EP2187796B1 - Procédé de nettoyage - Google Patents

Procédé de nettoyage Download PDF

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Publication number
EP2187796B1
EP2187796B1 EP08759944A EP08759944A EP2187796B1 EP 2187796 B1 EP2187796 B1 EP 2187796B1 EP 08759944 A EP08759944 A EP 08759944A EP 08759944 A EP08759944 A EP 08759944A EP 2187796 B1 EP2187796 B1 EP 2187796B1
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Prior art keywords
acid
dishwasher
process according
interior
previous
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German (de)
English (en)
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EP2187796B2 (fr
EP2187796A1 (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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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 crockery, wherein detergent is dosed with a time delay in the interior of a dishwasher.
  • Dishwashing detergents are available to the consumer in a variety of forms. In addition to the traditional liquid hand dishwashing detergents, machine dishwashing detergents are particularly important with the spread of household dishwashers. These automatic dishwashing agents are typically offered to the consumer in solid form, for example as powders or as tablets, but increasingly also in liquid form.
  • the cleaning agents were preferably added to new ingredients, for example, more effective surfactants, polymers or bleach.
  • new ingredients for example, more effective surfactants, polymers or bleach.
  • new ingredients are available only to a limited extent and the amount of ingredients used for each cleaning cycle can not be increased to any extent for ecological and economic reasons, this approach has natural limits.
  • Another approach to improving the performance profile of existing detergents or cleaners is to develop new ready-made forms, for example, in the combination of solid and liquid detergents or cleanser ingredients.
  • Corresponding detergents are combined, for example, in novel water-soluble packaging.
  • This application was based on the object to improve the known methods for machine dishwashing to the effect that these methods without the use of additional ingredients or an increase in the dosage even at low temperature cleaning cycles or cleaning cycles with low water consumption improved cleaning performance and improved drying of the cleaned dishes.
  • This object has been achieved by a special dishwashing method in which a surfactant- and polymer-containing detergent is metered in a time-displaced manner into the interior of a dishwasher.
  • the process according to the invention is carried out in the interior of a commercially available dishwashing machine, in particular a commercially available household dishwasher.
  • the machine cleaning program is usually determined in a dishwasher before the dishwashing process by the consumer by selecting from a list of programs, which in particular the temperature of the wash liquor during the cleaning process, the duration of the process or the cleaning agents and - tools used are defined (" 2in1 "and” 3in1 "programs).
  • the automatic dishwashing process or the consumer-selected dishwashing detergent program comprises at least two rinses selected from a pre-rinse cycle, a cleaning cycle, and a rinse cycle.
  • These rinses are characterized, for example, by different durations, water consumption and temperature profiles, wherein the aqueous rinse liquor located in the interior of the dishwasher is at least partially removed from the interior of the dishwasher between the rinses and optionally supplemented by the inflow of fresh water.
  • this replacement of the rinsing liquor takes place by means of a pump system integrated in the dishwasher.
  • the proportionate pumping out of the wash liquor from the interior of the dishwasher is preferably carried out such that at least 5 vol .-%, preferably 10 vol .-%, more preferably at least 20 vol .-%, most preferably at least 40 vol .-% and in particular at least 60 Vol .-% of the rinsing liquor are pumped out of the interior of the dishwasher.
  • at least 5 vol .-%, preferably 10 vol .-%, more preferably at least 20 vol .-%, most preferably at least 40 vol .-% and in particular at least 60 Vol .-% of the rinsing liquor are pumped out of the interior of the dishwasher.
  • between 5 and 99% by volume of the rinsing liquor preferably between 10 and 90% by volume of the rinsing liquor, more preferably between 20 and 80% by volume and in particular between 40 and 70% by volume of the rinsing liquor pumped out.
  • the inventive method is characterized in that both before and after the proportionate pumping out of the wash liquor from the interior of the dishwasher, a machine dishwashing detergent containing nonionic surfactants and anionic polymers in the interior of the dishwasher and thus in the interior of the wash liquor is metered.
  • the time interval between the times t1 and t2 may vary, wherein method according to the invention, characterized in that the time difference between the times t1 and t2 is 5 to 50 minutes, preferably 10 to 40 minutes and especially 15 to 30 minutes, are preferred.
  • the temperature of the rinsing liquor is preferably between 12 and 45 ° C., preferably between 15 and 40 ° C. and in particular between 20 and 35 ° C., and preferably between 30 and 65 ° C., preferably between 35 and 60 ° C., at time t 1 and in particular between 40 and 55 ° C.
  • the temperature of the rinsing liquor at time t2 is above the temperature of the rinsing liquor at time t1.
  • a corresponding temperature profile, at which the temperature of the rinsing liquor at time t2 is above the temperature of the rinsing liquor 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 wash liquor at time t2 is below the temperature of the wash liquor at time t1 or identical thereto.
  • the weight ratio of the metered quantities m1 and m2 in preferred process variants is between 20: 1 and 2: 1, preferably between 15: 1 and 3: 1 and in particular between 12: 1 and 4: 1.
  • Characteristic of the automatic dishwasher detergents used in the process according to the invention is their content of nonionic surfactants and anionic polymers.
  • the nonionic surfactants As particularly effective in terms of cleaning performance and drying, the nonionic surfactants have proven.
  • 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 is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which is a glycose unit having 5 or 6 C 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 of the amine oxide type for example N-cocoalkyl-N, N-dimethyl-amine oxide and N-tallow alkyl-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.
  • 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.
  • 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 which consist 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 mole of alcohol were 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.
  • the so-called “narrow range ethoxylates” are particularly preferred.
  • further combinations of one or more tallow fatty alcohols with 20 to 30 EO and silicone defoamers are used.
  • Nonionic surfactants which have a melting point above room temperature.
  • 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. Also, nonionic surfactants having waxy consistency at room temperature are preferred depending on their purpose.
  • 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 additionally having polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol content of such nonionic surfactant molecules preferably makes up 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. Become native sources used, the radical R 1 has an even number of carbon atoms and is usually unbranched, the linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, preferably are.
  • 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 have the required low viscosity in aqueous solution and can be used according to the invention 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 represents 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 ), -H 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 preferred according to the invention.
  • end-capped poly (oxyalkylated) nonionic surfactants which, in accordance with 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 is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 2 to 30 carbon atoms, preferably having from 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having from 1 to 30 carbon atoms, where x is from 1 to 30 carbon atoms 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.
  • surfactants of the formula 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 R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1.5 and y is a value of at least 15.
  • nonionic surfactants having a free hydroxyl group on one of the two terminal alkyl radicals By using the above-described nonionic surfactants having a free hydroxyl group on one of the two terminal alkyl radicals, the formation of deposits in machine dishwashing can be markedly improved compared to conventional polyalkoxylated fatty alcohols without a free hydroxyl group.
  • 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 is a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical 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 OCH (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, with 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 may be different if x ⁇ 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been chosen here by way of example and may well be greater, with the range of variation increasing with increasing x values and, 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.
  • the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.
  • nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.
  • Mixtures of 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 automatic dishwashing agent A contains, in each case based on the total weight of the automatic dishwashing agent A, nonionic surfactant in amounts of from 0.1 to 30% by weight, preferably from 0.2 to 20% by weight, particularly preferably 0.5 to 10 wt .-% and in particular from 1.0 to 8 wt .-%.
  • nonionic surfactant in which the nonionic surfactant is contained in the automatic dishwashing detergent A, based on its total weight, in amounts of from 0.5 to 5.0% by weight, are particularly preferred.
  • anionic or amphoteric surfactants preferably in combination with defoamers or foam inhibitors, in the machine dishwashing process according to the invention.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration.
  • alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
  • sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles 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.
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example of coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or of C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates which can be obtained as commercial products of Shell Oil Company under the name DAN ® , are suitable anionic surfactants.
  • EO ethylene oxide
  • Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which by themselves are nonionic surfactants.
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Suitable amphoteric surfactants are, for example, betaines or alkylamidoalkylamines.
  • 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 carbo-betaines, in particular the carbo-betaines of the formula A1 and A2, most preferably the alkylamido-betaines of the formula A2.
  • suitable betaines and sulfobetaines are the following compounds designated as INCI: almondamidopropyl betaines, apricotamidopropyl betaines, avocadamidopropyl betaines, babassuamidopropyl betaines, behenamidopropyl betaines, behenyl betaines, betaines, canolamidopropyl betaines, caprylic / capramidopropyl betaines, carnitines, cetyl betaines, cocamidoethyl betaines, cocamidopropyl Betaines, cocamidopropyl hydroxysultaines, coco-betaines, coco-hydroxysultaines, coco / oleamidopropy
  • a preferred amphoteric surfactant is cocamidopropyl betaine (cocoamidopropyl betaine).
  • a particularly preferred amphoteric surfactant is caprylic / Capramidopropyl Betaine (CAB), which is available for example under the trade name Tegotens ® B 810 from Th. Goldschmidt AG.
  • Suitable foam inhibitors are, inter alia, soaps, oils, fats, paraffins or silicone oils, which may optionally be applied to support materials.
  • Suitable carrier materials are, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the abovementioned materials.
  • preferred agents include paraffins, preferably unbranched paraffins (n-paraffins) and / or silicones, preferably linear-polymeric silicones, which are constructed 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.
  • 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 in each case based on the total weight of the automatic dishwashing agent A, contains the anionic polymer in amounts of from 0.1 to 40% by weight, preferably from 0.2 to 20% by weight, preferably 0.5 to 15 wt .-% and in particular from 1.0 to 10 wt .-%.
  • Corresponding agents have proved to be advantageous in the process according to the invention, in particular with regard to optimum cleaning and rinse-aid 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 having a relative molecular mass of from 500 to 70,000 g / mol.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • Inventive methods characterized in that it is the 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 may also contain sulfonic acid groups.
  • Particularly preferred sulfonic acid-containing monomers are 1-acrylamido-1-propane-sulfonic 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 -Sulfopropylmethacrylat, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their
  • the sulfonic acid groups may be wholly or partially in neutralized form, ie that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups against metal ions, preferably alkali metal ions and in particular against Sodium ions, can be replaced.
  • metal ions preferably alkali metal ions and in particular against Sodium ions.
  • the use of partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.
  • the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use.
  • Preferred automatic dishwashing agents are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
  • Particularly preferred carboxyl-containing monomers i) of the abovementioned hydrophobically modified anionic polymers are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid , Cinnamic acid or mixtures thereof.
  • Particularly preferred such monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1, 4,4-dimethylhexane-1, ethylcyclohexene, 1-octene, ⁇ -olefins having 10 or more
  • the copolymer d) in addition to the monomers i) and ii) further comprises a third monomer iii) from the group of sulfonic acid group-containing monomers.
  • Particularly preferred sulfonic acid-containing monomers are 1-acrylamido-1-propane-sulfonic 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 -Sulfopropylmethacrylat, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their
  • the sulfonic acid groups may be wholly or partially in neutralized form, i. in that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.
  • the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use.
  • Preferred automatic dishwashing agents are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
  • the automatic dishwashing agent A used in the process according to the invention may contain one or more builders.
  • the builders include in particular silicates, carbonates and organic cobuilders as well as the phosphates.
  • organic co-builders are polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and other organic cobuilders. These classes of substances are described below.
  • Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
  • the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • Particularly preferred machine dishwasher detergents according to the invention contain citrate as one of their essential builders.
  • Processes preferred according to the invention are characterized in that the dishwashing agent A, based in each case on the total weight of the automatic dishwashing agent A, contains 5 to 60 wt.%, Preferably 10 to 50 wt.% And in particular 15 to 40 wt.% Citrate.
  • alkali metal phosphates with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.
  • Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent limescale deposits on machine parts or Kalkinkrustationen in tissues and also contribute to the cleaning performance.
  • phosphates are the 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).
  • the sodium potassium tripolyphosphates are also preferably used according to the invention.
  • phosphates are used as washing or cleaning substances in the automatic dishwashing detergent in the context of the present application
  • preferred agents contain these phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentakalium triphosphate (sodium or Potassium tripolyphosphate), in amounts of 5 to 60% by weight, preferably 10 to 50% by weight and in particular 15 to 40% by weight, in each case 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.
  • the complex-forming phosphonates comprise a number of different compounds, such as, for example, diethylene triamine penta (methylene phosphonic acid) (DTPMP). Hydroxyalkane or aminoalkane phosphonates are particularly preferred in this application.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9).
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • automatic dishwashing detergents which contain as phosphonates 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta (methylenephosphonic acid) (DTPMP).
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylenetriaminepenta
  • the automatic dishwashing compositions of the invention may contain two or more different phosphonates.
  • those automatic dishwashing agents A which contain as phosphonates both 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylenetriaminepenta (methylenephosphonic acid) (DTPMP), the weight ratio of HEDP to DTPMP being between 20: 1 and 1:20 , preferably between 15: 1 and 1:15 and in particular between 10: 1 and 1:10.
  • the weight fraction of the phosphonate (s) in the total weight of the automatic dishwashing agent is less than the weight proportion of the polymer (s) 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 to 2: 1, most preferably 80: 1 to 3: 1 and in particular 50: 1 to 5: 1.
  • the proportion by weight of these complexing agents in particular the sum of the proportions by weight of 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and methylglycinediacetic acid (MGDA) is preferably 0.5 to 14% by weight, preferably 1 to 12% by weight and in particular 2 to 8 wt .-%.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • MGDA methylglycinediacetic acid
  • enzymes can also be used in the process according to the invention. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly. Detergents or cleaning agents contain enzymes preferably in total amounts of 1 ⁇ 10 -6 to 5 wt .-% based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • subtilisin type those of the subtilisin type are preferable.
  • these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus , subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis , B. amyloliquefaciens , B. stearothermophilus , Aspergillus niger and A. oryzae, as well as the further developments of the aforementioned amylases which are improved for use in detergents and cleaners. Furthermore, the ⁇ -amylase are off for this purpose Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • lipases or cutinases are also usable according to the invention.
  • these include, for example, the lipases originally obtainable from Humicola lanuginosa ( Thermomyces lanuginosus ) or further developed, in particular those with the amino acid exchange D96L.
  • the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens . It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii .
  • Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect.
  • the enzymes can be used in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are prepared by methods known per se, for example by Shaking or rolling granulation or applied in fluid-bed processes.
  • such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
  • a protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
  • Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
  • dishwashing processes in which the dishwashing agent A, in each case based on the total weight of the automatic dishwashing agent A, 0.2 to 5 wt .-%, preferably 0.5 to 5 wt .-% and in particular 1 to 4 wt. - contains% enzyme (s).
  • Preferably used machine dishwashing agents A further contain one or more bleaching agents.
  • bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • bleaching agents from the group of organic bleaching agents can also be used.
  • Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
  • dishwashing agent A in each case based on the total weight of the automatic dishwashing agent A, 1 to 20 wt .-%, preferably 2 to 15 wt .-% and in particular 4 to 12 wt .-% sodium percarbonate, are according to the invention prefers.
  • chlorine or bromine releasing substances can be used.
  • suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • the automatic dishwashing agents used according to the invention may additionally contain bleach activators.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given several times acylated alkylenediamines, with tetraacetylethylenediamine (TAED) has been found to be particularly suitable.
  • TAED tetraacetylethylenediamine
  • bleach activators in particular TAED, are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, especially 2 to 8% by weight and more preferably 2 to 6% by weight. , in each case based on the total weight of the bleach activator-containing agents used.
  • bleach catalysts can also be used.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • complexes of manganese in the oxidation state II, III, IV or IV which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S.
  • ligands are used which have nitrogen donor functions.
  • bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononan (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and or 2-methyl-1,4,7-triazacyclononane (Me / TACN).
  • Me-TACN 1,4,7-trimethyl-1,4,7-triazacyclononan
  • TACN 1,4,7-triazacyclononane
  • TACD 1,5,9-trimethyl-1,5,9-triazacyclododecane
  • Me-TACD 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane
  • 2-methyl-1,4,7-triazacyclononane
  • Machine dishwashing detergent characterized in that it further comprises a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me 3 -TACN ) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me 4 -TACN), are preferred according to the invention, since in particular the cleaning result can be significantly improved by the aforementioned bleach catalysts.
  • a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me 3 -TACN ) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me 4 -TACN), are preferred according to the invention, since in particular the cleaning result can be significantly improved by the aforementioned
  • the above-mentioned bleach-enhancing transition metal complexes in particular with the central atoms Mn and Co, in each case based on the total weight of the automatic dishwashing agent A, in conventional amounts, preferably in an amount up to 5 wt .-%, in particular Quantities of 0.01 to 2 wt .-%, preferably 0.02 to 1 wt.% And in particular 0.05 to 0.8 wt .-% used.
  • the pH of the automatic dishwashing detergent used has proven to be relevant for the cleaning, rinsing and drying results of the process according to the invention. Accordingly, particularly good results are achieved with automatic dishwashing agents whose 1% strength aqueous solution (20 ° C.) has a pH above 7, preferably between 7 and 12, particularly preferably between 9 and 11.
  • automatic dishwashing agents whose 1% strength aqueous solution (20 ° C.) has a pH above 7, preferably between 7 and 12, particularly preferably between 9 and 11.
  • the automatic dishwashing agent A has a pH (20 ° C., 1% strength 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.
  • the rinse water used for carrying out the method according to the invention therefore preferably has a hardness above 5 ° dH, preferably above 10 ° dH, more preferably above 15 ° dH and in particular above 20 ° dH.
  • the automatic dishwashing agents A used in accordance with the invention can be formulated in solid or liquid form but can also be present, for example, as a combination of solid and liquid forms.
  • Powder, granules, extrudates or compactates, in particular tablets, are particularly suitable as firm supply forms.
  • the liquid supply forms preferably based on water and / or organic solvents, may be thickened, in the form of gels.
  • the automatic dishwashing agents A used according to the invention can be formulated as single-phase or multi-phase products.
  • automatic dishwashing detergents with one, two, three or four phases are preferred.
  • Machine dishwashing detergents characterized in that they are in the form of a prefabricated dosing unit with two or more phases, are particularly preferred.
  • the individual phases of multiphase agents may have the same or different states of matter.
  • Machine dishwashing detergents which have at least two different solid phases and / or at least two liquid phases and / or at least one solid and at least one liquid phase are preferred.
  • Inventive method characterized in that the dishwashing agent A is in liquid form, but are preferred due to improved cleaning, rinsing and drying results.
  • the automatic dishwashing agents A are preferably prefabricated to dosage units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g.
  • the volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher.
  • the volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml and in particular between 15 and 25 ml.
  • the automatic dishwasher detergents according to the invention in particular the prefabricated metering units, have a water-soluble coating, with particular preference.
  • the automatic dishwashing agent A used in the method according to the invention can be metered 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 agent A is present, for example, in the form of separate partial formulations.
  • the water-insoluble storage container can be integrated in 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 improved cleaning and rinsing action, as well as improved drying of the cleaned dishes.
  • the use of a machine dishwashing process according to the invention for reducing the deposit formation in automatic dishwashing or for improving the drying in automatic dishwashing are further objects of this application.
  • the drying, coating and cleaning performance of a machine dishwashing process were determined as a function of the type of metering of the automatic dishwashing detergent used.
  • dishes were rinsed in a dishwashing machine (Miele 1730, program 55 ° normal 3in1 extra drying) with 33 ml (16.5 ml F1 and 16.5 ml F2) of a dishwasher detergent at a water hardness of 21 ° dH.
  • the composition of the dishwasher detergents F1 and F2 used can be found in the following table: raw material F1 [% by weight] F2 [% by weight] K-TTP 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 Hydroxymix ethers of the general formula C 6-24 -CH (OH) CH 2 O- (EO) 20-120 -C 2-26

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Claims (15)

  1. Procédé pour le nettoyage de la vaisselle dans un lave-vaisselle, au cours du déroulement duquel on élimine depuis l'intérieur du lave-vaisselle au moins en partie à un moment t le bain de lavage aqueux se trouvant à l'intérieur du lave-vaisselle, caractérisé en ce qu'on introduit de manière dosée un détergent A pour le lavage mécanique de la vaisselle contenant :
    a) un ou plusieurs agents tensioactifs non ioniques ;
    b) un ou plusieurs polymères anioniques ;
    à un moment t1 < t en une quantité m1 et à un moment t2 > t en une quantité m2 à l'intérieur du lave-vaisselle.
  2. Procédé selon la revendication 1, caractérisé en ce que le détergent A pour le lavage mécanique de la vaisselle contient, chaque fois rapportés au poids total du détergent pour le lavage mécanique de la vaisselle, l'agent tensioactif non ionique dans 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.
  3. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le détergent A pour le lavage mécanique de la vaisselle contient, chaque fois rapportés au poids total du détergent pour le lavage mécanique de la vaisselle, le polymère anionique dans des quantités de 0,1 à 40 % en poids, de préférence de 0,2 à 20 % en poids, de manière préférentielle de 0,5 à 15 % en poids et en particulier de 1,0 à 10 % en poids.
  4. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que, en ce qui concerne le polymère anionique, il s'agit d'un homopolymère et/ou d'un copolymère de l'acide acrylique ou de l'acide méthacrylique.
  5. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que, en ce qui concerne le polymère anionique, il s'agit d'un copolymère
    i) d'acides carboxyliques insaturés ;
    ii) de monomères contenant des groupes d'acides sulfoniques;
    iii) de manière facultative d'autres monomères ioniques ou non ionogènes.
  6. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le détergent A pour le lavage mécanique de la vaisselle contient :
    a) de 0,5 à 10 % en poids d'un ou de plusieurs agents tensioactifs non ioniques ;
    b) de 0,2 à 20 % en poids d'un ou de plusieurs polymères contenant des groupes d'acides sulfoniques ;
    c) de 10 à 40 % en poids de phosphate ou de 10 à 40 % en poids de citrate ;
    d) de 0,5 à 5 % en poids d'une ou de plusieurs enzymes.
  7. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le détergent A pour le lavage mécanique de la vaisselle contient, chaque fois rapportés au poids total du détergent A pour le lavage mécanique de la vaisselle, de 1 à 20 % en poids, de préférence de 2 à 15 % en poids et en particulier de 4 à 12 % en poids de percarbonate de sodium.
  8. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le détergent A pour le lavage mécanique de la vaisselle contient, chaque fois rapportés au poids total du détergent A pour le lavage mécanique de la vaisselle, de 0,01 à 2 % en poids, de préférence de 0,02 à 1 % en poids et en particulier de 0,05 à 0,8 % en poids d'un catalyseur du blanchiment.
  9. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le détergent A pour le lavage mécanique de la vaisselle est présent sous forme liquide.
  10. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le rapport pondéral des quantités m1 et m2 introduites de manière dosée se situe entre 20:1 et 2:1 de préférence entre 15:1 et 3:1 et en particulier entre 12:1 et 4:1.
  11. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le décalage temporaire entre les moments t1 et t2 s'élève de 5 à 50 minutes, de préférence de 10 à 40 minutes et en particulier de 15 à 30 minutes.
  12. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la température du bain de lavage au moment t1 se situe entre 12 et 45°C, de préférence entre 15 et 40 °C et en particulier entre 20 et 35°C.
  13. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la température du bain de lavage au moment t2 se situe entre 30 et 65°C, de préférence entre 35 et 60 °C et en particulier entre 40 et 55°C.
  14. Utilisation d'un procédé selon l'une quelconque des revendications précédentes pour améliorer le séchage lors du lavage mécanique de la vaisselle.
  15. Utilisation d'un procédé selon l'une quelconque des revendications 1 à 13 pour réduire la formation d'incrustations lors du lavage mécanique de la vaisselle.
EP08759944.5A 2007-09-10 2008-05-23 Procédé de nettoyage Active EP2187796B2 (fr)

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DE102007042859A DE102007042859A1 (de) 2007-09-10 2007-09-10 Reinigungsverfahren
PCT/EP2008/056343 WO2009033830A1 (fr) 2007-09-10 2008-05-23 Procédé de nettoyage

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EP (1) EP2187796B2 (fr)
AT (1) ATE554694T1 (fr)
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ES (1) ES2383245T5 (fr)
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WO2011051415A1 (fr) * 2009-10-30 2011-05-05 Henkel Ag & Co. Kgaa Procédé de lavage en machine
DE102009046220A1 (de) * 2009-10-30 2011-05-12 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülverfahren
ES2423580T5 (es) * 2009-12-10 2021-06-17 Procter & Gamble Método y uso de una composición para lavado de vajillas
ES2581934T3 (es) * 2009-12-10 2016-09-08 The Procter & Gamble Company Método para medir la capacidad de eliminación de suciedad de un producto limpiador
EP2333040B2 (fr) * 2009-12-10 2019-11-13 The Procter & Gamble Company Composition de détergent
EP2333042B1 (fr) 2009-12-10 2015-07-01 The Procter and Gamble Company Utilisation de détergent
EP2333041B1 (fr) * 2009-12-10 2013-05-15 The Procter & Gamble Company Procédé et utilisation d'une composition pour lave-vaisselle
ES2579217T3 (es) 2010-04-23 2016-08-08 The Procter & Gamble Company Partícula
ES2565192T3 (es) 2010-04-23 2016-04-01 The Procter & Gamble Company Método para perfumar
EP2383329A1 (fr) 2010-04-23 2011-11-02 The Procter & Gamble Company Particule
EP2380478A1 (fr) 2010-04-23 2011-10-26 The Procter & Gamble Company Produit de lave-vaisselle automatique
ES2533368T3 (es) 2010-04-23 2015-04-09 The Procter & Gamble Company Producto para lavavajillas
TR201810936T4 (tr) 2010-04-23 2018-08-27 Industrial Chemicals Group Ltd Deterjan bileşimi.
DE102010030021A1 (de) * 2010-06-14 2011-12-15 Henkel Ag & Co. Kgaa Maschinelles Reinigungsverfahren
EP2584028B1 (fr) 2011-10-19 2017-05-10 The Procter & Gamble Company Particule
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EP3974504B1 (fr) 2020-09-29 2023-07-26 The Procter & Gamble Company Composition de nettoyage pour lave-vaisselle automatique

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GB0111618D0 (en) † 2001-05-14 2001-07-04 Procter & Gamble Dishwashing
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ATE554694T1 (de) 2012-05-15
WO2009033830A1 (fr) 2009-03-19
US20100154832A1 (en) 2010-06-24
EP2187796B2 (fr) 2021-03-24
DE102007042859A1 (de) 2009-03-12
PL2187796T5 (pl) 2021-06-14
PL2187796T3 (pl) 2012-09-28
ES2383245T3 (es) 2012-06-19
EP2187796A1 (fr) 2010-05-26

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