EP0901512B1 - Reinigungsmittelzusammensetzung - Google Patents
Reinigungsmittelzusammensetzung Download PDFInfo
- Publication number
- EP0901512B1 EP0901512B1 EP97918151A EP97918151A EP0901512B1 EP 0901512 B1 EP0901512 B1 EP 0901512B1 EP 97918151 A EP97918151 A EP 97918151A EP 97918151 A EP97918151 A EP 97918151A EP 0901512 B1 EP0901512 B1 EP 0901512B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- detergent composition
- composition according
- detergent
- surfactant
- liquid
- 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.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims description 80
- 239000003599 detergent Substances 0.000 title claims description 35
- 239000004744 fabric Substances 0.000 claims description 30
- 230000000475 sunscreen effect Effects 0.000 claims description 29
- 239000000516 sunscreening agent Substances 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 20
- 239000003112 inhibitor Substances 0.000 claims description 19
- 230000008021 deposition Effects 0.000 claims description 15
- 125000002091 cationic group Chemical group 0.000 claims description 13
- 239000003945 anionic surfactant Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 239000002736 nonionic surfactant Substances 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 7
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 239000007844 bleaching agent Substances 0.000 description 21
- -1 wool Polymers 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- YBGZDTIWKVFICR-JLHYYAGUSA-N Octyl 4-methoxycinnamic acid Chemical compound CCCCC(CC)COC(=O)\C=C\C1=CC=C(OC)C=C1 YBGZDTIWKVFICR-JLHYYAGUSA-N 0.000 description 15
- 238000000151 deposition Methods 0.000 description 15
- 239000002304 perfume Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 229920000742 Cotton Polymers 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 10
- 150000002431 hydrogen Chemical group 0.000 description 10
- 239000010457 zeolite Substances 0.000 description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 108091005804 Peptidases Proteins 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 229910021536 Zeolite Inorganic materials 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 8
- 235000006708 antioxidants Nutrition 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 230000005855 radiation Effects 0.000 description 8
- 102000035195 Peptidases Human genes 0.000 description 7
- 239000000284 extract Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 229910000323 aluminium silicate Inorganic materials 0.000 description 6
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 5
- 102000004190 Enzymes Human genes 0.000 description 5
- 108090000790 Enzymes Proteins 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- FMRHJJZUHUTGKE-UHFFFAOYSA-N Ethylhexyl salicylate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1O FMRHJJZUHUTGKE-UHFFFAOYSA-N 0.000 description 5
- 239000004365 Protease Substances 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 229940088598 enzyme Drugs 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 229960004592 isopropanol Drugs 0.000 description 5
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- 150000001767 cationic compounds Chemical class 0.000 description 4
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 150000004965 peroxy acids Chemical class 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 229940045872 sodium percarbonate Drugs 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 108010056079 Subtilisins Proteins 0.000 description 3
- 102000005158 Subtilisins Human genes 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- 229910021538 borax Inorganic materials 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000005562 fading Methods 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920001983 poloxamer Polymers 0.000 description 3
- 229940024999 proteolytic enzymes for treatment of wounds and ulcers Drugs 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000004328 sodium tetraborate Substances 0.000 description 3
- 235000010339 sodium tetraborate Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CWRORZJYSUFYHO-UHFFFAOYSA-N (3z)-3-diazobicyclo[2.2.2]octane Chemical compound C1CC2C(=[N+]=[N-])CC1CC2 CWRORZJYSUFYHO-UHFFFAOYSA-N 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 2
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- LALVCWMSKLEQMK-UHFFFAOYSA-N 1-phenyl-3-(4-propan-2-ylphenyl)propane-1,3-dione Chemical compound C1=CC(C(C)C)=CC=C1C(=O)CC(=O)C1=CC=CC=C1 LALVCWMSKLEQMK-UHFFFAOYSA-N 0.000 description 2
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 description 2
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 2
- ZMWRRFHBXARRRT-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(N2N=C3C=CC=CC3=N2)=C1O ZMWRRFHBXARRRT-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- WSSJONWNBBTCMG-UHFFFAOYSA-N 2-hydroxybenzoic acid (3,3,5-trimethylcyclohexyl) ester Chemical compound C1C(C)(C)CC(C)CC1OC(=O)C1=CC=CC=C1O WSSJONWNBBTCMG-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 2
- ZYEMGPIYFIJGTP-UHFFFAOYSA-N O-methyleugenol Chemical compound COC1=CC=C(CC=C)C=C1OC ZYEMGPIYFIJGTP-UHFFFAOYSA-N 0.000 description 2
- WYWZRNAHINYAEF-UHFFFAOYSA-N Padimate O Chemical compound CCCCC(CC)COC(=O)C1=CC=C(N(C)C)C=C1 WYWZRNAHINYAEF-UHFFFAOYSA-N 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
- 229940022663 acetate Drugs 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- BLFLLBZGZJTVJG-UHFFFAOYSA-N benzocaine Chemical compound CCOC(=O)C1=CC=C(N)C=C1 BLFLLBZGZJTVJG-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 150000008366 benzophenones Chemical class 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- WXNRYSGJLQFHBR-UHFFFAOYSA-N bis(2,4-dihydroxyphenyl)methanone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1O WXNRYSGJLQFHBR-UHFFFAOYSA-N 0.000 description 2
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N cinnamic acid Chemical class OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 2
- 150000001860 citric acid derivatives Chemical class 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical class C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- MJVGBKJNTFCUJM-UHFFFAOYSA-N mexenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=C(C)C=C1 MJVGBKJNTFCUJM-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 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
- 238000012545 processing Methods 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
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- HEOCBCNFKCOKBX-RELGSGGGSA-N (1s,2e,4r)-4,7,7-trimethyl-2-[(4-methylphenyl)methylidene]bicyclo[2.2.1]heptan-3-one Chemical compound C1=CC(C)=CC=C1\C=C/1C(=O)[C@]2(C)CC[C@H]\1C2(C)C HEOCBCNFKCOKBX-RELGSGGGSA-N 0.000 description 1
- OIQXFRANQVWXJF-ACCUITESSA-N (2e)-2-benzylidene-4,7,7-trimethylbicyclo[2.2.1]heptan-3-one Chemical compound CC1(C)C2CCC1(C)C(=O)\C2=C\C1=CC=CC=C1 OIQXFRANQVWXJF-ACCUITESSA-N 0.000 description 1
- PDHSAQOQVUXZGQ-JKSUJKDBSA-N (2r,3s)-2-(3,4-dihydroxyphenyl)-3-methoxy-3,4-dihydro-2h-chromene-5,7-diol Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2OC)=CC=C(O)C(O)=C1 PDHSAQOQVUXZGQ-JKSUJKDBSA-N 0.000 description 1
- AALXZHPCKJILAZ-UHFFFAOYSA-N (4-propan-2-ylphenyl)methyl 2-hydroxybenzoate Chemical compound C1=CC(C(C)C)=CC=C1COC(=O)C1=CC=CC=C1O AALXZHPCKJILAZ-UHFFFAOYSA-N 0.000 description 1
- CIOXZGOUEYHNBF-UHFFFAOYSA-N (carboxymethoxy)succinic acid Chemical class OC(=O)COC(C(O)=O)CC(O)=O CIOXZGOUEYHNBF-UHFFFAOYSA-N 0.000 description 1
- MAAFMNFCKWEWLO-UHFFFAOYSA-N (diaminomethylideneamino)methylphosphonic acid Chemical compound NC(N)=NCP(O)(O)=O MAAFMNFCKWEWLO-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- GNMDORSUZRRMFS-UHFFFAOYSA-N 1,3-bis(4-methoxyphenyl)propane-1,3-dione Chemical compound C1=CC(OC)=CC=C1C(=O)CC(=O)C1=CC=C(OC)C=C1 GNMDORSUZRRMFS-UHFFFAOYSA-N 0.000 description 1
- WHQOKFZWSDOTQP-UHFFFAOYSA-N 2,3-dihydroxypropyl 4-aminobenzoate Chemical compound NC1=CC=C(C(=O)OCC(O)CO)C=C1 WHQOKFZWSDOTQP-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
- FACFHHMQICTXFZ-UHFFFAOYSA-N 2-(2-phenylimidazo[1,2-a]pyridin-3-yl)ethanamine Chemical compound N1=C2C=CC=CN2C(CCN)=C1C1=CC=CC=C1 FACFHHMQICTXFZ-UHFFFAOYSA-N 0.000 description 1
- LVVZBNKWTVZSIU-UHFFFAOYSA-N 2-(carboxymethoxy)propanedioic acid Chemical class OC(=O)COC(C(O)=O)C(O)=O LVVZBNKWTVZSIU-UHFFFAOYSA-N 0.000 description 1
- DNRJTBAOUJJKDY-UHFFFAOYSA-N 2-Acetyl-3,5,5,6,8,8-hexamethyl-5,6,7,8- tetrahydronaphthalene Chemical compound CC(=O)C1=C(C)C=C2C(C)(C)C(C)CC(C)(C)C2=C1 DNRJTBAOUJJKDY-UHFFFAOYSA-N 0.000 description 1
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- 239000001819 propan-2-yl (E)-3-phenylprop-2-enoate Substances 0.000 description 1
- WZXKPNYMUZGZIA-RMKNXTFCSA-N propyl (e)-3-(4-methoxyphenyl)prop-2-enoate Chemical compound CCCOC(=O)\C=C\C1=CC=C(OC)C=C1 WZXKPNYMUZGZIA-RMKNXTFCSA-N 0.000 description 1
- 230000002797 proteolythic effect Effects 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- SJOXEWUZWQYCGL-UHFFFAOYSA-N salicylic acid menthyl ester Natural products CC(C)C1CCC(C)CC1OC(=O)C1=CC=CC=C1O SJOXEWUZWQYCGL-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 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
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 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
- 239000002689 soil Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- 229940042585 tocopherol acetate Drugs 0.000 description 1
- 235000019149 tocopherols Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 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
- LOIYMIARKYCTBW-UHFFFAOYSA-N urocanic acid Chemical compound OC(=O)C=CC1=CNC=N1 LOIYMIARKYCTBW-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical group C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- ZFNVDHOSLNRHNN-UHFFFAOYSA-N xi-3-(4-Isopropylphenyl)-2-methylpropanal Chemical compound O=CC(C)CC1=CC=C(C(C)C)C=C1 ZFNVDHOSLNRHNN-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- QUEDXNHFTDJVIY-UHFFFAOYSA-N γ-tocopherol Chemical class OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-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
- C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/835—Mixtures of non-ionic with cationic 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/86—Mixtures of anionic, cationic, and non-ionic 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0063—Photo- activating 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
- C11D3/16—Organic compounds
- C11D3/18—Hydrocarbons
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2006—Monohydric alcohols
- C11D3/2034—Monohydric alcohols aromatic
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2072—Aldehydes-ketones
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2093—Esters; Carbonates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Definitions
- Protection from visible radiation with a wavelength of 400nm or greater is preferably achieved by using singlet oxygen quenchers, free radical traps and anti-oxidants.
- the photofading inhibitors must have a log P value of at least 1.9, more preferably of at least 2.5, most preferably greater than 3.5.
- the photofading inhibitor must be dispersed in a liquid, the liquid having a log P value of at least 1.9, more preferably of at least 2.5, most preferably greater than 3.5. It is also beneficial if the liquid in which the solid photofading inhibitor is to be dissolved is immiscible in water or only sparingly soluble. By sparingly soluble a solubility of no more than 0.04 moles/litre is meant.
- the sunscreen can be an oily liquid with a logP of at least 1.9 or a solid organic material that can be dissolved in a water immiscible or sparingly water soluble liquid, the liquid having a logP of greater than 1.9.
- the sunscreen absorbs light at a wavelength from about 280-400nm.
- Suitable sunscreens are described in: N.A. Saath, Cosmestics and Toiletries Vol 102 March 1987 page 21-39 Classifications given as table 2 on page 22,; N.A. Saath, Evolution of modern sunscreen chemicals pages 3-35; Cosmetics and Toiletries Vol 107 March 1992. Sunscreen use in cosmetic formulas, pages 45-47; Ultra violet absorbers by S.B. Miller, G.R. Lappin, and C.E. Tholstrup in 1968-1969 Modern Plastics Encyclopedia, pages 442-447 and; G.R. Lappin, Encyclopedia of polymer science and technology, vol 14, pages 125-148, Ultra violet radiation absorbers.
- the sunscreen compound containing at least one chromophore is selected from the group consisting of phenylbenzotriazoles, esters of cinnamic acid, benzophenones, esters of para aminobenzoic acid, esters of salicylic acid, dibenzoyl methane and mixtures thereof.
- R 4 is a hydrogen, a hydroxy group, a C 1 -C 22 alkyl group, preferably a hydrogen or a hydroxy group and most preferably a hydroxy group.
- R 5 is is a hydrogen, a hydroxy group, a C 1 -C 22 alkyl group, more preferably a C 1 -C 8 alkyl group and most preferably a tertiary amyl group or tertiary butyl group.
- R 8 is a hydrogen, a hydroxy group,C 1 -C 22 alkyl group,and mixtures thereof.
- R 9 is a hydrogen, a hydroxy group, C 1 -C 22 alkyl group, and mixtures thereof.
- R 10 is a hydrogen, or a C 1 -C 22 alkyl group.
- R 11 is a hydrogen, or a C 1 -C 22 alkyl group.
- R 14 is a C 1 -C 22 alkyl group
- R 15 is a hydrogen, methoxy or a C 1 -C 22 alkyl group.
- antioxidant refers to a non-fabric staining, light stable antioxidant compound, that is either an oily liquid with a logP of at least 1.9 or a solid organic material that can be dissolved in a water immiscible or sparingly water soluble liquid with a logP of greater than 1.9.
- antioxidant compounds and/or singlet oxygen quenchers include : ascorbic palmitate, butylated hydroxy anisole, tertiary butyl hydroquinone, natural tocopherols and derivatives such as vitamin E acetate and Irganox antioxidants as supplied by Ciba Geigy such as Irganox 1010 (tetrakis methylene (3,5-di-tert-butyl-4hydroxycinnamate)) methane), Irganox 1035 (thiodiethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)), Irganox 1076 (octadecyl propan-(3-benzene-3',5' di tert butyl-4' hydroxy)-oate, Irganox 1425 (calcium bis (monoethyl(3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate), Irganox 30
- Preferred materials include
- the nonionic surfactant is nonionic surfactant
- composition of the invention requires the presence of a nonionic surfactant.
- Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C8-C20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C10-C15 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).
- the level of nonionic surfactant is from 2 wt% to 40 wt%, preferably from 10 wt% to 30 wt% of the total product.
- detergent-active compound surfactant
- amount present will depend on the intended use of the detergent composition.
- surfactant systems may be chosen, as is well known to the skilled formulator, for handwashing products and for products intended for use in different types of washing machine.
- compositions of the invention may be present in compositions of the invention it is preferred if it is absent.
- the ratio of cationic material to anionic material is at least 2:1.
- suitable anionic surfactants include alkylbenzene sulphonate primary and secondary alkyl sulphates, particularly C 8 -C 15 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; ethercarboxylates; isothionates; sarcosinates and fatty acid ester sulphonates, Sodium salts are generally preferred.
- Detergent compositions suitable for use in most automatic fabric washing machines generally contain anionic non-soap surfactant, or nonionic surfactant, or combinations of the two in any ratio, optionally together with soap.
- the detergent surfactant is advantageously solid at room temperature as this provides crisp composition particles.
- compositions of the invention must contain a quaternary ammonium compound cationic compound.
- the quaternary ammonium compound is a quaternary ammonium compound having at least one C 12 -C 22 alkyl chain.
- the quaternary ammonium compound has the following formula: in which R 1 is a C 12 to C 22 alkyl or alkenyl chain, R 2 , R 3 and R 4 are independently selected from C 1 -C 4 alkyl chains and X - is a compatible anion.
- R 1 is a C 12 to C 22 alkyl or alkenyl chain
- R 2 , R 3 and R 4 are independently selected from C 1 -C 4 alkyl chains
- X - is a compatible anion.
- a preferred compound of this type is the quaternary ammonium compound cetyl trimethyl quaternary ammonium bromide.
- a second class of materials for use with the present invention are the quaternary ammonium compound having the following formula: in which R 1 and R 2 are independently selected from C 12 to C 22 alkyl or alkenyl chain; R 3 and R 4 are independently selected from C 1 -C 4 alkyl chains and X - is compatible anion.
- the ratio of cationic to nonionic surfactant is from 1:100 to 50:50, more preferably 1:50 to 20:50.
- the cationic compound may be present from 0.02 wt% to 20 wt% of the total weight of the composition.
- the cationic compound may be present from 0.05 wt% to 15 wt%, a more preferred composition range is from 0.2 wt% to 5 wt%, and most preferably the composition range is from 0.4 wt% to 2.5 wt% of the total weight of the composition.
- the level of cationic surfactant is 0.05 wt% to 15 wt% of the total weight of the composition.
- a more preferred composition range is from 0.2 wt% to 10 wt%, and the most preferred composition range is from 0.9 wt% to 3.0 wt% of the total weight of the composition.
- the detergent compositions of the invention will generally also contain one or more detergency builders.
- the total amount of detergency builder in the compositions will suitably range from 5 to 80 wt%, preferably from 10 to 60 wt%.
- Inorganic builders that may be present include sodium carbonate, if desired in combination with a crystallisation seed for calcium carbonate, as disclosed in GB 1 437 950 (Unilever); crystalline and amorphous aluminosilicates, for example, zeolites as disclosed in GB 1 473 201 (Henkel), amorphous aluminosilicates as disclosed in GB 1 473 202 (Henkel) and mixed crystalline/amorphous aluminosilicates as disclosed in GB 1 470 250 (Procter & Gamble); and layered silicates as disclosed in EP 164 514B (Hoechst).
- Inorganic phosphate builders for example, sodium orthophosphate, pyrophosphate and tripolyphosphate are also suitable for use with this invention.
- the detergent compositions of the invention preferably contain an alkali metal, preferably sodium, aluminosilicate builder.
- Sodium aluminosilicates may generally be incorporated in amounts of from 10 to 70% by weight (anhydrous basis), preferably from 25 to 50 wt%.
- the alkali metal aluminosilicate may be either crystalline or amorphous or mixtures thereof, having the general formula: 0.8-1.5 Na 2 O. Al 2 O 3 . 0.8-6 SiO 2
- the preferred sodium aluminosilicates contain 1.5-3.5 SiO 2 units (in the formula above). Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
- Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB 1 429 143 (Procter & Gamble).
- the preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof.
- the zeolite may be the commercially available zeolite 4A now widely used in laundry detergent powders.
- the zeolite builder incorporated in the compositions of the invention is maximum aluminium zeolite P (zeolite MAP) as described and claimed in EP 384 070A (Unilever).
- Zeolite MAP is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium ratio not exceeding 1.33, preferably within the range of from 0.90 to 1.33, and more 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 calcium binding capacity of zeolite MAP is generally at least 150 mg CaO per g of anhydrous material.
- Organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts. This list is not intended to be exhaustive.
- polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates
- monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates,
- Especially preferred 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.
- Fabric washing compositions may desirably contain 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.
- organic peroxides such as urea peroxide
- 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 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).
- the peroxy bleach compound is suitably present in an amount of from 0.1 to 35 wt%, preferably from 0.5 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 0.1 to 8 wt%, preferably from 0.5 to 5 wt%.
- Preferred bleach precursors are peroxycarboxylic acid precursors, more especially peracetic acid precursors and pernoanoic acid precursors.
- Especially preferred bleach precursors suitable for use in the present invention are N,N,N',N'-tetracetyl ethylenediamine (TAED) and sodium noanoyloxybenzene sulphonate (SNOBS).
- TAED N,N,N',N'-tetracetyl ethylenediamine
- SNOBS sodium noanoyloxybenzene sulphonate
- 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), and the cationic bleach precursors disclosed in EP 284 292A and EP 303 520A (Kao) are also of interest.
- the bleach system can be either supplemented with or replaced by a peroxyacid.
- peracids can be found in US 4 686 063 and US 5 397 501 (patent on TPCAP - Unilever).
- a preferred example is the imido peroxycarboxylic class of peracids described in EP A 325 288, EP A 349 940, DE 382 3172 and EP 325 289.
- a particularly preferred example is phtalimido peroxy caproic acid (PAP).
- PAP phtalimido peroxy caproic acid
- Such peracids are suitably present at 0.1 - 12%, preferably 0.5 - 10%.
- a bleach stabiliser may also be present.
- Suitable bleach stabilisers include ethylenediamine tetraacetate (EDTA), the polyphosphonates such as Dequest (Trade Mark) and non-phosphate stabilisers such as EDDS (ethylene diamine di-succinic acid). These Bleach stabilisers are also useful for stain removal, especially in products containing low levels of bleaching species or no bleaching species.
- An especially preferred bleach system comprises a peroxy bleach compound (preferably sodium percarbonate optionally together with a bleach activator), and a transition metal bleach catalyst as described and claimed in EP 458 397A, EP 458 398A and EP 509 787A (Unilever).
- a peroxy bleach compound preferably sodium percarbonate optionally together with a bleach activator
- a transition metal bleach catalyst as described and claimed in EP 458 397A, EP 458 398A and EP 509 787A (Unilever).
- Suitable enzymes include the proteases, amylases, cellulases, oxidases, peroxidases and lipases 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 and can be used in the instant invention.
- suitable proteolytic enzymes are the subtilisins, which are obtained from particular strains of B . subtilis and B . licheniformis, such as the commercially available subtilisins Maxatase (Trade Mark), as supplied by Gist-Brocades N.V., Delft, Holland, and Alcalase (Trade Mark), as supplied by Novo Industri A/S, Copenhagen, Denmark.
- protease obtained from a strain of Bacillus having maximum activity throughout the pH range of 8-12, being commercially available, e.g. from Novo Industri A/S under the registered trade-names Esperase (Trade Mark) and Savinase (Trade-Mark).
- Esperase Trade Mark
- Savinase Trade-Mark
- Other commercial proteases are Kazusase (Trade Mark) (obtainable from Showa-Denko of Japan), Optimase (Trade Mark) (from Miles Kali-Chemie, Hannover, West Germany), and Superase (Trade Mark) (obtainable from Pfizer of U.S.A.).
- compositions of the invention may contain alkali metal, preferably sodium carbonate, in order to increase detergency and ease processing.
- Sodium carbonate may suitably be present in amounts ranging from 1 to 60 wt%, preferably from 2 to 40 wt%.
- compositions containing little or no sodium carbonate are also within the scope of the invention.
- Powder flow may be improved by the incorporation of a small amount of a powder structurant, for example, a fatty acid (or fatty acid soap), a sugar, an acrylate or acrylate/maleate polymer, or sodium silicate.
- a powder structurant for example, a fatty acid (or fatty acid soap), a sugar, an acrylate or acrylate/maleate polymer, or sodium silicate.
- One preferred powder structurant is fatty acid soap, suitably present in an amount of from 1 to 5 wt%.
- detergent compositions of the invention include sodium silicate; antiredeposition agents such as cellulosic polymers; inorganic salts such as sodium sulphate; lather control agents or lather boosters as appropriate; proteolytic and lipolytic enzymes; dyes; coloured speckles; foam controllers; fabric softening compounds, soil release polymers, fluorescers and decoupling polymers. This list is not intended to be exhaustive.
- the detergent composition when diluted in the wash liquor (during a typical wash cycle) will give a pH of the wash liquor from 7 to 10.5.
- the detergent components of the present invention may be incorporated in detergent compositions of all physical types, for example, powders, liquids, gels and solid bars.
- Detergent compositions of the invention may be prepared by any suitable method.
- Particulate detergent compositions are suitably prepared by spray-drying a slurry of compatible heat-insensitive ingredients, and then spraying on or postdosing those ingredients unsuitable for processing via the slurry.
- the skilled detergent formulator will have no difficulty in deciding which ingredients should be included in the slurry and which should not.
- Particulate detergent compositions of the invention preferably have a bulk density of at least 400 g/l, more preferably at least 500 g/l.
- compositions have bulk densities of at least 650 g/litre, more preferably at least 700 g/litre.
- Such powders may be prepared either by post-tower densification of spray-dried powder, or by wholly non-tower methods such as dry mixing and granulation; in both cases a high-speed mixer/granulator may advantageously be used.
- Liquid detergent compositions can be prepared by admixing the essential and optional ingredients thereof in any desired order to provide compositions containing components in the requisite concentrations.
- Liquid compositions according to the present invention can also be in compact form which means it will contain a lower level of water compared to a conventional liquid detergent.
- the Parsol MCX present on the dry fabric was recovered by solvent extraction.
- a 3g piece of knitted cotton was placed in a 20 ml screw top vial, and 15 ml of high purity isopropyl alcohol added.
- the vial was roller mixed for 3 hours on a Luckham Multimix Major, before sonicating for 30 minutes in a small sonic bath.
- the concentration of Parsol MCX present in the extract was then determined by GC/MS analysis (Finnigan Magnum fitted with a 25 metre SGE BPX-5 (non-polar) glass capillary column of internal diameter 0.22mm with a film thickness of 0.25 ⁇ m). UV/visible absorbance procedures were also employed as a check of sunscreen deposition level.
- Coco 3EO NRE C 12-14 alcohol ethoxylate with a mean ethylene oxide chain length of 3.
- NRE Narrow range ethoxylate
- CTAB Cetyl trimethyl ammonium bromide.
- ARQUAD 2T dimethyl ditallow ammonium chloride (non-hardened)
- Synperonic A7 C 11-13 alcohol ethoxylate with a mean ethylene oxide chain length of 7
- Parsol MCX is 2-Ethylhexyl 4-methoxycinnamate with a log P value of 5.2. Deposition of Parsol MCX on cotton from duplicate washes containing Examples 2 and 3, 5, 6 and Example B and D. Deposition monitored as ppm of Parsol MCX in iso-propyl alcohol extract. Level determined by GC/MS. Product Duplicate experiment 1 Duplicate experiment 2 Example B 1.28 1.22 Example D 1.6 1.52 Example 3 10.35 11.23 Example 2 18.1 17.8 Deposition of Parsol MCX on cotton from duplicate washes containing Example B and Example 1. Deposition monitored as ppm of Parsol MCX in iso-propyl alcohol extract. Level determined by GC/MS.
- Example A Example 1 Number of Wash Cycles Duplicate Experiment 1 Duplicate Experiment 2 Duplicate Experiment 1 Duplicate Experiment 2 1 5.46 4.64 17.3 17.2 2 6.8 6.6 36.8 40.0 3 7.1 6.7 56.4 55.9 4 6.5 6.8 5.9 66.9 5 4.5 5.0 5.6 118.0 Deposition of Parsol MCX on cotton from duplicate washes containing Example A and Example 1. Deposition monitored as ppm of Parsol MCX in iso-propyl alcohol extract. Level determined by measurement of the optical density at the ⁇ max of Parsol MCX.
- Example A Example 1 Number of Wash Cycles Experiment 3 Experiment 4 Experiment 3 Experiment 4 1 2.8 2.7 23.0 21.5 2 3.6 3.3 57.8 50.3 3 4.0 - 88.9 - 4 4.15 3.5 97.5 103.6 5 2.3 2.5 115.5 118.0
- Table 6 shows the comparison of perfume components delivered to cotton fabric from a CTAB/nonionic (10/90) liquid product containing 17% total active.
- the perfume components are quoted as concentration (ppm) in a solvent extract from the washed and dried fabric.
- Table 6 shows the level of perfume deposited onto fabric.
- Example 4 contains diethylphthalate which has a logP of 2.15, and Example E contains 2-butoxyethanol which is water soluble and has a logP of 0.84.
- Example 4 (wt%)
- Example E (wt%)
- Ethyl alcohol 10 10 Tinuvin 328 0.1 0.1 Diethylphthalate 1.0 - 2-Butoxy ethanol - 1.0 Water to 100% to 100%
- Washes were carried out in a Tergotometer at 20°C using 6g/l of each product over a period of 20 minutes in the presence of 1.14g/l of borax buffer. An initial liquor volume of 1200ml was selected for the first wash. Fabrics were removed after each wash to determine the level of sunscreen deposited on the fabric. The wash liquor volume was reduced in the second and third washes to maintain the liquor to cloth ratio at 30:1. At the end of each wash the fabrics were squeezed to remove excess liquor and rinsed three times at a liquor to cloth ratio of 40:1, before air drying in the dark. Dry white cotton pieces measuring 5.08 cm x 11.43 cm (2" x 4.5") taken from each wash were each placed in a glass sample vial and 15ml of ethylacetate added.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Claims (9)
- Waschmittelzusammensetzung, umfassendi) ein nichtionisches Waschmitteltensid;ii) ein kationisches Material einer quaternären Ammoniumverbindung;iii) einen flüssigen Lichtverblassungsinhibitor mit einem logP-Wert von mindestens 1,9 oder einen festen Lichtverblassungsinhibitor, gelöst in einer Flüssigkeit, wobei die Flüssigkeit einen logP-Wert von mindestens 1,9 aufweist, oder Gemische davon; undiv) gegebenenfalls ein anionisches Tensid;
- Waschmittelzusammensetzung nach Anspruch 1, wobei das Verhältnis von (ii) kationischem Material zu (iv) anionischem Tensid mindestens 2:1 ist.
- Waschmittelzusammensetzung nach Anspruch 1 oder Anspruch 2, die kein anionisches Tensid umfaßt.
- Waschmittelzusammensetzung nach einem vorangehenden Anspruch, wobei der Anteil von kationischem Material zu nichtionischem Tensid 1:100 bis 50:50 ist.
- Waschmittelzusammensetzung nach einem vorangehenden Anspruch, wobei die quaternäre Ammoniumverbindung mindestens eine C12-C22-Alkyl- oder Alkenylkette aufweist.
- Waschmittelzusammensetzung nach einem vorangehenden Anspruch, die eine Flüssigkeit darstellt und in der der Gesamtanteil an kationischem Material 0,05 Gewichtsprozent bis 10 Gewichtsprozent des Gesamtgewichts der Zusammensetzung ist.
- Waschmittelzusammensetzung nach einem der Ansprüche 1 bis 5, in der die Zusammensetzung in Pulver- oder granulärer Form vorliegt und in der der Anteil von kationischem Material 0,05 Gewichtsprozent bis 15 Gewichtsprozent des Gesamtgewichts der Zusammensetzung ist.
- Waschmittelzusammensetzung nach einem vorangehenden Anspruch, in der der Anteil an Lichtverblassungsinhibitor 0,01 Gewichtsprozent bis 10 Gewichtsprozent des Gesamtgewichts der Zusammensetzung ist.
- Verwendung einer Waschmittelzusammensetzung nach Anspruch 1 zur Abscheidung eines Sonnenschutzmittels auf einem Textil.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB9610865.9A GB9610865D0 (en) | 1996-05-23 | 1996-05-23 | Detergent composition |
GB9610865 | 1996-05-23 | ||
PCT/EP1997/002000 WO1997044422A1 (en) | 1996-05-23 | 1997-04-17 | Detergent composition |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0901512A1 EP0901512A1 (de) | 1999-03-17 |
EP0901512B1 true EP0901512B1 (de) | 2000-06-21 |
Family
ID=10794233
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97918151A Expired - Lifetime EP0901512B1 (de) | 1996-05-23 | 1997-04-17 | Reinigungsmittelzusammensetzung |
Country Status (13)
Country | Link |
---|---|
EP (1) | EP0901512B1 (de) |
AR (1) | AR007188A1 (de) |
AU (1) | AU710428B2 (de) |
BR (1) | BR9709021A (de) |
CA (1) | CA2255854C (de) |
DE (1) | DE69702344T2 (de) |
ES (1) | ES2147672T3 (de) |
GB (1) | GB9610865D0 (de) |
ID (1) | ID16776A (de) |
IN (1) | IN188730B (de) |
TR (1) | TR199802388T2 (de) |
WO (1) | WO1997044422A1 (de) |
ZA (2) | ZA973494B (de) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9801078D0 (en) * | 1998-01-19 | 1998-03-18 | Unilever Plc | Improvements relating to hard surface cleaners |
GB9801082D0 (en) * | 1998-01-19 | 1998-03-18 | Unilever Plc | Improvements relating to hard surface cleaners |
HUP0202360A2 (en) * | 1999-07-12 | 2002-11-28 | Unilever Nv | Hard surface cleaning composition comprising a uva-filter |
GB9929693D0 (en) * | 1999-12-15 | 2000-02-09 | Unilever Plc | Fabric care composition |
DE10015086A1 (de) * | 2000-03-28 | 2001-10-04 | Basf Ag | Textilfaseraffine UV-Absorber-Mischung |
US6696398B2 (en) | 2001-10-25 | 2004-02-24 | Colgate-Palmolive Company | Stabilized composition comprising 2-(2-H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol |
GB0412225D0 (en) * | 2004-06-02 | 2004-07-07 | Unilever Plc | Bleaching composition |
GB0412223D0 (en) * | 2004-06-02 | 2004-07-07 | Unilever Plc | Bleaching composition |
US20130117946A1 (en) * | 2009-02-25 | 2013-05-16 | Fariborz Dawudian | Compositions and methods to use them to remove stains from garments including water sensitive protein fibers, without incurring any damage to the fibers or dye/color loss, in wet and dry cleaning processes |
PL2553073T3 (pl) * | 2010-03-26 | 2017-09-29 | Liquid Vanity Aps | Detergent piorący |
EP4277972A1 (de) * | 2021-01-13 | 2023-11-22 | Unilever IP Holdings B.V. | Waschmittelzusammensetzung |
WO2022152548A1 (en) * | 2021-01-13 | 2022-07-21 | Unilever Ip Holdings B.V. | Fabric conditioner |
EP4349942A1 (de) * | 2022-10-05 | 2024-04-10 | Unilever IP Holdings B.V. | Flüssigwaschmittelzusammensetzung |
EP4349945A1 (de) * | 2022-10-05 | 2024-04-10 | Unilever IP Holdings B.V. | Flüssigwaschmittelzusammensetzung |
EP4349943A1 (de) * | 2022-10-05 | 2024-04-10 | Unilever IP Holdings B.V. | Flüssigwaschmittelzusammensetzung |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0523956B2 (de) * | 1991-07-17 | 1999-02-03 | Unilever Plc | Wasserlösliches oder in Wasser dispergierbares Copolymer mit UV-Strahlen absorbierendem Monomer enthaltendes Wäschepflegemittel |
GB9326358D0 (en) * | 1993-12-23 | 1994-02-23 | Ciba Geigy Ag | Compositions for the treatment of textiles |
AU2969395A (en) * | 1994-07-26 | 1996-02-22 | Procter & Gamble Company, The | Rinse added fabric softener compositions containing sunscreens for sun-fade protection for fabrics |
-
1996
- 1996-05-23 GB GBGB9610865.9A patent/GB9610865D0/en active Pending
-
1997
- 1997-04-17 WO PCT/EP1997/002000 patent/WO1997044422A1/en active IP Right Grant
- 1997-04-17 TR TR1998/02388T patent/TR199802388T2/xx unknown
- 1997-04-17 DE DE69702344T patent/DE69702344T2/de not_active Expired - Fee Related
- 1997-04-17 BR BR9709021-2A patent/BR9709021A/pt not_active IP Right Cessation
- 1997-04-17 EP EP97918151A patent/EP0901512B1/de not_active Expired - Lifetime
- 1997-04-17 CA CA002255854A patent/CA2255854C/en not_active Expired - Fee Related
- 1997-04-17 AU AU26384/97A patent/AU710428B2/en not_active Ceased
- 1997-04-17 ES ES97918151T patent/ES2147672T3/es not_active Expired - Lifetime
- 1997-04-23 ZA ZA973494A patent/ZA973494B/xx unknown
- 1997-04-25 IN IN253BO1997 patent/IN188730B/en unknown
- 1997-05-07 ZA ZA973932A patent/ZA973932B/xx unknown
- 1997-05-19 AR ARP970102106A patent/AR007188A1/es unknown
- 1997-05-21 ID IDP971681A patent/ID16776A/id unknown
Also Published As
Publication number | Publication date |
---|---|
ZA973932B (en) | 1999-04-12 |
IN188730B (de) | 2002-11-02 |
AR007188A1 (es) | 1999-10-13 |
TR199802388T2 (xx) | 1999-02-22 |
WO1997044422A1 (en) | 1997-11-27 |
EP0901512A1 (de) | 1999-03-17 |
AU710428B2 (en) | 1999-09-23 |
DE69702344T2 (de) | 2000-10-19 |
AU2638497A (en) | 1997-12-09 |
BR9709021A (pt) | 2000-05-09 |
ID16776A (id) | 1997-11-06 |
DE69702344D1 (de) | 2000-07-27 |
GB9610865D0 (en) | 1996-07-31 |
CA2255854A1 (en) | 1997-11-27 |
ZA973494B (en) | 1998-10-23 |
ES2147672T3 (es) | 2000-09-16 |
CA2255854C (en) | 2002-09-17 |
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