EP3209762B1 - Détergent pour lave-vaisselle contenant des complexes métalliques - Google Patents

Détergent pour lave-vaisselle contenant des complexes métalliques Download PDF

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Publication number
EP3209762B1
EP3209762B1 EP15784043.0A EP15784043A EP3209762B1 EP 3209762 B1 EP3209762 B1 EP 3209762B1 EP 15784043 A EP15784043 A EP 15784043A EP 3209762 B1 EP3209762 B1 EP 3209762B1
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EP
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Prior art keywords
dishwashing detergent
linear
branched
substituted
unsubstituted
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German (de)
English (en)
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EP3209762A1 (fr
Inventor
Christian Kropf
Nadine BLUHM
Inga Kerstin Vockenroth
Noelle Wrubbel
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/043—Liquid or thixotropic (gel) compositions
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • 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
    • C11D3/168—Organometallic compounds or orgometallic complexes
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—Ethers
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected
    • C11D2111/14—

Definitions

  • the present invention relates to a machine dishwashing detergent which exhibits an improved cleaning performance in the removal of baked stains, the use of this dishwashing detergent and a method of automatic dishwashing using this dishwashing detergent.
  • a dishwashing agent according to the invention in a machine dishwashing process, in particular the use for improving the cleaning performance in an automatic dishwashing machine.
  • Yet another object of the invention is a machine dishwashing process in which a dishwasher detergent according to the invention is used, in particular for the purpose of improving the cleaning performance.
  • 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 metal complex means, for example, at least one type of metal complex, ie, one type of metal complex or a mixture of several different metal complexes. Together with weights this specification refers to all compounds of the specified type which are contained in the composition / mixture, ie that the composition contains no further compounds of this type beyond the specified 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 metal complexes used in the agents of the invention are those of the formula (I) M n + L (A m- ) n / m (I).
  • M is a metal cation selected from cations of Cu, Zn, Co, Cr, Ni, Ru, Rh, Bi, in particular cations of Cu, Zn, Co, Ni, and Bi, more preferably Cu 2+, Zn 2+, Co2 +, Co3 +, and Bi3 +, most preferably Cu2 +, Zn2 +, or Bi3 +, most preferably Cu2 + or Zn2 +, most preferably Zn2 +;
  • n denotes the valence of the metal cation and is an integer from 1 to 6, preferably 1 to 5, preferably 2 or 3.
  • A is any anion, in particular selected from the group consisting of inorganic anions such as F - , Cl - , Br - , I - , OH - , HSO 3 - , SO 3 2- , SO 4 2- , HSO 4 - , NO 2 - , NO 3 - , PO 4 3- , HPO 4 2- , H 2 PO 4 - , BF 4 - , PF 6 - and ClO 4 - , or organic anions such as acetate, citrate, formate, glutarate, lactate, malate, malonate, oxalate, pyruvate, tartrate, methanesulfonate (mesilate), methyl sulfate, tosylate and succinate.
  • inorganic anions such as F - , Cl - , Br - , I - , OH - , HSO 3 - , SO 3 2- , SO 4 2- , HSO 4 -
  • L is a neutral ligand of the formula (II) in which X is O or NR.
  • all X 0 or all X are NR.
  • Each R is independently selected from H, unsubstituted or substituted, linear or branched C 1-20 alkyl, preferably linear C 8-18 alkyl, unsubstituted or substituted, linear or branched C 1-20 heteroalkyl, in particular an alkyl radical having a substituted (poly) oxyalkylene, unsubstituted or substituted, linear or branched C 2-20 alkenyl, unsubstituted or substituted, linear or branched C 2-20 heteroalkenyl and unsubstituted or substituted, linear or branched C 2-20 alkynyl.
  • each R is independently selected from H, - (CH 2 ) o -CH 3 , where o is an integer selected from 3-13, - (CH 2 ) p -COOH and - (CH 2 ) p -OH, where p is an integer selected from 1-6.
  • at least one R is - (CH 2 ) o -CH 3 , where o is an integer selected from 5-9, especially 7.
  • at least one X preferably all X, NR.
  • At least one RH, preferably 2-3 RH, and at least one R, preferably exactly one R, is a - (CH 2 ) o -CH 3 , where o is an integer selected from 5-9, in particular is o 7.
  • the ligand of the formula (II) is an N-substituted cyclen (1,4,7,10-tetraazacyclododecane, in particular an N-mono-C 4-14 -alkyl cycle, preferably N-mono-C 6-10 - Alkylcycles, more preferably N-mono-octylcycles
  • the metal cation is preferably Zn 2+ and the anion is preferably SO 4 2- .
  • At least one X preferably all X, NR.
  • at least one RH preferably 2-3 RH, and at least one R, preferably exactly one R, is an alkyl radical as defined above, such as an octyl decyl, dodecyl, tetradecyl or hexadecyl radical.
  • the ligand of formula (II) is an N-substituted cyclen (1,4,7,10-tetraazacyclododecane), in particular an N-mono-alkylcyclene, preferably N-mono-octylcycles, N-mono-decylcycles, N-mono-dodecylcycles, N-mono-tetradecylcycles or N-mono-hexadecylcycles.
  • the metal cation is preferably Cu 2+ , Zn 2+ or Bi 3+ , more preferably Cu 2+ or Zn 2+ , in particular Zn 2+ .
  • the anion may further be a sulfate anion.
  • compositions of the invention contain the above-described metal complexes in amounts of 0.001 to 10% by weight, preferably 0.01 to 1% by weight, and more preferably about 0.1 to 1% by weight, based on the total weight of the dishwashing detergent. Absolute amounts are typically in the range of 0.01 to 0.2 g / job, preferably in the range of 0.05 to 0.2 g / job,
  • compositions according to the invention may contain at least one, preferably at least two further constituents, preferably selected from the group consisting of surfactants, in particular nonionic surfactants and / or anionic surfactants, builders, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, Glass corrosion inhibitors, foam inhibitors, dyes, fragrances, bitter substances, antimicrobial agents and disintegration aids.
  • surfactants in particular nonionic surfactants and / or anionic surfactants
  • builders enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, Glass corrosion inhibitors, foam inhibitors, dyes, fragrances, bitter substances, antimicrobial agents and disintegration aids.
  • the agents described herein preferably contain at least one nonionic surfactant.
  • nonionic surfactants it is possible to use all nonionic surfactants 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.
  • 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 having alternating ethylene oxide and alkylene oxide units may be preferred.
  • 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.
  • the group of these nonionic surfactants includes, for example, the C 2-26 fatty alcohol (PO) 1 - (EO) 15-40 -2-hydroxyalkyl ethers, in particular also the C 8-10 fatty alcohol (PO) 1 - (EO) 22 -2 -hydroxydecylether.
  • 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 comprise at least one nonionic surfactant, 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 2 wt.%, Preferably at least 5 wt. %.
  • the amounts used per application may be in the range of 0.5-10 g / job, preferably in the range of 1-5 g / job.
  • Suitable anionic surfactants in dishwashing detergents are all anionic surfactants. These are characterized by a water-solubilizing, anionic group such as. As a carboxylate, sulfate, sulfonate or phosphate 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 C 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 contain in various embodiments, at least one surfactant of the formula R 1 -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 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 in particular from 2 to 10. Most preferably, n stands for the numbers 2, 3, 4, 5, 6, 7 or 8.
  • X is a monovalent cation or the nth part of an n-valent cation, the alkali metal ions are preferred, and Na + or K + are preferred, 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 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 ⁇ 2Zn 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.
  • cationic and / or amphoteric surfactants such as betaines or quaternary ammonium compounds.
  • silicates As builders, which may be contained in the dishwashing detergent, in particular silicates, aluminum silicates (especially zeolites), carbonates, organic di- and polycarboxylic acids and aminocarboxylic acids or their salts, and - where there are no ecological prejudices against their use - also the phosphates. Of course, mixtures of these substances can also be used.
  • 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 sold, for example, by the company 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 .xH 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 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 ⁇ 3 H 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 ).
  • Machine dishwashing detergents typically 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 20% by weight, preferably from 0.2 to 15% by weight and in particular from 0, 4 to 10 wt .-%, each based on the total weight of these agents.
  • 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 to conventional amorphous sodium silicates can in various ways, for example by surface treatment, compounding, compaction / densification or by over-drying.
  • 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.
  • phosphates as builders are possible, unless such use should not be avoided for environmental reasons.
  • alkali metal phosphates with particular preference of pentasodium or pentakalium triphosphate (sodium or potassium tripolyphosphate) in the washing or dishwashing industry have the greatest importance.
  • Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
  • phosphates are the pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate) and corresponding mixed salts (Natriumkaliumtripolyphosphate).
  • the agents are phosphate-free.
  • phosphates are used as cleaning-active substances in dishwashing detergent
  • preferred agents comprise this phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) Amounts from 5 to 80 wt .-%, preferably from 10 to 60 wt .-% and in particular from 18 to 45 wt .-%, each based on the weight of the automatic dishwashing detergent.
  • the dishwashing detergents can in particular also contain phosphonates as further builder.
  • the phosphonate compound is preferably a hydroxyalkane and / or aminoalkane phosphonate used.
  • 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 0.5 to 8 wt .-%, each based on the total weight of the dishwashing detergent.
  • alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the alkali 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.
  • a builder system comprising a mixture of tripolyphosphate and sodium carbonate.
  • a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate.
  • 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 % By weight and in particular below 2% by weight, in each case based on the total weight of the automatic dishwashing detergent.
  • Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.
  • organic 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 builder substances are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, those of polycarboxylic acids being those Carboxylic acids are understood to 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
  • the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of the automatic dishwashing detergents.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • citric acid and / or citrates in these compositions has proven particularly advantageous for the cleaning and rinsing performance of the agents described herein.
  • 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 or its salts (EDDS).
  • MGDA methylglycinediacetic acid
  • GLDA glutamic diacetic acid
  • EDDS ethylenediaminediacetic acid or its salts
  • the content of these aminocarboxylic acids or their salts may for example be between 0.1 and 30% by weight, preferably between 1 and 25% by weight and in particular between 5 and 20% by weight.
  • Aminocarboxylic acids and their salts can be used together with the abovementioned builders, in particular also with the phosphate-free builders.
  • the dishwashing compositions of the invention may further comprise a sulfopolymer.
  • the proportion by weight of the sulfopolymer in the total weight of the dishwashing agent according to the invention is preferably from 0.1 to 20 wt .-%, in particular from 0.5 to 18 wt .-%, particularly preferably 1.0 to 15 wt .-%, in particular from 4 to 14 wt .-%, especially from 6 to 12 wt .-%.
  • the sulfopolymer is typically employed in the form of an aqueous solution, the aqueous solutions typically containing from 20 to 70 weight percent, more preferably from 30 to 50 weight percent, preferably from about 35 to 40 weight percent sulfopolymers.
  • the sulfopolymer used is preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate.
  • 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 , Sulfomethylmethacrylamid and mixtures of said acids or their water-
  • 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 .
  • the dishwashing agents may further contain other polymers.
  • Suitable polymers include, in particular, the cleaning-active polymers, for example the rinse-aid polymers and / or polymers which act as softeners.
  • 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 which cationically derivatized alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and the copolymers of unsaturated carboxylic acids 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 methacroylethylbetaine / methacrylate copolymers.
  • Useful cationic polymers come from the groups of the quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with acrylic acid and methacrylic acid and their esters and amides, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate 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 enzyme preparation or enzyme composition containing one or more enzymes.
  • Suitable enzymes include, but are not limited to, proteases, amylases, lipases, hemicellulases, cellulases, 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.
  • 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.
  • Be subtilases naturally formed by microorganisms. Of these, in particular, the subtilisins formed and secreted by Bacillus species are to be mentioned as the most important group within the subtilases.
  • subtilisin type proteases preferably used in washing and dishwashing detergents are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the protease from Bacillus lentus, in particular from Bacillus lentus DSM 5483, subtilisin DY and the the subtilases, but not the subtilisins in the narrower sense attributable enzyme thermitase, proteinase K and the proteases TW3 and TW7, as well as variants of said proteases, which have a relation to the parent protease modified amino acid sequence.
  • Proteases are selectively or randomly modified by methods known from the prior art and thus optimized, for example, for use in detergents and dishwashing detergents. These include point mutagenesis, deletion or insertion mutagenesis or fusion with other proteins or protein parts. Thus, correspondingly optimized variants are known for most proteases known from the prior art.
  • 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-splitting activities, but also in order to generate in situ peracids from suitable precursors.
  • 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, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or in the case of strongly different ones Redox potentials between the oxidizing enzymes and the soiling to ensure the flow of electrons (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.
  • preferred 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 wt .-% 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.
  • Bleaching agents are cleaning-active substances. 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. 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.
  • the dishwashing agents can, in various embodiments, 1 to 35 wt .-%, preferably 2.5 to 30 wt .-%, particularly preferably 3.5 to 20 wt .-% and in particular 5 to 15 wt .-% bleaching agent, preferably Sodium percarbonate, included.
  • 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.
  • Bleach activators are polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl or Isononanoyloxybenzolsulfonat (n- or iso-NOBS) is particularly preferably used.
  • TAED tetraacetylethylenediamine
  • DADHT 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine
  • TAGU t
  • bleach activators are preferably used in amounts of up to 10% by weight, in particular from 0.1% by weight to 8% by weight, especially from 2 to 8% by weight and more preferably from 2 to 6% by weight, based in each case on the total weight of the funds 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 7 to 9, especially greater than 7, especially in the range 7.5 to 8.5
  • the pH adjusting agents are acids and / or alkalis, preferably alkalis. Suitable acids are in particular organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid.
  • 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.
  • volatile alkali for example in the form of ammonia and / or alkanolamines, which may contain up to 9 carbon atoms in the molecule.
  • the alkanolamine here is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof.
  • the 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 originate from the group of the magnesium and zinc salts as well as the 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.
  • 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.
  • the dishwashing detergents can be present as shaped bodies.
  • disintegration aids so-called tablet disintegrants
  • 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 automatic dishwashing agents described herein are preferably prefabricated into dosage units. These metering units preferably comprise the amount of cleaning-active substances necessary for a cleaning cycle. Preferred metering units have a weight between 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 automatic dishwashing agents in particular the prefabricated metering units, have a water-soluble coating, with particular preference.
  • 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 Containing polyvinyl alcohol copolymer have a good stability with a sufficiently high water solubility, in particular cold water solubility on.
  • Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range of 10,000 to 1,000,000 gmol -1 , preferably 20,000 to 500,000 gmol -1 , more preferably 30,000 to 100,000 gmol -1 and especially from 40,000 to 80,000 gmol -1 .
  • 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.
  • Exemplary formulations of the agents of the invention include both phosphate-containing and phosphate-free dishwashing detergents.
  • Exemplary formulations in which the metal complexes described herein can be used in the stated amounts as an additional constituent are the following: Table 1: Phosphate-containing, solid dishwashing detergent formulation (Tab): raw material Amount (wt%) Phosphate (eg TPP) 18.00 to 45.00 Sodium citrate / citric acid 0.00 to 10.00 Phosphonate (eg HEDP) 0.00 to 2.00 silicate 0.00 to 6.00 soda 12.00 to 20.00 Na Percarbonate 10.00 to 16.00 bleach catalyst 0.01-0.10 TAED 1.00 to 2.70 nonionic surfactant 2.00 to 8.00 polyacrylate 0.00 to 5.00 sulfopolymer 5.00 to 10.00 Cationic acrylate copolymer 0.00 to 5.00 PEG 4000 powder 0.00 to 2.00 protease 0.50 to 7.00 amylase 0.10 to 2.50 Benzotriazole (silver protection) from 0.20 to 0.50 Perfume 0.05-0.20 dye 0.50 to 2.00 Zn a
  • tablets of 17-20 g are prepared, with 20 g tablets being preferred.
  • the corresponding use of the automatic dishwasher detergents according to the invention is likewise an object of the invention.
  • the invention likewise relates to a dishwashing process, in particular a machine dishwashing process, in which a dishwashing detergent according to the invention is used.
  • the subject matter of the present application is therefore furthermore a process for the cleaning of dishes in a dishwashing machine, in which the agent according to the invention is metered into the interior of a dishwasher during the passage of a dishwashing program before the main wash cycle or during the main wash cycle.
  • the metering or the entry of the agent according to the invention into the interior of the dishwasher can be done manually, but preferably the agent is metered by means of the metering chamber into the interior of the dishwasher.
  • 1,4,7,10-Tetraazacyclododecane (1g, 5.80 mmol) and triethylamine (0.24 mL, 1.74 mmol) were dissolved in 20 mL of freshly distilled chloroform. To the solution was added 1-bromododecane (0.35 mL, 1.45 mmol) in one portion, and the reaction solution was stirred at reflux for 15 hours. Subsequently, the reaction solution was cooled to room temperature and washed 3 times with 7 mL NaOH solution (1M). The organic phase was washed three times with 10 mL each of distilled water, dried with magnesium sulfate, filtered and the solvent removed under reduced pressure.
  • N-mono-dodecylcycles was obtained as a colorless oil (0.49 g, 1.44 mmol, yield 99%).
  • Analogous to this C 12 -cycling further, for example Cs-cyclene or C 16 -cyclen, are synthesized by using the corresponding bromoalkanes.
  • N-mono-dodecylcycles (0.5 g, 1.47 mmol) were dissolved in 10 mL of distilled water and heated to 65 ° C. To the milky white solution was slowly added dropwise zinc sulfate (422 mg, 1.47 mmol) dissolved in 4 mL of distilled water. The clear, colorless reaction solution was stirred for 20 h at 65 ° C, then filtered hot and cooled to room temperature. The cooled solution was freeze-dried to obtain the zinc complex of N-mono-dodecylcene (0.51 g, 1.02 mmol, yield 70%).
  • N-mono-dodecylcycles (0.49 g, 1.44 mmol) were dissolved in 10 mL of distilled water and heated to 65 ° C.
  • To the milky white solution was slowly added dropwise copper (II) sulfate (230 mg, 1.44 mmol) dissolved in 4 mL of distilled water.
  • the clear, dark blue reaction solution was stirred for 20 h at 65 ° C, then filtered hot and cooled to room temperature. The cooled solution was freeze-dried to obtain the copper complex of N-mono-dodecyl cyclic (0.71 g, 1.42 mmol, yield 99%).
  • Table 3 Phosphate-containing dishwashing detergent tablet Tab formulation Tripolyphosphate (% by weight) 35.9 Sodium carbonate (% by weight) 12.2 Phosphonate (wt%) 2.4 Sulfonic acid group-containing polymer (% by weight) 7.0 Polyacrylate (% by weight) 4.6 Nonionic surfactants (% by weight) 6.1 Percarbonate (wt%) 14.6 TAED (% by weight) 2.3 Bleach catalyst (wt%) 0.01 PVP (wt%) 1.5 Sodium silicate (wt.%) 3.0 Protease (wt%) 3.0 Amylase (% by weight) 1.0 Zinc acetate (wt%) 0.2 Residues (perfume, dyes, etc) (wt%) ad 100 % AS GLDA tetrasodium salt 18,80 glycerin 2.50 sulfopolymer 5.50 polyacrylate 2.70 citric acid
  • the cleaning performance was determined in Miele dishwashers in the 50 ° C program. Water hardness 21 ° dH. 20 g of the phosphate-containing solid formulation (Tab) shown in Table 3 in combination with 0.1 g of C 12 -cyclen-zinc (E1) or 20 g of the phosphate-free liquid formulation (Pouch) shown in Table 4 in combination with 0.1 g of the copper complex of Example 3 (E2) used.
  • Example 2 0.1 g of one of the metal complexes zinc complexes C 8 -cyclen-zinc, C 12 -cyclen-zinc and C 16 -cyclen-zinc shown in Example 2 were added in addition to 20 g of the formulation from Table 2 (phosphate-free tab) (E3 to E5).
  • the cleaning performance was again determined in Miele household machines in the 50 ° program (water hardness 21 ° dH). As before, that became Dishes visually scrapped after rinsing on a scale of 1-10. The higher the value, the better the cleaning performance.
  • E3 improves tea (Assam), minced meat (130 ° C), egg yolk, spaghetti, starch and creme brulee soiling compared to standard V4 and E4 and E5.
  • the purification performance decreases from C 8 -cyclen-Zn via C 12 -cyclen-Zn to C 16 -cyclen-Zn, ie the longer the alkyl chain on the cycle, the worse the performance.
  • E3 is also better than the standard at the tested soils.

Claims (13)

  1. Détergent pour nettoyer la vaisselle, en particulier détergent pour nettoyer au lave-vaisselle à la machine, contenant, rapporté au poids total du détergent, 0,001 à 10,0 % en poids, en particulier 0,01 à 1,0 % en poids d'au moins un complexe métallique de formule (I)

            Mn+L(Am-)n/m     (I)

    où
    M est un cation métallique choisi parmi les cations de Cu, Zn, Co, Cr, Ni, Ru, Rh, Bi, en particulier parmi les cations de Cu, Zn, Co, Ni et Bi, encore plus préférentiellement parmi Cu2+, Zn2+, Co2+, Co3+ et Bi3+, très préférentiellement Cu2+, Zn2+ ou Bi3+, et surtout privilégiés Cu2+ ou Zn2+, idéalement Zn2+ ;
    A est un anion au choix ;
    n et m sont des entiers choisis entre 1 et 6 ; et
    L est un ligand neutre de formule (II)
    Figure imgb0017
    où
    chaque X est indépendamment O ou NR ; et
    chaque R est choisi indépendamment parmi H, un C1-20-alkyle substitué ou non-substitué, linéaire ou ramifié, un C1-20-heteroalkyle substitué ou non-substitué, linéaire ou ramifié, un C2-20-alcényle substitué ou non-substitué, linéaire ou ramifié, un C2-20-hétéroalcényle substitué ou non-substitué, linéaire ou ramifié et un C2-20-alcynyle substitué ou non-substitué, linéaire ou ramifié.
  2. Détergent pour lave-vaisselle selon la revendication 1,
    en particulier détergent pour lave-vaisselle à la machine contenant, rapporté au poids total du produit pour nettoyer la vaisselle, 0,001 à 10,0 % en poids, en particulier 0,01 à 1,0 % en poids d'au moins un complexe métallique de formule (1)

            Mn+L(Am-)n/m     (I)

    où
    M est un cation métallique choisi parmi les cations de Cu, Zn, Co, Cr, Ni, Ru, Rh, Bi, en particulier parmi les cations de Cu, Zn, Co, Ni et Bi, encore plus préférentiellement parmi Cu2+, Zn2+, Co2+, Co3+ et Bi3+, très préférentiellement Cu2+, Zn2+ ou Bi3+, surtout privilégiés Cu2+ ou Zn2+, idéalement Zn2+ ;
    A est un anion au choix ;
    n et m sont des entiers choisis entre 1 et 5 ; et
    L est un ligand neutre de formule (II)
    Figure imgb0018
    où
    chaque X est indépendamment O ou NR ; et
    chaque R est choisi indépendamment parmi H, -(CH2)o-CH3, où o est un entier choisi entre 3 et 13, -(CH2)p-COOH et -(CH2)p-OH, où p est à chaque fois un entier choisi entre 1 - 6.
  3. Détergent pour lave-vaisselle selon une des revendications 1 ou 2, caractérisé en ce que A est choisi dans le groupe constitué de F-, Cl-, Br, I-, OH-, HSO3 -, SO3 2-, SO4 2-, HSO4 -, NO2 -, NO3 -, PO4 3-, HPO4 2-, H2PO4 -, BF4 -, PF6 -, ClO4 -, acétate, citrate, formiate, glutarate, lactate, malate, malonate, oxalate, pyruvate, tartrate, méthanesulfonate (mésylate), méthylsulfate, tosylate et succinate.
  4. Détergent pour lave-vaisselle selon une des revendications 1 à 3, caractérisé en ce que R dans la formule (II) est choisi parmi H, un C1-20-alkyle substitué ou non-substitué, linéaire ou ramifié, un C1-20-hétéroalkyle substitué ou non-substitué, linéaire ou ramifié, en particulier parmi H et un C8-18-alkyle linéaire.
  5. Détergent pour lave-vaisselle selon une des revendications 1 à 4, caractérisé en ce que
    (i) au moins un X, de préférence tous les X sont NR ; et/ou
    (ii) au moins un R, de préférence 2 ou 3 R sont H, et au moins un R, de préférence exactement un R est un résidu C8-18-alkyle linéaire ou C2-18-hétéroalkyle.
  6. Produit pour lave-vaisselle selon une des revendications 1 à 4, caractérisé en ce que
    (i) au moins un X, de préférence tous les X sont NR ; et/ou
    (ii) au moins un R, de préférence 2 ou 3 R sont H, et au moins un R, de préférence exactement un R est -(CH2)o-CH3, où o est un entier choisi entre 5 et 9, en particulier 7.
  7. Détergent pour lave-vaisselle selon une des revendications 1 à 6, caractérisé en ce que le ligand de formule (II) est un cyclène N-substitué (1,4,7,10-tétraazacyclododécane), en particulier un N-mono-alkylcyclène, de préférence un N-mono-octylcyclène, N-mono-décylcyclène, N-mono-dodécylcyclène, N-mono-tétradécylcyclène ou N-mono-hexadécylcyclène et le cation métallique est Cu2+, Zn2+ ou Bi3+.
  8. Détergent pour lave-vaisselle selon la revendication 7, caractérisé en ce que le ligand de formule (II) est un cyclène N-substitué (1,4,7,10-tétraazacyclododécane), en particulier un N-mono-C6-10-alkylcyclène, de préférence un N-mono-octylcyclène, le cation métallique est Zn2+ et 'anion est SO4 2-.
  9. Détergent pour lave-vaisselle selon une des revendications 1 à 8, caractérisé en ce que le détergent pour lave-vaisselle contient au moins un autre composant, de préférence au moins deux autres composants choisis dans le groupe constitué de tensioactifs, en particulier de tensioactifs non-ioniques et/ou anioniques, d'adjuvants, d'enzymes, d'épaississants, d'agents séquestrants, d'électrolytes, d'inhibiteurs de corrosion, en particulier d'agents de protection de l'argenterie, d'inhibiteurs de la corrosion du verre, d'inhibiteurs de mousse, de colorants, de parfums, d'amérisants, d'agents antimicrobiens et d'adjuvants de désintégration.
  10. Utilisation d'un détergent pour lave-vaisselle selon une des revendications 1 à 9 dans un procédé de nettoyage de la vaisselle à la machine.
  11. Procédé de nettoyage de la vaisselle à la machine, caractérisé en ce qu'on utilise un détergent pour lave-vaisselle selon une des revendications 1 à 9.
  12. Utilisation d'un complexe métallique de formule (I) pour améliorer l'efficacité de lavage d'un détergent pour nettoyer la vaisselle à la machine

            Mn+L(Am-)n/m     (I)

    où
    M est un cation métallique choisi parmi les cations de Cu, Zn, Co, Cr, Ni, Ru, Rh, Bi, en particulier parmi les cations de Cu, Zn, Co, Ni et Bi, encore plus préférentiellement parmi Cu2+, Zn2+, Co2+, Co3+ et Bi3+, très préférentiellement Cu2+, Zn2+ ou Bi3+, extraordinairement préférentiellement Cu2+ ou Zn2+, idéalement Zn2+ ;
    A est un anion au choix ;
    n et m sont des entiers choisis entre 1 et 6 ; et
    L est un ligand neutre de formule (II)
    Figure imgb0019
    où
    chaque X est indépendamment O ou NR ; et
    chaque R est choisi indépendamment parmi H, un C1-20-alkyle substitué ou non-substitué, linéaire ou ramifié, un C1-20-hétéroalkyle substitué ou non-substitué, linéaire ou ramifié, un C2-20-alcényle substitué ou non-substitué, linéaire ou ramifié, un C2-20-hétéroatcényle substitué ou non-substitué, linéaire ou ramifié et un C2-20-alcynyle substitué ou non-substitué, linéaire ou ramifié.
  13. Utilisation d'un complexe métallique de formule (I) selon la revendication 12 pour améliorer l'efficacité de lavage d'un détergent pour nettoyer la vaisselle à la machine

            Mn+L(Am-)n/m     (I)

    où
    M est un cation métallique choisi parmi les cations de Cu, Zn, Co, Cr, Ni, Ru, Rh, Bi, en particulier parmi les cations de Cu, Zn, Co, Ni et Bi, encore plus préférentiellement parmi Cu2+, Zn2+, Co2+, Co3+ et Bi3+, très préférentiellement Cu2+, Zn2+ ou Bi3+, extraordinairement préférentiellement Cu2+ ou Zn2+, idéalement Zn2+ ;
    A est un anion au choix ;
    n et m sont des entiers choisis entre 1 et 5 ; et
    L est un ligand neutre de formule (II)
    Figure imgb0020
    où
    chaque X est indépendamment O ou NR ; et
    chaque R est choisi indépendamment parmi H, -(CH2)o-CH3, où o est un entier choisi entre 3 et 13, -(CH2)p-COOH et -(CH2)p-OH, où p est à chaque fois un entier choisi entre 1 - 6.
EP15784043.0A 2014-10-23 2015-10-21 Détergent pour lave-vaisselle contenant des complexes métalliques Active EP3209762B1 (fr)

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PCT/EP2015/074415 WO2016062784A1 (fr) 2014-10-23 2015-10-21 Détergent pour lave-vaisselle contenant des complexes métalliques

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DE102021214708A1 (de) 2021-12-20 2023-06-22 Henkel Ag & Co. Kgaa Metallkomplexe und Geschirrspülmittel, die sie enthalten

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ES2901780T3 (es) * 2018-02-23 2022-03-23 Unilever Ip Holdings B V Película soluble en agua que comprende aminopolicarboxilato
US11193095B2 (en) * 2019-01-14 2021-12-07 Wizard Labs, Llc Rinsing solution for metal blades
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PL3872157T3 (pl) 2020-02-27 2023-04-17 Henkel Ag & Co. Kgaa Środek do mycia naczyń zawierający kompleksy metali
DE102020207791A1 (de) 2020-06-24 2021-12-30 Henkel Ag & Co. Kgaa Metallkomplexe und Geschirrspülmittel, die sie enthalten
DE102020202492A1 (de) 2020-02-27 2021-09-02 Henkel Ag & Co. Kgaa Metallkomplexe und Geschirrspülmittel, die sie enthalten
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DE102021214708A1 (de) 2021-12-20 2023-06-22 Henkel Ag & Co. Kgaa Metallkomplexe und Geschirrspülmittel, die sie enthalten

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US10358621B2 (en) 2019-07-23
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KR102402870B1 (ko) 2022-05-27
EP3209762A1 (fr) 2017-08-30
DE102014221581A1 (de) 2016-04-28

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