EP1195429A1 - Maschinelles Geschirreinigungsverfahren und maschinelle Geschirrspülmittel mit verbessertem Korrosionsschutz - Google Patents
Maschinelles Geschirreinigungsverfahren und maschinelle Geschirrspülmittel mit verbessertem Korrosionsschutz Download PDFInfo
- Publication number
- EP1195429A1 EP1195429A1 EP01123093A EP01123093A EP1195429A1 EP 1195429 A1 EP1195429 A1 EP 1195429A1 EP 01123093 A EP01123093 A EP 01123093A EP 01123093 A EP01123093 A EP 01123093A EP 1195429 A1 EP1195429 A1 EP 1195429A1
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- EP
- European Patent Office
- Prior art keywords
- acid
- surfactant
- agents
- cleaning
- weight
- Prior art date
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- SXLLDUPXUVRMEE-UHFFFAOYSA-N nonanediperoxoic acid Chemical compound OOC(=O)CCCCCCCC(=O)OO SXLLDUPXUVRMEE-UHFFFAOYSA-N 0.000 description 1
- LTUGGBOPBQPPGK-UHFFFAOYSA-A octadecasodium;hexaphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LTUGGBOPBQPPGK-UHFFFAOYSA-A 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RUVINXPYWBROJD-UHFFFAOYSA-N para-methoxyphenyl Natural products COC1=CC=C(C=CC)C=C1 RUVINXPYWBROJD-UHFFFAOYSA-N 0.000 description 1
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- PATMLLNMTPIUSY-UHFFFAOYSA-N phenoxysulfonyl 7-methyloctanoate Chemical compound CC(C)CCCCCC(=O)OS(=O)(=O)OC1=CC=CC=C1 PATMLLNMTPIUSY-UHFFFAOYSA-N 0.000 description 1
- 229940067107 phenylethyl alcohol Drugs 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 150000003109 potassium Chemical class 0.000 description 1
- OQZCJRJRGMMSGK-UHFFFAOYSA-M potassium metaphosphate Chemical compound [K+].[O-]P(=O)=O OQZCJRJRGMMSGK-UHFFFAOYSA-M 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 229940093916 potassium phosphate Drugs 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- WSHYKIAQCMIPTB-UHFFFAOYSA-M potassium;2-oxo-3-(3-oxo-1-phenylbutyl)chromen-4-olate Chemical compound [K+].[O-]C=1C2=CC=CC=C2OC(=O)C=1C(CC(=O)C)C1=CC=CC=C1 WSHYKIAQCMIPTB-UHFFFAOYSA-M 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 239000010670 sage oil Substances 0.000 description 1
- 239000010671 sandalwood oil Substances 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003470 sulfuric acid monoesters Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 238000005494 tarnishing Methods 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- 239000010679 vetiver oil Substances 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- ZFNVDHOSLNRHNN-UHFFFAOYSA-N xi-3-(4-Isopropylphenyl)-2-methylpropanal Chemical compound O=CC(C)CC1=CC=C(C(C)C)C=C1 ZFNVDHOSLNRHNN-UHFFFAOYSA-N 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3281—Heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
Definitions
- the present invention relates to agents for the mechanical cleaning of metallic surfaces as well as the use of these agents in household dishwashers and a cleaning process using these means.
- Detergent compositions for cleaning soiled dishes in dishwashers are widely described in the prior art.
- a disadvantage that these funds often have is however the cleaning performance on metal surfaces, for example tarnished silver surfaces. Since machine dishwashing detergent both with regard to the substrates to be treated as well as a variety of requirements with regard to the contamination that occurs certain task fields are not to the complete satisfaction of the user solved.
- corrosion inhibitors which is another Prevent tarnishing, but tarnished silver surfaces cannot clean.
- silver cleaning agents should be used which contain alkaline electrolyte, metal and at least 1% by weight of builder and nonionic surfactant.
- the metal must have a more negative standard potential than silver.
- the agents can also be incorporated as a component in conventional MGSM.
- a mechanical silver cleaning process is also claimed in this document.
- the proposed solutions of the prior art have the disadvantage that they can only be used as pure cleaning agents for metallic objects (hereinafter referred to as silver cleaning agents for short). However, since the consumer rarely provides an entire dishwasher filling only from metallic surfaces, the machine either has to run partially loaded, or one accepts poor cleaning performance on other objects, such as baking dishes, plates, tea cups, etc.
- the object of the present invention was to provide a cleaning agent which on the one hand, metallic objects well lined up and also good on tarnished surfaces Has cleaning performance, but on the other hand also a "full" cleaning agent for the normal mixed load condition of the dishwasher.
- a cleaning agent which on the one hand, metallic objects well lined up and also good on tarnished surfaces Has cleaning performance, but on the other hand also a "full" cleaning agent for the normal mixed load condition of the dishwasher.
- Detergents for household dishwashers are provided, which improve the cleaning performance achieved conventional means and improved the performance on metallic surfaces, so that comparable results are achieved with special cleaners. For cost reasons, these should Results can be achieved with the same or reduced use of corrosion inhibitors.
- the present invention relates to a method for the mechanical cleaning of dishes in a domestic dishwasher using a detergent composition which contains anticorrosive agents and surfactant (s), the anticorrosive agent (s) being released before the surfactant (s) into the application liquor ,
- a detergent composition which contains anticorrosive agents and surfactant (s)
- the anticorrosive agent (s) being released before the surfactant (s) into the application liquor
- surfactants are part of most automatic dishwashing detergents and that their use can be desired for a variety of reasons.
- Corresponding agents according to the invention contain representatives of both classes of substances (corrosion inhibitors and surfactants) and have suitable measures for realizing the above-mentioned release sequence.
- the aqueous application liquor for step a) of the cleaning process according to the invention is required in the household dishwasher by adding water to the Interior in which there is a detergent composition in addition to the dirty dishes which contains anti-corrosion agents.
- a detergent composition in addition to the anti-corrosion agent (s) as ingredient (s) surfactant (s), so these Protected against early release by suitable measures to create a surfactant-free application fleet to ensure for step a).
- the concentration of the anti-corrosion agent (s) in The application fleet depends on the one hand on the amount of water that goes into the dishwasher flows, on the other hand according to the amount of detergent composition and the concentration the anti-corrosion agents herein.
- the concentration of the corrosion protection agent (s) in the application liquor is 0.0001 to 1 g / l, preferably 0.001 to 0.5 g / l, particularly preferably 0.002 to 0.25 g / l and in particular 0.005 up to 0.1 g / l.
- Corrosion inhibitors are used, with silver protection agents in particular Machine dishwashing have a special meaning. They can be used known substances of the prior art.
- silver protection agents in particular selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes are used. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used.
- Chlorine-free cleaners are special Organic and redox-active compounds containing oxygen and nitrogen, such as divalent and trivalent Phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, Pyrogallol or derivatives of these classes of compounds. Also salt and complex inorganic Compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
- Zinc compounds can also be used to prevent corrosion be used on the wash ware.
- 1,2,4-triazoles substituted in the 5-position are again particularly preferred.
- Processes according to the invention which are characterized in that the application liquor substituted in the 5-position 3-amino-1,2,4-triazoles of the formula (I) or their mixtures and / or their salts, preferably with hydrochloric acid, sulfuric acid, phosphoric acid, Contains carbonic acid, sulfurous acid, organic carboxylic acids such as acetic, glycolic, citric, succinic acid or mixtures thereof in the R for a linear or branched, saturated or unsaturated, optionally substituted by hydroxyl or alkoxyl groups, alkyl radical having 1 to 15 carbon atoms or an aryl optionally substituted by hydroxyl, primary, secondary, tertiary amino groups, alkoxy, alkylthio or thiol groups -, furyl, te
- those substituted in the 5-position are 3-amino-1,2,4-triazoles selected from the group of 5-propyl, butyl, pentyl, heptyl, -Octyl-, -Nonyl-, -Decyl-, -Undecyl-, -Dodecyl-, -Isononyl-, -Versatic-10-acid alkyl-, -Phenyl-, -p-tolyl-, - (4-tert.butylphenyl) -, - (4-methoxyphenyl) -, - (2-, -3-, -4-pyridyl) -, - (2-thienyl) -, - (5-methyl-2- furyl) -, - (5-Oxo-2-pyrrolidinyl) -3-amino-1,2,4-triazoles.
- 5-Pentyl-, 5-heptyl-, 5-nonyl-, 5-undecyl-, 5-isononyl-, 5-versatic-10-acid-alkyl-3-amino-1,2,4-triazoles are very particularly effective as well as mixtures of these substances.
- preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, Carbonic acid, sulphurous acid, organic carboxylic acids such as vinegar, glycol, citric, Succinic acid.
- the alkylamino-1,2,4-triazoles or their physiological compatible salts usually in a concentration of 0.001 to 10 wt .-%, preferably 0.0025 to 2% by weight, particularly preferably 0.01 to 0.04% by weight, in each case based on the means used. Under normal household conditions, these quantities lead to the above concentrations mentioned in the application fleet.
- the application liquor can be used in the first step of the
- the cleaning method according to the invention naturally also contains other ingredients of cleaning agents included, wherein surfactant (s) are not present according to the invention in this step.
- further possible ingredients of the application liquor in the first process step are Builders, cobuilders, complexing agents, bleaches, bleach activators, enzymes, dyes, To name fragrances etc.
- the application liquor in step a) contains the application liquor in step a) in addition to the corrosion inhibitor (s) builders and / or cobuilders, polymers and / or complexing agents. It is also preferred if the Application liquor in step a) is free of bleaching agents and bleach activators.
- the crockery parts are also contacted a cleaning agent containing surfactant, which of course contains other ingredients from Cleaning agents, such as bleaches, bleach activators, builders, enzymes, fragrances, Dyes, etc., may contain.
- cleaning agents such as bleaches, bleach activators, builders, enzymes, fragrances, Dyes, etc.
- the surfactant component which is in the second step in the application liquor, come Anionic, nonionic, cationic and / or amphoteric surfactants into consideration, with nonionic Surfactants are preferred because of their foaming power.
- Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
- the surfactants of the sulfonate type are preferably C 9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12-18 monoolefins with an end or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
- alkanesulfonates obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
- the esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
- Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
- fatty acid glycerol esters the mono-, di- and triesters and their mixtures are to be understood as they are in the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol can be obtained.
- Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, Palmitic acid, stearic acid or behenic acid.
- Alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
- C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates as well as C 14 -C 15 alkyl sulfates are preferred from the point of view of washing technology.
- 2,3-Alkyl sulfates which can be obtained as commercial products from Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
- the sulfuric acid monoesters of the straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
- Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
- alcohols preferably fatty alcohols and especially ethoxylated fatty alcohols.
- Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures thereof.
- Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
- alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
- Soaps are particularly suitable as further anionic surfactants.
- Saturated ones are suitable Fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated Erucic acid and behenic acid and in particular from natural fatty acids, e.g. Coconut-, Palm kernel or tallow fatty acids, derived soap mixtures.
- the anionic surfactants including the soaps can be in the form of their sodium, potassium or Ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine, available.
- the anionic surfactants are preferably in the form of their sodium or potassium salts, especially in the form of the sodium salts.
- the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
- EO ethylene oxide
- alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
- the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 EO.
- the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
- Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
- fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
- alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
- the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
- nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.
- nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable.
- the amount of these nonionic surfactants is preferably no longer than that of ethoxylated fatty alcohols, especially not more than half of them.
- Suitable surfactants are polyhydroxy fatty acid amides of the formula (II), in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
- the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
- the group of polyhydroxy fatty acid amides also includes compounds of the formula (III) in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C 1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this rest.
- R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
- R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical
- [Z] is preferably obtained by reductive amination of a reduced sugar, for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- a reduced sugar for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- the N-alkoxy or N-aryloxy-substituted compounds can be reacted with fatty acid methyl esters in The presence of an alkoxide as a catalyst is converted into the desired polyhydroxy fatty acid amides become.
- the application liquor in step b) of the cleaning process according to the invention particularly preferably contains nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols.
- the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
- EO ethylene oxide
- alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
- the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 EO.
- the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
- Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
- fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
- step b) contains a nonionic surfactant which has a melting point above room temperature having.
- preferred cleaning methods are characterized in that the Application liquor in step b) 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 included.
- Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If nonionic surfactants which are highly viscous at room temperature are used, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.
- Preferred nonionic surfactants to be used at room temperature originate from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols, and mixtures of these surfactants with structurally more complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
- Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
- the is nonionic surfactant with a melting point above room temperature an ethoxylated nonionic surfactant resulting from the reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 carbon atoms with preferably at least 12 moles, particularly preferably at least 15 moles, in particular at least 20 moles Ethylene oxide per mole of alcohol or alkylphenol has emerged.
- a particularly preferred nonionic surfactant which is solid at room temperature is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol, of ethylene oxide , Among these, the so-called “narrow range ethoxylates" (see above) are particularly preferred.
- the application liquors in step b) is particularly preferred inventive cleaning method ethoxylated (s) nonionic surfactant (s), which / from C 6-20 monohydroxyalkanols or C 6- 20 -alkylphenols or C 16-20 fatty alcohols and more than 12 mole , preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained.
- ethoxylated (s) nonionic surfactant (s) which / from C 6-20 monohydroxyalkanols or C 6- 20 -alkylphenols or C 16-20 fatty alcohols and more than 12 mole , preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained.
- the nonionic surfactant which is solid at room temperature, preferably has additional propylene oxide units in the Molecule.
- Such PO units preferably make up to 25% by weight, particularly preferably up to up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic Surfactants.
- Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
- the alcohol or alkylphenol part of such nonionic surfactant molecules is preferred more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70 % By weight of the total molecular weight of such nonionic surfactants.
- Preferred cleaning methods are characterized in that the application liquor in step b) ethoxylated and propoxylated nonionic surfactants contain, in which the propylene oxide units in the molecule up to 25 wt .-%, preferred up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.
- nonionic surfactants to be used with particular preference with melting points above room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend, the 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with and containing trimethylolpropane 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylol propane.
- nonionic surfactants that can be used with particular preference are available under the name Poly Tergent® SLF-18 from Olin Chemicals.
- a further preferred cleaning method according to the invention is characterized in that the application liquor nonionic 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 ] contains, in which R 1 represents a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x denotes values between 0.5 and 1, 5 and y represents a value of at least 15.
- nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 represents H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5.
- R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred.
- H, -CH 3 or -CH 2 CH 3 are particularly preferred for the radical R 3 .
- Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
- each R 3 in the above formula can be different if x ⁇ 2.
- the value 3 for x has been chosen here by way of example and may well be larger, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
- R 1 , R 2 and R 3 are as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
- Particularly preferred are surfactants in which the radicals R 1 and R 2 have 9 to 14 carbon atoms, R 3 represents H and x assumes values from 6 to 15.
- step b) end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 contains in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5, with surfactants of the type R 1 O [CH 2 CH (R 3 ) O] x CH 2 CH (OH) CH 2 OR 2 in which x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to
- surfactant preferably nonionic (s) Surfactant (s) and in particular nonionic surfactant (s) from the group of the alkoxylated Contain alcohols.
- Step a) and step b) of the method according to the invention can be further described below in the description of agents according to the invention.
- Another object of the present invention is the use of surfactant-free aqueous Corrosion protection solutions for machine washing of dishes.
- the cleaning method according to the invention can be used, among other things by performing specially made cleaning agents in a household dishwasher brings in and runs a cleaning program.
- the Cleaning according to the invention dispenses with surfactants as intentionally added ingredients in the agents, thereby achieving essentially surfactant-free application liquors and the inventive ones Benefits are used.
- Substantially free from surfactants means that the agents are free from intentionally added surfactants are. Contamination of raw materials or manufacturing equipment can, however, result in small quantities of surfactants in agents that release them into the application liquor when used. A previous level can also result in a residual content with cleaning agents containing surfactants Stick surfactants to the crockery baskets or the spray arms of the dishwasher the application fleet of a subsequent cleaning process according to the invention is slight contaminated with surfactants.
- Another object of the present invention is therefore a dishwasher detergent, containing builders, corrosion inhibitors and possibly other ingredients of cleaning agents, which - based on its weight - contains a maximum of 0.5% by weight of surfactant (s).
- the residual content of surfactants on average can - as already mentioned - through contaminated manufacturing equipment or by raw materials that contain small amounts of surfactants. So be some raw materials are granulated or coated with the addition of small amounts of surfactant, resulting in a The product is exposed to tensides.
- agents according to the invention are preferred, the maximum 0.25% by weight, preferably at most 0.1% by weight, particularly preferably at most 0.05% by weight and in particular contain a maximum of 0.01% by weight (in each case based on the weight of the composition) of surfactants.
- Agents according to the invention which are free from surfactant (s) are particularly preferred.
- both automatic dishwashing detergents are the Builders, corrosion inhibitors, surfactants and possibly other ingredients of cleaning agents included and are characterized in that they the surfactant (s) in dissolving Contain form, as well as machine dishwashing detergent, containing builders, corrosion inhibitors, Surfactants and possibly other ingredients of cleaning agents that contain the corrosion inhibitor (s) in accelerated form, other items of present invention.
- a delay in the dissolution of surfactants can be achieved, for example, by coating surfactant compounds, by compounding alone or by embedding in dissolution-delayed matrices respectively.
- a release acceleration of corrosion inhibitors takes place, for example, by assembly with disintegration aids, shower systems, dissolving accelerators (easily soluble Substances) etc.
- the physical packaging can also accelerate or slow down the solution act, for example by a dishwasher detergent body, which surfactant (s) contains and is coated or "powdered” on its surface with corrosion inhibitor (s) dissolve before the molded body goes into solution.
- multi-phase moldings in which whole Phases are delayed in release (for example due to ingredients, high pressure and thus high compression with poor solubility, through coating etc.), while others accelerate dissolution are (for example, by using disintegration aids, by low Pressing pressure and thus low compression with better solubility, etc.) are used to carry out the Teaching according to the invention can be easily produced.
- the corrosion inhibitors are preferably released and can have their effect via a unfold for a certain period of time before surfactants enter the fleet.
- Another subject of The present invention is therefore a machine dishwashing detergent containing builders, Corrosion inhibitors, surfactants and possibly other ingredients of cleaning agents, which is characterized in that the surfactant (s) wholly or partially with a coating material coated or compounded or so physically made up that they are in the cleaning liquor after a period t1 of 10 s to 5 min. at most 10% and after t1 plus 1 minute up to 30 min. is at least 90% released, while the corrosion inhibitor (s) are so is compounded or physically assembled, that these are in the cleaning liquor a period t1 from 10 s to 5 min. is / are released to at least 90%.
- the surfactant or the surfactants are / are preferably in a period t1 of 10 s to 5 min. and especially preferably from 1 min. up to 5 min. at most 10% and preferably after t1 plus 5 min. to 15 minute and particularly preferably from t1 plus 7 min. up to 10 min. released at least 90%.
- the time t1 can be the start of the wash cycle be in the case of specially made-up agents (for example in the case of coated moldings)
- t1 can also mean the time of dissolution of the assembly (here: coating). It is crucial that there is a fixed time "starting point" from which to start First dissolve the corrosion inhibitors and then the surfactants in the application liquor. The the exact location of this point in time t1 in the washing program is not important.
- Enveloping materials fatty alcohols or fatty acids, which may be mixed with other enveloping substances can be mixed.
- a mixture of fatty alcohols and aluminum stearate is an example called.
- envelope materials known from the prior art are as follows summarized in key words: magnesium sulfate and sodium hexaphosphate, dihydrogen phosphate or pyrophosphates, phosphonic acids, sodium metaborate and silicate, water glass and sodium polyphosphate, Sodium sulfate and silicate, or sodium bicarbonate, borax and magnesium sulfate, Boric acid, but also some organic components such as fat derivatives, paraffins and waxes (Melting temperature of the compounds between 25 and 90 ° C), polyethylene glycols and fatty acid esters of which with a molecular weight of 300 to 1,700, combinations with magnesium oxide, Vinyl chloride-ethylene copolymer emulsions or vinyl chloride-ethylene methacrylate copolymer emulsions. Polycarboxylates or other water-soluble polymers.
- the coating materials can be applied from the melt or from solutions or dispersions, the solvent or emulsifier being removed by evaporation.
- Application as a fine powder for example by electrostatic techniques, is also possible, although this method leads to irregular and poorly adhering coatings.
- the coating materials can be applied to particles in agitators, mixers and granulators. However, it is preferred to apply the coating materials in a fluidized bed, it being possible for the particles to be sized at the same time. If the coating materials lead to sticky products under certain circumstances, it can make sense to apply fine particles to the coated particles ("powdering"). All fine-particle substances can be used as powdering agents, although other detergent components such as builder substances can also be used.
- Zeolites, silicates, polymeric polycarboxylates, carbonates, citrates, starch, cellulose derivatives etc. are preferably used as additional powdering agents. Part of an existing buffer system can also be used for powdering.
- the coating materials for particles containing surfactants are used in such amounts that an optimal interaction of the individual components and thus an exactly controlled release is made possible. Depending on the period within which the release is to be largely suppressed and depending on the size of the coated particles, the amount of coating material will be measured. Preferred embodiments use less than 20% by weight of shell material, based on the amount of the coated particles, in particular less than 10% by weight of shell material is preferred.
- a preferred "physical" way to delay the release of surfactants is to use them in compared to the other ingredients of poorly soluble form. For example can be achieved by varying the particle size of surfactant-containing particles, since Dissolve finely divided detergent ingredients faster due to the larger surface.
- the combination of differently densified ingredients is also preferred Way to realize different solubilities.
- powdered ingredients with more compressed, for example extruded, and thus more slowly soluble Surfactant particles can be combined.
- the "physical release delay" is particularly preferred to be realized within a molded body.
- detergent tablets can be produced are made up of several phases, one phase being less compressed as a different phase. The more easily compressed phase disintegrates faster in the cleaning process previously compressed premix, which increases solubility compared to a harder compressed phase is increased.
- particular preference is given to two-layer tablets in which one layer is softer pressed than the other, the harder pressed layer containing the surfactant (s) contains.
- the retardation of a phase can also have a lower content a de-integration aid contained in it can be achieved.
- the agents according to the invention generally contain one or more builders, in particular Zeolites, silicates, carbonates, organic cobuilders and - where no ecological prejudices against their use persists - including the phosphates.
- builders in particular Zeolites, silicates, carbonates, organic cobuilders and - where no ecological prejudices against their use persists - including the phosphates.
- the latter are particularly in detergent tablets for machine dishwashing preferred builders.
- the builders mentioned are also suitable as alkalizing agents.
- Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + 1 H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are.
- Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
- the delay in dissolution compared to conventional amorphous sodium silicates can have been brought about in various ways, for example by surface treatment, compounding, compacting / compaction, by overdrying or by coating.
- the term “amorphous” is also understood to mean “X-ray amorphous”.
- silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
- it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments.
- This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
- Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
- the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
- zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
- zeolite X and mixtures of A, X and / or P are also suitable.
- Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (approx ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula n Na 2 O (1-n) K 2 O Al 2 O 3 (2 - 2.5) SiO 2 (3.5 - 5.5) H 2 O can be described.
- Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
- the generally known phosphates are also used as builder substances possible if such use should not be avoided for ecological reasons.
- the alkali metal phosphates are among particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) of greatest importance in the detergent and cleaning agent industry.
- Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO 3 ) n 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 and lime incrustations in tissues and also contribute to cleaning performance.
- Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below).
- NaH 2 PO 4 is acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
- Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH 2 PO 4 , is a white salt with a density of 2.33 gcm -3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is light soluble in water.
- Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm -3 , water loss at 95 °), 7 mol. (Density 1.68 gcm -3 , melting point 48 ° with loss of 5 H 2 O) and 12 mol. Water ( Density 1.52 gcm -3 , melting point 35 ° with loss of 5 H 2 O), becomes anhydrous at 100 ° and changes to diphosphate Na 4 P 2 O 7 when heated more strongly. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is easily soluble in water.
- Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm -3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 .
- Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH.
- Tripotassium phosphate (tertiary or triphase potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder with a density of 2.56 gcm -3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises, for example, when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.
- Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) , Substances are colorless crystals that are soluble in water with an alkaline reaction.
- Na 4 P 2 O 7 is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying.
- the decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water.
- Potassium diphosphate potassium pyrophosphate
- K 4 P 2 O 7 exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.
- Sodium and potassium phosphates in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
- pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
- sodium tripolyphosphate sodium tripolyphosphate
- n 3
- Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and around 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate.
- pentasodium triphosphate In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P 2 O 5 , 25% K 2 O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry.
- sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH: (NaPO 3 ) 3 + 2 KOH ⁇ Na 3 K 2 P 3 O 10 + H 2 O
- Polycarboxylates in particular can be used as organic cobuilders in the agents according to the invention /
- Polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, others organic cobuilders (see below) and phosphonates are used. These substance classes are described below.
- Usable organic builders are, for example, those that can be used in the form of their sodium salts
- Polycarboxylic acids, polycarboxylic acids being understood to mean such carboxylic acids that have 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 from ecological Reasons is not objectionable, as well as mixtures of these.
- Preferred salts are the salts polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, Sugar acids and mixtures of these.
- the acids themselves can also be used.
- the acids have a builder effect typically also the property of an acidifying component and are therefore also used for Setting a lower and milder pH value for detergents or cleaning agents.
- the acids are citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and to name any mixtures of these.
- Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts polyacrylic acid or polymethacrylic acid, for example those with a relative Molecular mass from 500 to 70,000 g / mol.
- the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
- Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 2000 have up to 20,000 g / mol. Because of their superior solubility, this group can again the short-chain polyacrylates, the molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may be preferred.
- copolymeric polycarboxylates especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
- the 50 to 90 wt .-% acrylic acid and contain 50 to 10% by weight of maleic acid.
- Their relative molecular mass, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol, and in particular 30,000 to 40,000 g / mol.
- the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution become.
- the content of (co) polymeric polycarboxylates in the agents is preferably 0.5 up to 20% by weight, in particular 3 to 10% by weight.
- the polymers can also allylsulfonic acids, such as Allyloxybenzenesulfonic acid and methallylsulfonic acid, contained as a monomer.
- biodegradable polymers made from more than two different ones Monomer units, for example those which are salts of acrylic acid and Maleic acid and vinyl alcohol or vinyl alcohol derivatives or the salts of acrylic acid as monomers and the 2-alkylallylsulfonic acid and sugar derivatives.
- copolymers are those which preferably use acrolein and acrylic acid / acrylic acid salts as monomers or acrolein and vinyl acetate.
- polymeric aminodicarboxylic acids their To name salts or their precursors.
- Polyaspartic acids are particularly preferred or their salts and derivatives.
- polyacetals which are obtained by reacting dialdehydes with polyol carboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, can be obtained.
- Preferred polyacetals are derived from dialdehydes such as glyoxal, glutaraldehyde, Terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
- Suitable organic builder substances are dextrins, for example oligomers or Polymers of carbohydrates that can be obtained by partial hydrolysis of starches.
- the hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes be performed. They are preferably hydrolysis products with medium molecular weights in the range from 400 to 500000 g / mol.
- a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, are preferred, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 is.
- DE dextrose equivalent
- Both maltodextrins with a DE between 3 can be used and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol.
- the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
- Ethylene diamine N, N'-disuccinate (EDDS) is preferred used in the form of its sodium or magnesium salts.
- EDDS Ethylene diamine N, N'-disuccinate
- glycerol disuccinate and glycerol trisuccinate are 3 to 15% by weight.
- organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form and which at least 4 carbon atoms and at least one hydroxy group and a maximum of two acid groups contain.
- HEDP hydroxyalkane-1,1-diphosphonate
- Preferred aminoalkane phosphonates are Ethylene diamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. They are preferably in shape the neutral sodium salts, e.g. B.
- the class of phosphonates preferably HEDP used.
- the aminoalkanephosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it can, especially if the agent also bleach contain, be preferred to use aminoalkane phosphonates, in particular DTPMP, or To use mixtures of the phosphonates mentioned.
- all compounds that are able to form complexes with alkaline earth metal ions can be used as a cobuilder.
- the amount of builder is usually between 10 and 70 wt .-%, preferably between 15 and 60 wt .-% and in particular between 20 and 50 wt .-%, each based on the entire agent according to the invention.
- the invention contain Agents organic and / or in particular inorganic bleaching agents.
- Sodium percarbonate is of particular importance among the compounds which serve as bleaching agents and produce H 2 O 2 in water.
- Other useful bleaching agents are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate peroxypyrophosphate, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
- Bleaching agents from the group of organic bleaching agents can also be used.
- Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
- organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
- Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoxyacidoxy (PAP), )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxydalsoxyperiperyl
- the bleaching agent content of the agents can be 1 to 40% by weight and in particular 10 to 20% by weight. amount, advantageously using percarbonate or perborate mono- or tetrahydrate becomes.
- bleach activators can be incorporated.
- bleach activators compounds those under perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 up to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid result, are used.
- Multi-acylated alkylenediamines are preferred, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, in particular Tri
- Bleach catalysts can be included. These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo-salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru amine complexes are as Bleaching catalysts are suitable, preference being given to using compounds which are used in the DE 197 09 284 A1 are described.
- the cleaning agent according to the invention can be further conventional ingredients, in particular enzymes, Sequestering agents, electrolytes, and other auxiliary substances, such as foam regulators, additional Contain bleach activators, colors and fragrances.
- Enzymes in the agents according to the invention include in particular those from the classes of Hydrolases such as proteases, esterases, lipases or lipolytic enzymes, amylases, Glycosyl hydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases carry for the removal of stains such as stains containing protein, fat or starch. to Bleach can also be used with oxidoreductases.
- Bacterial strains are particularly suitable or mushrooms such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens and their genetically modified variants obtained enzymatic active ingredients.
- proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus are used.
- enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic acting enzymes or from protease, amylase and lipase or lipolytically acting enzymes or protease, lipase or lipolytic enzymes, but especially protease and / or mixtures containing lipase or mixtures with lipolytically active enzymes of particular importance Interest.
- Known cutinases are examples of such lipolytically active enzymes.
- Peroxidases or oxidases have also proven to be suitable in some cases.
- suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and Pectinases.
- the enzymes can be adsorbed on carriers or embedded in enveloping substances around them protect against premature decomposition.
- the percentage of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5% by weight, preferably 0.5 to about 4.5% by weight be.
- Agents preferred in the context of the present invention are characterized in that that they contain protease and / or amylase.
- Dyes and fragrances can be added to the automatic dishwashing detergents according to the invention to improve the aesthetic impression of the resulting products and the Consumers in addition to performance a visually and sensory "typical and distinctive" To provide product.
- perfume oils or fragrances individual fragrance compounds, e.g. synthetic products of the ester, ether, aldehyde, ketone, alcohol type and hydrocarbons are used. Fragrance compounds of the ester type are e.g.
- the ethers include, for example Benzyl ethyl ether, to the aldehydes e.g.
- the linear alkanals with 8-18 C atoms citral, citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, among the Ketones e.g. the Jonone, ⁇ -isomethylionon and methylcedryl ketone, to the alcohols anethole, Citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons mainly include the terpenes like limes and pinene. However, mixtures are preferred different fragrances are used, which together produce an appealing fragrance.
- perfume oils can also contain natural fragrance mixtures such as those from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
- natural fragrance mixtures such as those from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
- fragrances can be incorporated directly into the cleaning agents according to the invention can also be advantageous to apply the fragrances on carriers.
- the agents according to the invention In order to improve the aesthetic impression of the agents according to the invention, it (or parts of which) are dyed with suitable dyes.
- Preferred dyes the selection of which Specialist poses no difficulty, has a high storage stability and insensitivity compared to the other ingredients of the agents and against light and no pronounced Substantivity towards the substrates to be treated with the agents such as glass, ceramic or Plastic dishes so as not to stain them.
- the agents according to the invention can be provided in all known forms of offer, in particular powdered cleaners and detergent tablets being of particular importance. If detergent tablets are produced, they can contain disintegration aids, so-called tablet disintegrants, in order to facilitate the disintegration of highly compressed moldings and to shorten the disintegration times. According to Römpp (9th edition, vol. 6, p. 4440) and Voigt “Textbook of pharmaceutical technology” (6th edition, 1987, p. 182-184), tablet disintegrants or accelerators of decay are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in absorbable form.
- Preferred detergent tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration auxiliaries, in each case based on the weight of the tablet. If only the basic tablet contains disintegration aids, the information given relates only to the weight of the basic tablet. Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight .-% contain.
- Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and, formally speaking, is a ⁇ -1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
- Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
- celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
- the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
- CMC carboxymethyl cellulose
- the cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose.
- the content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.
- the cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be compressed.
- Detergent tablets which contain disintegrants in granular or, if appropriate, cogranulated form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO98 / 40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants.
- the particle sizes of such disintegrants are usually above 200 ⁇ m, preferably at least 90% by weight between 300 and 1600 ⁇ m and in particular at least 90% by weight between 400 and 1200 ⁇ m.
- the above-mentioned coarser disintegration aids based on cellulose which are described in more detail in the cited documents are preferably to be used as disintegration aids in the context of the present invention and are commercially available, for example, under the name Arbocel® TF-30-HG from the company Rettenmaier.
- microcrystalline cellulose As a further disintegrant based on cellulose or as a component of this component microcrystalline cellulose can be used.
- This microcrystalline cellulose is made by partial Hydrolysis of celluloses obtained under conditions that only the amorphous areas (approx. Attack 30% of the total cellulose mass) of the celluloses and completely dissolve the crystalline ones Leave areas (approx. 70%) undamaged.
- a subsequent disaggregation of the The hydrolysis of the microfine celluloses produces the microcrystalline celluloses, the primary particle sizes of about 5 ⁇ m and for example to granules with a medium Particle size of 200 microns can be compacted.
- Preferred detergent tablets in the context of the present invention additionally contain a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10 % By weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the molded body weight.
- a disintegration aid preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10 % By weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the molded body weight.
- Shaped detergent tablets according to the invention can also be a gas-evolving shower system included.
- the gas-developing shower system can consist of a single substance exist, which releases a gas on contact with water. Among these connections is particular to name the magnesium peroxide, which releases oxygen when in contact with water.
- the gas-releasing bubble system itself consists of at least two components, that react with each other to form gas. While here a variety of systems is conceivable and executable, which will release nitrogen, oxygen or hydrogen, for example the bubble system used in the detergent tablets according to the invention Choose both from an economic and an ecological point of view to let.
- Preferred shower systems consist of alkali metal carbonate and / or hydrogen carbonate and an acidifying agent which is suitable from the alkali metal salts to release carbon dioxide in aqueous solution.
- the alkali metal carbonates or bicarbonates the sodium and potassium salts are out Cost reasons clearly preferred over the other salts. Needless to say the pure alkali metal carbonates or bicarbonates concerned are not used; rather, mixtures of different carbonates and hydrogen carbonates may be preferred.
- shaped detergent bodies 2 to 20% by weight, preferably, are used as the shower system 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or hydrogen carbonate and 1 to 15, preferably 2 to 12 and in particular 3 to 10% by weight of one Acidifying agent, based in each case on the entire molded body.
- alkali metal dihydrogen phosphates and other inorganic salts can be used.
- organic acidifying agents are preferred used, the citric acid being a particularly preferred acidifying agent.
- the other solid mono-, oligo- and polycarboxylic acids can also be used in particular. From this group, tartaric acid, succinic acid, malonic acid, adipic acid, Maleic acid, fumaric acid, oxalic acid and polyacrylic acid.
- Organic sulfonic acids such as amidosulfonic acid can also be used.
- Sokalan® DCS trademark from BASF
- agents are preferred in which the corrosion inhibitor content of the agents is 0.001 to 10% by weight, preferably 0.0025 to 2 % By weight and in particular 0.01 to 0.04% by weight, in each case based on the total cleaning agent, is.
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Abstract
Description
Die Lösungsvorschläge des Standes der Technik besitzen den Nachteil, daß sie nur als reine Reinigungsmittel für metallische Gegenstände (nachfolgend kurz als Silberreinigungsmittel bezeichnet) benutzt werden können. Da der Verbraucher aber selten eine gesamte Spülmaschinenfüllung nur aus metallischen Oberflächen bereitstellt, muß die Maschine entweder teilbeladen laufen, oder man nimmt eine mangelhafte Reinigungsleistung an anderen Gegenständen, beispielsweise Auflaufformen, Tellern, Teetassen usw. in Kauf.
Diese Ausführungsform berücksichtigt, daß Tenside Bestandteil der meisten maschinellen Geschirrspülmittel sind und ihr Einsatz aus den unterschiedlichsten Gründen gewünscht sein kann. Entsprechende erfindungsgemäße Mittel (siehe weiter unten) enthalten Vertreter beider Substanzklassen (Korrosionsinhibitoren und Tenside) und verfügen über geeignete Maßnahmen, um die vorstehend genannte Freisetzungsreihenfolge zu verwirklichen.
Bevorzugt als bei Raumtemperatur feste einzusetzende Niotenside stammen aus den Gruppen der alkoxylierten Niotenside, insbesondere der ethoxylierten primären Alkohole und Mischungen dieser Tenside mit strukturell komplizierter aufgebauten Tensiden wie Polyoxypropylen/Polyoxyethylen/Polyoxypropylen (PO/EO/PO)-Tenside. Solche (PO/EO/PO)-Niotenside zeichnen sich darüberhinaus durch gute Schaumkontrolle aus.
Die Hüllmaterialien für tensidhaltige Teilchen werden in solchen Mengen eingesetzt, daß ein optimales Zusammenspiel der einzelnen Komponenten und somit eine exakt gesteuerte Freisetzung ermöglicht wird. Je nach dem Zeitraum, innerhalb dessen die Freisetzung weitgehend unterdrückt werden soll und je nach Größe de beschichteten Teilchen wird man die Menge an Hüllmaterial bemessen. Bevorzugte Ausführungsformen verwenden weniger als 20 Gew.-% Hüllmaterial, bezogen auf die Menge der beschichteten Teilchen, insbesondere sind weniger als 10 Gew.-% Hüllmaterialien bevorzugt.
Als bevorzugte Desintegrationsmittel werden im Rahmen der vorliegenden Erfindung Desintegrationsmittel auf Cellulosebasis eingesetzt, so daß bevorzugte Reinigungsmittelformkörper ein solches Desintegrationsmittel auf Cellulosebasis in Mengen von 0,5 bis 10 Gew.-%, vorzugsweise 3 bis 7 Gew.-% und insbesondere 4 bis 6 Gew.-% enthalten. Reine Cellulose weist die formale Bruttozusammensetzung (C6H10O5)n auf und stellt formal betrachtet ein β-1,4-Polyacetal von Cellobiose dar, die ihrerseits aus zwei Molekülen Glucose aufgebaut ist. Geeignete Cellulosen bestehen dabei aus ca. 500 bis 5000 Glucose-Einheiten und haben demzufolge durchschnittliche Molmassen von 50.000 bis 500.000. Als Desintegrationsmittel auf Cellulosebasis verwendbar sind im Rahmen der vorliegenden Erfindung auch Cellulose-Derivate, die durch polymeranaloge Reaktionen aus Cellulose erhältlich sind. Solche chemisch modifizierten Cellulosen umfassen dabei beispielsweise Produkte aus Veresterungen bzw. Veretherungen, in denen Hydroxy-Wasserstoffatome substituiert wurden. Aber auch Cellulosen, in denen die Hydroxy-Gruppen gegen funktionelle Gruppen, die nicht über ein Sauerstoffatom gebunden sind, ersetzt wurden, lassen sich als Cellulose-Derivate einsetzen. In die Gruppe der Cellulose-Derivate fallen beispielsweise Alkalicellulosen, Carboxymethylcellulose (CMC), Celluloseester und -ether sowie Aminocellulosen. Die genannten Cellulosederivate werden vorzugsweise nicht allein als Desintegrationsmittel auf Cellulosebasis eingesetzt, sondern in Mischung mit Cellulose verwendet. Der Gehalt dieser Mischungen an Cellulosederivaten beträgt vorzugsweise unterhalb 50 Gew.-%, besonders bevorzugt unterhalb 20 Gew.-%, bezogen auf das Desintegrationsmittel auf Cellulosebasis. Besonders bevorzugt wird als Desintegrationsmittel auf Cellulosebasis reine Cellulose eingesetzt, die frei von Cellulosederivaten ist.
Claims (13)
- Verfahren zur maschinellen Reinigung von Geschirr in einer Haushaltsgeschirrspülmaschine unter Verwendung einer Reinigungsmittelzusammensetzung, welche Korrosionsschutzmittel und Tensid(e) enthält, dadurch gekennzeichnet, daß das/die Korrosionsschutzmittel vor dem/den Tensid(en) in die Anwendungsflotte freigesetzt werden.
- Verfahren zur maschinellen Reinigung von Geschirr in einer Haushaltsgeschirrspülmaschine, gekennzeichnet durch die Schrittea) Kontaktieren des Geschirrs mit einer wäßrigen Anwendungsflotte, welche Korrosionsschutzmittel enthält und frei von Tensid(en) ist;b) Kontaktieren des Geschirrs mit einer wäßrigen Anwendungsflotte, welche Tensid(e) enthält;c) optionales Klarspülen und Trocknen des Geschirrs.
- Verfahren nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß die Konzentration des/der Korrosionsschutzmitttel(s) in der Anwendungsflotte 0,0001 bis 1 g/l, vorzugsweise 0,001 bis 0,5 g/l, besonders bevorzugt 0,002 bis 0,25 g/l und insbesondere 0,005 bis 0,1 g/l beträgt.
- Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Anwendungsflotte ein oder mehrere Korrosionsschutzmittel aus der Gruppe der Triazole, der Benzotriazole, der Bisbenzotriazole, der Aminotriazole, der Alkylaminotriazole und der Übergangsmetallsalze oder -komplexe enthält, wobei Benzotriazole und/oder Alkylaminotriazole bevorzugt sind.
- Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Anwendungsflotte in 5-Stellung substituierte3-Amino-1,2,4-triazole der Formel (I) bzw. deren Gemische und/oder deren Salze, bevorzugt mit Salzsäure, Schwefelsäure, Phosphorsäure, Kohlensäure, schweflige Säure, organische Carbonsäuren wie Essig-, Glykol-, Citronen-, Bernsteinsäure bzw. deren Gemische enthält in der R für einen linearen oder verzweigten, gesättigten oder ungesättigten, gegebenenfalls durch Hydroxy- oder Alkoxylgruppen substituierten Alkylrest mit 1 bis 15 C-Atomen oder eine gegebenenfalls durch Hydroxy-, primäre, sekundäre, tertiäre Aminogruppen, Alkoxy- Alkylthio- oder Thiolgruppen substituierte Aryl-, Furyl-, Tetrahydrofuryl, Thienyl-, Pyridyl-, Pyrrolidinyl-, 5-Oxo-2-pyrrolidinyl-, Pyrryl-, Imidazolyl-, Pyrimidylgruppe steht.
- Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die in 5-Stellung substituierten 3-Amino-1,2,4-triazole ausgewählt sind aus der Gruppe der 5-Propyl-, -Butyl-, -Pentyl-,-Heptyl-, -Octyl-, -Nonyl-, -Decyl-, -Undecyl-, -Dodecyl-, -Isononyl-, -Versatic-10-säurealkyl-,-Phenyl-, -p-Tolyl-, -(4-tert. Butylphenyl)-, -(4-Methoxyphenyl)-, -(2-, -3-, -4-Pyridyl)-, -(2-Thienyl)-, -(5-Methyl-2-furyl)-, -(5-Oxo-2-pyrrolidinyl) -3-amino-1,2,4-triazole.
- Verwendung von tensidfreien wäßrigen Lösungen von Korrosionsschutzmitteln zur maschinellen Reinigung von Geschirr.
- Maschinelles Geschirrspülmittel, enthaltend Gerüststoffe, Korrosionsinhibitoren sowie gegebenenfalls weitere Inhaltsstoffe von Reinigungsmitteln, dadurch gekennzeichnet, daß es-bezogen auf sein Gewicht - maximal 0,5 Gew.-% Tensid(e) enthält.
- Mittel nach Anspruch 8, dadurch gekennzeichnet, daß es frei von Tensid(en) ist.
- Maschinelles Geschirrspülmittel, enthaltend Gerüststoffe, Korrosionsinhibitoren, Tenside sowie gegebenenfalls weitere Inhaltsstoffe von Reinigungsmitteln, dadurch gekennzeichnet, daß es das/die Tensid(e) in löseverzögerter Form enthält.
- Maschinelles Geschirrspülmittel, enthaltend Gerüststoffe, Korrosionsinhibitoren, Tenside sowie gegebenenfalls weitere Inhaltsstoffe von Reinigungsmitteln, dadurch gekennzeichnet, daß es den/die Korrosionsinhibitor(en) in lösebeschleunigter Form enthält.
- Maschinelles Geschirrspülmittel, enthaltend Gerüststoffe, Korrosionsinhibitoren, Tenside sowie gegebenenfalls weitere Inhaltsstoffe von Reinigungsmitteln, dadurch gekennzeichnet, daß das/die Tensid(e) ganz oder teilweise mit einem Hüllmaterial beschichtet oder so compoundiert bzw. physikalisch konfektioniert ist/sind, daß diese(s) in der Reinigungsflotte nach einem Zeitraum t1 von 10 s bis 5 min. zu höchstens 10% und nach t1 plus 1 min. bis 30 min. zu mindestens 90% freigesetzt ist, während der/die Korrosionsinhibitor(en) so compoundiert bzw. physikalisch konfektioniert ist/sind, daß diese(r) in der Reinigungsflotte nach einem Zeitraum t1 von 10 s bis 5 min. zu mindestens 90% freigesetzt ist/sind.
- Mittel nach einem der Ansprüche 8 bis 13, dadurch gekennzeichnet, daß der Gehalt der Mittel an Korrosionsinhibitor 0,001 bis 10 Gew.-% , vorzugsweise 0,0025 bis 2 Gew.-% und insbesondere 0,01 bis 0,04 Gew.-%, jeweils bezogen auf das gesamte Reinigungsmittel, beträgt.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE10049657A DE10049657C2 (de) | 2000-10-07 | 2000-10-07 | Maschinelles Geschirreinigungsverfahren und maschinelle Geschirrspülmittel mit verbessertem Korrosionsschutz |
DE10049657 | 2000-10-07 |
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EP1195429A1 true EP1195429A1 (de) | 2002-04-10 |
EP1195429B1 EP1195429B1 (de) | 2006-06-07 |
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EP01123093A Expired - Lifetime EP1195429B1 (de) | 2000-10-07 | 2001-09-27 | Maschinelles Geschirreinigungsverfahren und maschinelle Geschirrspülmittel mit verbessertem Korrosionsschutz |
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EP (1) | EP1195429B1 (de) |
AT (1) | ATE328997T1 (de) |
DE (2) | DE10049657C2 (de) |
ES (1) | ES2266066T3 (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004055144A1 (de) * | 2002-12-17 | 2004-07-01 | Henkel Kommanditgesellschaft Auf Aktien | Silberschutz beim maschinellen geschirrspülen |
WO2008104240A1 (de) * | 2007-02-28 | 2008-09-04 | Henkel Ag & Co. Kgaa | Wirkstoffträgersysteme |
Citations (2)
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EP0928828A1 (de) * | 1997-12-31 | 1999-07-14 | Henkel KGaA | Alkylaminotriazolhaltige, granulare Komponente für den Einsatz in Maschinengeschirrspülmitteln (MGSM) und Verfahren zu deren Herstellung |
GB2335434A (en) * | 1998-03-19 | 1999-09-22 | Mcbride Robert Ltd | Encapsulated liquid incorporation in tableted compositions |
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US5480576A (en) * | 1993-10-14 | 1996-01-02 | Lever Brothers Company, Division Of Conopco, Inc. | 1,3-N azole containing detergent compositions |
DE4338626A1 (de) * | 1993-11-12 | 1995-05-18 | Henkel Kgaa | Additiv für die Glasflaschenreinigung und seine Verwendung zur Verringerung der Glaskorrosion |
DE19501645A1 (de) * | 1995-01-20 | 1996-07-25 | Henkel Kgaa | Silberkorrosionsschutzmittel |
DE19518693A1 (de) * | 1995-05-22 | 1996-11-28 | Henkel Kgaa | Maschinelle Geschirrspülmittel mit Silberkorrosionsschutzmittel |
DE19631787C2 (de) * | 1996-08-07 | 2000-06-29 | Henkel Kgaa | Benzotriazolhaltige, granulare Komponente für den Einsatz in Maschinengeschirrspülmitteln (MGSM) und Verfahren zu dessen Herstellung |
DE19701031C2 (de) * | 1997-01-15 | 1998-12-10 | Henkel Kgaa | Verwendung von 3-Amino-5-alkyl-1,2,4-Triozolen als Silberschutzmittel |
GB2325243A (en) * | 1997-05-13 | 1998-11-18 | Procter & Gamble | Removing tarnish from tarnished silverware |
DE19860670A1 (de) * | 1998-12-29 | 2000-08-10 | Benckiser Nv | Wasserlösliches Glas als Korrosionsschutz in einer Geschirrspülmaschine |
-
2000
- 2000-10-07 DE DE10049657A patent/DE10049657C2/de not_active Expired - Fee Related
-
2001
- 2001-09-27 AT AT01123093T patent/ATE328997T1/de not_active IP Right Cessation
- 2001-09-27 DE DE50110017T patent/DE50110017D1/de not_active Expired - Fee Related
- 2001-09-27 ES ES01123093T patent/ES2266066T3/es not_active Expired - Lifetime
- 2001-09-27 EP EP01123093A patent/EP1195429B1/de not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0928828A1 (de) * | 1997-12-31 | 1999-07-14 | Henkel KGaA | Alkylaminotriazolhaltige, granulare Komponente für den Einsatz in Maschinengeschirrspülmitteln (MGSM) und Verfahren zu deren Herstellung |
GB2335434A (en) * | 1998-03-19 | 1999-09-22 | Mcbride Robert Ltd | Encapsulated liquid incorporation in tableted compositions |
Non-Patent Citations (1)
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DATABASE WPI Section Ch Derwent World Patents Index; Class A97, AN 1973-01235U, XP002187399 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004055144A1 (de) * | 2002-12-17 | 2004-07-01 | Henkel Kommanditgesellschaft Auf Aktien | Silberschutz beim maschinellen geschirrspülen |
WO2008104240A1 (de) * | 2007-02-28 | 2008-09-04 | Henkel Ag & Co. Kgaa | Wirkstoffträgersysteme |
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DE50110017D1 (de) | 2006-07-20 |
ATE328997T1 (de) | 2006-06-15 |
EP1195429B1 (de) | 2006-06-07 |
ES2266066T3 (es) | 2007-03-01 |
DE10049657C2 (de) | 2003-02-27 |
DE10049657A1 (de) | 2002-04-25 |
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