EP2576746B1 - Compacted dishwasher formulation - Google Patents
Compacted dishwasher formulation Download PDFInfo
- 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
- Authority
- EP
- European Patent Office
- Prior art keywords
- chr
- automatic dishwashing
- independently
- carbon atoms
- functional group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title description 25
- 238000009472 formulation Methods 0.000 title description 2
- 238000004851 dishwashing Methods 0.000 claims description 98
- 125000004432 carbon atom Chemical group C* 0.000 claims description 53
- 239000003599 detergent Substances 0.000 claims description 48
- 239000002245 particle Substances 0.000 claims description 48
- 239000002736 nonionic surfactant Substances 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 33
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 29
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 29
- 239000007844 bleaching agent Substances 0.000 claims description 26
- 238000004140 cleaning Methods 0.000 claims description 25
- 229920001577 copolymer Polymers 0.000 claims description 23
- 102000004190 Enzymes Human genes 0.000 claims description 20
- 108090000790 Enzymes Proteins 0.000 claims description 20
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- 229920006395 saturated elastomer Polymers 0.000 claims description 17
- 229920005646 polycarboxylate Polymers 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 229920006318 anionic polymer Polymers 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000012190 activator Substances 0.000 claims description 8
- 229920003023 plastic Polymers 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- 235000013336 milk Nutrition 0.000 claims description 4
- 239000008267 milk Substances 0.000 claims description 4
- 210000004080 milk Anatomy 0.000 claims description 4
- 235000021395 porridge Nutrition 0.000 claims description 4
- 235000013616 tea Nutrition 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims 16
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims 3
- 125000003342 alkenyl group Chemical group 0.000 claims 2
- 241001122767 Theaceae Species 0.000 claims 1
- -1 hydroxylated alkyl radical Chemical class 0.000 description 60
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- 239000011572 manganese Substances 0.000 description 13
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- 229910019142 PO4 Inorganic materials 0.000 description 11
- 239000012459 cleaning agent Substances 0.000 description 11
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- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 6
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
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- 244000269722 Thea sinensis Species 0.000 description 5
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 5
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- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
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- 239000007884 disintegrant Substances 0.000 description 4
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- 239000007788 liquid Substances 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- LOTBYPQQWICYBB-UHFFFAOYSA-N methyl n-hexyl-n-[2-(hexylamino)ethyl]carbamate Chemical compound CCCCCCNCCN(C(=O)OC)CCCCCC LOTBYPQQWICYBB-UHFFFAOYSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 150000004965 peroxy acids Chemical class 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
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- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 3
- 108090000637 alpha-Amylases Proteins 0.000 description 3
- 239000002775 capsule Substances 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 125000002843 carboxylic acid group Chemical group 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 150000001860 citric acid derivatives Chemical class 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 3
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- 238000003825 pressing Methods 0.000 description 3
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- 150000003624 transition metals Chemical class 0.000 description 3
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 3
- UYXFOIMFLBVYDL-UHFFFAOYSA-N 1,2,4,7-tetramethyl-1,4,7-triazonane Chemical compound CC1CN(C)CCN(C)CCN1C UYXFOIMFLBVYDL-UHFFFAOYSA-N 0.000 description 2
- WLDGDTPNAKWAIR-UHFFFAOYSA-N 1,4,7-trimethyl-1,4,7-triazonane Chemical compound CN1CCN(C)CCN(C)CC1 WLDGDTPNAKWAIR-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- C—CHEMISTRY; METALLURGY
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- 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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- 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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Description
Die vorliegende Anmeldung beschreibt maschinelle Geschirrspülmittel, die als Formkörper vorliegen sowie maschinelle Geschirrspülverfahren unter Einsatz dieser maschinellen Geschirrspülmittel sowie die Verwendung dieser maschinellen Geschirrspülmittel zur Entfernung von Anschmutzungen beim maschinellen Geschirrspülen.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.
Geschirrspülmittel stehen dem Verbraucher in einer Vielzahl von Angebotsformen zur Verfügung. Neben den traditionellen flüssigen Handgeschirrspülmitteln haben mit der Verbreitung von Haushaltsgeschirrspülmaschinen insbesondere die maschinellen Geschirrspülmittel eine große Bedeutung. Diese maschinellen Geschirrspülmittel werden dem Verbraucher typischerweise in fester Form, beispielsweise als Pulver oder als Tabletten, zunehmend jedoch auch in flüssiger Form angeboten.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.
Die US Patentanmeldung
Eines der Hauptziele der Hersteller maschineller Reinigungsmittel ist die Verbesserung der Reinigungs- und Klarspülleistung dieser Mittel, wobei in jüngster Zeit ein verstärktes Augenmerk auf die Reinigungs- und Klarspülleistung bei Niedrigtemperatur-Reinigungsgängen bzw. in Reinigungsgängen mit verringertem Wasserverbrauch gelegt wird.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.
Dieser Anmeldung lag die Aufgabe zugrunde, ein maschinelles Geschirrspülmittel mit verbesserten Reinigungseigenschaften und/oder mit verbesserten Trocknungseigenschaften bereitzustellen, wobei diese verbesserten Reinigungs- und/oder Trocknungseigenschaften insbesondere auch bei Niedrigtemperatur-Reinigungsgängen, insbesondere in Reinigungsverfahren mit Spülflottentemperaturen von 50°C oder darunter, und/oder in kurz andauernden Reinigungsverfahren, insbesondere in Reinigungsverfahren mit einer Dauer von unter 60 Minuten, erzielt werden sollten.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.
Diese Aufgabe wurde durch einen Formkörper gelöst, der quervernetzte Polyvinylpyrrolidon-Partikel sowie bestimmte nichtionische Tenside enthält.This object was achieved by a molding which contains crosslinked polyvinylpyrrolidone particles and certain nonionic surfactants.
Ein erster Gegenstand der vorliegenden Erfindung sind daher Geschirrspülmittel in Gestalt eines Formkörpers, insbesondere eines Kompaktats, vor allem einer Tablette, dadurch gekennzeichnet, dass sie quervernetzte Polyvinylpyrrolidon-Partikel sowie mindestens ein nichtionisches Tensid der allgemeinen Formel
R1O(AlkO)xM(OAlk)yOR2
enthalten, wobei
- R1 und R2 unabhängig voneinander für einen verzweigten oder unverzweigten, gesättigten oder ungesättigten, gegebenenfalls hydroxylierten Alkylrest mit 4 bis 22 Kohlenstoffatomen stehen;
- Alk für einen verzweigten oder unverzweigten Alkylrest mit 2 bis 4 Kohlenstoffatomen steht;
- x und y unabhängig voneinander für Werte zwischen 1 und 70 stehen; und
- M für einen Alkylrest aus der Gruppe CH2, CHR3, CR3R4, CH2CHR3 und CHR3CHR4 steht, wobei
- R3 und R4 unabhängig voneinander für einen verzweigten oder unverzweigten, gesättigten oder ungesättigten Alkylrest mit 1 bis 18 Kohlenstoffatomen stehen.
R 1 O (AlkO) x M (OAlk) y OR 2
included, 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 consisting of CH 2 , CHR 3 , CR 3 R 4 , CH 2 CHR 3 and CHR 3 CHR 4 , where
- R 3 and R 4 independently of one another represent a branched or unbranched, saturated or unsaturated alkyl radical having 1 to 18 carbon atoms.
Die Polyvinylpyrrolidon-Partikel (PVP-Partikel) weisen hierbei vorzugsweise einen mittleren Teilchendurchmesser von 100 bis 150 µm auf und bestehen aus quervernetztem Polyvinylpyrrolidon.The polyvinylpyrrolidone particles (PVP particles) here preferably have an average particle diameter of 100 to 150 μm and consist of cross-linked polyvinylpyrrolidone.
Weiterer Gegenstand der vorliegenden Erfindung ist auch ein maschinelles Geschirrspülverfahren unter Einsatz der zuvor genannten Formkörper, insbesondere zur Entfernung von Anschmutzungen, insbesondere ausgewählt aus Anschmutzungen durch Tee, Milch, Haferbrei und/oder Stärke, vor allem Tee. Das Geschirrspülverfahren wird vorzugsweise bei einer Flottentemperatur unterhalb 60°C, vorzugsweise unterhalb 50°C durchgeführt. In einer bevorzugten Ausführungsform dauert das Geschirrspülverfahren maximal 90 Minuten, insbesondere maximal 75 Minuten, besonders bevorzugt maximal 60 Minuten. In besonderen Ausführungsformen dauert das Geschirrspülverfahren maximal 50, 40 oder 30 Minuten.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. In a preferred embodiment, the dishwashing process takes a maximum of 90 minutes, in particular a maximum of 75 minutes, particularly preferably a maximum of 60 minutes. In particular embodiments, the dishwashing process takes a maximum of 50, 40 or 30 minutes.
Weiterer Gegenstand der vorliegenden Erfindung ist auch ein maschinelles Geschirrspülverfahren unter Einsatz der zuvor genannten Formkörper zur Verbesserung der Trocknung des gespülten Geschirrs, insbesondere zur Verbesserung der Trocknung von Plastik-Geschirr.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.
Gegenstand der vorliegenden Erfindung ist ebenso die Verwendung einer Kombination aus quervernetzten Polyvinylpyrrolidon-Partikeln und mindestens einem nichtionischen Tensid gemäß Formel (I)
R1O(AlkO)xM(OAlk)yOR2 (I),
- wobei R1 und R2 unabhängig voneinander für einen verzweigten oder unverzweigten, gesättigten oder ungesättigten, gegebenenfalls hydroxylierten Alkylrest mit 4 bis 22 Kohlenstoffatomen stehen; Alk für einen verzweigten oder unverzweigten Alkylrest mit 2 bis 4 Kohlenstoffatomen steht;
- x und y unabhängig voneinander für einen Wert von 1 und 70 stehen; und
- M für einen Alkylrest aus der Gruppe CH2, CHR3, CR3R4, CH2CHR3 und CHR3CHR4 steht,
- wobei R3 und R4 unabhängig voneinander für einen verzweigten oder unverzweigten, gesättigten oder ungesättigten Alkylrest mit 1 bis 18 Kohlenstoffatomen stehen;
Geschirrs.The present invention also relates to the use of a combination of cross-linked polyvinylpyrrolidone particles and at least one nonionic surfactant according to formula (I)
R 1 O (AlkO) x M (OAlk) y OR 2 (I),
- 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 independently stand for a value of 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 having 1 to 18 carbon atoms;
Dishes.
Die vorliegende Anmeldung hat maschinelle Geschirrspülmittel zum Gegenstand. Als maschinelle Geschirrspülmittel werden nach Maßgabe dieser Anmeldung Zusammensetzungen bezeichnet, die zur Reinigung verschmutzten Geschirrs in einem maschinellen Geschirrspülverfahren eingesetzt werden können. Damit unterscheiden sich die erfindungsgemäßen maschinellen Geschirrspülmittel beispielsweise von den maschinellen Klarspülmitteln, die stets in Kombination mit maschinellen Geschirrspülmitteln eingesetzt werden und keine eigene Reinigungswirkung entfalten.The subject of the present application is automatic dishwashing detergents. In accordance with this application, 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.
Die erfindungsgemäßen maschinellen Geschirrspülmittel liegen in Form eines Formkörpers, vorzugsweise eines Kompaktats, vor allem einer Tablette, vor. Sie können jedoch auch in Kombination mit anderen Angebotsformen, insbesondere in Kombination mit festen Angebotsformen wie Pulver, Granulaten oder Extrudaten oder in Kombination mit flüssigen Angebotsformen auf Basis von Wasser und/oder organischen Lösungsmitteln vorliegen.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.
Erfindungsgemäße Mittel können als einphasige oder mehrphasige Produkte konfektioniert werden. Bevorzugt sind insbesondere maschinelle Geschirrspülmittel mit einer, zwei, drei oder vier Phasen. Maschinelle Geschirrspülmittel, dadurch gekennzeichnet, dass sie in Form einer vorgefertigten Dosiereinheit mit zwei oder mehr Phasen vorliegen, sind besonders bevorzugt. Besonders bevorzugt sind insbesondere zwei- oder mehrphasige Tabletten, beispielsweise Zweischichttabletten, insbesondere Zweischichttabletten mit Mulde und einem in der Mulde befindlichen Formkörper.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.
Erfindungsgemäße maschinelle Geschirrspülmittel werden vorzugsweise zu Dosiereinheiten vorkonfektioniert. Diese Dosiereinheiten umfassen vorzugsweise die für einen Reinigungsgang notwendige Menge an wasch- oder reinigungsaktiven Substanzen. Bevorzugte Dosiereinheiten weisen ein Gewicht zwischen 12 und 30 g, bevorzugt zwischen 14 und 26 g und insbesondere zwischen 15 und 22 g auf.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.
Das Volumen der vorgenannten Dosiereinheiten sowie deren Raumform sind mit besonderem Vorzug so gewählt, dass eine Dosierbarkeit der vorkonfektionierten Einheiten über die Dosierkammer einer Geschirrspülmaschine gewährleistet ist. Das Volumen der Dosiereinheit beträgt daher bevorzugt zwischen 10 und 35 ml, vorzugsweise zwischen 12 und 30 ml und insbesondere zwischen 15 und 25 ml.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.
Die erfindungsgemäßen maschinellen Geschirrspülmittel, insbesondere die vorgefertigten Dosiereinheiten, weisen mit besonderem Vorzug eine wasserlösliche Umhüllung auf.The automatic dishwashing detergents according to the invention, in particular the prefabricated dosing units, particularly preferably have a water-soluble coating.
Erfindungsgemäße Formkörper enthalten quervernetzte Polyvinylpyrrolidon-Partikel. Diese Partikel erleichtern unter anderem den Zerfall der Formkörper und dienen insofern als Desintegrationshilfsmittel bzw. Tablettensprengmittel. Zusätzlich hat sich jedoch herausgestellt, dass durch die Kombination der quervernetzten Polyvinylpyrrolidon-Partikel mit erfindungsgemäß einzusetzenden nichtionischen Tensiden auch die Reinigungsleistung erfindungsgemäßer Reinigungsmittel verbessert werden konnte. Die Funktion der PVP-Partikel ist insofern nicht alleine auf die Erleichterung des Zerfalls der Formkörper beschränkt.Moldings according to the invention contain cross-linked polyvinylpyrrolidone particles. Among other things, these particles facilitate the disintegration of the shaped body and serve as disintegration aids or tablet disintegrants. In addition, however, it has been found that by combining the cross-linked polyvinylpyrrolidone particles with 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.
Es hat sich erfindungsgemäß als besonders vorteilhaft herausgestellt, quervernetzte Polyvinylpyrrolidon-Partikel mit einem mittleren Teilchendurchmesser von 100 bis 150 µm, insbesondere mit einem mittleren Teilchendurchmesser von 110 bis 130 µm, einzusetzen.According to the invention, it has been found to be particularly advantageous to use crosslinked polyvinylpyrrolidone particles with an average particle diameter of 100 to 150 μm, in particular with an average particle diameter of 110 to 130 μm.
Unter dem Begriff "mittlerer Teilchendurchmesser" bzw. "mittlerer Durchmesser" ist im Rahmen der vorliegenden Erfindung der volumenmittlere Dso Teilchendurchmesser zu verstehen, der nach üblichen Verfahren bestimmt werden kann. Der volumenmittlere D50 Teilchendurchmesser ist derjenige Punkt in der Teilchengrößenverteilung, bei dem 50 Vol.-% der Teilchen einen kleineren und 50 Vol.-% der Teilchen einen größeren Durchmesser aufweisen. Die mittleren Teilchendurchmesser können insbesondere mit Hilfe dynamischer Lichtstreuung bestimmt werden, die üblicherweise an verdünnten Suspensionen, die z.B. 0,01 bis 1 Gew.-% Kapseln enthalten, durchgeführt werden.In the context of the present invention, the term “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.
Besonders bevorzugt weisen die PVP-Partikel nicht nur einen mittleren Teilchendurchmesser von 100 bis 150 µm, insbesondere von 110 bis 130 µm, auf, sondern darüber hinaus liegt die Teilchengröße der eingesetzten Partikel vorzugsweise vollständig in den angegebenen Intervallen. Dies wird dadurch sichergestellt, dass Korngrößenfraktionen mit den angegebenen Teilchengrößen, die durch ein Siebverfahren erhalten werden können, eingesetzt werden.The PVP particles particularly preferably not only have an average particle diameter of 100 to 150 μm, in particular 110 to 130 μm, 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.
Die Herstellung der erfindungsgemäßen Formkörper, insbesondere der Reinigungsmitteltabletten, erfolgt bevorzugt in dem Fachmann bekannter Weise durch Verpressung partikulärer Ausgangssubstanzen. Zur Herstellung der Tabletten wird das Vorgemisch in einer so genannten Matrize zwischen zwei Stempeln zu einem festen Komprimat verdichtet. Dieser Vorgang, der im Folgenden kurz als Tablettierung bezeichnet wird, gliedert sich in vier Abschnitte: Dosierung, Verdichtung (elastische Verformung), plastische Verformung und Ausstoßen. Die Tablettierung erfolgt dabei vorzugsweise auf so genannten Rundläuferpressen.The moldings according to the invention, in particular the detergent tablets, are preferably produced in a manner known to the person skilled in the art by compressing particulate starting substances. To produce the tablets, 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.
Bei der Tablettierung mit Rundläuferpressen hat es sich als vorteilhaft erwiesen, die Tablettierung mit möglichst geringen Gewichtschwankungen der Tablette durchzuführen. Auf diese Weise lassen sich auch die Härteschwankungen der Tablette reduzieren. Die Minimierung von Gewichtschwankungen kann auf folgende Weise erzielt werden:
- Verwendung von Kunststoffeinlagen mit geringen Dickentoleranzen
- Geringe Umdrehungszahl des Rotors
- Große Füllschuhe
- Abstimmung des Füllschuhflügeldrehzahl auf die Drehzahl des Rotors
- Füllschuh mit konstanter Pulverhöhe
- Entkopplung von Füllschuh und Pulvervorlage
- Use of plastic inserts with small thickness tolerances
- Low speed of the rotor
- Big filling shoes
- Adjustment of the filling shoe wing speed to the speed of the rotor
- Filling shoe with constant powder height
- Decoupling of the filling shoe and powder feed
Die zur Tablettierung vorgesehen Inhaltsstoffe können in Form eines gemeinsamen teilchenförmigen Vorgemisches zeitgleich oder in Form einzelner, separater Pulver oder Granulate zeitlich versetzt oder zeitgleich in die Matrize eingefüllt werden, wobei die Dosierung eines vorgefertigten teilchenförmigen Vorgemisches bevorzugt ist.The 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.
Erfindungsgemäß wurde überraschenderweise festgestellt, dass sich erfindungsgemäß zur Herstellung der Formkörper eingesetzte Granulate besonders gut verpressen lassen. So können vorzugsweise unter Anwendung einer Presskraft von 40 bis 65 kN, besonders bevorzugt von 48 bis 60 kN, Kompaktate mit einer Härte im Bereich von 150 bis 250 N, insbesondere im Bereich von 200 bis 230 N erhalten werden, die darüber hinaus ein besonders gutes Rieselverhalten aufweisen. Die Granulate lassen sich somit vorzugsweise mit relativ geringer Presskraft zu Kompaktaten mit relativ hoher Härte verpressen, die darüber hinaus vorzugsweise ein sehr gutes Rieselverhalten aufweisen. Entsprechend ist es umgekehrt von Vorteil, dass zur Herstellung von Kompaktaten geringerer Härte vorzugsweise eine geringere Presskraft aufgewandt werden muss, als zur Herstellung üblicher Kompaktate.According to the invention, it was surprisingly found that granulates used according to the invention for producing the shaped bodies can be compressed particularly well. Thus, preferably using 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. Conversely, it is correspondingly advantageous that, in order to produce compacts of lower hardness, a lower pressing force must preferably be applied than for the production of conventional compacts.
Ein weiterer erfindungsgemäß besonders bevorzugter Gegenstand stellt daher auch ein Formkörper, insbesondere eine Kompaktat, vor allem eine Reinigungstablette, dar, der eine Mischung aus quervernetzten Polyvinylpyrrolidon-Partikeln mit einem mittleren Teilchendurchmesser von 100 bis 150 µm, insbesondere von 110 bis 130 µm, und mindestens einem nichtionischen Tensid der allgemeinen Formel R1O(AlkO)xM(OAlk)yOR2 enthält und der vorzugsweise ein besonders gutes Rieselverhalten aufweist.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 μm, in particular 110 to 130 μm, 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.
Die quervernetzten PVP-Partikel sind in erfindungsgemäßen Zusammensetzungen vorzugsweise in einer Menge von 0,1 bis 5 Gew.-%, insbesondere in einer Menge von 0,2 bis 3 Gew.-%, vor allem in einer Menge von 0,3 bis 1,8 Gew.-%, enthaltenThe 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
Die Wirkung von Sprengmitteln besteht in der Regel darin, dass sie bei Wasserzutritt ihr Volumen vergrößern, wobei sich einerseits das Eigenvolumen vergrößert (Quellung), andererseits aber auch über die Freisetzung von Gasen ein Druck erzeugt werden kann, der die Tablette in kleinere Partikel zerfallen lässt. Zusätzlich zu den PVP-Partikeln können auch weitere Sprengmittel in erfindungsgemäßen Formkörpern enthalten sein, beispielsweise Carbonat/Citronensäure-Systeme oder Carbonat in Kombination mit anderen organischen Säuren, synthetische Polymere oder natürliche Polymere bzw. modifizierte Naturstoffe wie Cellulose und Stärke und ihre Derivate sowie Alginate oder Casein-Derivate. Weiterhin können als weitere Sprengmittel auch gasentwickelnde Brausesysteme eingesetzt werden. Bevorzugte Brausesysteme bestehen aus mindestens zwei Bestandteilen, die miteinander unter Gasbildung reagieren, beispielsweise aus Alkalimetallcarbonat und/oder -hydrogencarbonat sowie einem Acidifizierungsmittel, das geeignet ist, aus den Alkalimetallsalzen in wässriger Lösung Kohlendioxid freizusetzen. Ein Acidifizierungsmittel, das aus den Alkalisalzen in wässriger Lösung Kohlendioxid freisetzt, ist beispielsweise die Citronensäure.The effect of disintegrants is 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 . In addition to the PVP 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. Furthermore, 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.
Die weiteren Desintegrationshilfsmittel werden, sofern verwendet, vorzugsweise in Mengen von 0,1 bis 10 Gew.-%, vorzugsweise 0,2 bis 5 Gew.-% und insbesondere 0,5 bis 2 Gew.-%, jeweils bezogen auf das Gesamtgewicht des desintegrationshilfsmittelhaltigen Mittels, eingesetzt.The further disintegration aids, if used, 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.
In einer bevorzugten Ausführungsform enthält der erfindungsgemäße Formkörper außer den PVP-Partikeln keine weitere Desintegrationshilfsmittel.In a preferred embodiment, the shaped body according to the invention contains no further disintegration aids apart from the PVP particles.
Erfindungsgemäße maschinelle Geschirrspülmittel enthalten als weiteren Bestandteil mindestens ein nichtionisches Tensid der allgemeinen Formel R1O(AlkO)xM(OAlk)yOR2, wobei
R1 und R2 unabhängig voneinander für einen verzweigten oder unverzweigten, gesättigten oder ungesättigten, gegebenenfalls hydroxylierten Alkylrest mit 4 bis 22 Kohlenstoffatomen stehen;
Alk für einen verzweigten oder unverzweigten Alkylrest mit 2 bis 4 Kohlenstoffatomen steht;
x und y unabhängig voneinander für Werte zwischen 1 und 70 stehen; und M für einen Alkylrest aus der Gruppe CH2, CHR3, CR3R4, CH2CHR 3 und CHR3CHR4 steht, wobei R3 und R4 unabhängig voneinander für einen verzweigten oder unverzweigten, gesättigten oder ungesättigten Alkylrest mit 1 bis 18 Kohlenstoffatomen stehen.Automatic dishwashing agents according to the invention 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.
In einer bevorzugten Ausführungsform enthalten erfindungsgemäße maschinelle Geschirrspülmittel hierbei als nichtionisches Tensid ein Tensid der allgemeinen Formel
R1-CH(OH)CH2-O(CH2CH2O)xCH2CHR(OCH2CH2)yO-CH2CH(OH)-R2,
wobei
- R, R1 und R2 unabhängig voneinander für einen Alkylrest oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen;
- x und y unabhängig voneinander für Werte zwischen 1 und 40 stehen
R 1 -CH (OH) CH 2 -O (CH 2 CH 2 O) x CH 2 CHR (OCH 2 CH 2 ) y O-CH 2 CH (OH) -R 2 ,
in which
- R, R 1 and R 2 independently of one another represent an alkyl radical or alkenyl radical having 6 to 22 carbon atoms;
- x and y independently represent values between 1 and 40
Bevorzugt sind hierbei insbesondere Verbindungen der allgemeinen Formel R1-CH(OH)CH2-O(CH2CH2O)xCH2CHR(OCH2CH2)yO-CH2CH(OH)-R2, in denen R für einen linearen, gesättigten Alkylrest mit 8 bis 16 Kohlenstoffatomen, vorzugsweise 10 bis 14 Kohlenstoffatomen steht und x und y unabhängig voneinander Werte von 20 bis 30 aufweisen. Entsprechende Verbindungen können beispielsweise durch Umsetzung von Alkyldiolen HO-CHR-CH2-OH mit Ethylenoxid erhalten werden, wobei im Anschluss eine Umsetzung mit einem Alkylepoxid zum Verschluss der freien OH-Funktionen unter Ausbildung eines Dihydroxyethers erfolgt.In particular, compounds of the general formula R 1 —CH (OH) CH 2 —O (CH 2 CH 2 O) x CH 2 CHR (OCH 2 CH 2 ) y O — CH 2 CH (OH) —R 2 , in where R is a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and 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.
In einer weiteren bevorzugten Ausführungsform enthalten erfindungsgemäße maschinelle Geschirrspülmittel als nichtionisches Tensid ein Tensid der allgemeinen Formel
R1-O(CH2CH2O)xCR3R4(OCH2CH2)yO-R2,
in der
- R1 und R2 unabhängig voneinander für einen Alkylrest oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen;
- R3 und R4 unabhängig voneinander für H oder für einen Alkylrest oder Alkenylrest mit 1 bis 18 Kohlenstoffatomen und
- x und y unabhängig voneinander für Werte zwischen 1 und 40 stehen;
R 1 -O (CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2 ) y OR 2 ,
in the
- R 1 and R 2 independently of one another represent an alkyl radical or alkenyl radical having 4 to 22 carbon atoms;
- R 3 and R 4 independently of one another represent H or an alkyl radical or alkenyl radical having 1 to 18 carbon atoms and
- x and y are independently of one another for values between 1 and 40;
Bevorzugt sind hierbei insbesondere Verbindungen der allgemeinen Formel R1-O(CH2CH2O)xCR3R4(OCH2CH2)yO-R2, in der R3 und R4 für H stehen und die Indices x und y unabhängig voneinander Werte von 1 bis 40, vorzugsweise von 1 bis 15 annehmen.In particular, 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.
Besonders bevorzugt sind insbesondere Verbindungen der allgemeinen Formel R1-O(CH2CH2O)xCR3R4(OCH2CH2)yO-R2, in der die Reste R1 und R2 unabhängig voneinander gesättigte Alkylreste mit 4 bis 14 Kohlenstoffatome darstellen und die Indices x und y unabhängig voneinander Werte von 1 bis 15 und insbesondere von 1 bis 12 annehmen.Particularly preferred are 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 the radicals R 1 and R 2 independently of one another are saturated alkyl radicals with 4 to 14 represent carbon atoms and the indices x and y independently assume values from 1 to 15 and in particular from 1 to 12.
Weiterhin bevorzugt sind solche Verbindungen der allgemeinen Formel R1-O(CH2CH2O)xCR3R4(OCH2CH2)yO-R2, in der einer der Reste R1 und R2 verzweigt ist.Also preferred are those 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 one of the radicals R 1 and R 2 is branched.
Ganz besonders bevorzugt sind Verbindungen der allgemeinen Formel R1-O(CH2CH2O)xCR3R4(OCH2CH2)yO-R2, in der die Indices x und y unabhängig voneinander Werte von 8 bis 12 annehmen.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 the indices x and y independently assume values from 8 to 12, are very particularly preferred.
Der Gewichtsanteil des nichtionischen Tensids der allgemeinen Formel R1O(AlkO)xM(OAlk)yOR2 am Gesamtgewicht des erfindungsgemäßen maschinellen Geschirrspülmittels beträgt in einer bevorzugten Ausführungsform zwischen 0,05 und 10 Gew.-%, vorzugsweise zwischen 0,1 und 8 Gew.-%, bevorzugt zwischen 0,5 und 5 Gew.-% und insbesondere zwischen 1 und 3 Gew.-%.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.
Weiterer Gegenstand der vorliegenden Erfindung ist auch ein maschinelles Geschirrspülverfahren unter Einsatz der zuvor genannten nichtionischen Tenside zur Entfernung, insbesondere verbesserten Entfernung, von Anschmutzungen ausgewählt aus Anschmutzungen durch Tee, Milch, Haferbrei und/oder Stärke, vor allem Tee. Das Geschirrspülverfahren wird vorzugsweise bei einer Flottentemperatur unterhalb 60°C, vorzugsweise unterhalb 50°C durchgeführtThe 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
Es hat sich erfindungsgemäß weiterhin als besonders vorteilhaft herausgestellt, wenn erfindungsgemäße maschinelle Geschirrspülmittel als weiteren Bestandteil mindestens ein anionisches Polymer enthalten. Bevorzugte anionische Polymere sind hierbei die copolymeren Polycarboxylate und die copolymeren Polysulfonate.According to the invention, it has also been found to be particularly advantageous if 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.
Der Gewichtsanteil des anionischen Polymers am Gesamtgewicht des erfindungsgemäßen maschinellen Geschirrspülmittels beträgt in einer bevorzugten Ausführungsform von 0,1 bis 20 Gew.-%, vorzugsweise von 0,5 bis 18 Gew.-%, besonders bevorzugt von 1,0 bis 15 Gew.-% und insbesondere von 4 bis 14 Gew.-%.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.
Erfindungsgemäße maschinelle Geschirrspülmittel, dadurch gekennzeichnet, dass das copolymere anionische Polymer ausgewählt ist aus der Gruppe der hydrophob modifizierten Polycarboxylate und Polysulfonate ist ein besonders bevorzugter Gegenstand, da durch die hydrophobe Modifizierung der anionischen Copolymere eine Verbesserung der Klarspül- und Trocknungseigenschaften dieser Mittel bei gleichzeitig geringer Belagsbildung erreicht werden kann.Automatic dishwashing detergents according to the invention, 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.
Die Copolymere können zwei, drei, vier oder mehr unterschiedliche Monomereinheiten aufweisen.The copolymers can have two, three, four or more different monomer units.
Bevorzugte copolymere Polysulfonate enthalten neben Sulfonsäuregruppen-haltigem(n) Monomer(en) wenigstens ein Monomer aus der Gruppe der ungesättigten Carbonsäuren.Preferred copolymeric polysulfonates contain, in addition to monomer (s) containing sulfonic acid groups, at least one monomer from the group of unsaturated carboxylic acids.
Als ungesättigte Carbonsäure(n) wird/werden mit besonderem Vorzug ungesättigte Carbonsäuren der Formel R1R2)C=C(R3)COOH eingesetzt, in der R1 bis R3 unabhängig voneinander für-H, -CH3, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH2, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR4 steht, wobei R4 ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist.The unsaturated carboxylic acid (s) used is / are with particular preference unsaturated carboxylic acids of the formula R 1 R 2 ) C =C (R 3 ) COOH, in which R 1 to R 3 independently of one another represent -H, -CH 3 , a straight-chain or branched, saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted with -NH 2 , -OH or -COOH as defined above or for -COOH or -COOR 4 , where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
Besonders bevorzugte ungesättigte Carbonsäuren sind Acrylsäure, Methacrylsäure, Ethacrylsäure, α-Chloroacrylsäure, α-Cyanoacrylsäure, Crotonsäure, α-Phenyl-Acrylsäure, Maleinsäure, Maleinsäureanhydrid, Fumarsäure, Itaconsäure, Citraconsäure, Methylenmalonsäure, Sorbinsäure, Zimtsäure oder deren Mischungen. Einsetzbar sind selbstverständlich auch die ungesättigten Dicarbonsäuren.Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-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.
Als copolymere Polycarboxylate werden erfindungsgemäß besonders bevorzugt Copolymere der Acrylsäure mit Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure eingesetzt. Als besonders geeignet haben sich Copolymere der Acrylsäure mit Maleinsäure erwiesen, die 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Ihre relative Molekülmasse, bezogen auf freie Säuren, beträgt im allgemeinen 2000 bis 70000 g/mol, vorzugsweise 20000 bis 50000 g/mol und insbesondere 30000 bis 40000 g/mol.According to the invention, 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.
Bei den Sulfonsäuregruppen-haltigen Monomeren sind solche der Formel
R5(R6)C=C(R7)-X-SO3H
bevorzugt, in der R5 bis R7 unabhängig voneinander für -H, -CH3, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit - NH2, -OH oder -COOH substituierte Alkyl- oder Alkenylreste oder für -COOH oder -COOR4 steht, wobei R4 ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH2)n- mit n = 0 bis 4, -COO-(CH2)k- mit k = 1 bis 6, -C(O)-NH-C(CH3)2-, -C(O)-NH-C(CH3)2-CH2- und -C(O)-NH-CH(CH3)-CH2-.The monomers containing sulfonic acid groups are those of the formula
R 5 (R 6 ) C = C (R 7 ) -X-SO 3 H
preferred, in which R 5 to R 7 independently of one another for -H, -CH 3 , a straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical with 2 to 12 carbon atoms, with - NH 2 , -OH or -COOH-substituted alkyl or alkenyl radicals or -COOH or -COOR 4 , where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optionally present spacer group , which is selected from - (CH 2 ) n - with n = 0 to 4, -COO- (CH 2 ) k - with k = 1 to 6, -C (O) -NH-C (CH 3 ) 2 - , -C (O) -NH-C (CH 3 ) 2 -CH 2 - and -C (O) -NH-CH (CH 3 ) -CH 2 -.
Unter diesen Monomeren bevorzugt sind solche der Formeln
H2C=CH-X-SO3H
H2C=C(CH3)-X-SO3H
HO3S-X-(R6)C=C(R7)-X-SO3H,
in denen R6 und R7 unabhängig voneinander ausgewählt sind aus -H, -CH3, -CH2CH3, - CH2CH2CH3 und -CH(CH3)2 und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH2)n- mit n = 0 bis 4, -COO-(CH2)k- mit k = 1 bis 6, -C(O)-NH-C(CH3)2- , -C(O)-NH-C(CH3)2-CH2- und -C(O)-NH-CH(CH3)-CH2-.Preferred among these monomers are those of the formulas
H 2 C = CH-X-SO 3 H
H 2 C = C (CH 3 ) -X-SO 3 H
HO 3 SX- (R 6 ) C = C (R 7 ) -X-SO 3 H,
in which R 6 and R 7 are independently selected from -H, -CH 3, -CH 2 CH 3, - CH 2 CH 2 CH 3 and -CH (CH 3) 2 and X is an optionally present spacer group is selected from - (CH 2 ) n - with n = 0 to 4, -COO- (CH 2 ) k - with k = 1 to 6, -C (O) -NH-C (CH 3 ) 2 -, - C (O) -NH-C (CH 3 ) 2 -CH 2 - and -C (O) -NH-CH (CH 3 ) -CH 2 -.
Besonders bevorzugte Sulfonsäuregruppen-haltige Monomere sind dabei 1-Acrylamido-1-propansulfonsäure, 2-Acrylamido-2-propansulfonsäure, 2-Acrylamido-2-methyl-1-propansulfonsäure, 2-Methacrylamido-2-methyl-1-propansulfonsäure, 3-Methacrylamido-2-hydroxy-propansulfonsäure, Allylsulfonsäure, Methallylsulfonsäure, Allyloxybenzolsulfonsäure, Methallyloxybenzolsulfonsäure, 2-Hydroxy-3-(2-propenyloxy)propansulfonsäure, 2-Methyl-2-propen1-sulfonsäure, Styrolsulfonsäure, Vinylsulfonsäure, 3-Sulfopropylacrylat, 3-Sulfopropylmethacrylat, Sulfomethacrylamid, Sulfomethylmethacrylamid sowie Mischungen der genannten Säuren oder deren wasserlösliche Salze.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.
In den Polymeren können die Sulfonsäuregruppen ganz oder teilweise in neutralisierter Form vorliegen, d.h. dass das acide Wasserstoffatom der Sulfonsäuregruppe in einigen oder allen Sulfonsäuregruppen gegen Metallionen, vorzugsweise Alkalimetallionen und insbesondere gegen Natriumionen, ausgetauscht sein kann. Der Einsatz von teil- oder vollneutralisierten sulfonsäuregruppenhaltigen Copolymeren ist erfindungsgemäß bevorzugt.In the polymers, 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. The use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.
Die Monomerenverteilung der erfindungsgemäß bevorzugt eingesetzten Copolymere beträgt bei Copolymeren, die nur Carbonsäuregruppen-haltige Monomere und Sulfonsäuregruppen-haltige Monomere enthalten, vorzugsweise jeweils 5 bis 95 Gew.-%, besonders bevorzugt beträgt der Anteil des Sulfonsäuregruppen-haltigen Monomers 50 bis 90 Gew.-% und der Anteil des Carbonsäuregruppen-haltigen Monomers 10 bis 50 Gew.-%, die Monomere sind hierbei vorzugsweise ausgewählt aus den zuvor genannten.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.
Die Molmasse der erfindungsgemäß bevorzugt eingesetzten Sulfo-Copolymere kann variiert werden, um die Eigenschaften der Polymere dem gewünschten Verwendungszweck anzupassen. Bevorzugte maschinelle Geschirrspülmittel sind dadurch gekennzeichnet, dass die Copolymere Molmassen von 2000 bis 200.000 gmol-1, vorzugsweise von 4000 bis 25.000 gmol-1 und insbesondere von 5000 bis 15.000 gmol-1 aufweisen.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 .
In einer weiteren bevorzugten Ausführungsform umfassen die Copolymere neben Carboxylgruppen-haltigem Monomer und Sulfonsäuregruppen-haltigem Monomer weiterhin wenigstens ein nichtionisches, vorzugsweise hydrophobes Monomer. Durch den Einsatz dieser hydrophob modifizierten Polymere konnte insbesondere die Klarspülleistung erfindungsgemäßer maschineller Geschirrspülmittel verbessert werden.In a further preferred embodiment, the copolymers furthermore comprise at least one nonionic, preferably hydrophobic, monomer in addition to monomer containing carboxyl groups and monomer containing sulfonic acid groups. The use of these hydrophobically modified polymers made it possible, in particular, to improve the rinsing performance of automatic dishwashing agents according to the invention.
Maschinelle Geschirrspülmittel, dadurch gekennzeichnet, dass das maschinelle Geschirrspülmittel als anionisches Copolymer ein Copolymer, umfassend
- i) Carbonsäuregruppen-haltige Monomer(e)
- ii) Sulfonsäuregruppen-haltige Monomer(e)
- iii) nichtionische Monomer(e)
- i) Carboxylic acid group-containing monomer (s)
- ii) Monomer (s) containing sulfonic acid groups
- iii) nonionic monomer (s)
Als nichtionische Monomere werden vorzugsweise Monomere der allgemeinen Formel R1(R2)C=C(R3)-X-R4 eingesetzt, in der R1 bis R3 unabhängig voneinander für -H, -CH3 oder -C2H5 steht, X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -CH2-, -C(O)O- und -C(O)-NH-, und R4 für einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 22 Kohlenstoffatomen oder für einen ungesättigten, vorzugsweise aromatischen Rest mit 6 bis 22 Kohlenstoffatomen steht.The nonionic monomers used are preferably monomers of the general formula R 1 (R 2 ) C =C (R 3 ) -XR 4 , in which R 1 to R 3 independently of one another represent -H, -CH 3 or -C 2 H 5 , X stands for an optionally present spacer group which is selected from -CH 2 -, -C (O) O- and -C (O) -NH-, and R 4 stands for a straight-chain or branched, saturated alkyl radical having 2 to 22 carbon atoms or represents an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.
Besonders bevorzugte nichtionische Monomere sind Buten, Isobuten, Penten, 3-Methylbuten, 2-Methylbuten, Cyclopenten, Hexen, Hexen-1, 2-Methlypenten-1, 3-Methlypenten-1, Cyclohexen, Methylcyclopenten, Cyclohepten, Methylcyclohexen, 2,4,4-Trimethylpenten-1, 2,4,4-Trimethylpenten-2, 2,3-Dimethylhexen-1, 2,4-Diemthylhexen-1, 2,5-Dimethlyhexen-1, 3,5-Dimethylhexen-1, 4,4-Dimehtylhexan-1, Ethylcyclohexyn, 1-Octen, α-Olefine mit 10 oder mehr Kohlenstoffatomen wie beispielsweise 1-Decen, 1-Dodecen, 1-Hexadecen, 1-Oktadecen und C22-α-Olefin, 2-Styrol, α-Methylstyrol, 3-Methylstyrol, 4-Propylstryol, 4-Cyclohexylstyrol, 4-Dodecylstyrol, 2-Ethyl-4-Benzylstyrol, 1-Vinylnaphthalin, 2,Vinylnaphthalin, Acrylsäuremethylester, Acrylsäureethylester, Acrylsäurepropylester, Acrylsäurebutylester, Acrylsäurepentylester, Acrylsäurehexylester, Methacrylsäuremethylester, N-(Methyl)acrylamid, Acrylsäure-2-Ethylhexylester, Methacrylsäure-2-Ethylhexylester, N-(2-Ethylhexyl)acrylamid, Acrylsäureoctylester, Methacrylsäureoctylester, N-(Octyl)acrylamid, Acrylsäurelaurylester, Methacrylsäurelaurylester, N-(Lauryl)acrylamid, Acrylsäurestearylester, Methacrylsäurestearylester, N-(Stearyl)acrylamid, Acrylsäurebehenylester, Methacrylsäurebehenylester und N-(Behenyl)acrylamid oder deren Mischungen.Particularly preferred 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, α-olefins with 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22-α-olefin, 2-styrene, α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4- Dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2, vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methyl methacrylate, 2-methyl methacrylate, 2-ethylhexyl acrylamide, ethyl-hexyl-2-ethyl-acrylamide , N - (2-ethylhexyl) acrylamide, octyl acrylate, Methacrylsäureoctylester, N - (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N- (lauryl) acrylamide, stearyl acrylate, stearyl methacrylate, N - (stearyl) acrylamide, behenyl acrylate, Methacrylsäurebehenylester and N - ( Behenyl) acrylamide or their mixtures nong.
Erfindungsgemäße Geschirrspülmittel enthalten zur Gewährleistung ihrer Reinigungswirkung weiterhin vorzugsweise Gerüststoff(e) und Enzym(e).Dishwashing detergents according to the invention also preferably contain builder (s) and enzyme (s) to ensure their cleaning effect.
Als weiteren Bestandteil enthalten erfindungsgemäße maschinelle Geschirrspülmittel vorzugsweise einen oder mehrere Gerüststoff(e). Der Gewichtsanteil der Gerüststoffe am Gesamtgewicht erfindungsgemäßer maschineller Geschirrspülmittel beträgt vorzugsweise 15 bis 80 Gew.-% und insbesondere 20 bis 70 Gew.-%. Zu den Gerüststoffen zählen insbesondere Carbonate, Phosphate, Citrate, organische Cobuilder und Silikate.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.
Besonders bevorzugt ist der Einsatz von Carbonat(en) und/oder Hydrogencarbonat(en), vorzugsweise Alkalicarbonat(en), besonders bevorzugt Natriumcarbonat, in Mengen von 2 bis 30 Gew.-%, vorzugsweise von 4 bis 28 Gew.-% und insbesondere von 8 bis 24 Gew.-%, jeweils bezogen auf das Gewicht des maschinellen Geschirrspülmittels.
Bevorzugt ist weiterhin der Einsatz von Phosphat. Unter der Vielzahl der kommerziell erhältlichen Phosphate haben die Alkalimetallphosphate unter besonderer Bevorzugung von Pentanatrium- bzw. Pentakaliumtriphosphat (Natrium- bzw. Kaliumtripolyphosphat) in der Wasch- und Reinigungsmittel-Industrie die größte Bedeutung.The use of carbonate (s) and / or hydrogen carbonate (s), preferably alkali metal carbonate (s), particularly preferably sodium carbonate, in amounts of from 2 to 30% by weight, preferably from 4 to 28% by weight and in particular, is particularly preferred from 8 to 24% by weight, based in each case on the weight of the automatic dishwasher detergent.
The use of phosphate is also preferred. Of the large number of commercially available phosphates, 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.
Alkalimetallphosphate ist dabei die summarische Bezeichnung für die Alkalimetall- (insbesondere Natrium- und Kalium-) Salze der verschiedenen Phosphorsäuren, bei denen man Metaphosphorsäuren (HPO3), und Orthophosphorsäure H3PO4 neben höhermolekularen Vertretern unterscheiden kann. Die Phosphate vereinen dabei mehrere Vorteile in sich: Sie wirken als Alkaliträger, verhindern Kalkbeläge auf Maschinenteilen bzw. Kalkinkrustationen in Geweben und tragen überdies zur Reinigungsleistung bei.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.
Erfindungsgemäß besonders bevorzugte Phosphate sind das Pentanatriumtriphosphat, Na5P3O10 (Natriumtripolyphosphat) sowie das entsprechende Kaliumsalz Pentakaliumtriphosphat, K5P3O10 (Kaliumtripolyphosphat). Erfindungsgemäß bevorzugt eingesetzt werden weiterhin die Natriumkaliumtripolyphosphate.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.
Werden im Rahmen der vorliegenden Anmeldung Phosphate als wasch- oder reinigungsaktive Substanzen in den maschinellen Geschirrspülmitteln eingesetzt, so enthalten diese Phosphat(e), vorzugsweise Alkalimetallphosphat(e), besonders bevorzugt Pentanatrium- bzw. Pentakaliumtriphosphat (Natrium- bzw. Kaliumtripolyphosphat), in Mengen von 5 bis 60 Gew.-%, vorzugsweise von 15 bis 45 Gew.-% uns insbesondere von 20 bis 40 Gew.-%, jeweils bezogen auf das Gewicht des maschinellen Geschirrspülmittels.If, in the context of the present application, 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.
Als organische Cobuilder sind insbesondere Polycarboxylate / Polycarbonsäuren, polymere Carboxylate, Asparaginsäure, Polyacetale, Dextrine und organische Cobuilder zu nennen. Diese Stoffklassen werden nachfolgend beschrieben.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.
Brauchbare organische Gerüstsubstanzen sind beispielsweise die in Form der freien Säure und/oder ihrer Natriumsalze einsetzbaren Polycarbonsäuren, wobei unter Polycarbonsäuren solche Carbonsäuren verstanden werden, die mehr als eine Säurefunktion tragen. Beispielsweise sind dies Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Äpfelsäure, Weinsäure, Maleinsäure, Fumarsäure, Zuckersäuren, Aminocarbonsäuren, Nitrilotriessigsäure (NTA), sofern ein derartiger Einsatz aus ökologischen Gründen nicht zu beanstanden ist, sowie Mischungen aus diesen. Die freien Säuren besitzen neben ihrer Builderwirkung typischerweise auch die Eigenschaft einer Säuerungskomponente und dienen somit auch zur Einstellung eines niedrigeren und milderen pH-Wertes von Wasch- oder Reinigungsmitteln. Insbesondere sind hierbei Citronensäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Gluconsäure und beliebige Mischungen aus diesen zu nennen.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. For example, 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. In addition to their builder effect, 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.
Besonders bevorzugte erfindungsgemäße maschinelle Geschirrspülmittel enthalten als einen ihrer wesentlichen Gerüststoffe Citrat. Maschinelle Geschirrspülmittel, dadurch gekennzeichnet, dass sie 2 bis 40 Gew.-%, vorzugsweise 5 bis 30 Gew.-% und insbesondere 7 bis 20 Gew.-% Citrat enthalten, sind erfindungsgemäß bevorzugt.Particularly preferred automatic dishwashing agents according to the invention 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.
Die Citrate werden ebenso wie die Phoshate bevorzugt in Kombination mit Carbonaten und/oder Hydrogencarbonat eingesetzt. Bevorzugte maschinelle Geschirrspülmittel sind daher durch eine Gerüststoffkombination aus Phosphat und Carbonat/Hydrogencarbonat bzw. aus Citrat und Carbonat/Hydrogencarbonat gekennzeichnet (vgl. Tabelle 1a und 1b unten). Selbstverständlich sind jedoch auch Gerüststoffkombinationen aus Phosphat, Citrat und Carbonat/Hydrogencarbonat realisierbar.Like the phosphates, 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). Naturally, however, builder combinations of phosphate, citrate and carbonate / hydrogen carbonate can also be realized.
Besonders bevorzugte maschinelle Geschirrspülmittel sind dadurch gekennzeichnet, dass das Geschirrspülmittel mindestens zwei Gerüststoffe aus der Gruppe der Phosphate, Carbonate und Citrate enthält, wobei der Gewichtsanteil dieser Gerüststoffe, bezogen auf sein Gesamtgewicht des maschinellen Geschirrspülmittels, bevorzugt 5 bis 80 Gew.-%, vorzugsweise 15 bis 75 Gew.-% und insbesondere 30 bis 70 Gew.-% beträgt. Die Kombination von zwei oder mehr Gerüststoffen aus der oben genannten Gruppe hat sich für die Reinigungs- und Klarspülleistung erfindungsgemäßer maschineller Geschirrspülmittel als vorteilhaft erwiesen.Particularly preferred automatic 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.
Als Gerüststoffe sind weiterhin polymere Polycarboxylate geeignet, dies sind beispielsweise die Alkalimetallsalze der Polyacrylsäure oder der Polymethacrylsäure, beispielsweise solche mit einer relativen Molekülmasse von 500 bis 70000 g/mol.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.
Geeignete Polymere sind insbesondere Polyacrylate, die bevorzugt eine Molekülmasse von 2000 bis 20000 g/mol aufweisen. Aufgrund ihrer überlegenen Löslichkeit können aus dieser Gruppe wiederum die kurzkettigen Polyacrylate, die Molmassen von 2000 bis 10000 g/mol, und besonders bevorzugt von 3000 bis 5000 g/mol, aufweisen, bevorzugt sein.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.
Der Gehalt der maschinellen Geschirrspülmittel an (homo)polymeren Polycarboxylaten beträgt vorzugsweise 0,5 bis 20 Gew.-% und insbesondere 3 bis 10 Gew.-%.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.
Erfindungsgemäße maschinelle Geschirrspülmittel können als Gerüststoff kristalline schichtförmige Silikate der allgemeinen Formel NaMSixO2x+1 · yH2O, worin M Natrium oder Wasserstoff darstellt, x eine Zahl von 1,9 bis 22, vorzugsweise von 1,9 bis 4, wobei besonders bevorzugte Werte für x 2, 3 oder 4 sind, und y für eine Zahl von 0 bis 33, vorzugsweise von 0 bis 20 steht.
Einsetzbar sind auch amorphe Natriumsilikate mit einem Modul Na2O : SiO2 von 1:2 bis 1:3,3, vorzugsweise von 1:2 bis 1:2,8 und insbesondere von 1:2 bis 1:2,6, welche vorzugsweise löseverzögert sind und Sekundärwascheigenschaften aufweisen.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.
In bevorzugten erfindungsgemäßen maschinellen Geschirrspülmitteln wird der Gehalt an Silikaten, bezogen auf das Gesamtgewicht des maschinellen Geschirrspülmittels, auf Mengen unterhalb 10 Gew.-%, vorzugsweise unterhalb 5 Gew.-% und insbesondere unterhalb 2 Gew.-% begrenzt. Besonders bevorzugte erfindungsgemäße maschinelle Geschirrspülmittel sind Silikat-frei.In preferred automatic dishwashing agents according to the invention, the content of silicates, based on the total weight of the automatic dishwashing agent, 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.
Weitere geeignete Gerüststoffe, die als alleinige Gerüststoffe, insbesondere jedoch in Kombination mit Citrat, eingesetzt werden können, stellen die Methylgylcindiessigsäure (MGDA) sowie die Glutaminsäure-N,N-diessigsäure (GLDA) dar. Diese Gerüststoffe werden vorzugsweise in Mengen von 5 bis 60 Gew.-%, insbesondere 10 bis 40 Gew.-% in erfindungsgemäßen maschinellen Geschirrspülmitteln eingesetzt.Further suitable builders which can be used as the only builders, but in particular in combination with citrate, are methylgylcinediacetic acid (MGDA) and glutamic acid-N, N-diacetic acid (GLDA). These builders are preferably used in amounts of 5 to 60 % By weight, in particular 10 to 40% by weight, are used in automatic dishwashing agents according to the invention.
In Ergänzung zu den vorgenannten Gerüststoffen können die erfindungsgemäßen Mittel Alkalimetallhydroxide enthalten. Diese Alkaliträger werden in den Reinigungsmitteln bevorzugt nur in geringen Mengen, vorzugsweise in Mengen unterhalb 10 Gew.-%, bevorzugt unterhalb 6 Gew.-%, vorzugsweise unterhalb 5 Gew.-%, besonders bevorzugt zwischen 0,1 und 5 Gew.-% und insbesondere zwischen 0,5 und 5 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Reinigungsmittels eingesetzt. Alternative maschinelle Geschirrspülmittel sind frei von Alkalimetallhydroxiden.In addition to the aforementioned builders, 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.
Als weiteren Bestandteil enthalten erfindungsgemäße Geschirrspülmittel vorzugsweise Enzym(e). Hierzu gehören insbesondere Proteasen, Amylasen, Lipasen, Hemicellulasen, Cellulasen, Perhydrolasen oder Oxidoreduktasen, sowie vorzugsweise deren Gemische. Diese Enzyme sind im Prinzip natürlichen Ursprungs; ausgehend von den natürlichen Molekülen stehen für den Einsatz in Wasch- oder Reinigungsmitteln verbesserte Varianten zur Verfügung, die entsprechend bevorzugt eingesetzt werden. Wasch- oder Reinigungsmittel enthalten Enzyme vorzugsweise in Gesamtmengen von 1 x 10-6 bis 5 Gew.-% bezogen auf aktives Protein. Die Proteinkonzentration kann mit Hilfe bekannter Methoden, zum Beispiel dem BCA-Verfahren oder dem Biuret-Verfahren bestimmt werden.Dishwashing detergents according to the invention preferably contain enzyme (s) as a further component. These 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.
Unter den Proteasen sind solche vom Subtilisin-Typ bevorzugt. Beispiele hierfür sind die Subtilisine BPN' und Carlsberg sowie deren weiterentwickelte Formen, die Protease PB92, die Subtilisine 147 und 309, die Alkalische Protease aus Bacillus lentus, Subtilisin DY und die den Subtilasen, nicht mehr jedoch den Subtilisinen im engeren Sinne zuzuordnenden Enzyme Thermitase, Proteinase K und die Proteasen TW3 und TW7.Among the proteases, those of the subtilisin type are preferred. Examples of this are the 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.
Beispiele für erfindungsgemäß einsetzbare Amylasen sind die α-Amylasen aus Bacillus licheniformis, aus B. amyloliquefaciens, aus B. stearothermophilus, aus Aspergillus niger und A. oryzae sowie die für den Einsatz in Wasch- und Reinigungsmitteln verbesserten Weiterentwicklungen der vorgenannten Amylasen. Desweiteren sind für diesen Zweck die α-Amylase aus Bacillus sp. A 7-7 (DSM 12368) und die Cyclodextrin-Glucanotransferase (CGTase) aus B. agaradherens (DSM 9948) hervorzuheben.Examples of amylases which can be used according to the invention are the α-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 α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948) should be emphasized.
Erfindungsgemäß einsetzbar sind weiterhin Lipasen oder Cutinasen, insbesondere wegen ihrer Triglycerid-spaltenden Aktivitäten, aber auch, um aus geeigneten Vorstufen in situ Persäuren zu erzeugen. Hierzu gehören beispielsweise die ursprünglich aus Humicola lanuginosa (Thermomyces lanuginosus) erhältlichen, beziehungsweise weiterentwickelten Lipasen, insbesondere solche mit dem Aminosäureaustausch D96L.According to the invention, 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. These 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.
Weiterhin können Enzyme eingesetzt werden, die unter dem Begriff Hemicellulasen zusammengefaßt werden. Hierzu gehören beispielsweise Mannanasen, Xanthanlyasen, Pektinlyasen (=Pektinasen), Pektinesterasen, Pektatlyasen, Xyloglucanasen (=Xylanasen), Pullulanasen und β-Glucanasen.It is also possible to use enzymes which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.
Zur Erhöhung der bleichenden Wirkung können erfindungsgemäß Oxidoreduktasen, beispielsweise Oxidasen, Oxygenasen, Katalasen, Peroxidasen, wie Halo-, Chloro-, Bromo-, Lignin-, Glucose- oder Mangan-peroxidasen, Dioxygenasen oder Laccasen (Phenoloxidasen, Polyphenoloxidasen) eingesetzt werden. Vorteilhafterweise werden zusätzlich vorzugsweise organische, besonders bevorzugt aromatische, mit den Enzymen wechselwirkende Verbindungen zugegeben, um die Aktivität der betreffenden Oxidoreduktasen zu verstärken (Enhancer) oder um bei stark unterschiedlichen Redoxpotentialen zwischen den oxidierenden Enzymen und den Anschmutzungen den Elektronenfluss zu gewährleisten (Mediatoren).To increase the bleaching effect, 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. Advantageously, preferably 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.
Ein Protein und/oder Enzym kann besonders während der Lagerung gegen Schädigungen wie beispielsweise Inaktivierung, Denaturierung oder Zerfall etwa durch physikalische Einflüsse, Oxidation oder proteolytische Spaltung geschützt werden. Bei mikrobieller Gewinnung der Proteine und/oder Enzyme ist eine Inhibierung der Proteolyse besonders bevorzugt, insbesondere wenn auch die Mittel Proteasen enthalten. Wasch- oder Reinigungsmittel können zu diesem Zweck Stabilisatoren enthalten; die Bereitstellung derartiger Mittel stellt eine bevorzugte Ausführungsform der vorliegenden Erfindung dar.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. In the case of microbial production of the proteins and / or enzymes, 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.
Wasch- oder reinigungsaktive Proteasen und Amylasen werden in der Regel nicht in Form des reinen Proteins sondern vielmehr in Form stabilisierter, lager- und transportfähiger Zubereitungen bereitgestellt. Zu diesen vorkonfektionierten Zubereitungen zählen beispielsweise die durch Granulation, Extrusion oder Lyophilisierung erhaltenen festen Präparationen oder, insbesondere bei flüssigen oder gelförmigen Mitteln, Lösungen der Enzyme, vorteilhafterweise möglichst konzentriert, wasserarm und/oder mit Stabilisatoren oder weiteren Hilfsmitteln versetzt.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.
Alternativ können die Enzyme sowohl für die feste als auch für die flüssige Darreichungsform verkapselt werden, beispielsweise durch Sprühtrocknung oder Extrusion der Enzymlösung zusammen mit einem vorzugsweise natürlichen Polymer oder in Form von Kapseln, beispielsweise solchen, bei denen die Enzyme wie in einem erstarrten Gel eingeschlossen sind oder in solchen vom Kern-Schale-Typ, bei dem ein enzymhaltiger Kern mit einer Wasser-, Luft- und/oder Chemikalien-undurchlässigen Schutzschicht überzogen ist. In aufgelagerten Schichten können zusätzlich weitere Wirkstoffe, beispielsweise Stabilisatoren, Emulgatoren, Pigmente, Bleich- oder Farbstoffe aufgebracht werden. Derartige Kapseln werden nach an sich bekannten Methoden, beispielsweise durch Schüttel- oder Rollgranulation oder in Fluid-bed-Prozessen aufgebracht. Vorteilhafterweise sind derartige Granulate, beispielsweise durch Aufbringen polymerer Filmbildner, staubarm und aufgrund der Beschichtung lagerstabil.Alternatively, 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.
Weiterhin ist es möglich, zwei oder mehrere Enzyme zusammen zu konfektionieren, so dass ein einzelnes Granulat mehrere Enzymaktivitäten aufweist.Furthermore, it is possible to pack two or more enzymes together so that a single granulate has several enzyme activities.
Wie aus der vorherigen Ausführungen ersichtlich, bildet das Enzym-Protein nur einen Bruchteil des Gesamtgewichts üblicher Enzym-Zubereitungen. Erfindungsgemäß bevorzugt eingesetzte Protease- und Amylase-Zubereitungen enthalten zwischen 0,1 und 40 Gew.-%, bevorzugt zwischen 0,2 und 30 Gew.-%, besonders bevorzugt zwischen 0,4 und 20 Gew.-% und insbesondere zwischen 0,8 und 10 Gew.-% des Enzymproteins.As can be seen from the previous statements, 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.
Bevorzugt werden insbesondere solche maschinellen Geschirrspülmittel, die, jeweils bezogen auf ihr Gesamtgewicht, 0,1 bis 12 Gew.-%, vorzugsweise 0,2 bis 10 Gew.-% und insbesondere 0,5 bis 8 Gew.-% Enzym-Zubereitungen enthalten.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 .
Die erfindungsgemäßen maschinellen Geschirrspülmittel können neben den zuvor genannten erfindungsgemäß einzusetzenden nichtionischen Tensiden zusätzlich auch weitere nichtionische Tenside enthalten.In addition to the aforementioned nonionic surfactants to be used according to the invention, the automatic dishwashing agents according to the invention can also contain further nonionic surfactants.
Der Gewichtsanteil der weiteren nichtionischen Tensids am Gesamtgewicht des erfindungsgemäßen maschinellen Geschirrspülmittels beträgt in einer bevorzugten Ausführungsform zwischen 0,1 und 30 Gew.-%, vorzugsweise zwischen 0,5 und 20 Gew.-%, bevorzugt zwischen 1 und 10 Gew.-% und insbesondere zwischen 2 und 6 Gew.-%.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.
Bevorzugte weitere nichtionische Tenside weisen in einer bevorzugten Ausführungsform die allgemeine Formel R1O[CH2CH(CH3)O]x[CH2CH2O]y[CH2CH(CH3)O]zCH2CH(OH)R2 auf, in der R1 für einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 4 bis 22 Kohlenstoffatomen oder Mischungen hieraus steht, R2 einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen oder Mischungen hieraus bezeichnet und x und z für Werte zwischen 0 und 40 und y für einen Wert von mindestens 15 steht.In a preferred embodiment, 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.
Der Zusatz dieser nichtionischen Tenside hat sich insbesondere in Bezug auf die Klarspülleistung und die Trocknung als vorteilhaft erwiesen. In einer bevorzugten Ausführungsform enthält das maschinelle Geschirrspülmittel, bezogen auf sein Gesamtgewicht, nichtionisches Tensid der allgemeinen Formel R1O[CH2CH(CH3)O]x[CH2CH2O]y[CH2CH(CH3)O]zCH2CH(OH)R2in Mengen von 0,1 bis 15 Gew.-%, vorzugsweise 0,2 bis 10 Gew.-%, besonders bevorzugt 0,5 bis 8 Gew.-% und insbesondere von 1,0 bis 6 Gew.-%.The addition of these nonionic surfactants has proven to be particularly advantageous with regard to the rinsing performance and drying. In a preferred embodiment, 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%.
Bevorzugt sind insbesondere solche endgruppenverschlossene poly(oxyalkylierten) Niotenside, die, gemäß der Formel R1O[CH2CH2O]yCH2CH(OH)R2 enthält, in der R1 für einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 4 bis 22 Kohlenstoffatomen oder Mischungen hieraus steht, R2 einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen oder Mischungen hieraus bezeichnet und y für einen Wert zwischen 15 und 120 vorzugsweise 20 bis 100, insbesondere 20 bis 80 steht. Zur Gruppe dieser nichtionischen Tenside zählen beispielsweise Hydroxymischether der allgemeinen Formel C6-22-CH(OH)CH2O-(EO)20-120-C2-26, zum Beispiel die C8-12 Fettalkohol-(EO)22-2-hydroxydecylether und die C4-22 Fettalkohol-(EO)40-80-2-hydroxyalkylether.Particularly preferred are those end-capped poly (oxyalkylated) nonionic surfactants which, according to the formula R 1 O [CH 2 CH 2 O] y CH 2 CH (OH) R 2 , in which 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 and 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.
Erfindungsgemäße maschinelles Geschirrspülmittel, dadurch gekennzeichnet, dass als weiteres nichtionisches Tensid ein Tensid der allgemeinen Formel R1CH(OH)CH2O-(CH2CH2O)20-120- R2 eingesetzt wird, wobei R1 und R2 unabhängig voneinander für einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 2 bis 20 Kohlenstoffatomen stehen, sind besonders bevorzugt.Automatic dishwashing detergent according to the invention, 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.
Bevorzugt sind weiterhin Tenside der Formel R1O[CH2CH(CH3)O]x[CH2CH2O]yCH2CH(OH)R2, in der R1 für einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 4 bis 22 Kohlenstoffatomen oder Mischungen hieraus steht, R2 einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen oder Mischungen hieraus bezeichnet und x für Werte zwischen 0,5 und 4, vorzugsweise 0,5 bis 1,5, und y für einen Wert von mindestens 15 steht.Also preferred are 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.
Erfindungsgemäß sind weiterhin auch Tenside der allgemeinen Formel R1O[CH2CH(CH3)O]x[CH2CH2O]yCH2CH(OH)R2 bevorzugt, in der R1 für einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 4 bis 22 Kohlenstoffatomen oder Mischungen hieraus steht, R2 einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen oder Mischungen hieraus bezeichnet und x für einen Wert zwischen 1 und 40 und y für einen Wert zwischen 15 und 40 steht, wobei die Alkyleneinheiten [CH2CH(CH3)O] und [CH2CH2O] randomisiert, d.h. in Form einer statistischen, zufälligen Verteilung vorliegen.According to the invention, 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.
Zur Gruppe der bevorzugten endgruppenverschlossene poly(oxyalkylierten) Niotenside zählen auch Niotenside der Formel R1O[CH2CH2O]x[CH2CH(R3)O]yCH2CH(OH)R2, in der R1 und R2 unabhängig voneinander für einen linearen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht, R3 unabhängig voneinander ausgewählt ist aus -CH3, -CH2CH3, -CH2CH2-CH3, -CH(CH3)2, vorzugsweise jedoch für -CH3 steht, und x und y unabhängig voneinander für Werte zwischen 1 und 32 stehen, wobei Niotenside mit R3 = -CH3 und Werten für x von 15 bis 32 und y von 0,5 und 1,5 ganz besonders bevorzugt sind.The group of preferred end-capped poly (oxyalkylated) nonionic surfactants also includes nonionic surfactants of the formula R 1 O [CH 2 CH 2 O] x [CH 2 CH (R 3 ) O] y CH 2 CH (OH) R 2 , in which R 1 and R 2 independently of one another represents a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical with 2 to 26 carbon atoms, R 3 is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 - CH 3 , —CH (CH 3 ) 2 , but preferably —CH 3 , and x and y independently of one another have values between 1 and 32, nonionic surfactants with R 3 = —CH 3 and values for x from 15 to 32 and y of 0.5 and 1.5 are particularly preferred.
Durch den Einsatz der zuvor beschriebenen nichtionischen Tenside mit einer freien Hydroxylgruppe an einer der beiden endständigen Alkylreste kann im Vergleich zu herkömmlichen polyalkoxylierten Fettalkoholen ohne freie Hydroxylgruppe die Klarspülleistung und Trocknung deutlich verbessert werden.By using the nonionic surfactants described above with a free hydroxyl group on one of the two terminal alkyl radicals, the rinsing performance and drying can be significantly improved compared to conventional polyalkoxylated fatty alcohols without a free hydroxyl group.
Die angegebenen C-Kettenlängen sowie Ethoxylierungsgrade bzw. Alkoxylierungsgrade der vorgenannten Niotenside stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Aufgrund der Herstellverfahren bestehen Handelsprodukte der genannten Formeln zumeist nicht aus einem individuellen Vertreter, sondern aus Gemischen, wodurch sich sowohl für die C-Kettenlängen als auch für die Ethoxylierungsgrade bzw. Alkoxylierungsgrade Mittelwerte und daraus folgend gebrochene Zahlen ergeben können.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.
Selbstverständlich können die vorgenannten nichtionischen Tenside nicht nur als Einzelsubstanzen, sondern auch als Tensidgemische aus zwei, drei, vier oder mehr Tensiden eingesetzt werden. Als Tensidgemische werden dabei nicht Mischungen nichtionischer Tenside bezeichnet, die in ihrer Gesamtheit unter eine der oben genannten allgemeinen Formeln fallen, sondern vielmehr solche Mischungen, die zwei, drei, vier oder mehr nichtionische Tenside enthalten, die durch unterschiedliche der vorgenannten oder andere allgemeine Formeln beschrieben werden können.Of course, the aforementioned nonionic surfactants can be used not only as individual substances but also as surfactant mixtures of two, three, four or more surfactants. 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.
Insbesondere bevorzugt sind solche nichtionische Tenside, die einen Schmelzpunkt oberhalb Raumtemperatur aufweisen. Nichtionische(s) Tensid(e) mit einem Schmelzpunkt oberhalb von 20°C, vorzugsweise oberhalb von 25°C, besonders bevorzugt zwischen 25 und 60°C und insbesondere zwischen 26,6 und 43,3°C, ist/sind besonders bevorzugt.Those nonionic surfactants which have a melting point above room temperature are particularly preferred. Nonionic surfactant (s) with a melting point above 20 ° C., preferably above 25 ° C., particularly preferably between 25 and 60 ° C. and in particular between 26.6 and 43.3 ° C., is / are particularly preferred .
Besonders bevorzugte erfindungsgemäße maschinelle Geschirrspülmittel, enthalten
- a) 0,5 bis 5 Gew.-% eines nichtionischen Tensids der allgemeinen Formel
R1-CH(OH)CH2-O(CH2CH2O)xCH2CHR(OCH2CH2)yO-CH2CH(OH)-R2,
in der- R, R1 und R2 unabhängig voneinander für einen Alkylrest oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen;
- x und y unabhängig voneinander für Werte zwischen 1 und 40 stehen
- b) 0,1 bis 5 Gew.-% Polyvinylpyrrolidon-Partikel, vorzugsweise solche mit einem mittleren Teilchendurchmesser von 100 bis 150 µm, insbesondere von 110 bis 130 µm;
- c) 1 bis 15 Gew.-% eines copolymeren anionischen Polymers aus der Gruppe der hydrophob modifizierten Polycarboxylate und Polysulfonate.
- a) 0.5 to 5% by weight of a nonionic surfactant of the general formula
R 1 -CH (OH) CH 2 -O (CH 2 CH 2 O) x CH 2 CHR (OCH 2 CH 2 ) y O-CH 2 CH (OH) -R 2 ,
in the- R, R 1 and R 2 independently of one another represent an alkyl radical or alkenyl radical having 6 to 22 carbon atoms;
- x and y independently represent values between 1 and 40
- b) 0.1 to 5% by weight of polyvinylpyrrolidone particles, preferably those with an average particle diameter of 100 to 150 μm, in particular 110 to 130 μm;
- c) 1 to 15% by weight of a copolymeric anionic polymer from the group of the hydrophobically modified polycarboxylates and polysulfonates.
Weitere bevorzugte erfindungsgemäße maschinelle Geschirrspülmittel, enthalten
- a) 0,5 bis 5 Gew.-% eines nichtionischen Tensids der allgemeinen Formel
R1-O(CH2CH2O)xCH2(OCH2CH2)yO-R2,
in der- R1 und R2 unabhängig voneinander für einen Alkylrest oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen; und
- x und y unabhängig voneinander für Werte zwischen 1 und 40 stehen;
- b) 0,1 bis 5 Gew.-% Polyvinylpyrrolidon-Partikel, vorzugsweise solche mit einem mittleren Teilchendurchmesser von 100 bis 150 µm, insbesondere von 110 bis 130 µm;
- c) 1 bis 15 Gew.-% eines copolymeren anionischen Polymers aus der Gruppe der hydrophob modifizierten Polycarboxylate und Polysulfonate
- a) 0.5 to 5% by weight of a nonionic surfactant of the general formula
R 1 -O (CH 2 CH 2 O) x CH 2 (OCH 2 CH 2 ) y OR 2 ,
in the- R 1 and R 2 independently of one another represent an alkyl radical or alkenyl radical having 4 to 22 carbon atoms; and
- x and y are independently of one another for values between 1 and 40;
- b) 0.1 to 5% by weight of polyvinylpyrrolidone particles, preferably those with an average particle diameter of 100 to 150 μm, in particular 110 to 130 μm;
- c) 1 to 15% by weight of a copolymeric anionic polymer from the group of the hydrophobically modified polycarboxylates and polysulfonates
Neben den zuvor beschriebenen Inhaltsstoffen können die erfindungsgemäßen Mittel weitere wasch- oder reinigungsaktive Substanzen, vorzugsweise aus der Gruppe der Bleichmittel, Bleichaktivatoren und Bleichkatalysatoren, der Glaskorrosionsinhibitoren, Korrosionsinhibitoren, Duftstoffe und Parfümträger enthalten. Diese bevorzugten Inhaltsstoffe werden in der Folge näher beschrieben.In addition to the ingredients described above, 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.
Erfindungsgemäße maschinelle Geschirrspülmittel können als weiteren Bestandteil ein Bleichmittel enthalten, wobei Sauerstoffbleichmittel bevorzugt werden. Unter den als Bleichmittel dienenden, in Wasser H2O2 liefernden Verbindungen haben das Natriumpercarbonat, das Natriumperborattetrahydrat und das Natriumperboratmonohydrat besondere Bedeutung. Weitere brauchbare Bleichmittel sind beispielsweise Peroxypyrophosphate, Citratperhydrate sowie H2O2 liefernde persaure Salze oder Persäuren, wie Perbenzoate, Peroxophthalate, Diperazelainsäure, Phthaloiminopersäure oder Diperdodecandisäure.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.
Weiterhin können auch Bleichmittel aus der Gruppe der organischen Bleichmittel eingesetzt werden. Typische organische Bleichmittel sind die Diacylperoxide, wie z.B. Dibenzoylperoxid. Weitere typische organische Bleichmittel sind die Peroxysäuren, wobei als Beispiele besonders die Alkylperoxysäuren und die Arylperoxysäuren genannt werden.Furthermore, 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.
Bevorzugte erfindungsgemäße maschinelle Geschirrspülmittel sind dadurch gekennzeichnet, dass sie ein Sauerstoffbleichmittel, vorzugsweise Natriumpercarbonat, besonders bevorzugt ein beschichtetes Natriumpercarbonat enthalten. Der Gewichtsanteil des Bleichmittels, bezogen auf das Gesamtgewicht des Wasch- oder Reinigungsmittels, beträgt in bevorzugten Ausführungsformen zwischen 2 und 30 Gew.-%, vorzugsweise zwischen 4 und 20 Gew.-% und insbesondere zwischen 6 und 15 Gew.-%.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.
Als Bleichaktivatoren können die erfindungsgemäßen maschinellen Geschirrspülmittel Bleichaktivatoren enthalten. Diese Verbindungen ergeben unter Perhydrolysebedingungen aliphatische Peroxocarbonsäuren mit vorzugsweise 1 bis 10 Kohlenstoffatomen, insbesondere 2 bis 4 Kohlenstoffatomen, und/oder gegebenenfalls substituierte Perbenzoesäure. Geeignet sind Substanzen, die O- und/oder N-Acylgruppen der genannten Kohlenstoffatomzahl und/oder gegebenenfalls substituierte Benzoylgruppen tragen. Bevorzugt werden mehrfach acylierte Alkylendiamine, wobei sich Tetraacetylethylendiamin (TAED) als besonders geeignet erwiesen hat.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. Are 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, tetraacetylethylenediamine (TAED) having proven particularly suitable.
Maschinelle Geschirrspülmittel, dadurch gekennzeichnet, dass sie als Bleichaktivator einen Bleichaktivator aus der Gruppe der acetylierten Amine, vorzugsweise um Tetraacetylendiamin (TAED) handelt, werden erfindungsgemäß bevorzugt. Diese Bleichaktivatoren, insbesondere TAED, werden vorzugsweise in Mengen bis 10 Gew.-%, insbesondere 0,1 Gew.-% bis 10 Gew.-%, besonders 0,5 bis 8 Gew.-% und besonders bevorzugt 1,0 bis 6 Gew.-%, eingesetzt.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. These bleach activators, in particular TAED, are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 10% by weight, particularly 0.5 to 8% by weight and particularly preferably 1.0 to 6% by weight Wt .-%, used.
Zusätzlich oder alternativ zu den konventionellen Bleichaktivatoren enthalten die erfindungsgemäßen maschinellen Geschirrspülmittel vorzugsweise mindestens einen Bleichkatalysator. Bei diesen Stoffen handelt es sich um bleichverstärkende Übergangsmetallsalze bzw. Übergangsmetallkomplexe wie beispielsweise Mn-, Fe-, Co-, Ru - oder Mo-Salenkomplexe oder -carbonylkomplexe. Auch Mn-, Fe-, Co-, Ru-, Mo-, Ti-, V- und Cu-Komplexe mit N-haltigen Tripod-Liganden sowie Co-, Fe-, Cu- und Ru-Amminkomplexe sind als Bleichkatalysatoren verwendbar.In addition or as an alternative to the conventional bleach activators, 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.
Mit besonderem Vorzug werden Komplexe des Mangans in der Oxidationsstufe II, III, IV oder VI eingesetzt, die vorzugsweise einen oder mehrere makrocyclische(n) Ligand(en) mit den Donorfunktionen N, NR, PR, O und/oder S enthalten. Vorzugsweise werden Liganden eingesetzt, die Stickstoff-Donorfunktionen aufweisen. Dabei ist es besonders bevorzugt, Bleichkatalysator(en) in den erfindungsgemäßen Mitteln einzusetzen, welche als makromolekularen Liganden 1,4,7-Trimethyl-1,4,7-triazacyclononan (Me-TACN), 1,4,7-Triazacyclononan (TACN), 1,5,9-Trimethyl-1,5,9-triazacyclododecan (Me-TACD), 2-Methyl-1,4,7-trimethyl-1,4,7-triazacyclononan (Me/Me-TACN) und/oder 2-Methyl-1,4,7-triazacyclononan (Me/TACN) enthalten. Geeignete Mangankomplexe sind beispielsweise [MnIII 2(µ-O)1(µ-OAc)2(TACN)2](ClO4)2, [MnIIIMnIV(µ-O)2(µ-OAc)1(TACN)2](BPh4)2, [MnIV 4(µ-O)6(TACN)4](ClO4)4, [MnIII 2(µ-O)1(µ-OAc)2(Me-TACN)2](ClO4)2, [MnIIIMnIV(µ-O)1(µ-OAc)2(Me-TACN)2](ClO4)3, [MnIV 2(µ-O)3(Me-TACN)2](PF6)2 und [MnIV 2(µ-O)3(Me/Me-TACN)2](PF6)2 (OAc = OC(O)CH3).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. It is particularly preferred to use 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). Suitable manganese complexes are, for example, [Mn III 2 (μ-O) 1 (μ-OAc) 2 (TACN) 2 ] (ClO 4 ) 2 , [Mn III Mn IV (μ-O) 2 (μ-OAc) 1 (TACN ) 2 ] (BPh 4 ) 2 , [Mn IV 4 (µ-O) 6 (TACN) 4 ] (ClO 4 ) 4 , [Mn III 2 (µ-O) 1 (µ-OAc) 2 (Me-TACN ) 2 ] (ClO 4 ) 2 , [Mn III Mn IV (µ-O) 1 (µ-OAc) 2 (Me-TACN) 2 ] (ClO 4 ) 3 , [Mn IV 2 (µ-O) 3 ( Me-TACN) 2 ] (PF 6 ) 2 and [Mn IV 2 (µ-O) 3 (Me / Me-TACN) 2 ] (PF 6 ) 2 (OAc = OC (O) CH 3 ).
Maschinelle Geschirrspülmittel, dadurch gekennzeichnet, dass sie weiterhin einen Bleichkatalysator ausgewählt aus der Gruppe der bleichverstärkenden Übergangsmetallsalze und Übergangsmetallkomplexe, vorzugsweise aus der Gruppe der Komplexe des Mangans mit 1,4,7-trimethyl-1,4,7-triazacyclononan (Me3-TACN) oder 1,2, 4,7-tetramethyl-1,4,7-triazacyclononan (Me4-TACN) enthalten, werden erfindungsgemäß bevorzugt, da durch die vorgenannten Bleichkatalysatoren insbesondere das Reinigungsergebnis signifikant verbessert werden kann.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.
Die vorgenannten bleichverstärkenden Übergangsmetallkomplexe, insbesondere mit den Zentralatomen Mn und Co werden in üblichen Mengen, vorzugsweise in einer Menge bis zu 5 Gew.-%, insbesondere von 0,0025 Gew.-% bis 1 Gew.-% und besonders bevorzugt von 0,01 Gew.-% bis 0,30 Gew.-%, jeweils bezogen auf das Gesamtgewicht der bleichkatalysatorhaltigen Mittel, eingesetzt. In speziellen Fällen kann jedoch auch mehr Bleichkatalysator eingesetzt werden.The aforementioned bleach-intensifying transition metal complexes, in particular with the central atoms Mn and Co, 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.
Gegenstand der vorliegenden Erfindung ist weiterhin ein maschinelles Geschirrspülverfahren zur Entfernung von Anschmutzungen, insbesondere ausgewählt aus Anschmutzungen durch Tee, Milch, Haferbrei und/oder Stärke, dadurch gekennzeichnet, dass in mindestens einem Verfahrensschritt quervernetzte Polyvinylpyrrolidon-Partikel sowie ein nichtionisches Tensid der allgemeinen Formel (I)
R1O(AlkO)xM(OAlk)yOR2 (I)
eingesetzt werden, wobei
- R1 und R2 unabhängig voneinander für einen verzweigten oder unverzweigten, gesättigten oder ungesättigten, gegebenenfalls hydroxylierten Alkylrest mit 4 bis 22 Kohlenstoffatomen stehen;
- Alk für einen verzweigten oder unverzweigten Alkylrest mit 2 bis 4 Kohlenstoffatomen steht;
- x und y unabhängig voneinander für einen Wert von 1 und 70 stehen; und
- M für einen Alkylrest aus der Gruppe CH2, CHR3, CR3R4, CH2CHR3 und CHR3CHR4 steht, wobei R3 und R4 unabhängig voneinander für einen verzweigten oder unverzweigten, gesättigten oder ungesättigten Alkylrest mit 1 bis 18 Kohlenstoffatomen stehen,
- wobei das nichtionische Tensid vorzugsweise in einem gepressten Formkörper eingesetzt, wobei der gepresste Formkörper vorzugsweise quervernetzte Polyvinylpyrrolidon-Partikel mit einem mittleren Teilchendurchmesser von 100 bis 150 µm als Sprengmittel enthält.
R 1 O (AlkO) x M (OAlk) y OR 2 (I)
are used, 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 independently stand for a value of 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 are
- the nonionic surfactant preferably used in a pressed molded body, the pressed molded body preferably containing cross-linked polyvinylpyrrolidone particles with an average particle diameter of 100 to 150 μm as a disintegrant.
Die zuvor beschriebenen Wirkstoffkombinationen eignen sich insbesondere zur Reinigung von Geschirr in maschinellen Geschirrspülverfahren. Ein weiterer Gegenstand der vorliegenden Anmeldung ist ein Verfahren zur Reinigung von Geschirr in einer Geschirrspülmaschine, unter Einsatz eines erfindungsgemäßen maschinellen Geschirrspülmittels, wobei die maschinellen Geschirrspülmittel vorzugsweise während des Durchlaufens eines Geschirrspülprogramms, vor Beginn des Hauptspülgangs oder im Verlaufe des Hauptspülgangs in den Innenraum einer Geschirrspülmaschine eindosiert werden. Die Eindosierung bzw. der Eintrag des erfindungsgemäßen Mittels in den Innenraum der Geschirrspülmaschine kann manuell erfolgen, vorzugsweise wird das Mittel jedoch mittels der Dosierkammer der Geschirrspülmaschine in den Innenraum der Geschirrspülmaschine dosiert. Im Verlauf des Reinigungsverfahrens wird vorzugsweise kein zusätzlicher Wasserenthärter und kein zusätzlicher Klarspüler in den Innenraum der Geschirrspülmaschine dosiert. Ein Kit für eine Geschirrspülmaschine, umfassend
- a) ein erfindungsgemäßes maschinelles Geschirrspülmittel;
- b) eine Anleitung, die den Verbraucher darauf hinweist, das maschinelle Geschirrspülmittel ohne Zusatz eines Klarspülers und/oder eines Enthärtersalzes zu verwenden ist, ist ein weiterer Gegenstand dieser Anmeldung.
- a) an inventive automatic dishwashing agent;
- b) Instructions that advise the consumer to use the automatic dishwashing detergent without the addition of a rinse aid and / or a softening salt are another subject of this application.
Die erfindungsgemäßen maschinellen Geschirrspülmittel zeigen ihre vorteilhaften Reinigungs- und Trocknungseigenschaften insbesondere auch in Niedrigtemperatur-Reinigungsverfahren. Bevorzugte Geschirrspülverfahren unter Einsatz erfindungsgemäßer Mittel sind daher dadurch gekennzeichnet, dass die Geschirrspülverfahren bei einer Flottentemperatur unterhalb 60°C, vorzugsweise unterhalb 50°C durchgeführt werden.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.
Wie eingangs beschrieben, zeichnen sich erfindungsgemäße Mittel gegenüber herkömmlichen maschinellen Geschirrspülmitteln durch eine verbesserte Trocknungsleistung aus. Ein weiterer Gegenstand der vorliegenden Anmeldung ist daher die Verwendung eines erfindungsgemäßen maschinellen Geschirrspülmittels zur Verbesserung der Trocknung beim maschinellen Geschirrspülen.As described at the outset, 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.
Einige beispielhafte Rezepturen für bevorzugte erfindungsgemäße maschinelle Geschirrspülmitteltabletten können den nachfolgenden Tabellen entnommen werden:
In eine handelsübliche Reinigungsmitteltablette für das maschinelle Geschirrspülen, die ein Trocknungs-Tensid umfasst, wurden ca. 1 Gew.-% quervernetzte PVP-Partikel eingearbeitet. Anschließend wurde die Trocknungsleistung der Tablette in einem maschinellen Geschirrspülverfahren überprüft. Im Vergleich hierzu wurde die Trocknungsleistung der Tablette ohne quervernetzte PVP-Partikel getestet. Es wurde hierbei festgestellt, dass die Trocknung des gespülten Geschirrs bei Zusatz von PVP-Partikeln generell schneller erfolgt und zwar sowohl an Porzellan, Glas, Metall als auch an Plastik. Eine deutlich beschleunigte Trocknung war insbesondere an Plastik festzustellen.Approx. 1% by weight of cross-linked PVP particles were incorporated into a commercially available detergent tablet for machine dishwashing, which comprises a drying surfactant. The drying performance of the tablet was then checked in an automatic dishwashing process. In comparison, the drying performance of the tablet without cross-linked PVP particles was tested. It was found here that the drying of the washed dishes is generally faster with the addition of PVP particles, both at Porcelain, glass, metal and plastic. A significantly accelerated drying process was particularly evident on plastic.
Claims (12)
- An automatic dishwashing detergent in the form of a pressed shaped body, containing crosslinked polyvinylpyrrolidone particles and at least one non-ionic surfactant according to formula (I)
R1O(AlkO)xM(OAlk)yOR2 (I),
where R1 and R2 represent, independently of one another, a branched or unbranched, saturated or unsaturated, optionally hydroxylated, alkyl functional group having 4 to 22 carbon atoms;Alk represents a branched or unbranched alkyl functional group having 2 to 4 carbon atoms;x and y represent, independently of one another, a value of 1 and 70; andM represents an alkyl functional group from the group CH2, CHR3, CR3R4, CH2CHR3 and CHR3CHR4, where R3 and R4 represent, independently of one another, a branched or unbranched, saturated or unsaturated alkyl functional group having 1 to 18 carbon atoms. - The automatic dishwashing detergent according to claim 1, characterized in that the pressed shaped body is a compacted product, in particular a tablet.
- The automatic dishwashing detergent according to claim 1 or 2, characterized in that the polyvinylpyrrolidone particles have an average diameter of from 100 to 150 µm.
- The automatic dishwashing detergent according to one of claims 1 to 3, characterized in that the polyvinylpyrrolidone particles are contained in an amount of from 0.1 to 5 wt.%, in particular in an amount of from 0.2 to 3 wt.%, especially in an amount of from 0.3 to 1.8 wt.%.
- The automatic dishwashing detergent according to one of the preceding claims, characterized in that it additionally contains at least one anionic polymer, preferably selected from copolymeric polycarboxylates and copolymeric polysulfonates.
- The automatic dishwashing detergent according to one of the preceding claims, characterized in that it additionally contains at least one bleaching agent and/or a bleach activator and/or a bleach catalyst.
- The automatic dishwashing detergent according to one of the preceding claims, characterized in that it additionally contains at least one builder and at least one enzyme.
- The automatic dishwashing detergent according to one of the preceding claims, containinga) 0.5 to 5 wt.% of a non-ionic surfactant of general formula R1-CH(OH)CH2-O(CH2CH2O)xCH2CHR(OCH2CH2)yO-CH2CH(OH)-R2, where R, R1 and R2 represent, independently of one another, an alkyl functional group or alkenyl functional group having 6 to 22 carbon atoms;
x and y represent, independently of one another, values between 1 and 40;b) 0.1 to 5 wt.%, in particular 0.2 to 3 wt.%, especially 0.3 to 1.8 wt.%, polyvinylpyrrolidone particles, in particular having an average diameter of from 100 to 150 µm; andc) 1 to 15 wt.% of at least one copolymeric, anionic polymer from the group of hydrophobically modified polycarboxylates and polysulfonates. - The automatic dishwashing detergent according to one of claims 1 to 7, containinga) 0.5 to 5 wt.% of a non-ionic surfactant of general formula
R1-O(CH2CH2O)xCH2(OCH2CH2)yO-R2,
whereR1 and R2 represent, independently of one another, an alkyl functional group or alkenyl functional group having 4 to 22 carbon atoms;x and y represent, independently of one another, values between 1 and 40;b) 0.1 to 5 wt.%, in particular 0.2 to 3 wt.%, especially 0.3 to 1.8 wt.%, polyvinylpyrrolidone particles, in particular having an average diameter of from 100 to 150 µm; andc) 1 to 15 wt.% of at least one copolymeric, anionic polymer from the group of hydrophobically modified polycarboxylates and polysulfonates. - A method for cleaning dishes in a dishwasher using an automatic dishwashing detergent according to one of the preceding claims.
- An automatic dishwashing method for removing stains, in particular selected from stains caused by tea, milk, porridge and/or starch, characterized in that, in at least one method step, crosslinked polyvinylpyrrolidone particles and a non-ionic surfactant of general formula (I) are used
R1O(AlkO)xM(OAlk)yOR2 (I)
where R1 and R2 represent, independently of one another, a branched or unbranched, saturated or unsaturated, optionally hydroxylated, alkyl functional group having 4 to 22 carbon atoms;Alk represents a branched or unbranched alkyl functional group having 2 to 4 carbon atoms;x and y represent, independently of one another, a value of 1 and 70; andM represents an alkyl functional group from the group CH2, CHR3, CR3R4, CH2CHR3 and CHR3CHR4, where R3 and R4 represent, independently of one another, a branched or unbranched, saturated or unsaturated alkyl functional group having 1 to 18 carbon atoms. - The use of a combination of crosslinked polyvinylpyrrolidone particles and at least one non-ionic surfactant according to formula (I)
R1O(AlkO)xM(OAlk)yOR2 (I),
where R1 and R2 represent, independently of one another, a branched or unbranched, saturated or unsaturated, optionally hydroxylated, alkyl functional group having 4 to 22 carbon atoms;Alk represents a branched or unbranched alkyl functional group having 2 to 4 carbon atoms;x and y represent, independently of one another, a value of 1 and 70; andM represents an alkyl functional group from the group CH2, CHR3, CR3R4, CH2CHR3 and CHR3CHR4, where R3 and R4 represent, independently of one another, a branched or unbranched, saturated or unsaturated alkyl functional group having 1 to 18 carbon atoms;in a pressed shaped body in order to improve drying of washed dishes, in particular in order to improve drying of plastic dishes.
Applications Claiming Priority (2)
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DE102010029625A DE102010029625A1 (en) | 2010-06-02 | 2010-06-02 | Geschirrspülmittelkompaktate |
PCT/EP2011/058158 WO2011151188A1 (en) | 2010-06-02 | 2011-05-19 | Compacted dishwasher formulation |
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DE (1) | DE102010029625A1 (en) |
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US20020160930A1 (en) * | 2000-10-18 | 2002-10-31 | The Procter & Gamble Company | Detergent tablet |
DE102007042860A1 (en) * | 2007-09-10 | 2009-03-12 | Henkel Ag & Co. Kgaa | cleaning supplies |
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