EP0513136B1 - Composition de blanchissage liquide - Google Patents
Composition de blanchissage liquide Download PDFInfo
- Publication number
- EP0513136B1 EP0513136B1 EP91903653A EP91903653A EP0513136B1 EP 0513136 B1 EP0513136 B1 EP 0513136B1 EP 91903653 A EP91903653 A EP 91903653A EP 91903653 A EP91903653 A EP 91903653A EP 0513136 B1 EP0513136 B1 EP 0513136B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bleach
- weight
- composition
- compositions
- particle size
- 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 abstract description 76
- 239000007844 bleaching agent Substances 0.000 title claims abstract description 62
- 239000007788 liquid Substances 0.000 title claims abstract description 30
- 239000003599 detergent Substances 0.000 claims abstract description 50
- 239000002245 particle Substances 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 37
- 239000011149 active material Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 238000010952 in-situ formation Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 150000004682 monohydrates Chemical class 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 description 25
- 239000004094 surface-active agent Substances 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 13
- 239000011734 sodium Substances 0.000 description 13
- 229910052708 sodium Inorganic materials 0.000 description 13
- 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 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 9
- -1 aliphatic alcohols Chemical class 0.000 description 9
- 239000004615 ingredient Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 238000005185 salting out Methods 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 102000004882 Lipase Human genes 0.000 description 5
- 108090001060 Lipase Proteins 0.000 description 5
- 239000004367 Lipase Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 235000019421 lipase Nutrition 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 102000004190 Enzymes Human genes 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000003240 coconut oil Substances 0.000 description 4
- 235000019864 coconut oil Nutrition 0.000 description 4
- 229940088598 enzyme Drugs 0.000 description 4
- 238000000386 microscopy Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 239000012905 visible particle Substances 0.000 description 4
- 108010065511 Amylases Proteins 0.000 description 3
- 102000013142 Amylases Human genes 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 3
- 108091005804 Peptidases Proteins 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 235000019418 amylase Nutrition 0.000 description 3
- 229940025131 amylases Drugs 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 239000002304 perfume Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 102000005575 Cellulases Human genes 0.000 description 2
- 108010084185 Cellulases Proteins 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 102000035195 Peptidases Human genes 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 239000004365 Protease Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 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
- 108010056079 Subtilisins Proteins 0.000 description 2
- 102000005158 Subtilisins Human genes 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 125000003703 phosphorus containing inorganic group Chemical group 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000002195 soluble material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 108010067770 Endopeptidase K Proteins 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- SUZRRICLUFMAQD-UHFFFAOYSA-N N-Methyltaurine Chemical compound CNCCS(O)(=O)=O SUZRRICLUFMAQD-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 108090000787 Subtilisin Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical group CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 235000019402 calcium peroxide Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000002979 fabric softener Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 229940045996 isethionic acid Drugs 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000002535 lyotropic effect Effects 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 108010020132 microbial serine proteinases Proteins 0.000 description 1
- 238000001683 neutron diffraction Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 150000004976 peroxydisulfates Chemical class 0.000 description 1
- 125000005342 perphosphate group Chemical group 0.000 description 1
- 235000020030 perry Nutrition 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
- 239000003208 petroleum Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical class [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 235000013966 potassium salts of fatty acid Nutrition 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 description 1
- 235000013875 sodium salts of fatty acid 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
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 108010075550 termamyl Proteins 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010457 zeolite 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
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3947—Liquid compositions
Definitions
- the present invention relates to a liquid detergent composition
- a liquid detergent composition comprising an aqueous base, detergent active materials and a bleach material.
- EP 294 904 discloses the use of perborate bleach materials in liquid detergent compositions, whereby the bleach materials are present in the form of particles having a weight average particle diameter of from 0.5 to 20 micrometer and whereby said particles being formed by in situ crystallization.
- a problem in using these small particles is that they require a laborous mixing process, said process often requiring a vigorous mixing step which may lead to moussing of the product.
- these small particles may sometimes be prone to instability due to their relatively large surface area.
- liquid detergent compositions containing these small particles sometimes suffer from high viscosities.
- EP 368 575 relates to suspensions of perborate and thickening agents for incorporation into liquid detergent compositions.
- a problem in using suspensions of bleach materials for the preparation of liquid detergents is that the presence of an aqueous phase in the suspension leads to the dilution of the detergent composition, especially for concentrated liquid detergent compositions. Such a dilution step is often not desirable.
- the use of pre-suspensions of bleach materials leads to an extra processing and/or transporting step for preparing and/or transporting the suspension, generally this results in a cost increase for the liquid detergent composition.
- the present invention relates to a method for the preparation of a liquid detergent composition comprising less than 50% by weight of water, more than 15% by weight of detergent active materials and more than 1 % by weight of a perborate bleach material, said method comprising the in-situ formation of perborate bleach particles having a weight average particle size of more than 20 micrometer.
- a further aspect of the invention is that if the bleach particles having a weight average particle size of more than 20 micrometer are formed in situ, this allows the preparation of liquid detergent compositions which comprise relatively low amounts of water (say less than 50 % by weight, more preferably less than 40 % by weight, more preferably from 10 to 35 %) in combination with relatively high amount of detergent active materials (say more than 15 % by weight, more preferably more than 20 %, most preferably from 25 to 60 %) and relatively high amounts of bleach materials (say more than 1 %, more preferred more than 7 %, most preferred from 10 to 50 %).
- the invention also relates to a liquid detergent composition
- a liquid detergent composition comprising lamellar droplets of detergent active material and also comprising from 5-50 % by weight of water, more than 15 % of detergent active materials and more than 1 % by weight of bleach material, said bleach material having a weight average particle size of more than 20 micrometer.
- compositions according to the present invention comprise a bleach material, which is preferably a peroxygen bleach.
- This bleach component is present in the system at least partly in undissolved form, but generally at least a minor part of the peroxygen bleach will be solubilized.
- the solid particles will generally be suspended in the system.
- bleach compounds include the perborates, persulfates, peroxy disulfates, calcium- peroxides, perphosphates and the crystalline peroxyhydrates formed by reacting hydrogen peroxide with urea oralkali metal carbonate. Also encapsulated bleaches may be used. Especially preferred is the use of perborate or percarbonate bleaches.
- Typical amounts of bleach will be between 1 and 50 % by weight of the aqueous composition, more preferred from 7 to 30 %, especially preferred from 10 to 25 % by weight of the composition.
- the weight average particle size of the bleach particles is more than 20 micrometer, preferably from 22-150 micrometer, more preferably from 25 to 60 micrometer, most preferably from 30 to 50 or 45 micrometer.
- a suitable method for determining the weight average particle size involves the making of microscopy pictures of the liquid detergent composition at a magnification of between 50 and 600 (preferably about 150), followed by the manual or automatic counting of the visible particles, measuring the particle diameter for each particle and calculating the weight average particle size for the visible particles.
- the bleach material will be suspended in the system as agglomerates of small elementary bleach particles. Since it is believed that normally the size of the agglomerates rather than the size of the elementary bleach particles determines the characteristics of the final product, for the purpose of the invention, the bleach particle size refers to the weight average particle size of these agglomerates. If agglomerates of bleach particles are present, for determining the particle size, care has to be taken not to subject the measuring sample to unnecessary shear or pressure, because this may lead to the fragmentation of the agglomerates.
- compositions of the present invention also comprise detergent active materials.
- detergent active materials Surprisingly it has been found that physically stable bleach containing liquid detergent compositions can be obtained by the in-situ formation of bleach particles having a weight average particle size of more than 20 micrometer.
- the detergent active materials in general, may comprise one or more surfactants, and may be selected from anionic, cationic, nonionic, zwitterionic and amphoteric species, and (provided mutually compatible) mixtures thereof.
- surfactants may be chosen from any of the classes, sub-classes and specific materials described in "Surface Active Agents” Vol. I, by Schwartz & Perry, Interscience 1949 and “Surface Active Agents” Vol. II by Schwartz, Perry & Berch (Interscience 1958), in the current edition of "McCutcheon's Emulsifiers & Detergents” published by the McCutcheon division of Manufacturing Confectioners Company or in Tensid-Taschenburch", H. Stache, 2nd Edn., Carl Hanser Verlag, Munchen & Wien, 1981.
- Suitable nonionic surfactants include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
- Specific nonionic detergent compounds are alkyl (C 6 -C 18 ) primary or secondary linear or branched alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine.
- Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.
- salting out resistant active materials such as for example described in EP 328 177
- alkyl poly glycoside surfactants such as for example disclosed in EP 70 074.
- Suitable anionic surfactants are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
- suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher(C 8 -C l8 ) alcohols produced for example from tallow or coconut oil, sodium and potassium alkyl (C 9 -C ZO ) benzene sulphonates, particularly sodium linear secondary alkyl (C 10 -C 15 ) benzene sulphonates; sodium alkyl glyceryl ethersulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C 8 -C l8 ) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide; sodium and potassium salts of fatty acid amide
- an alkali metal soap of a fatty acid especially a soap of an acid having from 12 to 18 carbon atoms, for example oleic acid, ricinoleic acid, and fatty acids derived from castor oil, alkylsuccinic acid, rapeseed oil, groundnut oil, coconut oil, palmkernel oil or mixtures thereof.
- the sodium or potassium soaps of these acids can be used.
- the total detergent active material may be present at from 15% to 70% by weight of the total composition, for example from 20% to 60% and typically from 30% to 50% by weight.
- compositions of the invention may be un-structured (isotropic) but are preferably structured.
- Structured liquids of the invention may be internally structured whereby the structure is formed by the detergent active materials in the composition or externally structured, whereby the structure is provided by an external struc- turant.
- compositions of the invention are internally structured.
- compositions of the invention comprise a surfactant structure comprising lamellar droplets of detergent active materials.
- lamellar droplets are called "spherulites".
- the presence and identity of a surfactant structuring system in a liquid may be determined by means known to those skilled in the art for example, optical techniques, various rheometrical measurements, x-ray or neutron diffraction, and sometimes, electron microscopy.
- the aqueous continuous phase contains dissolved electrolyte.
- electrolyte means any ionic water soluble material.
- the electrolytes may be used, with one or more of the electrolytes being in the dissolved aqueous phase and one or more being substantially only in the suspended solid phase.
- Two or more electrolytes may also be distributed approximately proportionally, between these two phases. In part, this may depend on processing, e.g.
- salts includes all organic and inorganic materials which may be included, other than surfactants and water, whether or not they are ionic, and this term encompasses the sub-set of the electrolytes (water soluble materials).
- compositions where the detergent active material comprises blends of different surfactant types.
- Typical blends useful for fabric washing compositions include those where the primary surfactant(s) comprise nonionic and/or a non-alkoxylated anionic and/or an alkoxylated anionic surfactant.
- the compositions contain from 1% to 60%, especially from 10 to 45% of a salting-out electrolyte.
- Salting-out electrolyte has the meaning ascribed to in specification EP-A-79 646, that is salting-out electrolytes have a lyotropic number of less than 9.5.
- some salting-in electrolyte (as defined in the latter specification) may also be included, provided it is of a kind and in an amount compatible with the other components and the composition is still in accordance with the definition of the invention claimed herein.
- Some or all of the electrolyte may have detergency builder properties.
- compositions according to the present invention include detergency builder material, some or all of which may be electrolyte.
- the builder material is any capable of reducing the level of free calcium ions in the wash liquor and will preferably provide the composition with other beneficial properties such as the generation of an alkaline pH, the suspension of soil removed from the fabric and the dispersion of the fabric softening clay material.
- the salting-out electrolyte comprises citrate.
- Examples of phosphorus-containing inorganic detergency builders when present, include the water-soluble salts, especially alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates.
- Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, phosphates and hexametaphosphates. Phosphonate sequestrant builders may also be used.
- non-phosphorus-containing inorganic detergency builders when present, include water-soluble alkali metal carbonates, bicarbonates, silicates and crystalline and amorphous aluminosilicates. Specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonates, silicates and zeolites.
- organic detergency builders when present, include the alkaline metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetyl carboxylates and polyhydroxysulphonates. Specific examples include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilitriacetic acid, oxydisuccinic acid, CMOS, TMS, TDS, melitic acid, benzene polycarboxylic acids and citric acid.
- the level of non-soap builder material is from 0-50% by weight of the composition, more preferred from 5-40%, most preferred 10-35%.
- compositions of the present invention alternatively, or in addition to the partly dissolved polymer, yet another polymerwhich is substantially totally soluble in the aqueous phase and has an electrolyte resistance of more than 5 grams sodium nitrilotriacetate in 100mi of a 5% by weight aqueous solution of the polymer, said second polymer also having a vapour pressure in 20% aqueous solution, equal to or less than the vapour pressure of a reference 2% by weight or greater aqueous solution of polyethylene glycol having an average molecular weight of 6000; said second polymer having a molecular weight of at least 1000.
- Use of such polymers is generally described in our EP 301,883. Typical levels are from 0.5 to 4.5% by weight.
- compositions according to the present is preferably less than 2,500 mPa.s, more preferred less than 2,000 mPa.s, most preferred less than 1,500 mPa.s, especially preferred between 30 and 900 mPa.s at 21 s -1 .
- One way of regulating the viscosity and stability of compositions according to the present invention is to include viscosity regulating polymeric materials.
- Viscosity and/or stability regulating polymers which are preferred for incorporation in compositions according to the invention include deflocculating polymers having a hydrophilic backbone and at least one hydrophobic side chain. Such polymers are for instance described in our copending European application EP 89201530.6 (EP 346 995).
- the amount of viscosity regulating polymer is from 0.1 to 5% by weight of the total composition, more preferred from 0.2 to 2%.
- compositions of the invention may also comprise materials for adjusting the pH.
- weak acids especially the use of organic acids is preferred, more preferred is the use of C 1-8 carboxylic acids, most preferred is the use of citric acid.
- the use of these pH lowering agents is especially preferred when the compositions of the invention contain enzymes such as amylases, proteases and lipolases.
- lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, fabric softeners such as clays, amines and amine oxides, lather depressants, inorganic salts such as sodium sulphate, and, usually present in very minor amounts, fluorescent agents, perfumes, germicides colourants and enzymes such as proteases, cellulases, amylases and lipases (including Lipolase (Trade Mark) ex Novo).
- lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids
- fabric softeners such as clays, amines and amine oxides
- lather depressants such as inorganic salts such as sodium sulphate
- fluorescent agents such as fluorescent agents, perfumes, germicides colourants and enzymes such as proteases, cellulases, amylases and lipases (including Lipolase (Trade Mark) ex
- protease enzymes are Savinase® (ex Novo), Maxacal® (Gist-Brocades), Opticlean® (ex MKC) or AP122® (ex Showa Denko), Alcalase®, Maxatase®, Es- perase®, Optimase®, proteinase K and subtilisin BPN.
- Suitable lipases are for example Lipolase® (ex Novo), Amano lipases, Meito lipases, Lipozym®, SP 225, SP 285, Toyo Jozo lipase.
- Suitable amylases are for example Termamyl® (TM of Novo) and Maxamyl®.
- Suitable cellulases include Celluzym® (ex Novo).
- compositions of the invention preferably comprise from 5-50 % by weight of water, more preferably from 10-45%, most preferably from 15-35 %.
- Liquid detergent compositions according to the invention are preferably physically stable in that they show less than 2% by volume phase separation upon storage for 21 days after preparation at 25°C.
- Liquid detergent compositions according to the invention are preferably volume stable in that they show less than 25% preferably less than 10%, more preferably less than 5% volume increase during storage at a temperature between 20 and 37°C for a period of three months after preparation.
- compositions according to the invention have solid suspending properties, most preferably they do not yield any visible sedimentation after storage for three weeks at 21°C.
- compositions of the present invention may comprise one or more bleach precursor agents.
- Awell-known example of such an agent is TAED.
- the bleach precursor agent is present in the system in at least partly undissolved form.
- One way of ensuring that the precursor is present in undissolved form is to increase the amount of electrolyte in the composition, therewith reducing the solubility of the precursor in the system.
- Suitable electrolytes for this purpose are for instance the at least partially water soluble carbonate, sulphate and halogenide salts.
- compositions of the invention may also advantageously comprise one or more ingredients for the stabilization of bleach materials.
- Suitable materials are for example metaborate electrolytes and magnesium salts.
- the detergent compositions of the invention will be diluted with wash water to form a wash liquor for instance for use in a washing machine.
- concentration of liquid detergent composition in the wash liquor is preferably from 0.05 to 10 %, more preferred from 0.1 to 3% by weight.
- the liquid detergent compositions preferably are alkaline, and it is preferred that they should provide a pH within the range of about 7.0 to 12, preferably about 8 to about 11, when used in aqueous solutions of the composition at the recommended concentration.
- the undiluted liquid composition should preferably be of a pH above 7, for example about pH 8.0 to about 12.5. It should be noted that an excessively high pH, e.g. over about pH 13, is less desirable for domestic safety.
- One aspect of the invention is a process for the preparation of liquid bleach containing compositions, said process involving the in-situ formation of bleach particles having a weight average particle size of more than 20 micrometer.
- the in-situ formation of bleach particles relates to processes whereby the bleach particles such as present in the final composition, have been formed in-situ, for example by a dissolution/ recrystallization process orthe hydration of perborate monohydrate. It is believed to be well within the ability of the skilled person to adaptthe processing conditions such that the required particle sizes are obtained. Preferred parameters to be varied for obtaining the desired particles sizes are physical form of the bleach materials that are added to the composition, stirring conditions and order of addition.
- the bleach material is a perborate bleach material
- the bleach is added as perboratemo- nohydrate, which will be formed into perborate tetrahydrate in the composition.
- Another preferred method of bleach incorporation is the use of a combination of hydrogen peroxide and a borate material, which will in-situ react to form a perborate bleach.
- a preferred borate material is metaborate.
- the bleach materials are added into the composition under mild stirring conditions, preferably less than 10 c/s, more preferably less than 5 c/s, most preferably from 0.2 to 3 c/s.
- the tip-speed of the stirrer is preferably 0.01-10 m/s, more preferably 0.1 to 5 m/s, most preferred 0.5 to 2 m/s.
- a preferred order of addition involves the addition of electrolyte non-bleach materials to water of elevated temperature, followed by the addition of detergent active materials, the bleach material and the remaining ingredients.
- composition can be prepared by adding the citrate/citric acid and the polymer to water at elevated temperature, followed by addition of the detergent active materials as a premix and the bleach material.
- composition can be prepared several times on a 1 kg scale in a 2 litre glass with a 6 blade stirrer having a diameter of 8 cm, while the type of bleach and the stirring conditions are varied as follows:
- compositions can be stored for 24 hours at ambient temperature and microscopy pictures can be taken at a magnification of 150 ti mes.
- the weight average particle size of the bleach materials is determined by counting the visible particles.
- the physical stability, the volume stability and the solid suspending properties of the composition are determined.
- compositions were made by adding the citric acid/citrate to water, followed by the addition of the sodium metaborate, sodium hydroxide for neutralising the detergent active materials, the polymer, a premix of the detergent active materials in acid form the minor ingredients and the hydrogen peroxide or the perborate monohydrate.
- Each of the formulation was prepared on a 1 kg scale in a 2 litre glass with a 6 blade stirrer having a diameter of 8 cm.
- the stirring conditions were varied as indicated below.
- the particle size of the bleach was determined by applying a thin film of the product under moderate pressure onto a microscopy glass plate followed by the making of a microscopy picture at a magnification of about 400, whereafter the weight average particle size was -roughly- determined by counting the course fraction of the visible particles and measuring their particle size.
- the bleach was present in the form of agglomerates consisting of small elementary bleach particles. In the table below the average particle sizes of the agglomerates is given.
- compositions were prepared by adding the electrolyte together with the minor ingredients except for the perfume and the enzymes to water of elevated temperature, followed by the addition of the detergent active material as a premix under stirring and thereafter cooling the mixture and adding the enzymes, perfumes and the bleach.
- the obtained product had the following characteristics:
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- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
Claims (6)
Applications Claiming Priority (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP90200290 | 1990-02-08 | ||
EP90200290A EP0385522B1 (fr) | 1989-02-27 | 1990-02-08 | Composition détergente liquide |
WOPCT/EP90/01046 | 1990-06-27 | ||
PCT/EP1990/001046 WO1991000902A1 (fr) | 1989-07-13 | 1990-06-27 | Composition de blanchiment liquide |
EP90202308 | 1990-08-28 | ||
EP90202308 | 1990-08-28 | ||
PCT/EP1991/000259 WO1991012308A1 (fr) | 1990-02-08 | 1991-02-07 | Composition de blanchissage liquide |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0513136A1 EP0513136A1 (fr) | 1992-11-19 |
EP0513136B1 true EP0513136B1 (fr) | 1994-05-18 |
Family
ID=27222758
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91903653A Expired - Lifetime EP0513136B1 (fr) | 1990-02-08 | 1991-02-07 | Composition de blanchissage liquide |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0513136B1 (fr) |
JP (1) | JPH0772280B2 (fr) |
KR (1) | KR950008566B1 (fr) |
AU (1) | AU652736B2 (fr) |
CA (1) | CA2073563C (fr) |
DE (1) | DE69102059T2 (fr) |
ES (1) | ES2053321T3 (fr) |
WO (1) | WO1991012308A1 (fr) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU5690296A (en) * | 1995-04-20 | 1996-11-07 | Albright & Wilson Uk Limited | Stabilised aqueous suspensions of bleach containing perborat e particles |
US5633223A (en) * | 1995-08-30 | 1997-05-27 | Lever Brothers Company, Division Of Conopco, Inc. | Heavy duty liquid compositions comprising structuring solids of defined dimension and morphology |
US20040119048A1 (en) * | 2002-12-19 | 2004-06-24 | Unilever Home & Personal Care Usa, Divison Of Conopco, Inc. | Process of making aqueous perborate bleach composition |
US7067467B2 (en) | 2002-12-19 | 2006-06-27 | Unilever Home & Personal Care Usa Division Of Conopco, Inc. | Aqueous perborate bleach composition |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6021720B2 (ja) * | 1980-07-25 | 1985-05-29 | 花王株式会社 | 標白洗浄剤 |
DE3575574D1 (de) * | 1984-05-01 | 1990-03-01 | Unilever Nv | Fluessige bleichmittelzusammensetzungen. |
GB8713756D0 (en) * | 1987-06-12 | 1987-07-15 | Procter & Gamble | Liquid detergent |
GB8718217D0 (en) * | 1987-07-31 | 1987-09-09 | Unilever Plc | Liquid detergent compositions |
GB8826458D0 (en) * | 1988-11-11 | 1988-12-14 | Ici Plc | Bleach formulation & aqueous detergent compositions |
-
1991
- 1991-02-07 DE DE69102059T patent/DE69102059T2/de not_active Expired - Fee Related
- 1991-02-07 AU AU71873/91A patent/AU652736B2/en not_active Ceased
- 1991-02-07 JP JP3503439A patent/JPH0772280B2/ja not_active Expired - Fee Related
- 1991-02-07 ES ES91903653T patent/ES2053321T3/es not_active Expired - Lifetime
- 1991-02-07 CA CA002073563A patent/CA2073563C/fr not_active Expired - Fee Related
- 1991-02-07 WO PCT/EP1991/000259 patent/WO1991012308A1/fr active IP Right Grant
- 1991-02-07 EP EP91903653A patent/EP0513136B1/fr not_active Expired - Lifetime
- 1991-02-07 KR KR1019920701780A patent/KR950008566B1/ko not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
DE69102059D1 (de) | 1994-06-23 |
JPH0772280B2 (ja) | 1995-08-02 |
ES2053321T3 (es) | 1994-07-16 |
DE69102059T2 (de) | 1994-09-01 |
EP0513136A1 (fr) | 1992-11-19 |
WO1991012308A1 (fr) | 1991-08-22 |
CA2073563C (fr) | 1999-03-02 |
CA2073563A1 (fr) | 1991-08-09 |
AU652736B2 (en) | 1994-09-08 |
AU7187391A (en) | 1991-09-03 |
JPH05502907A (ja) | 1993-05-20 |
KR950008566B1 (ko) | 1995-08-03 |
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