EP2115113B1 - Détergents - Google Patents

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Publication number
EP2115113B1
EP2115113B1 EP07847827A EP07847827A EP2115113B1 EP 2115113 B1 EP2115113 B1 EP 2115113B1 EP 07847827 A EP07847827 A EP 07847827A EP 07847827 A EP07847827 A EP 07847827A EP 2115113 B1 EP2115113 B1 EP 2115113B1
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EP2115113A1 (fr
Inventor
Nadine Warkotsch
Johannes Zipfel
Arnd Kessler
Christian Nitsch
Arno DÜFFELS
Thomas Holderbaum
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D3/37—Polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers

Definitions

  • the present patent application describes detergents, in particular detergents for the machine cleaning of dishes.
  • the subject of this application are in particular phosphate-free automatic dishwashing detergents.
  • Machine-washed dishes are often subject to more stringent requirements today than manually-washed dishes. So the dishes after machine cleaning should not only be completely free of food particles free but also, for example, no whitish, based on water hardness or other mineral salts stains that come from lack of wetting agent from dried water drops.
  • Modern automatic dishwashing detergents meet these requirements by integrating cleansing, caring, water-softening and clear-rinsing active ingredients and are known to the consumer, for example, as “2in1" or "3in1" dishwashing detergents.
  • As essential for the cleaning as for the rinse aid success constituent intended for the private consumer dishwasher automatic dishwashing contain builders. On the one hand, these builders increase the alkalinity of the cleaning liquor, whereby fats and oils are emulsified and saponified with increasing alkalinity, and on the other hand reduce the water hardness of the cleaning liquor by complexing the calcium ions contained in the aqueous liquor.
  • Particularly effective builders have proved to be the alkali metal phosphates which, for this reason, form the main constituent of the vast majority of commercially available automatic dishwashing detergents.
  • phosphates are highly valued for their beneficial effect as a component of automatic dishwashing detergents, their use is not unproblematic from the environmental point of view, since a substantial portion of the phosphate enters the water via the domestic effluent and especially in stagnant waters (lakes , Barrages) plays a critical role in their over-fertilization.
  • eutrophication the use of pentasodium triphosphate in laundry detergents in a number of countries, e.g. USA, Canada, Italy, Sweden, Norway, significantly reduced by law and regulations. completely prohibited in Switzerland. In Germany, detergents since 1984 may contain no more than 20% of this builder.
  • nitrilotriacetic acid especially sodium aluminosilicates (zeolites) are used as phosphate substitutes or substitutes in textile detergents.
  • these substances are not suitable for use in automatic dishwashing detergents for various reasons.
  • alkali metal phosphates in automatic dishwashing detergents therefore, a number of substitutes are discussed in the literature, of which the citrates are particularly noteworthy.
  • Phosphate-free automatic dishwashing detergents which, in addition to a citrate, furthermore contain carbonates, bleaches and enzymes are described, for example, in the European patents EP 662 117 B1 (Henkel KGaA) and EP 692 020 B1 (Henkel KGaA).
  • MGDA methylglycine diacetic acid
  • the object of the present application was to provide a phosphate-free automatic dishwashing detergent, which is comparable in terms of its cleaning performance and in terms of its rinse results and its performance in terms of scale inhibition with conventional phosphate cleaning agents or even better.
  • automatic dishwashing detergents which, in addition to builder and bleach, furthermore also contain specific nonionic surfactants and specific hydrophobically modified copolymers, also have excellent coating inhibition and cleaning and rinsing performance even without the addition of alkali metal phosphates
  • a first essential ingredient of automatic dishwashing detergent according to the invention is the hydrophobically modified copolymer a) comprising the monomers i) and ii).
  • carboxyl-containing monomers i) are acrylic acid, methacrylic acid, ethacrylic acid, chloroacrylic acid, cyanoacrylic acid, crotonic acid, phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof.
  • Particularly preferred such monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1,2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexene, 1-octene, olefins having 10 or more carbon
  • Dishwasher detergents according to the invention have proved to be particularly effective with regard to optimum coating inhibition, cleaning and rinse-aid results, in which the weight fraction of the copolymer a) is from 4 to 18% by weight, preferably from 6 to 15 and in particular from 6 to 12% by weight. is.
  • the copolymer d) in addition to the monomers i) and ii) further comprises a third monomer iii) from the group of sulfonic acid group-containing monomers.
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble
  • the sulfonic acid groups may be wholly or partially in neutralized form, i. in that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.
  • the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use.
  • preferred Machine dishwashing detergents are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
  • Preferred automatic dishwasher detergents according to the invention have a weight fraction of this nonionic surfactant b) of from 1 to 10% by weight, preferably from 2 to 8% by weight and in particular from 3 to 6% by weight.
  • the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.
  • nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.
  • Tensigemische not mixtures of nonionic surfactants are referred to which fall in their entirety under one of the above general formulas, but rather those mixtures containing two, three, four or more nonionic surfactants, which can be described by different of the aforementioned general formulas ,
  • machine dishwashing detergents preferably contain one or more builders.
  • the builders include in particular silicates, carbonates and organic cobuilders.
  • organic co-builders are polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and other organic cobuilders. These classes of substances are described below.
  • Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
  • the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • Particularly preferred machine dishwasher detergents according to the invention contain citrate as one of their essential builders.
  • Automatic dishwashing agents according to the invention characterized in that they contain from 5 to 60% by weight, preferably from 10 to 50% by weight and in particular from 15 to 40% by weight, of citrate are preferred according to the invention.
  • Citrate or citric acid have become have proven to be the most effective builders in combination with the specific hydrophobically modified copolymers and the specific nonionic surfactants in terms of cleaning performance, such as rinse performance and scale inhibition.
  • automatic dishwashing agents contain as builder crystalline layered silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4 where particularly preferred values for x are 2, 3 or 4 and y is a number from 0 to 33, preferably from 0 to 20.
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.
  • Machine dishwashing detergents preferred in the context of the present invention comprise from 2 to 15% by weight, preferably from 3 to 12% by weight and in particular from 4 to 8% by weight, of silicate (s).
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of the automatic dishwashing agents in (co) polymeric polycarboxylates is preferably from 0.5 to 20% by weight and in particular from 3 to 10% by weight.
  • Preferred automatic dishwashing agents according to the invention also contain one or more bleaching agents.
  • bleaching agents include the compounds serving as bleaches in water H 2 O 2 .
  • sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • bleaching agents from the group of organic bleaching agents can also be used.
  • Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
  • Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Machine dishwashing detergents characterized in that they contain from 1 to 20% by weight, preferably from 2 to 15% by weight and in particular from 4 to 12% by weight, of sodium percarbonate are preferred according to the invention.
  • chlorine or bromine releasing substances can be used.
  • suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • the automatic dishwasher detergents according to the invention may additionally contain bleach activators.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • Preference is given to polyacylated alkylenediamines, with tetraacetylethylenediamine (TAED) having proven particularly suitable.
  • TAED tetraacetylethylenediamine
  • bleach activators in particular TAED, are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, especially 2 to 8% by weight and more preferably 2 to 6% by weight. , in each case based on the total weight of the bleach activator-containing agents used.
  • bleach catalysts can also be used.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • complexes of manganese in the oxidation state II, III, IV or IV which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S.
  • ligands are used which have nitrogen donor functions.
  • bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononan (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and or 2-methyl-1,4,7-triazacyclononane (Me / TACN).
  • Me-TACN 1,4,7-trimethyl-1,4,7-triazacyclononan
  • TACN 1,4,7-triazacyclononane
  • TACD 1,5,9-trimethyl-1,5,9-triazacyclododecane
  • Me-TACD 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane
  • 2-methyl-1,4,7-triazacyclononane
  • Machine dishwashing detergent characterized in that it further comprises a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me 3 -TACN ) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me 4 -TACN), are preferred according to the invention, since in particular the cleaning result can be significantly improved by the aforementioned bleach catalysts.
  • a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me 3 -TACN ) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me 4 -TACN), are preferred according to the invention, since in particular the cleaning result can be significantly improved by the aforementioned
  • the abovementioned bleach-enhancing transition metal complexes are used in customary amounts, preferably in an amount of up to 5% by weight, in particular of 0.0025% by weight to 1% by weight and more preferably of 0, 01 wt .-% to 0.30 wt .-%, each based on the total weight of the bleach activator-containing agents used. In special cases, however, more bleach activator can also be used.
  • Preferred automatic dishwashing agents according to the invention additionally contain a complexing agent, preferably 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and / or methylglycine diacetic acid (MGDA).
  • a complexing agent preferably 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and / or methylglycine diacetic acid (MGDA).
  • the complex-forming phosphonates comprise a number of different compounds such as, for example, diethylenetriaminepenta (methylenephosphonic acid) (DTPMP). Hydroxyalkane or aminoalkane phosphonates are particularly preferred in this application.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9).
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • automatic dishwashing detergents which contain as phosphonates 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta (methylenephosphonic acid) (DTPMP).
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylenetriaminepenta
  • the automatic dishwashing compositions of the invention may contain two or more different phosphonates. Particular preference is given to those automatic dishwashing compositions which contain as phosphonates both 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylenetriaminepenta (methylenephosphonic acid) (DTPMP), the weight ratio of HEDP to DTPMP being between 20: 1 and 1:20, preferably between 15: 1 and 1:15 and in particular between 10: 1 and 1:10.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylenetriaminepenta
  • the weight fraction of the phosphonate (s) in the total weight of the automatic dishwashing agent is less than the weight proportion of the polymer (s) a).
  • those agents are particularly preferred in which the ratio of the weight fraction of polymer a) to the weight fraction of the phosphonate is 200: 1 to 2: 1, preferably 150: 1 to 2: 1, particularly preferably 100: 1 to 2: 1, most preferably 80: 1 to 3: 1 and in particular 50: 1 to 5: 1.
  • the proportion by weight of these complexing agents in particular the sum of the proportions by weight of 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and methylglycinediacetic acid (MGDA) is preferably 0.5 to 14% by weight, preferably 1 to 12% by weight and in particular 2 to 8 wt .-%.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • MGDA methylglycinediacetic acid
  • ingredients described above such as builder, the bleach, the nonionic surfactant, the copolymer a) and the complexing agents preferred automatic dishwashing contain other ingredients, preferably active ingredients from the group of polymers, enzymes, corrosion inhibitors, fragrances or dyes.
  • the group of washing- or cleaning-active polymers includes, for example, the rinse aid polymers and / or polymers which act as softeners.
  • the rinse aid polymers and / or polymers which act as softeners include, for example, the rinse aid polymers and / or polymers which act as softeners.
  • cationic, anionic and amphoteric polymers can be used in detergents or cleaners in addition to nonionic polymers.
  • “Cationic polymers” in the context of the present invention are polymers which carry a positive charge in the polymer molecule. This can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain.
  • Particularly preferred cationic polymers come from the groups of quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino and methacrylates, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCl designations Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.
  • amphoteric polymers further comprise, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units.
  • These groups may be, for example, carboxylic acids, sulfonic acids or phosphonic acids.
  • Alkyl groups heteroatomic organic groups having at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one amino group having a positive charge in the partial range of the pH range of 2 to 11, or salts thereof, with the proviso that at least a radical R 1 , R 2 , R 3 , R 4 is a heteroatomic organic group having at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one amino group having a positive charge.
  • particularly preferred cationic or amphoteric polymers contain as monomer unit a compound of the general formula in which R 1 and R 4 are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R 2 and R 3 are independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group; x and y independently represent integers between 1 and 3.
  • X represents a counterion, preferably a counterion from the group consisting of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.
  • Preferred radicals R 1 and R 4 in the above formula are selected from -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -OH , -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , -CH (OH) -CH 2 -CH 3 , and - (CH 2 CH 2 -O) n H.
  • cationic or amphoteric polymers contain a monomer unit of the general formula in which R 1 , R 2 , R 3 , R 4 and R 5 independently of one another are a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , -CH (OH) CH 2 -CH 3 , and - (CH 2 CH 2 -O) n H and x is an integer between 1 and 6.
  • amphoteric polymers have not only cationic groups but also anionic groups or monomer units.
  • anionic monomer units are derived, for example, from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates or linear or branched, saturated or unsaturated sulfonates.
  • Preferred monomer units are the acrylic acid, the (meth) acrylic acid, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylessingic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or allylphosphonic acids.
  • Preferred employable amphoteric polymers are from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / - methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonion
  • Preferably usable zwitterionic polymers are selected from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the methacroylethylbetaine / methacrylate copolymers.
  • amphoteric polymers which comprise, in addition to one or more anionic monomers as cationic monomers, methacrylamidoalkyl trialkyl ammonium chloride and dimethyl (diallyl) ammonium chloride.
  • Particularly preferred amphoteric polymers are from the group of the Methacrylamidoalkyl-trialkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the Methacrylamidoalkyltrialkylammoniumchlorid / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the Methacrylamidoalkyltrialkylammoniumchlorid / dimethyl (diallyl) ammonium chloride / alkyl (meth) -acrylic acid copolymers and their alkali metal and ammonium salts.
  • amphoteric polymers from the group of the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers and the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth ) -acrylic acid copolymers and their alkali metal and ammonium salts.
  • Detergents or cleaning agents contain the aforementioned cationic and / or amphoteric polymers preferably in amounts of between 0.01 and 10 wt .-%, each based on the total weight of the detergent or cleaning agent.
  • detergents or cleaners enzymes can be used. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly.
  • Detergents or cleaning agents contain enzymes preferably in total amounts of 1 ⁇ 10 -6 to 5 wt .-% based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • subtilisin type those of the subtilisin type are preferable.
  • these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae and improved for use in detergents and cleaners further developments of the aforementioned amylases. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • lipases or cutinases are also usable according to the invention.
  • these include, for example, the lipases originally obtainable from Humicola lanuginosa ( Thermomyces lanuginosus ) or further developed, in particular those with the amino acid exchange D96L.
  • the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens . It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii .
  • 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 according to the invention to increase the bleaching effect.
  • the enzymes can be used in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
  • a protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
  • Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
  • Some exemplary formulations for such preferred phosphate-free automatic dishwashing detergents can be found in the following tables: ingredient Recipe 9 [% by weight] Recipe 10 [% by weight] Recipe 11 [% by weight] Recipe 12 [% by weight] citrate 5 to 60 10 to 55 15 to 50 15 to 50 sodium 1 to 20 2 to 15 4 to 10 4 to 10 enzyme 0.1 to 6 0.2 to 5 0.4 to 5 0.4 to 5 Copoylmer 1 0.1 to 30 0.5 to 25 1.0 to 20 1.0 to 20 Nonionic surfactant 2 1 to 10 2 to 8 2 to 8 3 to 6 Misc Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add
  • Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses.
  • Preferred glass corrosion inhibitors come from the group of magnesium and zinc salts and magnesium and zinc complexes.
  • the spectrum of the invention preferred zinc salts, preferably organic acids, particularly preferably organic carboxylic acids, ranging from salts which are difficult or insoluble in water, ie a solubility below 100 mg / l, preferably below 10 mg / l, in particular below 0.01 have mg / l, to those salts which have a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and in particular above 5 g / l (all solubilities at 20 ° C. water temperature).
  • the first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate
  • the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.
  • At least one zinc salt of an organic carboxylic acid particularly preferably a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and zinc citrate.
  • Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.
  • the content of zinc salt in detergents or cleaners 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.
  • the content of zinc in oxidized form (calculated as Zn 2+ ) between 0.01 to 1 wt .-%, preferably between 0.02 to 0.5 wt .-% and in particular between 0.04 to 0, 5 wt .-%, each based on the total weight of the glass corrosion inhibitor-containing agent.
  • Corrosion inhibitors serve to protect the items to be washed or the machine, with particular silver protectants being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole.
  • 3-amino-5-alkyl-1,2,4-triazoles or their physiologically tolerated salts preference is given to using 3-amino-5-alkyl-1,2,4-triazoles or their physiologically tolerated salts, these substances being particularly preferably used in a concentration of 0.001 to 10 wt .-%, preferably 0.0025 to 2 wt .-%, particularly preferably 0.01 to 0.04 wt .-% are used.
  • disintegration aids so-called disintegrants
  • Disintegration aids are preferably used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration assistant-containing agent.
  • Preferred disintegrating agents are cellulosic disintegrating agents, so that preferred washing or cleaning agents comprise such cellulose-based disintegrants in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight. % contain.
  • the cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted.
  • the particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns.
  • Preferred disintegration aids preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, are in the disintegrating agent-containing agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6 wt .-%, each based on the total weight of the disintegrating agent-containing agent.
  • gas-evolving effervescent systems can furthermore be used as tablet disintegration auxiliaries.
  • the gas-evolving effervescent system may consist of a single substance that releases a gas upon contact with water.
  • these compounds mention should be made in particular of magnesium peroxide, which liberates oxygen on contact with water.
  • preferred effervescent systems consist of at least two components which are together react under gas formation, for example from alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution.
  • Acidificationsmittel which release carbon dioxide from the alkali metal salts in aqueous solution, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used.
  • organic acidifying agents preference is given to using organic acidifying agents, the citric acid being a particularly preferred acidifying agent. Acidifying agents in the effervescent system from the group of organic di-, tri- and oligocarboxylic acids or mixtures are preferred.
  • perfume oils or perfumes within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance.
  • perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, Citrus, Jasmine, Patchouly, Rose or Ylang-Ylang oil.
  • the fragrances can be processed directly, but it can also be advantageous to apply the fragrances on carriers that provide a slower fragrance release for long-lasting fragrance.
  • carrier materials for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.
  • Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to the substrates to be treated with the dye-containing agents such as textiles, glass, ceramics or plastic dishes do not stain them.
  • the automatic dishwashing compositions according to the invention can be formulated in solid or liquid form but can also be present, for example, as a combination of solid and liquid forms.
  • Powder, granules, extrudates or compactates, in particular tablets, are particularly suitable as firm supply forms.
  • the liquid supply forms based on water and / or organic solvents may be thickened, in the form of gels.
  • Inventive agents can be formulated as single-phase or multi-phase products.
  • automatic dishwashing detergents with one, two, three or four phases are preferred.
  • Machine dishwashing detergents characterized in that they are in the form of a prefabricated dosing unit with two or more phases, are particularly preferred.
  • the individual phases of multiphase agents may have the same or different states of matter.
  • Machine dishwashing detergents which have at least two different solid phases and / or at least two liquid phases and / or at least one solid and at least one liquid phase are preferred.
  • Automatic dishwasher detergents according to the invention are preferably prefabricated to form metering units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g.
  • the volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher.
  • the volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml and in particular between 15 and 25 ml.
  • the automatic dishwasher detergents according to the invention in particular the prefabricated metering units, have a water-soluble coating, with particular preference.
  • the present application further relates to a method for cleaning dishes in a dishwasher using automatic dishwashing agents according to the invention, wherein the automatic dishwashing agents are preferably metered into the interior of a dishwasher during the passage of a dishwashing program, before the main wash cycle or during the main wash cycle.
  • the metering or the entry of the agent according to the invention into the interior of the dishwasher can be done manually, but preferably the agent is metered into the interior of the dishwasher by means of the metering chamber of the dishwasher.
  • no additional water softener and no additional rinse aid is dosed into the interior of the dishwasher.
  • compositions according to the invention are distinguished from conventional automatic dishwashing agents by an improved rinsing action.
  • a dishwasher detergent according to the invention as a rinse aid in automatic dishwashing is therefore a further subject matter of the present application.
  • soiled dishes were rinsed in a dishwasher with 21 g of a phosphate-free automatic dishwashing detergent E2 or 21 g of the phosphate-free machine dishwashing detergent E1 at a water hardness of 21 ° dH.
  • the composition of the dishwashing agents used can be found in the following table: raw material E1 E2 citrate 23 23 MGDA 8.0 8.0 Copolymer 1 12.0 12.0 HEDP 2.0 2.0 soda 28.0 28.0 sodium 10.0 10.0 TAED 2.4 2.4 protease 2.0 2.0 amylase 1.8 1.8 Nonionic surfactant 2 5.0 - Nonionic surfactant 3 - 5.0 Misc Add 100 Add 100 1 hydrophobically modified copolymer 2 Polyalkoxylated fatty alcohol of general formula C 12-18 - (EO) 1-6 - (PO) 1-6 - (EO) 1-6 - (PO) 1-6 -OH 3 hydroxy mixed ethers of the general formula C 6-24 -CH (OH) CH 2 O- (EO) 20-120 -C 2-26

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Claims (12)

  1. Agent sans phosphates pour le lavage mécanique de la vaisselle, comprenant un builder, un agent de blanchiment et en outre :
    a) un copolymère comprenant :
    i) des monomères choisis parmi le groupe des acides carboxyliques une ou plusieurs fois insaturés ;
    ii) des monomères répondant à la formule générale R1(R2)C=C(R3)-X-R4, dans laquelle les résidus R1 à R3 représentent, indépendamment l'un de l'autre, un atome d'hydrogène, un groupe -CH3 ou un groupe -C2H5, X représente un groupe faisant office d'espaceur présent de manière facultative, qui est choisi parmi un groupe -CH2-, un groupe -C(O)O- et un groupe -C(O)-NH-, et R4 représente un résidu alkyle saturé à chaîne droite ou ramifiée contenant de 2 à 22 atomes de carbone ou représente un résidu insaturé de préférence aromatique contenant de 6 à 22 atomes de carbone ;
    iii) de manière facultative, d'autres monomères ;
    b) un agent tensioactif non ionique répondant à la formule générale R1-CH(OH)CH2O-(AO)w-(A'O)x-(A"O)y-(A"'O)z-R2, dans laquelle
    - R1 représente un résidu alkyle ou alcényle en C6-C24 à chaîne droite ou ramifiée, saturé ou une, respectivement plusieurs fois insaturé ;
    - R2 représente un résidu d'hydrocarbure linéaire ou ramifié contenant de 2 à 26 atomes de carbone ;
    - A, A', A" et A"' représentent, indépendamment l'un de l'autre, un résidu choisi parmi le groupe comprenant : un groupe -CH2CH2, un groupe -CH2CH2-CH2, un groupe -CH2-CH(CH3), un groupe -CH2-CH2-CH2-CH2, un groupe -CH2-CH(CH3)-CH2-, un groupe -CH2-CH(CH2-CH3) ;
    - w, x, y et z représentent des valeurs entre 0,5 et 120, x, y et/ou z pouvant également être égaux à 0.
  2. Agent pour le lavage mécanique de la vaisselle selon la revendication 1, caractérisé en ce que la fraction pondérale du copolymère a) s'élève de 4 à 18 % en poids, de préférence de 6 à 15 et en particulier de 6 à 12 % en poids.
  3. Détergent sans phosphates pour lave-vaisselle selon l'une quelconque des revendications précédentes, caractérisé en ce que le copolymère a) contient, à titre de monomères iii), des monomères contenant des groupes d'acides sulfoniques.
  4. Agent pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications précédentes, caractérisé en ce que la fraction pondérale de l'agent tensioactif non ionique b) s'élève de 1 à 10 % en poids, de préférence de 2 à 8 % en poids et en particulier de 3 à 6 % en poids.
  5. Agent pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications précédentes, caractérisé en ce que l'agent tensioactif non ionique b) présente la formule générale R1-CH(OH)CH2O-(AO)w-R2, dans laquelle :
    - R1 représente un résidu alkyle ou alcényle en C6-C24 à chaîne droite ou ramifiée, saturé ou une, respectivement plusieurs fois insaturé ;
    - R2 représente un résidu d'hydrocarbure linéaire ou ramifié contenant de 2 à 26 atomes de carbone ;
    - A représente un résidu choisi parmi le groupe comprenant un groupe CH2CH2, un groupe -CH2CH2-CH2, un groupe -CH2-CH(CH3), et
    - w représente des valeurs entre 1 et 120, de préférence de 10 à 80, en particulier de 20 à 40.
  6. Agent pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il contient de 5 à 60 % en poids, de préférence de 10 à 50 % en poids et en particulier de 15 à 40 % en poids de citrate.
  7. Agent pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il contient de 1 à 20 % en poids, de préférence de 2 à 15 % en poids et en particulier de 4 à 12 % en poids de percarbonate de sodium.
  8. Agent pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il contient en outre un agent complexant, de préférence l'acide 1-hydroxyéthane-1,1-diphosphonique et/ou l'acide méthylglycinediacétique.
  9. Agent pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications précédentes, contenant
    a) un copolymère comprenant :
    i) des monomères choisis parmi le groupe des acides carboxyliques une ou plusieurs fois insaturés ;
    ii) des monomères répondant à la formule générale R1(R2)C=C(R3)-X-R4, dans laquelle les résidus R1 à R3 représentent, indépendamment l'un de l'autre, un atome d'hydrogène, un groupe -CH3 ou un groupe -C2H5, X représente un groupe faisant office d'espaceur présent de manière facultative, qui est choisi parmi un groupe -CH2-, un groupe -C(O)O- et un groupe -C(O)-NH-, et R4 représente un résidu alkyle saturé à chaîne droite ou ramifiée contenant de 2 à 22 atomes de carbone ou représente un résidu insaturé de préférence aromatique contenant de 6 à 22 atomes de carbone ;
    b) un agent tensioactif non ionique répondant à la formule générale R1-CH(OH)CH2O-(AO)w-R2, dans laquelle
    - R1 représente un résidu alkyle ou alcényle en C6-C24 à chaîne droite ou ramifiée, saturé ou une, respectivement plusieurs fois insaturé ;
    - R2 représente un résidu d'hydrocarbure linéaire ou ramifié contenant de 2 à 26 atomes de carbone ;
    - A représente un résidu choisi parmi le groupe comprenant : un groupe -CH2CH2, un groupe -CH2CH2-CH2, un groupe -CH2-CH(CH3) ; et
    - w représente des valeurs entre 1 et 120, de préférence de 10 à 80, en particulier de 20 à 40 ;
    c) de 10 à 50 % en poids de citrate :
    d) de 2 à 15 % en poids de percarbonate de sodium ;
    e) de 2 à 8 % en poids d'un agent complexant choisi parmi le groupe comprenant l'acide 1-hydroxyéthane-1,1-diphosphonique et l'acide méthylglycinediacétique.
  10. Agent pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications précédentes, contenant
    a) un copolymère comprenant :
    i) des monomères choisis parmi le groupe des acides carboxyliques une ou plusieurs fois insaturés ;
    ii) des monomères répondant à la formule générale R1(R2)C=C(R3)-X-R4, dans laquelle les résidus R1 à R3 représentent, indépendamment l'un de l'autre, un atome d'hydrogène, un groupe -CH3 ou un groupe -C2H5, X représente un groupe faisant office d'espaceur présent de manière facultative, qui est choisi parmi un groupe -CH2-, un groupe -C(O)O- et un groupe -C(O)-NH-, et R4 représente un résidu alkyle saturé à chaîne droite ou ramifiée contenant de 2 à 22 atomes de carbone ou représente un résidu insaturé de préférence aromatique contenant de 6 à 22 atomes de carbone ;
    b) un agent tensioactif non ionique répondant à la formule générale R1-CH(OH)CH2O-(AO)w-R2, dans laquelle
    - R1 représente un résidu alkyle ou alcényle en C6-C24 à chaîne droite ou ramifiée, saturé ou une, respectivement plusieurs fois insaturé ;
    - R2 représente un résidu d'hydrocarbure linéaire ou ramifié contenant de 2 à 26 atomes de carbone ;
    - A représente un résidu choisi parmi le groupe comprenant : un groupe -CH2CH2, un groupe -CH2CH2-CH2, un groupe -CH2-CH(CH3) ; et
    - w représente des valeurs entre 1 et 120, de préférence de 10 à 80, en particulier de 20 à 40 ;
    c) de 10 à 50 % en poids de citrate :
    d) de 2 à 15 % en poids de percarbonate de sodium ;
    e) de 2 à 8 % en poids d'un agent complexant choisi parmi le groupe comprenant l'acide 1-hydroxyéthane-1,1-diphosphonique et l'acide méthylglycinediacétique ;
    f) de 1,0 à 6 % en poids d'enzyme.
  11. Procédé pour le lavage de lave-vaisselle dans un lave-vaisselle, dans lequel on met en oeuvre l'agent pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications 1 à 10.
  12. Procédé selon la revendication 11, caractérisé en ce qu'on n'introduit de manière dosée aucun adoucisseur d'eau supplémentaire et aucun agent de rinçage supplémentaire à l'intérieur du lave-vaisselle au cours du processus de lavage.
EP07847827A 2007-02-06 2007-12-05 Détergents Revoked EP2115113B1 (fr)

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DE102007006629A DE102007006629A1 (de) 2007-02-06 2007-02-06 Reinigungsmittel
PCT/EP2007/063331 WO2008095563A1 (fr) 2007-02-06 2007-12-05 Détergents

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EP2115113A1 EP2115113A1 (fr) 2009-11-11
EP2115113B1 true EP2115113B1 (fr) 2012-11-28

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EP (1) EP2115113B1 (fr)
DE (1) DE102007006629A1 (fr)
ES (1) ES2396568T3 (fr)
PL (1) PL2115113T3 (fr)
WO (1) WO2008095563A1 (fr)

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DE102007006629A1 (de) 2008-08-07
PL2115113T3 (pl) 2013-04-30
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US8303721B2 (en) 2012-11-06
EP2115113A1 (fr) 2009-11-11
ES2396568T3 (es) 2013-02-22

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