WO1992016570A1 - Peinture de protection marine - Google Patents
Peinture de protection marine Download PDFInfo
- Publication number
- WO1992016570A1 WO1992016570A1 PCT/JP1992/000299 JP9200299W WO9216570A1 WO 1992016570 A1 WO1992016570 A1 WO 1992016570A1 JP 9200299 W JP9200299 W JP 9200299W WO 9216570 A1 WO9216570 A1 WO 9216570A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- antifouling paint
- marine antifouling
- formula
- polymer
- Prior art date
Links
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 41
- 239000003973 paint Substances 0.000 title claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 4
- 239000011230 binding agent Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract 3
- 239000001257 hydrogen Substances 0.000 claims abstract 3
- 229920001577 copolymer Polymers 0.000 claims description 67
- 239000013535 sea water Substances 0.000 claims description 13
- 241000251468 Actinopterygii Species 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 66
- 238000004519 manufacturing process Methods 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 20
- 238000010992 reflux Methods 0.000 description 19
- 239000000178 monomer Substances 0.000 description 18
- 239000012299 nitrogen atmosphere Substances 0.000 description 18
- -1 aryl alcohol Chemical compound 0.000 description 17
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 11
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 11
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 239000008096 xylene Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 5
- 239000002519 antifouling agent Substances 0.000 description 5
- 150000004820 halides Chemical class 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- OWZFULPEVHKEKS-UHFFFAOYSA-N ethyl 2-chloro-2-oxoacetate Chemical compound CCOC(=O)C(Cl)=O OWZFULPEVHKEKS-UHFFFAOYSA-N 0.000 description 4
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- KOAWAWHSMVKCON-UHFFFAOYSA-N 6-[difluoro-(6-pyridin-4-yl-[1,2,4]triazolo[4,3-b]pyridazin-3-yl)methyl]quinoline Chemical compound C=1C=C2N=CC=CC2=CC=1C(F)(F)C(N1N=2)=NN=C1C=CC=2C1=CC=NC=C1 KOAWAWHSMVKCON-UHFFFAOYSA-N 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- TUVYSBJZBYRDHP-UHFFFAOYSA-N acetic acid;methoxymethane Chemical compound COC.CC(O)=O TUVYSBJZBYRDHP-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- SWHBLHNCZXFGNK-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]-2-oxoacetic acid hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)C(O)=O SWHBLHNCZXFGNK-UHFFFAOYSA-N 0.000 description 2
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- CFCPJZHJJYBLHO-UHFFFAOYSA-N OC(C(OCC1=CC=CC=C1)=O)=O.Cl Chemical compound OC(C(OCC1=CC=CC=C1)=O)=O.Cl CFCPJZHJJYBLHO-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007123 defense Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- PKXZMCUFRWLMBT-UHFFFAOYSA-N (4-chlorophenyl)methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=C(Cl)C=C1 PKXZMCUFRWLMBT-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- MUZDXNQOSGWMJJ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-2-enoic acid Chemical class OC(=O)C=C.CC(=C)C(O)=O MUZDXNQOSGWMJJ-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- LIFFBWPIGFQNHW-UHFFFAOYSA-N 6-(4-hydroxyhex-5-enoxy)hex-1-en-3-ol Chemical compound C=CC(O)CCCOCCCC(O)C=C LIFFBWPIGFQNHW-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- YOZSRQSUXWJLEU-UHFFFAOYSA-N benzyl 2-chloro-2-oxoacetate Chemical compound ClC(=O)C(=O)OCC1=CC=CC=C1 YOZSRQSUXWJLEU-UHFFFAOYSA-N 0.000 description 1
- LMOLAERNKHNYLV-UHFFFAOYSA-N benzyl 3-bromo-2-oxopropanoate Chemical compound BrCC(=O)C(=O)OCC1=CC=CC=C1 LMOLAERNKHNYLV-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- FFYIWHUDKRDPBB-UHFFFAOYSA-N butyl 2-chloro-2-oxoacetate Chemical compound CCCCOC(=O)C(Cl)=O FFYIWHUDKRDPBB-UHFFFAOYSA-N 0.000 description 1
- HTHNEFPCPFIREV-UHFFFAOYSA-N butyl 3-bromo-2-oxopropanoate Chemical compound CCCCOC(=O)C(=O)CBr HTHNEFPCPFIREV-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- CRQQGFGUEAVUIL-UHFFFAOYSA-N chlorothalonil Chemical compound ClC1=C(Cl)C(C#N)=C(Cl)C(C#N)=C1Cl CRQQGFGUEAVUIL-UHFFFAOYSA-N 0.000 description 1
- BOIJGDQIIVTEIZ-UHFFFAOYSA-N cyclohexyl 2-chloro-2-oxoacetate Chemical compound ClC(=O)C(=O)OC1CCCCC1 BOIJGDQIIVTEIZ-UHFFFAOYSA-N 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- VICYTAYPKBLQFB-UHFFFAOYSA-N ethyl 3-bromo-2-oxopropanoate Chemical compound CCOC(=O)C(=O)CBr VICYTAYPKBLQFB-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical group 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000005439 maleimidyl group Chemical class C1(C=CC(N1*)=O)=O 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- MQONVZMIFQQQHA-UHFFFAOYSA-N methyl 3-bromo-2-oxopropanoate Chemical compound COC(=O)C(=O)CBr MQONVZMIFQQQHA-UHFFFAOYSA-N 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- VOXPNWBULDGYAH-UHFFFAOYSA-N octyl 2-chloro-2-oxoacetate Chemical compound CCCCCCCCOC(=O)C(Cl)=O VOXPNWBULDGYAH-UHFFFAOYSA-N 0.000 description 1
- ZWAHJKVTQLQIJC-UHFFFAOYSA-N octyl 3-bromo-2-oxopropanoate Chemical compound BrCC(C(=O)OCCCCCCCC)=O ZWAHJKVTQLQIJC-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- PNOYGMCDBUDMFV-UHFFFAOYSA-N phenyl 2-chloro-2-oxoacetate Chemical compound ClC(=O)C(=O)OC1=CC=CC=C1 PNOYGMCDBUDMFV-UHFFFAOYSA-N 0.000 description 1
- QKFJKGMPGYROCL-UHFFFAOYSA-N phenyl isothiocyanate Chemical compound S=C=NC1=CC=CC=C1 QKFJKGMPGYROCL-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- RLUCXJBHKHIDSP-UHFFFAOYSA-N propane-1,2-diol;propanoic acid Chemical compound CCC(O)=O.CC(O)CO RLUCXJBHKHIDSP-UHFFFAOYSA-N 0.000 description 1
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical compound SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical class CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/52—Amides or imides
- C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F20/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-acryloylmorpholine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1668—Vinyl-type polymers
Definitions
- the present invention relates to a marine antifouling paint for preventing marine organisms from adhering to underwater structures such as ships and fish nets, a method for protecting ships and fish nets using the paint, and a polymer used therefor.
- Marine antifouling paint using an organotin-containing copolymer is gradually hydrolyzed in seawater, and the organotin portion of the copolymer side chain is appropriately eluted from the coating film surface, and can exhibit a long-term antifouling effect It has been widely used.
- the use of marine antifouling agents using organotin-containing copolymers has recently been restricted due to the problem of marine pollution.
- an antifouling agent is introduced into the side chain of the polymer instead of the organotin compound, and the antifouling agent is released into seawater to release the antifouling agent.
- a submarine antifouling agent has been proposed which is found in the patent applications of Japanese Patent Application Laid-Open No. 60-500452 and Japanese Patent Application Laid-Open No. 61-26374, which exhibit high performance.
- ester moieties in the copolymers disclosed in these patent applications are not sufficiently hydrolyzed under weak alkaline conditions such as natural seawater (pH 8.0 to 8.9), and are therefore practically resistant to antifouling. There was a major drawback in that it was not effective.
- the present inventors have conducted intensive studies to solve the above-mentioned disadvantages of the prior art, and as a result, the antifouling coating film is appropriately hydrolyzed in natural seawater for a long time.
- the present inventors have found a marine antifouling paint and a polymer used therein, and have reached the present invention. That is, according to the present invention, a) an antifouling component b) a binder of the formula (I)
- R is an alkyl group, cycloalkyl group, aryl group or an aralkyl group which may be optionally substituted in the aryl group
- A is a hydrogen atom or a methyl group
- a marine antifouling paint comprising: a) a solvent and, if necessary, d) an additive. According to the present invention, further, the formula (I)
- ⁇ , ⁇ and R have the same meanings as described above, By polymerizing one or more unsaturated monomers represented by the general formula (1) or one or more unsaturated monomers represented by the general formula (() and another ethylenically unsaturated monomer It can be obtained by copolymerizing one or more monomers.
- Examples of the unsaturated monomer represented by the formula (1 ′) include the following:
- CH 2 C-C00 (CH 2 ) 2 -0C-C-0C 2 H 5 (A: H, CH 3 )
- CH 2 C-C00 (CH 2 ) 2-OC-C-OC4H9 (A: H, CH 3 ) A
- CH 2 C-C00 (CH 2 ) 2-0C-C-0CH 2 (A: H, CH 3 )
- CE 2 C-C00 (CH 2 ) 3-0C-C-0C 2 H 5 (A: H, CH 3 )
- I II II II CH 2 CC-CH 2 0C-C-0C 2 H 5 (A: H, CH 3 )
- the unsaturated monomer of the above formula ( ⁇ ') is represented by the formula (II) It is obtained by reacting an unsaturated monomer having a free hydroxyl group with an acid halide represented by the formula (III) in the presence of a base such as triethylamine, pyridine, sodium hydroxide, or sodium carbonate. .
- A is a hydrogen atom or a methyl group
- R 1 represents an alkylene group or a phenylene group, respectively.
- R represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and X represents a chlorine atom, a bromine atom or an iodine atom.
- unsaturated monomers having a free hydroxyl group represented by the formula (II) include, for example, aryl alcohol; 5-methallyl alcohol,
- Examples of the acid halide represented by the formula (III) include ethyl chloroglyoxylate, propyl bromoglyoxylate, butyl chloroglyoxylate, octyl chloroglyoxylate, phenyl chloroglyoxylate, benzyl chloroglyoxylate, Examples include acid chlorides such as cyclohexyl chloroglyoxylate and acid bromides obtained by substituting the bromo atom of the above compound with a bromo atom.
- the unsaturated monomer of the formula (1 ′) is obtained by converting an unsaturated monomer having a free carboxyl group (for example, acrylic acid or methacrylic acid) and a halide represented by the formula (IV) into triethylamine. It can also be obtained by reacting in the presence of a base such as pyridine, sodium hydroxide and sodium carbonate.
- a base such as pyridine, sodium hydroxide and sodium carbonate.
- halide represented by the formula (IV) examples include methyl bromopyruvate, ethyl bromopyruvate, butyl bromopyruvate, octyl bromopyruvate, phenyl bromopyruvate, benzyl bromopyruvate, and cyclobromopyruvate. Brominated compounds such as xyl, and chlorinated compounds obtained by substituting the prom atom of the above compound with a ketone atom are included.
- the polymer according to the present invention having a repeating unit represented by the formula (I) further comprises one or more unsaturated monomers having a free hydroxyl group represented by the formula (II).
- the resulting copolymer is mixed with an acid halide represented by the formula (III), triethylamine, pyridine It can also be obtained by reacting in the presence of a base such as sodium hydroxide, sodium carbonate and the like.
- a base such as sodium hydroxide, sodium carbonate and the like.
- the other ethylenically unsaturated monomer is not limited as long as it is a copolymerizable monomer.
- acrylate (methacrylic acid) esters such as methyl methacrylate, ethyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, vinylidene chloride, acrylonitrile, acrylamide, vinyl acetate, and vinyl pyrrolidone.
- the antifouling component contained in the marine antifouling paint of the present invention is not limited as long as it has a killing or repelling effect on marine fouling organisms.
- Compounds such as zinc oxide, rodane, and powder; organic compounds such as tetrachloroisophthalonitrile; 3,4-cycle-mouth phenylisothiocynate; zinc dithiolbamate; 2-mercaptopyridine N —Zinc compounds such as zinc oxide, thiuram compounds, maleimide compounds, etc., which can be used alone or as a mixture.
- the amount of the antifouling component in the marine antifouling paint of the present invention is not particularly limited, but is preferably from 10 to 200% by weight of the polymer having the repeating unit represented by the formula (I).
- the marine antifouling paint of the present invention further comprises a polymer having a repeating unit of the formula (I) and, if necessary, a rosin, a rubber chloride, an acryl resin, a vinyl chloride-vinyl acid copolymer (VYHH). Natural or synthetic resins such as the above can also be used in combination.
- the marine antifouling paint of the present invention can contain further additives as necessary.
- additives include pigments, dyes, and plasticizers.
- the marine antifouling paint of the present invention contains a solvent for the above polymer, but such a solvent is not particularly limited.
- a solvent is not particularly limited.
- methyl ethyl ketone, methyl isobutyl ketone, xylene, propylene glycol Monomethyl ether acetate and the like can be mentioned.
- the obtained yellow copolymer solution (copolymer solution A) had a viscosity of 630 cps, a heating residue of 38.9%, and a molecular weight of 140,000.
- the resulting dark brown copolymer solution (Copolymer Solution H) had a viscosity of 1200 cps, a heating residue of 48.2%, and a molecular weight of 81,000.
- Example 10 In a 50 Om 1 four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, 64 g of the benzyloxalyloxhexyl methacrylate obtained in Production Example 5, 16 g of methyl acrylate, and propylene 120 g of glycol monomethyl ether acetate and 2 g of azobisisobutyronitrile (AIBN) are added, and polymerized under a nitrogen atmosphere at 85 to 90 ° C for 4.5 hours to obtain a pale yellow copolymer. A solution (copolymer solution J) was obtained. The obtained copolymer solution J had a viscosity of 226 cps, a heating residue of 39.5%, and a molecular weight of 57,000.
- AIBN azobisisobutyronitrile
- copolymer solution N a pale yellow copolymer solution (copolymer solution N).
- the obtained copolymer solution N had a viscosity of 262 cps, a heating residue of 39.9%, and a molecular weight of 6,000.
- Comparative Example 1 The same procedure as in Example 1 was repeated, except that 90 g of funasyl acrylate was used in place of 90 g of 2-ethoxyoxalyloxyshetyl acrylate in Example 1. Polymerized for hours.
- the obtained funasyl ester-containing copolymer solution (comparative copolymer solution 1) had a viscosity of 850 cps, a heating residue of 49.2%, and a molecular weight of 43,000.
- benzyl ester-containing copolymer solution (comparative copolymer solution 2) had a viscosity of 980 cps, a heating residue of 49.1%, and a molecular weight of 38,000.
- a rotating drum with a diameter of 31.8 mm and a height of 450 mm was attached to the center of the water tank, and this could be rotated by a motor.
- a heating device and a cooling device were installed to keep the seawater temperature constant, and a pH automatic controller was installed to keep the seawater pH constant.
- Each of the copolymer solutions and marine antifouling paints obtained in Examples 1-34 and Comparative Examples 1-2 was coated on a 1 mm thick hard vinyl chloride plate so as to have a dry film thickness of about 100 microns. After drying, it was dried at 50 ° C. for 24 hours. The test plate coated with the marine antifouling paint is brought into contact with seawater on the rotating drum of the above rotating device.
- Example 18 34 and Comparative Example 34 were applied to both sides of a hard vinyl chloride plate so as to have a dry film thickness of 200 microns.
- the test plate was immersed 1.5 m below the sea surface in Oga Bay, Mie Prefecture, and the test plate was stained for 18 months with attached organisms. Table 4 shows the results.
- ⁇ Tolerable to use as a culture net due to the adhesion of living things.
- the polymer having a non-ketoester group of the present invention has excellent adhesion to base materials such as ship bottoms and fish nets, and the coating film is tough. As is clear from Table 3, it is moderately hydrolyzed in natural seawater.
- the marine antifouling coating composition of the present invention obtained by adding an antifouling component to the polymer can maintain the antifouling effect for a long period of time, and does not have to worry about marine pollution as seen in conventional antifouling coating compositions.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
Abstract
L'invention concerne un polymère présentant des unités à répétition et représenté par la formule générale (I), une peinture de protection marine comprenant un composant 'antifouling' et un solvant et contenant une résine comprenant le polymère en tant que liant, et procédé de protection des bateaux ou des filets de pêche par application de ladite peinture. Dans la formule (I), A représente hydrogène ou méthyle, B représente -C(=O)OR'O-, -OR'O-, -C(=O)OCH2-, -C(=O)NHCH2O-, -C(=O)R'O-, -OC(=O)R'O-, -O- ou -R'O-, où R' représente alkylène ou phénylène, et R représente alkyle, cycloalkyle, aryle ou aralkyle pouvant être éventuellement substitué au niveau du groupe aryle.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7698791 | 1991-03-15 | ||
JP3/76987 | 1991-03-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1992016570A1 true WO1992016570A1 (fr) | 1992-10-01 |
Family
ID=13621134
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1992/000299 WO1992016570A1 (fr) | 1991-03-15 | 1992-03-12 | Peinture de protection marine |
Country Status (1)
Country | Link |
---|---|
WO (1) | WO1992016570A1 (fr) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996041842A1 (fr) * | 1995-06-13 | 1996-12-27 | Jotun A/S | Polymeres pour des peintures maritimes et un procede pour leur preparation |
WO2014148241A1 (fr) * | 2013-03-22 | 2014-09-25 | Jsr株式会社 | Composition de résine sensible au rayonnement, procédé de formation de motif de réserve, polymère et procédé permettant de produire un composé |
JP2015141356A (ja) * | 2014-01-29 | 2015-08-03 | Jsr株式会社 | 感放射線性樹脂組成物、レジストパターン形成方法、重合体及び化合物 |
CN105175277A (zh) * | 2015-05-18 | 2015-12-23 | 中山大学肿瘤防治中心 | 一种3-磷酸甘油醛脱氢酶的抑制剂及其制备方法和应用 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02288844A (ja) * | 1989-01-12 | 1990-11-28 | Nippon Paint Co Ltd | 重合性化合物およびそれから得られる重合体 |
-
1992
- 1992-03-12 WO PCT/JP1992/000299 patent/WO1992016570A1/fr active Application Filing
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02288844A (ja) * | 1989-01-12 | 1990-11-28 | Nippon Paint Co Ltd | 重合性化合物およびそれから得られる重合体 |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996041842A1 (fr) * | 1995-06-13 | 1996-12-27 | Jotun A/S | Polymeres pour des peintures maritimes et un procede pour leur preparation |
WO2014148241A1 (fr) * | 2013-03-22 | 2014-09-25 | Jsr株式会社 | Composition de résine sensible au rayonnement, procédé de formation de motif de réserve, polymère et procédé permettant de produire un composé |
US20150323866A1 (en) * | 2013-03-22 | 2015-11-12 | Jsr Corporation | Radiation-sensitive resin composition, resist pattern-forming method, polymer, and method for producing compound |
JPWO2014148241A1 (ja) * | 2013-03-22 | 2017-02-16 | Jsr株式会社 | 感放射線性樹脂組成物、レジストパターン形成方法、重合体及び化合物の製造方法 |
US9703195B2 (en) | 2013-03-22 | 2017-07-11 | Jsr Corporation | Radiation-sensitive resin composition, resist pattern-forming method, polymer, and method for producing compound |
JP2015141356A (ja) * | 2014-01-29 | 2015-08-03 | Jsr株式会社 | 感放射線性樹脂組成物、レジストパターン形成方法、重合体及び化合物 |
CN105175277A (zh) * | 2015-05-18 | 2015-12-23 | 中山大学肿瘤防治中心 | 一种3-磷酸甘油醛脱氢酶的抑制剂及其制备方法和应用 |
CN105175277B (zh) * | 2015-05-18 | 2018-04-03 | 中山大学肿瘤防治中心 | 一种3‑磷酸甘油醛脱氢酶的抑制剂及其制备方法和应用 |
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