CA2023529A1 - Dish-washer detergent composition - Google Patents
Dish-washer detergent compositionInfo
- Publication number
- CA2023529A1 CA2023529A1 CA002023529A CA2023529A CA2023529A1 CA 2023529 A1 CA2023529 A1 CA 2023529A1 CA 002023529 A CA002023529 A CA 002023529A CA 2023529 A CA2023529 A CA 2023529A CA 2023529 A1 CA2023529 A1 CA 2023529A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- sodium
- dish
- detergent composition
- carbonate
- 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.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 85
- 239000003599 detergent Substances 0.000 title claims abstract description 59
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 98
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 84
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 49
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 42
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 42
- 238000004851 dishwashing Methods 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 239000007844 bleaching agent Substances 0.000 claims abstract description 8
- 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
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 20
- 229910019142 PO4 Inorganic materials 0.000 claims description 16
- 235000021317 phosphate Nutrition 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 12
- 239000010452 phosphate Substances 0.000 claims description 12
- 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
- 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
- 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
- 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
- 239000000243 solution Substances 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
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 4
- 239000003795 chemical substances by application Substances 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
- 239000002480 mineral oil Substances 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 235000019421 lipase Nutrition 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 24
- 229940001593 sodium carbonate Drugs 0.000 description 24
- 238000009472 formulation Methods 0.000 description 16
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 10
- 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 9
- 239000004115 Sodium Silicate Substances 0.000 description 9
- 229940088598 enzyme Drugs 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 229910052911 sodium silicate Inorganic materials 0.000 description 9
- 235000019795 sodium metasilicate Nutrition 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920002125 Sokalan® Polymers 0.000 description 4
- 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 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
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000306 component Substances 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- 239000004094 surface-active agent Substances 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- 235000009337 Spinacia oleracea Nutrition 0.000 description 2
- 239000001083 [(2R,3R,4S,5R)-1,2,4,5-tetraacetyloxy-6-oxohexan-3-yl] acetate Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004061 bleaching Methods 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
- 239000003112 inhibitor Substances 0.000 description 2
- 235000013372 meat Nutrition 0.000 description 2
- 108010020132 microbial serine proteinases Proteins 0.000 description 2
- 229960001922 sodium perborate Drugs 0.000 description 2
- 239000001488 sodium phosphate Substances 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
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 2
- 235000019801 trisodium phosphate Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 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
- 102000035195 Peptidases Human genes 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 101000983338 Solanum commersonii Osmotin-like protein OSML15 Proteins 0.000 description 1
- 241000219315 Spinacia Species 0.000 description 1
- 244000300264 Spinacia oleracea Species 0.000 description 1
- 244000269722 Thea sinensis Species 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
- 239000012190 activator Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229940025131 amylases Drugs 0.000 description 1
- 239000012752 auxiliary agent Substances 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
- JHUXOSATQXGREM-UHFFFAOYSA-N dodecanediperoxoic acid Chemical compound OOC(=O)CCCCCCCCCCC(=O)OO JHUXOSATQXGREM-UHFFFAOYSA-N 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
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000013020 final formulation Substances 0.000 description 1
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 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
- 239000000463 material 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
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 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
- -1 peroxy compound Chemical class 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 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
- 239000012418 sodium perborate tetrahydrate 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
- KWXLCDNSEHTOCB-UHFFFAOYSA-J tetrasodium;1,1-diphosphonatoethanol Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P(=O)([O-])C(O)(C)P([O-])([O-])=O KWXLCDNSEHTOCB-UHFFFAOYSA-J 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
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
Landscapes
- Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Washing And Drying Of Tableware (AREA)
- Bidet-Like Cleaning Device And Other Flush Toilet Accessories (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Catalysts (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Abstract The invention relates to a slightly alkaline machine dish-washing detergent composition which a) 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 and d) has a slightly alkaline pH value of less than 10.5 in 1% aqueous solution.
Description
2~23529 A Dish-Washer Detergent Composition The present invention relates to a machine dish-washing detergent composition.
Conventional dish-washer detergent compositions are substantially based on sodium tripolyphosphate, sodium metasilicate and sodium carbonate and are strongly alkaline. The pH value of these products is in general near 12 (in 1% solution) and is substantially attribut-able to the high content of sodium metasilicate and sodium carbonate. Irritations or acid burns of the skin and the mucous membranes, in particular if swallowed (infants) may occur at these pH values and, due to this, these products have increasingly become a subject of public controversy. Therefore there is a need of dish-washer detergents which are less alkaline. How-ever, a reduction of the dish washing performance was expected in the case of a reduction of alkalinity.
-:
Thus, the invention is based on the object to develop a dish-washer detergent which has a lower pH value than 2023~2~
conventional dish-washer detergents, and in particular a pH value of less than 10.5 (in 1% aqueous solution), but has nevertheless a good cleaning performance and is composed of components which do not pollute the en-vironment or pollute it only to the smallest possible degree.
A dish-washer detergent is known from EP-A 135 227 which is only slightly alkaline and has a pH value of about 9.3 to 10.8 (in 0.3% aqueous solution) and contains 25 to 50% by weight of sodium triphosphate, 7.5 to 40% by weight of sodium carbonate, 2 to 15% by weight of sodium silicate and a peroxy compound and an enzyme. It is found that the effectiveness and stabili-ty of such a slightly alkaline, enzymatic composition is a matter of the selection of the components in the right amount.
It was found according to the present invention that sodium metasilicate can be completely renounced in an effective dish-washer detergent, if, instead of it, a mixture of sodium carbonate and sodium hydrogen car-bonate is used. This mixture offers the possibility of varying the pH value of the final formulation in a greater pH range, the high alkalinity reserve being preserved. This high alkalinity reserve, on the other hand, allows the keeping of the enzyme content and the builder content of the formulation at a very low level.
It is even possible according to the invention to completely renounce phosphate builders.
In general, the dish-washer detergent compositions according to tne present invention comprise 20 to 80%
by weight, preferably 30 to 70% by weight and, in particular 45 to 55% by weight of sodium carbonate and . . . .
;~, ,, . , , ' . .
2~23~29 5 to 50% by weight, preferably 10 to 40% by weight and, in particular 15 to 36% by weight of sodium hydrogen carbonate (= sodium bicarbonate).
The US-PS 4 306 987 discloses strongly alkaline dish-washer detergents with special, low-foaming, non-ionic detergents. These known dish-washer detergents contain in general 20 to 80~ by weight of an alkaline detergent salt such as sodium carbonate, sodium hydrogen carbonate and mixtures thereof, di- and trisodium orthophosphate, sodium metasilicate, sodium sesquisilicate, borax and sodium borate and, as bleaching agent, 5 to 50% by weight, of hlorinated trisodium phosphate or, instead of this, a mixture of lithium hypochlorite or chlorinated cyanuric acid and trisodium phosphate.
Sodium silicate accounts in general for 20 to 80%, preferably 20 to 40%, in these known dish-washer detergents.
In its most general form the invention relates to a detergent composition for dish-washing machines, said composition containing at least 25% by weight of a combination of sodium carbonate and sodium hydrogen carbonate, said composition being free from metasilicates and chlorine bleaching agents and said composition having a slightly alkaline pH value of less than 10.5 in 1% aqueous solution.
The pH value of the dish-washer detergent compositions according to the invention is in general in the range of 9.0 to 10.5 or even less, preferably in the range of 9.9 to 10.4.
~.~.,.. :~.. : - , :
;::
2023~2~
In the combination of sodium carbonate and sodium hydrogen carbonate employed in this invention the ratio of sodium carbonate to sodium hydrogen carbonate in general is within the range of 4:1 up to 1:1, pre-ferably 3:1 up to 1:1.
Preferred dish-washing detergent compositions with a pH
value of 9.0 to 10.5, preferably 9.9 to 10.4, contain 20 to 80% by weight of sodium carbonate and 5 to 50% by weight of sodium hydrogen carbonate, the combination of sodium carbonate and sodium hydrogen carbonate account~
ing for at least 30% by weight of the total composi-tion.
The dish-washing detergent compositions accordin~ to the invention may contain a phosphate, conventionally sodium tripolyphosphate as a builder. A suited phos-phate-containing dish-washing detergent composition 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 hydroge~ carbonate being 30 to 70% by weight, and 10 to 40% by weight, pre-ferably 20 to 35% by weight, of phosphate, in par-ticular sodium tripolyphosphate.
However, dish-washer detergent compositions are espe-cially preferred which are free from phosphates.
Phosphate-free builder systems may be used instead of the phosphates, which wholly or partly replace the phosphate. Different systems have become known for this purpose. A copolymer of acrylic acid and maleic acid (e.g. the product Sokalan CP 5 ex BA5F) or a poly-acrylic acid (e.g. Acrysol LMW 45 ND ex Rhom ~ Haas) has proved to be specially suited for the purposes of the present invention; which possibly can be used .. ,~., :. i . . ~ . ~ , ,X
;~, 2023~29 together with small amounts of a phosphonic acid ~e.g.
l-hydroxy ethane-l,l-diphosponic acid/HEDP/). The ;
polymer serving as a phosphate substitute may 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 to 10, preferably 2 to 4% by weight. A phosphate-free builder system may also contain a small amount of low-molecular polymers on the basis of maleic acid or acrylic acid, e.g. Sokalan PM10 ex BASF or Sokalan PA15 ex BASF instead of small amounts of a phosphonic acid.
-:
The phosphate-free builder system may also contain nitrilo-triacetic acid instead of phosphonic acids and low-molecular polymers.
A suited phosphate-free dish-washer detergent composi-tion 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 car-bonate being 35 to 75% by weight, and 3 to 10~ by weight of a phosphate-free polymer builder.
The dish-washer detergent compositions according to the invention are preferably free from silicates. However, it became apparent that a small amount of disilicates or layer silicates as corrosion inhibitors may be advantageous. If such silicates are used as corrosion inhibitors, their amount shouid not exceed 15% by weight of the entire composition, their share being in general 5 to 10% by weight.
The dish-washer detergent compositions according to the invention contain preferably enzymes, which are, however, already effective in very small amounts in the compositions according to the invention.
2023~29 Proteases (e.g. the product Savinase 4.0 T ex Novo) and amylases ~e.g. the product Termamyl 60 T ex Novo) are preferably used, however, lipases may also be advan-tageous for specific soilings, in particular at low dish-washing temperatures.
The enzymes are in general used in amounts of 0 to 3%
by weight, preferably 0.4 to 1% by weight.
Chlorine bleaching agents such as sodium dichloroiso-cyanurate are avoided according to the invention, so that an impairment of enzyme stability and activity due to this is ruled out and any possible formation of chlorinated organic compounds as a result of such chlorine bleaching agents is avoided. Instead of this, oxygen bleaching agents can bc advantageousl~ used such as sodium perborate monohydrate, sodium perborate tetrahydrate, potassium monopersulphate, magnesium monoperoxyphthalate hexahydrate (H48), diperoxydode-canedioic acid (phlegmatized) and sodium percarbonate.
The dish-washer detergents according to the invention contain suitably 3 to 15~ by weight, preferably 3 to 10% by weight, and in particular 5 to 8% by weight, of sodium perborate monohydrate or sodium percarbonate.
For optiming the bleaching performance in particular at low temperatures a bleaching activator such as TAED (tetraacetyl ethylene diamine), TAGU (tetraacetyl glycoluril), GPA (glucose pentaacetate) and many more can be in-cluded in the formulation.
The compositions according to the invention may contain small amounts of a tenside, preferably a non-ionic tenside, r.amely suitably in an amount of up to 5% by weight, preferably up to 3% and in particular up to 1%
2023~29 by weight. In general, amounts of ranging from 0.2 to 2% by weight of a non-ionic tenside are fully suf-ficient. The used tensides must be low-foaming, there-fore non-ionic tensides are best suited. Low-foaming, non-ionic tensides with good biological degradability are used. They are e.g. adducts of ethylene oxide and propylene oxide or ethylene oxide and higher alkylene oxides on native or synthetic fatty alcohols or oxo ~ -alcohols. Corresponding adducts which are terminal-group-closed are also well suited.
The dish-washer detergent composition according to the invention may still contain further customary com-ponents such as dyes, perfumed oils or other auxiliary agents such as stabilizers for enzymes.
The effect of a reduced inflow capacity which can above all be observed in formulations containing a great amount of sodium carbonate/sodium bicarbonate can be overcome by the use of fatty acids and/or hydrocarbons (white mineral oils) (anticaking agent).
Among the fatty acids those with hydrocarbon chains from C12-C18 proved to be suited-Among the hydrocarbons mixtures of saturated, straight-chain and cyclic hydrocarbons with a flash point above 150C proved to be suited.
The fatty acids or hydrocarbons are used in amounts of 0 to 3% by weight, preferably 0.5 to 2% by weight, and in particular 0.7 to 1.5% by weight, based on the entire composition.
-,,~,`r 20~3~2~
Sodium sulphate also proved suited as anticaking agent and can be used instead of the white mineral oils.
Sodium sulphate is moreover suited as diluent. If the alkalinity of the formulation should be reduced, part of the amount of sodium carbonate and sodil~n hydrogen carbonate may be replaced by sodium sulphate, whereby, however, the minimum content of at least 25% by weight, preferably at least 30% by weight of the sodium car-bonate/sodium hydrogen carbonate combination must be maintained. The dishwasher detergents according to the invention may consequently contain 0 to 35% by weight of sodium sulphate.
A suited phosphate-containing composition according to the invention 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 mono-hydrate 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 part of the sodium carbonate/sodium hydrogen carbonate being replaceable by 0 to 20% by weight of sodium sulphate and has a pH value (in 1% solution J of 10.2 to 10.4.
An especially suited phosphate-free composition accord-ing to the invention 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 .
i ... . .. . . .
,~
2023~2~
g ::.
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 it being possible that part of the amount of sodium carbonate/ sodium hydroqen carbonate is replaced by 0 to 35% by weight of sodium sulphate, and has a pH value (in 1% solution) of 10.2 to 10.4.
Contrary to all expectations, the cleaning performance of the dish-washer detergent according to the invention is comparable to conventional, strongly alkaline dish-washer detergents on the basis of sodium meta-silicate. The formulations according to the invention are even superior in the case of special soilings such as oat flakes.
The results of corrosion tests with glass, porcelain and parts of cutlery were furthermore surprisingly positive. The attack is, however, extremely low instead of an increased glass corrosion which was expected due to the use of sodium carbonate instead of sodium silicate. The same applies in comparison to metasili-cate-containing usual commercially available deter- ~
gents. ;-. ~ .
' A further advantage of the compositions according to the invention is that due to the used small amounts of enzyme and phosphate, the costs of raw material of the formulations according to the invention are much lower than that of comparable known formulations.
-, -~, .
The dish-washer detergents according to the invention are in general formulated as dry powder or granular ~-.
2023~2~
:: - 10 - , material in custpmary fashion. Their use in the form of tablets, pouches, single-portion package units, but also in the form of liquid concentrates is, however, not excluded.
The invention is expained in more detail by means of the following examples.
Example 1 A dish-washer detergent of the following composition was formulated by dry mixing or granulating Sodium tripolyphosphate24.0% by weight Sodium carbonate49.0% by weight Sodium hydrogen carbonate18.0% by weight Sodium perborate monohydrate 7.0% by weight - .
Protease 0.5% by weight Amylase 0.5% by weight Non-ionic tenside1.0% by weight (Lutensol LF403) This composition had a pH value (in 1% aqueous solution~ of 10.3.
Example 2 .:
A dish-washer detergent of the following composition was formulated by dry mixing or granulating Sodium carbonate49.0% by weight Sodium hydrogen carbonate34.5% by weight Sodium perborate monohydrate 7.0% by weight Protease 0.5% by weight Amylase 0.5% by weight . .
2023~2~ :
Non-ionic tenside (Lutensol LF403) 1.0% by weight Copolymer of acrylic acid and maleic acid 5.0~ by weight Phosphonic acid 2.5% by weight This composition had a pH value (in 1% aqueous solution~
of lO.o Example 3 Sodium carbonate50.0% by weight Sodium hydrogen carbonate33.0% by weight Sodium perborate monohydrate6.0% by weight TAED 1.5~ by weight :~
Copolymer of acrylic acid and maleic acid 5.0% by weight Phosphonic acid (HEDP)2.5% by weight Fatty acid (C12-C18)1.0% by weight Protease 0.5% by weight Amylase 0.5% by weight :
This composition had a pH value (in 1% aqueous solu-tion) of 10.1.
ComParative tests :
The formulations according to the invention of examples 1 and 2 were compared with a formulation (formulation I) containing sodium metasilicate as regards their cleaning performance. The testing was carried out in accordance with the DIN 44990 regulation with the only difference that the evaluation of the cleaning perform~
ance for spinach, minced meat, oat flakes and tea was percentally weighted . ~ : :
~ . , ' ' ' .' ' ~'' ', ' ' ' . ' '"', .' , ' ' ' 2023~2~
The comparative for~mulation I had the following composition:
Sodium tripolyphosphate36.1% by weight Sodium metasilicate51~0% by weight Sodium caxbonate 9.65% by weight Sodium dichloroisocyanurate 2.25% by weight Tenside (Dehypon LT104)1.0% by weight For the further comparison a formulation according to EP-A 135 227 was tested as formulation II, which had the following composition:
Formulation: 45% of sodium tripolyphosphate, 15% of sodium carbonate, 10% of sodium perborate *4H20, 4%
TAED, 3% of Thermamyl 60T, 2% of Savinase 4.OT, 0.7 of Dequest 2016, 5% of sodium disilicate, 10% of sodium sulphate, 1.5% of Lutensol LF 403, water ad 100%.
The results of the comparative tests are summarized in the following table I.
The comparative tests show that the formulations according to the invention result in a comparable cleaning performance despite the lower alkalinity as compared with formulation I and despite the lower amount of enzyme and the lower amount of phosphate as compared with the formulation II.
jv~'' . ~ . :.
Table I
Soiling Comparison Comparison Ex.1 Ex.2 Ex.1, however form. I form. II without enzymes Water hardness 4d 20 d 20d 4d 20d 4d 20d 20d Egg yolk 4.95.0 5.0 4.94.9 5.05.0 4.9 Spinach 4.43.6 4.4 4.33.2 3.83.7 3.5 Minced meat 5.04.9 5.0 5.05.0 4.94.9 3.1 Oat flakes 4.24.1 4.5 4.84.5 4.74.4 4.0 ~-Tea 5.04.9 5.0 5.04.6 4.53.0 4.4 Marga- ~-rine 5.05.0 5.0 5.05.0 5.04.6 5.0 Milk 3.83.2 2.4 3.74.2 4.03.9 3.4 ~ .:
Total 4.64.5 4.6 4.84.6 4.64.3 4.3 A,'
Conventional dish-washer detergent compositions are substantially based on sodium tripolyphosphate, sodium metasilicate and sodium carbonate and are strongly alkaline. The pH value of these products is in general near 12 (in 1% solution) and is substantially attribut-able to the high content of sodium metasilicate and sodium carbonate. Irritations or acid burns of the skin and the mucous membranes, in particular if swallowed (infants) may occur at these pH values and, due to this, these products have increasingly become a subject of public controversy. Therefore there is a need of dish-washer detergents which are less alkaline. How-ever, a reduction of the dish washing performance was expected in the case of a reduction of alkalinity.
-:
Thus, the invention is based on the object to develop a dish-washer detergent which has a lower pH value than 2023~2~
conventional dish-washer detergents, and in particular a pH value of less than 10.5 (in 1% aqueous solution), but has nevertheless a good cleaning performance and is composed of components which do not pollute the en-vironment or pollute it only to the smallest possible degree.
A dish-washer detergent is known from EP-A 135 227 which is only slightly alkaline and has a pH value of about 9.3 to 10.8 (in 0.3% aqueous solution) and contains 25 to 50% by weight of sodium triphosphate, 7.5 to 40% by weight of sodium carbonate, 2 to 15% by weight of sodium silicate and a peroxy compound and an enzyme. It is found that the effectiveness and stabili-ty of such a slightly alkaline, enzymatic composition is a matter of the selection of the components in the right amount.
It was found according to the present invention that sodium metasilicate can be completely renounced in an effective dish-washer detergent, if, instead of it, a mixture of sodium carbonate and sodium hydrogen car-bonate is used. This mixture offers the possibility of varying the pH value of the final formulation in a greater pH range, the high alkalinity reserve being preserved. This high alkalinity reserve, on the other hand, allows the keeping of the enzyme content and the builder content of the formulation at a very low level.
It is even possible according to the invention to completely renounce phosphate builders.
In general, the dish-washer detergent compositions according to tne present invention comprise 20 to 80%
by weight, preferably 30 to 70% by weight and, in particular 45 to 55% by weight of sodium carbonate and . . . .
;~, ,, . , , ' . .
2~23~29 5 to 50% by weight, preferably 10 to 40% by weight and, in particular 15 to 36% by weight of sodium hydrogen carbonate (= sodium bicarbonate).
The US-PS 4 306 987 discloses strongly alkaline dish-washer detergents with special, low-foaming, non-ionic detergents. These known dish-washer detergents contain in general 20 to 80~ by weight of an alkaline detergent salt such as sodium carbonate, sodium hydrogen carbonate and mixtures thereof, di- and trisodium orthophosphate, sodium metasilicate, sodium sesquisilicate, borax and sodium borate and, as bleaching agent, 5 to 50% by weight, of hlorinated trisodium phosphate or, instead of this, a mixture of lithium hypochlorite or chlorinated cyanuric acid and trisodium phosphate.
Sodium silicate accounts in general for 20 to 80%, preferably 20 to 40%, in these known dish-washer detergents.
In its most general form the invention relates to a detergent composition for dish-washing machines, said composition containing at least 25% by weight of a combination of sodium carbonate and sodium hydrogen carbonate, said composition being free from metasilicates and chlorine bleaching agents and said composition having a slightly alkaline pH value of less than 10.5 in 1% aqueous solution.
The pH value of the dish-washer detergent compositions according to the invention is in general in the range of 9.0 to 10.5 or even less, preferably in the range of 9.9 to 10.4.
~.~.,.. :~.. : - , :
;::
2023~2~
In the combination of sodium carbonate and sodium hydrogen carbonate employed in this invention the ratio of sodium carbonate to sodium hydrogen carbonate in general is within the range of 4:1 up to 1:1, pre-ferably 3:1 up to 1:1.
Preferred dish-washing detergent compositions with a pH
value of 9.0 to 10.5, preferably 9.9 to 10.4, contain 20 to 80% by weight of sodium carbonate and 5 to 50% by weight of sodium hydrogen carbonate, the combination of sodium carbonate and sodium hydrogen carbonate account~
ing for at least 30% by weight of the total composi-tion.
The dish-washing detergent compositions accordin~ to the invention may contain a phosphate, conventionally sodium tripolyphosphate as a builder. A suited phos-phate-containing dish-washing detergent composition 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 hydroge~ carbonate being 30 to 70% by weight, and 10 to 40% by weight, pre-ferably 20 to 35% by weight, of phosphate, in par-ticular sodium tripolyphosphate.
However, dish-washer detergent compositions are espe-cially preferred which are free from phosphates.
Phosphate-free builder systems may be used instead of the phosphates, which wholly or partly replace the phosphate. Different systems have become known for this purpose. A copolymer of acrylic acid and maleic acid (e.g. the product Sokalan CP 5 ex BA5F) or a poly-acrylic acid (e.g. Acrysol LMW 45 ND ex Rhom ~ Haas) has proved to be specially suited for the purposes of the present invention; which possibly can be used .. ,~., :. i . . ~ . ~ , ,X
;~, 2023~29 together with small amounts of a phosphonic acid ~e.g.
l-hydroxy ethane-l,l-diphosponic acid/HEDP/). The ;
polymer serving as a phosphate substitute may 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 to 10, preferably 2 to 4% by weight. A phosphate-free builder system may also contain a small amount of low-molecular polymers on the basis of maleic acid or acrylic acid, e.g. Sokalan PM10 ex BASF or Sokalan PA15 ex BASF instead of small amounts of a phosphonic acid.
-:
The phosphate-free builder system may also contain nitrilo-triacetic acid instead of phosphonic acids and low-molecular polymers.
A suited phosphate-free dish-washer detergent composi-tion 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 car-bonate being 35 to 75% by weight, and 3 to 10~ by weight of a phosphate-free polymer builder.
The dish-washer detergent compositions according to the invention are preferably free from silicates. However, it became apparent that a small amount of disilicates or layer silicates as corrosion inhibitors may be advantageous. If such silicates are used as corrosion inhibitors, their amount shouid not exceed 15% by weight of the entire composition, their share being in general 5 to 10% by weight.
The dish-washer detergent compositions according to the invention contain preferably enzymes, which are, however, already effective in very small amounts in the compositions according to the invention.
2023~29 Proteases (e.g. the product Savinase 4.0 T ex Novo) and amylases ~e.g. the product Termamyl 60 T ex Novo) are preferably used, however, lipases may also be advan-tageous for specific soilings, in particular at low dish-washing temperatures.
The enzymes are in general used in amounts of 0 to 3%
by weight, preferably 0.4 to 1% by weight.
Chlorine bleaching agents such as sodium dichloroiso-cyanurate are avoided according to the invention, so that an impairment of enzyme stability and activity due to this is ruled out and any possible formation of chlorinated organic compounds as a result of such chlorine bleaching agents is avoided. Instead of this, oxygen bleaching agents can bc advantageousl~ used such as sodium perborate monohydrate, sodium perborate tetrahydrate, potassium monopersulphate, magnesium monoperoxyphthalate hexahydrate (H48), diperoxydode-canedioic acid (phlegmatized) and sodium percarbonate.
The dish-washer detergents according to the invention contain suitably 3 to 15~ by weight, preferably 3 to 10% by weight, and in particular 5 to 8% by weight, of sodium perborate monohydrate or sodium percarbonate.
For optiming the bleaching performance in particular at low temperatures a bleaching activator such as TAED (tetraacetyl ethylene diamine), TAGU (tetraacetyl glycoluril), GPA (glucose pentaacetate) and many more can be in-cluded in the formulation.
The compositions according to the invention may contain small amounts of a tenside, preferably a non-ionic tenside, r.amely suitably in an amount of up to 5% by weight, preferably up to 3% and in particular up to 1%
2023~29 by weight. In general, amounts of ranging from 0.2 to 2% by weight of a non-ionic tenside are fully suf-ficient. The used tensides must be low-foaming, there-fore non-ionic tensides are best suited. Low-foaming, non-ionic tensides with good biological degradability are used. They are e.g. adducts of ethylene oxide and propylene oxide or ethylene oxide and higher alkylene oxides on native or synthetic fatty alcohols or oxo ~ -alcohols. Corresponding adducts which are terminal-group-closed are also well suited.
The dish-washer detergent composition according to the invention may still contain further customary com-ponents such as dyes, perfumed oils or other auxiliary agents such as stabilizers for enzymes.
The effect of a reduced inflow capacity which can above all be observed in formulations containing a great amount of sodium carbonate/sodium bicarbonate can be overcome by the use of fatty acids and/or hydrocarbons (white mineral oils) (anticaking agent).
Among the fatty acids those with hydrocarbon chains from C12-C18 proved to be suited-Among the hydrocarbons mixtures of saturated, straight-chain and cyclic hydrocarbons with a flash point above 150C proved to be suited.
The fatty acids or hydrocarbons are used in amounts of 0 to 3% by weight, preferably 0.5 to 2% by weight, and in particular 0.7 to 1.5% by weight, based on the entire composition.
-,,~,`r 20~3~2~
Sodium sulphate also proved suited as anticaking agent and can be used instead of the white mineral oils.
Sodium sulphate is moreover suited as diluent. If the alkalinity of the formulation should be reduced, part of the amount of sodium carbonate and sodil~n hydrogen carbonate may be replaced by sodium sulphate, whereby, however, the minimum content of at least 25% by weight, preferably at least 30% by weight of the sodium car-bonate/sodium hydrogen carbonate combination must be maintained. The dishwasher detergents according to the invention may consequently contain 0 to 35% by weight of sodium sulphate.
A suited phosphate-containing composition according to the invention 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 mono-hydrate 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 part of the sodium carbonate/sodium hydrogen carbonate being replaceable by 0 to 20% by weight of sodium sulphate and has a pH value (in 1% solution J of 10.2 to 10.4.
An especially suited phosphate-free composition accord-ing to the invention 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 .
i ... . .. . . .
,~
2023~2~
g ::.
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 it being possible that part of the amount of sodium carbonate/ sodium hydroqen carbonate is replaced by 0 to 35% by weight of sodium sulphate, and has a pH value (in 1% solution) of 10.2 to 10.4.
Contrary to all expectations, the cleaning performance of the dish-washer detergent according to the invention is comparable to conventional, strongly alkaline dish-washer detergents on the basis of sodium meta-silicate. The formulations according to the invention are even superior in the case of special soilings such as oat flakes.
The results of corrosion tests with glass, porcelain and parts of cutlery were furthermore surprisingly positive. The attack is, however, extremely low instead of an increased glass corrosion which was expected due to the use of sodium carbonate instead of sodium silicate. The same applies in comparison to metasili-cate-containing usual commercially available deter- ~
gents. ;-. ~ .
' A further advantage of the compositions according to the invention is that due to the used small amounts of enzyme and phosphate, the costs of raw material of the formulations according to the invention are much lower than that of comparable known formulations.
-, -~, .
The dish-washer detergents according to the invention are in general formulated as dry powder or granular ~-.
2023~2~
:: - 10 - , material in custpmary fashion. Their use in the form of tablets, pouches, single-portion package units, but also in the form of liquid concentrates is, however, not excluded.
The invention is expained in more detail by means of the following examples.
Example 1 A dish-washer detergent of the following composition was formulated by dry mixing or granulating Sodium tripolyphosphate24.0% by weight Sodium carbonate49.0% by weight Sodium hydrogen carbonate18.0% by weight Sodium perborate monohydrate 7.0% by weight - .
Protease 0.5% by weight Amylase 0.5% by weight Non-ionic tenside1.0% by weight (Lutensol LF403) This composition had a pH value (in 1% aqueous solution~ of 10.3.
Example 2 .:
A dish-washer detergent of the following composition was formulated by dry mixing or granulating Sodium carbonate49.0% by weight Sodium hydrogen carbonate34.5% by weight Sodium perborate monohydrate 7.0% by weight Protease 0.5% by weight Amylase 0.5% by weight . .
2023~2~ :
Non-ionic tenside (Lutensol LF403) 1.0% by weight Copolymer of acrylic acid and maleic acid 5.0~ by weight Phosphonic acid 2.5% by weight This composition had a pH value (in 1% aqueous solution~
of lO.o Example 3 Sodium carbonate50.0% by weight Sodium hydrogen carbonate33.0% by weight Sodium perborate monohydrate6.0% by weight TAED 1.5~ by weight :~
Copolymer of acrylic acid and maleic acid 5.0% by weight Phosphonic acid (HEDP)2.5% by weight Fatty acid (C12-C18)1.0% by weight Protease 0.5% by weight Amylase 0.5% by weight :
This composition had a pH value (in 1% aqueous solu-tion) of 10.1.
ComParative tests :
The formulations according to the invention of examples 1 and 2 were compared with a formulation (formulation I) containing sodium metasilicate as regards their cleaning performance. The testing was carried out in accordance with the DIN 44990 regulation with the only difference that the evaluation of the cleaning perform~
ance for spinach, minced meat, oat flakes and tea was percentally weighted . ~ : :
~ . , ' ' ' .' ' ~'' ', ' ' ' . ' '"', .' , ' ' ' 2023~2~
The comparative for~mulation I had the following composition:
Sodium tripolyphosphate36.1% by weight Sodium metasilicate51~0% by weight Sodium caxbonate 9.65% by weight Sodium dichloroisocyanurate 2.25% by weight Tenside (Dehypon LT104)1.0% by weight For the further comparison a formulation according to EP-A 135 227 was tested as formulation II, which had the following composition:
Formulation: 45% of sodium tripolyphosphate, 15% of sodium carbonate, 10% of sodium perborate *4H20, 4%
TAED, 3% of Thermamyl 60T, 2% of Savinase 4.OT, 0.7 of Dequest 2016, 5% of sodium disilicate, 10% of sodium sulphate, 1.5% of Lutensol LF 403, water ad 100%.
The results of the comparative tests are summarized in the following table I.
The comparative tests show that the formulations according to the invention result in a comparable cleaning performance despite the lower alkalinity as compared with formulation I and despite the lower amount of enzyme and the lower amount of phosphate as compared with the formulation II.
jv~'' . ~ . :.
Table I
Soiling Comparison Comparison Ex.1 Ex.2 Ex.1, however form. I form. II without enzymes Water hardness 4d 20 d 20d 4d 20d 4d 20d 20d Egg yolk 4.95.0 5.0 4.94.9 5.05.0 4.9 Spinach 4.43.6 4.4 4.33.2 3.83.7 3.5 Minced meat 5.04.9 5.0 5.05.0 4.94.9 3.1 Oat flakes 4.24.1 4.5 4.84.5 4.74.4 4.0 ~-Tea 5.04.9 5.0 5.04.6 4.53.0 4.4 Marga- ~-rine 5.05.0 5.0 5.05.0 5.04.6 5.0 Milk 3.83.2 2.4 3.74.2 4.03.9 3.4 ~ .:
Total 4.64.5 4.6 4.84.6 4.64.3 4.3 A,'
Claims (26)
1. A detergent composition for dish-washing machines, said composition containing at least 25% by weight of a combination of sodium carbonate and sodium hydrogen carbonate, said composition being free from metasilicates and chlorine bleaching agents and said composition having a slightly alkaline pH value of less than 10.5 in 1%
aqueous solution.
aqueous solution.
2. 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.
by weight of a combination of sodium carbonate and sodium hydrogen carbonate.
3. A dish-washer detergent composition according to claim 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.
4. A dish-washer detergent composition according to claim 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 3:1 to 1:1.
4. A dish-washer detergent composition according to claim 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 3:1 to 1:1.
5. A dish-washer detergent composition according to claim 3, characterized in that it has a pH value of 9.0 to 10.5, and contains 20 to 80% by weight of sodium carbonate and 5 to 50% by weight of sodium hydrogen carbonate.
6. A dish-washer detergent composition according to claim 4, characterized in that it has a pH value of 9.0 to 10.5, and contains 20 to 80% by weight of sodium carbonate and 5 to 50% by weight of sodium hydrogen carbonate.
7. A dish-washer detergent composition according to claim 3, characterized in that it has a pH value 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.
8. A dish-washer detergent composition according to claim 4, characterized in that it has a pH value 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.
9. A dish-washer detergent composition according to claim 1, 2 or 3, 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 a phosphate, including sodium tripolyphosphate.
10. A dish-washer detergent composition according to claim 4, 5 or 6, 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 a phosphate, including sodium tripolyphosphate.
11. A dish-washer detergent composition according to claim 7 or 8, 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 a phosphate, including sodium tripolyphosphate.
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 a phosphate, including sodium tripolyphosphate.
12. A dish-washer detergent composition according to claim 5, characterized in that it is free from phosphates.
13. A dish-washer detergent composition according to claim 6, characterized in that it is free from phosphates.
14. A dish-washer detergent composition according to claim 12 or 13, 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.
15. A dish-washer detergent composition according to claim 2, characterized in that it contains up to 15% by weight, in particular 5 to 10% by weight, of disilicate.
16. A dish-washer detergent composition according to claim 15, characterized in that it contains at least one enzyme.
17. A dish-washer detergent composition according to claim 16, characterized in that it contains a protease and/or an amylase and/or a lipase.
18. A dish-washer detergent composition according to claim 16, characterized in that it contains an oxygen bleaching agent.
19. A dish-washer detergent composition according to claim 18, characterized in that it contains 3 to 15% by weight, preferably 3 to 10% by weight, of sodium perborate monohydrate or sodium percarbonate.
20. A dish-washer detergent composition according to claim 19, characterized in that it contains o to 5% by weight, preferably o to 1% by weight, of a non-ionic tenside.
21. A dish-washer detergent composition according to claim 20, 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.
22. A dish-washer detergent composition according to claim 21, characterized in that it contains 0 to 35% by weight of sodium sulphate.
23. A dish-washer detergent composition according to claim 9, 10 or 11, 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 whereby part of the sodium carbonate/sodium hydrogen carbonate may be replaced by 0 to 20% by weight of sodium sulphate and has a pH value (in 1% solution) of 10.2 to 10.4.
24. A dish-washer detergent composition according to claim 12 or 13, 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 whereby part of the amount of sodium carbonate/sodium hydrogen carbonate may be replaced by 0 to 35% by weight of sodium sulphate, and has a pH value (in 1% solution) of 10.2 to 10.4.
25. A dish-washer detergent composition according to claim 9, 10 or 11, 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 and has a pH value (in 1% solution) of 10.2 to 10.4.
26. A dish-washer detergent composition according to claim 12 or 13, 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 and has a pH value of 9.9 to 10.2.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3927714 | 1989-08-22 | ||
| DEP3927714.3 | 1989-08-22 | ||
| DEP3939494.8 | 1989-11-29 | ||
| DE3939494 | 1989-11-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2023529A1 true CA2023529A1 (en) | 1991-02-23 |
Family
ID=25884273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002023529A Abandoned CA2023529A1 (en) | 1989-08-22 | 1990-08-17 | Dish-washer detergent composition |
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) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8323945B2 (en) | 2008-06-06 | 2012-12-04 | Danisco Us Inc. | Variant alpha-amylases from Bacillus subtilis and methods of uses, thereof |
| US9040278B2 (en) | 2008-06-06 | 2015-05-26 | Danisco Us Inc. | Production of glucose from starch using alpha-amylases from Bacillus subtilis |
| US9040279B2 (en) | 2008-06-06 | 2015-05-26 | Danisco Us Inc. | Saccharification enzyme composition and method of saccharification thereof |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK166548B1 (en) * | 1991-03-15 | 1993-06-07 | Cleantabs As | PHOSPHATE-FREE MACHINE DISHWASH |
| EP0630400A1 (en) * | 1992-03-12 | 1994-12-28 | The Procter & Gamble Company | 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 |
| CA2175331C (en) * | 1993-11-03 | 2000-02-01 | Eugene Steven Sadlowski | Control of calcium carbonate precipitation in automatic dishwashing |
| ES2120074T3 (en) * | 1993-11-03 | 1998-10-16 | Procter & Gamble | CONTROL OF THE PRECIPITATION OF CALCIUM CARBONATE IN AUTOMATIC DISHWASHERS. |
| HUP9802080A3 (en) * | 1995-03-11 | 1999-03-01 | Procter & Gamble | 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 |
| US20100006123A1 (en) * | 2007-02-01 | 2010-01-14 | Johnsondiversey, Inc. | Detergent dispenser assembly and method, flowable detergent powders, and methods for making and using the same |
| BRPI0808513A2 (en) | 2007-03-09 | 2014-08-19 | Danisco Us Inc Genencor Div | ALPHA-AMILASE VARIANTS OF ALKALIFYL BACILLUS SPECIES, COMPOSITIONS UNDERSTANDING ALPHA-AMYLASE VARIANTS AND METHODS OF USE |
| JP5419303B2 (en) | 2008-09-25 | 2014-02-19 | ダニスコ・ユーエス・インク | Alpha amylase mixture and method of using the mixture |
| CA2778471A1 (en) | 2009-10-23 | 2011-04-28 | Danisco Us Inc. | Methods for reducing blue saccharide |
| CN113874485A (en) * | 2019-04-19 | 2021-12-31 | 仅一居家品牌有限公司 | Stable waterless dishwashing soap and manufacturing method thereof |
| DE102022131906A1 (en) | 2022-12-01 | 2024-06-06 | Henkel Ag & Co. Kgaa | Dishwasher cleaner with improved grease removal and additional limescale removal |
Family Cites Families (4)
| 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 |
| JPH01146998A (en) * | 1987-12-04 | 1989-06-08 | Matsushita Electric Ind Co Ltd | Detergent for dishwasher |
-
1990
- 1990-08-17 CA CA002023529A patent/CA2023529A1/en not_active Abandoned
- 1990-08-20 AU AU61131/90A patent/AU6113190A/en not_active Abandoned
- 1990-08-20 EP EP90115943A patent/EP0414197B1/en not_active Revoked
- 1990-08-20 AT AT90115943T patent/ATE161036T1/en not_active IP Right Cessation
- 1990-08-20 DE DE59010780T patent/DE59010780D1/en not_active Revoked
- 1990-08-20 ES ES90115943T patent/ES2112247T3/en not_active Expired - Lifetime
- 1990-08-20 DK DK90115943.4T patent/DK0414197T3/en active
- 1990-08-20 PL PL28656190A patent/PL286561A1/en unknown
- 1990-08-21 NO NO90903682A patent/NO903682L/en unknown
- 1990-08-21 PT PT95049A patent/PT95049A/en not_active Application Discontinuation
- 1990-08-21 JP JP2218270A patent/JPH03163199A/en active Pending
- 1990-08-22 FI FI904155A patent/FI904155A0/en not_active Application Discontinuation
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8323945B2 (en) | 2008-06-06 | 2012-12-04 | Danisco Us Inc. | Variant alpha-amylases from Bacillus subtilis and methods of uses, thereof |
| US8975056B2 (en) | 2008-06-06 | 2015-03-10 | Danisco Us Inc. | Variant alpha-amylases from Bacillus subtilis and methods of uses, thereof |
| US9040278B2 (en) | 2008-06-06 | 2015-05-26 | Danisco Us Inc. | Production of glucose from starch using alpha-amylases from Bacillus subtilis |
| US9040279B2 (en) | 2008-06-06 | 2015-05-26 | Danisco Us Inc. | Saccharification enzyme composition and method of saccharification thereof |
| US9090887B2 (en) | 2008-06-06 | 2015-07-28 | Danisco Us Inc. | Variant alpha-amylases from Bacillus subtilis and methods of use, thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0414197B1 (en) | 1997-12-10 |
| FI904155A0 (en) | 1990-08-22 |
| DK0414197T3 (en) | 1998-02-02 |
| EP0414197A2 (en) | 1991-02-27 |
| PT95049A (en) | 1991-04-18 |
| DE59010780D1 (en) | 1998-01-22 |
| PL286561A1 (en) | 1991-05-20 |
| NO903682L (en) | 1991-02-25 |
| ATE161036T1 (en) | 1997-12-15 |
| ES2112247T3 (en) | 1998-04-01 |
| NO903682D0 (en) | 1990-08-21 |
| EP0414197A3 (en) | 1992-03-04 |
| JPH03163199A (en) | 1991-07-15 |
| AU6113190A (en) | 1991-02-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |