EP0394998A2 - Liquid detergent - Google Patents
Liquid detergent Download PDFInfo
- Publication number
- EP0394998A2 EP0394998A2 EP90107835A EP90107835A EP0394998A2 EP 0394998 A2 EP0394998 A2 EP 0394998A2 EP 90107835 A EP90107835 A EP 90107835A EP 90107835 A EP90107835 A EP 90107835A EP 0394998 A2 EP0394998 A2 EP 0394998A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- liquid detergent
- formula
- hydrogen
- alkyl
- optical brightener
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003599 detergent Substances 0.000 title claims abstract description 54
- 239000007788 liquid Substances 0.000 title claims abstract description 40
- 239000001257 hydrogen Chemical group 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- -1 sulphonic acid radical Chemical group 0.000 claims abstract description 16
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims abstract description 9
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 9
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- 239000004744 fabric Substances 0.000 claims abstract description 5
- 239000004753 textile Substances 0.000 claims abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000001424 substituent group Chemical group 0.000 claims abstract description 3
- 230000003287 optical effect Effects 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 239000000460 chlorine Chemical group 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000004061 bleaching Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 description 22
- 239000002585 base Substances 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006266 etherification reaction Methods 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- AVGQTJUPLKNPQP-UHFFFAOYSA-N 1,1,1-trichloropropane Chemical compound CCC(Cl)(Cl)Cl AVGQTJUPLKNPQP-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 description 1
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZMLPKJYZRQZLDA-UHFFFAOYSA-N 1-(2-phenylethenyl)-4-[4-(2-phenylethenyl)phenyl]benzene Chemical group C=1C=CC=CC=1C=CC(C=C1)=CC=C1C(C=C1)=CC=C1C=CC1=CC=CC=C1 ZMLPKJYZRQZLDA-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 241000700196 Galea musteloides Species 0.000 description 1
- 101001096355 Homo sapiens Replication factor C subunit 3 Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-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
- 102100037855 Replication factor C subunit 3 Human genes 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 229940087091 dichlorotetrafluoroethane Drugs 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-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
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229940097407 palm kernel acid Drugs 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
- C11D3/42—Brightening agents ; Blueing agents
Definitions
- the present invention relates to new liquid detergents containing targeted disulfonated dibenzfuranylbiphenyls as optical brighteners, their preparation and their use.
- optical brighteners in liquid detergents is known. They soak on the items to be washed during treatment and, due to their special light absorption / emission properties, lead to an elimination of the yellowish tones or an improvement in the degree of whiteness.
- EP-A-167 205 proposes to use monosulfonated stilbene triazolyl, triazine or distyrylbiphenyl brighteners in anionic liquid detergents.
- X is a sulfonic acid residue, hydrogen or C1-C4-alkyl
- Y and Z independently of one another a sulfonic acid residue, hydrogen, C1-C4-alkyl, C1-C4-alkoxy, halogen, CN, phenoxy, benzyloxy, with the condition that either X or Y or Z is a sulfonic acid residue and the remaining substituents are not a sulfonic acid residue.
- halogens are fluorine, chlorine and bromine, but especially chlorine.
- C1-C4-alkyl or C1-C4-alkoxy
- C1-C4-alkyl or C1-C4-alkoxy
- alkyl (or alkoxy) residues can in turn be substituted with e.g. Aryl (phenyl, naphthyl), C1-C4 alkyl, C1-C4 alkoxy, OH or CN groups.
- M in the meaning of a non-chromophoric cation preferably represents alkali metal such as lithium, sodium, potassium and optionally substituted ammonium such as ammonium, mono-, di- or triethanolammonium, mono-, di- or tripropanolammonium or tri- or tetramethylammonium.
- R3 is independently hydrogen, methyl or ethyl and M is preferably sodium or potassium.
- SO3 / base complex are to be understood as addition compounds of SO3 with organic bases, for example dioxane, preferably nitrogen-containing bases, such as triethylamine, N-ethyldiisopropylamine, dimethylformamide (DMF) and in particular pyridine.
- organic bases for example dioxane, preferably nitrogen-containing bases, such as triethylamine, N-ethyldiisopropylamine, dimethylformamide (DMF) and in particular pyridine.
- DMF dimethylformamide
- pyridine dimethylformamide
- SO3 / base complexes are known and can be prepared by known methods (EE Gilbert, EP Jones, Ind. Enging. Chem. 49, No. 9, Part II, pp. 1553 ff (1957); Beilstein 20, III / IV , 2232).
- Inert organic solvents are for example, saturated aliphatic hydrocarbons such as gasoline, petroleum ether and ligroin, halogenated aliphatic hydrocarbons such as chloroform, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, dichloropropane, trichloropropane, dichlorodifluoromethane and dichlorotetrafluoroethane, chlorobenzenes such as mono-, di- and trichlorobenzene, nitrobenzenes as Nitrobenzene and nitrotoluene as well as dicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decalin.
- saturated aliphatic hydrocarbons such as gasoline, petroleum ether and ligroin
- halogenated aliphatic hydrocarbons such as chloroform, carbon tetrachloride, dichloroe
- the etherification in process d) takes place at temperatures from 60 ° to 140 ° C. and in particular 100 ° to 120 ° C. in a known manner by means of an equivalent of a base, such as a tert. Amine or a base mentioned in the following cyclization, or by already using the compounds of the formula XI or XII as the phenolate of this base.
- the process is carried out in a polar, aprotic solvent or solvent mixture, such as, for example, dimethylformamide, N-methylpyrrolidone, hexamethylphosphoric triamide, tetramethylurea or preferably dimethyl sulfoxide.
- the cyclization in process d) likewise takes place in a polar, aprotic solvent, preferably in the same one in which the etherification also takes place, at slightly elevated temperatures compared to the etherification and in the presence of a base, such as quaternary ammonium bases, alkaline earth metal hydroxides, alkali amides, alkali metal hydrides , Alkali metal carbonates, but preferably alkali metal alcoholates such as potassium t-butoxide and sodium methylate, and in particular alkali metal hydroxides such as sodium, potassium and lithium hydroxide.
- the basic condensing agents are in at least stoichiometric amounts, preferably in excess. It is advantageous to work in the absence of atmospheric oxygen and an inert gas atmosphere.
- Liquid detergents are understood to mean known and commercially available detergents such as are described, for example, in EP-A-167 205 or US-4,507,219 or GB 8712430.
- the optical brightener content in the liquid detergents is 0.01-2%, in particular 0.01-1%, particularly preferably 0.03-0.3%.
- the liquid detergents contain 1 to 60 anionic, nonionic, zwitterionic and optionally cationic surfactants and 25 to 65%, preferably 40 to 55%, water.
- the detergent contains 3 to 50% preferably 15 to 25% anionic surfactants, 2 to 30% preferably 4 to 15% nonionic surfactants, 3 to 30% preferably 5 to 20% optionally ethoxylated (C10-C14) - Fatty acids such as capric, lauric, myristic, coconut and palm kernel acid and mixtures thereof, 1 to 25% preferably 1 to 10% detergent builders and optionally 1 to 10% preferably 1 to 5% zwitterionic surfactants, 0.5 to 3% preferably 0.7 to 2% quaternary ammonium, amine or amine oxide surfactants, and 1 to 10% common detergent additives such as enzymes, enzyme stabilizers, antioxidants, preservatives and disinfectants, fragrances and dyes, complexing agents or sequestering
- surfactants are described, for example, in U.S. 4,285,841, U.S. 3,929,678, U.S. 4,284,532 and GB 2,041,986.
- the surfactants designated as preferred in EP-A-167 205 are used.
- optionally used as anionic surfactants are ethoxylated C1ate-C18 alkyl sulfates, for example in the form of the triethanolamine salts, C10-C15 alkylbenzenesulfonates or mixtures thereof and as nonionic surfactants, condensation products from one mole of (C10-C15) fatty alcohol with 3 to 8 moles of ethylene oxide .
- Suitable detergent builders are the preferably polycarboxylated compounds mentioned in US Pat. Nos. 4,321,165 and 4,284,532, such as citric acid.
- Targeted liquid detergents containing sulfonated dibenzofuranylbiphenyls can also be used e.g. in GB 8712430, contain bleach.
- Perborate is preferably used as the bleaching agent.
- a liquid detergent is prepared 15 parts of C11-C13 alkylbenzenesulfonate 14 parts of C14-C15 polyethoxy fatty alcohol (7 ethylene oxide) 10 parts of soap 9 parts of ethanol 5 parts of triethanolamine 4 parts Na citrate 43 parts of water and 0.1 part of the optical brightener of the formula forth.
- the stain test shows only a very slight formation of light stains with a very high degree of lightening.
- the detergent formulation is stable on storage.
- Example 1 a liquid detergent is prepared, but instead of compound (100) the compound of the formula contains.
- the properties of the liquid detergent correspond to those from Example 1.
- Example 1 a liquid detergent is prepared, but instead of compound (100) the compound of the formula contains.
- the properties of the liquid detergent correspond to those from Example 1.
- Example 1 a liquid detergent is prepared, but instead of compound (100) the compound of the formula contains.
- the detergent formulation is very stable in storage.
- the stain test shows only a very weak formation of light spots.
- Example 1 a liquid detergent is prepared, but instead of compound (100) the compound of the formula contains.
- the detergent formulation is very stable in storage.
- the stain test shows only a slight formation of light stains with high lightening effects.
- a liquid detergent is prepared 6.5 parts of triethanolamine 3.5 parts NaOH 6.5 parts of ethanol 1.5 parts of 1,2 propanediol 11.5 parts of C14-C15 polyethoxy fatty alcohol (7 ethylene oxide) 2.5 parts of coconut alkyl sulfate 10.5 parts of linear dodecylbenzenesulfonic acid 4.0 parts of oleic acid 10.5 parts of saturated C12-C14 acid 43.0 parts of deionized water and 0.1 part of the optical brightener of the formula forth.
- the detergent is opaque, homogeneous and very stable in storage.
- the stain test shows only a very slight formation of light stains with a very high degree of lightening.
- Example 6 a liquid detergent is prepared, but instead of the compound (200) the compound of the formula contains.
- the properties of the liquid detergent correspond to those from Example 6.
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Abstract
Description
Die vorliegende Erfindung betrifft neue flüssige Waschmittel enthaltend gezielt disulfonierte Dibenzfuranylbiphenyle als optische Aufheller deren Herstellung und deren Verwendung.The present invention relates to new liquid detergents containing targeted disulfonated dibenzfuranylbiphenyls as optical brighteners, their preparation and their use.
Die Verwendung von optischen Aufhellern in flüssigen Waschmitteln ist bekannt. Sie ziehen während der Behandlung auf das Waschgut auf und führen durch ihre spezielle Lichtabsorption/Emissionseigenschaft zu einer Elimination der gelblichen Töne bzw. zu einer Verbesserung des Weissgrades.The use of optical brighteners in liquid detergents is known. They soak on the items to be washed during treatment and, due to their special light absorption / emission properties, lead to an elimination of the yellowish tones or an improvement in the degree of whiteness.
Dieser Effekt ist aber auch verantwortlich für das Auftreten von hellen Flecken wenn Textilgewebe z.B. bei einer Vorbehandlung direkt mit dem flüssigen Waschmittel in Kontakt gerät. In der EP-A-167 205 wird zur Lösung dieses Problems vorgeschlagen, monosulfonierte Stilbentriazolyl-, -triazin- oder Distyrylbiphenyl-Aufheller in anionischen Flüssigwaschmitteln zu verwenden.This effect is also responsible for the appearance of light spots when textile fabrics e.g. comes into direct contact with the liquid detergent during pretreatment. To solve this problem, EP-A-167 205 proposes to use monosulfonated stilbene triazolyl, triazine or distyrylbiphenyl brighteners in anionic liquid detergents.
Ueberraschenderweise kann die Bildung heller Flecken, bei ausgezeichneter Aufhellwirkung und sehr gutem Lagerverhalten des flüssigen Waschmittels, auch durch optische Aufheller der Formel
Im einzelnen bedeutet:
X ein Sulfonsäurerest, Wasserstoff oder C₁-C₄-Alkyl, Y und Z unabhängig voneinander ein Sulfonsäurerest, Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, CN, Phenoxy, Benzyloxy, mit der Bedingung, dass entweder X oder Y oder Z ein Sulfonsäurerest ist und die restlichen Substituenten nicht ein Sulfonsäurerest sind.Specifically means:
X is a sulfonic acid residue, hydrogen or C₁-C₄-alkyl, Y and Z independently of one another a sulfonic acid residue, hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, CN, phenoxy, benzyloxy, with the condition that either X or Y or Z is a sulfonic acid residue and the remaining substituents are not a sulfonic acid residue.
Als Halogene kommen vor allem Fluor, Chlor und Brom in Frage, insbesondere jedoch Chlor.The most suitable halogens are fluorine, chlorine and bromine, but especially chlorine.
Als C₁-C₄-Alkylreste (bzw. C₁-C₄-Alkoxyreste) kommen unverzweigte oder verzweigte Alkyl- (bzw. Alkoxy-) reste in Betracht. Diese Alkyl- (bzw. Alkoxy-) reste können ihrerseits substituiert sein mit z.B. Aryl- (Phenyl-, Naphthyl-), C₁-C₄-Alkyl-, C₁-C₄-Alkoxy-, OH- oder CN-Gruppen.As C₁-C₄-alkyl (or C₁-C₄-alkoxy) are unbranched or branched alkyl (or alkoxy) into consideration. These alkyl (or alkoxy) residues can in turn be substituted with e.g. Aryl (phenyl, naphthyl), C₁-C₄ alkyl, C₁-C₄ alkoxy, OH or CN groups.
Bevorzugte Dibenzfuranylbiphenyle der Formel (1) sind solche der Formel
R₁ = Wasserstoff, C₁-C₄-Alkyl, Chlor, C₁-C₄-Alkoxy, Phenoxy oder Benzyloxy, R₂ = Wasserstoff oder C₁-C₄-Alkyl und M = Wasserstoff und/oder ein Aequivalent eines nicht chromophoren Kations bedeuten.Preferred dibenzfuranylbiphenyls of the formula (1) are those of the formula
R₁ = hydrogen, C₁-C₄-alkyl, chlorine, C₁-C₄-alkoxy, phenoxy or benzyloxy, R₂ = hydrogen or C₁-C₄-alkyl and M = hydrogen and / or an equivalent of a non-chromophoric cation.
M in der Bedeutung eines nicht-chromophoren Kations steht vorzugsweise für Alkalimetall wie Lithium, Natrium, Kalium sowie gegebenenfalls substituiertes Ammonium wie Ammonium, Mono-, Di- oder Triethanolammonium, Mono-, Di- oder Tripropanolammonium oder Tri- oder Tetramethylammonium.M in the meaning of a non-chromophoric cation preferably represents alkali metal such as lithium, sodium, potassium and optionally substituted ammonium such as ammonium, mono-, di- or triethanolammonium, mono-, di- or tripropanolammonium or tri- or tetramethylammonium.
Von besonderem Interesse sind jedoch Verbindungen der Formel
Die optischen Aufheller können hergestellt werden, indem man
a) ein Mol der Verbindung der Formel (X)
b) ein Mol der Verbindung der Formel (X) mit mindestens stöchiometrischen Mengen Chlorsulfonsäure, in einem inerten organischen Lösungsmittel, bei Temperaturen von 0° bis 40°C umsetzt oder
c) die Verbindung der Formel (X) mit konzentrierter Schwefelsäure oder mit Schwefelsäure/Eisessig bzw. Oleum/Eisessig auf Temperaturen von 40° bis 140°C erhitzt oder
d) ein Mol 4,4′-Bis-(halogenmethyl)-biphenyl mit mindestens 2 Mol Salicylaldehyd oder deren Anile der Formel (XI) bzw. (XII)
a) one mole of the compound of formula (X)
b) reacting one mole of the compound of formula (X) with at least stoichiometric amounts of chlorosulfonic acid, in an inert organic solvent, at temperatures from 0 ° to 40 ° C. or
c) the compound of formula (X) with concentrated sulfuric acid or with sulfuric acid / glacial acetic acid or oleum / glacial acetic acid to temperatures of 40 ° to 140 ° C or
d) one mole of 4,4'-bis (halogenomethyl) biphenyl with at least 2 moles of salicylaldehyde or their anils of the formula (XI) or (XII)
Die Ausgangsverbindungen der Formel (X), (XI) und (XII) sind bekannt und können nach bekannten Methoden hergestellt werden. Vorteilhafterweise wird das Verfahren d) jedoch als Eintopfverfahren ohne Isolierung der Zwischenprodukte (XIII) und (XIV) durchgeführt.The starting compounds of the formulas (X), (XI) and (XII) are known and can be prepared by known methods. However, process d) is advantageously carried out as a one-pot process without isolation of the intermediates (XIII) and (XIV).
Im einzelnen werden nach dem Verfahren a) die Verbindungen der Formel (III) und (IV) hergestellt.In detail, the compounds of the formulas (III) and (IV) are prepared by process a).
Unter SO₃/Basen-Komplex sind Additionsverbindungen von SO₃ an organische Basen, z.B. Dioxan, vorzugsweise stickstoffhaltige Basen, wie zum Beispiel Triethylamin, N-Ethyldiisopropylamin, Dimethylformamid (DMF) und insbesondere Pyridin zu verstehen. Die Stabilität dieser Additionsverbindungen ist dabei entscheidend für den Sulfonierungsgrad. So werden bei Verwendung von 2 bis 6, insbesondere 3 bis 5 Mol SO₃/Pyridin-Komplex (bezogen auf den SO₃-Gehalt) pro Mol der Verbindung der Formel (X) z.B. Verbindungen der Formel (III) und (V) hergestellt. SO₃/Basen-Komplexe sind bekannt und können nach bekannten Methoden hergestellt werden (E.E. Gilbert, E.P. Jones, Ind. Enging. Chem. 49, Nr. 9, Teil II, S. 1553 ff (1957); Beilstein 20, III/IV, 2232).SO₃ / base complex are to be understood as addition compounds of SO₃ with organic bases, for example dioxane, preferably nitrogen-containing bases, such as triethylamine, N-ethyldiisopropylamine, dimethylformamide (DMF) and in particular pyridine. The stability of these addition compounds is decisive for the degree of sulfonation. So when using 2 to 6, especially 3 to 5 moles of SO₃ / pyridine complex (based on the SO₃ content) per mole of the compound of formula (X), for example compounds of formula (III) and (V). SO₃ / base complexes are known and can be prepared by known methods (EE Gilbert, EP Jones, Ind. Enging. Chem. 49, No. 9, Part II, pp. 1553 ff (1957); Beilstein 20, III / IV , 2232).
Inerte organische Lösungsmittel sind beispielsweise gesättigte aliphatische Kohlenwasserstoffe wie Gasolin, Petrolether und Ligroin, halogenierte, aliphatische Kohlenwasserstoffe wie Chloroform, Tetrachlorkohlenstoff, Dichlorethan, Trichlorethan, Tetrachlorethan, Dichlorpropan, Trichlorpropan, Dichlordifluormethan und Dichlortetrafluorethan, Chlorbenzole wie Mono-, Di- und Trichlorbenzol, Nitrobenzole wie Nitrobenzol und Nitrotoluol sowie dicyclische Kohlenwasserstoffe wie Cyclohexan, Methylcyclohexan und Dekalin.Inert organic solvents are for example, saturated aliphatic hydrocarbons such as gasoline, petroleum ether and ligroin, halogenated aliphatic hydrocarbons such as chloroform, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, dichloropropane, trichloropropane, dichlorodifluoromethane and dichlorotetrafluoroethane, chlorobenzenes such as mono-, di- and trichlorobenzene, nitrobenzenes as Nitrobenzene and nitrotoluene as well as dicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decalin.
Nach dem Verfahren c) werden insbesondere die Verbindungen der Formel (II) und (IV) hergestellt.In particular, the compounds of the formulas (II) and (IV) are prepared by process c).
Die Veretherung bei Verfahren d) erfolgt bei Temperaturen von 60° bis 140°C und insbesondere 100° bis 120°C in bekannter Weise mittels einem Aequivalent einer Base, wie einem tert. Amin oder einer bei der folgenden Cyclisierung genannten Base, oder indem man die Verbindungen der Formel XI oder XII bereits als Phenolat dieser Base einsetzt. Man arbeitet in einem polaren, aprotischen Lösungsmittel oder Lösungsmittelgemisch wie zum Beispiel Dimethylformamid, N-Methylpyrrolidon, Hexamethylphosphorsäuretriamid, Tetramethylharnstoff oder vorzugsweise Dimethylsulfoxid.The etherification in process d) takes place at temperatures from 60 ° to 140 ° C. and in particular 100 ° to 120 ° C. in a known manner by means of an equivalent of a base, such as a tert. Amine or a base mentioned in the following cyclization, or by already using the compounds of the formula XI or XII as the phenolate of this base. The process is carried out in a polar, aprotic solvent or solvent mixture, such as, for example, dimethylformamide, N-methylpyrrolidone, hexamethylphosphoric triamide, tetramethylurea or preferably dimethyl sulfoxide.
Die Cyclisierung bei Verfahren d) erfolgt ebenfalls in einem polaren, aprotischen Lösungsmittel, vorzugsweise in demselben, in dem auch die Veretherung stattfindet, bei im Vergleich zur Veretherung leicht erhöhten Temperaturen und in Gegenwart einer Base, wie z.B. quaternären Ammoniumbasen, Erdalkalihydroxiden, Alkaliamiden, Alkalihydriden, Alkalicarbonaten, vorzugsweise aber Alkalialkoholaten wie Kalium-t-butylat und Natriummethylat sowie insbesondere Alkalihydroxiden wie Natrium-, Kalium- und Lithiumhydroxid. Die basischen Kondensationsmittel werden in mindestens stöchiometrischen Mengen, vorzugsweise im Ueberschuss, eingesetzt. Vorteilhaft arbeitet man unter Luftsauerstoffausschluss und Inertgasatmosphäre.The cyclization in process d) likewise takes place in a polar, aprotic solvent, preferably in the same one in which the etherification also takes place, at slightly elevated temperatures compared to the etherification and in the presence of a base, such as quaternary ammonium bases, alkaline earth metal hydroxides, alkali amides, alkali metal hydrides , Alkali metal carbonates, but preferably alkali metal alcoholates such as potassium t-butoxide and sodium methylate, and in particular alkali metal hydroxides such as sodium, potassium and lithium hydroxide. The basic condensing agents are in at least stoichiometric amounts, preferably in excess. It is advantageous to work in the absence of atmospheric oxygen and an inert gas atmosphere.
Unter Flüssigwaschmitteln sind bekannte und handelsübliche Waschmittel wie sie beispielsweise in der EP-A-167 205 oder US-4 507 219 oder GB 8712430 beschrieben werden, zu verstehen.Liquid detergents are understood to mean known and commercially available detergents such as are described, for example, in EP-A-167 205 or US-4,507,219 or GB 8712430.
Der Gehalt an optischem Aufheller in den flüssigen Waschmitteln beträgt 0,01-2 %, insbesondere 0,01-1 %, besonders bevorzugt 0,03-0,3 %.The optical brightener content in the liquid detergents is 0.01-2%, in particular 0.01-1%, particularly preferably 0.03-0.3%.
Insbesondere enthalten die Flüssigwaschmittel neben den optischen Aufhellern 1 bis 60 anionische, nichtionische, zwitterionische und gegebenenfalls kationische Tenside und 25 bis 65 % vorzugsweise 40 bis 55 % Wasser. Im einzelnen enthält das Waschmittel neben dem optischen Aufheller 3 bis 50 % vorzugsweise 15 bis 25 % anionische Tenside, 2 bis 30 % vorzugsweise 4 bis 15 % nichtionische Tenside, 3 bis 30 % vorzugsweise 5 bis 20 % gegebenenfalls ethoxylierte (C₁₀-C₁₄)-Fettsäuren wie Kaprin-, Laurin-, Myristin-, Kokusnuss- und Palmkernsäure sowie Mischungen davon, 1 bis 25 % vorzugsweise 1 bis 10 % Waschmittelaufbaustoffe sowie gegebenenfalls 1 bis 10% vorzugsweise 1 bis 5 % zwitterionische Tenside, 0,5 bis 3 % vorzugsweise 0,7 bis 2 % quaternäre Ammonium-, Amin- oder Aminoxid-Tenside, und 1 bis 10 % übliche Waschmittelzusätze wie zum Beispiel Enzyme, Enzymstabilisatoren, Antioxidantien, Konservierungs- und Desinfektionsmittel, Duft- und Farbstoffe, Komplexbildner bzw. Sequestriermittel und Lösungsmittel.In particular, in addition to the optical brighteners, the liquid detergents contain 1 to 60 anionic, nonionic, zwitterionic and optionally cationic surfactants and 25 to 65%, preferably 40 to 55%, water. In particular, in addition to the optical brightener, the detergent contains 3 to 50% preferably 15 to 25% anionic surfactants, 2 to 30% preferably 4 to 15% nonionic surfactants, 3 to 30% preferably 5 to 20% optionally ethoxylated (C₁₀-C₁₄) - Fatty acids such as capric, lauric, myristic, coconut and palm kernel acid and mixtures thereof, 1 to 25% preferably 1 to 10% detergent builders and optionally 1 to 10% preferably 1 to 5% zwitterionic surfactants, 0.5 to 3% preferably 0.7 to 2% quaternary ammonium, amine or amine oxide surfactants, and 1 to 10% common detergent additives such as enzymes, enzyme stabilizers, antioxidants, preservatives and disinfectants, fragrances and dyes, complexing agents or sequestering agents and solvents.
Brauchbare Tenside werden z.B. in der US-4 285 841, US-3 929 678, US-4 284 532 und GB-2 041 986 beschrieben. Insbesondere werden die in der EP-A-167 205 als bevorzugt bezeichneten Tenside eingesetzt. Vor allem verwendet man jedoch als anionische Tenside gegebenenfalls ethoxylierte C₁₀-C₁₈-Alkylsulfate z.B. in Form der Triethanolaminsalze, C₁₀-C₁₅-Alkylbenzolsulfonate oder Mischungen davon und als nichtionische Tenside Kondensationsprodukte aus einem Mol (C₁₀-C₁₅)-Fettalkohol mit 3 bis 8 Mol Ethylenoxid.Useful surfactants are described, for example, in U.S. 4,285,841, U.S. 3,929,678, U.S. 4,284,532 and GB 2,041,986. In particular, the surfactants designated as preferred in EP-A-167 205 are used. Above all, however, optionally used as anionic surfactants are ethoxylated C₁ate-C₁₈ alkyl sulfates, for example in the form of the triethanolamine salts, C₁₀-C₁₅ alkylbenzenesulfonates or mixtures thereof and as nonionic surfactants, condensation products from one mole of (C₁₀-C₁₅) fatty alcohol with 3 to 8 moles of ethylene oxide .
Als Waschmittelaufbaustoffe kommen die in der US-4 321 165 und US-4 284 532 erwähnten vorzugsweise polycarboxylierte Verbindungen wie zum Beispiel Zitronensäure in Betracht.Suitable detergent builders are the preferably polycarboxylated compounds mentioned in US Pat. Nos. 4,321,165 and 4,284,532, such as citric acid.
Gezielt sulfonierte Dibenzofuranylbiphenyle enthaltende flüssige Waschmittel können auch, wie z.B. in GB 8712430 beschrieben, Bleichmittel enthalten. Als Bleichmittel wird vorzugsweise Perborat verwendet.Targeted liquid detergents containing sulfonated dibenzofuranylbiphenyls can also be used e.g. in GB 8712430, contain bleach. Perborate is preferably used as the bleaching agent.
Die folgenden Beispiele dienen zur Erläuterung der Erfindung; Teile bedeuten Gewichtsteile und Prozente Gewichtsprozente; der Fleckentest wird folgendermassen durchgeführt:
- a) Aufheller/Waschmittel-Formulierung:
0,1 % (100 % Aktivsubstanz) optischer Aufheller oder Aufhellergemisch werden in einem flüssigen Waschmittel gelöst. 0,6 g dieses Aufheller enthaltenden Waschmittels (A) wird mit 400 ml Wasser (10°-12° dH) bei einer Temperatur von 30°C verdünnt (Waschflotte B). - b) Ein 20 g Stück gebleichtes Baumwollgewebe wird auf einem Spannrahmen befestigt.
- c) Auf eine vormarkierte, runde Fläche (5 cm Durchmesser) dieses Baumwollgewebes werden mit einer Pipette 0,6 ml der Waschmittellösung (A) gleichmässig aufgetragen, nach 30 Sekunden Einwirkzeit in die vorbereitete Waschflotte (B) gegeben und während 15 Minuten bei 30°C gewaschen. Anschliessend wird mit kaltem Wasser gespült und bei 70°C getrocknet.
- d) Der Unterschied des Weissgrades nach Ganz zwischen der Auftragsfläche und der Umgebung ist ein Mass für das sogenannte Spotting-Verhalten (Bildung von hellen Flecken) und wird bei einfacher Textillage mit einem RFC3-Photometer von Zeiss bestimmt.
- a) Brightener / detergent formulation:
0.1% (100% active substance) optical brightener or brightener mixture are dissolved in a liquid detergent. 0.6 g of this detergent (A) containing brightener is diluted with 400 ml of water (10 ° -12 ° dH) at a temperature of 30 ° C (wash liquor B). - b) A 20 g piece of bleached cotton fabric is attached to a tenter.
- c) 0.6 ml of the detergent solution (A) are evenly applied to a pre-marked, round surface (5 cm in diameter) of this cotton fabric, added to the prepared wash liquor (B) after 30 seconds of exposure and for 15 minutes at 30 ° C washed. It is then rinsed with cold water and dried at 70 ° C.
- d) The difference in whiteness according to Ganz between the application area and the surroundings is a measure of the so-called spotting behavior (formation of light spots) and is determined with a simple textile layer using an RFC3 photometer from Zeiss.
Man stellt ein flüssiges Waschmittel enthaltend
15 Teile C₁₁-C₁₃ Alkylbenzolsulfonat
14 Teile C₁₄-C₁₅ Polyethoxyfettalkohol (7 Ethylenoxid)
10 Teile Seife
9 Teile Ethanol
5 Teile Triethanolamin
4 Teile Na-Citrat
43 Teile Wasser
und 0,1 Teile des optischen Aufhellers der Formel
15 parts of C₁₁-C₁₃ alkylbenzenesulfonate
14 parts of C₁₄-C₁₅ polyethoxy fatty alcohol (7 ethylene oxide)
10 parts of soap
9 parts of ethanol
5 parts of triethanolamine
4 parts Na citrate
43 parts of water
and 0.1 part of the optical brightener of the formula
Der Fleckentest zeigt nur eine sehr geringe Bildung heller Flecken, bei sehr hohem Aufhellgrad.The stain test shows only a very slight formation of light stains with a very high degree of lightening.
Die Waschmittelformulierung ist lagerstabil.The detergent formulation is stable on storage.
Wie im Beispiel 1 wird ein flüssiges Waschmittel hergestellt, welches jedoch anstelle der Verbindung (100) die Verbindung der Formel
Das flüssige Waschmittel entspricht in seinen Eigenschaften demjenigen aus Beispiel 1.The properties of the liquid detergent correspond to those from Example 1.
Wie im Beispiel 1 wird ein flüssiges Waschmittel hergestellt, welches jedoch anstelle der Verbindung (100) die Verbindung der Formel
Das flüssige Waschmittel entspricht in seinen Eigenschaften demjenigen aus Beispiel 1.The properties of the liquid detergent correspond to those from Example 1.
Wie im Beispiel 1 wird ein flüssiges Waschmittel hergestellt, welches jedoch anstelle der Verbindung (100) die Verbindung der Formel
Die Waschmittelformulierung ist sehr lagerstabil. Der Fleckentest zeigt nur eine sehr schwache Bildung heller Flecken.The detergent formulation is very stable in storage. The stain test shows only a very weak formation of light spots.
Wie im Beispiel 1 wird ein flüssiges Waschmittel hergestellt, welches jedoch anstelle der Verbindung (100) die Verbindung der Formel
Die Waschmittelformulierung ist sehr lagerstabil. Der Fleckentest zeigt eine nur geringe Bildung heller Flecken, bei hohen Aufhelleffekten.The detergent formulation is very stable in storage. The stain test shows only a slight formation of light stains with high lightening effects.
Man stellt ein flüssiges Waschmittel enthaltend
6.5 Teile Triethanolamin
3.5 Teile NaOH
6.5 Teile Ethanol
1.5 Teile 1,2 Propandiol
11.5 Teile C₁₄-C₁₅ Polyethoxyfettalkohol (7 Ethylenoxid)
2.5 Teile Coconutalkylsulfat
10.5 Teile Lineare Dodecylbenzolsulfonsäure
4.0 Teile Oelsäure
10.5 Teile Gesättigte C₁₂-C₁₄ säure
43.0 Teile Deionisiertes Wasser
und 0.1 Teile des optischen Aufhellers der Formel
6.5 parts of triethanolamine
3.5 parts NaOH
6.5 parts of ethanol
1.5 parts of 1,2 propanediol
11.5 parts of C₁₄-C₁₅ polyethoxy fatty alcohol (7 ethylene oxide)
2.5 parts of coconut alkyl sulfate
10.5 parts of linear dodecylbenzenesulfonic acid
4.0 parts of oleic acid
10.5 parts of saturated C₁₂-C₁₄ acid
43.0 parts of deionized water
and 0.1 part of the optical brightener of the formula
Das Waschmittel ist opak, homogen und sehr lagerstabil. Der Fleckentest zeigt nur eine sehr geringe Bildung heller Flecken, bei sehr hohem Aufhellgrad.The detergent is opaque, homogeneous and very stable in storage. The stain test shows only a very slight formation of light stains with a very high degree of lightening.
Wie im Beispiel 6 wird ein flüssiges Waschmittel hergestellt, welches jedoch anstelle der Verbindung (200) die Verbindung der Formel
Das flüssige Waschmittel entspricht in seinen Eigenschaften demjenigen aus Beispiel 6.The properties of the liquid detergent correspond to those from Example 6.
Claims (10)
R₁ = Wasserstoff, C₁-C₄-Alkyl, Chlor, C₁-C₄-Alkoxy, Phenoxy oder Benzyloxy, R₂ = Wasserstoff oder C₁-C₄-Alkyl und M = Wasserstoff und/oder ein Aequivalent eines nicht chromophoren Kations bedeuten, enthält.2. Liquid detergent according to claim 1, characterized in that the liquid detergent is an optical brightener of the formula
R₁ = hydrogen, C₁-C₄-alkyl, chlorine, C₁-C₄-alkoxy, phenoxy or benzyloxy, R₂ = hydrogen or C₁-C₄-alkyl and M = hydrogen and / or an equivalent of a non-chromophoric cation.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH1630/89 | 1989-04-28 | ||
CH163089 | 1989-04-28 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0394998A2 true EP0394998A2 (en) | 1990-10-31 |
EP0394998A3 EP0394998A3 (en) | 1991-01-09 |
EP0394998B1 EP0394998B1 (en) | 1996-03-27 |
Family
ID=4214937
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90107835A Expired - Lifetime EP0394998B1 (en) | 1989-04-28 | 1990-04-25 | Liquid detergent |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0394998B1 (en) |
JP (1) | JP2685329B2 (en) |
AU (1) | AU628539B2 (en) |
CA (1) | CA2015565A1 (en) |
DE (1) | DE59010228D1 (en) |
ES (1) | ES2085296T3 (en) |
NZ (1) | NZ233443A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0548019A2 (en) * | 1991-12-19 | 1993-06-23 | Ciba-Geigy Ag | Storage-stable bleach dispersion |
WO1994011485A1 (en) * | 1992-11-17 | 1994-05-26 | Unilever N.V. | Liquid detergent compositions |
EP0601967A1 (en) * | 1992-11-17 | 1994-06-15 | Ciba-Geigy Ag | Liquid detergent composition |
US5604194A (en) * | 1992-11-17 | 1997-02-18 | The Procter & Gamble Company | Stable liquid detergent compositions comprising specific brightener and PVP to inhibit dye transfer |
DE19859575B4 (en) * | 1997-12-30 | 2011-12-22 | Kay Chemical Co. | Soaking agent with optical brightener |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4002423A (en) * | 1971-08-13 | 1977-01-11 | Hoechst Aktiengesellschaft | Benzofuran derivatives process for their preparation and their use as optical brighteners |
DE2843850A1 (en) * | 1978-10-07 | 1980-05-22 | Bayer Ag | DYE LASER |
EP0321715A2 (en) * | 1987-12-23 | 1989-06-28 | Ciba-Geigy Ag | Stable detergents containing optical brighteners |
DE3900651A1 (en) * | 1988-01-14 | 1989-07-27 | Ciba Geigy Ag | Stable bleaching composition containing optical brighteners |
EP0364027A2 (en) * | 1988-10-14 | 1990-04-18 | Unilever N.V. | Bleaching and detergent composition |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2065328T3 (en) * | 1987-11-26 | 1995-02-16 | Ciba Geigy Ag | STABLE DETERGENTS CONTAINING OPTIC BLEACHES. |
-
1990
- 1990-04-25 EP EP90107835A patent/EP0394998B1/en not_active Expired - Lifetime
- 1990-04-25 ES ES90107835T patent/ES2085296T3/en not_active Expired - Lifetime
- 1990-04-25 DE DE59010228T patent/DE59010228D1/en not_active Expired - Fee Related
- 1990-04-26 NZ NZ23344390A patent/NZ233443A/en unknown
- 1990-04-26 CA CA 2015565 patent/CA2015565A1/en not_active Abandoned
- 1990-04-27 JP JP2115021A patent/JP2685329B2/en not_active Expired - Lifetime
- 1990-04-27 AU AU54536/90A patent/AU628539B2/en not_active Ceased
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4002423A (en) * | 1971-08-13 | 1977-01-11 | Hoechst Aktiengesellschaft | Benzofuran derivatives process for their preparation and their use as optical brighteners |
DE2843850A1 (en) * | 1978-10-07 | 1980-05-22 | Bayer Ag | DYE LASER |
EP0321715A2 (en) * | 1987-12-23 | 1989-06-28 | Ciba-Geigy Ag | Stable detergents containing optical brighteners |
DE3900651A1 (en) * | 1988-01-14 | 1989-07-27 | Ciba Geigy Ag | Stable bleaching composition containing optical brighteners |
EP0364027A2 (en) * | 1988-10-14 | 1990-04-18 | Unilever N.V. | Bleaching and detergent composition |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0548019A2 (en) * | 1991-12-19 | 1993-06-23 | Ciba-Geigy Ag | Storage-stable bleach dispersion |
EP0548019A3 (en) * | 1991-12-19 | 1995-06-14 | Ciba Geigy Ag | Storage-stable bleach dispersion |
WO1994011485A1 (en) * | 1992-11-17 | 1994-05-26 | Unilever N.V. | Liquid detergent compositions |
EP0601967A1 (en) * | 1992-11-17 | 1994-06-15 | Ciba-Geigy Ag | Liquid detergent composition |
EP0672099A4 (en) * | 1992-11-17 | 1995-08-03 | Procter & Gamble | Stable liquid detergent compositions inhibiting dye transfer. |
EP0672099A1 (en) * | 1992-11-17 | 1995-09-20 | Procter & Gamble | Stable liquid detergent compositions inhibiting dye transfer. |
US5468884A (en) * | 1992-11-17 | 1995-11-21 | Ciba-Geigy Corporation | Liquid detergent compositions |
US5604194A (en) * | 1992-11-17 | 1997-02-18 | The Procter & Gamble Company | Stable liquid detergent compositions comprising specific brightener and PVP to inhibit dye transfer |
DE19859575B4 (en) * | 1997-12-30 | 2011-12-22 | Kay Chemical Co. | Soaking agent with optical brightener |
Also Published As
Publication number | Publication date |
---|---|
DE59010228D1 (en) | 1996-05-02 |
AU628539B2 (en) | 1992-09-17 |
JPH02302498A (en) | 1990-12-14 |
JP2685329B2 (en) | 1997-12-03 |
EP0394998A3 (en) | 1991-01-09 |
EP0394998B1 (en) | 1996-03-27 |
ES2085296T3 (en) | 1996-06-01 |
AU5453690A (en) | 1990-11-01 |
NZ233443A (en) | 1992-04-28 |
CA2015565A1 (en) | 1990-10-28 |
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