EP2576746B1 - Détergents pour lave-vaisselle en poudre comprimée - Google Patents

Détergents pour lave-vaisselle en poudre comprimée Download PDF

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Publication number
EP2576746B1
EP2576746B1 EP11720121.0A EP11720121A EP2576746B1 EP 2576746 B1 EP2576746 B1 EP 2576746B1 EP 11720121 A EP11720121 A EP 11720121A EP 2576746 B1 EP2576746 B1 EP 2576746B1
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EP
European Patent Office
Prior art keywords
chr
automatic dishwashing
independently
carbon atoms
functional group
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EP11720121.0A
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German (de)
English (en)
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EP2576746A1 (fr
Inventor
Johannes Zipfel
Thomas Eiting
Dorota SENDOR-MÜLLER
Arnd Kessler
Thorsten Bastigkeit
Christian Nitsch
Volker Blank
Konstantin Benda
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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers
    • 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
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • 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
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam
    • 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

Definitions

  • the present application describes automatic dishwashing agents which are in the form of shaped bodies and automatic dishwashing processes using these automatic dishwashing agents and the use of these automatic dishwashing agents to remove soiling in automatic dishwashing.
  • Dishwashing detergents are available to consumers in a variety of forms. In addition to 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.
  • the US patent application US 2002/0160930 A1 deals with the dissolving power combined with high strength and storage stability of detergent tablets.
  • the international patent application WO 2009/033972 discloses an automatic dishwashing agent containing a nonionic surfactant of a certain structure.
  • One of the main goals of the manufacturers of machine cleaning agents is to improve the cleaning and rinsing performance of these agents, with more recent attention being paid to the cleaning and rinsing performance in low-temperature cleaning cycles or in cleaning cycles with reduced water consumption.
  • This application was based on the object of providing an automatic dishwashing detergent with improved cleaning properties and / or with improved drying properties, these improved cleaning and / or drying properties in particular also in low-temperature cleaning processes, in particular in cleaning processes with washing liquor temperatures of 50 ° C or below, and / or should be achieved in short-lasting cleaning processes, in particular cleaning processes with a duration of less than 60 minutes.
  • This object was achieved by a molding which contains crosslinked polyvinylpyrrolidone particles and certain nonionic surfactants.
  • the polyvinylpyrrolidone particles here preferably have an average particle diameter of 100 to 150 ⁇ m and consist of cross-linked polyvinylpyrrolidone.
  • the present invention also relates to an automatic dishwashing process using the aforementioned molded bodies, in particular for removing soiling, in particular selected from soiling from tea, milk, porridge and / or starch, especially tea.
  • the dishwashing process is preferably carried out at a liquor temperature below 60.degree. C., preferably below 50.degree.
  • the dishwashing process takes a maximum of 90 minutes, in particular a maximum of 75 minutes, particularly preferably a maximum of 60 minutes.
  • the dishwashing process takes a maximum of 50, 40 or 30 minutes.
  • the present invention also relates to a machine dishwashing process using the aforementioned shaped bodies to improve the drying of the washed dishes, in particular to improve the drying of plastic dishes.
  • automatic dishwashing agents are compositions which can be used to clean soiled dishes in an automatic dishwashing process.
  • the automatic dishwashing agents according to the invention thus differ, for example, from the automatic rinse aid agents, which are always used in combination with automatic dishwashing agents and do not develop their own cleaning effect.
  • the automatic dishwashing detergents according to the invention are in the form of a shaped body, preferably a compact, especially a tablet. However, they can also be present in combination with other supply forms, in particular in combination with solid supply forms such as powder, granules or extrudates or in combination with liquid supply forms based on water and / or organic solvents.
  • Agents according to the invention can be packaged as single-phase or multi-phase products.
  • Automatic dishwashing detergents with one, two, three or four phases are particularly preferred.
  • Machine dishwashing agents, characterized in that they are in the form of a prefabricated dosage unit with two or more phases, are particularly preferred.
  • Particularly preferred are, in particular, two- or multiphase tablets, for example two-layer tablets, in particular two-layer tablets with a recess and a shaped body located in the recess.
  • Automatic dishwashing detergents according to the invention are preferably pre-packaged into metering units. These metering units preferably include 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.
  • Moldings according to the invention contain cross-linked polyvinylpyrrolidone particles.
  • these particles facilitate the disintegration of the shaped body and serve as disintegration aids or tablet disintegrants.
  • nonionic surfactants to be used according to the invention, the cleaning performance of cleaning agents according to the invention could also be improved.
  • the function of the PVP particles is therefore not limited solely to facilitating the disintegration of the moldings.
  • crosslinked polyvinylpyrrolidone particles with an average particle diameter of 100 to 150 ⁇ m, in particular with an average particle diameter of 110 to 130 ⁇ m.
  • mean particle diameter or “mean diameter” is to be understood as meaning the volume-mean D 50 particle diameter, which can be determined by customary methods.
  • the volume-average D 50 particle diameter is that point in the particle size distribution at which 50% by volume of the particles have a smaller diameter and 50% by volume of the particles have a larger diameter.
  • the mean particle diameter can in particular be determined with the aid of dynamic light scattering, which is usually carried out on dilute suspensions containing, for example, 0.01 to 1% by weight of capsules.
  • the PVP particles particularly preferably not only have an average particle diameter of 100 to 150 ⁇ m, in particular 110 to 130 ⁇ m, but also the particle size of the particles used is preferably completely within the specified intervals. This is ensured by using grain size fractions with the specified particle sizes, which can be obtained by a sieving process.
  • the moldings according to the invention are preferably produced in a manner known to the person skilled in the art by compressing particulate starting substances.
  • the premix is compressed in a so-called matrix between two punches to form a solid compact.
  • This process which is referred to as tabletting for short in the following, is divided into four sections: dosing, compression (elastic deformation), plastic deformation and ejection. Tableting is preferably carried out on what are known as rotary presses.
  • ingredients intended for tabletting can be filled into the die in the form of a common particulate premix at the same time or in the form of individual, separate powders or granules or at the same time, the dosage of a pre-prepared particulate premix being preferred.
  • granulates used according to the invention for producing the shaped bodies can be compressed particularly well.
  • a pressing force of 40 to 65 kN, particularly preferably 48 to 60 kN compacts with a hardness in the range from 150 to 250 N, in particular in the range from 200 to 230 N, which are also particularly good Have flow behavior.
  • the granules can thus preferably be pressed with a relatively low pressing force to give compacts with a relatively high hardness, which moreover preferably have very good flow behavior.
  • a lower pressing force must preferably be applied than for the production of conventional compacts.
  • Another object particularly preferred according to the invention therefore also represents a shaped body, in particular a compact, in particular a cleaning tablet, which is a mixture of cross-linked polyvinylpyrrolidone particles with an average particle diameter of 100 to 150 ⁇ m, in particular 110 to 130 ⁇ m, and at least a nonionic surfactant of the general formula R 1 O (AlkO) x M (OAlk) y OR 2 and which preferably has particularly good flow behavior.
  • the cross-linked PVP particles are preferably present in compositions according to the invention in an amount of 0.1 to 5% by weight, in particular in an amount of 0.2 to 3% by weight, especially in an amount of 0.3 to 1 , 8% by weight
  • disintegrants usually that they increase their volume when water gets in, whereby on the one hand the intrinsic volume increases (swelling), but on the other hand a pressure can be generated through the release of gases, which causes the tablet to disintegrate into smaller particles .
  • further disintegrants can also be contained in molded bodies according to the invention, for example carbonate / citric acid systems or carbonate in combination with other organic acids, synthetic polymers or natural polymers or modified natural substances such as cellulose and starch and their derivatives as well Alginates or casein derivatives.
  • gas-generating shower systems can also be used as further disintegrants.
  • Preferred effervescent systems consist of at least two components that react with one another to form gas, for example alkali metal carbonate and / or hydrogen carbonate and an acidifying agent which is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution.
  • An acidifying agent which releases carbon dioxide from the alkali salts in aqueous solution is, for example, citric acid.
  • the further disintegration aids are preferably used in amounts of 0.1 to 10% by weight, preferably 0.2 to 5% by weight and in particular 0.5 to 2% by weight, each based on the total weight of the disintegration aid containing agent used.
  • the shaped body according to the invention contains no further disintegration aids apart from the PVP particles.
  • Automatic dishwashing agents contain at least one nonionic surfactant of the general formula R 1 O (AlkO) x M (OAlk) y OR 2 as a further constituent, where R 1 and R 2 independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms; Alk represents a branched or unbranched alkyl radical having 2 to 4 carbon atoms; x and y are independently of one another for values between 1 and 70; and M represents an alkyl radical from the group CH 2 , CHR 3 , CR 3 R 4 , CH 2 CHR 3 and CHR 3 CHR 4 , where R 3 and R 4 independently of one another represent a branched or unbranched, saturated or unsaturated alkyl radical with 1 to 18 carbon atoms.
  • R 1 and R 2 independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4
  • R 1 —CH (OH) CH 2 —O (CH 2 CH 2 O) x CH 2 CHR (OCH 2 CH 2 ) y O — CH 2 CH (OH) —R 2
  • R is a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and x and y independently of one another have values of 20 to 30.
  • Corresponding compounds can be obtained, for example, by reacting alkyl diols HO-CHR-CH 2 -OH with ethylene oxide, followed by a reaction with an alkyl epoxide to close off the free OH functions with the formation of a dihydroxy ether.
  • compounds of the general formula R 1 -O (CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2 ) y OR 2 in which R 3 and R 4 are H and the indices x and y, are preferred independently of one another assume values from 1 to 40, preferably from 1 to 15.
  • the weight fraction of the nonionic surfactant of the general formula R 1 O (AlkO) x M (OAlk) y OR 2 in the total weight of the automatic dishwashing agent according to the invention is in a preferred embodiment between 0.05 and 10% by weight, preferably between 0.1 and 8% by weight, preferably between 0.5 and 5% by weight and in particular between 1 and 3% by weight.
  • the present invention also relates to an automatic dishwashing process using the aforementioned nonionic surfactants for removing, in particular improved removal, of soils selected from soils from tea, milk, porridge and / or starch, especially tea.
  • the dishwashing process is preferably carried out at a liquor temperature below 60.degree. C., preferably below 50.degree
  • automatic dishwashing agents according to the invention are at least one further component contain anionic polymer.
  • Preferred anionic polymers here are the copolymeric polycarboxylates and the copolymeric polysulfonates.
  • the proportion by weight of the anionic polymer in the total weight of the automatic dishwashing agent according to the invention is in a preferred embodiment from 0.1 to 20% by weight, preferably from 0.5 to 18% by weight, particularly preferably from 1.0 to 15% by weight. % and especially from 4 to 14% by weight.
  • Automatic dishwashing detergents characterized in that the copolymeric anionic polymer is selected from the group of the hydrophobically modified polycarboxylates and polysulfonates, is a particularly preferred subject, since the hydrophobic modification of the anionic copolymers improves the rinsing and drying properties of these agents while simultaneously reducing the formation of deposits can be reached.
  • the copolymers can have two, three, four or more different monomer units.
  • Preferred copolymeric polysulfonates contain, in addition to monomer (s) containing sulfonic acid groups, at least one monomer from the group of unsaturated carboxylic acids.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof.
  • the unsaturated dicarboxylic acids can of course also be used.
  • copolymers of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid are particularly preferably used as copolymeric polycarboxylates.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven particularly suitable.
  • Your relative molecular weight, based on free acids, is generally from 2000 to 70,000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3- Methacrylamido-2-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-sulphate , Sulfomethacrylamide, sulfomethyl methacrylamide and mixtures of the acids mentioned or their water-soluble salts.
  • the sulfonic acid groups can be wholly or partially in neutralized form, ie the acidic hydrogen atom 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 exchanged.
  • metal ions preferably alkali metal ions and in particular against Sodium ions.
  • the use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.
  • the monomer distribution of the copolymers preferably used according to the invention is, in the case of copolymers which only contain monomers containing carboxylic acid groups and monomers containing sulfonic acid groups, preferably in each case from 5 to 95% by weight; the proportion of the monomer containing sulphonic acid groups is particularly preferably 50 to 90% by weight. % and the proportion of the carboxylic acid group-containing monomer 10 to 50% by weight, the monomers here are preferably selected from those mentioned above.
  • 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 application.
  • Preferred automatic dishwashing detergents are characterized in that the copolymers have molar masses from 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
  • the copolymers furthermore comprise at least one nonionic, preferably hydrophobic, monomer in addition to monomer containing carboxyl groups and monomer containing sulfonic acid groups.
  • nonionic, preferably hydrophobic, monomer in addition to monomer containing carboxyl groups and monomer containing sulfonic acid groups.
  • nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2, 2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1, 4,4-dimethylhexane-1, ethylcyclohexyn, 1-octene, ⁇ -olefins with 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22- ⁇
  • Dishwashing detergents according to the invention also preferably contain builder (s) and enzyme (s) to ensure their cleaning effect.
  • Automatic dishwashing agents according to the invention preferably contain one or more builders as a further constituent.
  • the proportion by weight of the builders in the total weight of automatic dishwashing agents according to the invention is preferably 15 to 80% by weight and in particular 20 to 70% by weight.
  • the builders include in particular carbonates, phosphates, citrates, organic cobuilders and silicates.
  • phosphate is also preferred.
  • the alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of 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, which can be distinguished from metaphosphoric acids (HPO 3 ) and orthophosphoric acid 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 lime incrustations in fabrics and also contribute to cleaning performance.
  • Phosphates particularly preferred according to the invention 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 detergents, they contain quantities of phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) from 5 to 60% by weight, preferably from 15 to 45% by weight and in particular from 20 to 40% by weight, based in each case on the weight of the automatic dishwasher detergent.
  • phosphate preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) from 5 to 60% by weight, preferably from 15 to 45% by weight and in particular from 20 to 40% by weight, based in each case on the weight of the automatic dishwasher detergent.
  • Organic cobuilders that may be mentioned are, in particular, polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and organic cobuilders. These substance classes 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.
  • Automatic dishwashing agents contain citrate as one of their essential builders.
  • Automatic dishwashing detergents characterized in that they contain 2 to 40% by weight, preferably 5 to 30% by weight and in particular 7 to 20% by weight citrate, are preferred according to the invention.
  • the citrates are preferably used in combination with carbonates and / or hydrogen carbonate.
  • Preferred automatic dishwashing detergents are therefore characterized by a builder combination of phosphate and carbonate / hydrogen carbonate or of citrate and carbonate / hydrogen carbonate (cf. Tables 1a and 1b below).
  • builder combinations of phosphate, citrate and carbonate / hydrogen carbonate can also be realized.
  • dishwashing agents are characterized in that the dishwashing agent contains at least two builders from the group of phosphates, carbonates and citrates, the weight fraction of these builders, based on its total weight of the automatic dishwashing agent, preferably 5 to 80% by weight, preferably 15 to 75% by weight and in particular 30 to 70% by weight.
  • the combination of two or more builders from the above-mentioned group has proven to be advantageous for the cleaning and rinsing performance of automatic dishwashing agents according to the invention.
  • Polymeric polycarboxylates are also suitable as builders, for example 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 molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can be preferred.
  • the content of (homo) polymeric polycarboxylates in the automatic dishwashing detergents is preferably 0.5 to 20% by weight and in particular 3 to 10% by weight.
  • Machine dishwashing detergents according to the invention can be used as builder substance to use crystalline layered silicates of the general formula NaMSi x O 2x + 1 ⁇ yH 2 O, in which M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with especially preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.
  • Amorphous sodium silicates with a Na 2 O: SiO 2 module of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which can also be used are preferably delayed in dissolution and have secondary washing properties.
  • the content of silicates is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight.
  • Automatic dishwashing agents according to the invention which are particularly preferred are silicate-free.
  • MGDA methylgylcinediacetic acid
  • GLDA glutamic acid-N, N-diacetic acid
  • the agents according to the invention can contain alkali metal hydroxides.
  • These alkali carriers are preferably only used in small amounts in the cleaning agents, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below 5% by weight, particularly preferably between 0.1 and 5% by weight. and in particular between 0.5 and 5% by weight, each based on the total weight of the cleaning agent.
  • Alternative machine dishwashing detergents are free from alkali metal hydroxides.
  • Dishwashing detergents according to the invention preferably contain enzyme (s) as a further component.
  • enzyme include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof.
  • These enzymes are in principle of natural origin; Based on the natural molecules, improved variants are available for use in 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 using 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 lipases, in particular those with the amino acid substitution D96L.
  • oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases)
  • 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 concerned (enhancers) or to ensure the flow of electrons (mediators) in the event of greatly differing redox potentials between the oxidizing enzymes and the soiling.
  • a protein and / or enzyme can be protected against damage such as inactivation, denaturation or disintegration, for example due to physical influences, oxidation or proteolytic cleavage, particularly during storage.
  • damage such as inactivation, denaturation or disintegration, for example due to physical influences, oxidation or proteolytic cleavage, particularly during storage.
  • inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases. Washing or cleaning agents can contain stabilizers for this purpose; the provision of such means represents a preferred embodiment of the present invention.
  • Proteases and amylases that are active in washing or cleaning are generally not provided in the form of the pure protein, but rather in the form of stabilized, storable and transportable preparations.
  • These prefabricated preparations 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 with stabilizers or other auxiliaries.
  • 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 those of the core-shell type, in which an enzyme-containing core is coated with a protective layer 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 granules are advantageously low in dust, for example due to the application of polymeric film formers, and due to the coating are stable in storage.
  • the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10% by weight of the enzyme protein.
  • Automatic dishwashing agents which, based in each case on their total weight, contain 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight of enzyme preparations are particularly preferred .
  • the automatic dishwashing agents according to the invention can also contain further nonionic surfactants.
  • the proportion by weight of the further nonionic surfactant in the total weight of the automatic dishwashing agent according to the invention is in a preferred embodiment between 0.1 and 30% by weight, preferably between 0.5 and 20% by weight, preferably between 1 and 10% by weight in particular between 2 and 6% by weight.
  • preferred further nonionic surfactants have the general formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (CH 3 ) O] z CH 2 CH (OH ) R 2 , in which R 1 stands for a linear or branched aliphatic hydrocarbon radical with 4 to 22 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x and z for values between 0 and 40 and y is a value of at least 15.
  • the automatic dishwashing agent contains, based on its total weight, nonionic surfactant of the general formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (CH 3 ) O ] z CH 2 CH (OH) R 2 in amounts of 0.1 to 15% by weight, preferably 0.2 to 10% by weight, particularly preferably 0.5 to 8% by weight and in particular of 1, 0 to 6 wt%.
  • R 1 denotes a linear or branched aliphatic hydrocarbon radical with 4 up to 22 carbon atoms or mixtures thereof
  • R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof
  • y stands for a value between 15 and 120, preferably 20 to 100, in particular 20 to 80.
  • the group of these nonionic surfactants includes, for example, hydroxy mixed ethers of the general formula C 6-22 -CH (OH) CH 2 O- (EO) 20-120 -C 2-26 , for example the C 8-12 fatty alcohol (EO) 22 - 2-hydroxydecyl ethers and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ethers.
  • Automatic dishwashing detergent characterized in that a surfactant of the general formula R 1 CH (OH) CH 2 O- (CH 2 CH 2 O) 20-120 - R 2 is used as a further nonionic surfactant, R 1 and R 2 being independent each other for a linear or branched aliphatic hydrocarbon radical having 2 to 20 carbon atoms are particularly preferred.
  • surfactants of the formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 CH (OH) R 2 , in which R 1 is a linear or branched aliphatic hydrocarbon radical with 4 to 22 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof, and x represents values between 0.5 and 4, preferably 0.5 to 1.5, and y represents a value of at least 15 stands.
  • surfactants of the general formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 CH (OH) R 2 are also preferred, in which R 1 is a linear or branched aliphatic Hydrocarbon radical with 4 to 22 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x stands for a value between 1 and 40 and y stands for a value between 15 and 40, the alkylene units [CH 2 CH (CH 3 ) O] and [CH 2 CH 2 O] are randomized, ie in the form of a statistical, random distribution.
  • the rinsing performance and drying can be significantly improved compared to conventional polyalkoxylated fatty alcohols without a free hydroxyl group.
  • 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 an integer or a fraction. Due to 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.
  • nonionic surfactants can be used not only as individual substances but also as surfactant mixtures of two, three, four or more surfactants.
  • Surfactant mixtures are not mixtures of nonionic surfactants which in their entirety fall under one of the above general formulas, but rather those mixtures which contain two, three, four or more nonionic surfactants which are described by different ones of the above or other general formulas can be.
  • Nonionic surfactants which have a melting point above room temperature are particularly preferred.
  • the agents according to the invention can contain other washing or cleaning-active substances, preferably from the group of bleaches, bleach activators and bleach catalysts, glass corrosion inhibitors, corrosion inhibitors, fragrances and perfume carriers. These preferred ingredients are described in more detail below.
  • Automatic dishwashing agents according to the invention can contain a bleaching agent as a further constituent, oxygen bleaching agents being preferred.
  • 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 which 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, e.g. Dibenzoyl peroxide.
  • Further typical organic bleaching agents are the peroxy acids, the alkyl peroxy acids and the aryl peroxy acids being mentioned as examples.
  • Preferred automatic dishwashing agents according to the invention are characterized in that they contain an oxygen bleach, preferably sodium percarbonate, particularly preferably a coated sodium percarbonate.
  • the weight fraction of the bleach based on the total weight of the washing or cleaning agent, is in preferred embodiments between 2 and 30% by weight, preferably between 4 and 20% by weight and in particular between 6 and 15% by weight.
  • the automatic dishwashing detergents according to the invention can contain bleach activators as bleach activators. Under perhydrolysis conditions, these compounds give aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid.
  • bleach activators as bleach activators.
  • these compounds give aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid.
  • aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid.
  • suitable Substances which carry O- and / or N-acyl groups with the stated number of carbon atoms and / or optionally substituted benzoyl groups.
  • Multiple acylated alkylenediamines are preferred, tetraacetylethylene
  • Automatic dishwashing detergents characterized in that the bleach activator used is a bleach activator from the group of acetylated amines, preferably tetraacetylenediamine (TAED), are preferred according to the invention.
  • TAED tetraacetylenediamine
  • the automatic dishwashing agents according to the invention preferably contain at least one bleach catalyst.
  • 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 ammine complexes can also be used as bleach catalysts.
  • Manganese complexes in the II, III, IV or VI 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
  • Automatic dishwashing detergents characterized in that they also contain a bleach catalyst selected from the group of the bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of the 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 the abovementioned bleach catalysts in particular can significantly improve the cleaning result.
  • a bleach catalyst selected from the group of the bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of the 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 the abovementioned bleach catalysts
  • the aforementioned bleach-intensifying transition metal complexes are used in customary amounts, preferably in an amount up to 5% by weight, in particular from 0.0025% by weight to 1% by weight and particularly preferably from 0, 01% by weight to 0.30% by weight, based in each case on the total weight of the bleach catalyst-containing compositions, are used. In special cases, however, more bleach catalyst can also be used.
  • the automatic dishwashing detergents according to the invention show their advantageous cleaning and drying properties, especially in low-temperature cleaning processes.
  • Preferred dishwashing processes using agents according to the invention are therefore characterized in that the dishwashing processes are carried out at a liquor temperature below 60.degree. C., preferably below 50.degree.
  • agents according to the invention are distinguished from conventional automatic dishwashing agents by an improved drying performance.
  • the present application therefore also relates to the use of an automatic dishwashing agent according to the invention for improving drying in automatic dishwashing.

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Claims (12)

  1. Détergent pour lave-vaisselle sous forme d'un corps moulé pressé, contenant des particules de polyvinylpyrrolidone réticulées ainsi qu'au moins un tensioactif non ionique selon la formule (I)

            R1O(AlkO)xM(OAlk)yOR2     (I),

    R1 et R2 représentant, indépendamment l'un de l'autre, un radical alkyle ramifié ou non ramifié, saturé ou insaturé, éventuellement hydroxylé, comportant 4 à 22 atomes de carbone ;
    Alk représentant un radical alkyle ramifié ou non ramifié comportant 2 à 4 atomes de carbone ;
    x et y représentant, indépendamment l'un de l'autre, une valeur comprise entre 1 et 70 ; et
    M représentant un radical alkyle issu du groupe CH2, CHR3, CR3R4, CH2CHR3 et CHR3CHR4, R3 et R4 représentant, indépendamment l'un de l'autre, un radical alkyle ramifié ou non ramifié, saturé ou insaturé, comportant 1 à 18 atomes de carbone.
  2. Détergent pour lave-vaisselle selon la revendication 1, caractérisé en ce que le corps moulé pressé est une poudre comprimée, en particulier une pastille.
  3. Détergent pour lave-vaisselle selon la revendication 1 ou 2, caractérisé en ce que les particules de polyvinylpyrrolidone présentent un diamètre moyen compris entre 100 à 150 µm.
  4. Détergent pour lave-vaisselle selon l'une des revendications 1 à 3, caractérisé en ce que les particules de polyvinylpyrrolidone sont contenues en une quantité de 0,1 à 5 % en poids, en particulier en une quantité de 0,2 à 3 % en poids, plus particulièrement en une quantité de 0,3 à 1,8 % en poids.
  5. Détergent pour lave-vaisselle selon l'une des revendications précédentes, caractérisé en ce qu'il contient en outre au moins un polymère anionique, de préférence choisi parmi les polycarboxylates copolymères et les polysulfonates copolymères.
  6. Détergent pour lave-vaisselle selon l'une des revendications précédentes, caractérisé en ce qu'il contient en outre au moins un agent de blanchiment et/ou un activateur de blanchiment et/ou un catalyseur de blanchiment.
  7. Détergent pour lave-vaisselle selon l'une des revendications précédentes, caractérisé en ce qu'il contient en outre au moins un adjuvant et au moins une enzyme.
  8. Détergent pour lave-vaisselle selon l'une des revendications précédentes, contenant
    a) 0,5 à 5 % en poids d'un tensioactif non ionique de formule générale

            R1-CH(OH)CH2-O(CH2CH2O)xCH2CHR(OCH2CH2)yO-CH2CH(OH)-R2,

    dans laquelle
    - R1 et R2 représentent, indépendamment l'un de l'autre, un radical alkyle ou radical alcényle comportant 6 à 22 atomes de carbone ;
    - x et y représentent, indépendamment l'un de l'autre, des valeurs comprises entre 1 et 40 ;
    b) 0,1 à 5 % en poids, en particulier 0,2 à 3 % en poids, plus particulièrement 0,3 à 1,8 % en poids de particules de polyvinylpyrrolidone, en particulier comportant un diamètre moyen compris entre 100 à 150 µm ;
    c) 1 à 15 % en poids d'au moins un polymère anionique copolymère issu du groupe des polycarboxylates et polysulfonates hydrophobiquement modifiés.
  9. Détergent pour lave-vaisselle selon l'une des revendications 1 à 7, contenant
    a) 0,5 à 5 % en poids d'un tensioactif non ionique de formule générale

            R1-O(CH2CH2O)xCH2(OCH2CH2)yO-R2,

    dans laquelle
    - R1 et R2 représentent, indépendamment l'un de l'autre, un radical alkyle ou radical alcényle comportant 4 à 22 atomes de carbone ;
    - x et y représentent, indépendamment l'un de l'autre, des valeurs comprises entre 1 et 40 ;
    b) 0,1 à 5 % en poids, en particulier 0,2 à 3 % en poids, plus particulièrement 0,3 à 1,8 % en poids de particules de polyvinylpyrrolidone, en particulier comportant un diamètre moyen compris entre 100 à 150 µm ;
    c) 1 à 15 % en poids d'au moins un polymère anionique copolymère issu du groupe des polycarboxylates et polysulfonates hydrophobiquement modifiés.
  10. Procédé de nettoyage de vaisselle dans un lave-vaisselle au moyen d'un détergent pour lave-vaisselle selon l'une des revendications précédentes.
  11. Procédé pour lave-vaisselle permettant l'élimination de salissures, en particulier de salissures causées par du thé, du lait, du porridge et/ou de l'amidon, caractérisé en ce que, dans au moins une étape de procédé, des particules de polyvinylpyrrolidone réticulées ainsi qu'un tensioactif non ionique de formule générale (I)

            R1O(AlkO)xM(OAlk)yOR2     (I)

    sont utilisés,
    R1 et R2 représentant, indépendamment l'un de l'autre, un radical alkyle ramifié ou non ramifié, saturé ou insaturé, éventuellement hydroxylé, comportant 4 à 22 atomes de carbone ;
    Alk représentant un radical alkyle ramifié ou non ramifié comportant 2 à 4 atomes de carbone ;
    x et y représentant, indépendamment l'un de l'autre, une valeur comprise entre 1 et 70 ; et
    M représentant un radical alkyle issu du groupe CH2, CHR3, CR3R4, CH2CHR3 et CHR3CHR4, R3 et R4 représentant, indépendamment l'un de l'autre, un radical alkyle ramifié ou non ramifié, saturé ou insaturé, comportant 1 à 18 atomes de carbone.
  12. Utilisation d'une combinaison de particules de polyvinylpyrrolidone réticulées et d'au moins un tensioactif non ionique selon la formule (I)

            R1O(AlkO)xM(OAlk)yOR2     (I),

    R1 et R2 représentant, indépendamment l'un de l'autre, un radical alkyle ramifié ou non ramifié, saturé ou insaturé, éventuellement hydroxylé, comportant 4 à 22 atomes de carbone ;
    Alk représentant un radical alkyle ramifié ou non ramifié comportant 2 à 4 atomes de carbone ;
    x et y représentant, indépendamment l'un de l'autre, une valeur comprise entre 1 et 70 ; et
    M représentant un radical alkyle issu du groupe CH2, CHR3, CR3R4, CH2CHR3 et CHR3CHR4, R3 et R4 représentant, indépendamment l'un de l'autre, un radical alkyle ramifié ou non ramifié, saturé ou insaturé, comportant 1 à 18 atomes de carbone ;
    dans un corps moulé pressé pour l'amélioration du séchage de la vaisselle lavée, en particulier pour l'amélioration du séchage de vaisselle en plastique.
EP11720121.0A 2010-06-02 2011-05-19 Détergents pour lave-vaisselle en poudre comprimée Active EP2576746B1 (fr)

Applications Claiming Priority (2)

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DE102010029625A DE102010029625A1 (de) 2010-06-02 2010-06-02 Geschirrspülmittelkompaktate
PCT/EP2011/058158 WO2011151188A1 (fr) 2010-06-02 2011-05-19 Détergents pour lave-vaisselle en poudre comprimée

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