EP2187796B2 - Procédé de nettoyage - Google Patents

Procédé de nettoyage Download PDF

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Publication number
EP2187796B2
EP2187796B2 EP08759944.5A EP08759944A EP2187796B2 EP 2187796 B2 EP2187796 B2 EP 2187796B2 EP 08759944 A EP08759944 A EP 08759944A EP 2187796 B2 EP2187796 B2 EP 2187796B2
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EP
European Patent Office
Prior art keywords
dishwasher
und
acid
automatic dishwashing
weight
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EP08759944.5A
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German (de)
English (en)
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EP2187796A1 (fr
EP2187796B1 (fr
Inventor
Johannes Zipfel
Nadine Warkotsch
Arnd Kessler
Christian Nitsch
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL08759944T priority Critical patent/PL2187796T5/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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L15/00—Washing or rinsing machines for crockery or tableware
    • A47L15/0018—Controlling processes, i.e. processes to control the operation of the machine characterised by the purpose or target of the control
    • A47L15/0055—Metering or indication of used products, e.g. type or quantity of detergent, rinse aid or salt; for measuring or controlling the product concentration
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L15/00—Washing or rinsing machines for crockery or tableware
    • A47L15/0018—Controlling processes, i.e. processes to control the operation of the machine characterised by the purpose or target of the control
    • A47L15/0057—Cleaning of machines parts, e.g. removal of deposits like lime scale or proteins from piping or tub
    • 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
    • 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
    • C11D2111/40—Specific cleaning or washing processes
    • C11D2111/44—Multi-step processes

Definitions

  • the present application relates to a method for cleaning dishes.
  • this application relates to a method for cleaning dishes, in which cleaning agents are dosed into the interior of a dishwasher with a time delay.
  • Dishwashing detergents are available to consumers in a variety of forms. In addition to the traditional liquid hand dishwashing detergents, with the spread of household dishwashers, automatic dishwashing detergents in particular are of great importance. These automatic dishwashing detergents are typically offered to the consumer in solid form, for example as a powder or as tablets, but increasingly also in liquid form.
  • Another approach to improving the performance profile of existing detergents or cleaning agents consists in the development of new forms of packaging, for example in the combination of solid and liquid detergent or cleaning agent ingredients. Corresponding cleaning agents are combined with one another, for example, in new types of water-soluble packaging.
  • This object was achieved by a special dishwashing process in which a detergent containing surfactants and polymers is dosed into the interior of a dishwasher with a time delay.
  • the method according to the invention is carried out in the interior of a commercially available dishwasher, in particular a commercially available household dishwasher.
  • the automatic cleaning program is usually specified by the consumer before the dishwashing process is carried out by selecting from a program list, whereby in particular the temperature of the washing solution during the cleaning process, the duration of the process or the cleaning agents and aids used are defined (" 2in1 "and” 3in1 "programs).
  • the partial pumping of the washing liquor from the interior of the dishwasher is preferably carried out in such a way that at least 5% by volume, preferably 10% by volume, particularly preferably at least 20% by volume, very particularly preferably at least 40% by volume and in particular at least 60% by volume of the washing liquor are pumped out of the interior of the dishwasher.
  • at least 5% by volume preferably 10% by volume, particularly preferably at least 20% by volume, very particularly preferably at least 40% by volume and in particular at least 60% by volume of the washing liquor are pumped out of the interior of the dishwasher.
  • between 5 and 99% by volume of the washing liquor preferably between 10 and 90% by volume of the washing liquor, particularly preferably between 20 and 80% by volume and in particular between 40 to 70% by volume of the washing liquor pumped out.
  • washing liquor can also be pumped out completely, but the complete removal of the washing liquor from the interior of the dishwasher requires a comparatively large amount of time and energy and is therefore less preferred.
  • the method according to the invention is characterized in that both before and after the washing liquor has been partially pumped out of the interior of the dishwasher, an automatic dishwashing detergent containing nonionic surfactants and anionic polymers is metered into the interior of the dishwasher and thus into the washing liquor located in the interior.
  • the period of time between times t1 and t2 can vary, the method according to the invention, characterized in that the time difference between times t1 and t2 being 5 to 50 minutes, preferably 10 to 40 minutes and in particular 15 to 30 minutes, being preferred.
  • the temperature of the washing solution at time t1 is preferably between 12 and 45 ° C, preferably between 15 and 40 ° C and in particular between 20 and 35 ° C and at time t2 preferably between 30 and 65 ° C, preferably between 35 and 60 ° C and especially between 40 and 55 ° C.
  • the temperature of the washing solution at time t2 is above the temperature of the washing solution at time t1.
  • a corresponding temperature profile at which the temperature of the washing solution at time t2 is above the temperature of the washing solution at time t1 has proven to be superior in terms of cleaning and rinsing performance.
  • the dishwashing method according to the invention can of course also be carried out in such a way that the temperature of the washing solution at time t2 is below the temperature of the washing solution at time t1 or is identical to this.
  • the weight ratio of the metered amounts m1 and m2 is between 20: 1 and 2: 1, preferably between 15: 1 and 3: 1 and in particular between 12: 1 and 4: 1.
  • the automatic dishwashing detergents used in the process according to the invention are characterized by their content of nonionic surfactants and anionic polymers.
  • the nonionic surfactants have proven to be particularly effective in terms of cleaning performance and drying.
  • nonionic surfactants known to the person skilled in the art can be used as nonionic surfactants.
  • 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, in particular methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18 carbon atoms, and G the symbol is, which stands for a glycose unit with 5 or 6 carbon atoms, preferably for 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 which are 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 with 1 to 4 carbon atoms in the alkyl chain.
  • washing or cleaning agents in particular cleaning agents for automatic dishwashing, particularly preferably contain nonionic surfactants from the group of alkoxylated alcohols.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 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 may contain linear and methyl-branched radicals in the mixture, as they are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of native origin with 12 to 18 carbon atoms for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols 3 EO or 4 EO, C 9-11 alcohol with 7 EO, C 13-15 alcohol with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohol 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 mean values which, for a specific product, can correspond to a whole number 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 are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • ethoxylated nonionic surfactants made from C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide were obtained per mole of alcohol, used.
  • a particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol with 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 alcohol and at least 12 moles, preferably at least 15 moles and in particular at least 20 moles of ethylene oxide.
  • the so-called “narrow range ethoxylates” are particularly preferred.
  • Combinations of one or more tallow fatty alcohols with 20 to 30 EO and silicone defoamers are also used with particular preference.
  • Nonionic surfactants which have a melting point above room temperature are particularly preferred.
  • Suitable nonionic surfactants which have melting points or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can 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 a waxy consistency at room temperature, are also preferred depending on their intended use.
  • Nonionic surfactants from the group of alkoxylated alcohols particularly preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO nonionic surfactants, are also used with particular preference.
  • the nonionic surfactant which is solid at room temperature preferably has propylene oxide units in the molecule.
  • Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally contain polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol content of such nonionic surfactant molecules makes up preferably more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molar mass 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 are up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic Make up surfactants.
  • Surfactants to be used with preference come from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with structurally complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • structurally complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • Such (PO / EO / PO) non-ionic surfactants are also characterized by good foam control.
  • nonionic surfactants with melting points above room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which contains 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight.
  • Low-foaming non-ionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred nonionic surfactants in the context of the present invention.
  • surfactants with EO-AO-EO-AO blocks are again preferred, one to ten EO or AO groups being bonded to one another before a block from the other groups follows.
  • nonionic surfactants of the general formula preferably, in which R 1 stands for 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 of one another stand for whole numbers from 1 to 6.
  • the preferred nonionic surfactants of the above formula can be prepared from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide by known methods.
  • the radical R 1 in the above formula can 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 from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, or tallow fat Oleyl alcohol, are preferred.
  • Alcohols accessible from synthetic sources are, for example, the Guerbet alcohols or radicals which are methyl-branched in the 2-position or linear and methyl-branched radicals in a mixture, as they are usually present in oxo alcohol radicals.
  • nonionic surfactants in which R 1 in the above formula represents an alkyl radical with 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.
  • nonionic surfactants which have a C 9-15 -alkyl radical with 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 have the required low viscosity in aqueous solution and can be used with particular advantage according to the invention.
  • end-capped poly (oxyalkylated) nonionic surfactants which, according to the formula R 1 O [CH 2 CH 2 O] x CH 2 CH (OH) R 2 , in addition to a radical R 1 , which stands for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 2 to 30 carbon atoms, preferably with 4 to 22 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 with 1 to 30 carbon atoms, where x for values between 1 and 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.
  • R 1 which stands for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 2 to 30 carbon atoms, preferably with 4 to 22 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 with 1 to 30 carbon atoms, where x for values
  • R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH y O] y CH 2 CH (OH) R 2 , in which R 1 is a linear or branched aliphatic hydrocarbon radical with 4, are particularly preferred up to 18 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof, and x stands for values between 0.5 and 1.5 and y stands for a value of at least 15.
  • the formation of deposits during machine dishwashing can be significantly improved compared to conventional polyalkoxylated fatty alcohols without a free hydroxyl group.
  • nonionic surfactants which can be used with preference are the end group-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 , in which R 1 and R 2 represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon atoms, R 3 represents H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j for 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 OCH (OH) [CH 2 ] j OR 2 can be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred.
  • 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 can be different if x 2.
  • the value 3 for x has been chosen as an example and can be larger, the range of variation increasing with increasing x values and including, for example, a large number of (EO) groups combined with a small number of (PO) groups, or vice versa .
  • R 1 , R 2 and R 3 are as defined above and x stands for numbers 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 have 9 to 14 carbon atoms, R 3 stands for H and x assumes values of 6 to 15.
  • the specified carbon chain lengths and degrees of ethoxylation or degrees of alkoxylation of the aforementioned nonionic surfactants represent statistical mean values which, for a specific product, can be a whole number or a fractional number. Because of the manufacturing process, commercial products of the formulas mentioned mostly do not consist of an individual representative, but rather of mixtures, which can result in mean values and fractional numbers for both the carbon chain lengths and the degrees of ethoxylation or alkoxylation.
  • the automatic dishwashing agent A based in each case on the total weight of the automatic dishwashing agent A, contains nonionic surfactant in amounts of 0.1 to 30% by weight, preferably 0.2 to 20% by weight, particularly preferably 0.5 to 10% by weight and in particular from 1.0 to 8% by weight.
  • nonionic surfactant is contained in the automatic dishwashing detergent A in amounts of 0.5 to 5.0% by weight, based on its total weight, are particularly preferred.
  • anionic or amphoteric surfactants preferably in combination with defoamers or foam inhibitors, can also be used in the machine dishwashing process according to the invention.
  • the anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • Surfactants of the sulfonate type are preferably C 9-13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfonates, such as those obtained, for example, from C 12-18 monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is possible.
  • Alkane sulfonates obtained from C 12-18 alkanes for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization, are also suitable.
  • the esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the production by esterification of a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • the alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of the C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis and which have a degradation behavior similar to that of the appropriate compounds based on oleochemical raw materials.
  • C 12 -C 16 -alkyl sulfates and C 12 -C 15 -alkyl sulfates and also C 14 -C 15 -alkyl sulfates are preferred.
  • the sulfuric acid monoesters of the straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12-18 - Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Preferred amphoteric surfactants are the alkylbetaines of the formula A1, the alkylamidobetaines of the formula A2, the sulfobetaines of the formula A3 and the amidosulfobetaines of the formula A4, R'-N + (CH 3 ) 2 -CH 2 COO - (A1) R 1 -CO-NH-CH 2 ) 3 -N + (CH 3 ) 2 -CH 2 COO - (A2) R 1 -N + (CH 3 ) 2 -CH 2 CH (OH) CH 2 SO 3 - (A3) R 1 -CO-NH- (CH 2 ) 3 -N + (CH 3 ) 2 -CH 2 CH (OH) CH 2 SO 3 - (A4) in which R 1 has the same meaning as in formula A.
  • amphoteric surfactants are the carbobetaines, in particular the carbobetaines of the formulas A1 and A2, extremely preferably the alkylamido betaines of the formula A2.
  • suitable betaines and sulfobetaines are the following compounds named according to INCI: Almondamidopropyl Betaine, Apricotamidopropyl Betaine, Avocadamidopropyl Betaine, Babassuamidopropyl Betaine, Behenamidopropyl Betaine, Behenyl Betaine, Betaine, Canolamidopropyl Betaine, Capryl / Capramidopropyl Betaine, Carnitine, Cocamamidopropyl Betaine, Carnitine, Cetamido-propyl Betaine Betaines, Cocamidopropyl Hydroxysultaine, Coco-Betaine, Coco-Hydroxysultaine, Coco / Oleamidopropyl Betaine, Coco-Sultaine, Decyl Be
  • a preferred amphoteric surfactant is cocamidopropyl betaine (cocoamidopropyl betaine).
  • a particularly preferred amphoteric surfactant is caprylic / Capramidopropyl Betaine (CAB), for example, under the trade name Tegofens ® B 810th from Th Goldschmidt AG is available.
  • Foam inhibitors that can be used include soaps, oils, fats, paraffins or silicone oils, which can optionally be applied to carrier materials.
  • Suitable carrier materials are, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the aforementioned materials.
  • Agents preferred in the context of the present application contain paraffins, preferably unbranched paraffins (n-paraffins) and / or silicones, preferably linear polymeric silicones, which are built up according to the scheme (R 2 SiO) x and are also referred to as silicone oils.
  • the cleaning agents used in the process according to the invention contain anionic polymers as a second essential component.
  • anionic polymers it is possible to use all washing- or cleaning-active anionic polymers known to the person skilled in the art.
  • the automatic dishwashing agent A based in each case on the total weight of the automatic dishwashing agent A, contains the anionic polymer in amounts of 0.1 to 40% by weight, preferably 0.2 to 20% by weight, preferably 0.5 to 15% by weight and in particular from 1.0 to 10% by weight.
  • Corresponding agents have proven to be advantageous in the method according to the invention, particularly with regard to optimal cleaning and rinsing results.
  • Suitable anionic polymers are, for example, the polymeric polycarboxylates, in particular the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 2000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates from this group, which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred.
  • anionic polymer is a homo- and / or copolymer of acrylic acid or methacrylic acid, are preferred.
  • the anionic polymers used in the process according to the invention can also contain sulfonic acid groups.
  • 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-hydroxy-propanesulphonic acid, allylsulphonic acid, methallylsulphonic acid, allyloxybenzenesulphonic acid, methallyloxybenzenesulphonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulphonic acid, 2-methyl-2-propen1-sulphonic acid, 3-styrenesulphonic acid, vinylsulphonic acid, vinylsulphonic acid, 3-sulfylacrylate, 3-sulfonyl-sulfonic acid -Sulfopropyl methacrylate, sulfomethacrylamide, sulfomethyl methacrylamide and mixtures
  • the sulfonic acid groups can be wholly or partly in neutralized form, i.e. the acidic hydrogen atom 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 copolymers containing sulfonic acid groups is preferred according to the invention.
  • unsaturated carboxylic acids of the general formula R 1 (R 2 ) C RC (R 3 ) COOH are used with particular preference, in which R 1 to R 3 independently of one another are - H, -CH 3 , a straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical with 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted with -NH 2, -OH or -COOH as defined above or for -COOH or -COOR 4 , where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
  • the copolymer d) furthermore comprises, in addition to the monomers i) and ii), a third monomer iii) from the group of monomers containing sulfonic acid groups.
  • the sulfonic acid groups can be wholly or partly in neutralized form, i.e. the acidic hydrogen atom 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 copolymers containing sulfonic acid groups 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 intended 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 automatic dishwashing agent A used in the process according to the invention can contain one or more builders as a further constituent.
  • the builders include, in particular, silicates, carbonates and organic cobuilders, but also the phosphates.
  • Organic cobuilders that may be mentioned are, in particular, polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and other organic cobuilders. These classes of substances are described below.
  • Organic builder substances which can be used are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or its sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, as well as mixtures of these.
  • the free acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value in detergents or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these should be mentioned in particular.
  • Particularly preferred automatic dishwashing agents according to the invention contain citrate as one of their essential builders.
  • Processes preferred according to the invention are characterized in that the dishwashing detergent A, based in each case on the total weight of the automatic dishwashing detergent A, contains 5 to 60% by weight, preferably 10 to 50% by weight and in particular 15 to 40% by weight citrate.
  • alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of the greatest importance in the detergent and cleaning agent industry.
  • Alkali metal phosphate is the summary name for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which metaphosphoric acids (HPO 3 ) n and orthophosphoric acid H 3 PO 4 can be distinguished in addition to higher molecular representatives.
  • the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts or lime incrustations in fabrics and also contribute to cleaning performance.
  • phosphates are pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate).
  • Sodium potassium tripolyphosphates are also preferably used according to the invention.
  • phosphates are used as washing or cleaning-active substances in the automatic dishwashing detergent
  • preferred detergents contain these phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or pentapotassium triphosphate).
  • phosphate preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or pentapotassium triphosphate).
  • Potassium tripolyphosphate in amounts of 5 to 60% by weight, preferably 10 to 50% by weight and in particular 15 to 40% by weight, each based on the weight of the automatic dishwashing detergent A.
  • complexing agents preferably phosphonates
  • dishwashing agent A contains a complexing agent, preferably 1-hydroxyethane-1,1-diphosphonic acid and / or methylglycine diacetic acid.
  • Ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP) and their higher homologues are preferred as aminoalkanephosphonates. They are preferably in the form of the neutrally reacting sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta- and octasodium salt of DTPMP. From the class of phosphonates, HEDP is preferably used as the builder.
  • the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, especially if the agents also contain bleach, it can be preferred to use aminoalkanephosphonates, in particular DTPMP, or mixtures of the phosphonates mentioned.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylenetriaminepenta
  • phosphonates are particularly preferred.
  • the automatic dishwashing agents according to the invention can of course contain two or more different phosphonates.
  • Machine dishwashing detergents A are particularly preferred which contain both 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylenetriaminepenta (methylenephosphonic acid) (DTPMP) as phosphonates, the weight ratio of HEDP to DTPMP between 20: 1 and 1:20 , preferably between 15: 1 and 1:15 and in particular between 10: 1 and 1:10.
  • the proportion by weight of the phosphonate (s) in the total weight of the automatic dishwasher detergent is less than the proportion by weight of the polymer (s) b).
  • those agents are particularly preferred in which the ratio of the weight fraction of polymer b) to the weight fraction of the phosphonate is 200: 1 to 2: 1, preferably 150: 1 to 2: 1, particularly preferably 100: 1 up to 2: 1, very particularly preferably 80: 1 to 3: 1 and in particular 50: 1 to 5: 1.
  • the proportion by weight of these complexing agents is preferably 0.5 to 14% by weight, preferably 1 to 12% by weight and in particular 2 to 8% by weight.
  • enzymes can also be used in the method according to the invention. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in detergents or cleaning agents, and these are accordingly preferred. Washing or cleaning agents preferably contain enzymes in total amounts of 1 ⁇ 10 -6 to 5% by weight, based on active protein. The protein concentration can be determined with the aid of known methods, for example the BCA method or the biuret method.
  • subtilisin type those of the subtilisin type are preferred.
  • subtilisins BPN 'and Carlsberg as well as their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus , subtilisin DY and the subtilase enzymes, but no longer the subtilisins in the narrower sense of the term, thermitase, 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 the improved further developments of the aforementioned amylases for use in detergents and cleaning agents. Furthermore, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948) should be emphasized.
  • lipases or cutinases can also be used, in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ from suitable precursors.
  • suitable precursors include, for example, the lipases originally obtained from Humicola lanuginosa ( Thermomyces lanuginosus ) or further developed, in particular those with the amino acid substitution D96L.
  • the cutinases can be used which were originally isolated from Fusarium solani pisi and Humicola insolens. Lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii can also be used.
  • oxidoreductases for example oxidases, Oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases)
  • peroxidases such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases
  • phenol oxidases polyphenol oxidases
  • organic, particularly preferably aromatic, compounds interacting with the enzymes are added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the event of greatly differing redox potentials between the oxidizing enzymes and the soiling.
  • the enzymes can be used in any form established according to the prior art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with little water and / or mixed with stabilizers.
  • the enzymes can be encapsulated both for the solid and for the liquid dosage form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer which is impermeable to water, air and / or chemicals.
  • Additional active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, can also be applied in superimposed layers.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Such granulates are advantageously low in dust, for example through the application of polymeric film-forming agents, and, owing to the coating, are stable in storage.
  • dishwashing agent A based in each case on the total weight of the automatic dishwashing agent A, is 0.2 to 5% by weight, preferably 0.5 to 5% by weight and in particular 1 to 4% by weight.
  • -% enzyme (s) contains.
  • Machine dishwashing detergents A which are preferably used also contain one or more bleaches.
  • Sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance among the compounds which serve as bleaching agents and produce H 2 O 2 in water.
  • Further bleaching agents that can be used are, for example, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids which provide H 2 O 2 , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid.
  • bleaches from the group of organic bleaches can also be used.
  • Typical organic bleaching agents are the diacyl peroxides, such as, for example, dibenzoyl peroxide. Further typical organic bleaching agents are the peroxy acids, the alkyl peroxy acids and the aryl peroxy acids being mentioned as examples.
  • Process characterized in that the dishwashing detergent A, based in each case on the total weight of the automatic dishwashing detergent A, contains 1 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 12% by weight of sodium percarbonate are according to the invention prefers.
  • Substances releasing chlorine or bromine can also be used as bleaching agents.
  • Suitable materials releasing chlorine or bromine are, for example, heterocyclic N-bromo- and N-chloramides, 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 dishwashing detergents used according to the invention can additionally contain bleach activators.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Substances which carry O and / or N-acyl groups with the number of carbon atoms mentioned and / or optionally substituted benzoyl groups are suitable.
  • Polyacylated alkylenediamines are preferred, tetraacetylethylenediamine (TAED) having proven particularly suitable.
  • 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, particularly 2 to 8% by weight and particularly preferably 2 to 6% by weight , each based on the total weight of the bleach activator-containing agents.
  • bleach catalysts can also be used.
  • These substances are bleach-intensifying transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salen 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-amine complexes can also be used as bleach catalysts.
  • Manganese complexes in the II, III, IV or IV oxidation state which preferably contain one or more macrocyclic ligand (s) with the donor functions N, NR, PR, O and / or S, are used with particular preference.
  • Ligands are preferably used which have nitrogen donor functions.
  • bleach catalyst (s) in the agents according to the invention which have 1,4,7-trimethyl-1,4,7-triazacyclononane (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-triazacyclononane
  • TACN 1,4,7-triazacyclononane
  • TACD 1,5,9-trimethyl-1,5,9-triazacyclododecane
  • the aforementioned bleach-intensifying transition metal complexes are each based on the total weight of the automatic dishwashing detergent A, in the usual amounts, preferably in an amount of up to 5% by weight, in particular in amounts of 0.01 to 2% by weight %, preferably 0.02 to 1% by weight and in particular 0.05 to 0.8% by weight are used.
  • the pH value of the automatic dishwashing agent used has proven to be relevant for the cleaning, rinsing and drying results of the method according to the invention. Accordingly, particularly good results are achieved with automatic dishwashing detergents whose 1% aqueous solution (20 ° C.) has a pH value above 7, preferably between 7 and 12, particularly preferably between 9 and 11.
  • the automatic dishwashing detergent A has a pH (20 ° C., 1% aqueous solution) above 7, preferably between 7 and 12, particularly preferably between 9 and 11, are therefore also preferred according to the invention.
  • the surprising advantages of the process according to the invention are particularly evident in those automatic dishwashing processes in which no softened rinse water is used.
  • Rinsing water this is the Rinsing liquor called water.
  • the rinsing water used to carry out the method according to the invention therefore preferably has a hardness above 5 ° dH, preferably above 10 ° dH, particularly preferably above 15 ° dH and in particular above 20 ° dH.
  • the automatic dishwashing detergents A used according to the invention can be packaged in solid or liquid form, but also, for example, as a combination of solid and liquid supply forms.
  • Powders, granules, extrudates or compacts, in particular tablets, are particularly suitable as solid supply forms.
  • the liquid supply forms preferably based on water and / or organic solvents, can be thickened, in the form of gels.
  • the automatic dishwashing detergents A used according to the invention can be packaged as single-phase or multiphase products. Automatic 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 dosage unit with two or more phases, are particularly preferred.
  • the individual phases of multiphase agents can have the same or different states of aggregation.
  • Automatic dishwashing agents 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 particularly preferred.
  • Processes according to the invention, characterized in that the dishwashing detergent A is in liquid form, are preferred because of improved cleaning, rinsing and drying results.
  • the automatic dishwashing detergents A are preferably pre-packaged into metering units. These metering units preferably comprise the amount of washing or cleaning-active substances necessary for a cleaning cycle. Preferred dosing 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 shape are particularly preferably selected so that the pre-assembled units can be metered 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 detergents according to the invention in particular the prefabricated dosing units, particularly preferably have a water-soluble coating.
  • the automatic dishwashing detergents A used in the method according to the invention can be dosed into the interior of the dishwasher by means of a water-insoluble storage container.
  • This storage container preferably has two or more chambers in which the automatic dishwashing detergent A is present, for example, in the form of separate partial recipes.
  • the water-insoluble storage container can be integrated into the dishwasher, but can also have the shape of a conventional two- or multi-chamber bottle.
  • cleaning methods according to the invention are distinguished from conventional methods by an improved cleaning and rinsing effect, as well as an improved drying of the cleaned dishes.
  • the use of an automatic dishwashing process according to the invention to reduce the formation of deposits in automatic dishwashing or to improve drying in automatic dishwashing are further subjects of this application.
  • the drying, coating and cleaning performance of an automatic dishwashing process were determined as a function of the type of dosage of the automatic dishwashing agent used.
  • dishes were washed in a dishwasher (Miele 1730; 55 ° normal 3in1 extra drying program) with 33 ml (16.5 ml F1 and 16.5 ml F2) of an automatic dishwashing detergent with a water hardness of 21 ° dH.
  • the composition of the dishwashing detergents F1 and F2 used can be found in the table below: raw material F1 [% by weight] F2 [% by weight] KTTP 17.5 10.0 Nonionic surfactant 4.0 - Protease 2.0 - Amylase 1.0 - Phosphonate 3.0 5.0 Thickener 4.0 - Org. Solvent 3.0 3.0 Anionic polymer - 8.6 soda - 7.0 Water, misc Add 100 Add 100 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 (14)

  1. Procédé de nettoyage de vaisselle dans un lave-vaisselle, au cours duquel le liquide de rinçage aqueux se trouvant à l'intérieur du lave-vaisselle est éliminé, à un instant t, au moins partiellement, de l'intérieur du lave-vaisselle, caractérisé en ce qu'un agent détergent A pour lave-vaisselle contenant
    a) un ou plusieurs tensioactifs non ioniques
    b) un ou plusieurs polymères anioniques
    est ajouté de manière dosée à un instant t1 < t en une quantité m1 et à un instant t2 > t en une quantité m2 à l'intérieur du lave-vaisselle, le rapport pondéral des quantités ajoutées de manière dosée m1 et m2 étant compris entre 20:1 et 2:1, de préférence entre 15:1 et 3:1 et en particulier entre 12:1 et 4:1.
  2. Procédé selon la revendication 1, caractérisé en ce que l'agent détergent A pour lave-vaisselle contient un tensioactif non ionique en des quantités de 0,1 à 30 % en poids, de préférence de 0,2 à 20 % en poids, de manière particulièrement préférée de 0,5 à 10 % en poids et en particulier de 1,0 à 8 % en poids, respectivement par rapport au poids total de l'agent détergent A pour lave-vaisselle.
  3. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'agent détergent A pour lave-vaisselle contient le polymère anionique en des quantités de 0,1 à 40 % en poids, de préférence de 0,2 à 20 % en poids, de préférence de 0,5 à 15 % en poids et en particulier de 1,0 à 10 % en poids, respectivement par rapport au poids total de l'agent détergent A pour lave-vaisselle.
  4. Procédé selon l'une des revendications précédentes, caractérisé en ce que le polymère anionique est un homo- et/ou copolymère d'acide acrylique ou d'acide méthacrylique.
  5. Procédé selon l'une des revendications précédentes, caractérisé en ce que le polymère anionique est un copolymère constitué
    i) d'acides carboxyliques insaturés
    ii) de monomères contenant des groupes d'acide sulfonique
    iii) éventuellement d'autres monomères ioniques ou non ionogènes.
  6. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'agent détergent A pour lave-vaisselle contient
    a) 0,5 à 10 % en poids d'un ou plusieurs tensioactifs non ioniques
    b) 0,2 à 20 % en poids d'un ou plusieurs polymères contenant des groupes d'acide sulfonique
    c) 10 à 40 % en poids de phosphate ou 10 à 40 % en poids de citrate
    d) 0,5 à 5 % en poids d'une ou plusieurs enzymes.
  7. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'agent détergent A pour vaisselle contient 1 à 20 % en poids, de préférence 2 à 15 % en poids et en particulier de 4 à 12 % en poids de percarbonate de sodium, respectivement par rapport au poids total de l'agent détergent A pour lave-vaisselle.
  8. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'agent détergent A pour vaisselle contient 0,01 à 2 % en poids, de préférence 0,02 à 1 % en poids et en particulier 0,05 à 0,8 % en poids d'un catalyseur de blanchiment, respectivement par rapport au poids total de l'agent détergent A pour lave-vaisselle.
  9. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'agent détergent A pour vaisselle est présent sous forme liquide.
  10. Procédé selon l'une des revendications précédentes, caractérisé en ce que la différence temporelle entre les instants t1 et t2 est comprise entre 5 et 50 minutes, de préférence entre 10 et 40 minutes et en particulier entre 15 et 30 minutes.
  11. Procédé selon l'une des revendications précédentes, caractérisé en ce que la température du liquide de rinçage à l'instant t1 est comprise entre 12 et 45 °C, de préférence entre 15 et 40 °C et en particulier entre 20 et 35 °C.
  12. Procédé selon l'une des revendications précédentes, caractérisé en ce que la température du liquide de lavage à l'instant t2 est comprise entre 30 et 65 °C, de préférence entre 35 et 60 °C et en particulier entre 40 et 55 °C.
  13. Utilisation d'un procédé selon l'une des revendications précédentes pour améliorer le séchage lors du lavage automatique de vaisselle.
  14. Utilisation d'un procédé selon l'une des revendications 1 à 12 pour réduire la formation de dépôts lors du lavage automatique de vaisselle.
EP08759944.5A 2007-09-10 2008-05-23 Procédé de nettoyage Active EP2187796B2 (fr)

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DE102009046220A1 (de) * 2009-10-30 2011-05-12 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülverfahren
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PL2380963T3 (pl) 2010-04-23 2016-07-29 Procter & Gamble Sposób perfumowania
PL2380962T3 (pl) 2010-04-23 2017-01-31 The Procter And Gamble Company Cząstka
DE102010030021A1 (de) * 2010-06-14 2011-12-15 Henkel Ag & Co. Kgaa Maschinelles Reinigungsverfahren
PL2584028T3 (pl) 2011-10-19 2017-10-31 Procter & Gamble Cząstka
DE102012104951A1 (de) * 2012-06-08 2013-12-12 Stockmeier Chemie GmbH & Co.KG Verwendung einer phosphonsäure- und/oder phosphonsäurederivathaltigen Lösung bei der Entfettung von Metalloberflächen, entfettende Lösung und Verfahren zur Entfettung einer Metalloberfläche
ES2956240T3 (es) 2020-09-29 2023-12-15 Procter & Gamble Composición limpiadora para lavavajillas

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WO2002092747A1 (fr) † 2001-05-14 2002-11-21 The Procter & Gamble Company Procédé pour laver la vaisselle
WO2003006594A1 (fr) † 2001-07-07 2003-01-23 Henkel Kommanditgesellschaft Auf Aktien Detergents aqueux '3 en 1' pour lave-vaisselle
WO2003042347A1 (fr) † 2001-11-14 2003-05-22 The Procter & Gamble Company Composition pour lave-vaisselle automatique sous forme de dose unitaire comprenant un polymere anti-tartre
WO2004013269A1 (fr) † 2002-07-25 2004-02-12 Henkel Kommanditgesellschaft Auf Aktien Produits de lavage pour lave-vaisselle comprenant des agents d'inhibition du depot
EP1524313A1 (fr) † 2003-10-01 2005-04-20 Dalli-Werke GmbH & Co. KG Composition pour lave-vaisselle avec des proprietes de rincage ameliorees
WO2005093034A1 (fr) † 2004-03-09 2005-10-06 Henkel Kommanditgesellschaft Auf Aktien Pastilles a plusieurs phases permettant une meilleure perception de parfum

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PL2187796T3 (pl) 2012-09-28
EP2187796A1 (fr) 2010-05-26
WO2009033830A1 (fr) 2009-03-19
DE102007042859A1 (de) 2009-03-12
PL2187796T5 (pl) 2021-06-14
ES2383245T5 (es) 2021-10-14
US20100154832A1 (en) 2010-06-24
ES2383245T3 (es) 2012-06-19
EP2187796B1 (fr) 2012-04-25
ATE554694T1 (de) 2012-05-15

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