiment V1 thus represents the comparative example.

In experiment E2, 1% by weight of Turkish red oil from Zschimmer & Schwarz (Lahnstein, Germany), based on the total weight of the cleaning agent, was incorporated into the cleaning agent from V1.

Bosch

Tea (Assam) Tea (BOP) Creme brulee minced meat egg yolk spaghetti V1 4.7 7.9 4.9 2.4 3.0 0.7 E2 4.6 7.4 5.1 3.3 3.1 0.9 V1: Composition according to Example 1
E2: V1 + 1% by weight of turkey red oil (based on the total weight of the cleaning agent)

As can be seen from the attached table, the use of protease together with Turkish red oil leads to an improved purification of protease-sensitive persistent mincemeat soils compared to the commercially available dishwashing detergent.

Example 3: Rinse-up effect

To determine the rinse effect, selected and defined dishes are rinsed 4 times and visually scrapped after the 2nd, 3rd and 4th rinse cycles. The first rinse is used to condition the dishes. Rinse rinses based on the visual appearance of the dry items to be washed (porcelain, glasses, plastic parts and stainless steel) are assigned as parameters. Per rinse 100 g of dirt are dosed to simulate a normally dirty load.

A standard household dishwashing machine (Miele® GSL) was used in the 50 ° C program (50 ° C, 8 min holding time, 65 ° C rinse temperature) with a water hardness of 21 ° German hardness.

After completion of the rinse cycle, the machine is fully opened for 30 minutes and then the clear rinse effect is visually determined in the black box (black-painted room, D6500 daylight lamp). On the crockery and cutlery remaining dried water drops, streaks, coverings and films are scored on a scale of 1 to 5. 5 means no drops / films, 1 means strong dripping / filming. Glass stainless steel China (Friesland) China (Fun Fact.) plastic Filming (Miele) V1 3.4 3.9 2.4 2.9 3.5 V2 3.8 4.2 2.1 3.1 3.3 E1 3.5 4.6 2.4 3.2 4.1 V1: Composition according to Example 1
V2: V1 - 1% by weight of nonionic surfactant (based on the total weight of the cleaning agent)
E1: V2 + 1% by weight of Turkish red oil (based on the total weight of the cleaning agent)

It can be clearly seen that the combination according to the invention leads to an improvement in the filming (streaks, films, coverings) on stainless steel and plastic compared to the reference.

Claims (10)

Phosphate-free dishwashing detergent, in particular automatic dishwashing detergent, containing at least one surfactant and at least one protease, characterized in that the surfactant is an anionic surfactant from the group of sulfated or sulfonated triglycerides. A detergent according to claim 1, characterized in that the sulphated or sulphonated triglyceride saturated or unsaturated, linear or branched, substituted or unsubstituted hydrocarbon chains having a chain length of 3 to 25 carbon atoms, preferably 11 to 21 carbon atoms, more preferably contains 13 to 19 carbon atoms, characterized in that at least one of the chains is sulphated or sulphonated. Dishwashing composition according to one of the preceding claims, characterized in that the sulfated or sulfonated triglyceride contains at least one ricinoleic acid group, preferably it contains at least two ricinoleic acid groups, more preferably it contains three Ricinolsäure groups, wherein at least one Ricinolsäure group sulfated or sulfonated is. Dishwashing composition according to one of the preceding claims, characterized in that the sulfated or sulfonated triglyceride in an amount of 0.1 to 25 wt .-%, preferably in an amount of 0.2 to 10 wt .-%, particularly preferably in an amount from 0.5 to 5 wt .-% and most preferably in an amount of 0.7 to 1.5 wt .-%, based on the total weight of the dishwashing detergent is included. Dishwashing agent according to one of the preceding claims, characterized in that at least one further surfactant, preferably selected from the group of anionic, nonionic, amphoteric and cationic surfactants, more preferably from the group of nonionic surfactants, is included. Dishwashing detergent according to one of the preceding claims, characterized in that at least one builder selected from the group comprising silicates, aluminum silicates, carbonates, phosphonates, organic di- and polycarboxylic acids or their salts and mixtures thereof, is included. Dishwashing composition according to one of the preceding claims, characterized in that the dishwashing agent at least one further constituent, preferably at least two further constituents selected from the group comprising further Builders, other enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, especially silver protectants, glass corrosion inhibitors, polymers, bleaches, bleach catalysts, bleach activators, foam inhibitors, dyes, fragrances, bittering agents, antimicrobial agents and disintegration aids. A machine dishwashing method for cleaning dishes, characterized in that a dishwashing detergent according to one of claims 1 to 6 is used. Machine dishwashing process according to claim 7, characterized in that the cleaning at a temperature in the range of 30 ° C to 70 ° C, preferably from 35 ° C to 60 ° C, more preferably from 35 ° C to 50 ° C, particularly preferably at 40 to 45 ° C takes place. Use of at least one sulfated or sulfonated triglyceride as enzyme-enhancing agent and / or for improving the rinsing performance, preferably in automatic dishwashing compositions according to one of claims 1 to 7 and / or in automatic dishwashing processes according to one of claims 8 and 9.