EP2859078B1 - Détergents pour vaisselle - Google Patents

Détergents pour vaisselle Download PDF

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Publication number
EP2859078B1
EP2859078B1 EP13727587.1A EP13727587A EP2859078B1 EP 2859078 B1 EP2859078 B1 EP 2859078B1 EP 13727587 A EP13727587 A EP 13727587A EP 2859078 B1 EP2859078 B1 EP 2859078B1
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EP
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Prior art keywords
acid
dishwashing detergent
weight
preferred
dishwashing
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EP13727587.1A
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German (de)
English (en)
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EP2859078A1 (fr
Inventor
Nina Mussmann
Thomas Eiting
Christian Kropf
Konstantin Benda
Thorsten Bastigkeit
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL13727587T priority Critical patent/PL2859078T3/pl
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic 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
    • C11D3/18—Hydrocarbons
    • C11D3/185—Hydrocarbons cyclic
    • 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
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • dishwashing detergents which are preferably in the form of tablets, as well as automatic dishwashing processes using these dishwashing detergents, and the use of these dishwashing detergents for removing soiling and for inhibiting coating in automatic dishwashing.
  • Dishwashing detergents are available to the consumer in a variety of forms. In addition to the traditional liquid hand dishwashing detergents, in particular the automatic dishwashing detergents have gained great importance with the spread of household dishwashers.
  • Machine dishwashing detergents commonly used today generally contain phosphorus-containing ingredients, in particular phosphates and / or phosphonates, which are used as builders in the compositions.
  • Phosphate-free dishwashing detergents are used in GB 1470400 A .
  • US 4092348 A and US 3459670 A disclosed.
  • EP 0748864 A1 discloses liquid and partially phosphate-free cleaners for specific surface types.
  • a phosphate-containing machine dishwashing detergent which optionally may contain polycarboxylates, is disclosed in U.S. Pat DE 102007019457 A1 disclosed.
  • EP 0892040 A2 describes chelating compositions containing polycarboxylic acids of a particular formula.
  • phosphorus-containing ingredients are considered harmful to the environment and according to statutory regulations, a limitation of the use of phosphorus-containing ingredients is to be expected, there is a need to provide dishwashing detergents that even without phosphorus-containing ingredients an equivalent replacement for today's common phosphorus -containing, in particular phosphonate and / or phosphate-containing means.
  • One object was to provide phosphate- and / or phosphonate-free compositions which have an equivalent cleaning performance to corresponding phosphate and / or phosphonate-containing agents.
  • a further object was to provide agents with an equivalent secondary performance, in particular with an equivalent deposit inhibition.
  • these improved properties should preferably also in low-temperature cleaning operations, ie in cleaning processes with Spülflottentemperaturen of 50 ° C or below, and / or in short-term cleaning process, especially in cleaning process with a duration of less than 60 minutes, can be achieved.
  • dishwashing detergents which contain at least one cyclic compound having at least two carboxylate groups and at least one phosphorus-free builder and from 0.5 to 20 wt .-% phosphonate (s) according to claim 1, wherein the phosphorus-free builder is selected from the group consisting of citrate, (hydrogen) carbonate, MGDA (methyl glycine diacetic acid), GLDA (glutamic acid diacetate), ASDA (aspartic acid diacetate), HEIDA (hydroxyethyliminodiacetate), IDS (iminodisuccinate) and EDDS (ethylene diamine disuccinate) and mixtures thereof.
  • a first subject of the present invention are therefore dishwashing compositions which according to claim 1 contain at least one cyclic compound having at least two carboxylate groups and at least one phosphorus-free builder and from 0.5 to 20 wt .-% phosphonate (s), wherein the phosphorus-free builder is selected from the group consisting of citrate, (hydrogen) carbonate, MGDA (methylglycinediacetic acid), GLDA (glutamic acid diacetate), ASDA (aspartic acid diacetate), HEIDA (hydroxyethyliminodiacetate), IDS (iminodisuccinate) and EDDS (ethylenediaminedisuccinate), and mixtures thereof.
  • the dishwashing agent is preferably a solid dishwashing detergent.
  • a "solid dishwashing detergent” is to be understood as meaning a dishwashing detergent which is in a solid state of aggregation at 25 ° C. and a pressure of 1 bar.
  • the solid dishwashing detergent is in the form of a shaped body, in particular a compactate, above all a tablet.
  • the cyclic compound comprising at least two carboxylate groups may in particular be an alicyclic, a bicyclic or a saturated heterocyclic compound.
  • the alicyclic compound is preferably cyclopropane, cyclobutane, cyclopentane, cyclohexane or cycloheptane, more preferably cyclopropane, cyclobutane or cyclopentane, most preferably cyclopentane.
  • the saturated heterocyclic compound is preferably tetrahydrofuran.
  • the bicyclic compound is preferably bicyclo [2.2.1] heptane or bicyclo [2.2.2] octane.
  • the cyclic compound comprises at least two carboxylate groups, preferably at least three carboxylate groups, in particular at least four carboxylate groups.
  • the cyclic compound comprises four carboxylate groups.
  • a compound which is very particularly preferred according to the invention is the cyclopentane tetracarboxylate.
  • carboxylate in addition to the anionic form also includes the hydrogenated form of the carboxylate, ie the carboxylic acid group.
  • carboxylate according to the invention is also understood as meaning carboxylic anhydride groups. The formation of anhydride groups can be effected in this case in particular by adjacent carboxylate groups in the molecule.
  • At least two, preferably at least three, more preferably at least four carboxylate groups are located on the same side of the cyclic compound, that is, they are arranged in the cis configuration.
  • the following cyclic compounds are particularly preferably used molecules: 1c, 2c, 3c, 4c-cyclopentanetetracarboxylate, 1c, 2c, 3c, 4t-cyclopentanetetracarboxylate, 1c, 2c, 3t, 4t-cyclopentanetetracarboxylate, 1c , 2t, 3t, 4c-cyclopentane tetracarboxylate, tetrahydrofuran-2c, 3c, 4c, 5c-tetracarboxylate, tetrahydrofuran-2c, 3c, 4c, 5t-tetracarboxylate, tetrahydrofuran-2c, 3c, 4t, 5t-tetracarboxylate, tetrahydrofuran-2c, 3c, 4t, 5t-tetracarboxylate, tetrahydrofuran-2c, 3t , 4t, 5t-tetracarboxylate,
  • Very particularly preferred according to the invention is 1c, 2c, 3c, 4c-cyclopentanetetracarboxylate.
  • the cyclic compound which comprises at least two carboxylate groups is preferably present in agents according to the invention in an amount of from 0.01 to 10% by weight, more preferably in an amount of from 0.02 to 5% by weight, in particular in one Amount of 0.05 to 2 wt .-%, contained.
  • automatic dishwasher detergents according to the invention comprise one or more phosphorus-free builders.
  • the proportion by weight of the phosphorus-free builders in the total weight of automatic dishwashing detergents according to the invention is preferably from 5 to 80% by weight, more preferably from 15 to 75% by weight and in particular from 30 to 70% by weight.
  • the phosphorus-free builders are (hydrogen) carbonates, citrates, methylglycinediacetic acid (MGDA), glutamic acid diacetate (GLDA), aspartic acid diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS) and ethylenediamine disuccinate (EDDS).
  • MGDA methylglycinediacetic acid
  • GLDA glutamic acid diacetate
  • ASDA aspartic acid diacetate
  • HEIDA hydroxyethyliminodiacetate
  • IDS iminodisuccinate
  • EDDS ethylenediamine disuccinate
  • organic co-builders are polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals and dextrins. 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.
  • Machine dishwasher detergents contain citrate as one of their essential builders.
  • Machine dishwashing detergents characterized in that they contain 2 to 40% by weight, preferably 5 to 30% by weight and in particular 7 to 20% by weight citrate, are preferred according to the invention.
  • the citrates are preferably used in combination with carbonates and / or bicarbonates.
  • Preferred automatic dishwashing detergents are therefore characterized by a builder combination of citrate and carbonate / bicarbonate.
  • the dishwashing detergent contains, in addition to citrate and (hydrogen) carbonate, at least one further phosphorus-free builder, the further phosphorus-free builder preferably being selected from MGDA, GLDA, ASDA, HEIDA, IDS and EDDS, particularly preferably from MGDA and GLDA, wherein the weight fraction of the builders, based on the total weight of the automatic dishwashing agent, is preferably 5 to 80 wt .-%, preferably 15 to 75 wt .-% and in particular 30 to 70 wt .-%.
  • the wt .-% - proportion of (hydrogen) carbonate and citrate is preferably as stated above.
  • the percentage by weight of the further phosphorus-free builder, in particular of the MGDA and / or GLDA, is preferably from 2 to 40% by weight, in particular from 5 to 30% by weight, especially from 7 to 20% by weight.
  • the combination of at least three builders from the above-mentioned group has proved to be advantageous for the cleaning and rinsing performance of automatic dishwashing agents according to the invention.
  • 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.
  • the content of the automatic dishwashing agents on (homo) polymeric polycarboxylates is preferably 0.5 to 20% by weight and in particular 3 to 10% by weight.
  • Machine dishwashing detergents according to the invention can furthermore comprise, as builder, crystalline stratiform 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.
  • the content of silicates is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight.
  • Particularly preferred automatic dishwasher detergents according to the invention are silicate-free.
  • the agents according to the invention may contain alkali metal hydroxides.
  • These alkali carriers are preferred in the cleaning agents only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, preferably below 5 wt .-%, particularly preferably between 0.1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of the cleaning agent used.
  • Alternative automatic dishwashing detergents are free of alkali metal hydroxides.
  • Compositions according to the invention contain from 0.5 to 20% by weight of phosphonate (s).
  • Phosphonates which can be used according to the invention are preferably selected from aminotrimethylenephosphonic acid (ATMP); Ethylenediaminetetra (methylenephosphonic acid) (EDTMP); Diethylene triamine penta (methylenephosphonic acid) (DTPMP); 1-hydroxyethane-1,1-diphosphonic acid (HEDP); 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC); Hexamethylenediaminetetra (methylenephosphonic acid) (HDTMP) and nitrilotri (methylenephosphonic acid) (NTMP), with particular preference to 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylenetriaminepenta (methylenephosphonic acid) (DTPMP).
  • Phosphonate (s) are used in inventive compositions in amounts of 0.5 to 20 wt .-%, in particular from 0.5 to 10
  • Inventive agents are preferably largely phosphate-free.
  • the content of phosphates based on the total weight of the automatic dishwashing agent, is below 10% by weight, preferably below 5% by weight, in particular below 2% by weight, above all below 0.5 % By weight limited.
  • Particularly preferred automatic dishwasher detergents according to the invention are completely phosphate-free.
  • the content of phosphorus-containing builders based on the total weight of the automatic dishwashing agent, to amounts below 10 wt .-%, preferably below 5 wt .-%, especially below 2 wt .-%, especially below 0.5 wt .-% limited.
  • Particularly preferred machine dishwasher detergents according to the invention are generally free of phosphorus-containing builders.
  • Dishwashing agents according to the invention contain in a preferred embodiment as further constituent at least one zinc salt.
  • the zinc salt may be an inorganic or organic zinc salt.
  • the zinc salt to be used according to the invention preferably has a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and especially above 5 g / l (all solubilities at 20 ° C water temperature).
  • the inorganic zinc salt is preferably selected from the group consisting of zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate.
  • the organic zinc salt is preferably selected from the group consisting of zinc salts of monomeric or polymeric organic acids, in particular from the group zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate and zinc p-toluenesulfonate.
  • zinc acetate is used as the zinc salt.
  • the zinc salt is preferably present in dishwashing detergents according to the invention in an amount of from 0.01 to 3% by weight, more preferably in an amount of from 0.05 to 2% by weight, in particular in an amount of from 0.1 to 1% by weight. %, contain.
  • the dishwashing agent according to the invention contains at least one nonionic surfactant.
  • nonionic surfactants it is possible to use all nonionic surfactants known to the person skilled in the art.
  • Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) x in which R corresponds to a primary straight-chain or methyl-branched, especially methyl-branched, 2-position aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol is that for a glycose 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 1.2 to 1.4.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • polyhydroxy fatty acid amides of the formula wherein R is an aliphatic acyl radical having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • washing or cleaning agents in particular automatic dishwashing detergents, contain nonionic surfactants from the group of the alkoxylated alcohols.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • ethoxylated nonionic surfactants consisting of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol of ethylene oxide per mol Alcohol was used.
  • a particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 -alcohol and at least 12 mol, preferably at least 15 mol and especially at least 20 mol of ethylene oxide.
  • C 16-20 alcohol straight-chain fatty alcohol having 16 to 20 carbon atoms
  • C 18 -alcohol preferably a C 18 -alcohol
  • at least 12 mol preferably at least 15 mol and especially at least 20 mol of ethylene oxide.
  • the so-called “narrow range ethoxylates” are particularly preferred.
  • surfactants are further used which contain one or more tallow fatty alcohols with 20 to 30 EO in combination with a silicone defoamer.
  • Nonionic surfactants which have a melting point above room temperature.
  • Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pa ⁇ s, preferably above 35 Pa ⁇ s and in particular above 40 Pa ⁇ s. Nonionic surfactants which have waxy consistency at room temperature are also preferred.
  • Nonionic surfactants from the group of alkoxylated alcohols are also used with particular preference.
  • the nonionic surfactant solid at room temperature preferably has propylene oxide units in the molecule.
  • such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.
  • Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.
  • surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
  • More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
  • nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
  • surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
  • nonionic surfactants of the general formula in which R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 -alkyl or -alkenyl radical; each group R 2 or R 3 is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 and the indices w, x, y, z independently stand for integers from 1 to 6.
  • the preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
  • the radical R 1 in the above formula may vary depending on the origin of the alcohol. If native sources are used, the radical R 1 has an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of natural origin having 12 to 18 C atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred.
  • Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals.
  • nonionic surfactants in which R 1 in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.
  • alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide.
  • R 2 or R 3 are independently selected from -CH 2 CH 2 -CH 3 or CH (CH 3 ) 2 are suitable.
  • nonionic surfactants having a C 9-15 alkyl group having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units.
  • These surfactants exhibit in aqueous solution to the required low viscosity and are inventively used with particular preference.
  • R 1 -CH (OH) CH 2 O- (AO) w - (A'O) x (A "O) y - (A"'O) z -R 2 in which R 1 and R 2 independently of one another a straight-chain or branched, saturated or mono- or polyunsaturated C 2-40 alkyl or alkenyl radical;
  • A, A ', A "and A'” independently represent a radical from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH (CH 3 ) -CH 2 -, -CH 2 -CH (CH 2 -CH 3 ); and
  • w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0, are particularly preferred according to the invention.
  • nonionic surfactants of the general formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (CH 3 ) O] z CH 2 CH (OH) R 2 , in which R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 22, in particular 6 to 18, carbon atoms or mixtures thereof, R 2 is a linear or branched hydrocarbon radical having 2 to 26, in particular 4 to 20, carbon atoms or mixtures thereof and x and z are values between 0 and 40 and y is a value of at least 15, preferably from 15 to 120, particularly preferably from 20 to 80.
  • the automatic dishwashing detergent contains, based on its total weight, nonionic surfactant of the general formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (CH 3 ) O ] z CH 2 CH (OH) R 2 in amounts of from 0.1 to 15% by weight, preferably from 0.2 to 10% by weight, particularly preferably from 0.5 to 8% by weight and in particular from 1, 0 to 6 wt .-%.
  • R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 22, in particular 6 to 16, carbon atoms or mixtures thereof
  • R 2 denotes a linear or branched hydrocarbon radical having 2 to 26, in particular 4 to 20, carbon atoms or mixtures thereof
  • y for a value between 15 and 120, preferably 20 to 100, in particular 20 to 80 stands.
  • the group of these nonionic surfactants includes, for example, hydroxy mixed ethers of the general formula C 6-22 -CH (OH) CH 2 O- (EO) 20-120 -C 2 -26 , for example the C 8-12 fatty alcohol (EO) 22 - 2-hydroxydecyl ether and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ethers.
  • R 1 CH (OH) CH 2 O- (CH 2 CH 2 O) 20-120 -R 2 is used, wherein R 1 and R 2 are independently a linear or branched aliphatic hydrocarbon radical having 2 to 20, in particular 4 to 16 , Carbon atoms are particularly preferred.
  • R 1 is a linear or branched aliphatic hydrocarbon radical with 4 R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 4, preferably 0.5 to 1.5, and y for a value of at least 15 stands.
  • Also preferred according to the invention are also surfactants of the general formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 CH (OH) R 2 in which R 1 is a linear or branched aliphatic radical Hydrocarbon radical having 4 to 22 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 is a value between 1 and 40 and y is a value between 15 and 40, wherein the alkylene units [CH 2 CH (CH 3 ) O] and [CH 2 CH 2 O] randomized, ie in the form of a random random distribution.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 , in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the above formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 may be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred are.
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different if x ⁇ 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • nonionic surfactants are nonionic surfactants of the general formula R 1 O (AlkO) x M (OAlk) y OR 2 , where R 1 and R 2 independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms; Alk is a branched or unbranched alkyl radical having 2 to 4 carbon atoms; x and y independently represent values between 1 and 70; and M is an alkyl radical selected from the group CH 2 , CHR 3 , CR 3 R 4 , CH 2 CHR 3 and CHR 3 CHR 4 , where R 3 and R 4 independently of one another represent a branched or unbranched, saturated or unsaturated alkyl radical having 1 to 18 carbon atoms.
  • R 1 -CH (OH) CH 2 -O (CH 2 CH 2 O) x CH 2 CHR (OCH 2 CH 2 ) y O-CH 2 CH (OH) -R 2 in where R is a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and n and m independently of one another have values of 20 to 30.
  • Corresponding compounds can be obtained, for example, by reaction of alkyldiols HO-CHR-CH 2 -OH with ethylene oxide, followed by reaction with an alkyle epoxide to close the free OH functions to form a dihydroxy ether.
  • R 1 -O (CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2) y OR 2 are in which R 3 and R 4 is H, and the subscripts x and y are independently of one another assume values from 1 to 40, preferably from 1 to 15.
  • R 1 -O (CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2) y OR 2 in which the radicals R 1 and R 2 are independently saturated alkyl radicals having from 4 to Represent 14 carbon atoms and the indices x and y independently of one another assume values of 1 to 15 and in particular of 1 to 12.
  • 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. Of course, the aforementioned nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.
  • surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas ,
  • the proportion by weight of the nonionic surfactant in the total weight of the inventive automatic dishwashing agent in a preferred embodiment is from 0.1 to 20% by weight, more preferably from 0.5 to 15% by weight, in particular from 2.5 to 10% by weight. %.
  • the weight% ratio of anionic surfactant having at least one sulfate or sulfonate group to nonionic surfactant is from 3: 1 to 1: 3, especially from 2: 1 to 1: 2, more preferably from 1 , 5: 1 to 1: 1.5.
  • Another object of the present invention is also a machine dishwashing process using the aforementioned solid dishwashing detergent, in particular in the form of a previously mentioned shaped body, in particular for the removal, especially improved removal, of greasy soilings, especially for the removal of stains by egg yolk.
  • the dishwashing process is preferably carried out at a liquor temperature below 60 ° C, preferably below 50 ° C.
  • the dishwashing process takes a maximum of 90 minutes, in particular a maximum of 75 minutes, more preferably a maximum of 60 minutes.
  • the dishwashing process lasts for a maximum of 50, 40, or 30 minutes.
  • the present application relates to automatic dishwashing detergents.
  • Automatic dishwashing detergents are compositions which can be used to clean soiled dishes in a dishwasher automatic dishwashing process.
  • the automatic dishwasher detergents according to the invention differ, for example, from the machine rinse aid agents, which are always used in combination with automatic dishwashing detergents and do not develop their own cleaning action.
  • the automatic dishwashing compositions according to the invention are preferably in the form of a shaped body, in particular a compactate, in particular a tablet. You can, however, also in Combination with other forms of supply, in particular in combination with solid forms such as powders, granules or extrudates or in combination with liquid supply forms based on water and / or organic solvents.
  • the shaped body may, for example, also be a granulate which is contained in a bag or a casting mold.
  • Inventive agents can be formulated as single-phase or multi-phase products.
  • Machine dishwashing detergents with one, two, three or four phases are particularly 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.
  • Two-phase or multi-phase tablets for example two-layer tablets, in particular two-layer tablets with a trough and a shaped body located in the trough, are particularly 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 dishwashing compositions according to the invention in particular the prefabricated dosage units, in a preferred embodiment have a water-soluble coating.
  • Inventive moldings contain in a preferred embodiment polyvinylpyrrolidone particles. These particles facilitate, inter alia, the disintegration of the moldings and serve insofar as disintegration aids or tablet disintegrating agents. It has been found according to the invention to be particularly advantageous to use polyvinylpyrrolidone particles having an average particle diameter of 100 to 150 .mu.m, in particular having an average particle diameter of 110 to 130 .mu.m.
  • the term "average particle diameter” or “average diameter” is to be understood as meaning the volume-average D 50 particle diameter which can be determined by customary methods.
  • the volume average D 50 particle diameter is that point in the particle size distribution in which 50% by volume of the particles have a smaller diameter and 50% by volume of the particles have a larger diameter.
  • the mean particle diameter can be determined in particular by means of dynamic light scattering, which are usually carried out on dilute suspensions containing, for example, from 0.01 to 1% by weight of particles.
  • the PVP particles not only have an average particle diameter of 100 to 150 .mu.m, in particular from 110 to 130 .mu.m, but moreover, the particle size of the particles used is preferably completely in the specified intervals. This is ensured by using grain size fractions with the indicated particle sizes obtained by a sieving process.
  • the PVP particles are preferably present in compositions according to the invention in an amount of from 0.1 to 5% by weight, in particular in an amount of from 0.2 to 3% by weight, in particular in an amount of from 0.3 to 1, 8 wt .-%, contained.
  • disintegrants usually that they increase their volume upon ingress of water, whereby on the one hand increases the intrinsic volume (swelling), but on the other hand by the release of gases, a pressure can be generated, which can disintegrate the tablet into smaller particles .
  • other disintegrants may also be present in moldings according to the invention, for example carbonate / citric acid systems or carbonate in combination with other organic acids, synthetic polymers or natural polymers or modified natural substances such as cellulose and starch and their derivatives and Alginates or casein derivatives.
  • gas-evolving effervescent systems can also be used as further disintegrants.
  • Preferred effervescent systems consist of at least two constituents which react with one another to form gas, for example alkali metal carbonate and / or bicarbonate and an acidifier which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution.
  • An acidifying agent that releases carbon dioxide from the alkali salts in aqueous solution is, for example, citric acid.
  • the further disintegration aids are, if used, preferably in amounts of 0.1 to 10 wt .-%, preferably 0.2 to 5 wt .-% and in particular 0.5 to 2 wt .-%, each based on the total weight of desintegrationsakusstoffumblen agent used.
  • the shaped body according to the invention contains no further disintegration auxiliaries apart from the PVP particles.
  • the production of the shaped bodies according to the invention preferably takes place in a manner known to the person skilled in the art by compression of particulate starting substances.
  • the premix is compressed in a so-called matrix between two punches to form a solid compressed product.
  • This process in the following short referred to as tabletting, is divided into four sections: metering, compaction (elastic deformation), plastic deformation and ejection.
  • the tabletting is preferably carried out on so-called rotary presses.
  • the ingredients provided for tabletting can be added in the form of a common particulate premix at the same time or in the form of individual, separate powders or granules offset in time or at the same time in the mold, the dosage of a prefabricated particulate premix is preferred.
  • compacts having a hardness in the range from 150 to 250 N, in particular in the range from 200 to 230 N, which in addition is a particularly good one can preferably be obtained by using a pressing force of 40 to 65 kN, more preferably 48 to 60 kN Have trickle behavior.
  • the granules can thus preferably be pressed with relatively low pressing force into compact materials having a relatively high hardness, which moreover preferably have a very good trickling behavior. Accordingly, it is conversely advantageous for the production of compact materials of lower hardness preferably a lower pressing force must be used, as for the production of conventional compactates.
  • Automatic dishwashing detergents according to the invention contain as further constituent in a preferred embodiment at least one anionic polymer.
  • Preferred anionic polymers here are the copolymeric polycarboxylates and the copolymeric polysulfonates.
  • the proportion by weight of the anionic polymer in the total weight of the inventive automatic dishwashing agent in a preferred embodiment is from 0.1 to 20% by weight, preferably from 0.5 to 18% by weight, particularly preferably from 1.0 to 15% by weight. % and in particular from 4 to 14 wt .-%.
  • Automatic dishwashing detergents characterized in that the copolymeric anionic polymer is selected from the group of the hydrophobically modified polycarboxylates and polysulfonates is a particularly preferred object, since by the hydrophobic modification of the anionic copolymers an improvement of the rinsing and drying properties of these agents with simultaneously low deposit formation can be reached.
  • the copolymers may have two, three, four or more different monomer units.
  • Preferred copolymeric polysulfonates contain not only sulfonic acid group-containing monomer (s) but also at least one monomer selected from the group consisting of unsaturated carboxylic acids.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. It goes without saying that it is also possible to use the unsaturated dicarboxylic acids.
  • Copolymers of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid are particularly preferably used according to the invention as copolymeric polycarboxylates.
  • 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.
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble
  • the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.
  • the monomer distribution of the copolymers preferably used according to the invention in the case of copolymers containing only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably from 5 to 95% by weight, more preferably from 50 to 90% by weight of the sulfonic acid group-containing monomer. % and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are hereby preferably selected from the aforementioned.
  • 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 automatic dishwashing detergents are characterized in that the copolymers have molecular weights 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 copolymers in addition to the carboxyl group-containing monomer and the monomer containing the sulfonic acid group, the copolymers further comprise at least one nonionic, preferably hydrophobic monomer.
  • the use of these hydrophobically modified polymers has made it possible in particular to improve the rinse aid performance of automatic dishwashing detergents according to the invention.
  • nonionic 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, ethylcyclohexyn, 1-octene, ⁇ -olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C
  • Dishwashing agents according to the invention furthermore preferably contain enzyme (s) to ensure their cleaning action.
  • Dishwashing agents preferably comprise enzyme (s) as a further constituent.
  • enzyme 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, as well as 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, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors.
  • lipases or cutinases include, for example, the lipases originally obtainable from Humicola lanuginosa ( Thermomyces lanuginosus ) or further developed, in particular those with the amino acid exchange D96L.
  • Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect.
  • organic compounds are additionally preferably used aromatic, interacting with the enzymes compounds added to enhance the activity of the respective oxidoreductases (enhancer) or to ensure the electron flow at greatly varying redox potentials between the oxidizing enzymes and the stains (mediators).
  • 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.
  • Washing or cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storable and transportable preparations.
  • Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
  • the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • Protease and amylase preparations preferably used according to the invention 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 wt .-% of the enzyme protein.
  • compositions according to the invention may contain further washing or cleaning-active substances, preferably from the group of bleaches, bleach activators and bleach catalysts, glass corrosion inhibitors, corrosion inhibitors, fragrances and perfume carriers. These preferred ingredients will be described in more detail below.
  • Machine dishwashing detergents according to the invention may contain a bleaching agent as further constituent, with oxygen bleaches being preferred.
  • a bleaching agent as further constituent, with oxygen bleaches being preferred.
  • sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • bleaching agents from the group of organic bleaching agents can also be used.
  • Typical organic bleaching agents are the diacyl peroxides, e.g. Dibenzoyl.
  • Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred automatic dishwashing agents according to the invention are characterized in that they contain an oxygen bleaching agent, preferably sodium percarbonate, more preferably a coated sodium percarbonate.
  • the proportion by weight of the bleaching agent, based on the total weight of the washing or cleaning agent, in preferred embodiments is between 2 and 30% by weight, preferably between 4 and 20% by weight and in particular between 6 and 15% by weight.
  • the automatic dishwasher detergents according to the invention may contain bleach activators.
  • bleach activators These compounds give under perhydrolysis aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated carbon atom number and / or optionally substituted benzoyl groups.
  • TAED tetraacetylethylenediamine
  • Automatic dishwashing detergent characterized in that it is a bleach activator bleach activator from the group of acetylated amines, preferably tetraacetylenediamine (TAED), are preferred according to the invention.
  • bleach activators in particular TAED, are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 10% by weight, especially 0.5 to 8% by weight and more preferably 1.0 to 6 Wt .-%, used.
  • the automatic dishwasher detergents according to the invention preferably contain at least one bleach catalyst.
  • bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • complexes of manganese in the oxidation state II, III, IV or IV which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S.
  • ligands are used which have nitrogen donor functions.
  • bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononan (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and or 2-methyl-1,4,7-triazacyclononane (Me / TACN).
  • 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 catalyst-containing agents used. In special cases, however, more bleach catalyst can be used.
  • the active substance combinations described above are particularly suitable for cleaning dishes in automatic dishwashing processes.
  • Another object of the present application is therefore a method for cleaning dishes in a dishwasher using a dishwashing detergent according to the invention, wherein the dishwashing detergent is 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 dosing or the entry of the agent according to the invention in the interior of the dishwasher can be done manually, but preferably the agent is metered by means of the dosing of the dishwasher in the interior of the dishwasher.
  • no additional water softener and no additional rinse aid is dosed into the interior of the dishwasher.
  • the dishwasher detergents according to the invention exhibit their advantageous cleaning properties, in particular also in low-temperature cleaning processes and in short-lasting purification processes.
  • Preferred dishwashing processes using agents according to the invention are therefore characterized in that the dishwashing processes are carried out at a liquor temperature below 60 ° C., preferably below 50 ° C., and / or a time of less than 90 minutes, preferably less than 60 minutes, in particular less than 45 Minutes.
  • Example 1 Pad inhibition of a phosphate-free agent
  • the dishwasher contained the following load: 3 Willybecher 0,21, 3 whiskey cups, 3 black breakfast plates, 3 glass plates black, 3 blue Mepal melamine plates, 3 blue PP plates, 3 blue SAN dessert plates, 3 stainless steel knives from WMF, 3 stainless steel knives from BSF, 2 shiny ones Coffee trays, 2 stainless steel butter dishes.
  • CP-TCA cyclopentane tetracarboxylate
  • THF-TCA tetrahydrofuran tetracarboxylate
  • Example 2 Pad inhibition of a phosphate and phosphonate-free agent
  • the pad inhibition of a phosphate- and phosphonate-free dishwashing detergent containing, in addition to conventional ingredients, soda, citrate and MGDA and added to the cyclopentane tetracarboxylate was tested.
  • the scale inhibition of the same dishwashing detergent was checked without adding the cyclic compound.
  • the scale inhibition of the same dishwashing detergent to which phosphonate was added in place of the cyclopentane tetracarboxylate was checked.
  • the dishwashing detergent was used in the form of a tablet.
  • the cyclic compound or phosphonate was added in powder form (0.5 grams per rinse cycle).
  • the dosage of the dishwashing agent took place via the metering device of the dishwasher.
  • the dishwashing process was carried out in a dishwasher Miele G1355 SC (program: 50 ° C light turbo, water hardness 21 ° dH).
  • the dishwasher contained the following load: 3 Willybecher 0,21, 3 whiskey cups, 3 black breakfast plates, 3 glass plates black, 3 blue Mepal melamine plates, 3 blue PP plates, 3 blue SAN dessert plates, 3 stainless steel knives from WMF, 3 stainless steel knives from BSF, 2 shiny ones Coffee trays, 2 stainless steel butter dishes.
  • plaque inhibition results on plastic are shown in the following table: product Friesland plate Plastic SAN Phosphate and phosphonate-free agent 4.0 2.7 Phosphate- and phosphonate-free agent + CP-TCA 5.0 4.3 Phosphate-free agent + phosphonate 4.7 6.0
  • CP-TCA cyclopentane tetracarboxylate

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  • Detergent Compositions (AREA)

Claims (10)

  1. Détergent pour vaisselle, caractérisé en ce qu'il contient au moins un composé cyclique comportant au moins deux groupes carboxylate ainsi qu'au moins un adjuvant sans phosphore et à raison de 0,5 à 20 % en poids de phosphonate(s), l'adjuvant sans phosphore étant choisi dans le groupe constitué par le citrate, le carbonate (d'hydrogène), le MGDA (acide méthyleglycine diacétique), le GLDA (diacétate d'acide glutamique), l'ASDA (diacétate d'acide aspartique), l'HEIDA (hydroxyéthyliminodiacétate), l'IDS (iminodisuccinate) et l'EDDS (disuccinate d'éthylènediamine), et des mélanges de ceux-ci.
  2. Détergent pour vaisselle selon la revendication 1, caractérisé en ce que le composé cyclique comportant au moins deux groupes carboxylate est choisi dans le groupe constitué par le cyclopropane, le cyclobutane, le cyclopentane et le cyclohexane, de manière particulièrement préférée le cyclopentane, comprenant au moins trois, de préférence quatre ou cinq groupes carboxylate, et est de préférence présent en une quantité de 0,01 à 10 % en poids, de manière particulièrement préférée de 0,02 à 5 % en poids, en particulier de 0,05 à 2 % en poids.
  3. Détergent pour vaisselle selon la revendication 1 ou 2, caractérisé en ce que l'adjuvant sans phosphore est présent en une quantité de 5 à 80 % en poids, de manière particulièrement préférée de 15 à 75 % en poids, et en particulier de 30 à 70 % en poids.
  4. Détergent pour vaisselle selon l'une des revendications 1 à 3, caractérisé en ce qu'il contient 2 à 30 % en poids, de préférence 4 à 28 % en poids, et en particulier 8 à 24 % en poids de carbonate (d'hydrogène), 2 à 40 % en poids, de préférence 5 à 30 % en poids, et en particulier 7 à 20 % en poids de citrate et 2 à 40 % en poids, en particulier 5 à 30 % en poids, notamment 7 à 20 % en poids d'un autre adjuvant sans phosphore choisi parmi le MGDA (acide méthylglycine diacétique), le GLDA (diacétate d'acide glutamique), l'ASDA (diacétate d'acide aspartique), l'HEIDA (hydroxyéthyliminodiacétate), l'IDS (iminodisuccinate) et l'EDDS (disuccinate d'éthylènediamine), en particulier choisi parmi le MGDA (acide méthylglycine diacétique) et le GLDA (diacétate d'acide glutamique).
  5. Détergent pour vaisselle selon l'une des revendications précédentes, caractérisé en ce qu'il contient du cyclopentanetétracarboxylate en une quantité de 0,5 à 15 % en poids, en particulier de 1,5 à 7 % en poids, du carbonate d'hydrogène en une quantité de 2 à 30 % en poids, en particulier de 8 à 24 % en poids, du citrate en une quantité de 2 à 40 % en poids, en particulier de 7 à 20 % en poids et de MGDA (acide méthylglycine diacétique) en une quantité de 2 à 40 % en poids, en particulier de 7 à 20 % en poids.
  6. Détergent pour vaisselle selon l'une des revendications précédentes, caractérisé en ce qu'il contient moins de 10 % en poids, de préférence moins de 5 % en poids, en particulier moins de 2 % en poids, notamment moins de 0,5 % en poids, de manière particulièrement préférée, ne contient aucun phosphate.
  7. Détergent pour vaisselle selon l'une des revendications précédentes, caractérisé en ce qu'il contient 0,5 à 10 % en poids et notamment de 0,5 à 8 % en poids de phosphonate(s).
  8. Détergent pour vaisselle selon l'une des revendications 1 à 6, caractérisé en ce qu'il contient moins de 10 % en poids, de préférence moins de 5 % en poids, en particulier moins de 2 % en poids, notamment moins de 0,5 % en poids, de manière particulièrement préférée, ne contient aucun adjuvant phosphoré.
  9. Détergent pour vaisselle selon l'une des revendications 1 à 8, caractérisé en ce qu'il s'agit d'un détergent solide pour vaisselle et se présente de préférence sous la forme d'un corps façonné, en particulier d'un produit compacté, notamment d'une pastille.
  10. Procédé de lavage de vaisselle à la machine, caractérisé en ce que l'on utilise un détergent pour vaisselle pour le lavage en machine selon l'une des revendications précédentes.
EP13727587.1A 2012-06-06 2013-06-03 Détergents pour vaisselle Active EP2859078B1 (fr)

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DE102012209506A DE102012209506A1 (de) 2012-06-06 2012-06-06 Geschirrspülmittel
PCT/EP2013/061353 WO2013182508A1 (fr) 2012-06-06 2013-06-03 Détergents pour vaisselle

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EP2859078B1 true EP2859078B1 (fr) 2019-09-04

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DE102014208509A1 (de) 2014-05-07 2015-11-12 Henkel Ag & Co. Kgaa Reinigungsmittel
DE102014011023A1 (de) 2014-07-24 2016-01-28 Weylchem Wiesbaden Gmbh Wasch- und Reinigungsmittel enthaltend Manganoxalat, Geschirrspülverfahren und deren Verwendung
EP3456808A1 (fr) * 2017-09-13 2019-03-20 The Procter & Gamble Company Composition de nettoyage pour lave-vaisselle automatique
US20240218295A1 (en) * 2021-06-03 2024-07-04 Conopco Inc., D/B/A Unilever Machine dishwash detergent

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US3459670A (en) * 1966-07-01 1969-08-05 Monsanto Co Builders for synthetic detergents
CA925397A (en) * 1970-10-05 1973-05-01 H. Saylor Jay Detergent compositions
CH589713A5 (fr) * 1973-05-09 1977-07-15 Benckiser Gmbh Joh A
US4092348A (en) * 1977-03-03 1978-05-30 Monsanto Company Octasodium-1,1,2,2,4,4,5,5-cyclohexane octacarboxylate and compositions and methods employing same
ES2168350T3 (es) * 1995-06-12 2002-06-16 Procter & Gamble Composicion limpiadora y metodo para la limpieza de superficies delicadas.
EP0892040B1 (fr) * 1997-07-16 2003-03-05 Nippon Shokubai Co., Ltd. Utilisation des compositions chélatantes pour le nettoyage
DE102007019457A1 (de) * 2007-04-25 2008-10-30 Basf Se Maschinengeschirrspülmittel mit ausgezeichneter Klarspülleistung

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WO2013182508A1 (fr) 2013-12-12
PL2859078T3 (pl) 2020-02-28
EP2859078A1 (fr) 2015-04-15
ES2753073T3 (es) 2020-04-07
DE102012209506A1 (de) 2013-12-12

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