EP0414197B1 - Dishwashing compositions for dishwasher - Google Patents
Dishwashing compositions for dishwasher Download PDFInfo
- Publication number
- EP0414197B1 EP0414197B1 EP90115943A EP90115943A EP0414197B1 EP 0414197 B1 EP0414197 B1 EP 0414197B1 EP 90115943 A EP90115943 A EP 90115943A EP 90115943 A EP90115943 A EP 90115943A EP 0414197 B1 EP0414197 B1 EP 0414197B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- sodium
- dish
- detergent composition
- composition according
- 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.)
- Revoked
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- 239000000203 mixture Substances 0.000 title claims abstract description 56
- 238000004851 dishwashing Methods 0.000 title claims abstract description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 77
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 75
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 38
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 37
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 37
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000460 chlorine Substances 0.000 claims abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 5
- 239000003599 detergent Substances 0.000 claims description 51
- 229910019142 PO4 Inorganic materials 0.000 claims description 13
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 13
- 235000021317 phosphate Nutrition 0.000 claims description 13
- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 claims description 11
- 108010065511 Amylases Proteins 0.000 claims description 11
- 102000013142 Amylases Human genes 0.000 claims description 11
- 108091005804 Peptidases Proteins 0.000 claims description 11
- 239000004365 Protease Substances 0.000 claims description 11
- 235000019418 amylase Nutrition 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 11
- 239000010452 phosphate Substances 0.000 claims description 11
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 11
- 239000004382 Amylase Substances 0.000 claims description 10
- 102000004190 Enzymes Human genes 0.000 claims description 10
- 108090000790 Enzymes Proteins 0.000 claims description 10
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 claims description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 10
- 235000011152 sodium sulphate Nutrition 0.000 claims description 10
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 7
- 239000007844 bleaching agent Substances 0.000 claims description 7
- 239000011976 maleic acid Substances 0.000 claims description 7
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- 238000005187 foaming Methods 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 5
- 239000000194 fatty acid Substances 0.000 claims description 5
- 229930195729 fatty acid Natural products 0.000 claims description 5
- 150000004665 fatty acids Chemical class 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229940045872 sodium percarbonate Drugs 0.000 claims description 3
- 239000004367 Lipase Substances 0.000 claims description 2
- 102000004882 Lipase Human genes 0.000 claims description 2
- 108090001060 Lipase Proteins 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 235000019421 lipase Nutrition 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims 1
- 238000009472 formulation Methods 0.000 description 14
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 11
- 239000004115 Sodium Silicate Substances 0.000 description 10
- 229910052911 sodium silicate Inorganic materials 0.000 description 10
- 229940088598 enzyme Drugs 0.000 description 9
- 239000002736 nonionic surfactant Substances 0.000 description 9
- 235000019795 sodium metasilicate Nutrition 0.000 description 7
- 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 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 229920002125 Sokalan® Polymers 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 241000219315 Spinacia Species 0.000 description 2
- 235000009337 Spinacia oleracea Nutrition 0.000 description 2
- 244000269722 Thea sinensis Species 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 235000013372 meat Nutrition 0.000 description 2
- 108010020132 microbial serine proteinases Proteins 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229960001922 sodium perborate Drugs 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000001692 EU approved anti-caking agent Substances 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- 101100412856 Mus musculus Rhod gene Proteins 0.000 description 1
- 239000012425 OXONE® Substances 0.000 description 1
- 239000004435 Oxo alcohol Substances 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 101000983338 Solanum commersonii Osmotin-like protein OSML15 Proteins 0.000 description 1
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 1
- 239000001083 [(2R,3R,4S,5R)-1,2,4,5-tetraacetyloxy-6-oxohexan-3-yl] acetate Substances 0.000 description 1
- UAOKXEHOENRFMP-ZJIFWQFVSA-N [(2r,3r,4s,5r)-2,3,4,5-tetraacetyloxy-6-oxohexyl] acetate Chemical compound CC(=O)OC[C@@H](OC(C)=O)[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](OC(C)=O)C=O UAOKXEHOENRFMP-ZJIFWQFVSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229940025131 amylases Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000013345 egg yolk Nutrition 0.000 description 1
- 210000002969 egg yolk Anatomy 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000013020 final formulation Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- PMYUVOOOQDGQNW-UHFFFAOYSA-N hexasodium;trioxido(trioxidosilyloxy)silane Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])O[Si]([O-])([O-])[O-] PMYUVOOOQDGQNW-UHFFFAOYSA-N 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 235000014666 liquid concentrate Nutrition 0.000 description 1
- LWXVCCOAQYNXNX-UHFFFAOYSA-N lithium hypochlorite Chemical compound [Li+].Cl[O-] LWXVCCOAQYNXNX-UHFFFAOYSA-N 0.000 description 1
- FODOUIXGKGNSMR-UHFFFAOYSA-L magnesium;2-oxidooxycarbonylbenzoate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-]OC(=O)C1=CC=CC=C1C([O-])=O FODOUIXGKGNSMR-UHFFFAOYSA-L 0.000 description 1
- 235000013310 margarine Nutrition 0.000 description 1
- 239000003264 margarine Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 description 1
- 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 1
- 239000002304 perfume Substances 0.000 description 1
- -1 peroxy compound Chemical class 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 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
- 239000003381 stabilizer Substances 0.000 description 1
- 108010075550 termamyl Proteins 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 238000005406 washing Methods 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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3942—Inorganic per-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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/06—Phosphates, including polyphosphates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/08—Silicates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- 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
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
Definitions
- the present invention relates to a dishwasher detergent.
- the invention is therefore based on the object of developing a machine dishwashing detergent which has a lower pH than conventional dishwashing detergents and in particular has a pH below 10.5 (in a 1% strength aqueous solution), yet has good cleaning performance and consists of the environment is not composed or components that have as little pollution as possible.
- a dishwasher detergent is known from EP-A 135 227, which is only weakly alkaline and has a pH of about 9.3-10.8 (in 0.3% aqueous solution), 25-50% by weight.
- sodium metasilicate can be completely dispensed with in an effective dishwasher detergent if a mixture of sodium carbonate and sodium hydrogen carbonate is used instead.
- This mixture offers the possibility to vary the pH value of the final formulation in a larger pH range, while maintaining the high alkalinity reserve.
- this high reserve of alkalinity makes it possible to keep the enzyme content and builder content of the formulation very low. According to the invention, it is even possible to completely dispense with phosphate builders.
- the machine dishwashing detergents according to the invention generally contain 20-80% by weight, preferably 30-70% by weight and in particular 45-55% by weight of sodium carbonate and 5-50% by weight, preferably 10-40% by weight and in particular 15-36% by weight sodium hydrogen carbonate.
- US Pat. No. 4,306,987 discloses strongly alkaline dishwashing detergents with special low-foaming nonionic detergents.
- These known dishwashing detergents generally contain 20-80% by weight of an alkaline detergent salt such as e.g. Sodium carbonate, sodium hydrogen carbonate and mixtures thereof, di- and trisodium orthophosphate, sodium metasilicate, sodium sesquisilicate, borax and sodium borate, and as a bleaching agent 5-50% by weight chlorinated trisodium phosphate or instead a mixture of lithium hypochlorite or chlorinated cyanuric acid and trisodium phosphate.
- the sodium silicate generally makes up 20-80%, preferably 20-40%.
- JP-A 1 146 998 in the form of its Derwent abstract 89 210 121 discloses dishwashing detergents which necessarily contain 10 to 30% by weight of a hydroxycarboxylic acid salt and / or an aminopolycarboxylate.
- the pH of the dishwasher detergents according to the invention is generally in the range from 9.0 to 10.5 or even less, preferably in the range from 9.9 to 10.4.
- the ratio of sodium carbonate to sodium hydrogen carbonate is generally 4: 1 to 1: 1, preferably 3: 1 to 1: 1.
- Preferred dishwashing detergents according to the invention with a pH of 9.0-10.5, preferably 9.9-10.4, contain 20-80% by weight sodium carbonate and 5-50% by weight sodium hydrogen carbonate, the combination of Sodium carbonate and sodium bicarbonate make up at least 30 wt .-% of the total composition.
- the dishwashing detergents according to the invention can contain a phosphate, conventionally sodium tripolyphosphate as a builder.
- a suitable phosphate-containing dishwashing detergent contains 20-60% by weight sodium carbonate and 10-20% by weight sodium hydrogen carbonate, the sum of sodium carbonate and sodium hydrogen carbonate making up 30-70% by weight, and 10-40% by weight, preferably 20 - 35 wt .-% phosphate, especially sodium tripolyphosphate.
- dishwasher detergents that are free of phosphates are particularly preferred.
- phosphate-free builder systems can be used which replace the phosphate in whole or in part.
- An acrylic acid / maleic acid copolymer for example the product Sokalan® CP 5 ex BASF
- a polyacrylic acid for example Acrysol® LMW 45 ND ex Rhom & Haas
- small amounts of a phosphonic acid for example 1-hydroxyethane-1,1-diphosphonic acid / HEDP /
- a phosphonic acid for example 1-hydroxyethane-1,1-diphosphonic acid / HEDP /
- the polymer serving as a phosphate substitute can be used in an amount of 0 to 15% by weight, preferably 3 to 10% by weight.
- the phosphonic acid is used in an amount of 0-10, preferably 2-4% by weight.
- a phosphate-free builder system can also contain small amounts of low molecular weight polymers based on maleic acid or acrylic acid, e.g. small amounts of a phosphonic acid, e.g. Sokalan® PM10 ex BASF or Sokalan® PA15 ex BASF included.
- a suitable phosphate-free dishwasher detergent contains 25-60% by weight sodium carbonate and 10-35% by weight sodium hydrogen carbonate, the sum of sodium carbonate and sodium hydrogen carbonate making up 35-75% by weight, and 3-10% by weight of a phosphate-free polymeric builder.
- the machine dishwashing detergents according to the invention are preferably free of silicates.
- a small amount of disilicates or layered silicates can be advantageous as corrosion inhibitors. If such silicates are used as corrosion inhibitors, their amount should not exceed 15% by weight of the total composition, and in general their proportion is 5-10% by weight.
- the machine dishwashing detergents according to the invention preferably contain enzymes which, however, are effective in very small amounts in the compositions according to the invention.
- Proteases for example the product Savinase® 4.0 T ex Novo
- amylases for example the product Termamyl® 60 T ex Novo
- lipases for certain types of soiling can also be advantageous, especially at animal washing temperatures.
- the enzymes are generally used in amounts of 0-3% by weight, preferably 0.4-1% by weight.
- Chlorine bleaches such as sodium dichloroisocyanurate
- Chlorine bleaches are avoided according to the invention, so that there is no impairment of the enzyme stability and activity and a possible formation of chlorinated organic compounds as a result of such chlorine bleaches is avoided.
- oxygen bleaching agents are used, such as sodium perborate mononydrate, sodium perborate tetrahydrate, potassium monopersulfate, magnesium monoperoxyphthalate hexahydrate (H48), diperoxidodecanedioic acid (desensitized) and sodium percarbonate.
- the dishwasher detergents according to the invention expediently contain 3-15% by weight, preferably 3-10% by weight and in particular 5-8% by weight sodium perborate monohydrate or sodium percarbonate.
- compositions according to the invention can contain small amounts of a surfactant, preferably a nonionic surfactant, in an amount of up to 5% by weight, preferably up to 3% by weight and in particular up to 1% by weight. In general, amounts in the range of 0.2-2% by weight of a nonionic surfactant are completely sufficient.
- the surfactants used must be low-foaming, so non-ionic surfactants are the most suitable. Low-foaming nonionic surfactants with good biodegradability are preferably used. This is e.g. adducts of ethylene oxide and propylene oxide or ethylene oxide and higher alkylene oxides with native or synthetic fatty alcohols or oxo alcohols. Corresponding adducts which are end group-closed are also very suitable.
- the machine dishwashing detergent according to the invention may also contain other conventional ingredients, such as dyes, perfume oils or other auxiliaries, such as e.g. Stabilizers for enzymes.
- the fatty acids or hydrocarbons are used in amounts of 0-3% by weight, preferably 0.5-2% by weight and in particular 0.7-1.5% by weight, based on the total composition.
- Sodium sulfate has also proven to be suitable as an anticaking agent and can be used instead of the white oils. Sodium sulfate is also suitable as a diluent. If the alkalinity of the formulation is to be reduced, part of the amount of sodium carbonate / sodium hydrogen carbonate can be replaced by sodium sulfate, but the minimum content of 25% by weight, preferably 30% by weight, of the sodium carbonate / sodium hydrogen carbonate combination must be maintained .
- the machine dishwashing detergents according to the invention can therefore contain 0-35% by weight sodium sulfate.
- a suitable, phosphate-containing composition according to the invention consists of 20-35% by weight Sodium tripolyphosphate 35 - 55% by weight sodium 10 - 20% by weight Sodium bicarbonate 5 - 8% by weight Sodium perborate monohydrate 0.4-1% by weight Protease 0.4-1% by weight Amylase 0.2-2% by weight Nonionic surfactant part of the sodium carbonate / sodium hydrogen carbonate amount by 0 - 20 wt .-% sodium sulfate can be replaced, and has a pH (in 1% solution) of 10.2 - 10.4.
- a particularly suitable, phosphate-free composition according to the invention consists of 35 - 55% by weight sodium 20-35% by weight Sodium bicarbonate 5 - 8% by weight Sodium perborate monohydrate 0.4-1% by weight Protease 0.4-1% by weight Amylase 0.2-2% by weight Nonionic surfactant 3 - 10% by weight Acrylic acid / maleic acid / copolymer 0 - 4% by weight Phosphonic acid, part of the amount of sodium carbonate / sodium bicarbonate can be replaced by 0-35% by weight sodium sulfate, and has a pH (in 1% solution) of 10.2-10.4.
- the cleaning performance of the dishwasher detergents according to the invention is comparable to conventional, strongly alkaline dishwasher detergents based on sodium metasilicate.
- the formulations according to the invention are even superior.
- compositions according to the invention are much lower than those of comparable known formulations.
- the machine dishwashing detergents according to the invention are generally formulated as dry powders or granules in a conventional manner. Their use in the form of tablets, pouches, portion packs but also in the form of liquid concentrates is not excluded.
- a machine dishwashing detergent of the following composition was formulated by dry mixing or granulation: Sodium tripolyphosphate 24.0% by weight sodium 49.0% by weight Sodium bicarbonate 18.0% by weight Sodium perborate monohydrate 7.0% by weight Protease 0.5% by weight Amylase 0.5% by weight Nonionic surfactant (Lutensol® LF403) 1.0% by weight
- This composition had a pH (in 1% aqueous solution) of 10.3.
- a machine dishwashing detergent of the following composition was formulated by dry mixing or granulation: sodium 49.0% by weight Sodium bicarbonate 34.5% by weight Sodium perborate monohydrate 7.0% by weight Protease 0.5% by weight Amylase 0.5% by weight Nonionic surfactant (Lutensol® LF403) 1.0% by weight Acrylic acid / maleic acid copolymer 5.0% by weight Phosphonic acid (HEDP) 2.5% by weight
- This composition had a pH (in 1% aqueous solution) of 10.0.
- This composition had a pH (in 1% solution) of 10.1.
- formulations according to the invention of Examples 1 and 2 were compared with regard to their cleaning performance with a formulation containing sodium metasilicate (formulation I).
- the test was carried out in accordance with the DIN 44990 regulation, only with the difference that the evaluation of the cleaning performance for spinach, minced meat, oat flakes and tea was weighted as a percentage.
- Comparative recipe I had the following composition: Sodium tripolyphosphate 36.1% by weight Sodium metasilicate 51.0% by weight sodium 9.65% by weight Sodium dichloroisocyanurate 2.25% by weight Surfactant (Dehypon® LT104) 1.0% by weight.
- formulation II a formulation according to EP-A 135 227 was examined as formulation II, which had the following composition: Rec .: 45% sodium tripolyphosphate, 15% sodium carbonate, 10% sodium perborate * 4H20, 4% TAED, 3% Thermamyl® 60 T, 2% Savinase® 4.0 T, 0.7% Dequest® 2016, 5% sodium disilicate, 10% sodium sulfate , 1.5% Lutensol® LF 403, water ad 100%.
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Abstract
Description
Die vorliegende Erfindung betrifft ein Maschinengeschirrspülmittel.The present invention relates to a dishwasher detergent.
Herkömmliche Maschinengeschirrspülmittel basieren im wesentlichen auf Natriumtripolyphosphat, Natriummetasilikat und Natriumcarbonat und sind stark alkalisch. Der pH-Wert dieser Produkte liegt im allgemeinen bei 12 (in 1 %iger Lösung) und ist im wesentlichen auf den hohen Gehalt an Natriummetasilikat und Natriumcarbonat zurückzuführen. Bei diesen pH-Werten können Reizungen bzw. Verätzungen der Haut und der Schleimhäute, insbesondere beim Verschlucken (Kleinkinder) auftreten und dadurch sind diese Produkte zunehmend in die öffentliche Diskussion geraten. Es besteht daher ein Bedarf an Maschinengeschirrspülmitteln, die weniger alkalisch sind. Bei einer Verminderung der Alkalinität wurde aber eine Verminderung der Geschirrspülleistung erwartet.Conventional machine dishwashing detergents are essentially based on sodium tripolyphosphate, sodium metasilicate and sodium carbonate and are strongly alkaline. The pH of these products is generally 12 (in a 1% solution) and is essentially due to the high content of sodium metasilicate and sodium carbonate. At these pH values, irritation or burns to the skin and mucous membranes can occur, especially when swallowed (small children) and as a result, these products have increasingly come into public discussion. There is therefore a need for dishwasher detergents that are less alkaline. If the alkalinity was reduced, however, a reduction in the dishwasher performance was expected.
Der Erfindung liegt also die Aufgabe zugrunde ein Maschinengeschirrspülmittel zu entwickeln, welches einen niedrigeren pH-Wert als die herkömmlichen Geschirrspülmittel besitzt und insbesondere einen pH-Wert unterhalb von 10,5 (in 1 %iger wäßriger Lösung), dennoch eine gute Reinigungsleistung aufweist und aus die Umwelt nicht oder möglichst wenig belastenden Bestandteilen zusammengesetzt ist.The invention is therefore based on the object of developing a machine dishwashing detergent which has a lower pH than conventional dishwashing detergents and in particular has a pH below 10.5 (in a 1% strength aqueous solution), yet has good cleaning performance and consists of the environment is not composed or components that have as little pollution as possible.
Aus der EP-A 135 227 ist ein Maschinengeschirrspülmittel bekannt, welches nur schwach alkalisch ist und einen pH-Wert von etwa 9,3 - 10,8 (in 0,3 %iger wäßriger Lösung) aufweist, 25 - 50 Gew.-% Natriumtriphosphat, 7,5 - 40 Gew.-% Natriumcarbonat, 2 - 15 Gew.-% Natriumsilikat, sowie eine Peroxyverbindung und Enzym enthält. Es wird festgestellt, daß die Wirksamkeit und Stabilität einer solchen mild-alkalischen, enzymatischen Zusammensetzung eine Sache der Auswahl der Bestandteile in richtiger Menge ist.A dishwasher detergent is known from EP-A 135 227, which is only weakly alkaline and has a pH of about 9.3-10.8 (in 0.3% aqueous solution), 25-50% by weight. Sodium triphosphate, 7.5 - 40 wt .-% sodium carbonate, 2 - 15 wt .-% sodium silicate, and contains a peroxy compound and enzyme. It is found that the effectiveness and stability of such a mildly alkaline, enzymatic composition is a matter of choosing the right amount of ingredients.
Gemäß vorliegender Erfindung wurde festgestellt, daß auf Natriummetasilikat in einem wirksamen Maschinengeschirrspülmittel vollständig verzichtet werden kann, wenn statt dessen ein Gemisch aus Natriumcarbonat und Natriumhydrogencarbonat eingesetzt wird. Dieses Gemisch bietet die Möglichkeit, den pH-Wert aer Endrezeptur in einem größeren pH-Bereich zu variieren, wobei die hohe Alkalitätsreserve erhalten bleibt. Diese hohe Alkalitätsreserve andererseits erlaubt es, den Enzymgehalt und den Buildergehait der Rezeptur sehr niedrig zu halten. Erfindungsgemäß ist es sogar möglich auf Phosphatbuilder vollständig zu verzichten.According to the present invention, it has been found that sodium metasilicate can be completely dispensed with in an effective dishwasher detergent if a mixture of sodium carbonate and sodium hydrogen carbonate is used instead. This mixture offers the possibility to vary the pH value of the final formulation in a larger pH range, while maintaining the high alkalinity reserve. On the other hand, this high reserve of alkalinity makes it possible to keep the enzyme content and builder content of the formulation very low. According to the invention, it is even possible to completely dispense with phosphate builders.
Die erfindungsgemäßen Maschinengeschirrspülmittel enthalten im allgemeinen 20 - 80 Gew.-%, vorzugsweise 30 - 70 Gew.-% und insbesondere 45 - 55 Gew.-% Natriumcarbonat sowie 5 - 50 Gew.-%, vorzugsweise 10 - 40 Gew.-% und insbesondere 15 - 36 Gew.-% Natriumhydrogencarbonat.The machine dishwashing detergents according to the invention generally contain 20-80% by weight, preferably 30-70% by weight and in particular 45-55% by weight of sodium carbonate and 5-50% by weight, preferably 10-40% by weight and in particular 15-36% by weight sodium hydrogen carbonate.
Die US-P 4 306 987 offenbart stark alkalische Geschirrspülmittel mit speziellen niedrigschäumenden nichtionischen Detergentien. Diese bekannten Geschirrspülmittel enthalten im ailgemeinen 20 - 80 Gew.-% eines alkalischen Detergenssalzes wie z.B. Natriumcarbonat, Natriumhydrogencarbonat und Mischungen davon, Di- und Trinatriumorthophosphat, Natriummetasilikat, Natriumsesquisilikat, Borax und Natrium borat, sowie als Bleichmittel 5 - 50 Gew.-% chloriertes Trinatriumphosphat oder statt dessen eine Mischung aus Lithiumhypochlorit oder chlorierter Cyanursäure und Trinatriumphosphat. Das Natriumsilikat macht in diesen bekannten Geschirrspülmitteln im allgemeinen 20 - 80 %, vorzugsweise 20 - 40 % aus.US Pat. No. 4,306,987 discloses strongly alkaline dishwashing detergents with special low-foaming nonionic detergents. These known dishwashing detergents generally contain 20-80% by weight of an alkaline detergent salt such as e.g. Sodium carbonate, sodium hydrogen carbonate and mixtures thereof, di- and trisodium orthophosphate, sodium metasilicate, sodium sesquisilicate, borax and sodium borate, and as a bleaching agent 5-50% by weight chlorinated trisodium phosphate or instead a mixture of lithium hypochlorite or chlorinated cyanuric acid and trisodium phosphate. In these known dishwashing detergents, the sodium silicate generally makes up 20-80%, preferably 20-40%.
Die JP-A 1 146 998 in Form ihrer Derwent-Zusammenfassung 89 210 121 offenbart Geschirrspülmittel, die notwendigerweise 10 bis 30 Gew.-% eines Hydroxycarbonsäuresalzes und/oder eines Amminopolycarboxylats enthalten.JP-A 1 146 998 in the form of its Derwent abstract 89 210 121 discloses dishwashing detergents which necessarily contain 10 to 30% by weight of a hydroxycarboxylic acid salt and / or an aminopolycarboxylate.
In ihrer allgemeinsten Form betrifft die Erfindung ein Maschinengeschirrspülmittel, welches
- a) mindestens 25 Gew.-%, vorzugsweise mindestens 30 Gew.-%, einer Kombination aus Natriumcarbonat und Natriumhydrogencarbonat enthält;
- b) frei ist von Metasilikaten;
- c) frei ist von Chlorbleichmitteln,
- d) in 1 %iger wäßriger Lösung einen mild-alkalischen pH-Wert von weniger als 10,5 aufweist,
- e) ein Sauerstoffbleichmittel enthält und
- f) bis 5 Gew.-% eines schwach schäumenden, vorzugsweise nicht ionischen Tensides enthält,
- a) contains at least 25% by weight, preferably at least 30% by weight, of a combination of sodium carbonate and sodium hydrogen carbonate;
- b) is free of metasilicates;
- c) is free from chlorine bleach,
- d) in 1% aqueous solution has a mildly alkaline pH of less than 10.5,
- e) contains an oxygen bleach and
- f) contains up to 5% by weight of a low-foaming, preferably nonionic surfactant,
Der pH-Wert der erfindungsgemäßen Maschinengeschirrspülmittel liegt im allgemeinen im Bereich von 9,0 - 10,5 oder sogar darunter, vorzugsweise im Bereich von 9,9 - 10,4.The pH of the dishwasher detergents according to the invention is generally in the range from 9.0 to 10.5 or even less, preferably in the range from 9.9 to 10.4.
In der erfindungsgemäß eingesetzten Kombination aus Natriumcarbonat und Natriumhydrogencarbonat beträgt das Verhältnis von Natriumcarbonat zu Natriumhydrogencarbonat im allgemeinen 4:1 bis 1:1, vorzugsweise 3:1 bis 1:1.In the combination of sodium carbonate and sodium hydrogen carbonate used according to the invention, the ratio of sodium carbonate to sodium hydrogen carbonate is generally 4: 1 to 1: 1, preferably 3: 1 to 1: 1.
Bevorzugte erfindungsgemäße Geschirrspülmittel mit einem pH-Wert von 9,0 - 10,5, vorzugsweise von 9,9 - 10,4, enthalten 20 - 80 Gew.-% Natriumcarbonat und 5 - 50 Gew.-% Natriumhydrogencarbonat, wobei die Kombination aus Natriumcarbonat und Natriumnydrogencarbonat mindestens 30 Gew.-% der Gesamtzusammensetzung ausmacht.Preferred dishwashing detergents according to the invention with a pH of 9.0-10.5, preferably 9.9-10.4, contain 20-80% by weight sodium carbonate and 5-50% by weight sodium hydrogen carbonate, the combination of Sodium carbonate and sodium bicarbonate make up at least 30 wt .-% of the total composition.
Die erfindungsgemäßen Geschirrspülmittel können ein Phosphat, herkömmlicherweise Natriumtripolyphosphat als Builder enthalten. Ein geeignetes phosphathaltiges Geschirrspülmittel enthält 20 - 60 Gew.-% Natriumcarbonat und 10 - 20 Gew.-% Natriumhydrogencarbonat, wobei die Summe von Natriumcarbonat und Natriumhydrogencarbonat 30 - 70 Gew.-% ausmacht, und 10 - 40 Gew.-%, vorzugsweise 20 - 35 Gew.-% Phosphat, insbesondere Natriumtripolyphosphat.The dishwashing detergents according to the invention can contain a phosphate, conventionally sodium tripolyphosphate as a builder. A suitable phosphate-containing dishwashing detergent contains 20-60% by weight sodium carbonate and 10-20% by weight sodium hydrogen carbonate, the sum of sodium carbonate and sodium hydrogen carbonate making up 30-70% by weight, and 10-40% by weight, preferably 20 - 35 wt .-% phosphate, especially sodium tripolyphosphate.
Besonders bevorzugt werden jedoch Maschinengeschirrspülmittel, die frei von Phospnaten sind. Statt des Phosphats können phosphatfreie Buildersysteme eingesetzt werden, die das Phosphat ganz oder teilweise ersetzen. Für diesen Zweck sind verschiedene Systeme bekannt geworden. Als besonders geeignet für die Zwecke der vorliegenden Erfindung hat sich ein Acrylsäure/Maleinsäure-Copolymer (beispielsweise das Produkt Sokalan® CP 5 ex BASF), oder eine Polyacrylsäure (beispielsweise Acrysol® LMW 45 ND ex Rhom & Haas) erwiesen, welche gegebenenfalls zusammen mit geringen Mengen einer Phosphonsäure (beispielsweise 1-Hydroxyethan-1,1-diphosphonsäure/HEDP/) eingesetzt werden können. Das als Phosphatersatzstoff dienende Polymer kann in einer Menge von 0 - 15 Gew.-%, vorzugsweise 3 - 10 Gew.-% eingesetzt werden. Die Phosphonsäure wird in einer Menge von 0 - 10, vorzugsweise 2 - 4 Gew.-% eingesetzt. Ein phosphatfreies Buildersystem kann ansteile von geringen Mengen einer Phosphonsäure auch geringe Mengen niedrigmolekularer Polymerer aut Basis der Maleinsäure bzw. Acrylsäure z.B. Sokalan® PM10 ex BASF oder Sokalan® PA15 ex BASF enthalten.However, dishwasher detergents that are free of phosphates are particularly preferred. Instead of the phosphate, phosphate-free builder systems can be used which replace the phosphate in whole or in part. Various systems have become known for this purpose. An acrylic acid / maleic acid copolymer (for example the product Sokalan® CP 5 ex BASF) or a polyacrylic acid (for example Acrysol® LMW 45 ND ex Rhom & Haas), which optionally together with, has proven to be particularly suitable for the purposes of the present invention small amounts of a phosphonic acid (for example 1-hydroxyethane-1,1-diphosphonic acid / HEDP /) can be used. The polymer serving as a phosphate substitute can be used in an amount of 0 to 15% by weight, preferably 3 to 10% by weight. The phosphonic acid is used in an amount of 0-10, preferably 2-4% by weight. A phosphate-free builder system can also contain small amounts of low molecular weight polymers based on maleic acid or acrylic acid, e.g. small amounts of a phosphonic acid, e.g. Sokalan® PM10 ex BASF or Sokalan® PA15 ex BASF included.
Ein geeignetes phosphatfreies Maschinengeschirrspülmittel enthält 25 - 60 Gew.-% Natriumcarbonat und 10 - 35 Gew.-% Natriumhydrogencarbonat, wobei die Summe von Natriumcarbonat und Natriumhydrogencarbonat 35 - 75 Gew.-% ausmacht, sowie 3 - 10 Gew.-% eines phosphatfreien polymeren Builders.A suitable phosphate-free dishwasher detergent contains 25-60% by weight sodium carbonate and 10-35% by weight sodium hydrogen carbonate, the sum of sodium carbonate and sodium hydrogen carbonate making up 35-75% by weight, and 3-10% by weight of a phosphate-free polymeric builder.
Die erfindungsgemäßen Maschinengeschirrspülmittel sind vorzugsweise frei von Silikaten. Es hat sich jedoch herausgestellt, daß eine geringe Menge an Disilikaten oder Schichtsilikaten als Korrosionsinhibitoren vorteilhaft sein kann. Sofern solche Silikate als Korrosionsinhibitoren eingesetzt werden soll ihre Menge 15 Gew.-% der gesamten Zusammensetzung nicht überschreiten, im allgemeinen liegt ihr Anteil bei 5 - 10 Gew.-%.The machine dishwashing detergents according to the invention are preferably free of silicates. However, it has been found that a small amount of disilicates or layered silicates can be advantageous as corrosion inhibitors. If such silicates are used as corrosion inhibitors, their amount should not exceed 15% by weight of the total composition, and in general their proportion is 5-10% by weight.
Vorzugsweise enthalten die erfindungsgemäßen Maschinengeschirrspülmittel Enzyme, die jedoch in den erfindungsgemäßen Zusammensetzungen bereits in sehr geringen Mengen wirksam sind.The machine dishwashing detergents according to the invention preferably contain enzymes which, however, are effective in very small amounts in the compositions according to the invention.
Vorzugsweise verwendet man Proteasen (beispielsweise das Produkt Savinase® 4.0 T ex Novo) und Amylasen (beispielsweise das Produkt Termamyl® 60 T ex Novo), jedoch können auch, insbesondere bei tieren Waschtemperaturen, Lipasen für bestimmte Anschmutzungen vorteilhaft sein.Proteases (for example the product Savinase® 4.0 T ex Novo) and amylases (for example the product Termamyl® 60 T ex Novo) are preferably used, but lipases for certain types of soiling can also be advantageous, especially at animal washing temperatures.
Die Enzyme werden im allgemeinen in Mengen von 0 - 3 Gew.-%, vorzugsweise 0,4 - 1 Gew.-% eingesetzt.The enzymes are generally used in amounts of 0-3% by weight, preferably 0.4-1% by weight.
Chlorbleichmittel, wie beispielsweise Natriumdichlorisocyanurat werden erfinaungsgemäß vermieden, so daß eine dadurch bedingte Beeinträchtigung der Enzymstabilität und -aktivität entfällt und eine eventuell mögliche Bildung von chlorierten organischen Verbindungen als Folge solcher Chlorbleichmittel vermieden wird. Stattdessen werden Sauerstoffbleichmittel eingesetzt, wie beispielsweise Natriumperborat-Mononydrat, Natriumperborattetrahydrat, Kaliummonopersulfat, Magnesium-Monoperoxyphthalat Hexahydrat(H48), Diperoxidodecandisäure (phlegmatisiert) und Natriumpercarbonat. Die erfindungsgemäßen Maschinengeschirrspülmittel enthalten zweckmäßigerweise 3-15 Gew.-%, vorzugsweise 3-10 Gew.-% und insbesondere 5-8 Gew.-% Natriumperborat-Monohydrat oder Natriumpercarbonat.Chlorine bleaches, such as sodium dichloroisocyanurate, are avoided according to the invention, so that there is no impairment of the enzyme stability and activity and a possible formation of chlorinated organic compounds as a result of such chlorine bleaches is avoided. Instead, oxygen bleaching agents are used, such as sodium perborate mononydrate, sodium perborate tetrahydrate, potassium monopersulfate, magnesium monoperoxyphthalate hexahydrate (H48), diperoxidodecanedioic acid (desensitized) and sodium percarbonate. The dishwasher detergents according to the invention expediently contain 3-15% by weight, preferably 3-10% by weight and in particular 5-8% by weight sodium perborate monohydrate or sodium percarbonate.
Speziell bei tiefen Temperaturen kann zur Optimierung der Bleichleistung ein Bleichaktivator, wie z.B.
- TAED
- (Tetraacetylethylendiamin),
- TAGU
- (Tetraacetylglycoluril),
- GPA
- (Glucosepentaacetat) und andere
- TAED
- (Tetraacetylethylenediamine),
- TAGU
- (Tetraacetylglycoluril),
- GPA
- (Glucose pentaacetate) and others
Die erfindungsgemäßen Zusammensetzungen können geringe Mengen eines Tensids, vorzugsweise eines nichtionischen Tensids enthalten und zwar in einer Menge bis 5 Gew.-%, vorzugsweise bis 3 Gew.-% und insbesondere bis 1 Gew.-%. Im allgemeinen sind Mengen im Bereich von 0,2 - 2 Gew.-% eines nichtionischen Tensids voll ausreichend. Die eingesetzten Tenside müssen schwachschäumend sein, daher sind nichtionische Tenside am besten geeignet. Bevorzugt werden schwach schäumende nichtionische Tenside mit guter biologischer Abbaubarkeit eingesetzt. Dabei handelt es sich z.B. um Addukte von Ethylenoxid und Propylenoxid oder Ethylenoxid und höheren Alkylenoxiden an native bzw. synthetische Fettalkohole oder Oxoalkohole. Ebenfalls gut geeignet sind entsprechende Addukte die endgruppenverschlossen sind.The compositions according to the invention can contain small amounts of a surfactant, preferably a nonionic surfactant, in an amount of up to 5% by weight, preferably up to 3% by weight and in particular up to 1% by weight. In general, amounts in the range of 0.2-2% by weight of a nonionic surfactant are completely sufficient. The surfactants used must be low-foaming, so non-ionic surfactants are the most suitable. Low-foaming nonionic surfactants with good biodegradability are preferably used. This is e.g. adducts of ethylene oxide and propylene oxide or ethylene oxide and higher alkylene oxides with native or synthetic fatty alcohols or oxo alcohols. Corresponding adducts which are end group-closed are also very suitable.
Das erfindungsgemäße Maschinengeschirrspülmittel kann noch weitere übliche Bestandteile enthalten, wie Farbstoffe, Parfümöle oder sonstige Hilfsstoffe, wie z.B. Stabilisatoren für Enzyme.The machine dishwashing detergent according to the invention may also contain other conventional ingredients, such as dyes, perfume oils or other auxiliaries, such as e.g. Stabilizers for enzymes.
Der vor ailem bei stark Natriumcarbonat/Natriumbicarbonathaltigen Formulierungen zu beobachtende Effekt einer verminderten Einspülbarkeit kann durch den Einsatz von Fettsäuren und/oder Kohlenwasserstoffen (Weißölen) überwunden werden (Anticaking Mittel).The effect of reduced flushability, which can be observed in particular in formulations containing high sodium carbonate / sodium bicarbonate, can be overcome by using fatty acids and / or hydrocarbons (white oils) (anticaking agents).
Bei den Fettsäuren haben sich solche mit Kohlenwasserstoffketten im Bereich C12-C18 als geeignet erwiesen.In the case of fatty acids, those with hydrocarbon chains in the C 12 -C 18 range have proven suitable.
Bei den Kohlenwasserstoffen haben sich solche Gemische aus gesättigten geradkettigen und cyclischen Kohlenwasserstoffen mit einem Flammpunkt oberhalb 150° C als geeignet erwiesen.In the case of hydrocarbons, such mixtures of saturated straight-chain and cyclic hydrocarbons with a flash point above 150 ° C. have proven to be suitable.
Die Fettsäuren bzw. Kohlenwasserstoffe werden in Mengen von 0 - 3 Gew.-%, vorzugsweise 0,5 - 2 Gew.-% und insbesondere 0,7 - 1,5 Gew.-% bezogen auf die gesamte Zusammensetzung eingesetzt.The fatty acids or hydrocarbons are used in amounts of 0-3% by weight, preferably 0.5-2% by weight and in particular 0.7-1.5% by weight, based on the total composition.
Auch Natriumsulfat hat sich als Anticaking Mittel geeignet erwiesen und kann anstelle der Weißöle verwendet werden. Natriumsulfat eignet sich ferner als Verdünnungsstoff. Wenn die Alkalinität der Rezeptur vermindert werden soll, kann ein Teil der Natriumcarbonat/Natriumhydrogencarbonat-Menge durch Natriumsulfat ersetzt werden, wobei jedoch der Mindestgehalt von 25 Gew.-%, vorzugsweise 30 Gew.-% an der Natriumcarbonat/Natriumnydrogencarbonat-Kombination erhalten bleiben muß. Die erfindungsgemäßen Maschinengeschirrspülmittel können daher 0 - 35 Gew.-% Natriumsulfat enthalten.Sodium sulfate has also proven to be suitable as an anticaking agent and can be used instead of the white oils. Sodium sulfate is also suitable as a diluent. If the alkalinity of the formulation is to be reduced, part of the amount of sodium carbonate / sodium hydrogen carbonate can be replaced by sodium sulfate, but the minimum content of 25% by weight, preferably 30% by weight, of the sodium carbonate / sodium hydrogen carbonate combination must be maintained . The machine dishwashing detergents according to the invention can therefore contain 0-35% by weight sodium sulfate.
Eine geeignete, phosphathaltige erfindungsgemäße Zusammensetzung besteht aus
0 - 20 Gew.-% Natriumsulfat ersetzt werden kann, und weist einen pH-Wert (in 1 %iger Lösung) von 10,2 - 10,4 auf.A suitable, phosphate-containing composition according to the invention consists of
0 - 20 wt .-% sodium sulfate can be replaced, and has a pH (in 1% solution) of 10.2 - 10.4.
Eine besonders geeignete, phosphatfreie erfindungsgemäße Zusammensetzung besteht aus
Entgegen allen Erwartungen ist die Reinigungsleistung der erfindungsgemäßen Maschinengeschirrspülmittel vergleichbar mit herkömmlichen, stark alkalischen Maschinengeschirrspülmitteln auf der Basis von Natriummetasilikat. Für spezielle Anschmutzungen, wie z.B. Haferflocken, sind die erfindungsgemäßen Formulierungen sogar noch überlegen.Contrary to all expectations, the cleaning performance of the dishwasher detergents according to the invention is comparable to conventional, strongly alkaline dishwasher detergents based on sodium metasilicate. For special soiling, e.g. Oatmeal, the formulations according to the invention are even superior.
Des weiteren waren die Ergebnisse von Korrosionsversuchen an Glas, Porzellan und Besteckteilen überraschend positiv. Anstelle einer verstärkten Glaskorrosion, die durch die Verwendung von Natriumcarbonat anstelle von Natriumsilikat erwartet wurde, ist der Angriff aber äußerst gering. Das gleiche gilt im Vergleich zu marktüblichen metasilikatnaltigen Reinigern.Furthermore, the results of corrosion tests on glass, porcelain and cutlery were surprisingly positive. Instead of increased glass corrosion, which was expected by using sodium carbonate instead of sodium silicate, the attack is extremely low. The same applies in comparison to commercially available cleaners containing metasilicate.
Ein weiterer Vorteil der erfindungsgemäßen Zusammensetzungen ist der, daß wegen der geringen eingesetzten Enzym- und Phosphatmengen die Rohstoffkosten der erfindungsgemäßen Rezepturen viel niedriger sind als die vergleichbarer bekannter Rezepturen.Another advantage of the compositions according to the invention is that because of the small amounts of enzyme and phosphate used, the raw material costs of the formulations according to the invention are much lower than those of comparable known formulations.
Die erfindungsgemäßen Maschinengeschirrspülmittel werden im allgemeinen als trockene Pulver oder Granulate in herkömmlicher Weise formuliert. Ihr Einsatz in Form von Tabletten, Pouches, Portionspackungen aber auch in Form flüssiger Konzentrate ist jedoch nicht ausgeschlossen.The machine dishwashing detergents according to the invention are generally formulated as dry powders or granules in a conventional manner. Their use in the form of tablets, pouches, portion packs but also in the form of liquid concentrates is not excluded.
Die Erfindung wird anhand der nachstehenden Beispiele näher erläutert.The invention is illustrated by the examples below.
Durch Trockenvermischung bzw. Granulieren wurde ein Maschinengeschirrspülmittel folgender Zusammensetzung formuliert:
Diese Zusammensetzung besaß einen pH-Wert (in 1 %iger wäßriger Lösung) von 10,3.This composition had a pH (in 1% aqueous solution) of 10.3.
Durch Trockenvermischung bzw. Granulieren wurde ein Maschinengeschirrspülmittel folgender Zusammensetzung formuliert:
Diese Zusammensetzung besaß einen pH-Wert (in 1 %iger wäßriger Lösung) von 10,0.This composition had a pH (in 1% aqueous solution) of 10.0.
Diese Zusammensetzung besaß einen pH-Wert (in 1 %iger Lösung) von 10,1.This composition had a pH (in 1% solution) of 10.1.
Die erfindungsgemäßen Formulierungen der Beispiele 1 und 2 wurden in Bezug auf ihre Reinigungsleistung mit einer natriummetasilikathaltigen Formulierung (Rezeptur I) verglichen. Die Abprüfung erfolgte in Anlehnung an die DIN 44990-Vorscnrift, nur mit dem Unterschied, daß die Auswertung der Reinigungsleistung für Spinat, Hackfleisch, Haferflocken una Tee prozentual gewichtet wurde.The formulations according to the invention of Examples 1 and 2 were compared with regard to their cleaning performance with a formulation containing sodium metasilicate (formulation I). The test was carried out in accordance with the DIN 44990 regulation, only with the difference that the evaluation of the cleaning performance for spinach, minced meat, oat flakes and tea was weighted as a percentage.
Die Vergleicnsrezeptur I hatte folgende Zusammensetzung:
Zum weiteren Vergleich ist als Rezeptur II eine Formulierung gemäß EP-A 135 227 untersucht worden, die folgende Zusammensetzung aufwies:
Rez.: 45 % Natriumtripolyphosphat, 15 % Natriumcarbonat, 10 % Natriumperborat * 4H20, 4 % TAED, 3 % Thermamyl® 60 T, 2 % Savinase® 4.0 T, 0,7 % Dequest® 2016, 5 % Natriumdisilikat, 10 % Natriumsulfat, 1,5 % Lutensol® LF 403, Wasser ad 100 %.For further comparison, a formulation according to EP-A 135 227 was examined as formulation II, which had the following composition:
Rec .: 45% sodium tripolyphosphate, 15% sodium carbonate, 10% sodium perborate * 4H20, 4% TAED, 3% Thermamyl® 60 T, 2% Savinase® 4.0 T, 0.7% Dequest® 2016, 5% sodium disilicate, 10% sodium sulfate , 1.5% Lutensol® LF 403, water ad 100%.
Die Ergebnisse der Vergleichsversuche sind in der nachstehenden Tabelle I zusammengeraßt.The results of the comparative tests are summarized in Table I below.
Die Vergleichsversuche zeigen, aaß die erfindungsgemäßen Formulierungen eine vergleichbare Reinigungsleistung erbringen trotz der niedereren Alkalität gegenüber Rezeptur I una trotz der geringeren Enzymmenge und geringeren Phosphatmenge gegenüber Rezeptur II.
Claims (18)
- A machine dish-washing detergent composition whicha) contains at least 25% by weight of a combination of sodium carbonate and sodium hydrogen carbonate,b) is free from metasilicates,c) is free from chlorine bleaching agents,d) has a slightly alkaline pH value of less than 10.5 in 1% aqueous solution,e) contains an oxygen bleaching agent andf) contains up to 5% by weight of a low-foaming tenside, preferably a low-foaming non-ionic tenside,with the proviso that machine dish-washing detergent compositions containing a hydroxycarboxylic acid salt and/or an aminopolycarboxylate are excluded.
- A dish-washer detergent composition according to claim 1, characterized in that it contains at least 30% by weight of a combination of sodium carbonate and sodium hydrogen carbonate.
- A dish-washer detergent composition according to claim 1 or 2, characterized in that in the combination of sodium carbonate and sodium hydrogen carbonate the ratio of sodium carbonate to sodium hydrogen carbonate is from 4:1 to 1:1, preferably from 3:1 to 1:1.
- A dish-washer detergent composition according to any of the preceding claims, characterized in that it has a pH value of 9.0 to 10.5, preferably of 9.9 to 10.4, and contains 20 to 80% by weight of sodium carbonate and 5 to 50% by weight of sodium hydrogen carbonate.
- A dish-washer detergent composition according to any of the preceding claims, characterized in that it contains 20 to 60% by weight of sodium carbonate and 10 to 20% by weight of sodium hydrogen carbonate, the sum of sodium carbonate and sodium hydrogen carbonate being 30 to 70% by weight, and that it contains 10 to 40% by weight, preferably 20 to 35% by weight of phosphate, preferably sodium tripolyphosphate.
- A dish-washer detergent composition according to any of claims 1 to 4, characterized in that it is free from phosphates.
- A dish-washer detergent composition according to claim 6, characterized in that it contains 25 to 60% by weight of sodium carbonate and 10 to 35% by weight of sodium hydrogen carbonate, the sum of sodium carbonate and sodium hydrogen carbonate being 35 to 75% by weight, and that it contains 3 to 10% by weight of a phosphate-free polymeric builder.
- A dish-washer detergent composition according to any of the preceding claims, characterized in that it contains up to 15% by weight, in particular 5 to 10% by weight, of disilicate.
- A dish-washer detergent composition according to any of the preceding claims, characterized in that it contains one or several enzymes.
- A dish-washer detergent composition according to claim 9, characterized in that it contains a protease and/or an amylase and/or a lipase.
- A dish-washer detergent composition according to claim 1, characterized in that it contains 3 to 15% by weight, preferably 3 to 10% by weight, of sodium perborate monohydrate or sodium percarbonate.
- A dish-washer detergent composition according to any of the preceding claims, characterized in that it contains 0 to 5% by weight, preferably 0 to 1% by weight, of a non-ionic tenside.
- A dish-washer detergent composition according to any of the preceding claims, characterized in that it contains an addition of fatty acids (C12-C18) and/or white mineral oils in an amount of up to 3% by weight as anticaking agent.
- A dish-washer detergent composition according to any of the preceding claims, characterized in that it contains 0 to 35% by weight of sodium sulphate.
- A dish-washer detergent composition according to claim 5, characterized in that it consists of
20 to 35% by weight of sodium tripolyphosphate 35 to 55% by weight of sodium carbonate 10 to 20% by weight of sodium hydrogen carbonate 5 to 8% by weight of sodium perborate monohydrate 0.4 to 1% by weight of protease 0.4 to 1% by weight of amylase 0.2 to 2% by weight of non-ionic tenside
0 to 20% by weight of sodium sulphate and has a pH value (in 1% solution) of 10.2 to 10.4. - A dish-washer detergent composition according to claim 6, characterized in that it consists of
35 to 55% by weight of sodium carbonate 20 to 35% by weight of sodium hydrogen carbonate 5 to 8% by weight of sodium perborate monohydrate 0.4 to 1% by weight of protease 0.4 to 1% by weight of amylase 0.2 to 2% by weight of non-ionic tenside 3 to 10% by weight of acrylic acid/maleic acid copolymer 0 to 4% by weight of phosphonic acid
0 to 35% by weight of sodium sulphate,
and has a pH value (in 1% solution) of 10.2 to 10.4. - A dish-washer detergent composition according to claim 5, characterized in that it consists of
22 to 26% by weight of sodium tripolyphosphate 47 to 52% by weight of sodium carbonate 16 to 20% by weight of sodium hydrogen carbonate 6 to 8% by weight of sodium perborate monohydrate 0.4 to 0.6% by weight of protease 0.4 to 0.6% by weight of amylase 0.5 to 2% by weight of non-ionic tenside - A dish-washer detergent composition according to claim 6 characterized in that it consists of
47 to 52% by weight of sodium carbonate 32 to 36% by weight of sodium hydrogen carbonate 6 to 8% by weight of sodium perborate monohydrate 0.4 to 0.6% by weight of protease 0.4 to 0.6% by weight of amylase 0.5 to 2% by weight of non-ionic tenside 3 to 7% by weight of acrylic acid/maleic acid copolymer 2 to 4% by weight of phosphonic acid
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3927714 | 1989-08-22 | ||
| DE3927714 | 1989-08-22 | ||
| DE3939494 | 1989-11-29 | ||
| DE3939494 | 1989-11-29 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0414197A2 EP0414197A2 (en) | 1991-02-27 |
| EP0414197A3 EP0414197A3 (en) | 1992-03-04 |
| EP0414197B1 true EP0414197B1 (en) | 1997-12-10 |
Family
ID=25884273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90115943A Revoked EP0414197B1 (en) | 1989-08-22 | 1990-08-20 | Dishwashing compositions for dishwasher |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0414197B1 (en) |
| JP (1) | JPH03163199A (en) |
| AT (1) | ATE161036T1 (en) |
| AU (1) | AU6113190A (en) |
| CA (1) | CA2023529A1 (en) |
| DE (1) | DE59010780D1 (en) |
| DK (1) | DK0414197T3 (en) |
| ES (1) | ES2112247T3 (en) |
| FI (1) | FI904155A0 (en) |
| NO (1) | NO903682L (en) |
| PL (1) | PL286561A1 (en) |
| PT (1) | PT95049A (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK166548B1 (en) * | 1991-03-15 | 1993-06-07 | Cleantabs As | PHOSPHATE-FREE MACHINE DISHWASH |
| CA2130465C (en) * | 1992-03-12 | 1998-08-11 | Frederick A. Hartman | Low-dosage automatic dishwashing detergent with monopersulfate and enzymes |
| DE4232170C2 (en) | 1992-09-25 | 1999-09-16 | Henkel Kgaa | Weakly alkaline dish detergent |
| WO1994025556A1 (en) * | 1993-04-27 | 1994-11-10 | The Procter & Gamble Company | Liquid or granular automatic dishwashing detergent compositions |
| EP0726935B1 (en) * | 1993-11-03 | 2000-08-30 | The Procter & Gamble Company | Control of calcium carbonate precipitation in automatic dishwashing |
| CA2175329C (en) * | 1993-11-03 | 2000-01-18 | Eugene Steven Sadlowski | Control of calcium carbonate precipitation in automatic dishwashing |
| AU4984996A (en) * | 1995-03-11 | 1996-10-02 | Procter & Gamble Company, The | Detergent composition comprising a polymeric polycarboxylic compound, a chelant, and an amylase enzyme |
| JP3566015B2 (en) * | 1997-02-17 | 2004-09-15 | 花王株式会社 | Detergent composition for dishwashers |
| EP2117993A4 (en) * | 2007-02-01 | 2012-06-06 | Diversey Inc | Detergent dispenser assembly and method, flowable detergent powders, and methods for making and using the same |
| KR20100014954A (en) | 2007-03-09 | 2010-02-11 | 다니스코 유에스 인크. | Alkaliphilic bacillus species a-amylase variants, compositions comprising a-amylase variants, and methods of use |
| JP5599113B2 (en) | 2008-06-06 | 2014-10-01 | ダニスコ・ユーエス・インク | Saccharification enzyme composition and saccharification method thereof |
| JP2011522546A (en) | 2008-06-06 | 2011-08-04 | ダニスコ・ユーエス・インク | Mutant alpha amylase from Bacillus subtilis and methods of use thereof |
| EP2698434A1 (en) | 2008-06-06 | 2014-02-19 | Danisco US Inc. | Uses of an alpha-amylase from Bacillus subtilis |
| CN102224234B (en) | 2008-09-25 | 2014-04-16 | 丹尼斯科美国公司 | Alpha-amylase blends and methods for using said blends |
| BR112012009659A2 (en) | 2009-10-23 | 2015-09-15 | Danisco Us Inc | methods for reducing blue saccharide. |
| EP3956426A1 (en) * | 2019-04-19 | 2022-02-23 | One Home Brands, Inc. | Stable anhydrous dish soap and method of making same |
| DE102022131906A1 (en) | 2022-12-01 | 2024-06-06 | Henkel Ag & Co. Kgaa | Dishwasher cleaner with improved grease removal and additional limescale removal |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01146998A (en) * | 1987-12-04 | 1989-06-08 | Matsushita Electric Ind Co Ltd | Detergent for dishwasher |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4212761A (en) * | 1978-03-06 | 1980-07-15 | Novo Laboratories, Inc. | Method and composition for cleaning dairy equipment |
| JPS5823899A (en) * | 1981-08-03 | 1983-02-12 | 第一工業製薬株式会社 | Soap-blended automatic dishwashing detergent |
| SU1346668A1 (en) * | 1985-07-10 | 1987-10-23 | Завод "Химик" | Method of producing detergent for washing foodware |
-
1990
- 1990-08-17 CA CA002023529A patent/CA2023529A1/en not_active Abandoned
- 1990-08-20 AT AT90115943T patent/ATE161036T1/en not_active IP Right Cessation
- 1990-08-20 PL PL28656190A patent/PL286561A1/en unknown
- 1990-08-20 ES ES90115943T patent/ES2112247T3/en not_active Expired - Lifetime
- 1990-08-20 DE DE59010780T patent/DE59010780D1/en not_active Revoked
- 1990-08-20 EP EP90115943A patent/EP0414197B1/en not_active Revoked
- 1990-08-20 AU AU61131/90A patent/AU6113190A/en not_active Abandoned
- 1990-08-20 DK DK90115943.4T patent/DK0414197T3/en active
- 1990-08-21 JP JP2218270A patent/JPH03163199A/en active Pending
- 1990-08-21 NO NO90903682A patent/NO903682L/en unknown
- 1990-08-21 PT PT95049A patent/PT95049A/en not_active Application Discontinuation
- 1990-08-22 FI FI904155A patent/FI904155A0/en not_active Application Discontinuation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01146998A (en) * | 1987-12-04 | 1989-06-08 | Matsushita Electric Ind Co Ltd | Detergent for dishwasher |
Non-Patent Citations (1)
| Title |
|---|
| Nr. 169704s, Columbus, Ohio, US; & SU - A - 1346668 (V.A. BANOV et al.) 23.10. 1987 * |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE161036T1 (en) | 1997-12-15 |
| JPH03163199A (en) | 1991-07-15 |
| EP0414197A3 (en) | 1992-03-04 |
| CA2023529A1 (en) | 1991-02-23 |
| FI904155A0 (en) | 1990-08-22 |
| AU6113190A (en) | 1991-02-28 |
| NO903682D0 (en) | 1990-08-21 |
| EP0414197A2 (en) | 1991-02-27 |
| PT95049A (en) | 1991-04-18 |
| ES2112247T3 (en) | 1998-04-01 |
| PL286561A1 (en) | 1991-05-20 |
| DK0414197T3 (en) | 1998-02-02 |
| DE59010780D1 (en) | 1998-01-22 |
| NO903682L (en) | 1991-02-25 |
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