EP3481936B1 - Geschirrspülmittel enthaltend zuckersäure und aminocarbonsäure - Google Patents

Geschirrspülmittel enthaltend zuckersäure und aminocarbonsäure 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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EP
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Prior art keywords
acid
dishwashing detergent
weight
dishwashing
group
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German (de)
English (en)
French (fr)
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EP3481936A1 (de
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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/pl
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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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