EP1238052A1 - Detergent compositions - Google Patents
Detergent compositionsInfo
- Publication number
- EP1238052A1 EP1238052A1 EP00983141A EP00983141A EP1238052A1 EP 1238052 A1 EP1238052 A1 EP 1238052A1 EP 00983141 A EP00983141 A EP 00983141A EP 00983141 A EP00983141 A EP 00983141A EP 1238052 A1 EP1238052 A1 EP 1238052A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- detergent
- ids
- compound
- formula
- detergent composition
- 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.)
- Granted
Links
- 239000003599 detergent Substances 0.000 title claims abstract description 89
- 239000000203 mixture Substances 0.000 title claims abstract description 66
- 239000000843 powder Substances 0.000 claims abstract description 57
- 239000011575 calcium Substances 0.000 claims abstract description 33
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 13
- 239000003352 sequestering agent Substances 0.000 claims abstract description 9
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 8
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 34
- 239000004615 ingredient Substances 0.000 claims description 17
- 229910021645 metal ion Inorganic materials 0.000 claims description 14
- 238000004061 bleaching Methods 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 239000006227 byproduct Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims 1
- 229940080260 iminodisuccinate Drugs 0.000 abstract description 68
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 abstract description 67
- 239000011777 magnesium Chemical class 0.000 abstract description 14
- 229910052749 magnesium Chemical class 0.000 abstract description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical class [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011734 sodium Substances 0.000 abstract description 6
- 229910052708 sodium Inorganic materials 0.000 abstract description 4
- JPGSFSFMINKKJZ-UHFFFAOYSA-N 2-[1,2-dicarboxyethyl(hydroxy)amino]butanedioic acid Chemical compound OC(=O)CC(C(O)=O)N(O)C(CC(O)=O)C(O)=O JPGSFSFMINKKJZ-UHFFFAOYSA-N 0.000 abstract description 3
- 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 abstract description 3
- 150000001669 calcium Chemical class 0.000 abstract description 3
- 239000007844 bleaching agent Substances 0.000 description 22
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- -1 phosphonate compound Chemical class 0.000 description 16
- 239000010457 zeolite Substances 0.000 description 16
- 229910021536 Zeolite Inorganic materials 0.000 description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 13
- 239000004744 fabric Substances 0.000 description 13
- 239000002243 precursor Substances 0.000 description 13
- 159000000000 sodium salts Chemical group 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- 230000008901 benefit Effects 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 102000035195 Peptidases Human genes 0.000 description 6
- 108091005804 Peptidases Proteins 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 102000004190 Enzymes Human genes 0.000 description 5
- 108090000790 Enzymes Proteins 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000001110 calcium chloride Substances 0.000 description 5
- 229910001628 calcium chloride Inorganic materials 0.000 description 5
- 229940088598 enzyme Drugs 0.000 description 5
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000001694 spray drying Methods 0.000 description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- 239000004365 Protease Substances 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 102000005575 Cellulases Human genes 0.000 description 3
- 108010084185 Cellulases Proteins 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 229940045872 sodium percarbonate Drugs 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 102000013142 Amylases Human genes 0.000 description 2
- 108010065511 Amylases Proteins 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 235000019418 amylase Nutrition 0.000 description 2
- 229940025131 amylases Drugs 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical compound OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000001860 citric acid derivatives Chemical class 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000004851 dishwashing Methods 0.000 description 2
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000008233 hard water Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 150000002680 magnesium Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920005646 polycarboxylate Polymers 0.000 description 2
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 229940024999 proteolytic enzymes for treatment of wounds and ulcers Drugs 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CIOXZGOUEYHNBF-UHFFFAOYSA-N (carboxymethoxy)succinic acid Chemical class OC(=O)COC(C(O)=O)CC(O)=O CIOXZGOUEYHNBF-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical class OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 description 1
- TXEODFPNVFYFIP-UHFFFAOYSA-N 3-carboxyoxy-2-methoxy-3-oxopropanoic acid Chemical class COC(C(O)=O)C(=O)OC(O)=O TXEODFPNVFYFIP-UHFFFAOYSA-N 0.000 description 1
- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 description 1
- 240000008791 Antiaris toxicaria Species 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- RKWGIWYCVPQPMF-UHFFFAOYSA-N Chloropropamide Chemical compound CCCNC(=O)NS(=O)(=O)C1=CC=C(Cl)C=C1 RKWGIWYCVPQPMF-UHFFFAOYSA-N 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical class OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 description 1
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 102000004316 Oxidoreductases Human genes 0.000 description 1
- 108090000854 Oxidoreductases Proteins 0.000 description 1
- MQNVHUZWFZKETG-UHFFFAOYSA-N P1(OCCCCCO1)=O.NCCNCCN Chemical compound P1(OCCCCCO1)=O.NCCNCCN MQNVHUZWFZKETG-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 1
- 108700020962 Peroxidase Proteins 0.000 description 1
- 102000003992 Peroxidases Human genes 0.000 description 1
- 229920005439 Perspex® Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- YIQKLZYTHXTDDT-UHFFFAOYSA-H Sirius red F3B Chemical compound C1=CC(=CC=C1N=NC2=CC(=C(C=C2)N=NC3=C(C=C4C=C(C=CC4=C3[O-])NC(=O)NC5=CC6=CC(=C(C(=C6C=C5)[O-])N=NC7=C(C=C(C=C7)N=NC8=CC=C(C=C8)S(=O)(=O)[O-])S(=O)(=O)[O-])S(=O)(=O)O)S(=O)(=O)O)S(=O)(=O)[O-])S(=O)(=O)[O-].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+] YIQKLZYTHXTDDT-UHFFFAOYSA-H 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- WKGHJBXTMFXUNA-UHFFFAOYSA-N n,n,n',n'-tetrahexadecylethane-1,2-diamine Chemical compound CCCCCCCCCCCCCCCCN(CCCCCCCCCCCCCCCC)CCN(CCCCCCCCCCCCCCCC)CCCCCCCCCCCCCCCC WKGHJBXTMFXUNA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 229940055076 parasympathomimetics choline ester Drugs 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 125000005342 perphosphate group Chemical group 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
Definitions
- the present invention relates to particulate detergent compositions containing the sequestrant, iminodisuccinate or hydroxyiminodisuccinate .
- the invention is of especially interest for detergent powders of high bulk density . (so- called "compact" powders) and to tablets of compacted detergent powder.
- the invention is especially applicable to laundry detergent powders but is also relevant to powders or tablets for mechanical dishwashing.
- Iminodisuccinate (IDS) and hydroxyiminodisuccinate (HIDS) are known as detergency builders and, in bleaching detergent compositions, as stabilisers for peroxy bleach precursors.
- US 3 697 453 discloses detergent compositions having a pH of from 9 to 12, containing iminodisuccinate as a detergency builder, used together with detergent surfactant in a weight ratio of 0.25:1 to 10:1.
- IDS as a detergency builder is also disclosed in EP 757 094A (Bayer) .
- HIDS is disclosed in US 5 318 726 (Henkel) .
- EP 509 382A (W R Grace & Co/Hampshire Chemical Corporation) discloses a bleaching detergent composition comprising a bleaching agent and a bleach stabiliser of defined formula which includes IDS.
- the use of IDS as a bleach stabiliser is also disclosed in WO 97 20907A (Procter & Gamble) .
- WO 00/34427A discloses and claims non-bleaching laundry detergent compositions containing from 0.05 to
- the compositions provides improved maintenance and/or restoration of colour fidelity during the wash, especially at low wash pH.
- the IDS or HIDS is also an effective chlorine scavenger, reducing the in-wash fading of chlorine-sensitive dyes.
- the incorporation of the IDS or HIDS improves the stain removal performance of the composition.
- IDS is commercially available in sodium salt form, eg as IDS Na-salt from Bayer.
- the sodium salt is highly water-soluble and the material is supplied as an aqueous solution (approximate IDS Na-salt content 34%) and as a solid white powder prepared from the solution by spray-drying. If IDS is to be incorporated into an aqueous liquid detergent or into a spray-dried detergent powder via the slurry, the solution form is most conveniently used. However, it is not suitable for the preparation of a powder of high bulk density by a non-tower (non-spray-drying) route because the water content is too high. For such products it is necessary to use IDS in powder form.
- the powder is extremely hygroscopic and, according to the manufacturer Bayer's recommendation, must be stored in tightly closed containers. If stored in contact with the atmosphere it rapidly takes up water and deliquesces, ie becomes a liquid. The problem is exacerbated in humid atmospheres so that any storage or handling of the material causes major problems with stickiness. When this sticky raw material is incorporated into a detergent powder, poor powder properties result .
- the resulting Ca/Na or Mg/Na salts or complexes are stable solids which are significantly less hygroscopic than the sodium salt. They can readily be incorporated into particulate detergent compositions and, surprisingly, the resulting compositions show no loss of sequestrant activity as compared with similar compositions containing the sodium salt .
- GB 2 048 930A discloses bleaching detergent compositions containing an organic phosphonate sequestrant - ethylenediamine tetramethylene phosphonate (EDTMP) or diethylenetriamine pentamethylene phosphonate (DETPMP) present as a complex of a magnesium, calcium, zinc or aluminium ion, the molar ratio of the metal ion to the phosphonate compound being at least 1:1.
- ETMP organic phosphonate sequestrant - ethylenediamine tetramethylene phosphonate
- DETPMP diethylenetriamine pentamethylene phosphonate
- JP 09 110 813A and JP 09 104 897A disclose a builder powder of reduced hygroscopicity based on IDS, in which sodium IDS is compounded with an inorganic metal salt, preferably zeolite, sodium carbonate or sodium silicate .
- JP 09 100 497A discloses high bulk density detergent powders containing IDS, prepared by granulating together detergent ingredients including an inorganic builder salt, eg zeolite, and sodium IDS or HIDS (3-20 wt% of the final composition) .
- the hygroscopicity of the IDS is exploited to bind fine zeolite particles and thereby improve flow and reduce stickiness.
- the present invention provides a particulate detergent composition containing a sequestrant which is a compound of the formula I
- COOX COOX COOX COOX COOX COOX wherein Y is H or OH, and X is a countercation, the compound being in the form of a complex of a metal ion selected from calcium and magnesium ions, the molar ratio of the metal ion to the compound of the formula I being at least 2:1.
- the invention further provides a process for the preparation of a particulate detergent composition, which includes the step of mixing and/or granulating a compound of the formula I in powder form with other detergent ingredients, wherein the compound of the formula I is in the form of a complex of a metal ion selected from calcium and magnesium ions, the molar ratio of the metal ion to the compound of the formula I being at least 2:1.
- the detergent composition of the invention contains a compound of the formula I above as an essential ingredient.
- Y is H
- the compound is IDS
- Y is OH
- the compound is HIDS.
- IDS For convenience only IDS will be discussed in the description below, but this should be understood to refer equally to HIDS.
- IDS is a pentadentate ligand ie it can form complexes with metal ions in which bonds are formed with the nitrogen atom and all four carboxyl groups. Indeed its efficacy as a detergency builder is based on its capacity to form such complexes with calcium and magnesium ions, and its efficacy as a bleach stabiliser and for colour care is based on its capacity for forming such complexes with heavy metal ions such as iron and copper.
- IDS in the form of a 2:1 or higher complex with calcium or magnesium is substantially less hygroscopic than the sodium salt .
- the calcium complexes are especially preferred, more especially complexes having a Ca : IDS molar ratio of 2:1 or above, for example, 2:1 or 3:1.
- the 1:1 complex is also less hygroscopic than the sodium salt, but the benefit is significantly greater with the higher ratio complexes.
- the 3:1 complex is especially preferred.
- the magnesium complexes are also useful but the benefit observed is less than with the calcium complexes.
- the calcium or magnesium complexes may be prepared by reacting the sodium salt, in aqueous solution, with the appropriate amount of a soluble calcium or magnesium salt, preferably calcium or magnesium chloride. The reaction also produces a soluble inorganic sodium salt (eg sodium chloride) .
- a soluble calcium or magnesium salt preferably calcium or magnesium chloride.
- the soluble inorganic sodium salt produced as a by-product of the preparation process is removed by using a filtration step.
- a filtration step where this is possible, a further significant reduction of hygroscopicity has been observed.
- solubility between the complex and the inorganic salt byproduct, which is highly soluble.
- the CalDS and CaHIDS 3:1 complexes are especially preferred in this respect because their solubility is sufficiently reduced, compared with that of the sodium salt, to allow sodium chloride to be separated by filtration during their preparation, yet is sufficiently high for these materials to be delivered effectively into the wash liquor.
- an especially preferred embodiment of the invention involves the use of a CalDS or CaHIDS 3 : 1 complex which has been prepared by a method which includes removal of any inorganic salt by-product.
- the detergent compositions of the invention contain IDS (or HIDS) as an essential ingredient. This may be present at levels sufficient for detergency building, either alone or in conjunction with another detergency builder, or at the much lower levels appropriate for bleach stabilisation, or for colour care benefits and stain removal in non-bleaching formulations as disclosed in WO 00/34427A (Unilever) .
- the amount of IDS or HIDS present in the composition may therefore range very widely, for example, from 0.05 to 80 wt%. Suitable ranges are, for example, 5 to 80 wt% if IDS is the sole or principal builder; 1 to 20 wt% if it is present as cobuilder to, for example, zeolite, phosphate or carbonate; 0.5 to 10 wt% for bleach stabilisation; 0.05 to 2.5 wt% for colour care benefits in non-bleaching formulations .
- compositions of the invention may contain other conventional detergent ingredients as detailed below.
- a composition in which IDS is present as a cobuilder or a bleach stabiliser may comprise the following:
- a non-bleaching formulation in which a low level of IDS has been included for colour care benefits may suitably comprise :
- the detergent composition of the invention is in particulate form.
- the invention is especially applicable to powders of high bulk density, and to tablets prepared by compacting powder. In these products the use of a hygroscopic material would be especially problematic.
- the composition of the invention preferably has a bulk density of at least 500 g/1, and preferably from 600 to 1000 g/1, more preferably from 800 to 1000 g/1.
- the invention is also applicable to powders of lower bulk density.
- the IDS complex may be in admixture mixed with a spray-dried detergent base powder and optionally other conventional detergent ingredients.
- compositions of the invention may also be in tablet form.
- While the invention is primarily applicable to laundry detergent compositions, it is also relevant to mechanical dishwashing detergents, both powders and tablets, containing IDS.
- the invention is especially applicable to particulate detergent compositions of high bulk density.
- Such compositions may be prepared by non- tower (non-spray-drying) processes in which particulate raw materials are mixed and/or granulated.
- to prepare compositions of this type the IDS complex is mixed and/or granulated with other detergent ingredients.
- the mixing and/or granulation may suitably be carried out in a high-speed mixer/granulator, for example a Fukae (Trade Mark) FSG mixer or a Loedige Recycler (Trade Mark) .
- a detergent base powder may be prepared by conventional slurry-making and spray- drying processes, and other ingredients in powder form, including the IDS complex in accordance with the present invention, may be admixed (postdosed) to the base powder.
- IDS in a non-hygroscopic powder form adds further flexibility in the manufacture of detergent powders, and is especially valuable where different products of different bulk densities are manufactured on the same site.
- Tablets may be prepared by compacting powders containing the IDS complex.
- compositions of the invention also contain other conventional detergent ingredients.
- Essential ingredients are surfactants (detergent-active compounds) , and (unless IDS is the sole builder) detergency builders.
- the detergent compositions will contain, as essential ingredients, one or more detergent active compounds (surfactants) which may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent active compounds, and mixtures thereof.
- surfactants may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent active compounds, and mixtures thereof.
- surfactants may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent active compounds, and mixtures thereof.
- surfactants may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent active compounds, and mixtures thereof.
- suitable detergent active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Ber
- the preferred detergent active compounds that can be used are soaps and synthetic non-soap anionic and nonionic compounds .
- Anionic surfactants are well-known to those skilled in the art. Examples include alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of C 8 -C ⁇ 5 ; primary and secondary alkylsulphates , particularly C 8 -C ⁇ 5 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
- Sodium salts are generally preferred.
- Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C 8 -C2o aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C 10 -C ⁇ 5 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
- Non-ethoxylated nonionic surfactants include alkylpolyglycosides , glycerol monoethers, and polyhydroxyamides (glucamide) .
- Cationic surfactants that may be used include quaternary ammonium salts of the general formula R ⁇ R 2 R 3 RN + X " wherein the R groups are long or short hydrocarbyl chains, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is a solubilising cation (for example, compounds in which Ri is a C 8 _C 2 2 alkyl group, preferably a C 8 -C 10 or C ⁇ 2 -C 14 alkyl group, R 2 is a methyl group, and R 3 and R 4 , which may be the same or different, are methyl or hydroxyethyl groups); and cationic esters (for example, choline esters) .
- R groups are long or short hydrocarbyl chains, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups
- X is a solubilising cation
- Ri is a C 8 _C 2 2 alkyl group,
- Ri represents a C 8 -C ⁇ 0 or C ⁇ 2 -C ⁇ 13
- R and R 3 represent methyl groups, and R 4 presents a hydroxyethyl group.
- Amphoteric surfactants for example, amine oxides, and zwitterionic surfactants, for example, betaines, may also be present .
- the quantity of anionic surfactant is in the range of from 5 to 50% by weight of the total composition. More preferably, the quantity of anionic surfactant is in the range of from 8 to 35% by weight.
- Nonionic surfactant if present, is preferably used in an amount within the range of from 1 to 20% by weight.
- the total amount of surfactant present is preferably within the range of from 5 to 60 wt%.
- compositions may suitably contain from 10 to 80%, preferably from 15 to 70% by weight, of detergency builder.
- the quantity of builder is in the range of from 15 to 50% by weight.
- the detergent compositions may contain as builder a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate (zeolite) .
- a crystalline aluminosilicate preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate (zeolite) .
- the zeolite used as a builder may be the commercially available zeolite A (zeolite 4A) now widely used in laundry detergent powders.
- the zeolite may be maximum aluminium zeolite P (zeolite MAP) as described and claimed in EP 384 070B (Unilever) , and commercially available as Doucil (Trade Mark) A24 from Crosfield Chemicals Ltd, UK.
- Zeolite MAP is defined as an alkali metal aluminosilicate of zeolite P type having a silicon to aluminium ratio not exceeding 1.33, preferably within the range of from 0.90 to 1.33, preferably within the range of from 0.90 to 1.20.
- zeolite MAP having a silicon to aluminium ratio not exceeding 1.07, more preferably about 1.00.
- the particle size of the zeolite is not critical. Zeolite A or zeolite MAP of any suitable particle size may be used.
- phosphate builders especially sodium tripolyphosphate . This may be used in combination with sodium orthophosphate, and/or sodium pyrophosphate .
- inorganic builders that may be present additionally or alternatively include sodium carbonate, layered silicate, amorphous aluminosilicates .
- Organic builders that may be present, as well as IDS itself, include polycarboxylate polymers such as polyacrylates and acrylic/maleic copolymers; polyaspartates ; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-di- and trisuccinates, carboxymethyloxysuccinates , carboxy-methyloxymalonates , dipicolinates, hydroxyethyliminodiacetates , alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts .
- polycarboxylate polymers such as polyacrylates and acrylic/maleic copolymers
- polyaspartates monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-di- and trisuccinates, carboxymethyloxysuccinates , carboxy-methyloxymalonates , dipicolinate
- IDS and other organic builders may be used in minor amounts as supplements to inorganic builders such as phosphates and zeolites.
- Especially preferred supplementary organic builders are citrates, suitably used in amounts of from 5 to 30 wt %, preferably from 10 to 25 wt %; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt %, preferably from 1 to 10 wt%.
- Builders both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form.
- Detergent compositions according to the invention may also suitably contain a bleach system.
- a bleach system This is preferably based on peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, capable of yielding hydrogen peroxide in aqueous solution.
- Suitable peroxy bleach compounds include organic peroxides such as urea peroxide, and inorganic persalts such as the alkali metal perborates, percarbonates , perphosphates, persilicates and persulphates .
- Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate .
- sodium percarbonate having a protective coating against destabilisation by moisture Sodium percarbonate having a protective coating comprising sodium metaborate and sodium silicate is disclosed in GB 2 123 044B (Kao) . - 1 (
- the peroxy bleach compound is suitably present in an amount of from 5 to 35 wt%, preferably from 10 to 25 wt%.
- the peroxy bleach compound may be used in conjunction with a bleach activator (bleach precursor) to improve bleaching action at low wash temperatures.
- the bleach precursor is suitably present in an amount of from 1 to 8 wt%, preferably from 2 to 5 wt%.
- Preferred bleach precursors are peroxycarboxylic acid precursors, more especially peracetic acid precursors and peroxybenzoic acid precursors; and peroxycarbonic acid precursors.
- An especially preferred bleach precursor suitable for use in the present invention is N,N,N',N'- tetracetyl ethylenediamine (TAED) .
- TAED N,N,N',N'- tetracetyl ethylenediamine
- the novel quaternary ammonium and phosphonium bleach precursors disclosed in US 4 751 015 and US 4 818 426 (Lever Brothers Company) and EP 402 971A (Unilever) are also of great interest.
- Especially preferred are peroxycarbonic acid precursors, in particular cholyl-4-sulphophenyl carbonate.
- peroxybenzoic acid precursors in particular, N,N, N-trimethylammonium toluoyloxy benzene sulphonate; and the cationic bleach precursors disclosed in EP 284 292A and EP 303 520A (Kao) .
- a bleach stabiliser may also be present.
- suitable bleach stabilisers include ethylenediamine tetraacetate (EDTA) and the polyphosphonates such as Dequest (Trade Mark), EDTMP .
- the detergent compositions may also contain one or more enzymes. Suitable enzymes include the proteases, amylases, cellulases, oxidases, peroxidases and upases usable for incorporation in detergent compositions.
- Preferred proteolytic enzymes are catalytically active protein materials which degrade or alter protein types of stains when present as in fabric stains in a hydrolysis reaction. They may be of any suitable origin, such as vegetable, animal, bacterial or yeast origin.
- Proteolytic enzymes or proteases of various qualities and origins and having activity in various pH ranges of from 4-12 are available. Proteases of both high and low isoelectric point are suitable.
- enzymes that may suitably be present include lipases, amylases, and cellulases including high-activity cellulases such as "Carezyme”) .
- detergency enzymes are commonly employed in granular form in amounts of from about 0.1 to about 3.0 wt%. However, any suitable physical form of enzyme may be used in any effective amount.
- Antiredeposition agents for example cellulose esters and ethers, for example sodium carboxymethyl cellulose, may also be present .
- compositions may also contain soil release polymers, for example sulphonated and unsulphonated PET/POET polymers, both end-capped and non-end-capped, and polyethylene - I S
- soil release polymers for example sulphonated and unsulphonated PET/POET polymers, both end-capped and non-end-capped, and polyethylene - I S
- glycol/polyvinyl alcohol graft copolymers such as Sokolan (Trade Mark) HP22.
- Especially preferred soil release polymers are the sulphonated non-end-capped polyesters described and claimed in WO 95 32997A (Rhodia Chimie) .
- ingredients that may be present include solvents, hydrotropes, fluorescers, photobleaches , foam boosters or foam controllers (antifoams) as appropriate, sodium carbonate, sodium bicarbonate, sodium silicate, sodium sulphate, calcium chloride, other inorganic salts, fabric conditioning compounds, and perfumes.
- An 0.04M aqueous solution of NalDS (ex Bayer) was prepared and the pH adjusted to 12 with 1M NaOH solution.
- CaCl 2 or MgCl solution was added slowly while stirring to give a final mole ratio of Ca or Mg to IDS of 1:1, 2:1 or 3:1.
- a white precipitate formed with slow addition of the Ca or Mg salt solution.
- the Mg:IDS also formed a thicker, more gelatinous precipitate than Ca : IDS .
- the dry salt was obtained by collecting the total liquor and precipitate and freeze drying.
- the dry salt was ground up using a mortar and pestle.
- the dry salt was sieved to obtain a fraction with constant size and therefore constant surface area.
- the size fraction 355-500 micrometres was selected as being a representative portion of normal detergent powders.
- Approximately 1 g portions of these sieved Ca : IDS and Mg:IDS powders were weighed out into plastic dishes. These open dishes were stored in a humidity cabinet at 20°C/75% RH, the relative humidity being generated by an atmosphere of saturated NaCl (- 6M) . - 20
- the dishes were re-weighed periodically over a period of 7 days' storage under these conditions, and the % water uptake was calculated.
- Example shows the benefit of separating the sodium chloride formed as a by-product .
- the procedure was generally similar to that of Example 1, but with an added filtration step.
- a 0.04M solution of NalDS was prepared and the pH adjusted to 12 with 1M NaOH solution. 0.12M CaCl 2 solution was added slowly while stirring, to give a final mole ratio of 3:1 Ca:IDS) . A white precipitate formed with slow addition of the Ca salt solution. After the required amount of Ca salt solution had been added, the pH was re-adjusted back to 12.
- the slurry obtained was filtered under vacuum through a 542 filter paper fitted to a Buchner funnel . This removed the majority of the NaCl generated during the reaction of NalDS with CaCl 2 . The filter cake was dried in an oven overnight at 120°C.
- Example 3 1 CaHIDS complexes were prepared by the procedures described in Example 1 (without filtration) and Example 2 (with filtration) .
- the starting NaHIDS was ex Nippon Shokubai .
- a particulate detergent composition was prepared by a conventional slurry-making and spray-drying process to the following formulation:
- each ar was then transferred to open cardboard trays, and stored for a period of 7 days m a controlled temperature/humidity store, (37°C/70% RH) .
- Compression and caking were measured using an apparatus comprising a graduated open-ended perspex cylinder of height 80 mm and internal diameter 24 mm standing on an aluminium base plate and fitted at its upper end with a plunger having a large flat circular top on which cylindrical weights could be placed.
- the cylinder was filled with powder to a height of 30 mm, the plunger inserted until just touching the top of the powder, and a 1 kg weight placed on the top of the plunger.
- the weight was removed after 2 minutes, and the compression of the powder sample (the fall in its level, in mm) was measured using the graduations on the cylinder and recorded.
- the resulting "cake" of powder was expelled from the lower end of the cylinder, by means of the plunger, onto the base plate. 20g weights were added to the top of the powder cake until the cake disintegrated, and the total weight required to break up the cake (the unconfined compression test score or UCT, in g) was recorded. Higher UCT values were obtained when a higher level of compression was achieved, ie the "powder cakes" were stronger. Increased compression and higher UCT values were also generally linked to increased water uptake.
- the fabrics used were cotton dyed with Direct Red 80. They were pre-treated with demineralised water containing 0.5 ppm Cu 2+ ions and having the pH adjusted to 6.5 by means of sodium hydroxide. The pretreatment was carried out using tergotometers at 30°C, 90 rpm and a liquor to cloth ratio of 200:1, then the fabrics were line dried.
- the fabrics were then washed in a wash liquor containing 2.5 g/1 of the detergent composition (as used above), and 0.5 ppm Cu 2+ , in 20/6° Ca/Mg French hard water: the pH was adjusted from 9.9 to 9.5 using dilute sulphuric acid.
- the washes were carried out in tergotometers at 30°C, 90 rpm and a liquor to cloth ratio of 200:1.
- the washes were followed by two rinses in 20/6° Ca/Mg French hard water containing 0.05 ppm Cu 2+ at a liquor to cloth ratio of 200:1, and the fabrics were then line dried.
- the sequestrants where present, were dosed directly into the wash liquor in amounts to give the equivalent of 1.25% (by weight on the detergent composition) of NalDS or NaHIDS. - 30 -
- Colour changes were monitored by reflectance changes at 620 nm, the standard being the fabrics prior to pretreatment. All values were negative, the ideal being the smallest possible negative value. Colour changes were also recorded as degree or % recovery of copper damaged coloured fabrics, ie as a % of the maximum possible recovery.
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Abstract
A particulate detergent composition contains a sequestrant which is iminodisuccinate (IDS) or hydroxyiminodisuccinate (HIDS), in the form of a calcium or magnesium complex, the molar ratio of calcium or magnesium ion to (H) IDS being at least 2:1. The complex has significantly lower hygroscopicity than sodium (H) IDS. The composition is preferably a laundry detergent composition in the form of a powder, especially a compact powder, or a tablet.
Description
DETERGENT COMPOSITIONS
TECHNICAL FIELD
The present invention relates to particulate detergent compositions containing the sequestrant, iminodisuccinate or hydroxyiminodisuccinate . The invention is of especially interest for detergent powders of high bulk density . (so- called "compact" powders) and to tablets of compacted detergent powder. The invention is especially applicable to laundry detergent powders but is also relevant to powders or tablets for mechanical dishwashing.
BACKGROUND AND PRIOR ART
Iminodisuccinate (IDS) and hydroxyiminodisuccinate (HIDS) are known as detergency builders and, in bleaching detergent compositions, as stabilisers for peroxy bleach precursors.
US 3 697 453 (Pfizer) discloses detergent compositions having a pH of from 9 to 12, containing iminodisuccinate as a detergency builder, used together with detergent surfactant in a weight ratio of 0.25:1 to 10:1. IDS as a detergency builder is also disclosed in EP 757 094A (Bayer) . HIDS is disclosed in US 5 318 726 (Henkel) .
EP 509 382A (W R Grace & Co/Hampshire Chemical Corporation) discloses a bleaching detergent composition comprising a bleaching agent and a bleach stabiliser of defined formula
which includes IDS. The use of IDS as a bleach stabiliser is also disclosed in WO 97 20907A (Procter & Gamble) .
WO 00/34427A (Unilever) discloses and claims non-bleaching laundry detergent compositions containing from 0.05 to
2.5 wt% of IDS or HIDS. The compositions provides improved maintenance and/or restoration of colour fidelity during the wash, especially at low wash pH. The IDS or HIDS is also an effective chlorine scavenger, reducing the in-wash fading of chlorine-sensitive dyes. In addition, the incorporation of the IDS or HIDS improves the stain removal performance of the composition.
IDS is commercially available in sodium salt form, eg as IDS Na-salt from Bayer. The sodium salt is highly water-soluble and the material is supplied as an aqueous solution (approximate IDS Na-salt content 34%) and as a solid white powder prepared from the solution by spray-drying. If IDS is to be incorporated into an aqueous liquid detergent or into a spray-dried detergent powder via the slurry, the solution form is most conveniently used. However, it is not suitable for the preparation of a powder of high bulk density by a non-tower (non-spray-drying) route because the water content is too high. For such products it is necessary to use IDS in powder form.
However, the powder is extremely hygroscopic and, according to the manufacturer Bayer's recommendation, must be stored in tightly closed containers. If stored in contact with the atmosphere it rapidly takes up water and deliquesces, ie becomes a liquid. The problem is exacerbated in humid
atmospheres so that any storage or handling of the material causes major problems with stickiness. When this sticky raw material is incorporated into a detergent powder, poor powder properties result .
It has now been found that this problem can be substantially alleviated by converting the IDS partially into calcium or magnesium form, ie forming complexes with calcium or magnesium ions. The resulting Ca/Na or Mg/Na salts or complexes, especially the Ca/Na salts or complexes, are stable solids which are significantly less hygroscopic than the sodium salt. They can readily be incorporated into particulate detergent compositions and, surprisingly, the resulting compositions show no loss of sequestrant activity as compared with similar compositions containing the sodium salt .
GB 2 048 930A (Unilever) discloses bleaching detergent compositions containing an organic phosphonate sequestrant - ethylenediamine tetramethylene phosphonate (EDTMP) or diethylenetriamine pentamethylene phosphonate (DETPMP) present as a complex of a magnesium, calcium, zinc or aluminium ion, the molar ratio of the metal ion to the phosphonate compound being at least 1:1. The benefit is improved stability of the phosphonate compound in the detergent composition on storage.
JP 09 110 813A and JP 09 104 897A (Nippon Shokubai) disclose a builder powder of reduced hygroscopicity based on IDS, in which sodium IDS is compounded with an inorganic
metal salt, preferably zeolite, sodium carbonate or sodium silicate .
JP 09 100 497A (Lion) discloses high bulk density detergent powders containing IDS, prepared by granulating together detergent ingredients including an inorganic builder salt, eg zeolite, and sodium IDS or HIDS (3-20 wt% of the final composition) . The hygroscopicity of the IDS is exploited to bind fine zeolite particles and thereby improve flow and reduce stickiness.
B Karoleski and R Hampe of Bayer Corporation, m a paper entitled "Alternatives to Traditional Chelants and Dispersants" , HAPPI (Household and Personal Products Industry), Volume 36, No. 11 (November 1999), pages 114 - 118, discuss the sequestrant properties of IDS. The stability constants of complexes with various divalent and polyvalent metal ions, including calcium and magnesium, are disclosed.
DEFINITION OF THE INVENTION
The present invention provides a particulate detergent composition containing a sequestrant which is a compound of the formula I
Y - CH - CH - NH - CH - CH2 (I)
COOX COOX COOX COOX
wherein Y is H or OH, and X is a countercation, the compound being in the form of a complex of a metal ion selected from calcium and magnesium ions, the molar ratio of the metal ion to the compound of the formula I being at least 2:1.
The invention further provides a process for the preparation of a particulate detergent composition, which includes the step of mixing and/or granulating a compound of the formula I in powder form with other detergent ingredients, wherein the compound of the formula I is in the form of a complex of a metal ion selected from calcium and magnesium ions, the molar ratio of the metal ion to the compound of the formula I being at least 2:1.
DETAILED DESCRIPTION OF THE INVENTION
The IDS or HIDS salt or complex
The detergent composition of the invention contains a compound of the formula I above as an essential ingredient. When Y is H, the compound is IDS; when Y is OH, the compound is HIDS. For convenience only IDS will be discussed in the description below, but this should be understood to refer equally to HIDS.
IDS is a pentadentate ligand ie it can form complexes with metal ions in which bonds are formed with the nitrogen atom and all four carboxyl groups. Indeed its efficacy as a detergency builder is based on its capacity to form such
complexes with calcium and magnesium ions, and its efficacy as a bleach stabiliser and for colour care is based on its capacity for forming such complexes with heavy metal ions such as iron and copper.
The reaction between an iminodisuccinate acid anion IDSm~ and a metal cation Men+ is a reversible one, represented in the usual case of a 1:1 complex by the equation
IDS" Me1 IDS Me (m-n) -
Similar relationships hold for 2:1, 3:1 and higher complexes (the ratio being of the metal ion to the IDS anion) .
The present inventors have surprisingly found that IDS in the form of a 2:1 or higher complex with calcium or magnesium is substantially less hygroscopic than the sodium salt .
The calcium complexes are especially preferred, more especially complexes having a Ca : IDS molar ratio of 2:1 or above, for example, 2:1 or 3:1. The 1:1 complex is also less hygroscopic than the sodium salt, but the benefit is significantly greater with the higher ratio complexes. The 3:1 complex is especially preferred.
The magnesium complexes are also useful but the benefit observed is less than with the calcium complexes.
The calcium or magnesium complexes may be prepared by reacting the sodium salt, in aqueous solution, with the
appropriate amount of a soluble calcium or magnesium salt, preferably calcium or magnesium chloride. The reaction also produces a soluble inorganic sodium salt (eg sodium chloride) .
According to a preferred embodiment of the invention, the soluble inorganic sodium salt produced as a by-product of the preparation process is removed by using a filtration step. Where this is possible, a further significant reduction of hygroscopicity has been observed. However, it is only possible if there is sufficient difference in solubility between the complex and the inorganic salt byproduct, which is highly soluble. The higher the mole ratio of the complex, the lower its solubility, and the 1:1 complexes of both calcium and magnesium are both too soluble to allow separation of the sodium chloride by-product. With the 2:1 complexes partial separation is possible and this gives some improvement .
However, the CalDS and CaHIDS 3:1 complexes are especially preferred in this respect because their solubility is sufficiently reduced, compared with that of the sodium salt, to allow sodium chloride to be separated by filtration during their preparation, yet is sufficiently high for these materials to be delivered effectively into the wash liquor.
Thus, an especially preferred embodiment of the invention involves the use of a CalDS or CaHIDS 3 : 1 complex which has been prepared by a method which includes removal of any inorganic salt by-product.
Detergent compositions
The detergent compositions of the invention contain IDS (or HIDS) as an essential ingredient. This may be present at levels sufficient for detergency building, either alone or in conjunction with another detergency builder, or at the much lower levels appropriate for bleach stabilisation, or for colour care benefits and stain removal in non-bleaching formulations as disclosed in WO 00/34427A (Unilever) .
The amount of IDS or HIDS present in the composition may therefore range very widely, for example, from 0.05 to 80 wt%. Suitable ranges are, for example, 5 to 80 wt% if IDS is the sole or principal builder; 1 to 20 wt% if it is present as cobuilder to, for example, zeolite, phosphate or carbonate; 0.5 to 10 wt% for bleach stabilisation; 0.05 to 2.5 wt% for colour care benefits in non-bleaching formulations .
The compositions of the invention may contain other conventional detergent ingredients as detailed below. Typically a composition in which IDS is present as a cobuilder or a bleach stabiliser may comprise the following:
(a) from 5 to 60 wt% of one or more detergent surfactants,
(b) from 10 to 80 wt% of one or more detergency builders (other than IDS) ,
(c) from 0.5 to 20 wt% of a compound of the formula I,
(d) optionally other detergent ingredients to 100 wt%.
A non-bleaching formulation in which a low level of IDS has been included for colour care benefits may suitably comprise :
(a) from 5 to 60 wt% of one or more detergent surfactants,
(b) from 10 to 80 wt% of one or more detergency builders (other than IDS) ,
(c) from 0.05 to 2.5 wt% of a compound of the formula I,
(d) optionally other non-bleaching detergent ingredients to 100 wt%.
The detergent composition of the invention is in particulate form. The invention is especially applicable to powders of high bulk density, and to tablets prepared by compacting powder. In these products the use of a hygroscopic material would be especially problematic.
If in powder form, the composition of the invention preferably has a bulk density of at least 500 g/1, and preferably from 600 to 1000 g/1, more preferably from 800 to 1000 g/1.
However, the invention is also applicable to powders of lower bulk density. In such a product, for example, the IDS complex may be in admixture mixed with a spray-dried
detergent base powder and optionally other conventional detergent ingredients.
The compositions of the invention may also be in tablet form.
While the invention is primarily applicable to laundry detergent compositions, it is also relevant to mechanical dishwashing detergents, both powders and tablets, containing IDS.
Preparation of the detergent composition
As indicated previously, the invention is especially applicable to particulate detergent compositions of high bulk density. Such compositions may be prepared by non- tower (non-spray-drying) processes in which particulate raw materials are mixed and/or granulated. According to the invention, to prepare compositions of this type the IDS complex is mixed and/or granulated with other detergent ingredients. The mixing and/or granulation may suitably be carried out in a high-speed mixer/granulator, for example a Fukae (Trade Mark) FSG mixer or a Loedige Recycler (Trade Mark) .
The invention is also applicable to detergent powders of lower bulk density. For example, a detergent base powder may be prepared by conventional slurry-making and spray- drying processes, and other ingredients in powder form, including the IDS complex in accordance with the present invention, may be admixed (postdosed) to the base powder.
The availability of IDS in a non-hygroscopic powder form adds further flexibility in the manufacture of detergent powders, and is especially valuable where different products of different bulk densities are manufactured on the same site.
Tablets may be prepared by compacting powders containing the IDS complex.
Detergent components
The compositions of the invention also contain other conventional detergent ingredients. Essential ingredients are surfactants (detergent-active compounds) , and (unless IDS is the sole builder) detergency builders.
The detergent compositions will contain, as essential ingredients, one or more detergent active compounds (surfactants) which may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent active compounds, and mixtures thereof. Many suitable detergent active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
The preferred detergent active compounds that can be used are soaps and synthetic non-soap anionic and nonionic compounds .
Anionic surfactants are well-known to those skilled in the art. Examples include alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of C8-Cι5; primary and secondary alkylsulphates , particularly C8-Cι5 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates. Sodium salts are generally preferred.
Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C8-C2o aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C10-Cι5 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkylpolyglycosides , glycerol monoethers, and polyhydroxyamides (glucamide) .
Cationic surfactants that may be used include quaternary ammonium salts of the general formula RιR2R3RN+ X" wherein the R groups are long or short hydrocarbyl chains, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is a solubilising cation (for example, compounds in which Ri is a C8_C22 alkyl group, preferably a C8-C10 or Cι2-C14 alkyl group, R2 is a methyl group, and R3 and R4 , which may be the same or different, are methyl or hydroxyethyl groups); and cationic esters (for example, choline esters) .
In an especially preferred cationic surfactant of the general formula RιR2R3R4N+ X", Ri represents a C8-Cι0 or Cι2-Cι
13
alkyl group, R and R3 represent methyl groups, and R4 presents a hydroxyethyl group.
Amphoteric surfactants, for example, amine oxides, and zwitterionic surfactants, for example, betaines, may also be present .
Preferably, the quantity of anionic surfactant is in the range of from 5 to 50% by weight of the total composition. More preferably, the quantity of anionic surfactant is in the range of from 8 to 35% by weight.
Nonionic surfactant, if present, is preferably used in an amount within the range of from 1 to 20% by weight.
The total amount of surfactant present is preferably within the range of from 5 to 60 wt%.
The compositions may suitably contain from 10 to 80%, preferably from 15 to 70% by weight, of detergency builder. Preferably, the quantity of builder is in the range of from 15 to 50% by weight.
The detergent compositions may contain as builder a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate (zeolite) .
The zeolite used as a builder may be the commercially available zeolite A (zeolite 4A) now widely used in laundry detergent powders. Alternatively, the zeolite may be maximum
aluminium zeolite P (zeolite MAP) as described and claimed in EP 384 070B (Unilever) , and commercially available as Doucil (Trade Mark) A24 from Crosfield Chemicals Ltd, UK. Zeolite MAP is defined as an alkali metal aluminosilicate of zeolite P type having a silicon to aluminium ratio not exceeding 1.33, preferably within the range of from 0.90 to 1.33, preferably within the range of from 0.90 to 1.20.
Especially preferred is zeolite MAP having a silicon to aluminium ratio not exceeding 1.07, more preferably about 1.00. The particle size of the zeolite is not critical. Zeolite A or zeolite MAP of any suitable particle size may be used.
Also preferred according to the present invention are phosphate builders, especially sodium tripolyphosphate . This may be used in combination with sodium orthophosphate, and/or sodium pyrophosphate .
Other inorganic builders that may be present additionally or alternatively include sodium carbonate, layered silicate, amorphous aluminosilicates .
Organic builders that may be present, as well as IDS itself, include polycarboxylate polymers such as polyacrylates and acrylic/maleic copolymers; polyaspartates ; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-di- and trisuccinates, carboxymethyloxysuccinates , carboxy-methyloxymalonates , dipicolinates, hydroxyethyliminodiacetates , alkyl- and
alkenylmalonates and succinates; and sulphonated fatty acid salts .
IDS and other organic builders may be used in minor amounts as supplements to inorganic builders such as phosphates and zeolites. Especially preferred supplementary organic builders are citrates, suitably used in amounts of from 5 to 30 wt %, preferably from 10 to 25 wt %; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt %, preferably from 1 to 10 wt%.
Builders, both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form.
Detergent compositions according to the invention may also suitably contain a bleach system. This is preferably based on peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, capable of yielding hydrogen peroxide in aqueous solution. Suitable peroxy bleach compounds include organic peroxides such as urea peroxide, and inorganic persalts such as the alkali metal perborates, percarbonates , perphosphates, persilicates and persulphates . Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate . Especially preferred is sodium percarbonate having a protective coating against destabilisation by moisture. Sodium percarbonate having a protective coating comprising sodium metaborate and sodium silicate is disclosed in GB 2 123 044B (Kao) .
- 1 (
The peroxy bleach compound is suitably present in an amount of from 5 to 35 wt%, preferably from 10 to 25 wt%.
The peroxy bleach compound may be used in conjunction with a bleach activator (bleach precursor) to improve bleaching action at low wash temperatures. The bleach precursor is suitably present in an amount of from 1 to 8 wt%, preferably from 2 to 5 wt%.
Preferred bleach precursors are peroxycarboxylic acid precursors, more especially peracetic acid precursors and peroxybenzoic acid precursors; and peroxycarbonic acid precursors. An especially preferred bleach precursor suitable for use in the present invention is N,N,N',N'- tetracetyl ethylenediamine (TAED) . The novel quaternary ammonium and phosphonium bleach precursors disclosed in US 4 751 015 and US 4 818 426 (Lever Brothers Company) and EP 402 971A (Unilever) are also of great interest. Especially preferred are peroxycarbonic acid precursors, in particular cholyl-4-sulphophenyl carbonate. Also of interest are peroxybenzoic acid precursors, in particular, N,N, N-trimethylammonium toluoyloxy benzene sulphonate; and the cationic bleach precursors disclosed in EP 284 292A and EP 303 520A (Kao) .
A bleach stabiliser (heavy metal sequestrant) may also be present. Other than IDS, suitable bleach stabilisers include ethylenediamine tetraacetate (EDTA) and the polyphosphonates such as Dequest (Trade Mark), EDTMP .
The detergent compositions may also contain one or more enzymes. Suitable enzymes include the proteases, amylases, cellulases, oxidases, peroxidases and upases usable for incorporation in detergent compositions.
Preferred proteolytic enzymes (proteases) are catalytically active protein materials which degrade or alter protein types of stains when present as in fabric stains in a hydrolysis reaction. They may be of any suitable origin, such as vegetable, animal, bacterial or yeast origin.
Proteolytic enzymes or proteases of various qualities and origins and having activity in various pH ranges of from 4-12 are available. Proteases of both high and low isoelectric point are suitable.
Other enzymes that may suitably be present include lipases, amylases, and cellulases including high-activity cellulases such as "Carezyme") .
In particulate detergent compositions, detergency enzymes are commonly employed in granular form in amounts of from about 0.1 to about 3.0 wt%. However, any suitable physical form of enzyme may be used in any effective amount.
Antiredeposition agents, for example cellulose esters and ethers, for example sodium carboxymethyl cellulose, may also be present .
The compositions may also contain soil release polymers, for example sulphonated and unsulphonated PET/POET polymers, both end-capped and non-end-capped, and polyethylene
- I S
glycol/polyvinyl alcohol graft copolymers such as Sokolan (Trade Mark) HP22.
Especially preferred soil release polymers are the sulphonated non-end-capped polyesters described and claimed in WO 95 32997A (Rhodia Chimie) .
Other ingredients that may be present include solvents, hydrotropes, fluorescers, photobleaches , foam boosters or foam controllers (antifoams) as appropriate, sodium carbonate, sodium bicarbonate, sodium silicate, sodium sulphate, calcium chloride, other inorganic salts, fabric conditioning compounds, and perfumes.
EXAMPLES
The invention will be further illustrated by the following non-limiting Examples, in which parts and percentages are by weight unless otherwise stated.
19
EXAMPLE 1
Preparation of CalDS and MglDS
An 0.04M aqueous solution of NalDS (ex Bayer) was prepared and the pH adjusted to 12 with 1M NaOH solution. CaCl2 or MgCl solution was added slowly while stirring to give a final mole ratio of Ca or Mg to IDS of 1:1, 2:1 or 3:1. A white precipitate formed with slow addition of the Ca or Mg salt solution. In the case of low mole ratios of Ca or Mg : IDS the precipitate formed but then re-dissolved. The Mg:IDS also formed a thicker, more gelatinous precipitate than Ca : IDS . After the required amount of Ca or Mg chloride salt solution had been added, the pH was re-adjusted back to 12. The dry salt was obtained by collecting the total liquor and precipitate and freeze drying.
Water uptake measurements
The dry salt was ground up using a mortar and pestle. The dry salt was sieved to obtain a fraction with constant size and therefore constant surface area. The size fraction 355-500 micrometres was selected as being a representative portion of normal detergent powders. Approximately 1 g portions of these sieved Ca : IDS and Mg:IDS powders were weighed out into plastic dishes. These open dishes were stored in a humidity cabinet at 20°C/75% RH, the relative humidity being generated by an atmosphere of saturated NaCl (- 6M) .
- 20
The dishes were re-weighed periodically over a period of 7 days' storage under these conditions, and the % water uptake was calculated.
Example la
Water uptake of CalDS complexes
*some stickiness and lump formation observed **samples had liquefied
The CalDS 3:1 complex was still in free-flowing powder form after 7 days.
Example lb
Water uptake results on MglDS complexes
* samples showed signs of some liquid formation **samples had liquefied completely
EXAMPLE 2
Preparation of CalDS 3:1 complex
This Example shows the benefit of separating the sodium chloride formed as a by-product . The procedure was generally similar to that of Example 1, but with an added filtration step.
A 0.04M solution of NalDS was prepared and the pH adjusted to 12 with 1M NaOH solution. 0.12M CaCl2 solution was added slowly while stirring, to give a final mole ratio of 3:1 Ca:IDS) . A white precipitate formed with slow addition of the Ca salt solution. After the required amount of Ca salt solution had been added, the pH was re-adjusted back to 12.
The slurry obtained was filtered under vacuum through a 542 filter paper fitted to a Buchner funnel . This removed the majority of the NaCl generated during the reaction of NalDS with CaCl2. The filter cake was dried in an oven overnight at 120°C.
Water take-up of this material, and of a control sample prepared without a filtration step, was measured as in Example 1 and the results were as shown below.
Both samples remained as powders throughout the storage period. The sample prepared without filtration showed some slight stickiness after 21 days, although not earlier, while the sample prepared with a filtration step was completely free-flowing even after 21 days' storage.
The very low water uptake figures for the 3 : 1 CalDS without NaCl will be noted.
EXAMPLE 3
Preparation and water uptake of CaHIDS
3 : 1 CaHIDS complexes were prepared by the procedures described in Example 1 (without filtration) and Example 2 (with filtration) . The starting NaHIDS was ex Nippon Shokubai .
The water uptake results were as follows
**samples had liquefied
Both CaHIDS 3:1 samples were free-flowing powders after 7 days ' storage .
EXAMPLE 4
Detergent composition
A particulate detergent composition was prepared by a conventional slurry-making and spray-drying process to the following formulation:
Sample preparation and storage
50 g samples of the detergent base powder were weighed into glass ars, and 1.25% by weight IDS or HIDS salt (180-250 microns sieve fraction) were added. The ars were sealed, and the detergent powder thoroughly mixed with the IDS or
HIDS on a roller mixer for 1 hour.
The contents of each ar were then transferred to open cardboard trays, and stored for a period of 7 days m a controlled temperature/humidity store, (37°C/70% RH) .
The powders were re-weighed periodically and % water uptake calculated.
Example 4a
Water uptake measurements (detergent powder + IDS)
Example 4b
Water uptake measurements (detergent powder + HIDS]
Incorporation of NalDS or NaHIDS into detergent powder compositions resulted in increased water uptake of the detergent powders on storage as these materials are hygroscopic. This gave rise to increased stickiness of powders especially on storage. Use of the Ca form of IDS or
HIDS lowered the level of water uptake minimising any negatives on powder physical properties.
Measurement of caking
For measurement of caking, homogeneous samples of the stored detergent powders were first obtained by roller mixing in sealed glass jars for 1 hour.
Compression and caking were measured using an apparatus comprising a graduated open-ended perspex cylinder of height 80 mm and internal diameter 24 mm standing on an aluminium base plate and fitted at its upper end with a plunger having a large flat circular top on which cylindrical weights could be placed.
The cylinder was filled with powder to a height of 30 mm, the plunger inserted until just touching the top of the powder, and a 1 kg weight placed on the top of the plunger.
The weight was removed after 2 minutes, and the the compression of the powder sample (the fall in its level, in mm) was measured using the graduations on the cylinder and recorded.
The resulting "cake" of powder was expelled from the lower end of the cylinder, by means of the plunger, onto the base plate. 20g weights were added to the top of the powder cake until the cake disintegrated, and the total weight required to break up the cake (the unconfined compression test score or UCT, in g) was recorded.
Higher UCT values were obtained when a higher level of compression was achieved, ie the "powder cakes" were stronger. Increased compression and higher UCT values were also generally linked to increased water uptake.
Example 4c
Measurement of caking (detergent powder + IDS) :
Example 4d
Measurement of caking (detergent powder + HIDS)
EXAMPLE 5
Colour care performance of CalDS and CaHIDS in detergent powders : restoration/recovery of coloured fabrics that have been colour-damaged by exposure to copper ions
These experiments demonstrate that the benefits of IDS and HIDS in restoring colour-damaged coloured fabrics are retained if the IDS or HIDS is used in the form of a Ca complex.
The fabrics used were cotton dyed with Direct Red 80. They were pre-treated with demineralised water containing 0.5 ppm Cu2+ ions and having the pH adjusted to 6.5 by means of sodium hydroxide. The pretreatment was carried out using tergotometers at 30°C, 90 rpm and a liquor to cloth ratio of 200:1, then the fabrics were line dried.
The fabrics were then washed in a wash liquor containing 2.5 g/1 of the detergent composition (as used above), and 0.5 ppm Cu2+, in 20/6° Ca/Mg French hard water: the pH was adjusted from 9.9 to 9.5 using dilute sulphuric acid. The washes were carried out in tergotometers at 30°C, 90 rpm and a liquor to cloth ratio of 200:1. The washes were followed by two rinses in 20/6° Ca/Mg French hard water containing 0.05 ppm Cu2+ at a liquor to cloth ratio of 200:1, and the fabrics were then line dried.
The sequestrants , where present, were dosed directly into the wash liquor in amounts to give the equivalent of 1.25% (by weight on the detergent composition) of NalDS or NaHIDS.
- 30 -
Colour changes were monitored by reflectance changes at 620 nm, the standard being the fabrics prior to pretreatment. All values were negative, the ideal being the smallest possible negative value. Colour changes were also recorded as degree or % recovery of copper damaged coloured fabrics, ie as a % of the maximum possible recovery.
The results are shown in the Tables below.
No significant differences in performance were observed between the NalDS and the CalDS. These results show that there is no loss of colour care performance in the wash if IDS is incorporated as a Ca complex.
Example 5a: CalDS
Example 5b: CaHIDS
Claims
1 A particulate detergent composition containing a sequestrant which is a compound of the formula I
Y - CH - CH - NH - CH - CH2 (I)
COOX COOX COOX COOX
wherein Y is H or OH, and X is a countercation, characterised in that the compound of the formula I is in the form of a complex of a metal ion selected from calcium and magnesium ions, the molar ratio of the metal ion to the compound of the formula I being at least 2:1.
2 A detergent composition as claimed in claim 1, characterised in that the molar ratio of the metal ion to the compound of the formula I is from 2:1 to 3:1.
3 A detergent composition as claimed in claim 1 or claim 2, characterised in that the metal ion is calcium and the molar ratio of calcium ion to the compound of the formula I is 3:1.
4 A detergent composition as claimed in claim 1, characterised in that the complex of the compound of the formula I has been prepared by a method which includes removal of any inorganic salt by-product .
5 A detergent composition as claimed in claim 1, characterised in that it is a laundry detergent composition comprising
(a) from 5 to 60 wt% of one or more detergent surfactants,
(b) from 10 to 80 wt% of one or more detergency builders,
(c) from 0.5 to 20 wt% of a compound of the formula I,
(d) optionally other detergent ingredients to 100 wt%.
6 A detergent composition as claimed in claim 1, characterised in that it is a non-bleaching laundry detergent composition comprising:
(a) from 5 to 60 wt% of one or more detergent surfactants,
(b) from 10 to 80 wt% of one or more detergency builders,
(c) from 0.05 to 2.5 wt% of a compound of the formula I,
(d) optionally other non-bleaching detergent ingredients to 100 wt%.
7 A detergent composition as claimed in claim 1, characterised in that it is in powder form and has a bulk density of at least 500 g/1.
8 A detergent composition as claimed in claim 7, which has a bulk density of from 600 to 1000 g/1.
9 A detergent composition as claimed in claim 1, characterised in that it is in tablet form.
10 A process for the preparation of a particulate detergent composition as claimed in claim 1, which includes the step of mixing and/or granulating a compound of the formula I
Y - CH - CH - NH - CH - CH2 (I]
COOX COOX COOX COOX
wherein Y is H or OH, and X is a countercation, in powder form with other detergent ingredients, characterised in that the compound of the formula I is in the form of a complex of a metal ion selected from calcium and magnesium ions, the molar ratio of the metal ion to the compound of the formula I being at least 2:1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9929840 | 1999-12-16 | ||
| GBGB9929840.8A GB9929840D0 (en) | 1999-12-16 | 1999-12-16 | Detergent compositions |
| PCT/EP2000/011356 WO2001044428A1 (en) | 1999-12-16 | 2000-11-13 | Detergent compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1238052A1 true EP1238052A1 (en) | 2002-09-11 |
| EP1238052B1 EP1238052B1 (en) | 2004-04-07 |
Family
ID=10866500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP00983141A Expired - Lifetime EP1238052B1 (en) | 1999-12-16 | 2000-11-13 | Detergent compositions |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP1238052B1 (en) |
| CN (1) | CN1229479C (en) |
| AT (1) | ATE263828T1 (en) |
| AU (1) | AU760259B2 (en) |
| BR (1) | BR0016435A (en) |
| DE (1) | DE60009745T2 (en) |
| ES (1) | ES2217001T3 (en) |
| GB (1) | GB9929840D0 (en) |
| HU (1) | HUP0203587A2 (en) |
| PL (1) | PL355785A1 (en) |
| TR (1) | TR200401196T4 (en) |
| WO (1) | WO2001044428A1 (en) |
| ZA (1) | ZA200204545B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0013501D0 (en) | 2000-06-02 | 2000-07-26 | Unilever Plc | Detergent compositions |
| JP2007031594A (en) | 2005-07-27 | 2007-02-08 | Nippon Shokubai Co Ltd | Solid composition containing 3-hydroxy-2,2'-iminodisuccinic acid salts and method for producing the same |
| US9650205B2 (en) | 2013-06-14 | 2017-05-16 | S. C. Johnson & Son, Inc. | Chelating system for a polymer lined steel container |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4024552A1 (en) * | 1990-08-02 | 1992-02-06 | Henkel Kgaa | DERIVATIVE AMINO STINIC ACID AS A COMPLEXING AGENT |
| JP3623971B2 (en) * | 1993-02-26 | 2005-02-23 | ライオン株式会社 | High bulk density granular detergent composition |
| EP0678572A1 (en) * | 1994-04-20 | 1995-10-25 | The Procter & Gamble Company | Detergent powder compositions |
| JPH09279183A (en) * | 1996-04-10 | 1997-10-28 | Kao Corp | Granular high-density detergent composition |
-
1999
- 1999-12-16 GB GBGB9929840.8A patent/GB9929840D0/en not_active Ceased
-
2000
- 2000-11-13 WO PCT/EP2000/011356 patent/WO2001044428A1/en active Search and Examination
- 2000-11-13 PL PL00355785A patent/PL355785A1/en unknown
- 2000-11-13 AU AU20004/01A patent/AU760259B2/en not_active Ceased
- 2000-11-13 DE DE60009745T patent/DE60009745T2/en not_active Expired - Lifetime
- 2000-11-13 TR TR2004/01196T patent/TR200401196T4/en unknown
- 2000-11-13 AT AT00983141T patent/ATE263828T1/en not_active IP Right Cessation
- 2000-11-13 CN CN00818958.7A patent/CN1229479C/en not_active Expired - Fee Related
- 2000-11-13 HU HU0203587A patent/HUP0203587A2/en unknown
- 2000-11-13 ES ES00983141T patent/ES2217001T3/en not_active Expired - Lifetime
- 2000-11-13 BR BR0016435-6A patent/BR0016435A/en not_active Application Discontinuation
- 2000-11-13 EP EP00983141A patent/EP1238052B1/en not_active Expired - Lifetime
-
2002
- 2002-06-06 ZA ZA200204545A patent/ZA200204545B/en unknown
Non-Patent Citations (1)
| Title |
|---|
| See references of WO0144428A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2000401A (en) | 2001-06-25 |
| CN1434855A (en) | 2003-08-06 |
| CN1229479C (en) | 2005-11-30 |
| HUP0203587A2 (en) | 2003-02-28 |
| ZA200204545B (en) | 2003-08-18 |
| DE60009745T2 (en) | 2005-04-28 |
| BR0016435A (en) | 2002-10-01 |
| EP1238052B1 (en) | 2004-04-07 |
| ATE263828T1 (en) | 2004-04-15 |
| AU760259B2 (en) | 2003-05-08 |
| DE60009745D1 (en) | 2004-05-13 |
| GB9929840D0 (en) | 2000-02-09 |
| TR200401196T4 (en) | 2004-07-21 |
| WO2001044428A1 (en) | 2001-06-21 |
| PL355785A1 (en) | 2004-05-17 |
| ES2217001T3 (en) | 2004-11-01 |
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