JPS6357675A - Antifouling coating material - Google Patents
Antifouling coating materialInfo
- Publication number
- JPS6357675A JPS6357675A JP20251486A JP20251486A JPS6357675A JP S6357675 A JPS6357675 A JP S6357675A JP 20251486 A JP20251486 A JP 20251486A JP 20251486 A JP20251486 A JP 20251486A JP S6357675 A JPS6357675 A JP S6357675A
- Authority
- JP
- Japan
- Prior art keywords
- coating material
- group
- antifouling
- copolymer
- acrylate
- 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
- 239000011248 coating agent Substances 0.000 title claims abstract description 26
- 238000000576 coating method Methods 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 title claims abstract description 24
- 230000003373 anti-fouling effect Effects 0.000 title claims description 35
- 229920001577 copolymer Polymers 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- -1 vinyl compound Chemical class 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 239000003440 toxic substance Substances 0.000 abstract description 2
- 229920002554 vinyl polymer Polymers 0.000 abstract 2
- 239000000470 constituent Substances 0.000 abstract 1
- 231100000989 no adverse effect Toxicity 0.000 abstract 1
- 231100000167 toxic agent Toxicity 0.000 abstract 1
- 239000003973 paint Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 8
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 8
- 229940112669 cuprous oxide Drugs 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000002519 antifouling agent Substances 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 231100000614 poison Toxicity 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 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 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 230000007096 poisonous effect Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 150000003606 tin compounds Chemical class 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- GRJISGHXMUQUMC-UHFFFAOYSA-N silyl prop-2-enoate Chemical compound [SiH3]OC(=O)C=C GRJISGHXMUQUMC-UHFFFAOYSA-N 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- NIBPEHGZRFSWSY-UHFFFAOYSA-N tributylsilyl prop-2-enoate Chemical compound CCCC[Si](CCCC)(CCCC)OC(=O)C=C NIBPEHGZRFSWSY-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-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
- 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
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- GAFFKTSONYEPJI-UHFFFAOYSA-N C(C=C)(=O)O[Si](CCCCCCCCCC)(C)C Chemical compound C(C=C)(=O)O[Si](CCCCCCCCCC)(C)C GAFFKTSONYEPJI-UHFFFAOYSA-N 0.000 description 1
- RDMVWHUSOVJNAT-UHFFFAOYSA-N C(C=C)(=O)O[Si](CCCCCCCCCCCC)(C)C Chemical compound C(C=C)(=O)O[Si](CCCCCCCCCCCC)(C)C RDMVWHUSOVJNAT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- XPMWNXFIZJFOMB-UHFFFAOYSA-N [butyl(dimethyl)silyl] prop-2-enoate Chemical compound CCCC[Si](C)(C)OC(=O)C=C XPMWNXFIZJFOMB-UHFFFAOYSA-N 0.000 description 1
- NLCZMCYXCVUGGN-UHFFFAOYSA-N [cyclohexyl(dimethyl)silyl] prop-2-enoate Chemical compound C=CC(=O)O[Si](C)(C)C1CCCCC1 NLCZMCYXCVUGGN-UHFFFAOYSA-N 0.000 description 1
- XFKQCKRULWCPOQ-UHFFFAOYSA-N [dibutyl(ethyl)silyl] prop-2-enoate Chemical compound CCCC[Si](CC)(CCCC)OC(=O)C=C XFKQCKRULWCPOQ-UHFFFAOYSA-N 0.000 description 1
- UPNJVQREGXOKSG-UHFFFAOYSA-N [dibutyl(methyl)silyl] prop-2-enoate Chemical compound CCCC[Si](C)(CCCC)OC(=O)C=C UPNJVQREGXOKSG-UHFFFAOYSA-N 0.000 description 1
- IAPNEIWYIUTSEY-UHFFFAOYSA-N [dimethyl(octyl)silyl] prop-2-enoate Chemical compound CCCCCCCC[Si](C)(C)OC(=O)C=C IAPNEIWYIUTSEY-UHFFFAOYSA-N 0.000 description 1
- MJJAGRVJSHKNMG-UHFFFAOYSA-N [dimethyl(phenyl)silyl] prop-2-enoate Chemical compound C=CC(=O)O[Si](C)(C)C1=CC=CC=C1 MJJAGRVJSHKNMG-UHFFFAOYSA-N 0.000 description 1
- CJLXAFNZMDTTNS-UHFFFAOYSA-N [hexyl(dimethyl)silyl] 2-methylprop-2-enoate Chemical compound CCCCCC[Si](C)(C)OC(=O)C(C)=C CJLXAFNZMDTTNS-UHFFFAOYSA-N 0.000 description 1
- UWVFNMRIDLHMGY-UHFFFAOYSA-N [hexyl(dimethyl)silyl] prop-2-enoate Chemical compound CCCCCC[Si](C)(C)OC(=O)C=C UWVFNMRIDLHMGY-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- HXTLWOZJMYIANK-UHFFFAOYSA-N butyl acetate;methanol Chemical compound OC.CCCCOC(C)=O HXTLWOZJMYIANK-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- UPIWXMRIPODGLE-UHFFFAOYSA-N butyl benzenecarboperoxoate Chemical compound CCCCOOC(=O)C1=CC=CC=C1 UPIWXMRIPODGLE-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000002704 decyl 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])* 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 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
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000010438 heat treatment Methods 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
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229940065472 octyl acrylate Drugs 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
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 150000004045 organic chlorine compounds Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 125000002306 tributylsilyl group Chemical group C(CCC)[Si](CCCC)(CCCC)* 0.000 description 1
- LPUCKLOWOWADAC-UHFFFAOYSA-M tributylstannyl 2-methylprop-2-enoate Chemical compound CCCC[Sn](CCCC)(CCCC)OC(=O)C(C)=C LPUCKLOWOWADAC-UHFFFAOYSA-M 0.000 description 1
- HVMNIRCQQXUXRP-UHFFFAOYSA-N triphenylsilyl prop-2-enoate Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(OC(=O)C=C)C1=CC=CC=C1 HVMNIRCQQXUXRP-UHFFFAOYSA-N 0.000 description 1
- ZEVPGAHZONRGQP-UHFFFAOYSA-N tris(4-methylpentan-2-yloxy)silyl prop-2-enoate Chemical compound CC(C)CC(C)O[Si](OC(C)CC(C)C)(OC(C)CC(C)C)OC(=O)C=C ZEVPGAHZONRGQP-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
［発明の技術分野］
本発明は、水中構築物、漁網、船底等への水棲生物の付
着を阻止するための防汚性コーティング材に関する。Detailed Description of the Invention [Technical Field of the Invention] The present invention relates to an antifouling coating material for preventing aquatic organisms from adhering to underwater structures, fishing nets, ship bottoms, etc.
［発明の技術的背景とその問題点］
水中構築物、漁網、船底をはじめ水中で長期間使用する
物品には、使用中に水棲生物が付着、繁殖して外観を損
ねるばかりでなく、その機能に悪影響を与えることがあ
る。[Technical Background of the Invention and Problems Therein] Aquatic organisms attach to and breed on items that are used underwater for long periods of time, including underwater structures, fishing nets, and ship bottoms, which not only impair their appearance but also impair their functionality. May cause adverse effects.
船底の場合においては、水棲生物の付着が船全体の表面
粗度の増加につながり、さらには船速が低下するととも
に燃費が増大する。またこのため、ドックでの修復期間
が長くなり運航効率が著しく低下する。このほか、バク
テリア類の繁殖により水中構築物の腐敗、物性の劣化が
起こって著しく寿命が低下する等の重大な被害を生ずる
。In the case of the bottom of a ship, the adhesion of aquatic organisms leads to an increase in the surface roughness of the entire ship, which further reduces ship speed and increases fuel consumption. This also increases the period of repair at the dock, significantly reducing operational efficiency. In addition, the proliferation of bacteria causes serious damage such as rotting of underwater structures and deterioration of their physical properties, significantly shortening their lifespans.
従来より、このような被害を回避するために使用される
防汚剤としては、有機塩素系化合物、亜酸化銅、有機ス
ズ化合物等が知られている。Conventionally, organic chlorine compounds, cuprous oxide, organic tin compounds, and the like have been known as antifouling agents used to avoid such damage.
有機スズ化合物や亜酸化銅のような重金属を含有する生
理活性物質は、特に優れた防汚効果を有し、漁網や船底
用の塗料に必須の成分と考えられている。例えば米国特
許第３，１６７．４７３＠明細書には、有機スズ化合物
を用いた防汚処理剤のなかで「ポリマータイプ」といわ
れているものが記載されている。この防汚処理剤は、共
重合体の側鎖に有機スズ含有基を有し、微アルカリ性の
海水中で加水分解されて有機スズ化合物を放出し、防汚
効果を発揮すると同時に、加水分解された共重合体自身
も水溶化して海水中に溶解してゆくため、樹脂残査層を
残すことなく、常に活性な表面を保つことができる。ま
た特吋昭６０−２３１７７１号公報には、含有する有機
スズ化合物や亜酸化銅等の生理活性物質の溶出性を促進
させる目的で、これに併用する有機スズ含有共重合体の
単量体の一部として、加水分解性のシリル（メタ）アク
リレート、例えばトリブチルシリルアクリレートやトリ
フェニル′シリル（メタ）アクリレートを用いる方法が
記載されている。Physiologically active substances containing heavy metals, such as organotin compounds and cuprous oxide, have particularly excellent antifouling effects and are considered essential ingredients in paints for fishing nets and ship bottoms. For example, US Pat. No. 3,167.473@ describes a so-called "polymer type" antifouling agent using an organic tin compound. This antifouling treatment agent has an organotin-containing group in the side chain of the copolymer, and is hydrolyzed in slightly alkaline seawater to release an organotin compound, exhibiting an antifouling effect and at the same time being hydrolyzed. Since the copolymer itself becomes water-soluble and dissolves in seawater, an active surface can always be maintained without leaving any residual resin layer. In addition, Tokoku No. 60-231771 discloses that monomers of organotin-containing copolymers used in combination with organic tin compounds and cuprous oxide are used for the purpose of promoting the dissolution of physiologically active substances such as organotin compounds and cuprous oxide. Some methods have been described using hydrolyzable silyl (meth)acrylates, such as tributylsilyl acrylate and triphenyl'silyl (meth)acrylate.
しかしながらこれらの防汚処理剤は、保存安定性が悪く
、特に亜酸化銅を併用した場合には数日の内にゲル化し
てしまうという問題があった。しかもこれらの防汚処理
剤は、重金属や加水分解性の有機スズ含有基を含有する
ため、毒性が高く、特に有機スズ化合物は刺激性が強く
、皮膚に触れると炎症を起こす等、安全衛生面で問題が
あるのみならず、海水中への流出による海洋汚染、奇形
魚の発生、生態濃縮による人体への蓄積性等重大な問題
を抱えていた。However, these antifouling agents have a problem of poor storage stability and gelation within a few days, especially when cuprous oxide is used in combination. Moreover, these antifouling agents are highly toxic because they contain heavy metals and hydrolyzable organotin-containing groups, and organotin compounds in particular are highly irritating and cause irritation when they come in contact with the skin, which poses health and safety concerns. Not only was there a problem, but there were also serious problems such as marine pollution due to leakage into seawater, the occurrence of deformed fish, and the possibility of accumulation in the human body due to ecological concentration.
このため、特表昭６０−５００４５２号公報には、有機
スズ含有共重合体をもちいることなく、防汚効果を示す
船底塗料が記載されている。この船底塗料は、毒物およ
び自己研磨型ポリマーより構成されており、該ポリマー
単量体としてはトリス（４−メチル−２−ペントキシ）
シリルアクリレートのような加水分解性のシリル（メタ
）アクリレートが記載されている。For this reason, Japanese Patent Publication No. 60-500452 describes a ship bottom paint that exhibits an antifouling effect without using an organic tin-containing copolymer. This ship bottom paint is composed of a poisonous substance and a self-polishing polymer, and the polymer monomer is tris(4-methyl-2-pentoxy).
Hydrolyzable silyl (meth)acrylates such as silyl acrylate are described.
しかしながらこの船底塗料において、自己研磨型ポリマ
ーは、毒物供給系（ｄｅｌｉｖｅｒｙ ｓｙｓｔｅｍ）
として働くのみで、これ自身には防汚性能はないため、
毒物成分が必須のものである。この船底塗料においても
、毒物によって付着した水棲生物を殺すという防汚を果
たす基本的な原理は、従来の防汚処理剤と変っておらず
、重大な環境問題を回避することはできなかった。しか
も毒物として亜酸化銅を使用した場合には、保全安定性
が悪く、数日の内にゲル化してしまうという問題もあっ
た。However, in this ship bottom paint, the self-polishing polymer is used in a toxic delivery system.
It only works as an antifouling agent and does not have antifouling properties by itself.
Toxic components are essential. Even with this ship bottom paint, the basic principle of antifouling is the same as that of conventional antifouling agents, which is to kill attached aquatic organisms with poisonous substances, and serious environmental problems could not be avoided. Moreover, when cuprous oxide is used as a poisonous substance, there is a problem in that the storage stability is poor and it gels within a few days.
さらにここに挙げられているトリス（４−メチル−２−
ペントキシ）シリルアクリレートは、ケイ素原子とアル
コキシ基の間およびケイ素原子とエステル結合の間の２
種類の結合がいずれも加水分解性をもつので、加水分解
による共重合体の水への溶解度の制御が困難になるとい
う問題もあった。Furthermore, the tris(4-methyl-2-
pentoxy) silyl acrylate is a silyl acrylate that has 2 bonds between a silicon atom and an alkoxy group and between a silicon atom and an ester bond.
Since all types of bonds are hydrolyzable, there is also the problem that it becomes difficult to control the solubility of the copolymer in water by hydrolysis.
［発明の目的］
本発明は、重金属や毒物を含有せず、海洋の生態系に悪
影響を与えることのない防汚性コーティング材を提供す
ることを目的とする。[Object of the Invention] An object of the present invention is to provide an antifouling coating material that does not contain heavy metals or poisonous substances and does not have a negative impact on the marine ecosystem.
［発明の構成］
本発明者らは、防汚性コーティング材における自己研磨
性に注目し、毒物の併用がなくとも優れた防汚性を有し
、しかも保存安定性の良好なコーティング用組成物を見
出して本発明をなすに至った。[Structure of the Invention] The present inventors focused on the self-polishing properties of antifouling coating materials, and created a coating composition that has excellent antifouling properties even without the use of toxic substances and has good storage stability. This discovery led to the present invention.
すなわち本発明の防汚性ツーティング材は、共重合体側
鎖のシリル基が加水分解によって放出され、次いで共重
合体自身も水溶化する自己研磨作用のみで防汚性を発揮
するものであり、一般式
％式％
（式中、Ｒ１は水素原子またはメチル基、Ｒ２、Ｒ３、
Ｒ４はそれぞれ炭素数１〜１８のアルキル基、シクロア
ルキル基およびフェニル基からなる群より選ばれる１価
の炭化水素基で、うち少なくとも１個は炭素数４以上の
１価の炭化水素基を示す。）で表わされる少なくとも１
種の不飽和トリオルガノシリル単量体と、（メタ）アク
リル系およびビニル系化合物から選ばれる少なくとも１
種の有機単量体とを重合させて得られる共重合体より成
ることを特徴としている。In other words, the antifouling tooling material of the present invention exhibits antifouling properties only through the self-polishing action in which the silyl groups in the side chains of the copolymer are released by hydrolysis, and the copolymer itself then becomes water-soluble. General formula % formula % (wherein R1 is a hydrogen atom or a methyl group, R2, R3,
R4 is a monovalent hydrocarbon group selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, and a phenyl group, at least one of which represents a monovalent hydrocarbon group having 4 or more carbon atoms. . ) at least 1
a species of unsaturated triorganosilyl monomer and at least one selected from (meth)acrylic and vinyl compounds;
It is characterized by consisting of a copolymer obtained by polymerizing various organic monomers.
本発明に用いられる共重合体は、本発明において特徴的
な成分であり、トリオルガノシリル基のケイ素原子に結
合した有機基を選択することによって適度の加水分解性
を示し、水中で徐々に加水分解して親水性を増すため、
水に対して制御された溶解特性を示す。このような共重
合体は、１種または２種以上の不飽和トリオルガノシリ
ル単量体と、１種または２種以上の有機単口体とを重合
度５０〜１ｏｏｏｏ程度に重合させることによって得ら
れる。 不飽和トリオルガノシリル単量体と有機単量体
との構成比は特に限定されるものではないが、好ましく
は不飽和トリオルガノシリル単母体の量が１０〜９５重
量％、さらに好ましくは２０〜７０重量％の範囲である
。不飽和トリオルガノシリル単量体の伍が１０重量％未
満では必要な加水分解速度が得られず、充分な防汚性を
発揮しない。また９５重量％を越えると塗膜の物性が悪
く、ざらに加水分解速度が過剰となるため、短期間に溶
解してしまい防汚力が持続しない。The copolymer used in the present invention is a characteristic component in the present invention, and exhibits appropriate hydrolyzability by selecting an organic group bonded to the silicon atom of the triorganosilyl group, and gradually hydrolyzes in water. To decompose and increase hydrophilicity,
Exhibits controlled solubility properties in water. Such a copolymer can be obtained by polymerizing one or more unsaturated triorganosilyl monomers and one or more organic monomers to a degree of polymerization of about 50 to 1oooo. It will be done. The composition ratio of the unsaturated triorganosilyl monomer to the organic monomer is not particularly limited, but preferably the amount of the unsaturated triorganosilyl monomer is 10 to 95% by weight, more preferably 20 to 95% by weight. It is in the range of 70% by weight. If the amount of unsaturated triorganosilyl monomer is less than 10% by weight, the required hydrolysis rate will not be obtained and sufficient antifouling properties will not be exhibited. Moreover, if it exceeds 95% by weight, the physical properties of the coating film will be poor and the hydrolysis rate will be excessive, so that it will dissolve in a short period of time and the antifouling power will not last.
共重合体の一方の出発原料である不飽和トリオルガノシ
リル単量体において、Ｒ１は水素原子またはメチル基で
あり、Ｒ２、Ｒ３、Ｒ４はそれぞれ炭素数１〜１８の独
立した１価の炭化水素基で、直鎖状または分岐状のアル
キル基、シクロアルキル基およびフェニル基から選ばれ
るものである。In the unsaturated triorganosilyl monomer that is one of the starting materials for the copolymer, R1 is a hydrogen atom or a methyl group, and R2, R3, and R4 are each independent monovalent hydrocarbons having 1 to 18 carbon atoms. A group selected from linear or branched alkyl groups, cycloalkyl groups, and phenyl groups.
このアルキル基としては、メチル基、エチル基、プロピ
ル基、ブチル基、ヘキシル基、オクチル基、デシル基、
ドデシル基、ミリスチル基、ステアリル基等が例示され
、シクロアルキル基としては、シクロペンチル基、シク
ロヘキシル基等が例示される。適度な加水分解性を持ち
、そのことによってコーティング材の水に対する徐溶性
を制御するには、Ｒ２、Ｒ３、Ｒ４のうち少なくとも１
個が炭素数４以上のものであることが必要である。Examples of this alkyl group include methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group,
Examples of the cycloalkyl group include a dodecyl group, myristyl group, and stearyl group. Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group. At least one of R2, R3, and R4 should have appropriate hydrolyzability and thereby control the slow solubility of the coating material in water.
It is necessary that each of the carbon atoms has 4 or more carbon atoms.
このような不飽和トリオルガノシリル単量体としては、
ジメチルブチルシリルアクリレート、ジメチルへキシル
シリルアクリレート、ジメチルオクチルシリルアクリレ
ート、ジメチルデシルシリルアクリレート、ジメチルド
デシルシリルアクリレート、ジメチルシクロへキシルシ
リルアクリレート、ジメチルフェニルシリルアクリレー
ト、メチルジブチルシリルアクリレート、エチルジブチ
ルシリルアクリレート、ジブチルヘキシルシリルアクリ
レート、ジブチルフェニルシリルアクリレート、トリブ
チルシリルアクリレート、トリフェニルシリルアクリレ
ート等：およびこれらに対応するメタクリレートが例示
される。これらのうち、加水分解速度が遅く、合成の容
易なことと、造膜性の良いことでは、ジメチルへキシル
シリル（メタ）アクリレート、ジメチルデシルシリル（
メタ）アクリレートのような、Ｒ２、Ｒ３、Ｒ４のうち
２個がメチル基で残余が炭素数６以上の長鎖アルキル基
であるものが優れているが、水中で制御された加水分解
速度をもち、適度の徐溶性を得るためには、トリブチル
シリル（メタ）アクリレートが好ましい。Such unsaturated triorganosilyl monomers include:
Dimethylbutylsilyl acrylate, dimethylhexylsilyl acrylate, dimethyloctylsilyl acrylate, dimethyldecylsilyl acrylate, dimethyldodecylsilyl acrylate, dimethylcyclohexylsilyl acrylate, dimethylphenylsilyl acrylate, methyldibutylsilyl acrylate, ethyldibutylsilyl acrylate, dibutylhexyl Silyl acrylate, dibutylphenylsilyl acrylate, tributylsilyl acrylate, triphenylsilyl acrylate, etc. and methacrylates corresponding to these are exemplified. Among these, dimethylhexylsilyl (meth)acrylate, dimethyldecylsilyl (
Materials such as meth)acrylates, in which two of R2, R3, and R4 are methyl groups and the remainder is a long-chain alkyl group with 6 or more carbon atoms, are excellent, but they have a controlled hydrolysis rate in water. In order to obtain appropriate slow solubility, tributylsilyl (meth)acrylate is preferred.
共重合体の他方の出発原料である有機単量体は、（メタ
）アクリル系およびビニル系化合物から選ばれるもので
ある。この（メタ）アクリル系化合物としては、メチル
アクリレート、エチルアクリレート、ブチルアクリレー
ト、ヘキシルアクリレート、オクチルアクリレート（以
上のアルキル基は直鎖状でも分岐状でもよい）、２−ヒ
ドロキシエチルアクリレート、２−ヒドロキシプロピル
アクリレート、ジメチルアミノエチルアクリレート、ア
クリルアミド、アクリルニトリル等：およびこれらに対
応するメタクリル化合物が例示され、ビニル系化合物と
しては、酢酸ビニル、塩化ビニル、ビニルメチルエーテ
ル、ビニルエチルエーテル、ビニルプロピルエーテル、
ビニルイソブチルエーテル、ビニルピロリドン等が例示
される。The organic monomer that is the other starting material for the copolymer is selected from (meth)acrylic and vinyl compounds. Examples of the (meth)acrylic compounds include methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate (the above alkyl groups may be linear or branched), 2-hydroxyethyl acrylate, 2-hydroxypropyl Examples include acrylate, dimethylaminoethyl acrylate, acrylamide, acrylonitrile, etc., and methacrylic compounds corresponding to these. Examples of vinyl compounds include vinyl acetate, vinyl chloride, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether,
Examples include vinyl isobutyl ether and vinyl pyrrolidone.
重合は、例えば有機溶剤の存在下で不飽和トリオルガノ
シリル単量体と有機単量体とを混合し、重合開始剤を用
いて行われる。Polymerization is carried out, for example, by mixing an unsaturated triorganosilyl monomer and an organic monomer in the presence of an organic solvent and using a polymerization initiator.
有機溶剤は、重合の制御と反応中のゲルの形成防止のた
めのものであり、ベンゼン、トルエン、キシレンのよう
な炭化水素系溶剤；酢酸エチル、酢酸ブチルのようなエ
ステル系溶剤；メタノール、エタノールのようなアルコ
ール系溶剤；メチルエチルケトン、メチルイソブチルケ
トンのようなケトン系溶剤；およびジメチルホルムアミ
ド、ジメチルスルホキシドのような非プロトン系極性溶
剤が例示される。Organic solvents are used to control polymerization and prevent gel formation during the reaction, and include hydrocarbon solvents such as benzene, toluene, and xylene; ester solvents such as ethyl acetate and butyl acetate; methanol and ethanol. Alcohol solvents such as; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; and aprotic polar solvents such as dimethyl formamide and dimethyl sulfoxide.
有機溶剤の量は、単量体の合計量１００重量部に対して
２０〜１ｏｏｏ重醋部が好ましく、さらに好ましくは５
０〜５００重量部である。有機溶剤の母が２０重量部未
満では反応の制御が困難となり、また１０００重量部を
越えるとコーティング材を形成する際に濃縮工程が必要
となる。また、重合中および保存中の加水分解を避ける
ために、これらの有機溶剤は水分を除去して用いたほう
がよい。The amount of the organic solvent is preferably 20 to 100 parts by weight, more preferably 5 parts by weight, based on 100 parts by weight of the total amount of monomers.
It is 0 to 500 parts by weight. If the amount of the organic solvent is less than 20 parts by weight, it will be difficult to control the reaction, and if it exceeds 1,000 parts by weight, a concentration step will be required when forming the coating material. Furthermore, in order to avoid hydrolysis during polymerization and storage, it is better to use these organic solvents after removing moisture.
重合開始剤としては、ベンゾイルパーオキサイド、ｔ−
ブチルパーベンゾエート、メチルエチルケトンパーオキ
サイド、クメンヒドロパーオキサイド等の有機過酸化物
およびアゾビスイソブチロニトリル等のアゾ化合物が例
示される。As a polymerization initiator, benzoyl peroxide, t-
Examples include organic peroxides such as butyl perbenzoate, methyl ethyl ketone peroxide, and cumene hydroperoxide, and azo compounds such as azobisisobutyronitrile.
重合開始剤の量は、単量体の合計量１００重量部に対し
て０．０１〜１０重量部が一般的である。The amount of the polymerization initiator is generally 0.01 to 10 parts by weight based on 100 parts by weight of the total amount of monomers.
重合条件は特に限定されないが、窒素気流中で行なうこ
とが好ましく、また一般に重合開始剤が有機過酸化物の
場合には６０〜１２０°Ｃ、アゾ化合物の場合には４５
〜１００℃の温度で行われる。Although the polymerization conditions are not particularly limited, it is preferable to carry out the polymerization in a nitrogen stream, and generally the temperature is 60 to 120°C when the polymerization initiator is an organic peroxide, and 45°C when the polymerization initiator is an azo compound.
It is carried out at a temperature of ~100°C.
本発明のコーティング材は、前述の共重合体単独か必要
に応じて顔料、有機溶剤、揺変剤等を配合することによ
って得られる。防汚処理の対象が水中構築物、漁網、船
底等と多岐にわたるため、配合割合は特に限定できない
が、共重合体の配合口が１〜６０重但％の範囲が好まし
い。共重合体の配合量が１型組％未満では塗膜を形成し
にくく、また６０重量％を越えると見掛は粘度が上がっ
て作業性が低下する。The coating material of the present invention can be obtained by using the above-mentioned copolymer alone or by blending a pigment, an organic solvent, a thixotropic agent, etc. as necessary. Since the objects of antifouling treatment are wide-ranging, such as underwater structures, fishing nets, and ship bottoms, the blending ratio cannot be particularly limited, but it is preferable that the blending ratio of the copolymer is in the range of 1 to 60% by weight. When the amount of the copolymer is less than 1% by weight, it is difficult to form a coating film, and when it exceeds 60% by weight, the viscosity increases and workability decreases.
顔料としては、へんから、チタン白、タルク、シリカ、
炭酸カルシウム、硫酸バリウムのような海水不活性顔料
や酸化亜鉛、酸化カルシウムのような海水反応性顔料が
例示され、１種でも、また２種以上の併用でも差支えな
い。Pigments include common, titanium white, talc, silica,
Examples include seawater-inactive pigments such as calcium carbonate and barium sulfate, and seawater-reactive pigments such as zinc oxide and calcium oxide, and they may be used alone or in combination of two or more.
有機溶剤としては、前述した共重合体を得るための重合
工程で用いたものと同様なものが用いられる。The organic solvent used is the same as that used in the polymerization step to obtain the copolymer described above.
揺変材としては、ベントナイト、酸化ポリエチレンおよ
びアミド化合物が例示される。Examples of thixotropic materials include bentonite, polyethylene oxide, and amide compounds.
［発明の効果］
本発明で得られる防汚性コーティング材は、共重合体の
側鎖のトリオルガノシリル基が加水分解して親水性を増
し、水中で制御された溶解性、すなわち自己研磨性を示
すので、環境に影響を及ぼす有機スズ化合物や有機スズ
含有共重合体を用いることなく優れた防汚効果を発揮す
ることができる。[Effects of the Invention] In the antifouling coating material obtained by the present invention, the triorganosilyl group in the side chain of the copolymer is hydrolyzed to increase hydrophilicity, and it has controlled solubility in water, that is, self-polishing property. Therefore, it is possible to exhibit excellent antifouling effects without using organic tin compounds or organic tin-containing copolymers that affect the environment.
本発明の組成物は、水中構築物、漁網、船底等の水棲生
物の付着による汚染を防止するのに有効である。The composition of the present invention is effective in preventing contamination of underwater structures, fishing nets, ship bottoms, etc. due to adhesion of aquatic organisms.
［実施例］
以下本発明を実施例および比較例によって説明する。な
お、以下の実施例中の部は重量部を示す。[Example] The present invention will be explained below by referring to Examples and Comparative Examples. In addition, parts in the following examples indicate parts by weight.
（共重合体の合成）
冷却器、撹拌器および温度計を備えた反応容器にキシレ
ン３００部を仕込み、これにジメチルへキシルシリルメ
タクリレート１２０部、メチルメタクリレート１８０部
、およびアゾビスイソブチロニトリル２部を加え、８０
’Ｃで８時間加熱撹拌することによって重合を行った。(Synthesis of copolymer) 300 parts of xylene was charged into a reaction vessel equipped with a condenser, a stirrer, and a thermometer, and 120 parts of dimethylhexylsilyl methacrylate, 180 parts of methyl methacrylate, and 2 parts of azobisisobutyronitrile were added. add 80 parts
Polymerization was carried out by heating and stirring at 'C for 8 hours.
室温に冷却後、酢酸エチル６６部を追加して淡黄色透明
の共重合体溶液Ｖ−１を得た。Ｖ−’１（７）２５°Ｃ
ｌケル粘１１Ｊｆハ４８０ ＣＰ、固形分濃度は４４．
８％であった。After cooling to room temperature, 66 parts of ethyl acetate was added to obtain a pale yellow and transparent copolymer solution V-1. V-'1 (7) 25°C
1 Kelviscosity 11Jf 480 CP, solids concentration 44.
It was 8%.
Ｖ−１と重合後の有機溶剤の追加を行わない以外は同様
にして、第１表に示す有機溶剤、単量体および反応開始
剤から、淡黄色透明の共重合体溶液Ｖ−２〜Ｖ−７を得
た。得られた共重合体溶液の粘度と固形濃度は第１表に
示すとおりでおる。In the same manner as V-1 except that no organic solvent was added after polymerization, pale yellow and transparent copolymer solutions V-2 to V were prepared from the organic solvents, monomers, and reaction initiators shown in Table 1. -7 was obtained. The viscosity and solid concentration of the obtained copolymer solution are as shown in Table 1.
なお表中の配合量を示す数字は部を表わす。（以下同じ
。）
第１表
実施例１〜１０、比較例１〜４
以上のようにして得た共重合体溶液Ｖ−１〜Ｖ−７を用
いて、本発明の防汚性コーティング材を第２表に示す配
合により調製した。Note that the numbers indicating the blending amounts in the table represent parts. (The same applies hereinafter.) Table 1 Examples 1 to 10, Comparative Examples 1 to 4 Using the copolymer solutions V-1 to V-7 obtained as above, the antifouling coating material of the present invention was coated. It was prepared according to the formulation shown in Table 2.
また比較例１および２として、亜酸化銅とトリブチルス
ズメタクリレートとメチルメタクリレートとの共重合体
からなる第３表に示すワニスＡおよびＢを用いた防汚塗
料を第４表に示す配合により調整した。さらに比較例３
および４として、従来型の亜酸化銅を用いた防汚塗料を
第４表に示す配合により調整した。Further, as Comparative Examples 1 and 2, antifouling paints were prepared using varnishes A and B shown in Table 3, which were made of a copolymer of cuprous oxide, tributyltin methacrylate, and methyl methacrylate, according to the formulations shown in Table 4. Furthermore, comparative example 3
and 4, a conventional antifouling paint using cuprous oxide was prepared according to the formulation shown in Table 4.
（以下余白）
第２表
以上のように調整した各防汚性コーティング材と防汚塗
料とを用いて、下記の要領で塗膜の消耗度と水棲生物の
付着性の試験を行った。(Left below) Using each antifouling coating material and antifouling paint prepared as shown in Table 2, tests were conducted on the degree of wear of the paint film and the adhesion of aquatic organisms in the manner described below.
（塗膜の消耗度）
実施例１〜１０および比較例１〜４の各防汚性コーティ
ング材と防汚塗料をそれぞれ７０Ｘ １５０Ｘ２Ｉｒｎ
の硬質塩化ビニル板に、乾燥膜厚が１００μｍになるよ
うにアプリケーターで塗布し、海水中に設置した回転ド
ラムに取付け、周速１０ノツトで回転させて、１力月間
の消耗膜厚を測定した。その結果を第５表に示す。(Degree of wear of coating film) Each of the antifouling coating materials and antifouling paints of Examples 1 to 10 and Comparative Examples 1 to 4 was tested at 70X 150X2Irn, respectively.
It was applied to a hard vinyl chloride plate with an applicator to a dry film thickness of 100 μm, mounted on a rotating drum set in seawater, rotated at a circumferential speed of 10 knots, and measured the film thickness consumed over one month. . The results are shown in Table 5.
（水棲生物の付着性 ■）
実施例１〜１０および比較例１〜４の各防汚性コーティ
ング材と防汚塗料をそれぞれ防錆塗料を塗布した１００
Ｘ ３００Ｘ ３ｍｍの鋼板に、乾燥膜厚が１５０〜２
００μｍになるように塗布して試料を作成した。これら
の試料と比較例５として無処理の試料とをそれぞれ広島
湾宮島沖の海中に沈め、６力月ごとに水棲生物の付着面
積を調べた。各々の試料の付着面積を百分率で第６表に
示す。(Adhesion of Aquatic Organisms ■) 100 coated with each antifouling coating material and antifouling paint of Examples 1 to 10 and Comparative Examples 1 to 4 respectively.
X 300X 3mm steel plate, dry film thickness 150~2
A sample was prepared by coating the film to a thickness of 0.00 μm. These samples and an untreated sample as Comparative Example 5 were each submerged in the sea off the coast of Miyajima in Hiroshima Bay, and the adhering area of aquatic organisms was examined every 6 months. Table 6 shows the adhesion area of each sample in percentage.
（水棲生物の付着性 ■）
実施例１および５と比較例１および４の各防汚性コーテ
ィング材と防汚塗料をそれぞれ５０Ｘ５０ｃｍのポリ塩
化ビニル樹脂製フレームに取付けた網目の大ぎざが７節
のポリエステル製の漁網に浸漬塗布し試料を作成した。(Adhesion of Aquatic Organisms ■) The antifouling coating materials and antifouling paints of Examples 1 and 5 and Comparative Examples 1 and 4 were each attached to a 50 x 50 cm polyvinyl chloride resin frame with seven large knurled meshes. A sample was prepared by dipping and coating a polyester fishing net.
これらの試料と比較例５として無処理の試料とをそれぞ
れ富山溝の海中に沈め、２力月ごとに水棲生物の付着状
態を調べた。These samples and an untreated sample as Comparative Example 5 were each submerged in the sea of Toyama Groove, and the state of adhesion of aquatic organisms was examined every two months.
この結果を第７表に示す。The results are shown in Table 7.
（以下余白）
各試験結果が示すように、本発明の防汚性コーティング
材は、長期間において安定した防汚性を発揮する。(Hereinafter, blank spaces) As shown by the test results, the antifouling coating material of the present invention exhibits stable antifouling properties over a long period of time.
Claims (4)
＾３、Ｒ＾４はそれぞれ炭素数１〜１８のアルキル基、
シクロアルキル基およびフェニル基からなる群より選ば
れる１価の炭化水素基で、うち少なくとも１個は炭素数
４以上の１価の炭化水素基を示す。）で表わされる少な
くとも１種の不飽和トリオルガノシリル単量体と、（メ
タ）アクリル系およびビニル系化合物から選ばれる少な
くとも１種の有機単量体とを重合させて得られる共重合
体より成ることを特徴とする防汚性コーティング材。(1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1 is a hydrogen atom or a methyl group, R^2, R
^3 and R^4 are each an alkyl group having 1 to 18 carbon atoms,
A monovalent hydrocarbon group selected from the group consisting of a cycloalkyl group and a phenyl group, at least one of which represents a monovalent hydrocarbon group having 4 or more carbon atoms. ) and at least one organic monomer selected from (meth)acrylic and vinyl compounds. An antifouling coating material characterized by:
る特許請求の範囲第１項記載の防汚性コーティング材。(2) The antifouling coating material according to claim 1, wherein R^2, R^3, and R^4 are all butyl groups.
、残余が炭素数６以上のアルキル基である特許請求の範
囲第１項記載の防汚性コーティング材。(3) The antifouling coating material according to claim 1, wherein two of R^2, R^3, and R^4 are methyl groups, and the remainder is an alkyl group having 6 or more carbon atoms.
ル単量体の量が１０〜９５重量％である特許請求の範囲
第１項ないし第３項のいずれか１項記載の防汚性コーテ
ィング材。(4) The antifouling according to any one of claims 1 to 3, wherein the amount of unsaturated triorganosilyl monomer among the monomers of the copolymer is 10 to 95% by weight. coating material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20251486A JPS6357675A (en) | 1986-08-28 | 1986-08-28 | Antifouling coating material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20251486A JPS6357675A (en) | 1986-08-28 | 1986-08-28 | Antifouling coating material |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6258168A Division JP2833493B2 (en) | 1994-10-24 | 1994-10-24 | Antifouling coating material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6357675A true JPS6357675A (en) | 1988-03-12 |
| JPH0582865B2 JPH0582865B2 (en) | 1993-11-22 |
Family
ID=16458748
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20251486A Granted JPS6357675A (en) | 1986-08-28 | 1986-08-28 | Antifouling coating material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6357675A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01306479A (en) * | 1988-06-06 | 1989-12-11 | Chugoku Marine Paints Ltd | Non-toxic anti-foul coating composition |
| JPH07150076A (en) * | 1994-10-24 | 1995-06-13 | Chugoku Marine Paints Ltd | Antifouling coating material |
| JPH09194790A (en) * | 1995-11-15 | 1997-07-29 | Chugoku Marine Paints Ltd | Antifouling coating material composition, coating film formed from the same composition, antifouling method by using the same composition and ship body or underwater structure coated with the same coating film |
| US6458878B1 (en) | 1998-12-28 | 2002-10-01 | Chuogoku Marine Paints, Ltd. | Silyl (meth) acrylate copolymers, processes for preparing the same, antifouling paint compositions containing the silyl (meth) acrylate copolymers, antifouling coating films formed from the antifouling paint compositions, antifouling methods using the antifouling paint compositions, and hulls or underwater structures coated with the antifouling coating films |
| US6828030B2 (en) | 2000-10-25 | 2004-12-07 | Chugoku Marine Paints, Ltd. | (poly)oxyalkylene block silyl ester copolymer, antifouling coating composition, antifouling coating formed from antifouling coating composition, antifouling method using antifouling coating composition and hull or underwater structure covered with antifouling coating |
| JP2004346317A (en) * | 2003-05-21 | 2004-12-09 | Atofina Chemicals Inc | Triarylsilyl(meth)acryloyl-containing polymer for marine coating material composition |
| US6916860B2 (en) | 2002-03-06 | 2005-07-12 | Chugoku Marine Paints, Ltd. | Antifouling coating composition, coating film therefrom, base material covered with the coating film and antifouling method |
| JP2007162031A (en) * | 1995-11-15 | 2007-06-28 | Chugoku Marine Paints Ltd | Antifouling coating composition, coating film formed from antifouling coating composition, antifouling method using antifouling coating composition and hull or underwater structure coated with coating film |
| JP2012117077A (en) * | 1995-11-15 | 2012-06-21 | Chugoku Marine Paints Ltd | Antifouling coating composition, coated film formed from the same, antifouling method using the same, and hull or underwater structure coated with the coated film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4021392A (en) * | 1974-04-03 | 1977-05-03 | The International Paint Company Limited | Marine paint |
| US4593055A (en) * | 1983-01-17 | 1986-06-03 | M&T Chemicals Inc. | Erodible ship-bottom paints for control of marine fouling |
| JPH0532433A (en) * | 1991-07-30 | 1993-02-09 | Central Glass Co Ltd | Functional membrane-containing glass coated with protecting coating film |
-
1986
- 1986-08-28 JP JP20251486A patent/JPS6357675A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4021392A (en) * | 1974-04-03 | 1977-05-03 | The International Paint Company Limited | Marine paint |
| US4593055A (en) * | 1983-01-17 | 1986-06-03 | M&T Chemicals Inc. | Erodible ship-bottom paints for control of marine fouling |
| JPH0532433A (en) * | 1991-07-30 | 1993-02-09 | Central Glass Co Ltd | Functional membrane-containing glass coated with protecting coating film |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01306479A (en) * | 1988-06-06 | 1989-12-11 | Chugoku Marine Paints Ltd | Non-toxic anti-foul coating composition |
| JPH07150076A (en) * | 1994-10-24 | 1995-06-13 | Chugoku Marine Paints Ltd | Antifouling coating material |
| JPH09194790A (en) * | 1995-11-15 | 1997-07-29 | Chugoku Marine Paints Ltd | Antifouling coating material composition, coating film formed from the same composition, antifouling method by using the same composition and ship body or underwater structure coated with the same coating film |
| JP2007162031A (en) * | 1995-11-15 | 2007-06-28 | Chugoku Marine Paints Ltd | Antifouling coating composition, coating film formed from antifouling coating composition, antifouling method using antifouling coating composition and hull or underwater structure coated with coating film |
| JP2012117077A (en) * | 1995-11-15 | 2012-06-21 | Chugoku Marine Paints Ltd | Antifouling coating composition, coated film formed from the same, antifouling method using the same, and hull or underwater structure coated with the coated film |
| US6458878B1 (en) | 1998-12-28 | 2002-10-01 | Chuogoku Marine Paints, Ltd. | Silyl (meth) acrylate copolymers, processes for preparing the same, antifouling paint compositions containing the silyl (meth) acrylate copolymers, antifouling coating films formed from the antifouling paint compositions, antifouling methods using the antifouling paint compositions, and hulls or underwater structures coated with the antifouling coating films |
| US6828030B2 (en) | 2000-10-25 | 2004-12-07 | Chugoku Marine Paints, Ltd. | (poly)oxyalkylene block silyl ester copolymer, antifouling coating composition, antifouling coating formed from antifouling coating composition, antifouling method using antifouling coating composition and hull or underwater structure covered with antifouling coating |
| US6916860B2 (en) | 2002-03-06 | 2005-07-12 | Chugoku Marine Paints, Ltd. | Antifouling coating composition, coating film therefrom, base material covered with the coating film and antifouling method |
| JP2004346317A (en) * | 2003-05-21 | 2004-12-09 | Atofina Chemicals Inc | Triarylsilyl(meth)acryloyl-containing polymer for marine coating material composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0582865B2 (en) | 1993-11-22 |
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