JPH0119432B2 - - Google Patents
Info
- Publication number
- JPH0119432B2 JPH0119432B2 JP6465882A JP6465882A JPH0119432B2 JP H0119432 B2 JPH0119432 B2 JP H0119432B2 JP 6465882 A JP6465882 A JP 6465882A JP 6465882 A JP6465882 A JP 6465882A JP H0119432 B2 JPH0119432 B2 JP H0119432B2
- Authority
- JP
- Japan
- Prior art keywords
- antifouling
- ester
- parts
- resin
- antifouling paint
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 230000003373 anti-fouling effect Effects 0.000 claims description 36
- 239000003973 paint Substances 0.000 claims description 30
- 229920001577 copolymer Polymers 0.000 claims description 16
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 8
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 6
- 150000007519 polyprotic acids Polymers 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical group COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 claims description 2
- 125000005156 substituted alkylene group Chemical group 0.000 claims description 2
- -1 ester compound Chemical class 0.000 description 29
- 239000011347 resin Substances 0.000 description 23
- 229920005989 resin Polymers 0.000 description 23
- 239000011159 matrix material Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 13
- 239000002519 antifouling agent Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 11
- 239000013535 sea water Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000008096 xylene Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000010828 elution Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- YSEKNCXYRGKTBJ-UHFFFAOYSA-N dimethyl 2-hydroxybutanedioate Chemical compound COC(=O)CC(O)C(=O)OC YSEKNCXYRGKTBJ-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 5
- 125000005907 alkyl ester group Chemical group 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 150000003606 tin compounds Chemical class 0.000 description 3
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 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 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
- 239000005749 Copper compound Substances 0.000 description 2
- 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 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000007227 biological adhesion Effects 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000001880 copper compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- IEPRKVQEAMIZSS-AATRIKPKSA-N diethyl fumarate Chemical compound CCOC(=O)\C=C\C(=O)OCC IEPRKVQEAMIZSS-AATRIKPKSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000036314 physical performance Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000002966 varnish Substances 0.000 description 2
- NIDNOXCRFUCAKQ-UMRXKNAASA-N (1s,2r,3s,4r)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical group C1[C@H]2C=C[C@@H]1[C@H](C(=O)O)[C@@H]2C(O)=O NIDNOXCRFUCAKQ-UMRXKNAASA-N 0.000 description 1
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 description 1
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
- AYAUWVRAUCDBFR-ONEGZZNKSA-N (e)-4-oxo-4-propoxybut-2-enoic acid Chemical compound CCCOC(=O)\C=C\C(O)=O AYAUWVRAUCDBFR-ONEGZZNKSA-N 0.000 description 1
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-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
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- PSZAEHPBBUYICS-UHFFFAOYSA-N 2-methylidenepropanedioic acid Chemical compound OC(=O)C(=C)C(O)=O PSZAEHPBBUYICS-UHFFFAOYSA-N 0.000 description 1
- AHWAAQOJHMFNIV-UHFFFAOYSA-N 2-tert-butylperoxy-2-ethylhexanoic acid Chemical compound CCCCC(CC)(C(O)=O)OOC(C)(C)C AHWAAQOJHMFNIV-UHFFFAOYSA-N 0.000 description 1
- GQZXRLWUYONVCP-UHFFFAOYSA-N 3-[1-(dimethylamino)ethyl]phenol Chemical compound CN(C)C(C)C1=CC=CC(O)=C1 GQZXRLWUYONVCP-UHFFFAOYSA-N 0.000 description 1
- JDOZUYVDIAKODH-SNAWJCMRSA-N 4-o-ethyl 1-o-methyl (e)-but-2-enedioate Chemical compound CCOC(=O)\C=C\C(=O)OC JDOZUYVDIAKODH-SNAWJCMRSA-N 0.000 description 1
- JDOZUYVDIAKODH-PLNGDYQASA-N 4-o-ethyl 1-o-methyl (z)-but-2-enedioate Chemical compound CCOC(=O)\C=C/C(=O)OC JDOZUYVDIAKODH-PLNGDYQASA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000238586 Cirripedia Species 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 241000237503 Pectinidae Species 0.000 description 1
- 241000206607 Porphyra umbilicalis Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 241000251555 Tunicata Species 0.000 description 1
- 241000196251 Ulva arasakii Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229940091181 aconitic acid Drugs 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- NJYYHBHYDNPAJM-UHFFFAOYSA-N bis(2-methoxyethyl) 2-methylidenebutanedioate Chemical compound COCCOC(=O)CC(=C)C(=O)OCCOC NJYYHBHYDNPAJM-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- VYXGXXYXSAMWBM-ONEGZZNKSA-N dimethyl (e)-2-chlorobut-2-enedioate Chemical compound COC(=O)\C=C(\Cl)C(=O)OC VYXGXXYXSAMWBM-ONEGZZNKSA-N 0.000 description 1
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 1
- 229960004419 dimethyl fumarate Drugs 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-L fumarate(2-) Chemical class [O-]C(=O)\C=C\C([O-])=O VZCYOOQTPOCHFL-OWOJBTEDSA-L 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000020637 scallop Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical class CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical class CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 1
- SBXWFLISHPUINY-UHFFFAOYSA-N triphenyltin Chemical class C1=CC=CC=C1[Sn](C=1C=CC=CC=1)C1=CC=CC=C1 SBXWFLISHPUINY-UHFFFAOYSA-N 0.000 description 1
Description
本発明は塗膜が強靭でかつ適度な水可溶性樹脂
をビヒクルとする防汚塗料に関するものである。
橋りようなどの海中建設物、船舶、漁網にはフ
ジツボ、セルプラ、ホヤ、カキ、フサコケムシ、
アオサ、アオノリなどの海中生物が付着し短期間
で生長し、腐食など、各種の被害を与える。例え
ば船舶の場合海水との摩擦抵抗増大による燃料の
過剰使用、漁網の場合には網目が閉塞され潮通し
不良による漁類の発育低下など、付着生物による
被害は甚大なものがあり、長期間にわたり安定し
た防汚性能を有する防汚塗料の出現が望まれてい
る。
防汚塗料は周知のように、ビヒクルとして用い
る樹脂に防汚剤を分散させたものであり、この樹
脂の海水への溶解性の有無によつて、不溶解マト
リクス型と溶解マトリクス型とに分けられる。
不溶解マトリクス型は、塩化ビニル、塩化ゴム
スチレン−ブタジエンなどの水に全く溶解しない
樹脂にロジンなどの水溶性物質と防汚剤を配合し
たものが一般的である。この場合、防汚剤はロジ
ンと共に溶出するが、軸脂自体は残査層として残
るため経時的に樹脂残査層が厚くなり防汚剤の溶
出が困難となる。このため防汚期間は12〜16ケ月
と短いものである。
他方、溶解マトリクス型は防汚剤の溶出と共に
樹脂自体も溶解していく型のもので、樹脂残査層
がないため防汚剤の溶出が容易であり、防汚期間
も膜厚を厚くすることにより、２〜３年は可能で
ある。
溶解マトリクス型防汚塗料のビヒクルとして、
既に実用化されているものに、下記一般式
で表わされる有機スズエステル化合物の重合体を
ビヒクルとするものがある（特公昭40−21426号、
特公昭44−9579号、特公昭51−12049号）。該重合
体をビヒクルとする防汚塗料の塗膜を海水に浸漬
すると、海水中でスズエステル基が加水分解さ
れ、放出されたスズ化合物が防汚剤として働き、
又樹脂自体は水溶性に変り、このため徐々に溶解
して樹脂残査層を形成しないというものである。
これは樹脂の溶解性がエステル基の加水分解によ
つて始めて現れるものであり、溶解マトリクス型
防汚塗料の中でも加水分解型と称されているもの
である。この加水分解型の場合、エステル基が容
易に加水分解される必要があるが、その性質を有
するものとして実用化されているものは上記有機
スズエステル化合物の重合体のみである。しかし
この重合体については、微溶解性は優れているも
のの、その溶解が加水分解によるため海水のPHに
敏感で海域により溶出速度が異ること、またモノ
マーである前記一般式で示される化合物の合成が
難しく、また貯蔵安定性が悪いことなど実用上の
難点があつた。そこで加水分解型でない溶解マト
リクスを得る目的で、樹脂自体に微水溶性をもた
せようとする試みがある。例えば、特開昭55−
36230では防汚剤として用いる銅化合物、スズ化
合物と反応しやすいカルボキシル基や水酸基を有
しない、微水溶性のある樹脂として不飽和２塩基
酸の低級アルキルエステルを含む重合体が記され
ている。しかし不飽和２塩基酸のアルキルエステ
ルの重合体の水溶性に限界があり、このため樹脂
の水溶解性を単量体の組成変化で調節しうる溶解
速度の範囲も狭いことなどの欠点があつた。
本発明者らは鋭意研究の結果、溶解マトリクス
型の防汚塗料用のビヒクルとして、特定の３成分
からなる、上記欠点のない広範囲の溶解速度を持
つ共重合体を見出し、本発明に到達した。
すなわち、本発明は、重合可能なエチレン性不
飽和基をもつ多塩基酸の全エステルであり、エス
テル残基の少くとも１つが下記一般式(1)
−COO−（R1−Ｏ）−oＸ ………(1)
〔但しR1はアルキレン基又は置換アルキレン基
を示し、Ｘは低級アルキル基又はアリール基を、
ｎは１〜30の整数を示し、ｎが１より大きい時の
R1は互いに同じでも異つていてもよい。〕
である化合物(A)と、マレイン酸ジアルキルエステ
ルまたはフマル酸ジアルキルエステルと、酢酸ビ
ニルとの共重合体をビヒクルとして含むことを特
徴とする防汚塗料を提供するものである。
本発明で用いる化合物(A)の具体例としてはマレ
イン酸、フマル酸、イタコン酸、シトラコン酸、
メサコン酸、アコニツト酸、グルタコン酸、メチ
レンマロン酸、テトラハイドロフタル酸、３，６
−エンドメチレンテトラハイドロフタル酸などの
重合可能なエチレン性不飽和基をもつ多塩基酸の
２−メトキシエチルエステル、２−エトキシエチ
ルエステル、２−ブトキシエチルエステル、２−
フエノキシエチルエステル、メトキシジエチレン
グリコールエステル、エトキシジエチレングリコ
ールエステル、ブトキシジエチレングリコールエ
ステル、フエノキシジエチレングリコールエステ
ル、メトキシトリエチレングリコールエステル、
エトキシトリエチレングリコールエステル、ブト
キシトリエチレングリコールエステル、フエノキ
シトリエチレングリコールエステル、メトキシテ
トラエチレングリコールエステル、エトキシテト
ラエチレングリコールエステル、ブトキシテトラ
エチレングリコールエステル、フエノキシテトラ
エチレングリコールエステル、メトキシプロピレ
ングリコールエステル、エトキシプロピレングリ
コールエステル、ブトキシプロピレングリコール
エステル、フエノキシプロピレングリコールエス
テル、メトキシジプロピレングリコールエステ
ル、エトキシジプロピレングリコールエステル、
ブトキシジプロピレングリコールエステル、フエ
ノキシジプロピレングリコールエステルなどであ
り、これらのエステル基は多塩基酸のカルボキシ
ル基の全部であつてもよく、部分であつてもよ
い。又上記部分エステルの場合は残りのカルボキ
シル基もエステルであることが必要であり、メチ
ル、エチル、ブチル、イソプロピルなどの低級ア
ルキルエステルであることが望ましい。
これらのエステルの合成は、相当する多塩基酸
とアルコールの混合物を、ｐ−トルエンスルホン
酸などの触媒下、キシレンなどの溶媒中で加熱還
流させ共沸脱水させる通常の方法で容易に合成で
きるが、特にこの方法に限定するものでなく、他
の方法たとえば、エステル交換法、カルボキシル
基にアルキレンオキサイドを付加させた後末端ア
ルコールを封鎖する方法など必要に応じてとるこ
とができる。
本発明で用いるマレイン酸ジアルキルエステル
またはフマル酸ジアルキルエステルの例として
は、ジメチルマレート、ジエチルマレート、メチ
ルエチルマレート、ジプロピルマレート、ジメチ
ルフマレート、ジエチルフマレート、メチルエチ
ルフマレート、ジプロピルフマレートなどがあ
る。この他にクロロマレイン酸ジメチルのような
上記化合物のハロゲン置換体も使用できる。
本発明に用いる共重合体を得る場合、各単量体
の配合割合は化合物(A)１〜80モル％、マレイン酸
ジアルキルエステルまたはフマル酸ジアルキルエ
ステル１〜80モル％、酢酸ビニル１〜80モル％の
範囲である。化合物(A)の量が多すぎると共重合体
の水溶性が大きくなりすぎ、また他の２成分の量
が少なすぎると共重合体の塗膜としての強度が低
下するので、これらの釣合いから上記の範囲が好
ましい。
本発明に用いる共重合体は、ラジカル重合触媒
の存在下で溶液、乳化、懸濁、塊状などの重合方
法のほか、イオン重合、光重合などでも合成でき
るが、塗料用ワニスとして使用する場合は溶液重
合法または乳化重合法で得るのが簡便である。
本発明に用いる共重合体の分子量は、特に制限
はないが塗膜としての強度を保持できかつ塗装作
業性の良好さから、通常、重量平均分子量で1000
〜1000000、好ましくは1000〜200000である。
本発明において、このようにして得られた共重
合体は、単独でビヒクルとして使用するほかに、
従来公知の油性ワニス、塩化ビニル樹脂、塩化ゴ
ム、スチレン−ブタジエン樹脂、アクリル樹脂な
どの不溶解マトリクス型樹脂、有機スズ重合体、
二塩基性不飽和酸低級アルキルエステル重合体な
どの溶解マトリクス型樹脂との併用も可能であ
り、新たな溶解マトリクス型混合樹脂を得ること
も可能である。
本発明の防汚塗料に使用される防汚剤として
は、亜酸化銅、トリブチルスズ化合物、トリフエ
ニルスズ化合物、チウラム化合物を始め従来公知
の防汚剤はすべて使用することができる。そのほ
か顔料、添加剤等も従来公知のものが使用可能で
ある。また本発明の防汚塗料の塗料化も公知のい
ずれの方法を用いてもよい。
本発明に用いる共重合体が溶解マトリクス型防
汚塗料のピヒクルとなりうるのは、その溶解機構
が有機スズ共重合体のような加水分解型でなく樹
脂自体の微水溶性によるものであり、それが一般
式(1)で示されるエステル残基の存在によつて強調
されているため特に分子量に関係なく均一な溶解
性をもつことが本発明の特徴である。
また、その溶解速度は、分子量によつて変わる
ことはないが、特に化合物(A)の種類およびその配
合量、重合体中の単量体の配列のしかたによつて
変わる。それ故、ビヒクルの溶解速度を任意に調
節することが可能であり、このため本発明の防汚
塗料の防汚期間の調節は、膜厚の他に単量体の配
合割合によつても可能である。
本発明の防汚塗料は、貯蔵中ゲル化を起すこと
もなくきわめて安定であり、その塗膜は適度の強
度と海水溶解性をもつているので、３年以上もの
長期間優れた防汚性能を発揮する。
次に製造例、実施例によつて、本発明を具体的
に説明する。例中の部は重量部、粘度は25℃にお
ける測定値、分子量はGPC法による重量平均分
子量を表わす。
製造例 １
攪拌機付きのフラスコに、キシレン80部を仕込
み、窒素を吹き込みつつ加熱し還流させる。これ
に、ビス（２−メトキシエチル）マレート37.4
部、ジメチルマレート92.7部、酢酸ビニル69.2
部、ターシヤリーブチルパーオキシイソプロピル
カーボネート4.8部の混合液を3.0時間かけて滴下
し、さらに同じ還流状態で3.0時間攪拌を続けた。
次いで、キシレン80部、ターシヤリーブチルパー
オキシイソプロピルカーボネート1.2部の混合液
を加え、さらに１時間攪拌を続けた後、加熱を止
めキシレン40部を加え、冷却し溶液Ａを得た。得
られた溶液は透明で粘度が0.5ポイズ、樹脂の分
子量が6500の共重合体溶液であつた。
製造例 ２
攪拌器付きのフラスコに、酢酸ブチル80部を仕
込み、窒素を吹き込みつつ110℃に昇温し、これ
にビス（２−メトキシエチル）マレート65.8部、
ジエチルフマレート73.2部、酢酸ビニル61.0部、
ターシヤリーブチルパーオキシ（２−エチルヘキ
サノエート）4.8部の混合液を同温度で3.0時間か
けて滴下した。次いで同温度で3.0時間攪拌を続
けた後、酢酸ブチル80部、ターシヤリーブチルパ
ーオキシ（２−エチルヘキサノエート）1.2部の
混合液を加え同温度で1.0時間攪拌を続けた後、
加熱を止め、酢酸ブチル40.0部を加えて冷却し、
溶液Ｂを得た。得られた溶液は透明で、粘度が
1.5ポイズ、樹脂の分子量が12000の共重合体溶液
であつた。
製造例 ３
攪拌機付きのフラスコにキシレン40部、エチル
セロソルブ40部を仕込み、窒素を吹き込みながら
加熱し還流させる。これにマレイン酸のメトキシ
ジエチレングリコールのジエステルを48.3部、ジ
メチルマレート87.0部、酢酸ビニル64.9部、ター
シヤリ−ブチルパーオキシイソプロピルカーボネ
ート4.8部の混合液を3.0時間で滴下し、さらに同
じ還流状態で3.0時間攪拌を続けた。次いで、キ
シレン40部、エチルセロソルブ40部、ターシヤリ
ーブチルパーオキシイソプロピルカーボネート
1.2部の混合液を加え、さらに１時間攪拌を続け
た後、加熱を止めキシレン40部を加え、冷却し溶
液Ｃを得た。得られた溶液は、透明で粘度が1.2
ポイズ、樹脂の分子量が8000の共重合体溶液であ
つた。
製造例 ４
攪拌機付きのフラスコに、キシレン160部、ビ
ス（２−メトキシエチル）イタコネート66.2部、
ジメチルマレート98.5部、酢酸ビニル35.3部、過
酸化ベンゾイル2.0部を加え、窒素気流中90℃で、
6.0時間加熱攪拌し重合した。続いてキシレン40
部、ベンゾイルパーオキサイド0.1部の混合液を
加え100℃で１時間、さらに120℃に昇温して1.0
時間攪拌を続け重合を完結させた。得られた溶液
Ｄは、透明で粘度が2.0ポイズ、樹脂の分子量が
25000の共重合体溶液であつた。
実施例 １〜４
塗料化
製造例１〜４で得た共重合体溶液Ａ〜Ｄを用い
て第１表に示した塗料配合に従つて混練分散を行
い、実施例１〜４の防汚塗料の製造を行つた。他
に一般市販の溶解マトリクス型防汚塗料の例とし
て比較例１、不溶解マトリクス型の例として比較
例２を製造した。
浸漬板の作成
実施例１〜４、比較例１、２の防汚塗料を、サ
ンドプラスト鋼板にあよかじめ防錆塗料を塗布し
てある塗板に、乾燥膜厚として150μとなるごと
く刷毛塗りを２回行い、防汚性能試験板を作成し
た。同様に一定の10cm×20cmの面積にのみ防汚塗
料を塗布した防汚剤の溶出速度測定用試験板を作
成した。同様に４cm×２cmの面積に防汚塗料を塗
布した11cm×157cmのアルミニウム板を円形のド
ラムに巻き付けた消耗膜厚測定用のロータリード
ラムを作成した。
浸漬試験
兵庫県州本市由良湾において、防汚性能試験板
および溶出速度測定用試験板については36ケ月の
海中浸漬を、消耗膜厚測定用のロータリードラム
については２ケ月の海中回転を行つた。
浸漬試験結果
浸漬試験による防汚性能試験結果を第２表に、
銅の溶出速度測定結果を第３表に、錫の溶出速度
測定結果を第４表に、消耗膜厚測定結果を第５表
に示す。
一般に海水中での防汚剤それぞれ単独の最低防
汚限界濃度は、銅化合物では銅として10γ／cm2／
日、錫化合物では錫として1γ／cm2／日であると
されている。
The present invention relates to an antifouling paint that has a tough coating film and uses a suitable water-soluble resin as a vehicle. Undersea structures such as bridges, ships, and fishing nets contain barnacles, serpura, sea squirts, oysters, scallops,
Sea creatures such as sea lettuce and green laver attach to the surface and grow in a short period of time, causing various damage such as corrosion. For example, in the case of ships, the excessive use of fuel due to increased frictional resistance with seawater, and in the case of fishing nets, the growth of fish due to blocked fishing nets and poor water passage. It is desired that an antifouling paint with stable antifouling performance be developed. As is well known, antifouling paints are made by dispersing antifouling agents in a resin used as a vehicle, and are divided into insoluble matrix types and soluble matrix types depending on the solubility of this resin in seawater. It will be done. The insoluble matrix type is generally made by blending a water-soluble substance such as rosin and an antifouling agent with a resin that does not dissolve in water at all, such as vinyl chloride, chlorinated rubber, styrene-butadiene, etc. In this case, the antifouling agent is eluted together with the rosin, but since the stem fat itself remains as a residual layer, the resin residual layer becomes thicker over time, making it difficult to elute the antifouling agent. Therefore, the antifouling period is short, 12 to 16 months. On the other hand, the dissolving matrix type is a type in which the resin itself dissolves as the antifouling agent elutes, and since there is no residual resin layer, the antifouling agent can be easily eluted, and the film thickness can be increased even during the antifouling period. Depending on the situation, it is possible for 2 to 3 years. As a vehicle for dissolving matrix type antifouling paint,
The following general formula is already in practical use: There is a vehicle that uses a polymer of an organotin ester compound represented by
Special Publication No. 44-9579, Special Publication No. 51-12049). When a coating film of an antifouling paint containing this polymer as a vehicle is immersed in seawater, the tin ester group is hydrolyzed in the seawater, and the released tin compound acts as an antifouling agent.
In addition, the resin itself becomes water-soluble, so it gradually dissolves and does not form a resin residual layer.
The solubility of the resin first appears through hydrolysis of the ester group, and this type is called a hydrolyzable type among dissolved matrix type antifouling paints. In the case of this hydrolyzable type, the ester group needs to be easily hydrolyzed, but the only thing that has been put into practical use as having this property is the polymer of the above-mentioned organotin ester compound. However, although this polymer has excellent slight solubility, its dissolution is due to hydrolysis, so it is sensitive to the pH of seawater and the elution rate varies depending on the sea area. There were practical difficulties, such as difficult synthesis and poor storage stability. Therefore, in order to obtain a non-hydrolyzable dissolution matrix, attempts have been made to make the resin itself slightly water-soluble. For example, JP-A-55-
36230 describes a polymer containing a lower alkyl ester of an unsaturated dibasic acid as a slightly water-soluble resin that does not have carboxyl or hydroxyl groups that easily react with copper compounds and tin compounds used as antifouling agents. However, the water solubility of polymers of alkyl esters of unsaturated dibasic acids is limited, and therefore the range of dissolution rates in which the water solubility of the resin can be adjusted by changing the composition of the monomers is also narrow. Ta. As a result of extensive research, the present inventors have discovered a copolymer consisting of three specific components that has a wide range of dissolution rates without the above-mentioned drawbacks and has arrived at the present invention as a vehicle for dissolution matrix type antifouling paints. . That is, the present invention is a total ester of a polybasic acid having a polymerizable ethylenically unsaturated group, and at least one of the ester residues has the following general formula (1) -COO-(R 1 -O)- o X......(1) [However, R 1 represents an alkylene group or a substituted alkylene group, X represents a lower alkyl group or an aryl group,
n indicates an integer from 1 to 30, and when n is greater than 1
R 1 may be the same or different. ] The present invention provides an antifouling paint characterized by containing a copolymer of compound (A), maleic acid dialkyl ester or fumaric acid dialkyl ester, and vinyl acetate as a vehicle. Specific examples of the compound (A) used in the present invention include maleic acid, fumaric acid, itaconic acid, citraconic acid,
Mesaconic acid, aconitic acid, glutaconic acid, methylenemalonic acid, tetrahydrophthalic acid, 3,6
-2-methoxyethyl ester, 2-ethoxyethyl ester, 2-butoxyethyl ester, 2- of polybasic acids having polymerizable ethylenically unsaturated groups such as endomethylenetetrahydrophthalic acid,
Phenoxyethyl ester, methoxydiethylene glycol ester, ethoxydiethylene glycol ester, butoxydiethylene glycol ester, phenoxydiethylene glycol ester, methoxytriethylene glycol ester,
Ethoxytriethylene glycol ester, butoxytriethylene glycol ester, phenoxytriethylene glycol ester, methoxytetraethylene glycol ester, ethoxytetraethylene glycol ester, butoxytetraethylene glycol ester, phenoxytetraethylene glycol ester, methoxypropylene glycol ester, Ethoxypropylene glycol ester, butoxypropylene glycol ester, phenoxypropylene glycol ester, methoxydipropylene glycol ester, ethoxydipropylene glycol ester,
These include butoxydipropylene glycol ester, phenoxydipropylene glycol ester, etc., and these ester groups may be all or a portion of the carboxyl group of the polybasic acid. Further, in the case of the above partial ester, the remaining carboxyl group must also be an ester, and is preferably a lower alkyl ester such as methyl, ethyl, butyl, or isopropyl. These esters can be easily synthesized by the usual method of heating and refluxing a mixture of the corresponding polybasic acid and alcohol in a solvent such as xylene under a catalyst such as p-toluenesulfonic acid for azeotropic dehydration. However, the present invention is not particularly limited to this method, and other methods such as transesterification, adding an alkylene oxide to a carboxyl group, and then capping the terminal alcohol can be used as necessary. Examples of dialkyl maleates or dialkyl fumarates used in the present invention include dimethyl maleate, diethyl maleate, methyl ethyl maleate, dipropyl maleate, dimethyl fumarate, diethyl fumarate, methyl ethyl fumarate, dimethyl Examples include propyl fumarate. In addition, halogen-substituted products of the above compounds such as dimethyl chloromaleate can also be used. When obtaining the copolymer used in the present invention, the blending ratio of each monomer is 1 to 80 mol% of compound (A), 1 to 80 mol% of dialkyl maleate or dialkyl fumarate, and 1 to 80 mol of vinyl acetate. % range. If the amount of compound (A) is too large, the water solubility of the copolymer will be too high, and if the amount of the other two components is too small, the strength of the copolymer as a coating will decrease, so from the balance of these The above ranges are preferred. The copolymer used in the present invention can be synthesized by polymerization methods such as solution, emulsification, suspension, and bulk in the presence of a radical polymerization catalyst, as well as ionic polymerization, photopolymerization, etc.; however, when used as a paint varnish, It is convenient to obtain it by solution polymerization method or emulsion polymerization method. The molecular weight of the copolymer used in the present invention is not particularly limited, but it is usually 1000 in weight average molecular weight because it can maintain strength as a coating film and has good coating workability.
~1000000, preferably 1000-200000. In the present invention, the copolymer thus obtained is used not only as a vehicle alone but also as a vehicle.
Conventionally known oil-based varnishes, vinyl chloride resins, chlorinated rubber, styrene-butadiene resins, insoluble matrix resins such as acrylic resins, organic tin polymers,
It is also possible to use it in combination with a dissolved matrix type resin such as a dibasic unsaturated acid lower alkyl ester polymer, and it is also possible to obtain a new dissolved matrix type mixed resin. As the antifouling agent used in the antifouling paint of the present invention, all conventionally known antifouling agents including cuprous oxide, tributyltin compounds, triphenyltin compounds, and thiuram compounds can be used. In addition, conventionally known pigments, additives, etc. can be used. Moreover, any known method may be used to form the antifouling paint of the present invention into a paint. The reason why the copolymer used in the present invention can act as a vehicle for dissolved matrix type antifouling paints is that its dissolution mechanism is not hydrolyzable like that of organotin copolymers, but is due to the slight water solubility of the resin itself. is emphasized by the presence of the ester residue represented by the general formula (1), and therefore, a feature of the present invention is that it has uniform solubility regardless of the molecular weight. Further, the dissolution rate does not change depending on the molecular weight, but it changes depending on the type and amount of compound (A), and the arrangement of the monomers in the polymer. Therefore, it is possible to arbitrarily adjust the dissolution rate of the vehicle, and therefore the antifouling period of the antifouling paint of the present invention can be adjusted not only by the film thickness but also by the blending ratio of monomers. It is. The antifouling paint of the present invention is extremely stable without gelation during storage, and its coating film has appropriate strength and seawater solubility, so it has excellent antifouling performance for a long period of more than three years. demonstrate. Next, the present invention will be specifically explained using manufacturing examples and examples. In the examples, parts are parts by weight, viscosity is a value measured at 25°C, and molecular weight is a weight average molecular weight determined by GPC method. Production Example 1 80 parts of xylene is placed in a flask equipped with a stirrer, and heated to reflux while blowing nitrogen. To this, bis(2-methoxyethyl)malate 37.4
parts, dimethyl malate 92.7 parts, vinyl acetate 69.2 parts
A mixed solution of 4.8 parts of tert-butyl peroxyisopropyl carbonate was added dropwise over 3.0 hours, and stirring was continued for an additional 3.0 hours under the same reflux condition.
Next, a mixed solution of 80 parts of xylene and 1.2 parts of tert-butylperoxyisopropyl carbonate was added, and stirring was continued for an additional hour. After that, heating was stopped, 40 parts of xylene was added, and solution A was obtained by cooling. The resulting solution was a transparent copolymer solution with a viscosity of 0.5 poise and a resin molecular weight of 6,500. Production Example 2 80 parts of butyl acetate was placed in a flask equipped with a stirrer, and the temperature was raised to 110°C while blowing nitrogen. To this was added 65.8 parts of bis(2-methoxyethyl) malate,
73.2 parts of diethyl fumarate, 61.0 parts of vinyl acetate,
A mixed solution of 4.8 parts of tert-butylperoxy(2-ethylhexanoate) was added dropwise at the same temperature over 3.0 hours. Next, stirring was continued at the same temperature for 3.0 hours, and then a mixture of 80 parts of butyl acetate and 1.2 parts of tert-butyl peroxy (2-ethylhexanoate) was added, and stirring was continued at the same temperature for 1.0 hours.
Stop heating, add 40.0 parts of butyl acetate and cool.
Solution B was obtained. The resulting solution is clear and has a viscosity of
It was a copolymer solution with a molecular weight of 1.5 poise and a resin of 12,000. Production Example 3 40 parts of xylene and 40 parts of ethyl cellosolve are placed in a flask equipped with a stirrer, and heated to reflux while blowing nitrogen. A mixture of 48.3 parts of methoxydiethylene glycol diester of maleic acid, 87.0 parts of dimethyl malate, 64.9 parts of vinyl acetate, and 4.8 parts of tertiary-butylperoxyisopropyl carbonate was added dropwise to this over 3.0 hours, and the mixture was further kept under the same reflux condition for 3.0 hours. Continued stirring. Next, 40 parts of xylene, 40 parts of ethyl cellosolve, tertiary butyl peroxyisopropyl carbonate
After adding 1.2 parts of the liquid mixture and continuing stirring for an additional hour, heating was stopped, 40 parts of xylene was added, and solution C was obtained by cooling. The resulting solution is clear and has a viscosity of 1.2
Poise was a copolymer solution with a resin having a molecular weight of 8,000. Production Example 4 In a flask equipped with a stirrer, 160 parts of xylene, 66.2 parts of bis(2-methoxyethyl)itaconate,
Add 98.5 parts of dimethyl malate, 35.3 parts of vinyl acetate, and 2.0 parts of benzoyl peroxide, and at 90°C in a nitrogen stream,
The mixture was heated and stirred for 6.0 hours to polymerize. followed by xylene 40
Add a mixture of 1 part and 0.1 part of benzoyl peroxide at 100°C for 1 hour, and then raise the temperature to 120°C to 1.0 parts.
Stirring was continued for hours to complete polymerization. The resulting solution D is transparent, has a viscosity of 2.0 poise, and has a resin molecular weight of
25,000 copolymer solution. Examples 1 to 4 Paints The copolymer solutions A to D obtained in Production Examples 1 to 4 were kneaded and dispersed according to the paint formulations shown in Table 1 to produce the antifouling paints of Examples 1 to 4. was manufactured. In addition, Comparative Example 1 was produced as an example of a generally commercially available soluble matrix type antifouling paint, and Comparative Example 2 was produced as an example of an insoluble matrix type. Preparation of immersed plate The antifouling paints of Examples 1 to 4 and Comparative Examples 1 and 2 were applied with a brush to a coated plate that had been coated with rust preventive paint on a sandplast steel plate to a dry film thickness of 150μ. This was carried out twice to create an antifouling performance test plate. Similarly, a test plate for measuring the elution rate of the antifouling agent was prepared by applying the antifouling paint only to a fixed area of 10 cm x 20 cm. Similarly, a rotary drum for measuring the wear film thickness was prepared by wrapping an 11 cm x 157 cm aluminum plate coated with antifouling paint over a 4 cm x 2 cm area around a circular drum. Immersion test In Yura Bay, Shumoto City, Hyogo Prefecture, the antifouling performance test plate and the elution rate measurement test plate were immersed in the sea for 36 months, and the rotary drum for measuring the wear film thickness was rotated in the sea for 2 months. . Immersion test results Table 2 shows the antifouling performance test results from the immersion test.
The results of measuring the copper elution rate are shown in Table 3, the results of measuring the tin elution rate are shown in Table 4, and the results of measuring the consumed film thickness are shown in Table 5. In general, the minimum antifouling limit concentration of each antifouling agent in seawater is 10γ/cm 2 / as copper for copper compounds.
In tin compounds, the amount of tin is said to be 1γ/cm 2 /day.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
注 ＊印は生物付着等により測定不能
のため０と表示する。
[Table] Note: * indicates 0 because measurement is impossible due to biofouling, etc.
【表】
注 ＊印は生物付着により測定不能の
ため０とする。
[Table] Note: *marks are 0 because measurement is impossible due to biofouling.
【表】
第２表の防汚性能試験については、実施例の全
てと公知の溶解マトリクス型である比較例１は、
36ケ月経過後においても生物の付着は０％である
が、不溶解マトリクスである比較例２において
は、12ケ月以後著しい生物の付着がみられる。
第３表、第４表の銅、錫の溶出速度試験につい
ては、実施例は、比較例１と同様、36ケ月経過後
も最低防汚限界以上の溶出速度をもつていること
を示している。
また第５表の消耗膜厚測定結果においては、実
施例の全ては、有機錫重合体を用いた比較例１と
同様、徐々に膜厚の減つていくのがみられるが、
比較例２では膜厚の消耗はみられない。
塗膜の物理性能試験
実施例１〜４、比較例１、２の防汚塗料を用
い、塗膜の物登性能の比較を行つた。試験結果を
第６表に示す。[Table] Regarding the antifouling performance test in Table 2, all of the examples and Comparative Example 1, which is a known dissolution matrix type,
Even after 36 months, the amount of biological adhesion is 0%, but in Comparative Example 2, which is an insoluble matrix, significant biological adhesion is observed after 12 months. Regarding the elution rate tests for copper and tin in Tables 3 and 4, the example shows that, like Comparative Example 1, the elution rate is higher than the minimum antifouling limit even after 36 months. . Furthermore, in the measurement results of the ablated film thickness shown in Table 5, it can be seen that in all of the examples, the film thickness gradually decreases, similar to Comparative Example 1 using an organic tin polymer.
In Comparative Example 2, no loss of film thickness was observed. Physical Performance Test of Paint Film The antifouling paints of Examples 1 to 4 and Comparative Examples 1 and 2 were used to compare the physical performance of the paint film. The test results are shown in Table 6.
【表】
実施例においては、耐衝撃性、耐屈曲性の両試
験とも、比較例１と同様いづれも合格するが、比
較例２では、耐屈曲性のみ合格し、耐衝撃性は不
合格となつた。
以上の塗膜性能試験結果、海水浸漬試験結果、
消耗膜厚試験結果から認められるように、本発明
の防汚塗料から得られた塗膜は、強度があり、し
かも適度な海水溶解性があり、非常に優れた長期
防汚性能をもつものであることが明らかである。
比較例１は防汚性能および塗膜の性能も優れて
いるが、有機錫重合体を用いているので、前述の
ように貯蔵安定性が悪く、溶出速度が海水のPHに
より敏感に変るなど実用上の難点が多い。[Table] In the example, both the impact resistance and bending resistance tests were passed, as in Comparative Example 1, but in Comparative Example 2, only the bending resistance was passed, and the impact resistance was failed. Summer. The above coating performance test results, seawater immersion test results,
As confirmed by the results of the abrasion film thickness test, the coating film obtained from the antifouling paint of the present invention is strong, has appropriate seawater solubility, and has excellent long-term antifouling performance. One thing is clear. Comparative Example 1 has excellent antifouling performance and coating performance, but since it uses an organic tin polymer, it has poor storage stability as mentioned above, and the elution rate changes sensitively depending on the pH of seawater, making it difficult to put into practical use. There are many problems with the above.
Claims (1)
酸の全エステルであり、エステル残基の少くとも
１つが下記一般式(1) −COO−（R1−Ｏ）−oＸ ………(1) 〔但しR1はアルキレン基又は置換アルキレン基
を示し、Ｘは低級アルキル基又はアリール基を、
ｎは１〜30の整数を示し、ｎが１より大きい時の
R1は互いに同じでも異つていてもよい。〕 である化合物(A)と、マレイン酸ジアルキルエステ
ルまたはフマル酸ジアルキルエステルと、酢酸ビ
ニルとの共重合体をビヒクルとして含むことを特
徴とする防汚塗料。 ２ 化合物(A)が、一般式(1)において、R1＝CH2
−CH2−であり、ｎ＝１、Ｘ＝CH3で示される残
基をもつビス−２−メトキシエチルマレート又は
ビス−２−メトキシエチルフマレートである特許
請求の範囲第１項記載の防汚塗料。 ３ マレイン酸ジアルキルエステルがマレイン酸
ジメチルである特許請求の範囲第１項または第２
項記載の防汚塗料。[Scope of Claims] 1 All esters of polybasic acids having a polymerizable ethylenically unsaturated group, in which at least one ester residue has the following general formula (1) -COO-(R 1 -O)- o X......(1) [However, R 1 represents an alkylene group or a substituted alkylene group,
n indicates an integer from 1 to 30, and when n is greater than 1
R 1 may be the same or different. ] An antifouling paint characterized by containing a copolymer of the compound (A), a dialkyl maleate or a dialkyl fumarate, and vinyl acetate as a vehicle. 2 Compound (A) is represented by the general formula (1), where R 1 =CH 2
-CH2- , and is bis-2-methoxyethyl maleate or bis-2-methoxyethyl fumarate having a residue represented by n=1 and X= CH3 . Antifouling paint. 3. Claim 1 or 2, wherein the maleic acid dialkyl ester is dimethyl maleate.
Antifouling paint as described in section.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6465882A JPS58183761A (en) | 1982-04-20 | 1982-04-20 | Antistaining coating material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6465882A JPS58183761A (en) | 1982-04-20 | 1982-04-20 | Antistaining coating material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58183761A JPS58183761A (en) | 1983-10-27 |
| JPH0119432B2 true JPH0119432B2 (en) | 1989-04-11 |
Family
ID=13264534
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6465882A Granted JPS58183761A (en) | 1982-04-20 | 1982-04-20 | Antistaining coating material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58183761A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6092367A (en) * | 1983-10-26 | 1985-05-23 | Nippon Paint Co Ltd | Self-polishing paint |
| JPS6149778A (en) * | 1984-08-20 | 1986-03-11 | Hitachi Zosen Corp | Automatic welding method |
| JPS6186445U (en) * | 1984-11-14 | 1986-06-06 | ||
| CN109054608B (en) * | 2018-06-15 | 2021-03-19 | 苏州益可泰电子材料有限公司 | Metal material and preparation method thereof |
| CN109054635B (en) * | 2018-06-15 | 2021-03-19 | 苏州益可泰电子材料有限公司 | Polymer material and preparation method thereof |
-
1982
- 1982-04-20 JP JP6465882A patent/JPS58183761A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58183761A (en) | 1983-10-27 |
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