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EP3498810A1 - Détergent pour lave-vaisselle à performance de rinçage et de nettoyage améliorée, procédé reposant sur l'utilisation dudit détergent ainsi que l'utilisation dudit détergent - Google Patents

Détergent pour lave-vaisselle à performance de rinçage et de nettoyage améliorée, procédé reposant sur l'utilisation dudit détergent ainsi que l'utilisation dudit détergent Download PDF

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Publication number
EP3498810A1
EP3498810A1 EP18206521.9A EP18206521A EP3498810A1 EP 3498810 A1 EP3498810 A1 EP 3498810A1 EP 18206521 A EP18206521 A EP 18206521A EP 3498810 A1 EP3498810 A1 EP 3498810A1
Authority
EP
European Patent Office
Prior art keywords
dishwashing
acid
group
sulfated
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP18206521.9A
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German (de)
English (en)
Inventor
Inga Kerstin Vockenroth
Doris Dahlmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP3498810A1 publication Critical patent/EP3498810A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • oxo alcohols or their derivatives which are obtainable, for example, by the ROELEN's oxo synthesis can also be used correspondingly.
  • 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.
  • 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.
  • 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.
  • 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 ,
  • 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.
  • 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.
  • 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.
  • the triglyceride contains at least one hydrocarbon chain having at least one double bond.
  • the triglyceride contains at least two hydrocarbon chains each having at least one double bond.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • surfactants are the polyhydroxy fatty acid amides known as PHFA.
  • aminal alkoxylates or sorbitan esters can also be present in the compositions according to the invention.
  • low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants.
  • 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.
  • 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).
  • structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • Such (PO / EO / PO) nonionic surfactants are characterized by good foam control.
  • nonionic surfactants are those which have alternating ethylene oxide and alkylene oxide units.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • each R 3 in the above formula may be different if x ⁇ 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • 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 ,
  • 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.
  • 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.
  • 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 + .
  • 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.
  • 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 + , 1 ⁇ 2Zn 2+ , 1 ⁇ 2Mg 2+ , 1 ⁇ 2Ca 2+ , 1 ⁇ 2Mn 2+ , and mixtures thereof.
  • the agents may additionally or alternatively contain at least one surfactant of the formula R 5 -A-SO 3 - Y + .
  • 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.
  • certain radicals R 5 are preferred.
  • 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 + , 1 ⁇ 2Zn 2+ , 1 ⁇ 2Mg 2+ , 1 ⁇ 2Ca 2+ , 1 ⁇ 2Mn 2+ , and mixtures thereof.
  • R 5 preferably represents a linear or branched unsubstituted alkylaryl radical.
  • 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 +, 1 ⁇ 2 Zn 2+, 1 ⁇ 2Mg 2+, 1 ⁇ 2Ca 2+, 1 ⁇ 2Mn 2+, and mixtures thereof.
  • Such surfactants may be selected from linear or branched alkyl benzene sulfonates.
  • 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.
  • quaternary surface-active compounds in particular having a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents.
  • the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.
  • 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.
  • 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.
  • 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.
  • 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.
  • silicates 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.
  • both ⁇ - and ⁇ -sodium disilicates are Na 2 Si 2 O 5 .yH 2 O and furthermore especially Na-SKS-5 ( ⁇ -Na 2 Si 2 O 5 ), Na-SKS-7 ( ⁇ -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 ( ⁇ -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.
  • the agents are free of such silicates.
  • 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.
  • 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.
  • the agents are free of these silicates.
  • 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.
  • 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.
  • 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.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • 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.
  • 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.
  • 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.
  • NTA nitrilotriacetic acid
  • 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.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • 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.
  • aminocarboxylic acids and / or their salts 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.
  • MGDA methylglycinediacetic acid
  • GLDA glutamic diacetic acid
  • EDDS ethylenediaminediacetic acid
  • 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.
  • 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.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -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.
  • 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
  • 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.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • 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 .
  • 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.
  • 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.
  • 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.
  • acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts 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 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, ⁇ -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.
  • amylases examples include the ⁇ -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 ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • lipases or cutinases in particular because of their triglyceride-cleaving activities, but also in order to generate in situ peracids from suitable precursors.
  • lipases include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L.
  • 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.
  • 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.
  • damage such as inactivation, denaturation or disintegration such as by physical influences, oxidation or proteolytic cleavage.
  • 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.
  • 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.
  • 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.
  • such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
  • 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.
  • 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.
  • compositions described herein may also include enzyme stabilizers.
  • 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.
  • peptide aldehydes that is oligopeptides with a reduced C-terminus, especially those of 2 to 50 monomers are used for this purpose.
  • peptidic reversible protease inhibitors include ovomucoid and leupeptin.
  • specific, reversible peptide inhibitors for the protease subtilisin and fusion proteins from proteases and specific peptide inhibitors are suitable.
  • 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.
  • a bleaching agent as further constituent, with oxygen bleaches being preferred.
  • 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.
  • 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.
  • 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 .-%.
  • the automatic dishwashing agents additionally contain at least one bleach activator.
  • 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.
  • 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.
  • TAED especially in combination with a percarbonate bleach, preferably sodium percarbonate, is most preferred.
  • 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.
  • the automatic dishwasher detergents according to the invention preferably contain at least one bleach catalyst.
  • 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.
  • 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.
  • ligands are used which have nitrogen donor functions.
  • 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.
  • 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 /
  • 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.
  • 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
  • the aforementioned bleach-enhancing transition metal complexes 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.
  • 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.
  • 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.
  • a dishwasher detergent for example a tablet
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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-
  • 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.
  • 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.
  • low in water 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.
  • 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.
  • 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.
  • Tablet disintegrants 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.
  • 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 .
  • polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible.
  • 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%.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the detergent 1 corresponded to the above-mentioned composition.
  • Experiment V1 thus represents the comparative example.
  • 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.
  • the machine 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.
  • 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)

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP18206521.9A 2017-12-18 2018-11-15 Détergent pour lave-vaisselle à performance de rinçage et de nettoyage améliorée, procédé reposant sur l'utilisation dudit détergent ainsi que l'utilisation dudit détergent Withdrawn EP3498810A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102017223121.1A DE102017223121A1 (de) 2017-12-18 2017-12-18 Maschinelles Geschirrspülmittel mit verbesserter Klarspül- und Reinigungsleistung, Verfahren unter Einsatz dieses Mittels sowie Verwendung des Mittels

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4112501A1 (de) * 1991-04-17 1992-10-22 Henkel Kgaa Verwendung von sulfierungsprodukten ungesaettigter fettsaeureglycerinester als schaumregulierungsmittel
WO1993012215A1 (fr) * 1991-12-17 1993-06-24 Henkel Kommanditgesellschaft Auf Aktien Procede de fabrication de triglycerides hydrophilises
US20040033924A1 (en) * 2002-08-14 2004-02-19 Murphy Dennis Stephen Methods for conferring fabric care benefits during laundering
US20050075258A1 (en) * 2001-08-17 2005-04-07 Arnd Kessler Dishwasher detergent with improved protection against glass corrosion

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4112501A1 (de) * 1991-04-17 1992-10-22 Henkel Kgaa Verwendung von sulfierungsprodukten ungesaettigter fettsaeureglycerinester als schaumregulierungsmittel
WO1993012215A1 (fr) * 1991-12-17 1993-06-24 Henkel Kommanditgesellschaft Auf Aktien Procede de fabrication de triglycerides hydrophilises
US20050075258A1 (en) * 2001-08-17 2005-04-07 Arnd Kessler Dishwasher detergent with improved protection against glass corrosion
US20040033924A1 (en) * 2002-08-14 2004-02-19 Murphy Dennis Stephen Methods for conferring fabric care benefits during laundering

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SÖFW-JOURNAL, vol. 142, June 2016 (2016-06-01), pages 34 - 48

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