EP3481936B1 - Dishwashing composition containing sugar acid and amino carboxylic acid - Google Patents

Dishwashing composition containing sugar acid and amino carboxylic acid Download PDF

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Publication number
EP3481936B1
EP3481936B1 EP17734730.9A EP17734730A EP3481936B1 EP 3481936 B1 EP3481936 B1 EP 3481936B1 EP 17734730 A EP17734730 A EP 17734730A EP 3481936 B1 EP3481936 B1 EP 3481936B1
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Prior art keywords
acid
dishwashing detergent
weight
dishwashing
group
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EP17734730.9A
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German (de)
French (fr)
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EP3481936A1 (en
Inventor
Inga Kerstin Vockenroth
Christian Kropf
Thomas Weber
Noelle Wrubbel
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL17734730T priority Critical patent/PL3481936T3/en
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    • 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
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids

Definitions

  • the present invention relates to a phosphate-free machine dishwashing detergent which exhibits improved inhibition of deposits on items to be washed, the use of this dishwashing composition and a method for machine dishwashing using this dishwashing composition.
  • Machine-washed dishes are often subject to higher requirements today than hand-washed dishes. After machine cleaning, the crockery should not only be completely free of food residues, but also, for example, not have any whitish stains caused by water hardness or other mineral salts that result from dried water droplets due to a lack of wetting agents.
  • Modern machine dishwashing detergents meet these requirements by integrating cleaning, care, water-softening and rinsing active ingredients and are known to consumers, for example, as “2in1" or “3in1" dishwashing detergents.
  • the machine dishwashing detergents intended for private end users contain builders as an essential component for the cleaning and rinsing success. On the one hand, these builders increase the alkalinity of the cleaning liquor, with fats and oils being emulsified and saponified with increasing alkalinity, and on the other hand they reduce the water hardness of the cleaning liquor by complexing the calcium ions contained in the aqueous liquor.
  • the alkali metal phosphates which for this reason form the main component of the majority of commercially available machine dishwashing detergents, have proven to be particularly effective builders.
  • phosphates are highly valued in terms of their beneficial effect as a component of automatic dishwashing detergents, their use is not unproblematic from the point of view of environmental protection, since a significant part of the phosphate ends up in water bodies via household wastewater, and in particular in stagnant water bodies (lakes , barrages) plays a critical role in their over-fertilization.
  • sodium aluminum silicates in particular are used as phosphate substitutes or substitutes in laundry detergents.
  • these substances are unsuitable for use in machine dishwashing detergents for various reasons. A number of substitutes are therefore discussed in the literature as alternatives to the alkali metal phosphates in machine dishwashing detergents, of which the citrates are particularly noteworthy.
  • Phosphate-free machine dishwashing detergents which in addition to a citrate also contain carbonates, bleaches and enzymes, are described, for example, in European patents EP 662 117 B1 (Henkel KGaA ) and EP 692 020 B1 (Henkel KGaA ) described.
  • MGDA methylglycine diacetic acid
  • Machine dishwashing detergents containing MGDA are described, for example, in the European patent EP 906 407 B1 (Reckitt Benckiser ) or in the European patent application EP 1 113 070 A2 (Reckitt Benckiser ) described. Also in the German patent application DE 10 2007 006 628 A1 a dishwashing detergent containing methylglycinediacetic acid is described.
  • the international patent application WO 2007/141635 A2 describes the use of at least one sodium salt selected from iminodisuccinic acid tetrasodium salt (IDS), glutamic acid N,N-diacetic acid tetrasodium salt (GLDA), sodium glucoheptonate, sodium gluconate in detergents.
  • IDS iminodisuccinic acid tetrasodium salt
  • GLDA glutamic acid N,N-diacetic acid tetrasodium salt
  • sodium glucoheptonate sodium gluconate in detergents.
  • the object of the present application was therefore to provide a phosphate-free automatic dishwashing detergent which is comparable to or even surpasses conventional phosphate-containing detergents in terms of its cleaning performance as well as in terms of its rinsing results and its performance in terms of deposit inhibition.
  • a first aspect of the present invention therefore relates to a phosphate-free dishwashing detergent, in particular automatic dishwashing detergent, containing at least one sugar acid in an amount of 0.1 to 30% by weight, preferably 1 to 25% by weight, based on the total weight of the dishwashing detergent. , and at least one aminocarboxylic acid or at least one salt of an aminocarboxylic acid in an amount of, based on the total weight of the dishwashing detergent, 0.1 to 30% by weight, preferably 1 to 25% by weight, the sugar acid and optionally a salt of a Sugar acid in a total amount of 0.1 to 30% by weight, preferably 1 to 25% by weight, based on the total weight of the dishwashing detergent.
  • the present invention also relates to the use of a dishwashing detergent according to the invention in an automatic dishwashing process, in particular the use to improve the cleaning performance in an automatic dishwashing machine.
  • a further object of the invention is an automatic dishwashing method in which a dishwashing 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, i.e. 1, 2, 3, 4, 5, 6, 7, 8, 9 or more.
  • the information refers to the type of ingredient and not to the absolute number of molecules.
  • At least one surfactant thus means, for example, at least one type of surfactant, i.e. one type of surfactant or a mixture of several different surfactants can be meant.
  • the information refers to all compounds of the type specified that are contained in the composition/mixture, i.e. the composition does not contain any other compounds of this type beyond the specified amount of the corresponding compounds.
  • fatty acids or fatty alcohols or their derivatives are representative of branched or unbranched carboxylic acids or alcohols or their derivatives preferably having 6 to 22 carbon atoms.
  • the oxo-alcohols or their derivatives which can be obtained, for example, by ROELEN's oxo-synthesis can also be used accordingly.
  • alkaline earth metals are mentioned below as counterions for monovalent anions, this means that the alkaline earth metal is of course only present in half the amount of substance - sufficient for charge equalization - as the anion.
  • the dishwashing detergents according to the invention are free from phosphates and contain a builder combination of at least one sugar acid and at least one aminocarboxylic acid.
  • the agents as described herein are machine dishwashing agents.
  • Phosphates are generally known builders, but their use should be avoided due to their eutrophicating properties.
  • alkali metal phosphates with particular preference for pentasodium triphosphate or pentapotassium triphosphate (sodium tripolyphosphate or potassium tripolyphosphate), are of great importance in the detergent and dishwashing detergent industry.
  • Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO 3 ) n and orthophosphoric acid H 3 PO 4 in addition to higher-molecular representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts and lime incrustations in fabrics and also contribute to the cleaning performance.
  • the dishwashing detergents as described herein contain at least one sugar acid and also at least one amino carboxylic acid or at least one salt of an amino carboxylic acid.
  • the dishwashing detergents according to the invention are essentially phosphate-free, i.e. contain phosphate in amounts of less than 1% by weight, preferably less than 0.1% by weight, and/or contain no deliberately added phosphate.
  • sugar acid refers to a polyhydroxycarboxylic acid which is the oxidation product of a monosaccharide and includes both the D and the L configuration.
  • the salts of a sugar acid are the alkali and alkaline earth metal salts, preferably the alkali metal salts, in particular the sodium and potassium salts of a sugar acid.
  • the at least one sugar acid contained in the compositions as described herein is selected from the group consisting of aldonic acids, uronic acids, aldaric acids and ketoaldonic acids.
  • the at least one sugar acid is selected from the group consisting of gluconic acid, glucuronic acid, glucoheptonic acid, glucaric acid, tartaric acid, mucinic acid, gulonic acid, galacturonic acid, iduronic acid, mannonic acid and 2-oxo-D-gluconic acid.
  • the at least one sugar acid is glucaric acid, in particular D -glucaric acid (2S,3S, 4S , 5R ) -2,3,4,5 -tetrahydroxyhexanedioic acid).
  • the agents according to the invention contain at least one sugar acid in amounts of 0.1 to 30% by weight, preferably 1 to 25% by weight and in particular 5 to 20% by weight, the sugar acid and optionally a salt of a sugar acid in a Total amount of 0.1 to 30 wt .-%, preferably 1 to 25 wt .-%, based on the total weight of the dishwashing detergent contained.
  • aminocarboxylic acid refers to an amino acid or a derivative of an amino acid.
  • Particularly preferred representatives of the class of aminocarboxylic acids are methylglycinediacetic acid (MGDA) or its salts and glutaminediacetic acid (GLDA) or its salts or ethylenediaminediacetic acid or its salts (EDDS).
  • MGDA methylglycinediacetic acid
  • GLDA glutaminediacetic acid
  • EDDS ethylenediaminediacetic acid or its salts
  • IDS iminodisuccinic acid
  • IDA iminodiacetic acid
  • the salts of an aminocarboxylic acid are the alkali and alkaline earth metal salts, preferably the alkali metal salts, in particular the sodium and potassium salts, of an aminocarboxylic acid.
  • the at least one aminocarboxylic acid contained in the agents as described herein is selected from the group consisting of methylglycine diacetic acid (MGDA), glutamic diacetic acid (GLDA), ethylenediamine diacetic acid (EDDS), iminodisuccinic acid (IDS) and iminodiacetic acid (IDA).
  • MGDA methylglycine diacetic acid
  • GLDA glutamic diacetic acid
  • EDDS ethylenediamine diacetic acid
  • IDS iminodisuccinic acid
  • IDA iminodiacetic acid
  • the at least one amino carboxylic acid is MGDA.
  • the agents according to the invention contain at least one aminocarboxylic acid or at least one salt of an aminocarboxylic acid in amounts of 0.1 to 30% by weight, preferably 1 to 25% by weight and in particular 5 to 20% by weight.
  • the at least one sugar acid and the at least one aminocarboxylic acid are present together in the dishwashing detergent in an amount of 0.1 to 40% by weight, in particular 5 to 30% by weight, based on the total weight of the dishwashing detergent.
  • the at least one sugar acid and the at least one aminocarboxylic acid are present in the dishwashing detergent in a mass ratio of from 80:20 to 20:80, in particular 50:50.
  • the agents according to the invention can contain at least one, preferably at least two, further components, preferably selected from the group consisting of surfactants, in particular nonionic surfactants and/or anionic surfactants, other 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
  • other 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.
  • compositions described herein preferably contain at least one nonionic surfactant. All nonionic surfactants known to those skilled in the art can be used as nonionic surfactants.
  • Suitable nonionic surfactants are alkyl glycosides of the general formula RO(G) x , where R is a primary straight-chain or methyl-branched aliphatic radical, especially methyl-branched in the 2-position, having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol is, which is a glucose unit with 5 or 6 carbon 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 from 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 alkanolamide type can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of it.
  • Suitable surfactants are the polyhydroxy fatty acid amides known as PHFA.
  • low-foaming nonionic surfactants in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants.
  • the machine dishwashing detergents particularly preferably contain nonionic surfactants from the group of alkoxylated alcohols.
  • nonionic surfactants that can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants is accordingly alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain.
  • Surfactants to be used with preference come from the groups of ethoxylated primary alcohols and mixtures of these surfactants with surfactants with a more complex structure such as Polyoxypropylene/polyoxyethylene/polyoxypropylene ((PO/EO/PO) surfactants). Such (PO/EO/PO) nonionic surfactants are distinguished by good foam control.
  • nonionic surfactants are those which have alternating ethylene oxide and alkylene oxide units.
  • preference is in turn given to surfactants with EO-AO-EO-AO blocks, in which case one to ten EO or AO groups are bonded to one another before a block of the other groups follows.
  • nonionic surfactants of the general formula preferably 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 are independent of one another are integers from 1 to 6.
  • nonionic surfactants having a C 9-15 alkyl radical containing 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.
  • R 1 which represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore one linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having 1 to 30 carbon atoms, where x is a value between 1 and 90, preferably a value between 30 and 80 and in particular a value between 30 and 60.
  • R 1 O[CH 2 CH(CH 3 )O] x [CH 2 CH 2 O] y CH 2 CH(OH)R 2
  • R 1 represents a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof
  • R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x has values between 0.5 and 1.5 and y has 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 -hydroxydecyl ether.
  • 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 represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 represents H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2- butyl or 2-methyl-2-butyl radical, x is between 1 and 30, k and j are 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 can 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, radicals having 8 to 18 carbon atoms being particularly preferred.
  • H, -CH 3 or -CH 2 CH 3 are particularly preferred for the radical R 3 .
  • 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.
  • the value 3 for x was selected here as an example and can certainly be larger, with the range of variation increasing with increasing x values and including, for example, a large number of (EO) groups combined with a small number of (PO) groups, or vice versa .
  • R 1 , R 2 and R 3 are as defined above and x is a number from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • the group of these nonionic surfactants includes, for example, the C 4-22 fatty alcohol (EO) 10-80 -2-hydroxyalkyl ethers, in particular the C 8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ether and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ether.
  • the agents 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 agent of at least 2% by weight, preferably at least 5% by weight. %.
  • the absolute ones used per application Amounts can be, for example, in the range of 0.5-10 g/job, preferably in the range of 1-5 g/job.
  • anionic surface-active substances are suitable as anionic surfactants in dishwashing detergents. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 8 to 30 carbon atoms.
  • the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups.
  • Suitable anionic surfactants are preferably present in the form of the sodium, potassium and ammonium salts and 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 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule.
  • the dishwashing detergents therefore 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, particularly 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, the representatives with an even number of C atoms are preferred.
  • radicals R 1 are derived from C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C 10 -C 20 oxo alcohols.
  • AO stands for an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably for an ethylene oxide moiety.
  • the index n is an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. n is very particularly preferably the numbers 2, 3, 4, 5, 6, 7 or 8.
  • X is a monovalent cation or the nth part of an n-valent cation, preference being given to the alkali metal ions and including Na + or K + , with Na + being extremely preferred. Further cations X + can be selected from NH 4 + , 1 ⁇ 2 Zn 2+ , 1 ⁇ 2 Mg 2+ , 1 ⁇ 2 Ca 2+ , 1 ⁇ 2 Mn 2+ , and mixtures thereof.
  • the agents can also additionally or alternatively contain at least one surfactant of the formula R 5 -A-SO 3 - Y + .
  • R 5 represents a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical and the group -A- represents -O- or a chemical bond.
  • certain radicals R 5 are preferred.
  • R 5 is preferably a linear, unsubstituted alkyl radical, particularly 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, the representatives with an even number of C atoms are preferred.
  • Particularly preferred radicals R 5 are derived from C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C 10 -C 20 oxo alcohols.
  • Y is a monovalent cation or the nth part of an n-valent cation, preference being given to the alkali metal ions and including Na + or K + , with Na + being extremely preferred.
  • Further cations Y+ can be selected from NH 4+ , 1 ⁇ 2 Zn 2+ , 1 ⁇ 2 Mg 2+ , 1 ⁇ 2 Ca 2+ , 1 ⁇ 2 Mn 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, preference being given to the alkali metal ions and including Na + or K + , with Na + being extremely preferred.
  • Further cations X+ can be selected from NH 4+ , 1 ⁇ 2 Zn 2+ , 1 ⁇ 2 Mg 2+ , 1 ⁇ 2 Ca 2+ , 1 ⁇ 2 Mn 2+ , and mixtures thereof .
  • Such surfactants can be selected from linear or branched alkyl benzene sulfonates.
  • Cationic and/or amphoteric surfactants such as betaines or quaternary ammonium compounds, can also be used instead of the surfactants mentioned or in conjunction with them. However, it is preferred that no cationic and/or amphoteric surfactants are used.
  • Further builders that can be contained in the dishwashing detergent are, in particular, silicates, aluminum silicates (especially zeolites), carbonates and organic di- and polycarboxylic acids or their salts. Mixtures of these substances can of course also be used.
  • crystalline layered silicates of the general formula NaMSi x O 2x+1 ⁇ y H 2 O can be used, where M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particular 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 layered silicates of the formula NaMSi x O 2x+1 ⁇ y H 2 O are marketed, for example, 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 x H 2 O, makatite).
  • Crystalline phyllosilicates of the formula NaMSi x O 2x+1 .yH 2 O, in which x is 2, are particularly suitable for the purposes of the present invention.
  • both ß- and ⁇ -sodium disilicates are Na 2 Si 2 O 5 ⁇ y H 2 O and, above all, Na-SKS-5 ( ⁇ -Na 2 Si 2 O 5 ), Na-SKS-7 (ß-Na 2 Si 2 O 5 , Natrosilit), 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 ) is preferred.
  • Automatic dishwashing detergents typically contain a proportion by weight of the crystalline layered silicate of the formula NaMSi x O 2x+1 y H 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% by weight, based in each case on the total weight of these agents.
  • Amorphous sodium silicates with an Na 2 O:SiO 2 modulus of 1:2 to 1:3.3, preferably of 1:2 to 1:2.8 and in particular of 1:2 to 1:2.6, can also be used are preferably delayed in dissolution and have secondary washing properties.
  • the delay in dissolving compared to conventional amorphous sodium silicates can have been brought about in various ways, for example by surface treatment, compounding, compacting/densification or by overdrying.
  • amorphous means that the silicates do not provide sharp X-ray reflections in X-ray diffraction experiments, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle , cause.
  • these silicate(s), preferably alkali metal silicates, particularly preferably crystalline or amorphous alkali metal disilicates, are present in amounts in the agents from 1 to 40% by weight, preferably from 2 to 35% by weight, in each case based on the weight of the machine dishwashing detergent.
  • the dishwashing detergents can also contain, in particular, phosphonates as a further builder.
  • a hydroxyalkane and/or aminoalkane phosphonate is preferably used as the phosphonate compound.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues.
  • the detergents preferably contain phosphonates in amounts of from 0.1 to 10% by weight, in particular in amounts of from 0.5 to 8% by weight, based in each case on the total weight of the dishwashing detergent.
  • alkali carriers are alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, the alkali metal silicates mentioned, alkali metal metasilicates and mixtures of the aforementioned substances, with preference being given to using the alkali metal carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, for the purposes of this invention.
  • a builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred.
  • a builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred.
  • the optional alkali metal hydroxides are preferably used only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, particularly preferably below 4 % by weight and in particular below 2% by weight, in each case based on the total weight of the machine dishwashing detergent.
  • Agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides are particularly preferred.
  • detergents which, based on the weight of the automatic dishwashing detergent, contain less than 20% by weight, preferably less than 17% by weight, preferably less than 13% by weight and in particular less than 9% by weight of carbonate(s ) and/or hydrogen carbonate(s), preferably alkali metal carbonate(s), particularly preferably sodium carbonate.
  • organic builders which should be mentioned are, in particular, polycarboxylates/polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders and the phosphonates already mentioned above as builders.
  • Organic builder substances which can be used are, in particular, for example the polycarboxylic acids which can be used in the form of the free acid and/or their sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, nitrilotriacetic acid (NTA), provided such use is not objectionable for ecological reasons, and mixtures of these.
  • NTA nitrilotriacetic acid
  • the free acids typically also have the property of an acidifying component and are therefore also used to set a lower and milder pH in the machine dishwashing detergents.
  • citric acid, succinic acid, glutaric acid, adipic acid and any mixtures of these are particularly, for example the polycarboxylic acids which can be used in the form of the free acid and/or their sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which
  • Automatic dishwashing detergents are therefore preferred, characterized in that the automatic dishwashing detergent contains citric acid or a salt of citric acid.
  • the dishwashing detergents according to the invention can also contain a sulfopolymer.
  • the proportion by weight of the sulfopolymer in the total weight of the dishwashing detergent according to the invention is preferably from 0.1 to 20% by weight, in particular from 0.5 to 18% by weight, particularly preferably from 1.0 to 15% by weight, in particular from 4 to 14% by weight, especially from 6 to 12% by weight.
  • the sulfopolymer is usually used in the form of an aqueous solution, the aqueous solutions typically containing 20 to 70% by weight, in particular 30 to 50% by weight, preferably about 35 to 40% by weight, of sulfopolymers.
  • a copolymeric polysulfonate preferably a hydrophobically modified copolymeric polysulfonate, is preferably used as the sulfopolymer.
  • copolymers can have two, three, four or more different monomer units.
  • preferred copolymeric polysulfonates contain at least one monomer from the group of unsaturated carboxylic acids.
  • the unsaturated carboxylic acid(s) used is/are particularly preferably unsaturated carboxylic acids of the formula R 1 (R 2 )C ⁇ C(R 3 )COOH, in which R 1 to R 3 independently represent -H, -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, one straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH 2 , -OH or -COOH-substituted alkyl or alkenyl radicals as defined above or -COOH or -COOR 4 , where R 4 is a saturated or is an unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof.
  • unsaturated dicarboxylic acids can also be used.
  • Particularly preferred sulfonic acid group-containing monomers 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-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of the acids mentioned or their
  • some or all of the sulfonic acid groups can be present in neutralized form, i.e. the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular sodium ions.
  • metal ions preferably alkali metal ions and in particular sodium ions.
  • the monomer distribution of the copolymers preferably used is preferably 5 to 95% by weight in each case, and the proportion of the sulfonic acid group-containing monomer is particularly preferably 50 to 90% by weight. and the proportion of the carboxylic acid group-containing monomer is 10 to 50% by weight, the monomers here preferably being selected from those mentioned above.
  • the molar mass of the sulfo-copolymers preferably used can be varied in order to adapt the properties of the polymers to the desired application.
  • Preferred dishwashing detergents are characterized in that the copolymers have molecular weights 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 detergents can also contain other polymers.
  • the group of suitable polymers includes, in particular, the cleaning-active polymers, for example the rinse-aid polymers and/or polymers that act as softeners.
  • Preferred polymers that can be used come from the group of alkylacrylamide/acrylic acid copolymers, alkylacrylamide/methacrylic acid copolymers, alkylacrylamide/methylmethacrylic acid copolymers, alkylacrylamide/acrylic acid/alkylaminoalkyl (meth)acrylic acid copolymers, alkylacrylamide/methacrylic acid/alkylaminoalkyl (meth) -acrylic acid copolymers, the alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkyl acrylamide / alkyl methacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally other ionic or nonionic monomers.
  • acrylamidoalkyltrialkylammonium chloride/acrylic acid copolymers and their alkali metal and ammonium salts acrylamidoalkyltrialkylammonium chloride/methacrylic acid copolymers and their alkali metal and ammonium salts and methacroylethylbetaine/methacrylate copolymers.
  • Cationic polymers that can be used come from the groups of quaternized cellulose derivatives, polysiloxanes with quaternary groups, cationic guar derivatives, polymeric dimethyldiallylammonium salts and their copolymers with acrylic acid and methacrylic acid and their esters and amides, 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 in principle of natural origin; Based on the natural molecules, improved variants are available for use in dishwashing detergents, which are used with preference accordingly.
  • the agents preferably contain enzymes in total amounts of 1 ⁇ 10 -6 to 5% by weight, based on active protein.
  • the protein concentration can be determined using known methods, for example the BCA method or the Biuret method.
  • proteases are among the most technically important enzymes of all. They break down proteinaceous soiling on the items to be cleaned. Among these, proteases of the subtilisin type (subtilases, subtilopeptidases, EC 3.4.21.62) are particularly important, which are serine proteases because of the catalytically active amino acids. They act as non-specific endopeptidases and hydrolyze any acid amide bonds that are inside peptides or proteins. Their optimum pH is usually in the clearly alkaline range. Subtilases are naturally produced by microorganisms. Among these, the subtilisins formed and secreted by Bacillus species should be mentioned in particular as the most important group within the subtilases.
  • subtilisin-type proteases preferably used in detergents 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 no longer the subtilisins in the narrower sense, thermitase, proteinase K and the proteases TW3 and TW7, as well as variants of the proteases mentioned, which have an altered amino acid sequence compared to the starting protease.
  • Proteases are modified in a targeted or random manner using methods known from the prior art and are 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. Correspondingly optimized variants are known for most of the 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 , and the further developments of the aforementioned amylases which have been 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 can also be used, in particular because of their triglyceride-splitting activities, but also in order to generate peracids in situ from suitable precursors. This includes for example the lipases originally available from Humicola lanuginosa (Thermomyces lanuginosus) or developed further, in particular those with the amino acid substitution 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 that interact with the enzymes are additionally added in order to increase the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons in the case of greatly differing redox potentials between the oxidizing enzymes and the soiling (mediators).
  • An enzyme can be protected against damage such as, for example, inactivation, denaturation or decomposition, for example due to physical influences, oxidation or proteolytic cleavage, particularly during storage.
  • damage such as, for example, inactivation, denaturation or decomposition, for example due to physical influences, oxidation or proteolytic cleavage, particularly during storage.
  • inhibition of proteolysis is particularly preferred, particularly if the agents also contain proteases.
  • Dishwashing detergents may contain stabilizers for this purpose; the provision of such means represents 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 preparations that can be stored and transported.
  • These ready-made preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel-like preparations, solutions of the enzymes, advantageously as concentrated as possible, low in water and/or mixed with stabilizers or other auxiliaries.
  • the enzymes can be encapsulated for both the solid and the liquid dosage form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer, or in the form of capsules, for example those in which the enzymes are enclosed as in a set gel or in those of the core-shell type, in which an enzyme-containing core is impermeable to water, air and/or chemicals protective layer is coated.
  • Additional active substances for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can also be applied in superimposed layers.
  • 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 due to the application of polymeric film formers, produce little dust and are stable in storage due to the coating.
  • the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • Protease and amylase preparations used with preference contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0.8 and 10% 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 are particularly preferred.
  • compositions herein may also include enzyme stabilizers.
  • stabilizers are reversible protease inhibitors.
  • Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are often used for this purpose, including above all derivatives with aromatic groups, such as ortho-, meta- or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or the salts or Esters of said compounds.
  • Peptide aldehydes ie oligopeptides with a reduced C-terminus, in particular those composed of 2 to 50 monomers, are also 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 also suitable for this.
  • enzyme stabilizers are amino alcohols such as mono-, di-, triethanolamine and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C 12 such as succinic acid, other dicarboxylic acids or salts of the acids mentioned. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Other enzyme stabilizers are known to those skilled in the art from the prior art.
  • Bleaching agents are active cleaning substances.
  • Sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance among the compounds which serve as bleaching agents and yield H 2 O 2 in water.
  • bleaches which can be used are peroxypyrophosphates, citrate perhydrates and peracid salts or peracids which supply H 2 O 2 , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid. All other inorganic or organic peroxy bleaches known to those skilled in the art from the prior art can also be used.
  • the percarbonates and here in particular sodium percarbonate are particularly preferred as bleaching agents.
  • the dishwashing detergents can contain 1 to 35% by weight, preferably 2.5 to 30% by weight, particularly preferably 3.5 to 20% by weight and in particular 5 to 15% by weight of bleach, preferably sodium percarbonate.
  • the machine dishwashing detergents additionally contain at least one bleach activator.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, produce aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon 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 is very particularly preferred as the bleach activator, especially in combination with a percarbonate bleach, preferably sodium percarbonate.
  • bleach activators are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6% by weight, in each case based on the total weight of the funds.
  • the pH of the dishwashing detergent can be adjusted using customary pH regulators, with the pH being selected depending on the desired application.
  • the pH is in a range from 5.5 to 10.5, preferably from 5.5 to 9.5, more preferably from 7 to 9, in particular greater than 7, especially in the range from 7.5 to 8.5 .
  • Acids and/or alkalis, preferably alkalis are used as pH adjusters.
  • Suitable acids are, in particular, organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid and malic acid or amidosulfonic acid.
  • the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof can also be used.
  • Suitable bases come from the group of alkali metal and alkaline earth metal hydroxides and carbonates, in particular the alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide are preferred.
  • alkali metal hydroxides of which potassium hydroxide and especially sodium hydroxide are preferred.
  • volatile alkali for example in the form of ammonia and/or alkanolamines, which can contain up to 9 carbon atoms in the molecule.
  • the alkanolamine is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof.
  • the agent according to the invention can also contain one or more buffer substances (INCI buffering agents), usually in amounts of 0.001 to 5% by weight. Buffer substances which are at the same time complexing agents or even chelating agents (chelators, INCI chelating agents) are preferred. Particularly preferred buffer substances are citric acid or citrates, in particular sodium and potassium citrates, for example trisodium citrate ⁇ 2H 2 O and tripotassium citrate ⁇ H 2 O.
  • ICI buffering agents buffer substances which are at the same time complexing agents or even chelating agents (chelators, INCI chelating agents) are preferred.
  • Particularly preferred buffer substances are citric acid or citrates, in particular sodium and potassium citrates, for example trisodium citrate ⁇ 2H 2 O and tripotassium citrate ⁇ H 2 O.
  • Glass corrosion inhibitors prevent clouding, streaks and scratches from occurring, but also iridescence on the glass surface of machine-cleaned glasses.
  • Preferred glass corrosion inhibitors come from the group consisting of magnesium and zinc salts and magnesium and zinc complexes.
  • the content of zinc salt in dishwashing detergents is preferably between 0.1 and 5% by weight, preferably between 0.2 and 4% by weight and in particular between 0.4 and 3% by weight, or the content of zinc in oxidized form (calculated as Zn 2+ ) 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 agent containing glass corrosion inhibitor.
  • Perfume oils or fragrances which can be used in the context of the present invention are individual odorant compounds, for example synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance note. Perfume oils of this type can also contain natural mixtures of fragrances, such as those obtainable from vegetable sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
  • preservatives can be contained in the agents.
  • preservatives from the groups of alcohols, aldehydes, antimicrobial acids and/or salts thereof, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen and nitrogen acetals and formals, benzamidines, isothiazoles and derivatives thereof are suitable such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surfactants, guanidines, antimicrobial amphoterics Compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl carbamate, iodine, iodophors and peroxides.
  • Preferred antimicrobial agents are preferably selected from the group consisting of 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'-methylene-bis(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,
  • 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 machine dishwashing detergents described herein can be packaged in different ways.
  • the agents can be presented in solid or liquid form or as a combination of solid and liquid forms. Powders, granules, extrudates, compacts, in particular tablets, are particularly suitable as solid supply forms.
  • the liquid supply forms based on water and/or organic solvents can be thickened and in the form of gels.
  • the agents can be packaged in the form of single-phase or multi-phase products.
  • the individual phases of multi-phase agents can have the same or different states of aggregation.
  • the dishwashing detergents can be in the form of shaped bodies.
  • disintegration aids so-called tablet disintegrants
  • Tablet disintegrants or disintegrants are understood as meaning excipients which ensure that tablets disintegrate rapidly in water or other media and that the active ingredients are released quickly.
  • Disintegration aids can preferably be used in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight, based in each case on the total weight of the composition containing disintegration aids.
  • the machine dishwashing detergents described herein are preferably prepackaged to form dosing units. These dosing units preferably include the amount of cleaning-active substances required for one cleaning cycle.
  • Preferred dosage units weigh between 12 and 30 g, preferably between 14 and 26 g and in particular between 16 and 22 g.
  • the volume of the aforementioned dosing units and their three-dimensional shape are selected with particular preference in such a way that the prefabricated units can be dosed via the dosing chamber of a dishwasher.
  • the volume of the dosage unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml.
  • the machine dishwashing detergents in particular the prefabricated dosing units, particularly preferably have a water-soluble coating.
  • the water-soluble cover is preferably formed from a water-soluble film material which is selected from the group consisting of polymers or polymer mixtures.
  • the cover can be formed from one or from two or more layers of the water-soluble film material.
  • the water-soluble film material of the first layer and the further layers, if any, can be the same or different. Films are particularly preferred which can be glued and/or sealed to form packaging such as tubes or pillows after they have been filled with an agent.
  • the water-soluble packaging can have one or more compartments.
  • the agent can be contained in one or more compartments, if any, of the water-soluble coating.
  • the amount of agent preferably corresponds to the full or half dose required for one rinse.
  • the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
  • Water-soluble coatings that contain polyvinyl alcohol or a polyvinyl alcohol copolymer have good stability with sufficiently high water solubility, especially cold water solubility.
  • Suitable water-soluble films for producing the water-soluble covering are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range from 10,000 to 1,000,000 gmol -1 , preferably from 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 produced by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers which are correspondingly produced from polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol %, preferably 80 to 90 mol %, particularly preferably 81 to 89 mol % and in particular 82 to 88 mol %.
  • a polyvinyl alcohol-containing film material suitable for producing the water-soluble casing can additionally have a polymer selected from the group consisting of (meth)acrylic acid-containing (co)polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, Polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above polymers may be added.
  • a preferred additional polymer are polylactic acids.
  • preferred polyvinyl alcohol copolymers include 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 which are also preferred include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its ester.
  • Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof.
  • the film material contains other additives.
  • the film material can 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, anti-blocking agents, anti-adhesive agents or mixtures thereof.
  • Suitable water-soluble films for use in the water-soluble wrappers of the water-soluble packages of the invention are films sold by MonoSol LLC, for example, under the designation M8630, C8400 or M8900.
  • Other suitable films include Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL films from Aicello Chemical Europe GmbH or Kuraray VF-HP films.
  • Exemplary base formulations in which the combination of builders described herein can be used in the specified amounts by replacing some of the builders contained with at least one sugar acid or the salt thereof are as follows: Table 1: Phosphate-free, solid dishwashing detergent formulation (tab) raw material Amount (% by weight) sodium citrate 15.00-20.00 Phosphonate (e.g.
  • HEDP 0.00-7.50 MGDA/GLDA 5.00-25.00 silicate 10.00-35.00 soda 12.50-25.00 Na percarbonate 10.00-15.00 bleach catalyst 0.02-0.50 TAED 2.00-3.00 nonionic surfactant 2.50-10.00 polycarboxylate 5.00-10.00 Cationic acrylate copolymer 0.25-0.75 PVP (crosslinked) 0.00-1.50 protease 1.50-5.00 amylase 0.50-3.00 Benzotriazole (silver protection) 0.00-0.50 Perfume 0.05-0.15 dye 0.00-1.00 Zn acetate anhydrous 0.10-0.30 sodium sulfate 0.00-25.00 water 0.00-1.50 pH adjuster 1.00-1.50 process aids 0.00-5.00
  • the corresponding use of the machine dishwashing detergents according to the invention is also a subject of the invention.
  • the invention also relates to a dishwashing method, in particular a machine dishwashing method, in which a dishwashing detergent according to the invention is used.
  • the subject matter of the present application is therefore also a method for cleaning dishes in a dishwasher, in which the agent according to the invention is metered into the interior of a dishwasher while running through a dishwashing program before the start of the main wash cycle or during the course of the main wash cycle.
  • the agent according to the invention can be dosed or introduced into the interior of the dishwasher manually, but the agent is preferably dosed into the interior of the dishwasher by means of the dosing chamber.
  • Table 2 Formula ranges raw material Total phosphate-free formula ranges % g/job sodium citrate 15.00-20.00 3.00-4.000 Phosphonate (HEDP) 2.50-7.50 0.50-1.500 MGDA 0.00-25.00 0.00-5.000 Na disilicate 5.00-35.00 1.00-7.000 soda 12.50-25.00 2.50-5,000 Na percarbonate 10.00-15.00 2.00-3.000 Bleach catalyst (Mn-based) 0.02-0.50 0.003-0.100 TAED 2.00-3.00 0.40-0.600
  • Non-ionic surfactant 20-40 EO end-capped possible 2.50-10.00 0.50-2.000 polycarboxylate 5.00-10.00 1.00-2.000 Cationic co-polymer 0.25-0.75 0.05-0.150
  • the deposit inhibition was determined in Miele domestic machines in the 65 °C program after 30 cycles including dirt loading.
  • half of the MGDA has been replaced by glucaric acid.
  • the entire amount of MGDA was exchanged for glucaric acid.
  • the combination of the two complexing agents shows an improvement in scale inhibition on metal with the same performance on glass.
  • the performance increase is greater when replacing a part of the MGDA compared to replacing it completely.

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Description

Die vorliegende Erfindung betrifft ein phosphatfreies, maschinelles Geschirrspülmittel, das eine verbesserte Belagsinhibierung auf Spülgut zeigt, die Verwendung dieses Geschirrspülmittels sowie ein Verfahren zum maschinellen Geschirrspülen unter Verwendung dieses Geschirrspülmittels.The present invention relates to a phosphate-free machine dishwashing detergent which exhibits improved inhibition of deposits on items to be washed, the use of this dishwashing composition and a method for machine dishwashing using this dishwashing composition.

An maschinell gespültes Geschirr werden heute häufig höhere Anforderungen gestellt als an manuell gespültes Geschirr. So soll das Geschirr nach der maschinellen Reinigung nicht nur völlig frei von Speiseresten sein, sondern beispielsweise auch keine weißlichen, auf Wasserhärte oder anderen mineralischen Salzen beruhenden Flecken aufweisen, die mangels Netzmittel aus eingetrockneten Wassertropfen stammen.Machine-washed dishes are often subject to higher requirements today than hand-washed dishes. After machine cleaning, the crockery should not only be completely free of food residues, but also, for example, not have any whitish stains caused by water hardness or other mineral salts that result from dried water droplets due to a lack of wetting agents.

Moderne maschinelle Geschirrspülmittel erfüllen diese Anforderungen durch die Integration reinigender, pflegender, wasserenthärtender und klarspülaktiver Wirkstoffe und sind dem Verbraucher beispielsweise als "2in1"- oder "3in1" Geschirrspülmittel bekannt. Als für den Reinigungs- wie für den Klarspülerfolg wesentlichen Bestandteil enthalten die für den privaten Endverbraucher vorgesehenen maschinellen Geschirrspülmittel Gerüststoffe. Diese Gerüststoffe erhöhen zum einen die Alkalität der Reinigungsflotte, wobei mit steigender Alkalität Fette und Öle emulgiert und verseift werden, und vermindern zum anderen durch Komplexierung der in der wässrigen Flotte enthaltenen Calciumionen die Wasserhärte der Reinigungsflotte. Als besonders wirkungsvolle Gerüststoffe haben sich die Alkalimetallphosphate erwiesen, die aus diesem Grund den Hauptbestandteil der überwiegenden Zahl kommerziell erhältlicher maschineller Geschirrspülmittel bilden.Modern machine dishwashing detergents meet these requirements by integrating cleaning, care, water-softening and rinsing active ingredients and are known to consumers, for example, as "2in1" or "3in1" dishwashing detergents. The machine dishwashing detergents intended for private end users contain builders as an essential component for the cleaning and rinsing success. On the one hand, these builders increase the alkalinity of the cleaning liquor, with fats and oils being emulsified and saponified with increasing alkalinity, and on the other hand they reduce the water hardness of the cleaning liquor by complexing the calcium ions contained in the aqueous liquor. The alkali metal phosphates, which for this reason form the main component of the majority of commercially available machine dishwashing detergents, have proven to be particularly effective builders.

Während die Phosphate also im Hinblick auf ihre vorteilhafte Wirkung als Bestandteil maschineller Geschirrspülmittel sehr geschätzt werden, ist ihr Einsatz unter dem Blickwinkel des Umweltschutzes jedoch nicht unproblematisch, da ein wesentlicher Teil des Phosphats über das Haushaltsabwasser in die Gewässer gelangt und insbesondere in stehenden Gewässern (Seen, Staustufen) eine bedenkliche Rolle bei deren Überdüngung spielt.While phosphates are highly valued in terms of their beneficial effect as a component of automatic dishwashing detergents, their use is not unproblematic from the point of view of environmental protection, since a significant part of the phosphate ends up in water bodies via household wastewater, and in particular in stagnant water bodies (lakes , barrages) plays a critical role in their over-fertilization.

Als Phosphat-Ersatz- oder -austauschstoffe werden in Textilwaschmitteln neben Nitrilotriessigsäure vor allem Natriumaluminiumsilicate (Zeolithe) eingesetzt. Diese Substanzen sind jedoch für den Einsatz in maschinellen Geschirrspülmitteln aus verschiedenen Gründen nicht geeignet. Als Alternativen zu den Alkalimetallphosphaten in maschinellen Geschirrspülmitteln wird daher in der Literatur eine Reihe von Ersatzstoffen diskutiert, von denen die Citrate besonders hervorzuheben sind.In addition to nitrilotriacetic acid, sodium aluminum silicates (zeolites) in particular are used as phosphate substitutes or substitutes in laundry detergents. However, these substances are unsuitable for use in machine dishwashing detergents for various reasons. A number of substitutes are therefore discussed in the literature as alternatives to the alkali metal phosphates in machine dishwashing detergents, of which the citrates are particularly noteworthy.

Phosphatfreie maschinelle Geschirrspülmittel, die neben einem Citrat weiterhin Carbonate, Bleichmittel und Enzyme enthalten, werden beispielsweise in den europäischen Patenten EP 662 117 B1 (Henkel KGaA ) und EP 692 020 B1 (Henkel KGaA ) beschrieben.Phosphate-free machine dishwashing detergents, which in addition to a citrate also contain carbonates, bleaches and enzymes, are described, for example, in European patents EP 662 117 B1 (Henkel KGaA ) and EP 692 020 B1 (Henkel KGaA ) described.

Eine weitere Alternative zu den Alkalimetallphosphaten, die als alleiniger Gerüststoff, vorzugsweise jedoch in Kombination mit Citraten eingesetzt wird, ist die Methylglycindiessigsäure (MGDA). MGDAhaltige maschinelle Geschirrspülmittel werden beispielsweise in dem europäischen Patent EP 906 407 B1 (Reckitt Benckiser ) oder in der europäischen Patentanmeldung EP 1 113 070 A2 (Reckitt Benckiser ) beschrieben. Auch in der deutschen Patentanmeldung DE 10 2007 006 628 A1 wird ein Methylglycindiessigsäure-haltiges Geschirrspülmittel beschrieben.Another alternative to the alkali metal phosphates, which is used as the sole builder, but preferably in combination with citrates, is methylglycine diacetic acid (MGDA). Machine dishwashing detergents containing MGDA are described, for example, in the European patent EP 906 407 B1 (Reckitt Benckiser ) or in the European patent application EP 1 113 070 A2 (Reckitt Benckiser ) described. Also in the German patent application DE 10 2007 006 628 A1 a dishwashing detergent containing methylglycinediacetic acid is described.

Die internationale Patentanmeldung WO 2007/141635 A2 beschreibt den Einsatz von mindestens einem Natriumsalz aus gewählt aus Iminodisuccinsäure-Tetranatriumsalz (IDS), Glutaminsäure-N, N-diessigsäure-Tetranatriumsalz (GLDA), Natriumglucoheptonat, Natriumgluconat in Reinigungsmitteln.The international patent application WO 2007/141635 A2 describes the use of at least one sodium salt selected from iminodisuccinic acid tetrasodium salt (IDS), glutamic acid N,N-diacetic acid tetrasodium salt (GLDA), sodium glucoheptonate, sodium gluconate in detergents.

Die internationale Patentanmeldung WO 2015/104068 A1 beschreibt den Einsatz einer Kombination von mehreren Komplexbildnern oder Komplexierungshilfsmitteln in Reinigungsmittel.The international patent application WO 2015/104068 A1 describes the use of a combination of several complexing agents or complexing aids in cleaning agents.

Die amerikanische Patentanmeldung US 2005/0075258A1 beschreibt den Einsatz von Natriumsalzen unterschiedlicher organischer Säuren, unter anderem Zuckersäuren.The American patent application US2005/0075258A1 describes the use of sodium salts of different organic acids, including sugar acids.

In der deutschen Patentanmeldung DE 10 2007 044 418 A1 wird Carboxymethylinulin gemeinsam mit Phosphonat in einem maschinellen Geschirrspülmittel eingesetzt.In the German patent application DE 10 2007 044 418 A1 Carboxymethyl inulin is used together with phosphonate in a dishwasher detergent.

Trotz der bisherigen Bemühungen ist es den Herstellern maschineller Geschirrspülmittel bisher nicht gelungen, phosphatfreie maschinelle Geschirrspülmittel bereitzustellen, die hinsichtlich ihrer Reinigungs- und Klarspülleistung sowie insbesondere auch ihrer belagsinhibierenden Leistung phosphathaltigen Reinigungsmitteln vergleichbar sind oder diese gar übertreffen. Eine solche Leistungsgleichheit ist jedoch Voraussetzung für die erfolgreiche Markteinführung phosphatfreier Reinigungsmittel.Despite previous efforts, manufacturers of automatic dishwashing detergents have not yet succeeded in providing phosphate-free automatic dishwashing detergents which are comparable to or even surpass phosphate-containing cleaning agents in terms of their cleaning and rinsing performance and, in particular, their scale-inhibiting performance. However, such equality of performance is a prerequisite for the successful market launch of phosphate-free cleaning agents.

In Anbetracht dieser Ausgangssituation bestand demnach die Aufgabe der vorliegenden Anmeldung in der Bereitstellung eines phosphatfreien maschinellen Geschirrspülmittels, welches sowohl in Bezug auf seine Reinigungsleistung als auch in Bezug auf seine Klarspülergebnisse und seine Leistung bezüglich der Belagsinhibierung mit herkömmlichen phosphathaltigen Reinigungsmitteln vergleichbar ist oder diese sogar übertrifft.In view of this initial situation, the object of the present application was therefore to provide a phosphate-free automatic dishwashing detergent which is comparable to or even surpasses conventional phosphate-containing detergents in terms of its cleaning performance as well as in terms of its rinsing results and its performance in terms of deposit inhibition.

Es wurde festgestellt, dass die Belagsbildung in Phosphat-freien Systemen durch die Kombination einer Zuckersäure mit einer Aminocarbonsäure vorteilhaft beeinflusst werden kann.It was found that the formation of deposits in phosphate-free systems can be advantageously influenced by combining a sugar acid with an aminocarboxylic acid.

Ein erster Aspekt der vorliegenden Erfindung betrifft daher ein phosphatfreies Geschirrspülmittel, insbesondere maschinelles Geschirrspülmittel, enthaltend mindestens eine Zuckersäure in einer Menge von, bezogen auf das Gesamtgewicht des Geschirrspülmittels, 0,1 bis 30 Gew.-%, vorzugsweise 1 bis 25 Gew.-%, und mindestens eine Aminocarbonsäure oder mindestens ein Salz einer Aminocarbonsäure in einer Menge von, bezogen auf das Gesamtgewicht des Geschirrspülmittels, 0,1 bis 30 Gew.-%, vorzugsweise 1 bis 25 Gew.-%, wobei die Zuckersäure und gegebenenfalls ein Salz einer Zuckersäure in einer Gesamtmenge von 0,1 bis 30 Gew.-%, vorzugsweise 1 bis 25 Gew.-%, bezogen auf das Gesamtgewicht des Geschirrspülmittels, enthalten sind.A first aspect of the present invention therefore relates to a phosphate-free dishwashing detergent, in particular automatic dishwashing detergent, containing at least one sugar acid in an amount of 0.1 to 30% by weight, preferably 1 to 25% by weight, based on the total weight of the dishwashing detergent. , and at least one aminocarboxylic acid or at least one salt of an aminocarboxylic acid in an amount of, based on the total weight of the dishwashing detergent, 0.1 to 30% by weight, preferably 1 to 25% by weight, the sugar acid and optionally a salt of a Sugar acid in a total amount of 0.1 to 30% by weight, preferably 1 to 25% by weight, based on the total weight of the dishwashing detergent.

Ebenfalls Gegenstand der vorliegenden Erfindung ist die Verwendung eines erfindungsgemäßen Geschirrspülmittels in einem maschinellen Geschirrspülverfahren, insbesondere die Verwendung zur Verbesserung der Reinigungsleistung in einer automatischen Geschirrspülmaschine.The present invention also relates to the use of a dishwashing detergent according to the invention in an automatic dishwashing process, in particular the use to improve the cleaning performance in an automatic dishwashing machine.

Noch ein weiterer Gegenstand der Erfindung ist ein maschinelles Geschirrspülverfahren, bei dem ein erfindungsgemäßes Geschirrspülmittel insbesondere zu dem Zweck, die Reinigungsleistung zu verbessern, zum Einsatz kommt.A further object of the invention is an automatic dishwashing method in which a dishwashing detergent according to the invention is used in particular for the purpose of improving the cleaning performance.

Diese und weitere Aspekte, Merkmale und Vorteile der Erfindung werden für den Fachmann aus dem Studium der folgenden detaillierten Beschreibung und Ansprüche ersichtlich. Dabei kann jedes Merkmal aus einem Aspekt der Erfindung in jedem anderen Aspekt der Erfindung eingesetzt werden. Ferner ist es selbstverständlich, dass die hierin enthaltenen Beispiele die Erfindung beschreiben und veranschaulichen sollen, diese aber nicht einschränken und insbesondere die Erfindung nicht auf diese Beispiele beschränkt ist. Alle Prozentangaben sind, sofern nicht anders angegeben, Gewichts-%. Numerische Bereiche, die in dem Format "von x bis y" angegeben sind, schließen die genannten Werte ein. Wenn mehrere bevorzugte numerische Bereiche in diesem Format angegeben sind, ist es selbstverständlich, dass alle Bereiche, die durch die Kombination der verschiedenen Endpunkte entstehen, ebenfalls erfasst werden.These and other aspects, features and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Each feature from one aspect of the invention can be used in any other aspect of the invention. Furthermore, it should be understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular the invention is not limited to these examples. All percentages are % by weight unless otherwise specified. Numerical ranges given in the format "from x to y" include the stated values. Where multiple preferred numeric ranges are given in this format, it is understood that any ranges resulting from the combination of the different endpoints are also included.

"Mindestens ein", wie hierin verwendet, bedeutet 1 oder mehr, d.h. 1, 2, 3, 4, 5, 6, 7, 8, 9 oder mehr. Bezogen auf einen Inhaltsstoff bezieht sich die Angabe auf die Art des Inhaltsstoffs und nicht auf die absolute Zahl der Moleküle. "Mindestens ein Tensid" bedeutet somit beispielsweise mindestens eine Art von Tensid, d.h. dass eine Art von Tensid oder eine Mischung mehrerer verschiedener Tenside gemeint sein kann. Zusammen mit Gewichtsangaben bezieht sich die Angabe auf alle Verbindungen der angegebenen Art, die in der Zusammensetzung/Mischung enthalten sind, d.h. dass die Zusammensetzung über die angegebene Menge der entsprechenden Verbindungen hinaus keine weiteren Verbindungen dieser Art enthält."At least one" as used herein means 1 or more, i.e. 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. With regard to an ingredient, the information refers to the type of ingredient and not to the absolute number of molecules. "At least one surfactant" thus means, for example, at least one type of surfactant, i.e. one type of surfactant or a mixture of several different surfactants can be meant. Together with weight information, the information refers to all compounds of the type specified that are contained in the composition/mixture, i.e. the composition does not contain any other compounds of this type beyond the specified amount of the corresponding compounds.

Alle Prozentangaben, die im Zusammenhang mit den hierin beschriebenen Zusammensetzungen gemacht werden, beziehen sich, sofern nicht explizit anders angegeben auf Gew.-%, jeweils bezogen auf die betreffende Mischung.Unless explicitly stated otherwise, all percentages given in connection with the compositions described herein relate to % by weight, based in each case on the mixture in question.

Im Rahmen der vorliegenden Erfindung stehen Fettsäuren bzw. Fettalkohole bzw. deren Derivate - soweit nicht anders angegeben - stellvertretend für verzweigte oder unverzweigte Carbonsäuren bzw. Alkohole bzw. deren Derivate mit vorzugsweise 6 bis 22 Kohlenstoffatomen. Insbesondere sind auch die beispielsweise nach der ROELENschen Oxo-Synthese erhältlichen Oxo-Alkohole bzw. deren Derivate entsprechend einsetzbar.In the context of the present invention, fatty acids or fatty alcohols or their derivatives—unless otherwise stated—are representative of branched or unbranched carboxylic acids or alcohols or their derivatives preferably having 6 to 22 carbon atoms. In particular, the oxo-alcohols or their derivatives which can be obtained, for example, by ROELEN's oxo-synthesis can also be used accordingly.

Wann immer im Folgenden Erdalkalimetalle als Gegenionen für einwertige Anionen genannt sind, so bedeutet das, dass das Erdalkalimetall natürlich nur in der halben - zum Ladungsausgleich ausreichenden - Stoffmenge wie das Anion vorliegt.Whenever alkaline earth metals are mentioned below as counterions for monovalent anions, this means that the alkaline earth metal is of course only present in half the amount of substance - sufficient for charge equalization - as the anion.

Die erfindungsgemäßen Geschirrspülmittel sind frei von Phosphaten und enthalten eine Gerüststoffkombination aus mindestens einer Zuckersäure und mindestens einer Aminocarbonsäure. Insbesondere handelt es sich bei den wie hierin beschriebenen Mitteln um maschinelle Geschirrspülmittel.The dishwashing detergents according to the invention are free from phosphates and contain a builder combination of at least one sugar acid and at least one aminocarboxylic acid. In particular, the agents as described herein are machine dishwashing agents.

Bei Phosphaten handelt es sich um allgemein bekannte Buildersubstanzen, deren Einsatz es jedoch aufgrund ihrer eutrophierenden Eigenschaften zu vermeiden gilt. Unter der Vielzahl der kommerziell erhältlichen Phosphate sind insbesondere die Alkalimetallphosphate unter besonderer Bevorzugung von Pentanatrium- bzw. Pentakaliumtriphosphat (Natrium- bzw. Kaliumtripolyphosphat) in der Wasch- oder Geschirrspülmittel-Industrie von großer Bedeutung.Phosphates are generally known builders, but their use should be avoided due to their eutrophicating properties. Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium triphosphate or pentapotassium triphosphate (sodium tripolyphosphate or potassium tripolyphosphate), are of great importance in the detergent and dishwashing detergent industry.

Alkalimetallphosphate ist dabei die summarische Bezeichnung für die Alkalimetall- (insbesondere Natrium- und Kalium-) Salze der verschiedenen Phosphorsäuren, bei denen man Metaphosphorsäuren (HPO3)n und Orthophosphorsäure H3PO4 neben höhermolekularen Vertretern unterscheiden kann. Die Phosphate vereinen dabei mehrere Vorteile in sich: Sie wirken als Alkaliträger, verhindern Kalkbeläge auf Maschinenteilen bzw. Kalkinkrustationen in Geweben und tragen überdies zur Reinigungsleistung bei.Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO 3 ) n and orthophosphoric acid H 3 PO 4 in addition to higher-molecular representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts and lime incrustations in fabrics and also contribute to the cleaning performance.

Als Ersatz für Gerüststoffe der Klasse der Phosphate enthalten die wie hierin beschriebenen Geschirrspülmittel mindestens eine Zuckersäure und des Weiteren mindestens eine Aminocarbonsäure oder mindestens ein Salz einer Aminocarbonsäure. Dies bedeutet, dass die erfindungsgemäßen Geschirrspülmittel im Wesentlichen phosphatfrei sind, d.h. Phosphat in Mengen weniger 1 Gew.-%, vorzugsweise weniger 0,1 Gew.-% enthalten, und/oder kein bewusst zugesetztes Phosphat enthalten.As a substitute for builders of the phosphate class, the dishwashing detergents as described herein contain at least one sugar acid and also at least one amino carboxylic acid or at least one salt of an amino carboxylic acid. This means that the dishwashing detergents according to the invention are essentially phosphate-free, i.e. contain phosphate in amounts of less than 1% by weight, preferably less than 0.1% by weight, and/or contain no deliberately added phosphate.

Der Begriff "Zuckersäure", wie hierin verwendet, bezeichnet dabei eine Polyhydroxycarbonsäure, die das Oxidationsprodukt eines Monosaccharids ist, und schließt sowohl die D- als auch die L-Konfiguration mit ein. Bei den Salzen einer Zuckersäure handelt es sich, im Kontext der vorliegenden Erfindung, um die Alkali- und Erdalkalimetallsalze, vorzugsweise die Alkalimetallsalze, insbesondere die Natrium- und Kaliumsalze einer Zuckersäure.The term "sugar acid" as used herein refers to a polyhydroxycarboxylic acid which is the oxidation product of a monosaccharide and includes both the D and the L configuration. In the context of the present invention, the salts of a sugar acid are the alkali and alkaline earth metal salts, preferably the alkali metal salts, in particular the sodium and potassium salts of a sugar acid.

In verschiedenen Ausführungsformen ist die in den wie hierin beschriebenen Mitteln enthaltenen mindestens eine Zuckersäure ausgewählt aus der Gruppe bestehend aus Aldonsäuren, Uronsäure, Aldarsäuren und Ketoaldonsäuren.In various embodiments, the at least one sugar acid contained in the compositions as described herein is selected from the group consisting of aldonic acids, uronic acids, aldaric acids and ketoaldonic acids.

In verschiedenen Ausführungsformen ist die mindestens eine Zuckersäure ausgewählt aus der Gruppe bestehend aus Gluconsäure, Glucuronsäure, Glucoheptonsäure, Glucarsäure, Weinsäure, Mucinsäure, Gulonsäure, Galacturonsäure, Iduronsäure, Mannonsäure und 2-Oxo-D-gluconsäure.In various embodiments, the at least one sugar acid is selected from the group consisting of gluconic acid, glucuronic acid, glucoheptonic acid, glucaric acid, tartaric acid, mucinic acid, gulonic acid, galacturonic acid, iduronic acid, mannonic acid and 2-oxo-D-gluconic acid.

In bevorzugten Ausführungsformen handelt es sich bei der mindestens einen Zuckersäure um Glucarsäure, insbesondere D-Glucarsäure (2S,3S,4S,5R)-2,3,4,5-tetrahydroxyhexandisäure).In preferred embodiments, the at least one sugar acid is glucaric acid, in particular D -glucaric acid (2S,3S, 4S , 5R ) -2,3,4,5 -tetrahydroxyhexanedioic acid).

Die erfindungsgemäßen Mittel enthalten die mindestens eine Zuckersäure in Mengen von 0,1 bis 30 Gew.-%, vorzugsweise 1 bis 25 Gew.-% und insbesondere 5 bis 20 Gew.-%, wobei die Zuckersäure und gegebenenfalls ein Salz einer Zuckersäure in einer Gesamtmenge von 0,1 bis 30 Gew.-%, vorzugsweise 1 bis 25 Gew.-%, bezogen auf das Gesamtgewicht des Geschirrspülmittels, enthalten sind.The agents according to the invention contain at least one sugar acid in amounts of 0.1 to 30% by weight, preferably 1 to 25% by weight and in particular 5 to 20% by weight, the sugar acid and optionally a salt of a sugar acid in a Total amount of 0.1 to 30 wt .-%, preferably 1 to 25 wt .-%, based on the total weight of the dishwashing detergent contained.

Der Begriff "Aminocarbonsäure", wie hierin verwendet, bezeichnet eine Aminosäure oder ein Derivat einer Aminosäure. Besonders bevorzugte Vertreter der Klasse der Aminocarbonsäuren sind Methylglycindiessigsäure (MGDA) oder ihre Salze sowie Glutamindiessigsäure (GLDA) oder ihre Salze oder Ethylendiamindiessigsäure oder ihre Salze (EDDS). Ebenfalls geeignet sind Iminodibernsteinsäure (IDS) und Iminodiessigsäure (IDA). Bei den Salzen einer Aminocarbonsäure handelt es sich, im Kontext der vorliegenden Erfindung, um die Alkali- und Erdalkalimetallsalze, vorzugsweise die Alkalimetallsalze, insbesondere die Natrium- und Kaliumsalze einer Aminocarbonsäure.The term "aminocarboxylic acid" as used herein refers to an amino acid or a derivative of an amino acid. Particularly preferred representatives of the class of aminocarboxylic acids are methylglycinediacetic acid (MGDA) or its salts and glutaminediacetic acid (GLDA) or its salts or ethylenediaminediacetic acid or its salts (EDDS). Also suitable are iminodisuccinic acid (IDS) and iminodiacetic acid (IDA). In the context of the present invention, the salts of an aminocarboxylic acid are the alkali and alkaline earth metal salts, preferably the alkali metal salts, in particular the sodium and potassium salts, of an aminocarboxylic acid.

In verschiedenen Ausführungsformen ist die in den wie hierin beschriebenen Mitteln enthaltene mindestens eine Aminocarbonsäure ausgewählt aus der Gruppe bestehend aus Methylglycindiessigsäure (MGDA), Glutamindiessigsäure (GLDA), Ethylendiamindiessigsäure (EDDS), Iminodibernsteinsäure (IDS) und Iminodiessigsäure (IDA).In various embodiments, the at least one aminocarboxylic acid contained in the agents as described herein is selected from the group consisting of methylglycine diacetic acid (MGDA), glutamic diacetic acid (GLDA), ethylenediamine diacetic acid (EDDS), iminodisuccinic acid (IDS) and iminodiacetic acid (IDA).

In verschiedenen Ausführungsformen handelt es sich bei der mindestens einen Aminocarbonsäure um MGDA.In various embodiments, the at least one amino carboxylic acid is MGDA.

Die erfindungsgemäßen Mittel enthalten die mindestens eine Aminocarbonsäure oder das mindestens eine Salz einer Aminocarbonsäure in Mengen von 0,1 bis 30 Gew.-%, vorzugsweise 1 bis 25 Gew.-% und insbesondere 5 bis 20 Gew.-%.The agents according to the invention contain at least one aminocarboxylic acid or at least one salt of an aminocarboxylic acid in amounts of 0.1 to 30% by weight, preferably 1 to 25% by weight and in particular 5 to 20% by weight.

In verschiedenen Ausführungsformen sind die mindestens eine Zuckersäure und die mindestens eine Aminocarbonsäure zusammen in einer Menge von 0,1 bis 40 Gew.-%, insbesondere 5 bis 30 Gew.-%, bezogen auf das Gesamtgewicht des Geschirrspülmittels, in dem Geschirrspülmittel enthalten.In various embodiments, the at least one sugar acid and the at least one aminocarboxylic acid are present together in the dishwashing detergent in an amount of 0.1 to 40% by weight, in particular 5 to 30% by weight, based on the total weight of the dishwashing detergent.

In verschiedenen Ausführungsformen sind die mindestens eine Zuckersäure und die mindestens eine Aminocarbonsäure in einem Massenverhältnis von 80:20 bis 20:80, insbesondere 50:50 in dem Geschirrspülmittel enthalten.In various embodiments, the at least one sugar acid and the at least one aminocarboxylic acid are present in the dishwashing detergent in a mass ratio of from 80:20 to 20:80, in particular 50:50.

Die erfindungsgemäßen Mittel können mindestens einen, vorzugsweise mindestens zwei weitere Bestandteil enthalten, vorzugsweise ausgewählt aus der Gruppe bestehend aus Tensiden, insbesondere nichtionischen Tensiden und/oder anionischen Tensiden, weiteren Gerüststoffen, Enzymen, Verdickern, Sequestrierungsmitteln, Elektrolyten, Korrosionsinhibitoren, insbesondere Silberschutzmitteln, Glaskorrosionsinhibitoren, Schauminhibitoren, Farbstoffen, Duftstoffen, Bitterstoffen, antimikrobiellen Wirkstoffen und Desintegrationshilfsmitteln.The agents according to the invention can contain at least one, preferably at least two, further components, preferably selected from the group consisting of surfactants, in particular nonionic surfactants and/or anionic surfactants, other 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.

Die hierin beschriebenen Mittel enthalten vorzugsweise mindestens ein nichtionisches Tensid. Als nichtionische Tenside können alle dem Fachmann bekannten nichtionischen Tenside eingesetzt werden.The compositions described herein preferably contain at least one nonionic surfactant. All nonionic surfactants known to those skilled in the art can be used as nonionic surfactants.

Als nichtionische Tenside eignen sich beispielsweise Alkylglykoside der allgemeinen Formel RO(G)x, in der R einem primären geradkettigen oder methylverzweigten, insbesondere in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen entspricht und G das Symbol ist, das für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Oligomerisierungsgrad x, der die Verteilung von Monoglykosiden und Oligoglykosiden angibt, ist eine beliebige Zahl zwischen 1 und 10; vorzugsweise liegt x bei 1,2 bis 1,4.Examples of suitable nonionic surfactants are alkyl glycosides of the general formula RO(G) x , where R is a primary straight-chain or methyl-branched aliphatic radical, especially methyl-branched in the 2-position, having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol is, which is a glucose unit with 5 or 6 carbon 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 from 1.2 to 1.4.

Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealkanolamide können geeignet sein. Die Menge dieser nichtionischen Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon.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 alkanolamide type can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of it.

Weitere geeignete Tenside sind die als PHFA bekannten Polyhydroxyfettsäureamide.Other suitable surfactants are the polyhydroxy fatty acid amides known as PHFA.

Bevorzugt werden allerdings schwachschäumende nichtionische Tenside eingesetzt, insbesondere alkoxylierte, vor allem ethoxylierte, schwachschäumende nichtionische Tenside. Mit besonderem Vorzug enthalten die maschinellen Geschirrspülmittel nichtionische Tenside aus der Gruppe der alkoxylierten Alkohole.However, preference is given to using low-foaming nonionic surfactants, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants. The machine dishwashing detergents particularly preferably contain nonionic surfactants from the group of alkoxylated alcohols.

Eine Klasse einsetzbarer nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden eingesetzt werden können, sind demnach alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette.One class of nonionic surfactants that can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants is accordingly alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain.

Bevorzugt einzusetzende Tenside stammen aus den Gruppen der ethoxylierten primären Alkohole und Mischungen dieser Tenside mit strukturell komplizierter aufgebauten Tensiden wie Polyoxypropylen/Polyoxyethylen/Polyoxypropylen ((PO/EO/PO)-Tenside). Solche (PO/EO/PO)-Niotenside zeichnen sich durch gute Schaumkontrolle aus.Surfactants to be used with preference come from the groups of ethoxylated primary alcohols and mixtures of these surfactants with surfactants with a more complex structure such as Polyoxypropylene/polyoxyethylene/polyoxypropylene ((PO/EO/PO) surfactants). Such (PO/EO/PO) nonionic surfactants are distinguished by good foam control.

Besonders bevorzugte Niotenside sind solche, welche alternierende Ethylenoxid- und Alkylenoxideinheiten aufweisen. Unter diesen sind wiederum Tenside mit EO-AO-EO-AO-Blöcken bevorzugt, wobei jeweils eine bis zehn EO- bzw. AO-Gruppen aneinander gebunden sind, bevor ein Block aus den jeweils anderen Gruppen folgt. Hier sind nichtionische Tenside der allgemeinen Formel

Figure imgb0001
bevorzugt, in der R1 für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C6-24-Alkyl- oder -Alkenylrest steht; jede Gruppe R2 bzw. R3 unabhängig voneinander ausgewählt ist aus -CH3, -CH2CH3, -CH2CH2-CH3, CH(CH3)2 und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.Particularly preferred nonionic surfactants are those which have alternating ethylene oxide and alkylene oxide units. Among these, preference is in turn given to surfactants with EO-AO-EO-AO blocks, in which case one to ten EO or AO groups are bonded to one another before a block of the other groups follows. Here are nonionic surfactants of the general formula
Figure imgb0001
 preferably 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 are independent of one another are integers from 1 to 6.

Somit sind insbesondere nichtionische Tenside bevorzugt, die einen C9-15-Alkylrest mit 1 bis 4 Ethylenoxideinheiten, gefolgt von 1 bis 4 Propylenoxideinheiten, gefolgt von 1 bis 4 Ethylenoxideinheiten, gefolgt von 1 bis 4 Propylenoxideinheiten aufweisen.Thus, particularly preferred are nonionic surfactants having a C 9-15 alkyl radical containing 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.

Bevorzugte nichtionische Tenside sind hierbei solche der allgemeinen Formel

        R1-CH(OH)CH2O-(AO)w-(A'O)x-(A"O)y-(A‴O)z-R2,

in der

  • R1 für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C6-24-Alkyl- oder -Alkenylrest steht;
  • R2 für H oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
  • A, A', A" und A'" unabhängig voneinander für einen Rest aus der Gruppe -CH2CH2, -CH2CH2-CH2, -CH2-CH(CH3), -CH2-CH2-CH2-CH2, -CH2-CH(CH3)-CH2-, - CH2-CH(CH2-CH3) stehen,
  • w, x, y und z für Werte zwischen 0,5 und 120 stehen, wobei x, y und/oder z auch 0 sein können.
Preferred nonionic surfactants here are those of the general formula

R 1 -CH(OH)CH 2 O-(AO) w -(A'O) x -(A"O) y -(A‴O) z -R 2 ,

in the
  • R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical;
  • R 2 is H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
  • A, A', A" and A'" independently represent a radical from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH(CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH(CH 3 )-CH 2 -, -CH 2 -CH(CH 2 -CH 3 ),
  • w, x, y and z stand for values between 0.5 and 120, where x, y and/or z can also be 0.

Bevorzugt werden insbesondere solche endgruppenverschlossene, poly(oxyalkylierten) Niotenside, die, gemäß der Formel R1O[CH2CH2O]xCH2CH(OH)R2, neben einem Rest R1, welcher für lineare oder verzweigte, gesättigte oder ungesättigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 2 bis 30 Kohlenstoffatomen, vorzugsweise mit 4 bis 22 Kohlenstoffatomen steht, weiterhin einen linearen oder verzweigten, gesättigten oder ungesättigten, aliphatischen oder aromatischen Kohlenwasserstoffrest R2 mit 1 bis 30 Kohlenstoffatomen aufweisen, wobei x für Werte zwischen 1 und 90, vorzugsweise für Werte zwischen 30 und 80 und insbesondere für Werte zwischen 30 und 60 steht.Preference is given in particular to those end-capped, poly(oxyalkylated) nonionic surfactants which, according to the formula R 1 O[CH 2 CH 2 O] x CH 2 CH(OH)R 2 , in addition to a radical R 1 , which represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore one linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having 1 to 30 carbon atoms, where x is a value between 1 and 90, preferably a value between 30 and 80 and in particular a value between 30 and 60.

Besonders bevorzugt sind Tenside der Formel R1O[CH2CH(CH3)O]x[CH2CH2O]yCH2CH(OH)R2, in der R1 für einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 4 bis 18 Kohlenstoffatomen oder Mischungen hieraus steht, R2 einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen oder Mischungen hieraus bezeichnet und x für Werte zwischen 0,5 und 1,5 sowie y für einen Wert von mindestens 15 steht.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 are particularly preferred, in which R 1 represents a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x has values between 0.5 and 1.5 and y has a value of at least 15.

Zur Gruppe dieser nichtionischen Tenside zählen beispielsweise die C2-26 Fettalkohol-(PO)1-(EO)15-40-2-hydroxyalkylether, insbesondere auch die C8-10 Fettalkohol-(PO)1-(EO)22-2-hydroxydecylether. Besonders bevorzugt werden weiterhin solche endgruppenverschlossene poly(oxyalkylierten) Niotenside der Formel R1O[CH2CH2O]x[CH2CH(R3)O]yCH2CH(OH)R2, in der R1 und R2 unabhängig voneinander für einen linearen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht, R3 unabhängig voneinander ausgewählt ist aus -CH3, -CH2CH3, -CH2CH2-CH3, -CH(CH3)2, vorzugsweise jedoch für -CH3 steht, und x und y unabhängig voneinander für Werte zwischen 1 und 32 stehen, wobei Niotenside mit R3 = -CH3 und Werten für x von 15 bis 32 und y von 0,5 und 1,5 ganz besonders bevorzugt sind.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 -hydroxydecyl ether. Particular preference is also given to end-capped poly(oxyalkylated) nonionic surfactants of the formula R 1 O[CH 2 CH 2 O] x [CH 2 CH(R 3 )O] y CH 2 CH(OH)R 2 , in which R 1 and R 2 independently of one another represents a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R 3 is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , -CH(CH 3 ) 2 , but preferably represents -CH 3 , and x and y independently represent values between 1 and 32, where nonionic surfactants with R 3 = -CH 3 and values for x from 15 to 32 and y of 0.5 and 1.5 are most preferred.

Weitere bevorzugt einsetzbare Niotenside sind die endgruppenverschlossenen poly(oxyalkylierten) Niotenside der Formel R1O[CH2CH(R3)O]x[CH2]kCH(OH)[CH2]jOR2, in der R1 und R2 für lineare oder verzweigte, gesättigte oder ungesättigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 1 bis 30 Kohlenstoffatomen stehen, R3 für H oder einen Methyl-, Ethyl-, n-Propyl-, iso-Propyl, n-Butyl-, 2-Butyl- oder 2-Methyl-2-Butylrest steht, x für Werte zwischen 1 und 30, k und j für Werte zwischen 1 und 12, vorzugsweise zwischen 1 und 5 stehen. Wenn der Wert x ≥ 2 ist, kann jedes R3 in der oben stehenden Formel R1O[CH2CH(R3)O]x[CH2]kCH(OH)[CH2]jOR2 unterschiedlich sein. R1 und R2 sind vorzugsweise lineare oder verzweigte, gesättigte oder ungesättigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 6 bis 22 Kohlenstoffatomen, wobei Reste mit 8 bis 18 C-Atomen besonders bevorzugt sind. Für den Rest R3 sind H, -CH3 oder -CH2CH3 besonders bevorzugt. Besonders bevorzugte Werte für x liegen im Bereich von 1 bis 20, insbesondere von 6 bis 15.Other preferably usable 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 represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 represents H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2- butyl or 2-methyl-2-butyl radical, x is between 1 and 30, k and j are between 1 and 12, preferably between 1 and 5. When the value of x ≥ 2, each R 3 in the above formula R 1 O[CH 2 CH(R 3 )O] x [CH 2 ] k CH(OH)[CH 2 ] j OR 2 can 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, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH 3 or -CH 2 CH 3 are particularly preferred for the radical R 3 . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

Wie vorstehend beschrieben, kann jedes R3 in der oben stehenden Formel unterschiedlich sein, falls x ≥ 2 ist. Hierdurch kann die Alkylenoxideinheit in der eckigen Klammer variiert werden. Steht x beispielsweise für 3, kann der Rest R3 ausgewählt werden, um Ethylenoxid- (R3 = H) oder Propylenoxid- (R3 = CH3) Einheiten zu bilden, die in jedweder Reihenfolge aneinandergefügt sein können, beispielsweise (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO) und (PO)(PO)(PO). Der Wert 3 für x ist hierbei beispielhaft gewählt worden und kann durchaus größer sein, wobei die Variationsbreite mit steigenden x-Werten zunimmt und beispielsweise eine große Anzahl (EO)-Gruppen, kombiniert mit einer geringen Anzahl (PO)-Gruppen einschließt, oder umgekehrt.As described above, when x ≥ 2, each R 3 in the above formula may be different. This allows the alkylene oxide unit in the square brackets to be varied. For example, when x is 3, the R 3 group can be selected to form ethylene oxide (R 3 = H) or propylene oxide (R 3 = CH 3 ) units attached in any order e.g. (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)( EO) and (PO)(PO)(PO). The value 3 for x was selected here as an example and can certainly be larger, with the range of variation increasing with increasing x values and including, for example, a large number of (EO) groups combined with a small number of (PO) groups, or vice versa .

Besonders bevorzugte endgruppenverschlossene poly(oxyalkylierte) Alkohole der oben stehenden Formel weisen Werte von k = 1 und j = 1 auf, so dass sich die vorstehende Formel zu R1O[CH2CH(R3)O]xCH2CH(OH)CH2OR2 vereinfacht. In der letztgenannten Formel sind R1, R2 und R3 wie oben definiert und x steht für Zahlen von 1 bis 30, vorzugsweise von 1 bis 20 und insbesondere von 6 bis 18. Besonders bevorzugt sind Tenside, bei denen die Reste R1 und R2 9 bis 14 C-Atome aufweisen, R3 für H steht und x Werte von 6 bis 15 annimmt.Particularly preferred endcapped poly(oxyalkylated) alcohols of the above formula have values of k=1 and j=1 such that the above formula translates to R 1 O[CH 2 CH(R 3 )O] x CH 2 CH(OH )CH 2 OR 2 simplified. In the latter formula, R 1 , R 2 and R 3 are as defined above and x is a number from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Surfactants in which the radicals R 1 and R 2 has 9 to 14 carbon atoms, R 3 is H and x has values from 6 to 15.

Als besonders wirkungsvoll haben sich schließlich die nichtionischen Tenside der allgemeinen Formel R1-CH(OH)CH2O-(AO)w-R2 erwiesen, in der

  • R1 für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C6-24-Alkyl- oder-Alkenylrest steht;
  • R2 für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
  • A für einen Rest aus der Gruppe CH2CH2, CH2CH2CH2, CH2CH(CH3), vorzugsweise für CH2CH2 steht, und
  • w für Werte zwischen 1 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht
Finally, the nonionic surfactants of the general formula R 1 -CH(OH)CH 2 O-(AO) w -R 2 have proven to be particularly effective
  • R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical;
  • R 2 represents a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
  • A is a radical from the group CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH(CH 3 ), preferably CH 2 CH 2 , and
  • w is between 1 and 120, preferably 10 to 80, especially 20 to 40

Zur Gruppe dieser nichtionischen Tenside zählen beispielsweise die C4-22 Fettalkohol-(EO)10-80-2-hydroxyalkylether, insbesondere auch die C8-12 Fettalkohol-(EO)22-2-hydroxydecylether und die C4-22 Fettalkohol-(EO)40-80-2-hydroxyalkylether.The group of these nonionic surfactants includes, for example, the C 4-22 fatty alcohol (EO) 10-80 -2-hydroxyalkyl ethers, in particular the C 8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ether and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ether.

In verschiedenen Ausführungsformen der Erfindung können anstelle der oben definierten endgruppenverschlossenen Hydroxymischether auch die entsprechenden nicht endgruppenverschlossenen Hydroxymischether eingesetzt werden. Diese können den obigen Formeln genügen, wobei R2 aber Wasserstoff ist und R1, R3, A, A', A", A‴, w, x, y und z wie oben definiert sind.In various embodiments of the invention, instead of the end-capped hydroxy mixed ethers defined above, it is also possible to use the corresponding non-end-capped hydroxy mixed ethers. These may satisfy the formulas above except that R 2 is hydrogen and R 1 , R 3 , A, A', A", A‴, w, x, y and z are as defined above.

Die hierin beschriebenen Mittel, die mindestens ein nichtionisches Tensid, vorzugsweise ein nichtionisches Tensid aus der Gruppe der Hydroxymischether, umfassen, enthalten das Tensid in verschiedenen Ausführungsformen in einer Menge bezogen auf das Gesamtgewicht des Mittels von mindestens 2 Gew.%, vorzugsweise mindestens 5 Gew.%. Die absolut pro Anwendung eingesetzten Mengen können beispielsweise im Bereich von 0,5-10 g/job, vorzugsweise im Bereich von 1-5 g/job liegen.The agents 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 agent of at least 2% by weight, preferably at least 5% by weight. %. The absolute ones used per application Amounts can be, for example, in the range of 0.5-10 g/job, preferably in the range of 1-5 g/job.

Als anionische Tenside eignen sich in den Geschirrspülmitteln alle anionischen oberflächenaktiven Stoffe. Diese sind gekennzeichnet durch eine wasserlöslich machende, anionische Gruppe wie z. B. eine Carboxylat-, Sulfat-, Sulfonat- oder Phosphat-Gruppe und eine lipophile Alkylgruppe mit etwa 8 bis 30 C-Atomen. Zusätzlich können im Molekül Glykol- oder Polyglykolether-Gruppen, Ester-, Ether-und Amidgruppen sowie Hydroxylgruppen enthalten sein. Geeignete anionische Tenside liegen vorzugsweise in Form der Natrium-, Kalium- und Ammonium- sowie der Mono-, Di- und Trialkanolammoniumsalze mit 2 bis 4 C-Atomen in der Alkanolgruppe vor.All anionic surface-active substances are suitable as anionic surfactants in dishwashing detergents. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups. Suitable anionic surfactants are preferably present in the form of the sodium, potassium and ammonium salts and the mono-, di- and trialkanolammonium salts having 2 to 4 carbon atoms in the alkanol group.

Bevorzugte anionische Tenside sind Alkylsulfate, Alkylpolyglykolethersulfate und Ethercarbonsäuren mit 10 bis 18 C-Atomen in der Alkylgruppe und bis zu 12 Glykolethergruppen im Molekül.Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule.

Die Geschirrspülmittel enthalten daher in verschiedenen Ausführungsformen mindestens ein Tensid der Formel R4-O-(AO)n-SO3- X+.In various embodiments, the dishwashing detergents therefore contain at least one surfactant of the formula R 4 —O-(AO) n —SO 3 — X + .

In dieser Formel steht R4 für einen linearen oder verzweigten, substituierten oder unsubstituierten Alkyl-, Aryl- oder Alkylarylrest, vorzugsweise für einen linearen, unsubstituierten Alkylrest, besonders bevorzugt für einen Fettalkoholrest. Bevorzugte Reste R1 sind ausgewählt aus Decyl-, Undecyl-, Dodecyl-, Tridecyl-, Tetradecyl, Pentadecyl-, Hexadecyl-, Heptadecyl-, Octadecyl-, Nonadecyl-, Eicosylresten und deren Mischungen, wobei die Vertreter mit gerader Anzahl an C-Atomen bevorzugt sind. Besonders bevorzugte Reste R1 sind abgeleitet von C12-C18-Fettalkoholen, beispielsweise von Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder von C10-C20-Oxoalkoholen.In this formula, R 4 is a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical, preferably a linear, unsubstituted alkyl radical, particularly 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, the representatives with an even number of C atoms are preferred. Particularly preferred radicals R 1 are derived from C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C 10 -C 20 oxo alcohols.

AO steht für eine Ethylenoxid- (EO) oder Propylenoxid- (PO) Gruppierung, vorzugsweise für eine Ethylenoxidgruppierung. Der Index n steht für eine ganze Zahl von 1 bis 50, vorzugsweise von 1 bis 20 und insbesondere von 2 bis 10. Ganz besonders bevorzugt steht n für die Zahlen 2, 3, 4, 5, 6, 7 oder 8. X steht für ein einwertiges Kation oder den n-ten Teil eines n-wertigen Kations, bevorzugt sind dabei die Alkalimetallionen und darunter Na+ oder K+, wobei Na+ äußerst bevorzugt ist. Weitere Kationen X+ können ausgewählt sein aus NH4 +, ½ Zn2+,½ Mg2+,½ Ca2+,½ Mn2+, und deren Mischungen.AO stands for an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably for an ethylene oxide moiety. The index n is an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. n is very particularly preferably the numbers 2, 3, 4, 5, 6, 7 or 8. X is a monovalent cation or the nth part of an n-valent cation, preference being given to the alkali metal ions and including Na + or K + , with Na + being extremely preferred. Further cations X + can be selected from NH 4 + , ½ Zn 2+ , ½ Mg 2+ , ½ Ca 2+ , ½ Mn 2+ , and mixtures thereof.

Besonders bevorzugte anionische Tenside werden ausgewählt aus Fettalkoholethersulfaten der Formel A-1

Figure imgb0002
mit k = 11 bis 19, n = 2, 3, 4, 5, 6, 7 oder 8. Ganz besonders bevorzugte Vertreter sind Na-C12-14 Fettalkoholethersulfate mit 2 EO (k = 11-13, n = 2 in Formel A-1).Particularly preferred anionic surfactants are selected from fatty alcohol ether sulfates of formula A-1
Figure imgb0002
 with k = 11 to 19, n = 2, 3, 4, 5, 6, 7 or 8. Very particularly preferred representatives are Na-C 12-14 fatty alcohol ether sulfates with 2 EO (k = 11-13, n = 2 in formula A-1).

Die Mittel können ferner zusätzlich oder alternativ mindestens ein Tensid der Formel R5-A-SO3- Y+ enthalten.The agents can also additionally or alternatively contain at least one surfactant of the formula R 5 -A-SO 3 - Y + .

In dieser Formel steht R5 für einen linearen oder verzweigten, substituierten oder unsubstituierten Alkyl-, Aryl- oder Alkylarylrest und die Gruppierung -A- für -O- oder eine chemische Bindung. In anderen Worten lassen sich durch die vorstehende Formel Sulfat- (A = O) oder Sulfonat- (A = chemische Bindung) -tenside beschreiben. In Abhängigkeit von der Wahl der Gruppierung A sind bestimmte Reste R5 bevorzugt. Bei den Sulfattensiden (A = O) steht R5 vorzugsweise für einen linearen, unsubstituierten Alkylrest, besonders bevorzugt für einen Fettalkoholrest. Bevorzugte Reste R5 sind ausgewählt aus Decyl-, Undecyl-, Dodecyl-, Tridecyl-, Tetradecyl, Pentadecyl-, Hexadecyl-, Heptadecyl-, Octadecyl-, Nonadecyl-, Eicosylresten und deren Mischungen, wobei die Vertreter mit gerader Anzahl an C-Atomen bevorzugt sind. Besonders bevorzugte Reste R5 sind abgeleitet von C12-C18-Fettalkoholen, beispielsweise von Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder von C10-C20-Oxoalkoholen. Y steht für ein einwertiges Kation oder den n-ten Teil eines n-wertigen Kations, bevorzugt sind dabei die Alkalimetallionen und darunter Na+ oder K+, wobei Na+ äußerst bevorzugt ist. Weitere Kationen Y+ können ausgewählt sein aus NH4 +, ½ Zn2+,½ Mg2+,½ Ca2+,½ Mn2+, und deren Mischungen.In this formula, R 5 represents a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical and the group -A- represents -O- or a chemical bond. In other words, the above formula can be used to describe sulfate (A=O) or sulfonate (A=chemical bond) surfactants. Depending on the choice of grouping A, certain radicals R 5 are preferred. In the sulfate surfactants (AO), R 5 is preferably a linear, unsubstituted alkyl radical, particularly 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, the representatives with an even number of C atoms are preferred. Particularly preferred radicals R 5 are derived from C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C 10 -C 20 oxo alcohols. Y is a monovalent cation or the nth part of an n-valent cation, preference being given to the alkali metal ions and including Na + or K + , with Na + being extremely preferred. Further cations Y+ can be selected from NH 4+ , ½ Zn 2+ , ½ Mg 2+ , ½ Ca 2+ , ½ Mn 2+ , and mixtures thereof .

Solche besonders bevorzugten Tenside sind ausgewählt aus Fettalkoholsulfaten der Formel

Figure imgb0003
mit k = 11 bis 19. Ganz besonders bevorzugte Vertreter sind Na-C12-14 Fettalkoholsulfate (k = 11-13).Such particularly preferred surfactants are selected from fatty alcohol sulfates of the formula
Figure imgb0003
 with k=11 to 19. Very particularly preferred representatives are Na—C 12-14 fatty alcohol sulfates (k=11-13).

Bei den Sulfonattensiden (A = chemische Bindung) steht R5 vorzugsweise für einen linearen oder verzweigten unsubstituierten Alkylarylrest. Auch hier steht X für ein einwertiges Kation oder den n-ten Teil eines n-wertigen Kations, bevorzugt sind dabei die Alkalimetallionen und darunter Na+ oder K+, wobei Na+ äußerst bevorzugt ist. Weitere Kationen X+ können ausgewählt sein aus NH4 +, ½ Zn2+,½ Mg2+,½ Ca2+,½ Mn2+, und deren Mischungen. Solche Tenside können ausgewählt sein aus linearen oder verzweigten Alkylbenzolsulfonaten.In the case of the sulfonate surfactants (A=chemical bond), R 5 preferably represents a linear or branched, unsubstituted alkylaryl radical. Here, too, X is a monovalent cation or the nth part of an n-valent cation, preference being given to the alkali metal ions and including Na + or K + , with Na + being extremely preferred. Further cations X+ can be selected from NH 4+ , ½ Zn 2+ , ½ Mg 2+ , ½ Ca 2+ , ½ Mn 2+ , and mixtures thereof . Such surfactants can be selected from linear or branched alkyl benzene sulfonates.

An Stelle der genannten Tenside oder in Verbindung mit ihnen können auch kationische und/oder amphotere Tenside, wie Betaine oder quartäre Ammoniumverbindungen, eingesetzt werden. Es ist allerdings bevorzugt, dass keine kationischen und/oder amphoteren Tenside eingesetzt werden. Weitere Gerüststoffe, die in dem Geschirrspülmittel enthalten sein können, sind insbesondere Silikate, Aluminiumsilikate (insbesondere Zeolithe), Carbonate und organische Di- und Polycarbonsäuren bzw. deren Salze. Mischungen dieser Stoffe sind natürlich ebenfalls einsetzbar.Cationic and/or amphoteric surfactants, such as betaines or quaternary ammonium compounds, can also be used instead of the surfactants mentioned or in conjunction with them. However, it is preferred that no cationic and/or amphoteric surfactants are used. Further builders that can be contained in the dishwashing detergent are, in particular, silicates, aluminum silicates (especially zeolites), carbonates and organic di- and polycarboxylic acids or their salts. Mixtures of these substances can of course also be used.

Es können beispielsweise kristalline schichtförmige Silikate der allgemeinen Formel NaMSixO2x+1 · y H2O eingesetzt werden, worin M Natrium oder Wasserstoff darstellt, x eine Zahl von 1,9 bis 22, vorzugsweise von 1,9 bis 4, wobei besonders bevorzugte Werte für x 2, 3 oder 4 sind, und y für eine Zahl von 0 bis 33, vorzugsweise von 0 bis 20 steht. Die kristallinen schichtförmigen Silikate der Formel NaMSixO2x+1 · y H2O werden beispielsweise von der Firma Clariant GmbH (Deutschland) unter dem Handelsnamen Na-SKS vertrieben. Beispiele für diese Silikate sind Na-SKS-1 (Na2Si22O45 · x H2O, Kenyait), Na-SKS-2 (Na2Si14O29 · x H2O, Magadiit), Na-SKS-3 (Na2Si8O17 · x H2O) oder Na-SKS-4 (Na2Si4O9 · x H2O, Makatit). Für die Zwecke der vorliegenden Erfindung besonders geeignet sind kristalline Schichtsilikate der Formel NaMSixO2x+1 · y H2O, in denen x für 2 steht. Insbesondere sind sowohl ß- als auch δ-Natriumdisilikate Na2Si2O5 · y H2O sowie weiterhin vor allem Na-SKS-5 (α-Na2Si2O5), Na-SKS-7 (ß-Na2Si2O5, Natrosilit), Na-SKS-9 (NaHSi2O5 · H2O), Na-SKS-10 (NaHSi2O5 · 3 H2O, Kanemit), Na-SKS-11 (t-Na2Si2O5) und Na-SKS-13 (NaHSi2O5), insbesondere aber Na-SKS-6 (δ-Na2Si2O5) bevorzugt.For example, crystalline layered silicates of the general formula NaMSi x O 2x+1 · y H 2 O can be used, where M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particular 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 layered silicates of the formula NaMSi x O 2x+1 · y H 2 O are marketed, for example, by Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na 2 Si 22 O 45 .xH 2 O, kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 .xH 2 O, magadiite), Na-SKS -3 (Na 2 Si 8 O 17 x H 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 x H 2 O, makatite). Crystalline phyllosilicates of the formula NaMSi x O 2x+1 .yH 2 O, in which x is 2, are particularly suitable for the purposes of the present invention. In particular, both ß- and δ-sodium disilicates are Na 2 Si 2 O 5 · y H 2 O and, above all, Na-SKS-5 (α-Na 2 Si 2 O 5 ), Na-SKS-7 (ß-Na 2 Si 2 O 5 , Natrosilit), 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 (δ-Na 2 Si 2 O 5 ) is preferred.

Maschinelle Geschirrspülmittel enthalten typischerweise einen Gewichtsanteil des kristallinen schichtförmigen Silikats der Formel NaMSixO2x+1 · y H2O von 0,1 bis 20 Gew.-%, bevorzugt von 0,2 bis 15 Gew.-% und insbesondere von 0,4 bis 10 Gew.-%, jeweils bezogen auf das Gesamtgewicht dieser Mittel.Automatic dishwashing detergents typically contain a proportion by weight of the crystalline layered silicate of the formula NaMSi x O 2x+1 y H 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% by weight, based in each case on the total weight of these agents.

Einsetzbar sind auch amorphe Natriumsilikate mit einem Modul Na2O:SiO2 von 1:2 bis 1:3,3, vorzugsweise von 1:2 bis 1:2,8 und insbesondere von 1:2 bis 1:2,6, welche vorzugsweise löseverzögert sind und Sekundärwascheigenschaften aufweisen. Die Löseverzögerung gegenüber herkömmlichen amorphen Natriumsilikaten kann dabei auf verschiedene Weise, beispielsweise durch Oberflächenbehandlung, Compoundierung, Kompaktierung/Verdichtung oder durch Übertrocknung hervorgerufen worden sein. Im Rahmen dieser Erfindung wird unter dem Begriff "amorph" verstanden, dass die Silikate bei Röntgenbeugungsexperimenten keine scharfen Röntgenreflexe liefern, wie sie für kristalline Substanzen typisch sind, sondern allenfalls ein oder mehrere Maxima der gestreuten Röntgenstrahlung, die eine Breite von mehreren Gradeinheiten des Beugungswinkels aufweisen, hervorrufen.Amorphous sodium silicates with an Na 2 O:SiO 2 modulus of 1:2 to 1:3.3, preferably of 1:2 to 1:2.8 and in particular of 1:2 to 1:2.6, can also be used are preferably delayed in dissolution and have secondary washing properties. The delay in dissolving compared to conventional amorphous sodium silicates can have been brought about in various ways, for example by surface treatment, compounding, compacting/densification or by overdrying. In the context of this invention, the term "amorphous" means that the silicates do not provide sharp X-ray reflections in X-ray diffraction experiments, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle , cause.

Im Rahmen der vorliegenden Erfindung ist es bevorzugt, dass diese(s) Silikat(e), vorzugsweise Alkalisilikate, besonders bevorzugt kristalline oder amorphe Alkalidisilikate, in den Mitteln in Mengen von 1 bis 40 Gew.-%, vorzugsweise von 2 bis 35 Gew.-% jeweils bezogen auf das Gewicht des maschinellen Geschirrspülmittels, enthalten sind.In the context of the present invention, it is preferred that these silicate(s), preferably alkali metal silicates, particularly preferably crystalline or amorphous alkali metal disilicates, are present in amounts in the agents from 1 to 40% by weight, preferably from 2 to 35% by weight, in each case based on the weight of the machine dishwashing detergent.

Die Geschirrspülmittel können als weiteren Gerüststoff insbesondere auch Phosphonate enthalten. Als Phosphonat-Verbindung wird vorzugsweise ein Hydroxyalkan- und/oder Aminoalkanphosphonat eingesetzt. Unter den Hydroxyalkanphosphonaten ist das 1-Hydroxyethan-1,1-diphosphonat (HEDP) von besonderer Bedeutung. Als Aminoalkanphosphonate kommen vorzugsweise Ethylendiamintetramethylenphosphonat (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) sowie deren höhere Homologe in Frage. Phosphonate sind in den Mitteln vorzugsweise in Mengen von 0,1 bis 10 Gew.-%, insbesondere in Mengen von 0,5 bis 8 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Geschirrspülmittels, enthalten.The dishwashing detergents can also contain, in particular, phosphonates as a further builder. A hydroxyalkane and/or aminoalkane phosphonate is preferably used as the phosphonate compound. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. The detergents preferably contain phosphonates in amounts of from 0.1 to 10% by weight, in particular in amounts of from 0.5 to 8% by weight, based in each case on the total weight of the dishwashing detergent.

Weitere Gerüststoffe sind die Alkaliträger. Als Alkaliträger gelten beispielsweise Alkalimetallhydroxide, Alkalimetallcarbonate, Alkalimetallhydrogencarbonate, Alkalimetallsesquicarbonate, die genannten Alkalisilikate, Alkalimetasilikate, und Mischungen der vorgenannten Stoffe, wobei im Sinne dieser Erfindung bevorzugt die Alkalicarbonate, insbesondere Natriumcarbonat, Natriumhydrogencarbonat oder Natriumsesquicarbonat eingesetzt werden können. Besonders bevorzugt ist ein Buildersystem enthaltend eine Mischung aus Tripolyphosphat und Natriumcarbonat. Ebenfalls besonders bevorzugt ist ein Buildersystem enthaltend eine Mischung aus Tripolyphosphat und Natriumcarbonat und Natriumdisilikat. Aufgrund ihrer im Vergleich mit anderen Buildersubstanzen geringen chemischen Kompatibilität mit den übrigen Inhaltsstoffen von maschinellen Geschirrspülmitteln, werden die optionalen Alkalimetallhydroxide bevorzugt nur in geringen Mengen, vorzugsweise in Mengen unterhalb 10 Gew.-%, bevorzugt unterhalb 6 Gew.-%, besonders bevorzugt unterhalb 4 Gew.-% und insbesondere unterhalb 2 Gew.-%, jeweils bezogen auf das Gesamtgewicht des maschinellen Geschirrspülmittels, eingesetzt. Besonders bevorzugt werden Mittel, welche bezogen auf ihr Gesamtgewicht weniger als 0,5 Gew.-% und insbesondere keine Alkalimetallhydroxide enthalten.Other builders are the alkali carriers. Examples of alkali carriers are alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, the alkali metal silicates mentioned, alkali metal metasilicates and mixtures of the aforementioned substances, with preference being given to using the alkali metal carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, for the purposes of this invention. A builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred. A builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred. Due to their low chemical compatibility with the other ingredients of machine dishwashing detergents compared to other builder substances, the optional alkali metal hydroxides are preferably used only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, particularly preferably below 4 % by weight and in particular below 2% by weight, in each case based on the total weight of the machine dishwashing detergent. Agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides are particularly preferred.

Besonders bevorzugt ist der Einsatz von Carbonat(en) und/oder Hydrogencarbonat(en), vorzugsweise Alkalicarbonat(en), besonders bevorzugt Natriumcarbonat, in Mengen von 2 bis 50 Gew.-%, vorzugsweise von 5 bis 40 Gew.-% und insbesondere von 7,5 bis 30 Gew.-%, jeweils bezogen auf das Gewicht des maschinellen Geschirrspülmittels. Besonders bevorzugt werden Mittel, welche bezogen auf das Gewicht des maschinellen Geschirrspülmittels weniger als 20 Gew.-%, vorzugsweise weniger als 17 Gew.-%, bevorzugt weniger als 13 Gew.-% und insbesondere weniger als 9 Gew.-% Carbonat(e) und/oder Hydrogencarbonat(e), vorzugsweise Alkalicarbonat(e), besonders bevorzugt Natriumcarbonat enthalten.Particular preference is given to using carbonate(s) and/or bicarbonate(s), preferably alkali metal carbonate(s), particularly preferably sodium carbonate, in amounts of from 2 to 50% by weight, preferably from 5 to 40% by weight and in particular from 7.5 to 30% by weight, based in each case on the weight of the machine dishwashing detergent. Particular preference is given to detergents which, based on the weight of the automatic dishwashing detergent, contain less than 20% by weight, preferably less than 17% by weight, preferably less than 13% by weight and in particular less than 9% by weight of carbonate(s ) and/or hydrogen carbonate(s), preferably alkali metal carbonate(s), particularly preferably sodium carbonate.

Als weitere organische Gerüststoffe sind insbesondere Polycarboxylate / Polycarbonsäuren, polymere Polycarboxylate, Asparaginsäure, Polyacetale, Dextrine, weitere organische Cobuilder sowie die bereits oben als Gerüststoffe genannten Phosphonate zu nennen.Other organic builders which should be mentioned are, in particular, polycarboxylates/polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders and the phosphonates already mentioned above as builders.

Brauchbare organische Gerüstsubstanzen sind insbesondere beispielsweise die in Form der freien Säure und/oder ihrer Natriumsalze einsetzbaren Polycarbonsäuren, wobei unter Polycarbonsäuren solche Carbonsäuren verstanden werden, die mehr als eine Säurefunktion tragen. Beispielsweise sind dies Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Maleinsäure, Fumarsäure, Nitrilotriessigsäure (NTA), sofern ein derartiger Einsatz aus ökologischen Gründen nicht zu beanstanden ist, sowie Mischungen aus diesen. Die freien Säuren besitzen neben ihrer Builderwirkung typischerweise auch die Eigenschaft einer Säuerungskomponente und dienen somit auch zur Einstellung eines niedrigeren und milderen pH-Wertes der maschinellen Geschirrspülmittel. Insbesondere sind hierbei Citronensäure, Bernsteinsäure, Glutarsäure, Adipinsäure, und beliebige Mischungen aus diesen zu nennen.Organic builder substances which can be used are, in particular, for example the polycarboxylic acids which can be used in the form of the free acid and/or their sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, nitrilotriacetic acid (NTA), provided such use is not objectionable for ecological reasons, and mixtures of these. In addition to their builder effect, the free acids typically also have the property of an acidifying component and are therefore also used to set a lower and milder pH in the machine dishwashing detergents. Particular mention should be made here of citric acid, succinic acid, glutaric acid, adipic acid and any mixtures of these.

Als besonders vorteilhaft für die Reinigungs- und Klarspülleistung der hierin beschriebenen Mittel hat sich der Einsatz von Citronensäure und/oder Citraten in diesen Mitteln erwiesen. Bevorzugt werden daher maschinelle Geschirrspülmittel, dadurch gekennzeichnet, dass das maschinelle Geschirrspülmittel Citronensäure oder ein Salz der Citronensäure enthält.The use of citric acid and/or citrates in these agents has proven to be particularly advantageous for the cleaning and rinsing performance of the agents described herein. Automatic dishwashing detergents are therefore preferred, characterized in that the automatic dishwashing detergent contains citric acid or a salt of citric acid.

Die erfindungsgemäßen Geschirrspülmittel können ferner ein Sulfopolymer enthalten. Der Gewichtsanteil des Sulfopolymers am Gesamtgewicht des erfindungsgemäßen Geschirrspülmittels beträgt vorzugsweise von 0,1 bis 20 Gew.-%, insbesondere von 0,5 bis 18 Gew.-%, besonders bevorzugt 1,0 bis 15 Gew.-%, insbesondere von 4 bis 14 Gew.-%, vor allem von 6 bis 12 Gew.-%. Das Sulfopolymer wird üblicheweise in Form einer wässrigen Lösung eingesetzt, wobei die wässrigen Lösungen typischerweise 20 bis 70 Gew.-%, insbesondere 30 bis 50 Gew.-%, vorzugsweise etwa 35 bis 40 Gew.-% Sulfopolymere enthalten.The dishwashing detergents according to the invention can also contain a sulfopolymer. The proportion by weight of the sulfopolymer in the total weight of the dishwashing detergent according to the invention is preferably from 0.1 to 20% by weight, in particular from 0.5 to 18% by weight, particularly preferably from 1.0 to 15% by weight, in particular from 4 to 14% by weight, especially from 6 to 12% by weight. The sulfopolymer is usually used in the form of an aqueous solution, the aqueous solutions typically containing 20 to 70% by weight, in particular 30 to 50% by weight, preferably about 35 to 40% by weight, of sulfopolymers.

Als Sulfopolymer wird vorzugsweise ein copolymeres Polysulfonat, vorzugsweise ein hydrophob modifiziertes copolymeres Polysulfonat, eingesetzt.A copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate, is preferably used as the sulfopolymer.

Die Copolymere können zwei, drei, vier oder mehr unterschiedliche Monomereinheiten aufweisen. Bevorzugte copolymere Polysulfonate enthalten neben Sulfonsäuregruppen-haltigem(n) Monomer(en) wenigstens ein Monomer aus der Gruppe der ungesättigten Carbonsäuren.The copolymers can have two, three, four or more different monomer units. In addition to monomer(s) containing sulfonic acid groups, preferred copolymeric polysulfonates contain at least one monomer from the group of unsaturated carboxylic acids.

Als ungesättigte Carbonsäure(n) wird/werden mit besonderem Vorzug ungesättigte Carbonsäuren der Formel R1(R2)C=C(R3)COOH eingesetzt, in der R1 bis R3 unabhängig voneinander für -H, -CH3, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH2, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR4 steht, wobei R4 ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist.The unsaturated carboxylic acid(s) used is/are particularly preferably unsaturated carboxylic acids of the formula R 1 (R 2 )CC(R 3 )COOH, in which R 1 to R 3 independently represent -H, -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, one straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH 2 , -OH or -COOH-substituted alkyl or alkenyl radicals as defined above or -COOH or -COOR 4 , where R 4 is a saturated or is an unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Besonders bevorzugte ungesättigte Carbonsäuren sind Acrylsäure, Methacrylsäure, Ethacrylsäure, α-Chloroacrylsäure, α-Cyanoacrylsäure, Crotonsäure, α-Phenyl-Acrylsäure, Maleinsäure, Maleinsäureanhydrid, Fumarsäure, Itaconsäure, Citraconsäure, Methylenmalonsäure, Sorbinsäure, Zimtsäure oder deren Mischungen. Einsetzbar sind selbstverständlich auch die ungesättigten Dicarbonsäuren.Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. Of course, the unsaturated dicarboxylic acids can also be used.

Bei den Sulfonsäuregruppen-haltigen Monomeren sind solche der Formel

        R5(R6)C=C(R7)-X-SO3H

bevorzugt, in der R5 bis R7 unabhängig voneinander für -H, -CH3, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit - NH2, -OH oder -COOH substituierte Alkyl- oder Alkenylreste oder für -COOH oder -COOR4 steht, wobei R4 ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH2)n- mit n = 0 bis 4, -COO-(CH2)k- mit k = 1 bis 6, -C(O)-NH-C(CH3)2-, -C(O)-NH-C(CH3)2-CH2- und -C(O)-NH-CH(CH3)-CH2-.The monomers containing sulfonic acid groups are those of the formula

R 5 (R 6 )C=C(R 7 )-X-SO 3 H

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

Unter diesen Monomeren bevorzugt sind solche der Formeln

        H2C=CH-X-SO3H

        H2C=C(CH3)-X-SO3H

        HO3S-X-(R6)C=C(R7)-X-SO3H,

in denen R6 und R7 unabhängig voneinander ausgewählt sind aus -H, -CH3, -CH2CH3, -CH2CH2CH3 und -CH(CH3)2 und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus - (CH2)n- mit n = 0 bis 4, -COO-(CH2)k- mit k = 1 bis 6, -C(O)-NH-C(CH3)2-, -C(O)-NH-C(CH3)2-CH2-und -C(O)-NH-CH(CH3)-CH2-.Preferred among these monomers are those of the formulas

H2C =CH-X- SO3H

H 2 C=C(CH 3 )-X-SO 3 H

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

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

Besonders bevorzugte Sulfonsäuregruppen-haltige Monomere sind dabei 1-Acrylamido-1-propansulfonsäure, 2-Acrylamido-2-propansulfonsäure, 2-Acrylamido-2-methyl-1-propansulfonsäure, 2-Methacrylamido-2-methyl-1-propansulfonsäure, 3-Methacrylamido-2-hydroxy-propansulfonsäure, Allylsulfonsäure, Methallylsulfonsäure, Allyloxybenzolsulfonsäure, Methallyloxybenzolsulfonsäure, 2-Hydroxy-3-(2-propenyloxy)propansulfonsäure, 2-Methyl-2-propen1-sulfonsäure, Styrolsulfonsäure, Vinylsulfonsäure, 3-Sulfopropylacrylat, 3-Sulfopropylmethacrylat, Sulfomethacrylamid, Sulfomethylmethacrylamid sowie Mischungen der genannten Säuren oder deren wasserlösliche Salze.Particularly preferred sulfonic acid group-containing monomers 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-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of the acids mentioned or their water-soluble salts.

In den Polymeren können die Sulfonsäuregruppen ganz oder teilweise in neutralisierter Form vorliegen, d.h. dass das acide Wasserstoffatom der Sulfonsäuregruppe in einigen oder allen Sulfonsäuregruppen gegen Metallionen, vorzugsweise Alkalimetallionen und insbesondere gegen Natriumionen, ausgetauscht sein kann. Der Einsatz von teil- oder vollneutralisierten sulfonsäuregruppenhaltigen Copolymeren ist erfindungsgemäß bevorzugt.In the polymers, some or all of the sulfonic acid groups can be present in neutralized form, i.e. the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular sodium ions. The use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.

Die Monomerenverteilung der bevorzugt eingesetzten Copolymere beträgt bei Copolymeren, die nur Carbonsäuregruppen-haltige Monomere und Sulfonsäuregruppen-haltige Monomere enthalten, vorzugsweise jeweils 5 bis 95 Gew.-%, besonders bevorzugt beträgt der Anteil des Sulfonsäuregruppen-haltigen Monomers 50 bis 90 Gew.-% und der Anteil des Carbonsäuregruppenhaltigen Monomers 10 bis 50 Gew.-%, die Monomere sind hierbei vorzugsweise ausgewählt aus den zuvor genannten.In the case of copolymers which contain only carboxylic acid group-containing monomers and sulfonic acid group-containing monomers, the monomer distribution of the copolymers preferably used is preferably 5 to 95% by weight in each case, and the proportion of the sulfonic acid group-containing monomer is particularly preferably 50 to 90% by weight. and the proportion of the carboxylic acid group-containing monomer is 10 to 50% by weight, the monomers here preferably being selected from those mentioned above.

Die Molmasse der bevorzugt eingesetzten Sulfo-Copolymere kann variiert werden, um die Eigenschaften der Polymere dem gewünschten Verwendungszweck anzupassen. Bevorzugte Geschirrspülmittel sind dadurch gekennzeichnet, dass die Copolymere Molmassen von 2000 bis 200.000 gmol-1, vorzugsweise von 4000 bis 25.000 gmol-1 und insbesondere von 5000 bis 15.000 gmol-1 aufweisen.The molar mass of the sulfo-copolymers preferably used can be varied in order to adapt the properties of the polymers to the desired application. Preferred dishwashing detergents are characterized in that the copolymers have molecular weights 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 .

Die Geschirrspülmittel können ferner weitere Polymere enthalten. Zur Gruppe geeigneter Polymere zählen insbesondere die reinigungsaktiven Polymere, beispielsweise die Klarspülpolymere und/oder als Enthärter wirksame Polymere.The dishwashing detergents can also contain other polymers. The group of suitable polymers includes, in particular, the cleaning-active polymers, for example the rinse-aid polymers and/or polymers that act as softeners.

Bevorzugte einsetzbare Polymere stammen aus der Gruppe der Alkylacrylamid/Acrylsäure-Copolymere, der Alkylacrylamid/Methacrylsäure-Copolymere, der Alkylacrylamid/Methylmethacrylsäure-Copolymere, der Alkylacrylamid/Acrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymere, der Alkylacrylamid/Methacrylsäure/Alkylaminoalkyl(meth)-acrylsäure-Copolymere, der Alkylacrylamid/Methylmethacrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymere, der Alkylacrylamid/Alkymethacrylat/Alkylaminoethylmethacrylat/Alkylmethacrylat-Copolymere sowie der Copolymere aus ungesättigten Carbonsäuren, kationisch derivatisierten ungesättigten Carbonsäuren und gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren.Preferred polymers that can be used come from the group of alkylacrylamide/acrylic acid copolymers, alkylacrylamide/methacrylic acid copolymers, alkylacrylamide/methylmethacrylic acid copolymers, alkylacrylamide/acrylic acid/alkylaminoalkyl (meth)acrylic acid copolymers, alkylacrylamide/methacrylic acid/alkylaminoalkyl (meth) -acrylic acid copolymers, the alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkyl acrylamide / alkyl methacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally other ionic or nonionic monomers.

Weitere einsetzbare Polymere stammen aus der Gruppe der Acrylamidoalkyltrialkylammoniumchlorid/Acrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze, der Acrylamidoalkyltrialkylammoniumchlorid/Methacrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze und der Methacroylethylbetain/Methacrylat-Copolymere.Other usable polymers come from the group of acrylamidoalkyltrialkylammonium chloride/acrylic acid copolymers and their alkali metal and ammonium salts, acrylamidoalkyltrialkylammonium chloride/methacrylic acid copolymers and their alkali metal and ammonium salts and methacroylethylbetaine/methacrylate copolymers.

Einsetzbare kationische Polymere stammen aus den Gruppen der quaternierten Cellulose-Derivate, der Polysiloxane mit quaternären Gruppen, der kationischen Guar-Derivate, der polymeren Dimethyldiallylammoniumsalze und deren Copolymere mit Acrylsäure und Methacrylsäure und deren Estern und Amiden, der Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats und -methacrylats, der Vinylpyrrolidon-Methoimidazoliniumchlorid-Copolymere, der quaternierter Polyvinylalkohole oder der unter den INCI-Bezeichnungen Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 und Polyquaternium 27 angegeben Polymere.Cationic polymers that can be used come from the groups of quaternized cellulose derivatives, polysiloxanes with quaternary groups, cationic guar derivatives, polymeric dimethyldiallylammonium salts and their copolymers with acrylic acid and methacrylic acid and their esters and amides, 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.

Die vorstehend für die beschriebenen Tenside und Gerüststoffe angegebenen Mengen beziehen sich üblicherweise auf die Mengen, die eingesetzt werden, wenn das jeweilige Tensid oder der jeweilige Gerüststoffe allein eingesetzt wird, sofern nicht explizit anders angegeben. Es ist daher selbstverständlich, dass beim Einsatz mehrerer Tenside oder Gerüststoffe, die Mengenangaben entsprechend anzupassen sind.The amounts given above for the surfactants and builders described usually relate to the amounts used when the particular surfactant or the particular builder is used alone, unless explicitly stated otherwise. It is therefore self-evident that if several surfactants or builders are used, the quantities must be adjusted accordingly.

Vorzugsweise enthalten die Mittel der vorliegenden Erfindung mindestens eine Enzymzubereitung oder Enzymzusammensetzung, die ein oder mehrere Enzyme enthalten. Geeignete Enzyme umfassen, ohne darauf beschränkt zu sein, Proteasen, Amylasen, Lipasen, Hemicellulasen, Cellulasen, Perhydrolasen oder Oxidoreduktasen, sowie vorzugsweise deren Gemische. Diese Enzyme sind im Prinzip natürlichen Ursprungs; ausgehend von den natürlichen Molekülen stehen für den Einsatz in Geschirrspülmitteln verbesserte Varianten zur Verfügung, die entsprechend bevorzugt eingesetzt werden. Die Mittel enthalten Enzyme vorzugsweise in Gesamtmengen von 1 x 10-6 bis 5 Gew.-% bezogen auf aktives Protein. Die Proteinkonzentration kann mit Hilfe bekannter Methoden, zum Beispiel dem BCA-Verfahren oder dem Biuret-Verfahren bestimmt werden.Preferably, 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 in principle of natural origin; Based on the natural molecules, improved variants are available for use in dishwashing detergents, which are used with preference accordingly. The agents preferably contain enzymes in total amounts of 1×10 -6 to 5% by weight, based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the Biuret method.

Proteasen gehören zu den technisch bedeutendsten Enzymen überhaupt. Sie bewirken den Abbau proteinhaltiger Anschmutzungen auf dem Reinigungsgut. Hierunter sind wiederum Proteasen vom Subtilisin-Typ (Subtilasen, Subtilopeptidasen, EC 3.4.21.62) besonders wichtig, welche aufgrund der katalytisch wirksamen Aminosäuren Serin-Proteasen sind. Sie wirken als unspezifische Endopeptidasen und hydrolysieren beliebige Säureamidbindungen, die im Inneren von Peptiden oder Proteinen liegen. Ihr pH-Optimum liegt meist im deutlich alkalischen Bereich. Subtilasen werden natürlicherweise von Mikroorganismen gebildet. Hierunter sind insbesondere die von Bacillus-Spezies gebildeten und sezernierten Subtilisine als bedeutendste Gruppe innerhalb der Subtilasen zu erwähnen.Proteases are among the most technically important enzymes of all. They break down proteinaceous soiling on the items to be cleaned. Among these, proteases of the subtilisin type (subtilases, subtilopeptidases, EC 3.4.21.62) are particularly important, which are serine proteases because of the catalytically active amino acids. They act as non-specific endopeptidases and hydrolyze any acid amide bonds that are inside peptides or proteins. Their optimum pH is usually in the clearly alkaline range. Subtilases are naturally produced by microorganisms. Among these, the subtilisins formed and secreted by Bacillus species should be mentioned in particular as the most important group within the subtilases.

Beispiele für die in Wasch- und Geschirrspülmitteln bevorzugt eingesetzten Proteasen vom Subtilisin-Typ sind die Subtilisine BPN' und Carlsberg, die Protease PB92, die Subtilisine 147 und 309, die Protease aus Bacillus lentus, insbesondere aus Bacillus lentus DSM 5483, Subtilisin DY und die den Subtilasen, nicht mehr jedoch den Subtilisinen im engeren Sinne zuzuordnenden Enzyme Thermitase, Proteinase K und die Proteasen TW3 und TW7, sowie Varianten der genannten Proteasen, die eine gegenüber der Ausgangsprotease veränderte Aminosäuresequenz aufweisen. Proteasen werden durch aus dem Stand der Technik bekannte Verfahren gezielt oder zufallsbasiert verändert und so beispielsweise für den Einsatz in Wasch- und Geschirrspülmitteln optimiert. Dazu gehören Punktmutagenese, Deletions- oder Insertionsmutagenese oder Fusion mit anderen Proteinen oder Proteinteilen. So sind für die meisten aus dem Stand der Technik bekannten Proteasen entsprechend optimierte Varianten bekannt.Examples of the subtilisin-type proteases preferably used in detergents 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 no longer the subtilisins in the narrower sense, thermitase, proteinase K and the proteases TW3 and TW7, as well as variants of the proteases mentioned, which have an altered amino acid sequence compared to the starting protease. Proteases are modified in a targeted or random manner using methods known from the prior art and are 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. Correspondingly optimized variants are known for most of the proteases known from the prior art.

Beispiele für einsetzbare Amylasen sind die α-Amylasen aus Bacillus licheniformis, aus B. amyloliquefaciens, aus B. stearothermophilus, aus Aspergillus niger und A. oryzae sowie die für den Einsatz in Geschirrspülmitteln verbesserten Weiterentwicklungen der vorgenannten Amylasen. Des Weiteren sind für diesen Zweck die α-Amylase aus Bacillus sp. A 7-7 (DSM 12368) und die Cyclodextrin-Glucanotransferase (CGTase) aus B. agaradherens (DSM 9948) hervorzuheben.Examples of usable amylases are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae , and the further developments of the aforementioned amylases which have been improved for use in dishwashing detergents. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

Einsetzbar sind weiterhin Lipasen oder Cutinasen, insbesondere wegen ihrer Triglycerid-spaltenden Aktivitäten, aber auch, um aus geeigneten Vorstufen in situ Persäuren zu erzeugen. Hierzu gehören beispielsweise die ursprünglich aus Humicola lanuginosa (Thermomyces lanuginosus) erhältlichen, beziehungsweise weiterentwickelten Lipasen, insbesondere solche mit dem Aminosäureaustausch D96L.Lipases or cutinases can also be used, in particular because of their triglyceride-splitting activities, but also in order to generate peracids in situ from suitable precursors. This includes for example the lipases originally available from Humicola lanuginosa (Thermomyces lanuginosus) or developed further, in particular those with the amino acid substitution D96L.

Weiterhin können Enzyme eingesetzt werden, die unter dem Begriff Hemicellulasen zusammengefasst werden. Hierzu gehören beispielsweise Mannanasen, Xanthanlyasen, Pektinlyasen (=Pektinasen), Pektinesterasen, Pektatlyasen, Xyloglucanasen (=Xylanasen), Pullulanasen und β-Glucanasen.It is also possible to use enzymes which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (=pectinases), pectinesterases, pectate lyases, xyloglucanases (=xylanases), pullulanases and β-glucanases.

Zur Erhöhung der bleichenden Wirkung können Oxidoreduktasen, beispielsweise Oxidasen, Oxygenasen, Katalasen, Peroxidasen, wie Halo-, Chloro-, Bromo-, Lignin-, Glucose- oder Mangan-Peroxidasen, Dioxygenasen oder Laccasen (Phenoloxidasen, Polyphenoloxidasen) eingesetzt werden. Vorteilhafterweise werden zusätzlich vorzugsweise organische, besonders bevorzugt aromatische, mit den Enzymen wechselwirkende Verbindungen zugegeben, um die Aktivität der betreffenden Oxidoreduktasen zu verstärken (Enhancer) oder um bei stark unterschiedlichen Redoxpotentialen zwischen den oxidierenden Enzymen und den Anschmutzungen den Elektronenfluss zu gewährleisten (Mediatoren).Oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used to increase the bleaching effect. Advantageously, preferably organic, particularly preferably aromatic, compounds that interact with the enzymes are additionally added in order to increase the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons in the case of greatly differing redox potentials between the oxidizing enzymes and the soiling (mediators).

Ein Enzym kann besonders während der Lagerung gegen Schädigungen wie beispielsweise Inaktivierung, Denaturierung oder Zerfall etwa durch physikalische Einflüsse, Oxidation oder proteolytische Spaltung geschützt werden. Bei mikrobieller Gewinnung der Proteine und/oder Enzyme ist eine Inhibierung der Proteolyse besonders bevorzugt, insbesondere wenn auch die Mittel Proteasen enthalten. Geschirrspülmittel können zu diesem Zweck Stabilisatoren enthalten; die Bereitstellung derartiger Mittel stellt eine bevorzugte Ausführungsform der vorliegenden Erfindung dar.An enzyme can be protected against damage such as, for example, inactivation, denaturation or decomposition, for example due to physical influences, oxidation or proteolytic cleavage, particularly during storage. In the case of microbial production of the proteins and/or enzymes, inhibition of proteolysis is particularly preferred, particularly if the agents also contain proteases. Dishwashing detergents may contain stabilizers for this purpose; the provision of such means represents a preferred embodiment of the present invention.

Reinigungsaktive Proteasen und Amylasen werden in der Regel nicht in Form des reinen Proteins sondern vielmehr in Form stabilisierter, lager- und transportfähiger Zubereitungen bereitgestellt. Zu diesen vorkonfektionierten Zubereitungen zählen beispielsweise die durch Granulation, Extrusion oder Lyophilisierung erhaltenen festen Präparationen oder, insbesondere bei flüssigen oder gelförmigen Mitteln, Lösungen der Enzyme, vorteilhafterweise möglichst konzentriert, wasserarm und/oder mit Stabilisatoren oder weiteren Hilfsmitteln versetzt.Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized preparations that can be stored and transported. These ready-made preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel-like preparations, solutions of the enzymes, advantageously as concentrated as possible, low in water and/or mixed with stabilizers or other auxiliaries.

Alternativ können die Enzyme sowohl für die feste als auch für die flüssige Darreichungsform verkapselt werden, beispielsweise durch Sprühtrocknung oder Extrusion der Enzymlösung zusammen mit einem vorzugsweise natürlichen Polymer oder in Form von Kapseln, beispielsweise solchen, bei denen die Enzyme wie in einem erstarrten Gel eingeschlossen sind oder in solchen vom Kern-Schale-Typ, bei dem ein enzymhaltiger Kern mit einer Wasser-, Luft- und/oder Chemikalienundurchlässigen Schutzschicht überzogen ist. In aufgelagerten Schichten können zusätzlich weitere Wirkstoffe, beispielsweise Stabilisatoren, Emulgatoren, Pigmente, Bleich- oder Farbstoffe aufgebracht werden. Derartige Kapseln werden nach an sich bekannten Methoden, beispielsweise durch Schüttel- oder Rollgranulation oder in Fluid-bed-Prozessen aufgebracht. Vorteilhafterweise sind derartige Granulate, beispielsweise durch Aufbringen polymerer Filmbildner, staubarm und aufgrund der Beschichtung lagerstabil.Alternatively, the enzymes can be encapsulated for both the solid and the liquid dosage form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer, or in the form of capsules, for example those in which the enzymes are enclosed as in a set gel or in those of the core-shell type, in which an enzyme-containing core is impermeable to water, air and/or chemicals protective layer is coated. Additional active substances, for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can also be applied in superimposed layers. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example due to the application of polymeric film formers, produce little dust and are stable in storage due to the coating.

Weiterhin ist es möglich, zwei oder mehrere Enzyme zusammen zu konfektionieren, so dass ein einzelnes Granulat mehrere Enzymaktivitäten aufweist.Furthermore, it is possible to formulate two or more enzymes together, so that a single granulate has several enzyme activities.

Wie aus der vorherigen Ausführungen ersichtlich, bildet das Enzym-Protein nur einen Bruchteil des Gesamtgewichts üblicher Enzym-Zubereitungen. Bevorzugt eingesetzte Protease- und Amylase-Zubereitungen enthalten zwischen 0,1 und 40 Gew.-%, bevorzugt zwischen 0,2 und 30 Gew.-%, besonders bevorzugt zwischen 0,4 und 20 Gew.-% und insbesondere zwischen 0,8 und 10 Gew.-% des Enzymproteins.As can be seen from the above, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Protease and amylase preparations used with preference contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0.8 and 10% by weight of the enzyme protein.

Bevorzugt werden insbesondere solche Geschirrspülmittel, die, jeweils bezogen auf ihr Gesamtgewicht, 0,1 bis 12 Gew.-%, vorzugsweise 0,2 bis 10 Gew.-% und insbesondere 0,5 bis 8 Gew.-% Enzym-Zubereitungen enthalten.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 are particularly preferred.

Die hierin beschriebenen Zusammensetzungen können auch Enzymstabilisatoren beinhalten. Eine Gruppe von Stabilisatoren sind reversible Proteaseinhibitoren. Häufig werden hierfür Benzamidin-Hydrochlorid, Borax, Borsäuren, Boronsäuren oder deren Salze oder Ester eingesetzt, darunter vor allem Derivate mit aromatischen Gruppen, etwa ortho-, meta- oder para-substituierte Phenylboronsäuren, insbesondere 4-Formylphenyl-Boronsäure, beziehungsweise die Salze oder Ester der genannten Verbindungen. Auch Peptidaldehyde, das heißt Oligopeptide mit reduziertem C-Terminus, insbesondere solche aus 2 bis 50 Monomeren werden zu diesem Zweck eingesetzt. Zu den peptidischen reversiblen Proteaseinhibitoren gehören unter anderem Ovomucoid und Leupeptin. Auch spezifische, reversible Peptid-Inhibitoren für die Protease Subtilisin sowie Fusionsproteine aus Proteasen und spezifischen Peptid-Inhibitoren sind hierfür geeignet.The compositions herein may also include enzyme stabilizers. One group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are often used for this purpose, including above all derivatives with aromatic groups, such as ortho-, meta- or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or the salts or Esters of said compounds. Peptide aldehydes, ie oligopeptides with a reduced C-terminus, in particular those composed of 2 to 50 monomers, are also 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 also suitable for this.

Weitere Enzymstabilisatoren sind Aminoalkohole wie Mono-, Di-, Triethanol- und -Propanolamin und deren Mischungen, aliphatische Carbonsäuren bis zu C12, wie beispielsweise Bernsteinsäure, andere Dicarbonsäuren oder Salze der genannten Säuren. Auch endgruppenverschlossene Fettsäureamidalkoxylate sind für diesen Zweck geeignet. Weitere Enzymstabilisatoren sind dem Fachmann aus dem Stand der Technik bekannt.Other enzyme stabilizers are amino alcohols such as mono-, di-, triethanolamine and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C 12 such as succinic acid, other dicarboxylic acids or salts of the acids mentioned. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Other enzyme stabilizers are known to those skilled in the art from the prior art.

Bleichmittel sind reinigungsaktive Substanzen. Unter den als Bleichmittel dienenden, in Wasser H2O2 liefernden Verbindungen haben das Natriumpercarbonat, das Natriumperborattetrahydrat und das Natriumperboratmonohydrat besondere Bedeutung. Weitere brauchbare Bleichmittel sind beispielsweise Peroxypyrophosphate, Citratperhydrate sowie H2O2 liefernde persaure Salze oder Persäuren, wie Perbenzoate, Peroxophthalate, Diperazelainsäure, Phthaloiminopersäure oder Diperdodecandisäure. Einsetzbar sind außerdem alle weiteren dem Fachmann aus dem Stand der Technik bekannten anorganischen oder organischen Peroxybleichmittel. Als Bleichmittel werden die Percarbonate und hier insbesondere Natriumpercarbonat besonders bevorzugt.Bleaching agents are active cleaning substances. Sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance among the compounds which serve as bleaching agents and yield H 2 O 2 in water. Examples of other bleaches which can be used are peroxypyrophosphates, citrate perhydrates and peracid salts or peracids which supply H 2 O 2 , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid. All other inorganic or organic peroxy bleaches known to those skilled in the art from the prior art can also be used. The percarbonates and here in particular sodium percarbonate are particularly preferred as bleaching agents.

Die Geschirrspülmittel können, in verschiedenen Ausführungsformen, 1 bis 35 Gew.-%, vorzugsweise 2,5 bis 30 Gew.-%, besonders bevorzugt 3,5 bis 20 Gew.-% und insbesondere 5 bis 15 Gew.-% Bleichmittel, vorzugsweise Natriumpercarbonat, enthalten.In various embodiments, the dishwashing detergents can contain 1 to 35% by weight, preferably 2.5 to 30% by weight, particularly preferably 3.5 to 20% by weight and in particular 5 to 15% by weight of bleach, preferably sodium percarbonate.

In verschiedenen Ausführungsformen der Erfindung enthalten die maschinellen Geschirrspülmittel zusätzlich mindestens einen Bleichaktivator. Als Bleichaktivatoren können Verbindungen, die unter Perhydrolysebedingungen aliphatische Peroxocarbonsäuren mit vorzugsweise 1 bis 10 C-Atomen, insbesondere 2 bis 4 C-Atomen, und/oder gegebenenfalls substituierte Perbenzoesäure ergeben, eingesetzt werden. Von allen dem Fachmann aus dem Stand der Technik bekannten Bleichaktivatoren werden mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin (TAED), acylierte Triazinderivate, insbesondere 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin (DADHT), acylierte Glykolurile, insbesondere Tetraacetylglykoluril (TAGU), N-Acylimide, insbesondere N-Nonanoylsuccinimid (NOSI), acylierte Phenolsulfonate, insbesondere n-Nonanoyl-oder Isononanoyloxybenzolsulfonat (n- bzw. iso-NOBS) besonders bevorzugt eingesetzt. Auch Kombinationen konventioneller Bleichaktivatoren können eingesetzt werden. Als Bleichaktivator wird TAED, insbesondere in Kombination mit einem Percarbonat-Bleichmittel, vorzugsweise Natriumpercarbonat, ganz besonders bevorzugt.In various embodiments of the invention, the machine dishwashing detergents additionally contain at least one bleach activator. Bleach activators which can be used are compounds which, under perhydrolysis conditions, produce aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and/or optionally substituted perbenzoic acid. Of all the bleach activators known to the person skilled in the art from the prior art, polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), are acylated Glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) are particularly preferably used. Combinations of conventional bleach activators can also be used. TAED is very particularly preferred as the bleach activator, especially in combination with a percarbonate bleach, preferably sodium percarbonate.

Diese Bleichaktivatoren werden vorzugsweise in Mengen bis 10 Gew.-%, insbesondere 0,1 Gew.-% bis 8 Gew.-%, besonders 2 bis 8 Gew.-% und besonders bevorzugt 2 bis 6 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Mittel, eingesetzt.These bleach activators are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6% by weight, in each case based on the total weight of the funds.

Generell kann der pH-Wert des Geschirrspülmittels mittels üblicher pH-Regulatoren eingestellt werden, wobei der pH-Wert abhängig von dem gewünschten Einsatzzweck gewählt wird. In verschiedenen Ausführungsformen liegt der pH-Wert in einem Bereich von 5,5 bis 10,5, vorzugsweise 5,5 bis 9,5, noch bevorzugter 7 bis 9, insbesondere größer 7, vor allem im Bereich 7,5 bis 8,5. Als pH-Stellmittel dienen Säuren und/oder Alkalien, vorzugsweise Alkalien. Geeignete Säuren sind insbesondere organische Säuren wie die Essigsäure, Zitronensäure, Glycolsäure, Milchsäure, Bernsteinsäure, Adipinsäure und Äpfelsäure oder auch Amidosulfonsäure. Daneben können aber auch die Mineralsäuren Salzsäure, Schwefelsäure und Salpetersäure bzw. deren Mischungen eingesetzt werden. Geeignete Basen stammen aus der Gruppe der Alkali- und Erdalkalimetallhydroxide und -carbonate, insbesondere der Alkalimetallhydroxide, von denen Kaliumhydroxid und vor allem Natriumhydroxid bevorzugt ist. Besonders bevorzugt ist allerdings flüchtiges Alkali, beispielsweise in Form von Ammoniak und/oder Alkanolaminen, die bis zu 9 C-Atome im Molekül enthalten können. Das Alkanolamin ist hierbei vorzugsweise ausgewählt aus der Gruppe bestehend aus Mono-, Di-, Triethanol- und -Propanolamin und deren Mischungen.In general, the pH of the dishwashing detergent can be adjusted using customary pH regulators, with the pH being selected depending on the desired application. In various embodiments, the pH is in a range from 5.5 to 10.5, preferably from 5.5 to 9.5, more preferably from 7 to 9, in particular greater than 7, especially in the range from 7.5 to 8.5 . Acids and/or alkalis, preferably alkalis, are used as pH adjusters. Suitable acids are, in particular, organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid and malic acid or amidosulfonic acid. Besides However, the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof can also be used. Suitable bases come from the group of alkali metal and alkaline earth metal hydroxides and carbonates, in particular the alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide are preferred. However, particular preference is given to volatile alkali, for example in the form of ammonia and/or alkanolamines, which can contain up to 9 carbon atoms in the molecule. The alkanolamine is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof.

Zur Einstellung und/oder Stabilisierung des pH-Werts kann das erfindungsgemäße Mittel auch ein oder mehrere Puffersubstanzen (INCI Buffering Agents) enthalten, üblicherweise in Mengen von 0,001 bis 5 Gew.-%. Bevorzugt sind Puffersubstanzen, die zugleich Komplexbildner oder sogar Chelatbildner (Chelatoren, INCI Chelating Agents) sind. Besonders bevorzugte Puffersubstanzen sind die Citronensäure bzw. die Citrate, insbesondere die Natrium- und Kaliumcitrate, beispielsweise Trinatriumcitrat·2H2O und Trikaliumcitrat·H2O.To adjust and/or stabilize the pH, the agent according to the invention can also contain one or more buffer substances (INCI buffering agents), usually in amounts of 0.001 to 5% by weight. Buffer substances which are at the same time complexing agents or even chelating agents (chelators, INCI chelating agents) are preferred. Particularly preferred buffer substances are citric acid or citrates, in particular sodium and potassium citrates, for example trisodium citrate·2H 2 O and tripotassium citrate·H 2 O.

Glaskorrosionsinhibitoren verhindern das Auftreten von Trübungen, Schlieren und Kratzern aber auch das Irisieren der Glasoberfläche von maschinell gereinigten Gläsern. Bevorzugte Glaskorrosionsinhibitoren stammen aus der Gruppe der Magnesium- und Zinksalze sowie der Magnesium-und Zinkkomplexe. Im Rahmen der vorliegenden Erfindung beträgt der Gehalt an Zinksalz in Geschirrspülmitteln vorzugsweise zwischen 0,1 bis 5 Gew.-%, bevorzugt zwischen 0,2 bis 4 Gew.-% und insbesondere zwischen 0,4 bis 3 Gew.-%, bzw. der Gehalt an Zink in oxidierter Form (berechnet als Zn2+) zwischen 0,01 bis 1 Gew.-%, vorzugsweise zwischen 0,02 bis 0,5 Gew.-% und insbesondere zwischen 0,04 bis 0,2 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Glaskorrosionsinhibitor-haltigen Mittels.Glass corrosion inhibitors prevent clouding, streaks and scratches from occurring, but also iridescence on the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group consisting of magnesium and zinc salts and magnesium and zinc complexes. In the context of the present invention, the content of zinc salt in dishwashing detergents is preferably between 0.1 and 5% by weight, preferably between 0.2 and 4% by weight and in particular between 0.4 and 3% by weight, or the content of zinc in oxidized form (calculated as Zn 2+ ) 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 agent containing glass corrosion inhibitor.

Als Parfümöle bzw. Duftstoffe können im Rahmen der vorliegenden Erfindung einzelne Riechstoffverbindungen, z.B. die synthetischen Produkte vom Typ der Ester, Ether, Aldehyde, Ketone, Alkohole und Kohlenwasserstoffe verwendet werden. Bevorzugt werden jedoch Mischungen verschiedener Riechstoffe verwendet, die gemeinsam eine ansprechende Duftnote erzeugen. Solche Parfümöle können auch natürliche Riechstoffgemische enthalten, wie sie aus pflanzlichen Quellen zugänglich sind, z.B. Pinien-, Citrus-, Jasmin-, Patchouli-, Rosen- oder Ylang-Ylang-Öl.Perfume oils or fragrances which can be used in the context of the present invention are individual odorant compounds, for example synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance note. Perfume oils of this type can also contain natural mixtures of fragrances, such as those obtainable from vegetable sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.

Weiterhin können Konservierungsmittel in den Mitteln enthalten sein. Geeignet sind beispielsweise Konservierungsmittel aus den Gruppen der Alkohole, Aldehyde, antimikrobiellen Säuren und/oder deren Salze, Carbonsäureester, Säureamide, Phenole, Phenolderivate, Diphenyle, Diphenylalkane, Harnstoffderivate, Sauerstoff-, Stickstoff-Acetale sowie -Formale, Benzamidine, Isothiazole und deren Derivate wie Isothiazoline und Isothiazolinone, Phthalimidderivate, Pyridinderivate, antimikrobiellen oberflächenaktiven Verbindungen, Guanidine, antimikrobiellen amphoteren Verbindungen, Chinoline, 1,2-Dibrom-2,4-dicyanobutan, lodo-2-propynyl-butyl-carbamat, Iod, lodophore und Peroxide. Bevorzugte antimikrobielle Wirkstoffe werden vorzugsweise ausgewählt aus der Gruppe umfassend Ethanol, n-Propanol, i-Propanol, 1,3-Butandiol, Phenoxyethanol, 1,2-Propylenglykol, Glycerin, Undecylensäure, Zitronensäure, Milchsäure, Benzoesäure, Salicylsäure, Thymol, 2-Benzyl-4-chlorphenol, 2,2'-Methylen-bis-(6-brom-4-chlorphenol), 2,4,4'-Trichlor-2'-hydroxydiphenylether, N-(4-Chlorphenyl)-N-(3,4-dichlorphenyl)-harnstoff, N,N'-(1,10-decandiyldi-1-pyridinyl-4-yliden)-bis-(1-octanamin)-dihydrochlorid, N,N'-Bis-(4-Chlorphenyl)-3,12-diimino-2,4,11,13-tetraazatetradecandiimidamid, antimikrobielle quaternäre oberflächenaktive Verbindungen, Guanidine. Besonders bevorzugte Konservierungsmittel sind jedoch ausgewählt aus der Gruppe umfassend Salicylsäure, quaternäre Tenside, insbesondere Benzalkoniumchlorid und Isothiazole und deren Derivate wie Isothiazoline und Isothiazolinone.Furthermore, preservatives can be contained in the agents. For example, preservatives from the groups of alcohols, aldehydes, antimicrobial acids and/or salts thereof, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen and nitrogen acetals and formals, benzamidines, isothiazoles and derivatives thereof are suitable such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surfactants, guanidines, antimicrobial amphoterics Compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl carbamate, iodine, iodophors and peroxides. Preferred antimicrobial agents are preferably selected from the group consisting of 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'-methylene-bis(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-tetraazatetradecanediimidamide, antimicrobial quaternary surfactants, guanidines. However, particularly preferred preservatives are selected from the group comprising salicylic acid, quaternary surfactants, in particular benzalkonium chloride and isothiazoles and their derivatives such as isothiazolines and isothiazolinones.

Generell kann die Konfektionierung hierin beschriebener maschineller Geschirrspülmittel in unterschiedlicher Weise erfolgen. Die Mittel können in fester oder flüssiger sowie als Kombination fester und flüssiger Angebotsformen vorliegen. Als feste Angebotsformen eignen sich insbesondere Pulver, Granulate, Extrudate, Kompaktate, insbesondere Tabletten. Die flüssigen Angebotsformen auf Basis von Wasser und/oder organischen Lösungsmitteln können verdickt, in Form von Gelen vorliegen. Die Mittel können in Form einphasiger oder mehrphasiger Produkte konfektioniert werden. Die einzelnen Phasen mehrphasiger Mittel können gleiche oder unterschiedliche Aggregatzustände aufweisen.In general, the machine dishwashing detergents described herein can be packaged in different ways. The agents can be presented in solid or liquid form or as a combination of solid and liquid forms. Powders, granules, extrudates, compacts, in particular tablets, are particularly suitable as solid supply forms. The liquid supply forms based on water and/or organic solvents can be thickened and in the form of gels. The agents can be packaged in the form of single-phase or multi-phase products. The individual phases of multi-phase agents can have the same or different states of aggregation.

Die Geschirrspülmittel können als Formkörper vorliegen. Um den Zerfall solcher vorgefertigter Formkörper zu erleichtern, ist es möglich, Desintegrationshilfsmittel, so genannte Tablettensprengmittel, in diese Mittel einzuarbeiten, um die Zerfallszeiten zu verkürzen. Unter Tablettensprengmitteln bzw. Zerfallsbeschleunigern werden Hilfsstoffe verstanden, die für den raschen Zerfall von Tabletten in Wasser oder anderen Medien und für die zügige Freisetzung der Wirkstoffe sorgen. Bevorzugt können Desintegrationshilfsmittel in Mengen von 0,5 bis 10 Gew.-%, vorzugsweise 3 bis 7 Gew.-% und insbesondere 4 bis 6 Gew.-%, jeweils bezogen auf das Gesamtgewicht des desintegrationshilfsmittelhaltigen Mittels, eingesetzt werden.The dishwashing detergents can be in the form of shaped bodies. In order to facilitate the disintegration of such prefabricated shaped bodies, it is possible to incorporate disintegration aids, so-called tablet disintegrants, into these agents in order to shorten the disintegration times. Tablet disintegrants or disintegrants are understood as meaning excipients which ensure that tablets disintegrate rapidly in water or other media and that the active ingredients are released quickly. Disintegration aids can preferably be used in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight, based in each case on the total weight of the composition containing disintegration aids.

Die hierin beschriebenen maschinellen Geschirrspülmittel werden vorzugsweise zu Dosiereinheiten vorkonfektioniert. Diese Dosiereinheiten umfassen vorzugsweise die für einen Reinigungsgang notwendige Menge an reinigungsaktiven Substanzen. Bevorzugte Dosiereinheiten weisen ein Gewicht zwischen 12 und 30 g, bevorzugt zwischen 14 und 26 g und insbesondere zwischen 16 und 22 g auf. Das Volumen der vorgenannten Dosiereinheiten sowie deren Raumform sind mit besonderem Vorzug so gewählt, dass eine Dosierbarkeit der vorkonfektionierten Einheiten über die Dosierkammer einer Geschirrspülmaschine gewährleistet ist. Das Volumen der Dosiereinheit beträgt daher bevorzugt zwischen 10 und 35 ml, vorzugsweise zwischen 12 und 30 ml.The machine dishwashing detergents described herein are preferably prepackaged to form dosing units. These dosing units preferably include the amount of cleaning-active substances required for one cleaning cycle. Preferred dosage units weigh between 12 and 30 g, preferably between 14 and 26 g and in particular between 16 and 22 g. The volume of the aforementioned dosing units and their three-dimensional shape are selected with particular preference in such a way that the prefabricated units can be dosed via the dosing chamber of a dishwasher. The volume of the dosage unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml.

Die maschinellen Geschirrspülmittel, insbesondere die vorgefertigten Dosiereinheiten weisen mit besonderem Vorzug eine wasserlösliche Umhüllung auf.The machine dishwashing detergents, in particular the prefabricated dosing units, particularly preferably have a water-soluble coating.

Die wasserlösliche Umhüllung wird vorzugsweise aus einem wasserlöslichen Folienmaterial, welches ausgewählt ist aus der Gruppe, bestehend aus Polymeren oder Polymergemischen, gebildet. Die Umhüllung kann aus einer oder aus zwei oder mehr Lagen aus dem wasserlöslichen Folienmaterial gebildet werden. Das wasserlösliche Folienmaterial der ersten Lage und der weiteren Lagen, falls vorhanden, kann gleich oder unterschiedlich sein. Besonders bevorzugt sind Folien, die beispielsweise zu Verpackungen wie Schläuchen oder Kissen verklebt und/oder versiegelt werden können, nachdem sie mit einem Mittel befüllt wurden.The water-soluble cover is preferably formed from a water-soluble film material which is selected from the group consisting of polymers or polymer mixtures. The cover can be formed from one or from two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if any, can be the same or different. Films are particularly preferred which can be glued and/or sealed to form packaging such as tubes or pillows after they have been filled with an agent.

Die wasserlösliche Verpackung kann eine oder mehr Kammern aufweisen. Das Mittel kann in einer oder mehreren Kammern, falls vorhanden, der wasserlöslichen Umhüllung enthalten sein. Die Menge an Mittel entspricht vorzugsweise der vollen oder halben Dosis, die für einen Spülgang benötigt wird.The water-soluble packaging can have one or more compartments. The agent can be contained in one or more compartments, if any, of the water-soluble coating. The amount of agent preferably corresponds to the full or half dose required for one rinse.

Es ist bevorzugt, dass die wasserlösliche Umhüllung Polyvinylalkohol oder ein Polyvinylalkoholcopolymer enthält. Wasserlösliche Umhüllungen, die Polyvinylalkohol oder ein Polyvinylalkoholcopolymer enthalten, weisen eine gute Stabilität bei einer ausreichend hohen Wasserlöslichkeit, insbesondere Kaltwasserlöslichkeit, auf.It is preferred that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble coatings that contain polyvinyl alcohol or a polyvinyl alcohol copolymer have good stability with sufficiently high water solubility, especially cold water solubility.

Geeignete wasserlösliche Folien zur Herstellung der wasserlöslichen Umhüllung basieren bevorzugt auf einem Polyvinylalkohol oder einem Polyvinylalkoholcopolymer, dessen Molekulargewicht im Bereich von 10.000 bis 1.000.000 gmol-1, vorzugsweise von 20.000 bis 500.000 gmol-1, besonders bevorzugt von 30.000 bis 100.000 gmol-1 und insbesondere von 40.000 bis 80.000 gmol-1 liegt.Suitable water-soluble films for producing the water-soluble covering are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range from 10,000 to 1,000,000 gmol -1 , preferably from 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 .

Die Herstellung von Polyvinylalkohol geschieht üblicherweise durch Hydrolyse von Polyvinylacetat, da der direkte Syntheseweg nicht möglich ist. Ähnliches gilt für Polyvinylalkoholcopolymere, die aus entsprechend aus Polyvinylacetatcopolymeren hergestellt werden. Bevorzugt ist, wenn wenigstens eine Lage der wasserlöslichen Umhüllung einen Polyvinylalkohol umfasst, dessen Hydrolysegrad 70 bis 100 Mol-%, vorzugsweise 80 bis 90 Mol-%, besonders bevorzugt 81 bis 89 Mol-% und insbesondere 82 bis 88 Mol-% ausmacht.Polyvinyl alcohol is usually produced by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers which are correspondingly produced from polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol %, preferably 80 to 90 mol %, particularly preferably 81 to 89 mol % and in particular 82 to 88 mol %.

Einem zur Herstellung der wasserlöslichen Umhüllung geeignetem Polyvinylalkohol-enthaltendem Folienmaterial kann zusätzlich ein Polymer ausgewählt aus der Gruppe umfassend (Meth)Acrylsäure-haltige (Co)Polymere, Polyacrylamide, Oxazolin-Polymere, Polystyrolsulfonate, Polyurethane, Polyester, Polyether, Polymilchsäure oder Mischungen der vorstehenden Polymere zugesetzt sein. Ein bevorzugtes zusätzliches Polymer sind Polymilchsäuren.A polyvinyl alcohol-containing film material suitable for producing the water-soluble casing can additionally have a polymer selected from the group consisting of (meth)acrylic acid-containing (co)polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, Polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above polymers may be added. A preferred additional polymer are polylactic acids.

Bevorzugte Polyvinylalkoholcopolymere umfassen neben Vinylalkohol Dicarbonsäuren als weitere Monomere. Geeignete Dicarbonsäuren sind Itaconsäure, Malonsäure, Bernsteinsäure und Mischungen daraus, wobei Itaconsäure bevorzugt ist.In addition to vinyl alcohol, preferred polyvinyl alcohol copolymers include dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.

Ebenfalls bevorzugte Polyvinylalkoholcopolymere umfassen neben Vinylalkohol eine ethylenisch ungesättige Carbonsäure, deren Salz oder deren Ester. Besonders bevorzugt enthalten solche Polyvinylalkoholcopolymere neben Vinylalkohol Acrylsäure, Methacrylsäure, Acrylsäureester, Methacrylsäureester oder Mischungen daraus.Polyvinyl alcohol copolymers which are also preferred include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its ester. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof.

Es kann bevorzugt sein, dass das Folienmaterial weitere Zusatzstoffe enthält. Das Folienmaterial kann beispielsweise Weichmacher wie Dipropylenglycol, Ethylenglycol, Diethylenglycol, Propylenglycol, Glycerin, Sorbitol, Mannitol oder Mischungen daraus enthalten. Weitere Zusatzstoffe umfassen beispielsweise Freisetzungshilfen, Füllmittel, Vernetzungsmittel, Tenside, Antioxidationsmittel, UV-Absorber, Antiblockmittel, Antiklebemittel oder Mischungen daraus.It can be preferred that the film material contains other additives. The film material can 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, anti-blocking agents, anti-adhesive agents or mixtures thereof.

Geeignete wasserlösliche Folien zum Einsatz in den wasserlöslichen Umhüllungen der wasserlöslichen Verpackungen gemäß der Erfindung sind Folien, die von der Firma MonoSol LLC beispielsweise unter der Bezeichnung M8630, C8400 oder M8900 vertrieben werden. Andere geeignete Folien umfassen Folien mit der Bezeichnung Solublon® PT, Solublon® GA, Solublon® KC oder Solublon® KL von der Aicello Chemical Europe GmbH oder die Folien VF-HP von Kuraray.Suitable water-soluble films for use in the water-soluble wrappers of the water-soluble packages of the invention are films sold by MonoSol LLC, for example, under the designation M8630, C8400 or M8900. Other suitable films include Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL films from Aicello Chemical Europe GmbH or Kuraray VF-HP films.

Beispielhafte Basisrezepturen, in denen die hierin beschriebene Gerüststoffkombination in den angegebenen Mengen eingesetzt werden kann, indem ein Teil der enthaltenen Builder durch mindestens eine Zuckersäure bzw. das Salz davon ersetzt werden, sind die folgenden: Tabelle 1: Phosphatfreie, feste Geschirrspülmittelformulierung (Tab) Rohstoff Menge (Gew.-%) Na-Citrat 15,00-20,00 Phosphonat (z.B. HEDP) 0,00-7,50 MGDA/GLDA 5,00-25,00 Silikat 10,00-35,00 Soda 12,50-25,00 Na-Percarbonat 10,00-15,00 Bleichkatalysator 0,02-0,50 TAED 2,00-3,00 Niotensid 2,50-10,00 Polycarboxylat 5,00-10,00 Kationisches Acrylat-Copolymer 0,25-0,75 PVP (quervernetzt) 0,00-1,50 Protease 1,50-5,00 Amylase 0,50-3,00 Benzotriazol (Silberschutz) 0,00-0,50 Parfüm 0,05-0,15 Farbstoff 0,00-1,00 Zn-Acetat wasserfrei 0,10-0,30 Na-Sulfat 0,00-25,00 Wasser 0,00-1,50 pH-Stellmittel 1,00-1,50 Prozesshilfsmittel 0,00-5,00 Exemplary base formulations in which the combination of builders described herein can be used in the specified amounts by replacing some of the builders contained with at least one sugar acid or the salt thereof are as follows: Table 1: Phosphate-free, solid dishwashing detergent formulation (tab) raw material Amount (% by weight) sodium citrate 15.00-20.00 Phosphonate (e.g. HEDP) 0.00-7.50 MGDA/GLDA 5.00-25.00 silicate 10.00-35.00 soda 12.50-25.00 Na percarbonate 10.00-15.00 bleach catalyst 0.02-0.50 TAED 2.00-3.00 nonionic surfactant 2.50-10.00 polycarboxylate 5.00-10.00 Cationic acrylate copolymer 0.25-0.75 PVP (crosslinked) 0.00-1.50 protease 1.50-5.00 amylase 0.50-3.00 Benzotriazole (silver protection) 0.00-0.50 Perfume 0.05-0.15 dye 0.00-1.00 Zn acetate anhydrous 0.10-0.30 sodium sulfate 0.00-25.00 water 0.00-1.50 pH adjuster 1.00-1.50 process aids 0.00-5.00

Die entsprechende Verwendung der erfindungsgemäßen maschinellen Geschirrspülmittel ist ebenfalls Gegenstand der Erfindung. Ebenso betrifft die Erfindung ein Geschirrspülverfahren, insbesondere maschinelles Geschirrspülverfahren, bei welchem ein Geschirrspülmittel gemäß der Erfindung eingesetzt wird. Gegenstand der vorliegenden Anmeldung ist daher weiterhin ein Verfahren zur Reinigung von Geschirr in einer Geschirrspülmaschine, bei welchem das erfindungsgemäße Mittel während des Durchlaufens eines Geschirrspülprogramms vor Beginn des Hauptspülgangs oder im Verlaufe des Hauptspülgangs in den Innenraum einer Geschirrspülmaschine eindosiert wird. Die Eindosierung bzw. der Eintrag des erfindungsgemäßen Mittels in den Innenraum der Geschirrspülmaschine kann manuell erfolgen, vorzugsweise wird das Mittel jedoch mittels der Dosierkammer in den Innenraum der Geschirrspülmaschine dosiert.The corresponding use of the machine dishwashing detergents according to the invention is also a subject of the invention. The invention also relates to a dishwashing method, in particular a machine dishwashing method, in which a dishwashing detergent according to the invention is used. The subject matter of the present application is therefore also a method for cleaning dishes in a dishwasher, in which the agent according to the invention is metered into the interior of a dishwasher while running through a dishwashing program before the start of the main wash cycle or during the course of the main wash cycle. The agent according to the invention can be dosed or introduced into the interior of the dishwasher manually, but the agent is preferably dosed into the interior of the dishwasher by means of the dosing chamber.

Die im Kontext mit den erfindungsgemäßen Mitteln beschriebenen Ausführungsformen sind ohne weiteres auch auf die erfindungsgemäßen Verfahren und Verwendungen übertragbar und umgekehrt.The embodiments described in the context of the agents according to the invention can also easily be transferred to the methods and uses according to the invention and vice versa.

Beispiele: Tabelle 2: Formelbereiche Rohstoff Phosphatfreie Formelbereiche gesamt % g/job Na-Citrat 15,00-20,00 3,00-4,000 Phosphonat (HEDP) 2,50-7,50 0,50-1,500 MGDA 0,00-25,00 0,00-5,000 Na-Disilicat 5,00-35,00 1,00-7,000 Soda 12,50-25,00 2,50-5,000 Na-Percarbonat 10,00-15,00 2,00-3,000 Bleichkatalysator (Mn-basiert) 0,02-0,50 0,003-0,100 TAED 2,00-3,00 0,40-0,600 Nicht-ionisches Tensid 20-40 EO, endgruppenverschlossen möglich 2,50-10,00 0,50-2,000 Polycarboxylat 5,00-10,00 1,00-2,000 Kationisches Co-Polymer 0,25-0,75 0,05-0,150 Vernetztes Polyvinylpyrrolidon-Desintegrationsmittel 0,00-1,50 0,00-0,300 Protease 1,50-5,00 0,30-1,000 Amylase 0,50-3,00 0,10-0,600 Benzotriazol (Silberschutz) 0,00-0,50 0,00-0,100 Parfüm 0,05-0,15 0,01-0,030 Farbstofflösung 0,00-1,00 0,00-0,200 Zn-Acetat 0,10-0,30 0,02-0,060 Na-Sulfat 0,00-25,00 0,00-5,000 Wasser 0,00-1,50 0,00-0,300 pH-Stellmittel (Citronensäure) 1,00-1,50 0,20-0,300 Prozesshilfsmittel 0,00-5,00 0,00-1,000 57,92-196,20 11,6-39,24 Examples: Table 2: Formula ranges raw material Total phosphate-free formula ranges % g/job sodium citrate 15.00-20.00 3.00-4.000 Phosphonate (HEDP) 2.50-7.50 0.50-1.500 MGDA 0.00-25.00 0.00-5.000 Na disilicate 5.00-35.00 1.00-7.000 soda 12.50-25.00 2.50-5,000 Na percarbonate 10.00-15.00 2.00-3.000 Bleach catalyst (Mn-based) 0.02-0.50 0.003-0.100 TAED 2.00-3.00 0.40-0.600 Non-ionic surfactant 20-40 EO, end-capped possible 2.50-10.00 0.50-2.000 polycarboxylate 5.00-10.00 1.00-2.000 Cationic co-polymer 0.25-0.75 0.05-0.150 Crosslinked polyvinylpyrrolidone disintegrant 0.00-1.50 0.00-0.300 protease 1.50-5.00 0.30-1.000 amylase 0.50-3.00 0.10-0.600 Benzotriazole (silver protection) 0.00-0.50 0.00-0.100 Perfume 0.05-0.15 0.01-0.030 dye solution 0.00-1.00 0.00-0.200 Zn acetate 0.10-0.30 0.02-0.060 sodium sulfate 0.00-25.00 0.00-5.000 water 0.00-1.50 0.00-0.300 pH adjuster (citric acid) 1.00-1.50 0.20-0.300 process aids 0.00-5.00 0.00-1.000 57.92-196.20 11:6-39:24

Berechnet auf 20 g Tablette. Tablette kann aber auch 17-20 g wiegen. Tabelle 3: Verwendete Rezeptur Rohstoff % Na-Citrat 9,0 HEDP 5,2 MGDA 11,5 Silicat 2,8 Soda 18,0 Percarbonat 12,8 Mn-Komplex 0,03 TAED 2,7 Nicht-ionisches Tensid 20-40 EO, endgruppenverschlossen möglich 4,2 Benzotriazol 0,3 Dehypon DA (Niotensid) 2,0 Polycarboxylat 8,0 PEG 4000 0,7 Proteasegranulat 4,8 Amylasegranulat 1,3 Parfüm 0,2 Farbstofflösung 0,9 Zinksalz 0,2 pH-Stellmittel anwesend Prozesshilfsmittel anwesend Wasser Rest Calculated on 20 g tablet. However, the tablet can also weigh 17-20 g. Table 3: Recipe used raw material % sodium citrate 9.0 HEDP 5.2 MGDA 11.5 silicate 2.8 soda 18.0 percarbonate 12.8 Mn complex 0.03 TAED 2.7 Non-ionic surfactant 20-40 EO, end-capped possible 4.2 benzotriazole 0.3 Dehypon DA (nonionic surfactant) 2.0 polycarboxylate 8.0 PEG 4000 0.7 protease granules 4.8 amylase granules 1.3 Perfume 0.2 dye solution 0.9 zinc salt 0.2 pH adjuster present process aids present water rest

Die Belagsinhibierung wurde in Miele Haushaltsmaschinen im 65 °C Programm nach 30 Zyklen inkl. Schmutzbeladung bestimmt. In der erfindungsgemäßen Rezeptur wurde die Hälfte des MGDA durch Glucarsäure ausgetauscht. Als weiterer Vergleich wurde die gesamte Menge MGDA gegen Glucarsäure ausgetauscht. Produkt Glas Altbiergläser Besteck WMF Messer Solid Besteck BSF Messer Melody Servierplatte Butterdose Formel mit MGDA 3,7 7,0 7,0 7,0 Formel mit 50 % MGDA/50 % Glucarsäure 3,7 8,0 8,3 7,5 Formel mit 100 % Glucarsäure 3,3 7,7 7,7 6,5 The deposit inhibition was determined in Miele domestic machines in the 65 °C program after 30 cycles including dirt loading. In the formulation according to the invention, half of the MGDA has been replaced by glucaric acid. As a further comparison, the entire amount of MGDA was exchanged for glucaric acid. product Glass Altbier glasses Cutlery WMF Knife Solid Cutlery BSF knife Melody Platter Butter Dish Formula with MGDA 3.7 7.0 7.0 7.0 50% MGDA/50% Glucaric Acid formula 3.7 8.0 8.3 7.5 Formula with 100% glucaric acid 3.3 7.7 7.7 6.5

Wie man erkennt, zeigt die Kombination der beiden Komplexbildner eine Verbesserung der Belagsinhibierung an Metall bei gleicher Leistung an Glas. Die Leistungssteigerung ist stärker beim Austausch eines Teils des MGDA im Vergleich zum Komplettaustausch.As can be seen, the combination of the two complexing agents shows an improvement in scale inhibition on metal with the same performance on glass. The performance increase is greater when replacing a part of the MGDA compared to replacing it completely.

Claims (10)

  1. A phosphate-free dishwashing detergent, in particular an automatic dishwashing detergent, containing at least one saccharic acid in an amount of 0.1 to 30 wt.%, preferably 1 to 25 wt.%, based on the total weight of the dishwashing detergent, and at least one aminocarboxylic acid or at least one salt of an aminocarboxylic acid in an amount of 0.1 to 30 wt.%, preferably 1 to 25 wt.%, based on the total weight of the dishwashing detergent, wherein the saccharic acid and optionally a salt of a saccharic acid are contained in a total amount of 0.1 to 30 wt.%, preferably 1 to 25 wt.%, based on the total weight of the dishwashing detergent.
  2. The dishwashing detergent according to claim 1, characterized in that the at least one saccharic acid is selected from the group consisting of aldonic acids, uronic acid, aldaric acids and ketoaldonic acids.
  3. The dishwashing detergent according to claim 1 or 2, characterized in that the at least one saccharic acid is selected from the group consisting of gluconic acid, glucuronic acid, glucaric acid, glucoheptonic acid, tartaric acid, mucic acid, gulonic acid, galacturonic acid, iduronic acid, mannonic acid and 2-oxo-D-gluconic acid.
  4. The dishwashing detergent according to one of claims 1 to 3, characterized in that the at least one saccharic acid is glucaric acid.
  5. The dishwashing detergent according to one of claims 1 to 4, characterized in that the at least one aminocarboxylic acid is selected from the group consisting of methylglycinediacetic acid (MGDA), glutaminediacetic acid (GLDA), ethylenediaminediacetic acid (EDDS), iminodisuccinic acid (IDS) and iminodiacetic acid (IDA).
  6. The dishwashing detergent according to one of claims 1 to 5, characterized in that the at least one aminocarboxylic acid is MGDA.
  7. The dishwashing detergent according to one of claims 1 to 6, characterized in that
    (1) the at least one saccharic acid and the at least one aminocarboxylic acid are together contained in the dishwashing detergent in an amount of 5 to 40 wt.%, in particular 5 to 30 wt.%, based on the total weight of the dishwashing detergent; and/or
    (2) the at least one saccharic acid and the at least one aminocarboxylic acid are contained in the dishwashing detergent in a ratio of 80:20 to 20:80, in particular 50:50.
  8. The dishwashing detergent according to one of claims 1 to 7, characterized in that the dishwashing detergent contains at least one further constituent, preferably at least two further constituents, selected from the group consisting of surfactants, in particular nonionic and/or anionic surfactants, further builders, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protecting agents, glass corrosion inhibitors, foam inhibitors, dyes, fragrances, bitterns, antimicrobial active ingredients and disintegration agents.
  9. The use of a dishwashing detergent according to one of claims 1 to 8 in an automatic dishwashing process.
  10. An automatic dishwashing process, characterized in that a dishwashing detergent according to one of claims 1 to 8 is used.
EP17734730.9A 2016-07-05 2017-07-03 Dishwashing composition containing sugar acid and amino carboxylic acid Active EP3481936B1 (en)

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PCT/EP2017/066464 WO2018007298A1 (en) 2016-07-05 2017-07-03 Dishwasher agent containing saccharic acid and amino carboxylic acid

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JP2021515057A (en) 2018-02-23 2021-06-17 ユニリーバー・ナームローゼ・ベンノートシヤープ Detergent solid composition containing aminopolycarboxylate and inorganic acid
KR102575423B1 (en) * 2018-08-20 2023-09-05 현대자동차주식회사 Eco-friendly cleaning agent for metal materials and method for preparing the same

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DE4232170C2 (en) 1992-09-25 1999-09-16 Henkel Kgaa Weakly alkaline dish detergent
DE4315048A1 (en) 1993-04-01 1994-10-06 Henkel Kgaa Process for the production of stable, bifunctional, phosphate, metasilicate and polymer-free, low-alkaline detergent tablets for automatic dishwashing
EP0906407B1 (en) 1996-06-21 2001-09-05 Reckitt Benckiser N.V. Low-alkaline mgda-containing dishwasher rinsing agent
HUP0401286A3 (en) * 2001-08-17 2009-06-29 Henkel Ag & Co Kgaa Dishwasher detergent with improved protection against glass corrosion
ITCR20060016A1 (en) * 2006-06-07 2007-12-08 Silvia Palladini DETERGENT FORMULATIONS AT LOW ENVIRONMENTAL IMPACT
DE102007044418A1 (en) * 2007-09-17 2009-03-19 Henkel Ag & Co. Kgaa cleaning supplies
DE102007006628A1 (en) * 2007-02-06 2008-08-07 Henkel Ag & Co. Kgaa cleaning supplies
DE102014100234A1 (en) * 2014-01-10 2015-07-16 Budich International Gmbh Phosphate substitutes for alkaline machine cleaners

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ES2908611T3 (en) 2022-05-03

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