JPS62290768A - Antifouling paint composition - Google Patents
Antifouling paint compositionInfo
- Publication number
- JPS62290768A JPS62290768A JP13286186A JP13286186A JPS62290768A JP S62290768 A JPS62290768 A JP S62290768A JP 13286186 A JP13286186 A JP 13286186A JP 13286186 A JP13286186 A JP 13286186A JP S62290768 A JPS62290768 A JP S62290768A
- Authority
- JP
- Japan
- Prior art keywords
- group
- formula
- tables
- polymerizable unsaturated
- formulas
- 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
- 239000003973 paint Substances 0.000 title claims abstract description 41
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 38
- 239000000203 mixture Substances 0.000 title claims description 20
- -1 polysiloxane Polymers 0.000 claims abstract description 23
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 17
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 9
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 8
- 230000003000 nontoxic effect Effects 0.000 abstract description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 abstract description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 15
- 229920006163 vinyl copolymer Polymers 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 229920002554 vinyl polymer Polymers 0.000 description 9
- 239000008199 coating composition Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 231100000614 poison Toxicity 0.000 description 7
- 239000003440 toxic substance Substances 0.000 description 7
- 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 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 4
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 4
- 229940112669 cuprous oxide Drugs 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 150000003606 tin compounds Chemical class 0.000 description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- 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 3
- 239000004593 Epoxy Substances 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 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 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000004066 1-hydroxyethyl group Chemical group [H]OC([H])([*])C([H])([H])[H] 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- YYNNRJWNBXEQTP-UHFFFAOYSA-N 2-[(4-bromophenyl)sulfonylamino]-3-phenylpropanoic acid Chemical compound C=1C=C(Br)C=CC=1S(=O)(=O)NC(C(=O)O)CC1=CC=CC=C1 YYNNRJWNBXEQTP-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
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000282472 Canis lupus familiaris Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 101100536300 Pasteurella multocida (strain Pm70) talB gene Proteins 0.000 description 1
- 241000219289 Silene Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000010427 ball clay Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 229910021488 crystalline silicon dioxide Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000001177 diphosphate Substances 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- NNBRCHPBPDRPIT-UHFFFAOYSA-N ethenyl(tripropoxy)silane Chemical compound CCCO[Si](OCCC)(OCCC)C=C NNBRCHPBPDRPIT-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- BFWMWWXRWVJXSE-UHFFFAOYSA-M fentin hydroxide Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(O)C1=CC=CC=C1 BFWMWWXRWVJXSE-UHFFFAOYSA-M 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- MOVRCMBPGBESLI-UHFFFAOYSA-N prop-2-enoyloxysilicon Chemical compound [Si]OC(=O)C=C MOVRCMBPGBESLI-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- PWYVVBKROXXHEB-UHFFFAOYSA-M trimethyl-[3-(1-methyl-2,3,4,5-tetraphenylsilol-1-yl)propyl]azanium;iodide Chemical compound [I-].C[N+](C)(C)CCC[Si]1(C)C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 PWYVVBKROXXHEB-UHFFFAOYSA-M 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 238000001363 water suppression through gradient tailored excitation Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は防汚塗料組成物に関し、さらに詳しくは、船舶
や海上補遺物の没水部分における水棲生物の付着防止を
目的とする無毒型防汚塗料組成物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an antifouling paint composition, and more particularly to a nontoxic antifouling paint composition for preventing aquatic organisms from adhering to submerged parts of ships and marine relics.
従来、船舶や海上構造物等の没水部分には、亜酸化銅や
有機錫化合物を配合した塗料が塗装され、水棲生物の付
着防止に大きな効果をあげているが、反面、銅化合物や
有機錫化合物等の有毒物質の塗膜からの溶出による環境
汚染の問題があり、このため銅化合物や有機錫化合物等
の毒物を含まない無毒形の防汚塗料の開発が要望されて
いる。Conventionally, submerged parts of ships and offshore structures have been painted with paints containing cuprous oxide and organic tin compounds, which have been highly effective in preventing aquatic organisms from adhering to them. There is a problem of environmental pollution due to the elution of toxic substances such as tin compounds from paint films, and therefore there is a demand for the development of non-toxic antifouling paints that do not contain toxic substances such as copper compounds and organic tin compounds.
もつとも、従来においても無毒型防汚塗料を示g a
nd Its PreventionJAnnap
olis、 Maryland:U、 S、Nava
l r n5titute(1952)には、パラフ
ィンやワックスの使用が無毒型防汚塗料としての可能性
があることが示唆されており、またRlE、Baler
発表[P roSpect for N onto
xic FoulingResistant Pa
1ntsJProc。However, in the past, non-toxic antifouling paints have also been proposed.
nd Its Prevention
olis, Maryland: U,S,Nava
RlE, Baler et al. (1952) suggests that paraffin and wax may be used as non-toxic antifouling paints.
Announcement [ProSpect for N onto
xic Fouling Resistant Pa
1ntsJProc.
Annu、 Conf、 Mar、 Techno
gy Sac、 (1973)には、メチル基とヒド
ロキシル基とが混在した塗膜表面を提供することによっ
て基材表面に防汚性を付与できることが示唆されている
。Annu, Conf, Mar, Techno
gy Sac, (1973) suggests that antifouling properties can be imparted to the surface of a substrate by providing a coating surface containing a mixture of methyl groups and hydroxyl groups.
さらに、米国特許第3,702.778号、第4゜09
8.925号、第4.234,340号などにも無毒型
防汚塗料が開示されているが、いずれもその防汚性能が
従来の亜酸化銅や有機錫化合物を含有した防汚塗料に及
ばず、なお改良の余地が残されているというのが実情で
ある。Additionally, U.S. Patent No. 3,702.778, 4°09
Non-toxic antifouling paints are also disclosed in No. 8.925 and No. 4.234, 340, but both have antifouling performance that is inferior to conventional antifouling paints containing cuprous oxide or organic tin compounds. The reality is that there is still room for improvement.
そこで、本発明者らは、R境汚染の原因となる金属化合
物や有機金属類などの毒物を含まず且つ防汚性能が従来
のがかる毒物を含む型の防汚塗料と遜色のない無毒型の
防汚塗料を開発すべく鋭意研究を重ねた結果、水棲生物
の塗膜に対する付着傾向は、塗膜の表面エネルギーが低
いほど、また塗膜成分に極性成分が少ないほど、さらに
塗膜表面に水滴を滴下した場合水滴が下落しやすい塗膜
表面はど生物の付着が起こり難く、しかも生物が付着し
た場合でも付着力が弱いことを見い出し、この目的に合
致する特定の塗膜形成成分を開発することによって本発
明を完成するに至った。Therefore, the present inventors developed a non-toxic type antifouling paint that does not contain toxic substances such as metal compounds and organic metals that cause R environment pollution, and whose antifouling performance is comparable to conventional antifouling paints containing toxic substances. As a result of intensive research to develop antifouling paints, we found that the tendency of aquatic organisms to adhere to paint films is that the lower the surface energy of the paint film, and the less polar components there are in the paint film, the more likely water droplets will form on the paint film surface. We discovered that the surface of the paint film, where water droplets tend to fall when dropped, is difficult for organisms to adhere to, and even if organisms do adhere to it, the adhesion force is weak, and we developed a specific paint film-forming component that meets this purpose. This led to the completion of the present invention.
かくして、本発明に従えば、
(A)一般式
式中、
Xlは式CH2=C−又はCH2=C−COO−の基(
ここで、R6は水素原子又はメチル基を表わす)を表わ
し;
R,、R2、R1及びR1は同一もしくは相異なり、そ
れぞれ炭素原子数1〜4個のアルキル基、アリール基又
は7ラルキル基を表ゎし;
Rsは炭素原子数1〜4個のフルキル基、又は水酸基を
1〜3個合有する炭素原子数1〜6個のヒドロキシアル
キル基を表わし;身
alj:X、が式Cl2=C−の基を表わすときにはO
R1
でA’)、X、が式C112= C−C000M ヲ表
わすとこには1〜5の整数であり;
bは3〜i 、o o oの数である、で示される重合
性不飽和ポリシロキサン化合物1〜50重量%
([3) 一般式
式中、
R,R。Thus, according to the invention: (A) in the general formula, Xl is a group of the formula CH2=C- or CH2=C-COO-;
Here, R6 represents a hydrogen atom or a methyl group); R,, R2, R1 and R1 are the same or different and each represents an alkyl group, an aryl group or a 7-ralkyl group having 1 to 4 carbon atoms; Rs represents a furkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 6 carbon atoms having 1 to 3 hydroxyl groups; O when representing a group of
R1 is a polymerizable unsaturated polyester represented by A'), X is an integer of 1 to 5; Siloxane compound 1 to 50% by weight ([3) In the general formula, R, R.
X 2 ハ式CH2= C−又1i CI!2 = C
−Coo−(7) J& (コ’::−テ、R6は水素
原子又はメチル基を表わす)を表わし;
R7は炭素原子数1〜4個のアルキル基を表わし;
dはX2が式CH,=C−の尤を表わすときにはOR。X 2 C-formula CH2= C-also 1i CI! 2 = C
-Coo-(7) J&(Co'::-te, R6 represents a hydrogen atom or a methyl group); R7 represents an alkyl group having 1 to 4 carbon atoms; d represents X2 with the formula CH, =OR to express the likelihood of C-.
であり、X2が式CIl□=C−COO−の基を表わす
ときには1〜5のg数である、
で示される重合性不飽和アルコキシシラン化合物O〜3
0重景%
及び
(C) 前記(A)及び(B)の化合物以外の重合性
不飽和ビニル系単量体 20〜99重量%を
共重合させることにより得られるビニル系共重合体を皮
膜形成成分として含有することを特徴とする防汚塗料組
成物が提供される。and when X2 represents a group of the formula CIl□=C-COO-, the number of grams is from 1 to 5.
Forming a film with a vinyl copolymer obtained by copolymerizing 0 weight percent and (C) 20 to 99 weight percent of a polymerizable unsaturated vinyl monomer other than the compounds of (A) and (B) above. Provided is an antifouling paint composition containing the following components.
本発明の防汚塗料組成物は水中に毒物を溶出することが
なく、それから形成される塗膜は表面エネルギーが低く
、しかも塗膜表面は水滴が落下しやすいため防汚性に優
れ、また生物が付着しても容易に除去することが可能で
あり、従来の金属化合物や有機金属類などの毒物を溶出
する型の防汚塗料に比べて遜色のない防汚性能を発揮す
る。The antifouling coating composition of the present invention does not elute toxic substances into water, the coating film formed from it has low surface energy, and water droplets easily fall on the coating surface, so it has excellent antifouling properties. Even if it adheres, it can be easily removed, and it exhibits antifouling performance comparable to conventional antifouling paints that elute toxic substances such as metal compounds and organic metals.
本明細書において「アルキル基」は直鎖状及ゾ分岐鎖状
のいずれのタイプのものであってもよく、例えば、メチ
ル、エチル、n−プロピル、1so−プロピル、n−ブ
チル、5ee−ブチル、1so−ブチル、ters−ブ
チル、n−ペンチル、n−ヘキシル基等が包含される。In the present specification, the "alkyl group" may be either linear or so-branched, such as methyl, ethyl, n-propyl, 1so-propyl, n-butyl, 5ee-butyl. , 1so-butyl, ters-butyl, n-pentyl, n-hexyl, and the like.
また、「アリール基」にはフェニル基、トルイル基、キ
シリル基、ナフチル基等が挙げられ、さらに[−アラル
キル基」にはペンノル展や7エネチル基等が包含される
。Further, the "aryl group" includes a phenyl group, tolyl group, xylyl group, naphthyl group, etc., and the [-aralkyl group] includes pennol group, 7enethyl group, etc.
以下、本発明の防汚塗料組成物を構成する主要成分につ
いて具体的に説明する。Hereinafter, the main components constituting the antifouling paint composition of the present invention will be specifically explained.
(八) l企ユ311ボリシロキサンイ今一本発明の防
汚塗料組成物におけるビニル系重合体の構成成分である
重合性不飽和ポリシロキサン化合物(△)は下記一般式
式中、X4、R1、R2、R3、R4、R5、a及びb
は11;I記の意味を有する、
で示されるー・方の末端に重合性のビニル基1夷。(8) The polymerizable unsaturated polysiloxane compound (△) which is a constituent component of the vinyl polymer in the antifouling paint composition of the present invention is represented by the following general formula, X4, R1 , R2, R3, R4, R5, a and b
has the meaning of 11; I, and has a polymerizable vinyl group at the end of the terminal.
(CI+、=C−)を有するポリシロキサン化合物であ
る。It is a polysiloxane compound having (CI+,=C-).
上記式(1)において、■り1、R2、[り、及びRt
は同一もしくは相異なり、それぞれ炭素原子I!1.1
〜4個のアルキル基、7リール基又はアラルキル基を表
わすが、アルキル基、殊にメチル基がビニル系共重合体
から形成される塗膜表面の表面エネルギーを最も小さく
するので好適である。In the above formula (1), ■ri1, R2, [ri, and Rt
are the same or different, and each carbon atom I! 1.1
~4 alkyl groups, 7-aryl groups, or aralkyl groups, but alkyl groups, especially methyl groups, are preferred because they minimize the surface energy of the coating film formed from the vinyl copolymer.
R5は炭素原子数1〜4個のアルキル基又は水酸基を1
〜3個含有する炭素原子数1〜6個のヒドロキシアルキ
ル基を表わし、後者のヒドロキシアルキル基がより好適
である。その理由は、R3が該ヒドロキシアルキル基を
表わす場合の本発明の塗料組成物は、前述のR,E、B
a1erが提唱したメチル基とヒドロキシル基が混在し
た塗B!、!表面を与えるからである。そのようなヒド
ロキシアルキル基としては、例えばヒドロキシメチル、
2−ヒドロキシエチル、1−ヒドロキシエチル、1゜2
−ノヒドロキシエチル、3−ヒドロキシプロピル、2.
3−ノヒドロキシプロビル、1,2.3−トリヒドロキ
シプロピル、4−ヒドロキシブチル、3.4−ジヒドロ
キシブチル、5−ヒドロキシペンチル、11,5−ノヒ
ドロキシベンチル、4.5−ジヒドロ−4−メチル−ペ
ンチル、4,4.5−)リヒドロキシベンチルなどが挙
げられる。R5 is an alkyl group having 1 to 4 carbon atoms or 1 hydroxyl group
It represents a hydroxyalkyl group having 1 to 6 carbon atoms, and the latter hydroxyalkyl group is more preferred. The reason for this is that in the case where R3 represents the hydroxyalkyl group, the coating composition of the present invention has the above-mentioned R, E, B
Coating B with a mixture of methyl and hydroxyl groups proposed by a1er! ,! This is because it provides a surface. Such hydroxyalkyl groups include, for example, hydroxymethyl,
2-hydroxyethyl, 1-hydroxyethyl, 1゜2
-hydroxyethyl, 3-hydroxypropyl, 2.
3-nohydroxypropyl, 1,2,3-trihydroxypropyl, 4-hydroxybutyl, 3,4-dihydroxybutyl, 5-hydroxypentyl, 11,5-nohydroxybentyl, 4,5-dihydro-4 -methyl-pentyl, 4,4.5-)lyhydroxybentyl, and the like.
H6
また、Xlが式CH2=C−の基を表わすときには、a
は0である、すなわち、該基は−(−CH、←−を介す
ることなく直接にSiに結合し、他方、Xlが式%式%
好ましくは2〜4の整数である。H6 Furthermore, when Xl represents a group of the formula CH2=C-, a
is 0, i.e. the group is bonded directly to Si without -(-CH, ←-), while Xl is preferably an integer from 2 to 4.
さらに、前記式(1)中のらはシロキサン単位0001
好ましくは30〜500、さらに好ましくは50〜30
0の範囲内の数であり、デルパーミニジョンクロマトグ
ラフィーにより求められる値である。Furthermore, in the above formula (1), the siloxane unit is 0001
Preferably 30-500, more preferably 50-30
It is a number within the range of 0, and is a value determined by delper minision chromatography.
しかして、重合性不飽和シロキサン化合物(A)として
好適にJljいちれるものの具体例としては以下に述べ
るものが挙げられる:
これらの中入手の容易さからして特に■及び■の化合物
が好適である。Therefore, specific examples of compounds suitable as the polymerizable unsaturated siloxane compound (A) include the following: In view of their ease of availability, compounds ① and ① are particularly preferred. be.
(B) u −ζ アルコキシシラン A本発明
におけるビニル系共重合体の慴成成かでありうる重合性
不飽和アルコキシシラン化合物(B)は下記一般式
式中、X2、R7及びdは前記の意味を有する、R1
で示される重合性のビニル基(C11□=C−)を含有
するフルコキシシラン化合物である。(B) u -ζ Alkoxysilane A In the present invention, the polymerizable unsaturated alkoxysilane compound (B) which can be a synthetic compound of the vinyl copolymer is the following general formula, where X2, R7 and d are the above-mentioned It is a flukoxysilane compound containing a polymerizable vinyl group (C11□=C-) represented by R1.
上記式(n)において、R,により表わされる炭素原子
数1〜4個のアルキル基の中では待にメチル基が好まし
い、また、X2が式Cl2=C−の基を表わすときには
dは0である、すなわち、該基は式中のSii子に直接
結合し、他方、X2が式CH,=C−COO−の基を表
わすときにはdは1〜5、好ましくは2〜4の整数であ
る。In the above formula (n), among the alkyl groups having 1 to 4 carbon atoms represented by R, a methyl group is most preferable, and when X2 represents a group of the formula Cl2=C-, d is 0. i.e., the group is directly bonded to the Si atom in the formula, while when X2 represents a group of the formula CH,=C-COO-, d is an integer from 1 to 5, preferably from 2 to 4.
しかして、上記式(II)の重合性不飽和アルコキシシ
ラン化合物(B)の具体例としては、ビニルトリメトキ
シシラン、ビニルトリエトキシシラン、ビニルトリプロ
ポキシシラン、ビニルトリエトキシシラン、(メタ)ア
クリロキシメチルトリメトキシシラン、(メタ)アクリ
ロキシエチルトリメトキシシラン、(メタ)アクリロキ
シプロピルトリメトキシシラン、(メタ)7クリロキシ
プロビルトリエトキシシラン、(メタ)アクリロキシエ
チルトリエトキシシラン、(メタ)アクリロキシプロピ
ルトリプトキシシランなどを挙げることができる。これ
らの中で特に好適なものは、(メタ)アクリロキシプロ
ピルトリメトキシシランである。Therefore, specific examples of the polymerizable unsaturated alkoxysilane compound (B) of the above formula (II) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriethoxysilane, (meth)acryloxysilane, Methyltrimethoxysilane, (meth)acryloxyethyltrimethoxysilane, (meth)acryloxypropyltrimethoxysilane, (meth)7cryloxyprobyltriethoxysilane, (meth)acryloxyethyltriethoxysilane, (meth) Examples include acryloxypropyltriptoxysilane. Particularly preferred among these is (meth)acryloxypropyltrimethoxysilane.
(C) ム ・ 和ビニル、1
本発明におけるビニル系共重合体の構成成分である前記
した前記(A)及び(B)の化合物以外の重合性不飽和
ビニル系単量体(C)としては、前記(A)及び/又は
(8)の化合物とラジカル重合して、皮膜形成性の高分
子物質を与えるものであれば特に制限はないが、一般に
は、ラジカル重合性のa、β−エチレン性不飽和結合を
1個又は2個、好ましくは1個含有する化合物が好適で
ある。(C) Mu・Japanese vinyl, 1 As the polymerizable unsaturated vinyl monomer (C) other than the above-mentioned compounds (A) and (B), which are the constituent components of the vinyl copolymer in the present invention, There is no particular restriction as long as it radically polymerizes with the compound (A) and/or (8) above to give a film-forming polymeric substance, but in general, radically polymerizable a, β-ethylene is used. Compounds containing one or two, preferably one, sexually unsaturated bond are suitable.
そのような重合性不飽和ビニル系単量体(C)の具体的
代表例としては次のものが挙げられる:(a)(メタ)
アクリル酸メチル、(メタ)アクリル酸エチル、(メタ
)アクリル酸プロピル、(メタ)アクリル酸インプロピ
ル、(メタ)アクリル酸ブチル、(メタ)アクリル酸ヘ
キシル、(メタ)アクリル酸2−エチルヘキシル、(メ
タ)アクリル酸オクチル、(メタ)アクリル酸ラウリル
などの(メタ)アクリル酸C1〜+□アルキルエステル
;(b)(メタ)アクリル酸2−ヒドロキシエチル、(
メタ)アクリル酸2−ヒドロキシプロピルなどの(メタ
)アフリルミC2〜Bヒドロキシアルキルエステル;
(C) グリシツル(メタ)7クリレート、アリルグ
リシツルエーテルなどのグリシジル含有ビニル系単量体
;
(d)(メタ)アクリル酸、イタコン酸、クロトン酸な
どのカルボキシル含有ビニル系単量体;(e) アリ
ル(メタ)アクリレートなど(メタ)アクリル酸C2〜
、アルケニルエステル;
(r) スチレン、α−メチルスチレン、ビニルトル
エンなどのビニル芳香族化合物:
<iz> その他:(メタ)アクリロニトリル、(メ
タ)アクロレイン、ブタジェン、イソプレンなど。Specific representative examples of such polymerizable unsaturated vinyl monomers (C) include the following: (a) (meth)
Methyl acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, impropyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ( (meth)acrylic acid C1~+□ alkyl ester such as octyl meth)acrylate, lauryl (meth)acrylate; (b) 2-hydroxyethyl (meth)acrylate, (
(meth) aphryl C2-B hydroxyalkyl esters such as 2-hydroxypropyl acrylate; (C) glycidyl-containing vinyl monomers such as glycitul (meth) 7 acrylate, allyl glycitulu ether; (d) (meth) ) Carboxyl-containing vinyl monomers such as acrylic acid, itaconic acid, and crotonic acid; (e) (meth)acrylic acids C2~ such as allyl (meth)acrylate;
, alkenyl esters; (r) Vinyl aromatic compounds such as styrene, α-methylstyrene, and vinyltoluene; <iz> Others: (meth)acrylonitrile, (meth)acrolein, butadiene, isoprene, etc.
これら重合性不飽和ビニル系単量体はそれぞれ卓独で使
用することができ、或いは2種又はそれ以上併用しても
よい。上記ビニル系単量体中、特に好適なものとしては
、(メタ)アクリル酸エチル、(メタ)アクリル酸ブチ
ル、(メタ)アクリル酸2−ヒにロキシエチル、スチレ
ンなどが挙げられる。These polymerizable unsaturated vinyl monomers can be used individually, or two or more kinds can be used in combination. Among the above vinyl monomers, particularly preferred ones include ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and styrene.
友1色
前記した重合性不飽和ポリシロキサン化合物(A)、重
合性不飽和アルコキシシラン化合物(B)及び重合性不
飽和ビニル系単量体(0は相互に共重合させることによ
り、本発明に従うビニル系共重合体とされる。その際の
上記(A)、(B)、(C)の各成分の使用割合は下記
のとおりとすることができる。The above-mentioned polymerizable unsaturated polysiloxane compound (A), polymerizable unsaturated alkoxysilane compound (B) and polymerizable unsaturated vinyl monomer (0 represents the present invention by copolymerizing with each other) A vinyl copolymer is used.The proportions of each of the components (A), (B), and (C) mentioned above can be as follows.
(八) 1〜50 5〜30
8〜20(B)0〜30 3〜15
5〜10(C) 20〜9955〜9270〜8
7本重量%は(A)、(B)、(Qの3成分の合計量を
基準とした重量百分率である。(8) 1-50 5-30
8-20 (B) 0-30 3-15
5-10 (C) 20-9955-9270-8
7% by weight is a weight percentage based on the total amount of the three components (A), (B), and (Q).
上記の共重合は不活性有機溶媒中で、それ自体既知のラ
ジカル重合法に従って行なうことができる。共重合に際
して用いうる有磯溶媒としては、例えば、酢酸エチル、
酢酸ブチルなどのエステルiiw;ベンゼン、トルエン
、キシレンなどの芳香族炭化水素溶媒;メチルエチルケ
トン、メチルイソブチルケトンなどのケトン系溶媒;イ
ソプロピルアルコール、ブタメールなどのアルコール系
溶媒;或いはこれら溶媒の2種もしくはそれ以上の混合
物が挙げられる。また、ラジカル重合開始剤としては、
例えば、ベンゾイルパーオキサイド、アゾビスイソブチ
ロニトリル、ラウロイルパーオキサイド、クメンヒドロ
パーオキサイドなどの通常ラジカル重合に使用されてい
る重合開始剤が挙げられる。The above copolymerization can be carried out in an inert organic solvent according to radical polymerization methods known per se. Examples of Aiso solvents that can be used in copolymerization include ethyl acetate,
Esters such as butyl acetate; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; alcohol solvents such as isopropyl alcohol and butamele; or two or more of these solvents. Mixtures of the above may be mentioned. In addition, as a radical polymerization initiator,
Examples include polymerization initiators commonly used in radical polymerization, such as benzoyl peroxide, azobisisobutyronitrile, lauroyl peroxide, and cumene hydroperoxide.
上記の共重合反応は通常、約80〜約200 ’(:、
好ましくは約100〜約120℃の温度において行なう
ことができ、かがる条件下に2〜20時間、好ましくは
5〜10時間程時間外らせることができる。The above copolymerization reaction is usually carried out over a period of about 80 to about 200' (:,
Preferably, it can be carried out at a temperature of about 100 to about 120 DEG C., and can be allowed to stand for about 2 to 20 hours, preferably 5 to 10 hours, under harsh conditions.
このようにしてgJ&遺されるビニル系共重合体は、一
般に、約3,000−約200,000.好ましくは約
5,000〜約100,000の範囲内の重M’l/−
均分子fit (M w )を有し、また、−30−1
00゛C1好ましくは一10〜30℃の範囲内のガラス
転移温度(Tg)をもっことが好ましい。The vinyl-based copolymer thus left behind generally has a gJ of about 3,000 to about 200,000. Weight M'l/- preferably within the range of about 5,000 to about 100,000
It has a uniform molecular fit (Mw) and also -30-1
It is preferable to have a glass transition temperature (Tg) in the range of 00°C1, preferably -10 to 30°C.
空1Ju先支!−凋一驚
本発明の塗料組成物は、前記の如くして製造されるビニ
ル系共重合体を適当な溶剤中に溶解乃至分散させること
により調製することができる。Sky 1 Ju branch first! The coating composition of the present invention can be prepared by dissolving or dispersing the vinyl copolymer produced as described above in an appropriate solvent.
該塗料組成物の調製に使用しうる溶剤としては、常温で
比較的揮発性のあるものが使用され、例えば、アセトン
、メチルエチルケトンなどのケトン系溶剤;酢酸エチル
、酢酸ブチルなどのエステル系m剤:ベンゼン、トルエ
ン、〜シレンなどの芳香族炭化水素溶剤;イソプロピル
アルール、ブチルアルコールなどのアルコール系溶剤;
ミネラルスピリット、芳香族石油ナフサなどの石油系溶
剤;或いはこれらの2種もしくはそれ以上の混合溶剤が
挙げられる。Solvents that can be used to prepare the coating composition include those that are relatively volatile at room temperature, such as ketone solvents such as acetone and methyl ethyl ketone; ester magents such as ethyl acetate and butyl acetate; Aromatic hydrocarbon solvents such as benzene, toluene, and silene; Alcohol solvents such as isopropyl alcohol and butyl alcohol;
Examples include petroleum solvents such as mineral spirit and aromatic petroleum naphtha; or mixed solvents of two or more of these solvents.
本発明の塗料組成物には、上記ビニル系共重合体に加え
て、さらに下記一般式
式中、
R2゜、R11% R2及びR13は同一もしくは相異
なり、それぞれ炭素原子数1〜4個のアルキル基、アリ
ール基又はアラルキル基を表わし;
pは1〜5の整数であり;
qは3〜1 、OOOの数である、
で示される両末端に第1級水酸基を有するシロキサン化
合物を含ませてもよい、これにより、該塗料組成物がも
つ防汚性能をより一層向上させることができる。In addition to the above-mentioned vinyl copolymer, the coating composition of the present invention further contains an alkyl group having 1 to 4 carbon atoms, in which R2°, R11%, R2 and R13 are the same or different, and each has 1 to 4 carbon atoms. represents a group, an aryl group, or an aralkyl group; p is an integer of 1 to 5; q is a number of 3 to 1, OOO; This can further improve the antifouling performance of the coating composition.
上記式(III)において、R1゜、R1、R12及(
/R,コはそれぞれメチル基であることが好ましく、p
は2〜4の範囲内にあることが好ましく、qはシロキサ
ン化合物
30〜500、特に50〜300の範囲内にあるのが好
適である。In the above formula (III), R1°, R1, R12 and (
/R, co are each preferably a methyl group, p
is preferably in the range of 2 to 4, and q is preferably in the range of 30 to 500, particularly 50 to 300 for the siloxane compound.
しかして、上記式(III’)のシロキサン化合物の具
体例としては犬のものが挙げられる:
q’=30〜500
これら式(Ill)のシロキサン化合物は、前記のビニ
ル系共重合体100重量部当り一般に1〜50重量部、
好ましくは5〜30重量部、さらに好ましくは8〜20
重量部の割合で配合するのが好都合である。Therefore, specific examples of the siloxane compounds of the above formula (III') include those of dogs: q' = 30 to 500 These siloxane compounds of the formula (Ill) can be prepared by adding 100 parts by weight of the above-mentioned vinyl copolymer. generally 1 to 50 parts by weight,
Preferably 5 to 30 parts by weight, more preferably 8 to 20 parts by weight
Conveniently, they are incorporated in parts by weight.
本発明の塗料組成物にはさらに必要に応じて、通常の塗
料添加物、例えば着色顔料(例:ベン柄、亜沿革、酸化
チタン、黄鉛など)、体質顔料(例:タルク、クレー、
炭酸カルシウムなど)、防錆顔料(例:鉛丹、ジンクク
ロメート、クロム酸鉛なと)、可塑剤(例ニリン酸トリ
クレジル、塩素化パラフィン、7タル酸エステルなど)
、タレ止め剤(例:微細シリカ、ステアリン酸アルミニ
ウム、ステアリン酸亜鉛など)をそれぞれ一般に使用さ
れている範囲内の量で配合してもよい。The coating composition of the present invention may further contain conventional coating additives, such as coloring pigments (e.g., benzene, subsynthesis, titanium oxide, yellow lead, etc.), extender pigments (e.g., talc, clay, etc.), as necessary.
Calcium carbonate, etc.), anti-rust pigments (e.g. red lead, zinc chromate, lead chromate, etc.), plasticizers (e.g. tricresyl diphosphate, chlorinated paraffin, heptatarate, etc.)
, an anti-sagging agent (eg, fine silica, aluminum stearate, zinc stearate, etc.) may be added in amounts within commonly used ranges.
本発明の防汚塗料m産物の31!製は、以上に述べた各
成分を前述の溶剤中に、ボールミル、アトライター等の
分散装置を用いて混合分散することにより行なうことが
できる。31 of the antifouling paint product of the present invention! The preparation can be carried out by mixing and dispersing the above-mentioned components in the above-mentioned solvent using a dispersion device such as a ball mill or attritor.
該組成物中の本発明に従う前記のビニル系共重合体の配
合量は散密に制限されるものではなく、塗付すべき基材
の種類や場所等に応じて広範にわたり変えうろことがで
きるが、一般的にいって、組成物の重量を基準にして1
5〜70重量%、好ましくは30〜50重量%の範囲内
とすることができる。The amount of the vinyl copolymer according to the present invention in the composition is not strictly limited, and can be varied over a wide range depending on the type and location of the substrate to be coated. , generally speaking, 1 based on the weight of the composition.
It can be in the range of 5 to 70% by weight, preferably 30 to 50% by weight.
#1目1
本発明により提供される防汚塗料組成物は、後述の実施
例により立証されているように、塗膜のすべり摩擦角度
及び臨界表面張力が小さく、水接生物の付着に対する優
れた抵抗性をしており、その防汚性能は従来の金属化合
物や有8!金属などの毒物を溶出する型の防汚塗料と同
等乃至それ以上である。しかも、本発明の防汚塗料組成
物は、水棲生物が付着しても容易に除去することができ
無毒型の防汚塗料として極めて優れたものである。#1 Item 1 The antifouling coating composition provided by the present invention has a small sliding friction angle and critical surface tension of the coating film, and has excellent resistance to adhesion of organisms in contact with water, as evidenced by the examples described below. It is resistant to dirt, and its antifouling performance is 8 times higher than that of conventional metal compounds! It is equivalent to or even better than antifouling paints that elute toxic substances such as metals. In addition, the antifouling paint composition of the present invention can be easily removed even if aquatic organisms adhere to it, making it extremely excellent as a non-toxic antifouling paint.
しがして、本発明の防汚塗料組成物は、生物の付着をき
らう各種の船舶、水中及び水上横fJ!物(例えば切削
リブ、浮ドツク、水門、ブイなど)の没水部分の塗装に
使用することができる。However, the antifouling paint composition of the present invention can be applied to various types of ships, underwater and above-water fJ! It can be used to paint submerged parts of objects (e.g. cutting ribs, floating docks, water gates, buoys, etc.).
以下、実施例によって本発明をさらに説明するが、本発
明は実施例のみに限定されるものではなく、本発明の要
萱の範囲内で種々の変形が可能であることを理解すべき
である。なお実施例、比較例中の部及び%は特に断らな
い限り重量部及び重量%を示す。The present invention will be further explained below with reference to Examples, but it should be understood that the present invention is not limited only to the Examples, and that various modifications can be made within the scope of the invention. . In addition, parts and % in Examples and Comparative Examples indicate parts by weight and % by weight unless otherwise specified.
ビニル系−【人体の製造 1
反応容器中で、メタクリロキシプロビルポリツメチルシ
ロキサン
メチルメタクリレート40部及びn−ブチルメタクリレ
ート40部をキシレン/酢酸ブチル=8/2の混合溶剤
67部に溶解し、ベンゾイルパーオキサイド1.0部を
加え攪拌しながら90〜100°Cで6時間反応し、7
g20“C1重量平均分子量30.0(、O及1固形分
60%のビニル系共重合体溶液を得た。Vinyl system - [Production of human body] 1 In a reaction vessel, 40 parts of methacryloxypropyl polymethylsiloxane methyl methacrylate and 40 parts of n-butyl methacrylate were dissolved in 67 parts of a mixed solvent of xylene/butyl acetate = 8/2, Add 1.0 part of benzoyl peroxide and react at 90 to 100°C for 6 hours with stirring.
A vinyl copolymer solution having a weight average molecular weight of 30.0 (60%, O and 1 solids content) was obtained.
ビニル系 A゛の製造12
反応容器中で、メタクリロキンブロビル4,5−ノヒド
ロキシー4−メチルペンチルポリジメチルシロキサン
20部、メタクリロキシプロピルトリメトキシシラン2
0部、インブチルアクリレート40部及び入子レノ20
部をキシレン/酢酸ブチル=8/2の混合溶剤67部に
溶解し、アゾビスイソブチロニトリル0.5部を加え攪
拌しながら90〜100°Cで6時間反応し、Tg−1
0℃、重量平均分子!i45,000及び固形分60%
のビニル系共重合体溶液を得た。Production of vinyl-based A゛12 In a reaction vessel, 20 parts of methacryloquine brobyl 4,5-nohydroxy-4-methylpentylpolydimethylsiloxane, 2 parts of methacryloxypropyltrimethoxysilane
0 parts, 40 parts of inbutyl acrylate and 20 parts of Nested Reno
was dissolved in 67 parts of a mixed solvent of xylene/butyl acetate = 8/2, and 0.5 parts of azobisisobutyronitrile was added thereto and reacted at 90 to 100°C for 6 hours with stirring to obtain Tg-1.
0℃, weight average molecule! i45,000 and solids content 60%
A vinyl copolymer solution was obtained.
炙玉土五諾1澄)LIA遣↓
製造例1で用いたメタクリロキシプロピルポリrすJ
J−11,ニア0番廿ン30合に−メタクリロキシプロ
ピルトリメトキシシラン30部及びL−ブチルメタクリ
レート40部を製造例1と同様の方法で重合して7g3
0、重量平均分子i30,000及び固形分60%のビ
ニル系共重合体溶液を得な。Roasted ball clay 1 clear) LIA delivery ↓ Methacryloxypropyl polys J used in Production Example 1
J-11, 30 parts of methacryloxypropyltrimethoxysilane and 40 parts of L-butyl methacrylate were polymerized in the same manner as in Production Example 1 to obtain 7g3
0. Obtain a vinyl copolymer solution with a weight average molecular weight i of 30,000 and a solid content of 60%.
ビニル、(介゛の製ai!!I±
反応容器中で、アクリロキシプロビルボリノメチルシロ
キサン
アクリロキシプロビルトリエトキシシラン10部、t−
ブチルメタクリレ−) 30 ff1s及びインブチル
メタクリレ−)30部をキシレン/酢酸ブチル−8部2
混合溶剤67部に18解し、アゾビスイソブチロニトリ
ル1.0部を加え100〜110’Cで6時間反応しT
gl、!°C1l!!i平均分子f130 、0()(
)及び固形’I) 609bのビニル系共重合体溶液を
得な。In a reaction vessel, 10 parts of acryloxypropylborinomethylsiloxane, t-
butyl methacrylate) 30 ff1s and butyl methacrylate) 30 parts xylene/butyl acetate -8 parts 2
It was dissolved in 67 parts of a mixed solvent, 1.0 part of azobisisobutyronitrile was added, and the mixture was reacted for 6 hours at 100-110'C.
gl,! °C1l! ! i average molecule f130 , 0()(
) and a solid 'I) 609b vinyl copolymer solution.
実施例1
製造例1で得たビニル系共重合体溶液80部、エロノル
l$200(西独デグサ社製晶S i O2微粉末)0
.5部及びキシレン19.5部をペイントコンディショ
ナーで混合分散して本発明の防汚塗料組成物を得た。そ
の塗膜性能試験結果を後記表−2に示す。Example 1 80 parts of the vinyl copolymer solution obtained in Production Example 1, Elonorl $200 (Crystalline SiO2 fine powder manufactured by Degussa, Germany) 0
.. 5 parts and 19.5 parts of xylene were mixed and dispersed with a paint conditioner to obtain an antifouling paint composition of the present invention. The coating film performance test results are shown in Table 2 below.
実施例2〜8
表−1に示す配合割合で実施例1と同様にして防汚塗料
組成物を調製した。その塗膜性能試験結果を後記表−2
に示す。Examples 2 to 8 Antifouling paint compositions were prepared in the same manner as in Example 1 using the blending ratios shown in Table 1. The coating film performance test results are shown in Table 2 below.
Shown below.
比較例1〜4
下記の配合で防汚塗料組成物を実施例1と同様にして′
fIJ4製した。その塗膜性能試験結果を後記表−2に
示す。Comparative Examples 1 to 4 Antifouling paint compositions were prepared in the same manner as in Example 1 with the following formulations.
It was manufactured by fIJ4. The coating film performance test results are shown in Table 2 below.
く比較例1〉
塩化ビニル樹脂 10.0(部)ロジ
ン 10.0トリクレノル
ホス7エイト 4.0トリフエニル錫フルオ
ライド 10.0タルク
5.0ペン柄 5.
0キジロール 28.0メチルイ
ソブチルケトン 28.0計 100.0
(部)
く比較例2〉
塩化ゴムU4脂 5.0(部)ロ
ジン 15.0トリクレジ
ルホス7エイト 4.0亜酸化銅
30.0タルク
5.O(部)バリタ
3.0ペン柄 4.0キジ
ロール 34.0計 100.
0(#)
く比較例3〉
塩化ビニル!f脂 5.5(部)ロ
ジン 5.5トリクレジル
ホス7エイト 2.0亜酸化銅
30.0トリフエニル錫ハイドロオキサイ
ド10.0硫酸バリウム 4.0
タル2 11.0(部)ベン
ガラ 10.0キジロール
11.0メチルイソブチルケトン
11.0#t 100.0(部)
く比較例4〉
常温硬化型シリコン樹脂 50 (部)Nシ
ロール 50計 100
(部)
立退mえ
上記の実施例1〜8及び比較例1〜4で得た塗料を大さ
さ100100X300X2のサンドブラスト処理銅板
にジンクエポキシ系ショッププライマー(乾燥膜115
μ)及びエポキシ系防錆塗料(同200μ)を予め塗装
した被塗板に、乾燥i厚が50μになるように塗装して
試験板とし、7日間乾燥した後に供試した。Comparative Example 1> Vinyl chloride resin 10.0 (parts) Rosin 10.0 Triclenorphos 7ate 4.0 Triphenyltin fluoride 10.0 Talc
5.0 Pen handle 5.
0 Kijirol 28.0 Methyl isobutyl ketone 28.0 Total 100.0
(Parts) Comparative Example 2> Chlorinated rubber U4 fat 5.0 (parts) Rosin 15.0 Tricresyl phosphate 7ate 4.0 Cuprous oxide
30.0 talc
5. O (Part) Barita
3.0 Pen handle 4.0 Kijiroll 34.0 Total 100.
0 (#) Comparative Example 3> Vinyl chloride! f-fat 5.5 (parts) Rosin 5.5 Tricresylphos7ate 2.0 Cuprous oxide
30.0 Triphenyltin hydroxide 10.0 Barium sulfate 4.0
Tal 2 11.0 (parts) Red Garla 10.0 Kijiroll
11.0 Methyl isobutyl ketone 11.0 #t 100.0 (parts) Comparative example 4> Room temperature curing silicone resin 50 (parts) N silole 50 total 100
(Part) Evacuation The paints obtained in Examples 1 to 8 and Comparative Examples 1 to 4 above were applied to a sandblasted copper plate measuring 100,100 x 300 x 2 with zinc epoxy shop primer (dry film 115
A test plate was prepared by coating a coated board with epoxy anticorrosion paint (200μ) and epoxy anticorrosion paint (200μ) to give a dry thickness of 50μ, and after drying for 7 days, it was tested.
(1)水滴のすべりまさつ試襞
塗膜上に0.03m1の水滴をおき、1yaを徐々に待
ち上げていき水滴がすべりはじめる塗板の角度を測定す
る。(1) Water droplet sliding test Place a 0.03 ml water droplet on the coating film, gradually raise it to 1ya, and measure the angle of the coated plate at which the water droplet begins to slide.
(2)臨界表面張力の測定
水及びパラフィンの液滴による接触角を測定し、塗面の
臨界表面張力を求める。(2) Measurement of critical surface tension The contact angle between water and paraffin droplets is measured to determine the critical surface tension of the coated surface.
(3) 防汚性試論
試験板を三重県鳥羽湾に12ケノ1浸漬して生物の付着
状況を副査する。数値は付着面積の%である。(3) The antifouling test board was immersed in Toba Bay, Mie Prefecture, for 12 minutes, and the state of adhesion of organisms was sub-inspected. Values are in % of the attached area.
表−2
表−2より明らかなように、本発明の防汚塗料組成物は
、従来の亜酸化鋼、有機錫を用いた塗料とくらべ遜色の
ない性能を示す。Table 2 As is clear from Table 2, the antifouling paint composition of the present invention exhibits performance comparable to that of conventional paints using suboxide steel and organic tin.
Claims (1)
式、化学式、表等があります▼の基(ここで、R_6は
水素原子又はメチル基を表わす)を表わし; R_1、R_2、R_3及びR_4は同一もしくは相異
なり、それぞれ炭素原子数1〜4個のアルキ ル基、アリール基又はアラルキル基を表わ し; R_5は炭素原子数1〜4個のアルキル基、又は水酸基
を1〜3個含有する炭素原子数1 〜6個のヒドロキシアルキル基を表わし; aはX_1が式▲数式、化学式、表等があります▼の基
を表わすときには0であり、X_1が式▲数式、化学式
、表等があります▼の基を表わす とこには1〜5の整数であり; bは3〜1,000の数である、 で示される重合性不飽和ポリシロキサン化合物1〜50
重量% (B)一般式 ▲数式、化学式、表等があります▼(II) 式中、 X_2は式▲数式、化学式、表等があります▼は▲数式
、化学式、表等があります▼の基(ここで、 R_6は水素原子又はメチル基を表わす)を表わし; R_7は炭素原子数1〜4個のアルキル基を表わし; dはX_2が式▲数式、化学式、表等があります▼の基
を表わすときには0であり、X_2が式▲数式、化学式
、表等があります▼の基を表わす ときには1〜5の整数である、 で示される重合性不飽和アルコキシシラン化合物0〜3
0重量% 及び (C)前記(A)及び(B)の化合物以外の重合性不飽
和ビニル系単量体20〜99重量% を共重合させることにより得られるビニル系共重合体を
皮膜形成成分として含有することを特徴とする防汚塗料
組成物。[Claims] 1. (A) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) In the formula, X_1 is a formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ Numerical formulas, chemical formulas, tables, etc. represents a group ▼ (where R_6 represents a hydrogen atom or a methyl group); R_1, R_2, R_3 and R_4 are the same or different and each represents an alkyl group having 1 to 4 carbon atoms, an aryl group, or represents an aralkyl group; R_5 represents an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 6 carbon atoms containing 1 to 3 hydroxyl groups; , tables, etc. When representing the group ▼, it is 0, and when X_1 represents the group ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, it is an integer from 1 to 5; b is 3 to 1,000. A polymerizable unsaturated polysiloxane compound represented by 1 to 50, which is the number of
Weight% (B) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) In the formula, X_2 is the group of the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. Here, R_6 represents a hydrogen atom or a methyl group; R_7 represents an alkyl group having 1 to 4 carbon atoms; d represents a group where X_2 is the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Sometimes it is 0, and when X_2 represents a group of the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, it is an integer from 1 to 5.
0% by weight and (C) 20 to 99% by weight of a polymerizable unsaturated vinyl monomer other than the compounds (A) and (B) above. An antifouling paint composition characterized by containing:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61132861A JPH0645770B2 (en) | 1986-06-10 | 1986-06-10 | Antifouling paint composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61132861A JPH0645770B2 (en) | 1986-06-10 | 1986-06-10 | Antifouling paint composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS62290768A true JPS62290768A (en) | 1987-12-17 |
JPH0645770B2 JPH0645770B2 (en) | 1994-06-15 |
Family
ID=15091249
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP61132861A Expired - Lifetime JPH0645770B2 (en) | 1986-06-10 | 1986-06-10 | Antifouling paint composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0645770B2 (en) |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS636067A (en) * | 1986-06-26 | 1988-01-12 | Nippon Paint Co Ltd | Water-repellent antifouling coating composition |
EP0273457A2 (en) * | 1986-12-30 | 1988-07-06 | Nippon Oil And Fats Company, Limited | Antifouling paint |
JPS6411167A (en) * | 1987-07-02 | 1989-01-13 | Toray Silicone Co | Covering material composition |
JPH0249079A (en) * | 1988-05-23 | 1990-02-19 | Sanyo Chem Ind Ltd | Coating composition |
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WO1997022641A1 (en) * | 1995-12-19 | 1997-06-26 | Toyo Ink Manufacturing Co., Ltd. | Aqueous resin dispersion and process for preparing the same |
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JPS55152745A (en) * | 1979-05-17 | 1980-11-28 | Kanegafuchi Chem Ind Co Ltd | Curable composition |
JPS56136854A (en) * | 1980-03-29 | 1981-10-26 | Kansai Paint Co Ltd | Paint composition |
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JPS5819361A (en) * | 1981-07-27 | 1983-02-04 | Kanegafuchi Chem Ind Co Ltd | One-pack type room temperature curing composition |
JPS5978236A (en) * | 1982-10-28 | 1984-05-07 | Toagosei Chem Ind Co Ltd | Production of vinyl-polymerizable high-molecular straight-chain silicone monomer |
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Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS636067A (en) * | 1986-06-26 | 1988-01-12 | Nippon Paint Co Ltd | Water-repellent antifouling coating composition |
EP0273457A2 (en) * | 1986-12-30 | 1988-07-06 | Nippon Oil And Fats Company, Limited | Antifouling paint |
JPS6411167A (en) * | 1987-07-02 | 1989-01-13 | Toray Silicone Co | Covering material composition |
JPH0249079A (en) * | 1988-05-23 | 1990-02-19 | Sanyo Chem Ind Ltd | Coating composition |
JPH0662918B2 (en) * | 1988-05-23 | 1994-08-17 | 三洋化成工業株式会社 | Coating composition |
JPH05230161A (en) * | 1992-02-18 | 1993-09-07 | Shin Etsu Chem Co Ltd | Graft copolymer and coating composition using the same |
WO1997022641A1 (en) * | 1995-12-19 | 1997-06-26 | Toyo Ink Manufacturing Co., Ltd. | Aqueous resin dispersion and process for preparing the same |
JP2003176444A (en) * | 1996-04-17 | 2003-06-24 | Nippon Yushi Basf Coatings Kk | Coating material composition |
JP2003176442A (en) * | 1996-04-17 | 2003-06-24 | Nippon Yushi Basf Coatings Kk | Coating material composition |
JP2003176443A (en) * | 1996-04-17 | 2003-06-24 | Nippon Yushi Basf Coatings Kk | Method for producing coating material composition |
DE10216608A1 (en) * | 2002-04-15 | 2003-10-30 | Wacker Polymer Systems Gmbh | Extrudable, low-migration silicone organocopolymers with high transparency, their production and use |
US7153581B2 (en) | 2002-04-15 | 2006-12-26 | Wacker Polymer Systems Gmbh & Co. Kg | Extrudable, low-migration organic silicone copolymers of high transparency, their preparation and use |
US7670743B2 (en) | 2005-03-04 | 2010-03-02 | Ricoh Company, Ltd. | Image forming method |
US7785762B2 (en) | 2005-12-15 | 2010-08-31 | Ricoh Company, Ltd. | Image forming apparatus and image forming method |
JP2010235948A (en) * | 2010-05-07 | 2010-10-21 | Ricoh Co Ltd | Dispersion liquid |
US10409129B2 (en) | 2016-05-11 | 2019-09-10 | Ricoh Company, Ltd. | Electrochromic element |
US10429710B2 (en) | 2016-05-13 | 2019-10-01 | Ricoh Company, Ltd. | Electrochromic device |
US10975296B2 (en) | 2017-01-26 | 2021-04-13 | Ricoh Company, Ltd. | Electrochromic compound, electrochromic composition, and electrochromic element |
US11106106B2 (en) | 2018-03-19 | 2021-08-31 | Ricoh Company, Ltd. | Electrochromic device, electronic dimming eyeglasses, augmented reality eyeglasses, and camera |
US11370963B2 (en) | 2018-07-25 | 2022-06-28 | Ricoh Company, Ltd. | Electrochromic compound, electrochromic composition, and electrochromic element |
US11859131B2 (en) | 2018-07-25 | 2024-01-02 | Ricoh Company, Ltd. | Electrochromic compound, electrochromic composition, and electrochromic element |
Also Published As
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JPH0645770B2 (en) | 1994-06-15 |
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