JP5122767B2 - Water-based antifouling paint composition - Google Patents
Water-based antifouling paint composition Download PDFInfo
- Publication number
- JP5122767B2 JP5122767B2 JP2006172812A JP2006172812A JP5122767B2 JP 5122767 B2 JP5122767 B2 JP 5122767B2 JP 2006172812 A JP2006172812 A JP 2006172812A JP 2006172812 A JP2006172812 A JP 2006172812A JP 5122767 B2 JP5122767 B2 JP 5122767B2
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- JP
- Japan
- Prior art keywords
- water
- weight
- parts
- group
- based antifouling
- 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.)
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- 230000003373 anti-fouling effect Effects 0.000 title claims description 127
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 109
- 239000003973 paint Substances 0.000 title claims description 89
- 239000000203 mixture Substances 0.000 title claims description 51
- 239000000839 emulsion Substances 0.000 claims description 110
- 239000011230 binding agent Substances 0.000 claims description 46
- -1 1,1,2-trifluoro-2-trifluoromethoxyethoxy group Chemical group 0.000 claims description 45
- 229920005989 resin Polymers 0.000 claims description 43
- 239000011347 resin Substances 0.000 claims description 43
- 239000007787 solid Substances 0.000 claims description 40
- 239000008199 coating composition Substances 0.000 claims description 36
- 239000005871 repellent Substances 0.000 claims description 27
- 230000002940 repellent Effects 0.000 claims description 27
- 229920001296 polysiloxane Polymers 0.000 claims description 26
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 20
- 239000003960 organic solvent Substances 0.000 claims description 17
- 239000002270 dispersing agent Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000004925 Acrylic resin Substances 0.000 claims description 9
- 229920000178 Acrylic resin Polymers 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 9
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims description 9
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 9
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229940126214 compound 3 Drugs 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical group CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 239000004480 active ingredient Substances 0.000 claims description 5
- YBBJKCMMCRQZMA-UHFFFAOYSA-N pyrithione Chemical compound ON1C=CC=CC1=S YBBJKCMMCRQZMA-UHFFFAOYSA-N 0.000 claims description 5
- 150000003568 thioethers Chemical class 0.000 claims description 4
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 229920000180 alkyd Polymers 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 239000012736 aqueous medium Substances 0.000 claims description 3
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 3
- 229940125904 compound 1 Drugs 0.000 claims description 3
- 229940125782 compound 2 Drugs 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 3
- 229940035429 isobutyl alcohol Drugs 0.000 claims description 3
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 3
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 3
- 229940011051 isopropyl acetate Drugs 0.000 claims description 3
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 3
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920001225 polyester resin Polymers 0.000 claims description 3
- 239000004645 polyester resin Substances 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 229920006174 synthetic rubber latex Polymers 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 125000000962 organic group Chemical group 0.000 claims description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 2
- 229960004592 isopropanol Drugs 0.000 claims 1
- 239000011248 coating agent Substances 0.000 description 28
- 238000000576 coating method Methods 0.000 description 28
- 238000003860 storage Methods 0.000 description 19
- 238000012360 testing method Methods 0.000 description 17
- 238000001035 drying Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000013535 sea water Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 5
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 5
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 5
- 229940112669 cuprous oxide Drugs 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- RFGCEKMQDQHCQP-UHFFFAOYSA-J CC(C(N(C([S-])=S)C(N)=S)C)N(C([S-])=S)C(N)=S.CC(C(N(C([S-])=S)C(N)=S)C)N(C([S-])=S)C(N)=S.[Zn+2].[Zn+2] Chemical compound CC(C(N(C([S-])=S)C(N)=S)C)N(C([S-])=S)C(N)=S.CC(C(N(C([S-])=S)C(N)=S)C)N(C([S-])=S)C(N)=S.[Zn+2].[Zn+2] RFGCEKMQDQHCQP-UHFFFAOYSA-J 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 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 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 239000002519 antifouling agent Substances 0.000 description 3
- 238000009360 aquaculture Methods 0.000 description 3
- 244000144974 aquaculture Species 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 229920001083 polybutene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- JMZRZEXRYJUHEB-UHFFFAOYSA-N 2-carbamothioylsulfanylethyl carbamodithioate;zinc Chemical compound [Zn].NC(=S)SCCSC(N)=S JMZRZEXRYJUHEB-UHFFFAOYSA-N 0.000 description 2
- 241000206761 Bacillariophyta Species 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- NCEXYHBECQHGNR-UHFFFAOYSA-N chembl421 Chemical compound C1=C(O)C(C(=O)O)=CC(N=NC=2C=CC(=CC=2)S(=O)(=O)NC=2N=CC=CC=2)=C1 NCEXYHBECQHGNR-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
- WJSXSXUHWBSPEP-UHFFFAOYSA-N pyridine;triphenylborane Chemical compound C1=CC=NC=C1.C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 WJSXSXUHWBSPEP-UHFFFAOYSA-N 0.000 description 2
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- 238000013112 stability test Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000010257 thawing Methods 0.000 description 2
- NJYFRQQXXXRJHK-UHFFFAOYSA-N (4-aminophenyl) thiocyanate Chemical compound NC1=CC=C(SC#N)C=C1 NJYFRQQXXXRJHK-UHFFFAOYSA-N 0.000 description 1
- WBYWKMUGWXSFIH-UHFFFAOYSA-N 1-(decyltetrasulfanyl)decane Chemical compound CCCCCCCCCCSSSSCCCCCCCCCC WBYWKMUGWXSFIH-UHFFFAOYSA-N 0.000 description 1
- DWXUFQGAQNIMSO-UHFFFAOYSA-N 1-(dodecyltetrasulfanyl)dodecane Chemical compound CCCCCCCCCCCCSSSSCCCCCCCCCCCC DWXUFQGAQNIMSO-UHFFFAOYSA-N 0.000 description 1
- HEGKYDWLIATKCZ-UHFFFAOYSA-N 1-(nonylpentasulfanyl)nonane Chemical compound CCCCCCCCCSSSSSCCCCCCCCC HEGKYDWLIATKCZ-UHFFFAOYSA-N 0.000 description 1
- SYPMTHVZNBWTIK-UHFFFAOYSA-N 1-(nonyltetrasulfanyl)nonane Chemical compound CCCCCCCCCSSSSCCCCCCCCC SYPMTHVZNBWTIK-UHFFFAOYSA-N 0.000 description 1
- PBCMRNUMIAQRBZ-UHFFFAOYSA-N 1-(octadecyltetrasulfanyl)octadecane Chemical compound CCCCCCCCCCCCCCCCCCSSSSCCCCCCCCCCCCCCCCCC PBCMRNUMIAQRBZ-UHFFFAOYSA-N 0.000 description 1
- QAHRXZPUWCQRAC-UHFFFAOYSA-N 1-(octylpentasulfanyl)octane Chemical compound CCCCCCCCSSSSSCCCCCCCC QAHRXZPUWCQRAC-UHFFFAOYSA-N 0.000 description 1
- VAKWIIMMZSTGAI-UHFFFAOYSA-N 1-(octyltetrasulfanyl)octane Chemical compound CCCCCCCCSSSSCCCCCCCC VAKWIIMMZSTGAI-UHFFFAOYSA-N 0.000 description 1
- AYLVHFIBUXKEED-UHFFFAOYSA-N 1-(pentylpentasulfanyl)pentane Chemical compound CCCCCSSSSSCCCCC AYLVHFIBUXKEED-UHFFFAOYSA-N 0.000 description 1
- BEUFFHMNIMJUHH-UHFFFAOYSA-N 1-(pentyltetrasulfanyl)pentane Chemical compound CCCCCSSSSCCCCC BEUFFHMNIMJUHH-UHFFFAOYSA-N 0.000 description 1
- VIZHWCWXKJJNRU-UHFFFAOYSA-N 2,2,4-trimethyl-4-(2,4,4-trimethylpentan-2-ylpentasulfanyl)pentane Chemical compound CC(C)(C)CC(C)(C)SSSSSC(C)(C)CC(C)(C)C VIZHWCWXKJJNRU-UHFFFAOYSA-N 0.000 description 1
- YAUCKEPYKXHCFF-UHFFFAOYSA-N 2-carbamothioylsulfanylethyl carbamodithioate;manganese Chemical compound [Mn].NC(=S)SCCSC(N)=S YAUCKEPYKXHCFF-UHFFFAOYSA-N 0.000 description 1
- ZNEZESLWGHMTHL-UHFFFAOYSA-N 2-methyl-2-(2-methyloctan-2-ylpentasulfanyl)octane Chemical compound CCCCCCC(C)(C)SSSSSC(C)(C)CCCCCC ZNEZESLWGHMTHL-UHFFFAOYSA-N 0.000 description 1
- ORINIFVNZFZTBF-UHFFFAOYSA-N 3,4-dichloro-1-(2,6-diethylphenyl)pyrrole-2,5-dione Chemical compound CCC1=CC=CC(CC)=C1N1C(=O)C(Cl)=C(Cl)C1=O ORINIFVNZFZTBF-UHFFFAOYSA-N 0.000 description 1
- NHRFTZYCKHERKF-UHFFFAOYSA-N 3,4-dichloro-1-(2-ethyl-6-methylphenyl)pyrrole-2,5-dione Chemical compound CCC1=CC=CC(C)=C1N1C(=O)C(Cl)=C(Cl)C1=O NHRFTZYCKHERKF-UHFFFAOYSA-N 0.000 description 1
- PORQOHRXAJJKGK-UHFFFAOYSA-N 4,5-dichloro-2-n-octyl-3(2H)-isothiazolone Chemical compound CCCCCCCCN1SC(Cl)=C(Cl)C1=O PORQOHRXAJJKGK-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000700108 Ctenophora <comb jellyfish phylum> Species 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
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- 229910000831 Steel Inorganic materials 0.000 description 1
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- CRQQGFGUEAVUIL-UHFFFAOYSA-N chlorothalonil Chemical compound ClC1=C(Cl)C(C#N)=C(Cl)C(C#N)=C1Cl CRQQGFGUEAVUIL-UHFFFAOYSA-N 0.000 description 1
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- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
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- 125000001400 nonyl 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])[H] 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
- 125000000913 palmityl 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])[H] 0.000 description 1
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- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical compound SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 description 1
- FGVVTMRZYROCTH-UHFFFAOYSA-N pyridine-2-thiol N-oxide Chemical compound [O-][N+]1=CC=CC=C1S FGVVTMRZYROCTH-UHFFFAOYSA-N 0.000 description 1
- 229960002026 pyrithione Drugs 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000007592 spray painting technique Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 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
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229940043810 zinc pyrithione Drugs 0.000 description 1
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical compound [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 description 1
- BUOWQAOYRYWTTQ-UHFFFAOYSA-L zinc;n,n-dimethylcarbamate Chemical compound [Zn+2].CN(C)C([O-])=O.CN(C)C([O-])=O BUOWQAOYRYWTTQ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Farming Of Fish And Shellfish (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Paints Or Removers (AREA)
Description
本発明は、水系防汚塗料組成物、該水系防汚塗料組成物を塗布されてなる漁網等の漁網具および該水系防汚塗料組成物を用いる漁網具の防汚方法に関する。さらに詳しくは、本発明は、従来の有機溶剤型防汚塗料と比較して防汚性に優れるうえ、揮発性の高い有機溶剤を多く含まないため環境や作業者に与える影響が極めて少なく、凍結融解安定性など貯蔵安定性に優れ、また低温における造膜性や付着性能にも優れ、長期に安定した防汚性能を発揮する水系防汚塗料組成物及び該水系防汚塗料組成物を塗布させてなる漁網具に関する。
The present invention relates to a water-based antifouling paint composition, a fishing net tool such as a fishing net coated with the water-based antifouling paint composition, and a method for antifouling a fishing net tool using the water-based antifouling paint composition. More specifically, the present invention is superior in antifouling properties as compared with conventional organic solvent-type antifouling paints, and does not contain a large amount of highly volatile organic solvents, so it has very little impact on the environment and workers, and is freezing. A water-based antifouling paint composition that is excellent in storage stability such as melting stability, is excellent in film-forming property and adhesion performance at low temperatures, and exhibits stable antifouling performance over a long period of time, and the water-based antifouling paint composition is applied. It relates to fishing net equipment .
船舶や海洋構造物、養殖用または定置用の漁網などは海中に長期保存させるために、珪藻類、アオサ、アオノリ、イギスなどの海藻類、ヒドロ虫、フジツボ、セルプラ、コケムシ、軟体動物類などの海棲汚損生物の付着が激しく、その結果、本来の機能が損なわれることがある。さらに海棲動植物の他にそれらの生物の排泄物、死骸などの有機汚物およびいわゆるスライムなどの付着によっても機能が損なわれることがある。例えば船舶などでは、前述海棲生物の付着により海水中での摩擦抵抗が増加し燃費が増加する。また発電所では、冷却水として海水を用いる際、生物が付着することによって熱交換を著しく阻害する。また漁網の場合、養殖網や定置網などに付着生物が付着すると網が重くなり、沈下により魚が逃げ、また、網自体が流失する恐れがある。そのため頻繁に取替えを要することが多く、それらの保守に多大の労力と費用をかけているのが現状である。 Ships, marine structures, aquaculture or stationary fishing nets are stored in the sea for a long time. Ridge-fouling organisms are heavily attached, and as a result, their original functions may be impaired. In addition to marine plants and animals, the function may be impaired by the attachment of excrement of such organisms, organic filth such as dead bodies, and so-called slime. For example, in a ship or the like, frictional resistance in seawater increases due to adhesion of the marine organisms, and fuel consumption increases. Moreover, in a power plant, when seawater is used as cooling water, heat exchange is remarkably inhibited by the attachment of living organisms. In the case of fishing nets, if attached organisms adhere to aquaculture nets or stationary nets, the nets become heavier, fish may escape due to settlement, and the nets themselves may be washed away. Therefore, frequent replacement is often required, and the present situation is that much labor and cost are spent on the maintenance.
従来からこれらの海棲生物の付着を防止する目的で有機錫化合物を主成分とする防汚塗料が広く使用されてきた。しかしながら、その毒性の強さから環境に与える影響も大きいため、有機錫化合物含有の防汚塗料はその使用が制限されている。その後、この有機錫化合物に代わるものとして様々な低毒性の海棲生物忌避剤を用いた防汚塗料が開発され、使用されている。 Conventionally, antifouling paints based on organotin compounds have been widely used for the purpose of preventing adhesion of these marine organisms. However, the use of organic tin compound-containing antifouling paints is limited because of its strong toxicity and large impact on the environment. Since then, antifouling paints using various low-toxic marine organism repellents have been developed and used as an alternative to the organotin compounds.
しかしながら、これらの防汚塗料は、現在あるもののほとんどが芳香族系溶剤を主とする有機溶剤を溶媒として用いて来た。そのため近隣住民への影響、さらには温暖化など地球規模の環境に与える影響も懸念されている。こういった問題を解決すべく、種々の水系防汚塗料が提案されている。 However, most of these antifouling paints currently use an organic solvent mainly composed of an aromatic solvent as a solvent. For this reason, there are concerns about the impact on neighboring residents and the impact on the global environment such as global warming. In order to solve such problems, various water-based antifouling paints have been proposed.
例えば、特許文献１乃至４等には水系防汚塗料が提案されているが、いずれも要求される防汚性能を満たしているとは言いがたい。 For example, Patent Documents 1 to 4 propose water-based antifouling paints, but it is difficult to say that all satisfy the required antifouling performance.
特許文献５では、アクリル樹脂エマルジョン等の水系ポリマーエマルジョンをバインダーとして含有し、海棲生物忌避剤として効果の高いピリジン−トリフェニルボラン、ピリチオン金属塩、ビスジメチルジチオカルバモイルジンクエチレンビスジチオカーバメート、チオカーバメート化合物を微粒分散化した水系防汚塗料組成物が提案されているが、微粒分散化に多大な労力をかけねばならず、また微粒子化による粘度上昇などの貯蔵安定性やこれら海棲生物忌避剤の早期溶出による長期防汚性に問題がある。また、これらの水系防汚塗膜を形成するためには、配合されているバインダー構成成分の造膜温度以上で乾燥させるか、造膜助剤として高沸点溶剤を配合させる必要がある。造膜温度の低いバインダーとして上記の特許では、ガラス転移点の低い水系ポリマーエマルションを用いているが、形成塗膜が柔らかく、タックや塗膜流出など実際の使用には問題が残る。造膜温度の高いバインダーを用い、造膜助剤として高沸点溶剤を配合した場合、水系防汚塗料としての安全性が得られないだけでなく、従来の使用方法では、高沸点溶剤が揮発するまでに時間を要するなど、乾燥設備等がない場合には有効な防汚効果が発揮できるための塗膜を得ることが出来ない。また、いずれの場合も従来のエマルジョン型防汚塗料の欠点として、凍結した場合は解凍後に樹脂分が分離または凝集する所謂凍結融解安定性などの貯蔵安定性が極端に悪いことから、寒冷地などでの使用に耐え得るものではない。 In Patent Document 5, pyridine-triphenylborane, pyrithione metal salt, bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate, thiocarbamate, which contains an aqueous polymer emulsion such as an acrylic resin emulsion as a binder and is highly effective as a marine organism repellent. Water-based antifouling paint compositions in which compounds are finely dispersed have been proposed. However, great efforts must be made to disperse fine particles, and storage stability such as increase in viscosity due to the formation of fine particles and these marine organism repellents. There is a problem with long-term antifouling properties due to early dissolution of In addition, in order to form these water-based antifouling coating films, it is necessary to dry the film at a temperature equal to or higher than the film forming temperature of the blended binder component, or to add a high boiling point solvent as a film forming aid. In the above patent, a water-based polymer emulsion having a low glass transition point is used as a binder having a low film forming temperature, but the formed coating film is soft, and problems remain in actual use such as tack and coating film outflow. When a binder with a high film-forming temperature is used and a high-boiling solvent is blended as a film-forming auxiliary, not only the safety as a water-based antifouling paint can be obtained, but the high-boiling solvent volatilizes in the conventional method of use. If there is no drying equipment or the like, it is not possible to obtain a coating film that can exhibit an effective antifouling effect. In either case, the disadvantage of the conventional emulsion type antifouling paint is that the storage stability such as so-called freeze-thaw stability in which the resin component separates or aggregates after thawing when frozen is extremely poor. It cannot withstand use in
特許文献６では、バインダーにポリブテンのエマルジョンを含むことで低温造膜性と貯蔵安定性を改善した水性防汚塗料組成物が提案されている。しかしながら、ポリブテンを含むだけでは被塗物に対する付着性が十分でなく、また形成塗膜の柔軟性が得られないため、特に漁網のような被塗物上で防汚塗膜を維持することが出来ず、長期防汚に耐え得る防汚塗膜を得ることは出来ていない。
以上の水系防汚塗料を実際に塗装する場合、最も大きな問題点は、乾燥性である。水は有機溶剤などと比べて乾燥が遅く、乾きにくい欠点を有している。また、水系防汚剤を完全に乾燥せずに海に展開した場合、塗膜が海水中に溶け出して、効果が失われてしまうばかりか、海洋環境を汚染してしまう。
なぜ、漁網に塗布する防汚塗料の場合、乾燥性が問題になるかを以下に説明する。
When the above water-based antifouling paint is actually applied, the biggest problem is dryness. Water has a drawback that it is slower to dry than organic solvents and is difficult to dry. In addition, when the water-based antifouling agent is deployed in the sea without being completely dried, the coating film dissolves in the seawater and the effect is lost, and the marine environment is contaminated.
The reason why dryness becomes a problem in the case of antifouling paints applied to fishing nets will be described below.
漁網や、漁網具に防汚塗料を塗装する場合、スプレー塗装やハケ塗ではなく、一般に浸漬塗装が行われる。スプレー塗装やハケヌリでは、網を広げたり、表裏両面を塗装する必要があり大変手間が掛かる。また、塗着効率（塗着した塗料/塗装に要した塗料）が極端に悪く、塗装に要する塗料の多くがミストなどで消えてしまう。 When an antifouling paint is applied to a fishing net or fishing net equipment, dip coating is generally performed instead of spray coating or brush coating. In spray painting and hakenuri, it is necessary to spread the net or paint both sides, which is very time consuming. In addition, the coating efficiency (paint applied / paint required for painting) is extremely poor, and most of the paint required for painting disappears due to mist.
そこで、網をコンパクトに折りたたみ、塗料溶液の中に網を浸漬することによって、ムラなく楽に、また塗着効率もよく塗装することが出来る。塗装後、乾燥は網を広げて行うことが好ましいが、定置網や、養殖網など、大型の網の場合、場所的に広げて長期間乾燥することは困難で、折りたたんだまま乾燥させている。従来の溶剤型防汚塗料の場合、折りたたまれた状態でもある程度乾燥し、なかんずく乾燥が不十分であっても塗膜が海水中に溶け出ることはなかった。 Therefore, by folding the net compactly and immersing the net in the coating solution, it is possible to apply the coating comfortably and with good coating efficiency. After painting, drying is preferably performed by spreading the net. However, in the case of a large net such as a stationary net or an aquaculture net, it is difficult to spread it for a long time and to dry for a long time, and it is dried while folded. In the case of a conventional solvent-type antifouling paint, it dries to some extent even in a folded state, and the coating film does not dissolve in seawater even if the drying is insufficient.
ところが、上記のような水系漁網防汚剤の場合、溶剤型に比べて乾燥が悪くまた、乾燥が不十分なまま海水中で使用された場合塗膜が海水中に溶け込み効果が失われてしまう。そのため、従来の有機溶剤型防汚塗料に比べてより充分に乾燥する必要があり、乾燥に要する手間が極端に掛かる結果となっている。 However, in the case of the water-based fishing net antifouling agent as described above, the drying effect is poor compared to the solvent type, and when used in seawater with insufficient drying, the coating effect is lost in seawater. . Therefore, it is necessary to dry more sufficiently than the conventional organic solvent-type antifouling paint, resulting in extremely troublesome work for drying.
以上のようにこれまでの水系防汚塗料では、従来の有機溶剤型防汚塗料の代替品として使用に耐え得るものはなかった。 As described above, none of the conventional water-based antifouling paints can withstand use as a substitute for conventional organic solvent-type antifouling paints.
従って、本発明の目的は、従来の有機溶剤型防汚塗料と比較して、防汚性に優れるうえ、揮発性の高い有機溶剤を多く含まないため環境や作業者に与える影響が少なく、凍結融解安定性など貯蔵安定性に優れ、また低温における造膜性や付着性能にも優れた、長期に安定した防汚性能を発揮する防汚塗膜を形成する水系防汚塗料組成物、漁網用水系防汚塗料組成物及び該漁網用水系防汚塗料組成物を施工した漁網具を提供することにある。
Accordingly, the object of the present invention is superior in antifouling properties compared to conventional organic solvent type antifouling paints, and has little influence on the environment and workers because it does not contain a lot of highly volatile organic solvents. excellent storage stability such as melting stability and excellent film formability and adhesion performance at low temperature, long-term water-based antifouling paint composition to form an antifouling coating film which exhibits a stable antifouling performance, fishing net and to provide a use aqueous antifouling paint composition and fishing nets instrument was constructed the fishing nets for aqueous antifouling paint composition.
本発明者らは、上記の課題を解決すべく鋭意研究を重ねた結果、水系防汚塗料中のバインダー構成成分が、（Ａ）一般式（I）
Ｒ１−（Ｓ）ｎ−Ｒ２ （I）
（式中、Ｒ１、Ｒ２は炭素数１〜２０の直鎖または分岐状のアルキル基を、ｎは1〜２０の整数を示す)で表されるジアルキルサルファイド化合物と（Ｃ）親水性親油性バランス（ＨＬＢ）が１〜７であるオキシアルキレン基含有鎖状オルガノポリシロキサンとの水分散エマルジョンと、該水分散エマルジョン以外のバインダー構成成分として（Ｂ）樹脂エマルジョンとを含むことを特徴とし、下記化合物１［化１］、化合物２［化２］、化合物３を含有しない水系防汚塗料組成物とすることで、低温における造膜性や柔軟性に優れ、被塗物への付着性が良好な防汚塗膜を形成し、凍結融解安定性などの貯蔵安定性にも優れた水系防汚塗料組成物を得ることに成功し、本発明を完成するに至った。
（化合物３）
（Ａ）トリオルガノシリル基含有重合性不飽和モノマー及び（Ｂ）その他の重合性不飽和モノマーを含む混合物（Ｉ）を、水性媒体中に平均粒子径が５００ｎｍ以下となるように微分散させ、得られる乳化物を重合させることを特徴とするトリオルガノシリル基含有樹脂。
即ち、請求項１に係る発明は、水系防汚塗料中のバインダー構成成分が、（Ａ）一般式（I）
Ｒ１−（Ｓ）ｎ−Ｒ２ （I）
（式中、Ｒ１、Ｒ２は炭素数１〜２０の直鎖または分岐状のアルキル基を、ｎは1〜２０の整数を示す)で表されるジアルキルサルファイド化合物と（Ｃ）親水性親油性バランス（ＨＬＢ）が１〜７であるオキシアルキレン基含有鎖状オルガノポリシロキサンとの水分散エマルジョンと、該水分散エマルジョン以外のバインダー構成成分として（Ｂ）樹脂エマルジョンとを含むことを特徴とする水系防汚塗料組成物（但し、下記化合物１［化１］、化合物２［化２］、化合物３を含有しない
（化合物３）
（Ａ）トリオルガノシリル基含有重合性不飽和モノマー及び（Ｂ）その他の重合性不飽和モノマーを含む混合物（Ｉ）を、水性媒体中に平均粒子径が５００ｎｍ以下となるように微分散させ、得られる乳化物を重合させることを特徴とするトリオルガノシリル基含有樹脂。）に関し、それにより低温における造膜性や柔軟性に優れ、被塗物への付着性が良好な防汚塗膜を形成し、凍結融解安定性などの貯蔵安定性にも優れた水系防汚塗料組成物を提供するものである。なお、オキシアルキレン基含有鎖状オルガノポリシロキサンの水分散エマルジョンを水系防汚塗料中のバインダー構成成分に含むことにより、上記Ｒ １ −（Ｓ）ｎ−Ｒ ２
（I）の化合物のみを含む場合に比べて、上記の造膜性や柔軟性、付着性能を損なうことなく、より高い防汚性能を得ることが出来る。
本発明に係る水系防汚塗料組成物の好ましい態様として、以下（１）〜（１３）が挙げられる。（１）〜（１３）の任意の組合せも、特に矛盾あるいは不利益が生じない限り本発明の好ましい態様と考えられる。
（１）該水系防汚塗料組成物のバインダー構成成分の固形分１００重量部中（Ａ）該ジアルキルサルファイド化合物エマルジョンの固形分が０．１重量部〜９９重量部であり、好ましくは、1重量部〜９９重量部である。この構成によって、上記本発明の効果がより優れたものとなる。
（２）前記水系防汚塗料組成物のバインダー構成成分中（Ａ）該ジアルキルサルファイド化合物と（Ｃ）親水性親油性バランス（ＨＬＢ）が１〜７であるオキシアルキレン基含有鎖状オルガノポリシロキサンとの水分散エマルジョン以外のバインダー構成成分として、（Ｂ）アクリル樹脂エマルジョン、アクリルスチレン樹脂エマルジョン、酢酸ビニル樹脂エマルジョン、酢酸ビニルアクリル樹脂エマルジョン、酢酸ビニルベオバ樹脂エマルジョン、エチレン酢酸ビニル樹脂エマルジョン、合成ゴムラテックス、ウレタン樹脂エマルジョン、エポキシ樹脂エマルジョン、フェノール樹脂エマルジョン、アルキッド樹脂エマルジョン、ポリエステル樹脂エマルジョン、塩化ビニル樹脂エマルジョン並びに塩化ビニリデン樹脂エマルジョンの中から選ばれる１種または２種以上の樹脂エマルジョンを含む。
As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the binder component in the water-based antifouling paint is: (A) General formula (I)
R 1 - (S) n- R 2 (I)
(Wherein R 1 and R 2 represent a linear or branched alkyl group having 1 to 20 carbon atoms, and n represents an integer of 1 to 20) and (C) a hydrophilic parent and a water-dispersed emulsion of the oxyalkylene group-containing chain organopolysiloxane is an oily balance (HLB) is 1 to 7, characterized in that it comprises (B) a resin emulsion as a binder component other than the water-dispersible emulsion By using a water-based antifouling coating composition that does not contain the following compound 1 [Chemical Formula 1], Compound 2 [Chemical Formula 2], and Compound 3, it has excellent film-forming properties and flexibility at low temperatures, and adheres to the object to be coated. Has succeeded in obtaining a water-based antifouling paint composition excellent in storage stability such as freeze-thaw stability and the like, and has completed the present invention.
(Compound 3)
(A) Mixture (I) containing a triorganosilyl group-containing polymerizable unsaturated monomer and (B) other polymerizable unsaturated monomer is finely dispersed in an aqueous medium so that the average particle size is 500 nm or less, A triorganosilyl group-containing resin obtained by polymerizing the obtained emulsion.
That is, in the invention according to claim 1, the binder component in the water-based antifouling paint is: (A) General formula (I)
R 1 - (S) n- R 2 (I)
(Wherein R 1 and R 2 represent a linear or branched alkyl group having 1 to 20 carbon atoms, and n represents an integer of 1 to 20) and (C) a hydrophilic parent A water dispersion emulsion with an oxyalkylene group-containing chain organopolysiloxane having an oil balance (HLB) of 1 to 7 and (B) a resin emulsion as a binder component other than the water dispersion emulsion Water-based antifouling paint composition (however , it does not contain the following compound 1 [chemical formula 1], compound 2 [chemical formula 2], and compound 3)
(Compound 3)
(A) Mixture (I) containing a triorganosilyl group-containing polymerizable unsaturated monomer and (B) other polymerizable unsaturated monomer is finely dispersed in an aqueous medium so that the average particle size is 500 nm or less, A triorganosilyl group-containing resin obtained by polymerizing the obtained emulsion. ) In respect, whereby excellent film forming property and flexibility at low temperature, adhesion to a coating object to form a good antifouling coating film, water proof excellent in storage stability, such as freeze-thaw stability A soil coating composition is provided. In addition, by including an aqueous dispersion emulsion of an oxyalkylene group-containing chain organopolysiloxane as a binder component in the water-based antifouling paint, the above R 1- (S) nR 2
Compared with the case where only the compound (I) is contained, higher antifouling performance can be obtained without impairing the film forming property, flexibility and adhesion performance.
Preferred embodiments of the water-based antifouling coating composition according to the present invention include the following (1) to (13). Any combination of (1) to (13) is also considered to be a preferred embodiment of the present invention as long as no contradiction or disadvantage occurs.
(1) The solid content of the dialkyl sulfide compound emulsion in the solid content of 100 parts by weight of the binder component of the water-based antifouling coating composition is 0.1 to 99 parts by weight, preferably 1 part by weight. Part to 99 parts by weight. With this configuration, the effect of the present invention is further improved.
(2) In the binder component of the water-based antifouling coating composition, (A) the dialkyl sulfide compound and (C) an oxyalkylene group-containing chain organopolysiloxane having a hydrophilic / lipophilic balance (HLB) of 1 to 7; As a binder component other than the water-dispersed emulsion of (B), an acrylic resin emulsion, an acrylic styrene resin emulsion, a vinyl acetate resin emulsion, a vinyl acetate acrylic resin emulsion, a vinyl acetate resin resin emulsion, an ethylene vinyl acetate resin emulsion, a synthetic rubber latex, a urethane or resin emulsion, epoxy resin emulsion, a phenol resin emulsion, alkyd resin emulsion, a polyester resin emulsion, in the vinyl chloride resin emulsion and a vinylidene chloride resin emulsion Comprising one or more resin emulsion selected.
上記バインダー成分と概ジアルキルサルファイド化合物を組み合わせることにより、水系防汚塗料の漁網具への付着性を向上させ、また海棲生物忌避剤の溶出を制御できる。
By combining the approximate and the binder component dialkyl sulfide compounds, to improve adhesion to the fishing nets instrument aqueous antifouling paints, also possible to control the dissolution of the sea棲生product repellents.
親水性親油性バランス（ＨＬＢ）は、オキシアルキレン基含有鎖状オルガノポリシロキサンの場合、下記式で表される。 In the case of an oxyalkylene group-containing chain organopolysiloxane, the hydrophilic / lipophilic balance (HLB) is represented by the following formula.
ＨＬＢ＝（高分子のポリオキシエチレン重量％）÷５
上記式より、ＨＬＢ値が大きい程、親水性が高くなる。
（３）前記水系防汚塗料組成物のバインダー構成成分の固形分１００重量部中、（Ｂ）該樹脂エマルジョンの固形分が０．１〜９９．９重量部、（Ｃ）該オキシアルキレン基含有鎖状オルガノポリシロキサンエマルジョンの固形分を９９重量部以下で配合する。このようにすることによって、上記本発明に係る水系防汚塗料組成物の性能が最も効果的に発揮される。
（４）（Ａ）該ジアルキルサルファイド化合物が、前記一般式（I）のｎが３〜６にて表されるジアルキルサルファイド化合物の少なくとも１種である。この場合、本発明の水系防汚塗料組成物の優れた効果が良好に発揮される。さらに、（Ａ）該ジアルキルサルファイド化合物が、前記一般式（I）のＲ１とＲ２が共にｔｅｒｔ−ノニルであるジーｔｅｒｔ−ノニルサルファイド化合物の少なくとも１種、および/または前記一般式（I）のＲ１とＲ２が共にｔｅｒｔ−オクチルであるジ−ｔｅｒｔ−オクチルサルファイド化合物の少なくとも１種であることが好ましい。この場合には、水系防汚塗料の漁網具への付着性を向上させ、また海棲生物忌避剤の溶出を制御でき、より好ましい。
（５）水系防汚塗料組成物のバインダー構成成分の固形分１００重量部に対し海棲生物忌避剤としての有効成分が、固形分換算で０．１〜１０００重量部含まれる。このような構成をとることによって、該海棲生物忌避剤の効果を有効に発揮し得る防汚塗膜を得られる。
（６）前記海棲生物忌避剤として、（Ｄ）分散剤を用いて平均粒子径が２〜２０μｍになるよう水に分散したビスジメチルジチオカルバモイルエチレンビスジチオカルバミン酸亜鉛を塗料組成物のバインダー構成成分の固形分１００重量部に対し０．１〜３００重量部含まれる。この構成をとることによって、特にヒドロ虫等の腔腸動物の付着防止効果が高く、全く沈降のない貯蔵安定性の高い水系防汚塗料が得られる。また、ビスジメチルジチオカルバモイルエチレンビスジチオカルバミン酸亜鉛の水分散液の塗料組成物への分散についても従来の有機溶剤型塗料組成物の場合と何ら異なることのない方法で可能である。
（７）海棲生物忌避剤としての有効成分は、（Ｅ）分散剤を用いて平均粒子径が２〜２０μｍになるよう水に分散した金属が銅あるいは亜鉛であるビス（２−ピリジンチオール−１−オキシド）金属塩のうち少なくとも１種を有効成分とする。特に、塗料組成物のバインダー構成成分の固形分１００重量部に対し０．１〜３００重量部含有する。
HLB = (Polyoxyethylene weight% of polymer) ÷ 5
From the above formula, the higher the HLB value, the higher the hydrophilicity.
( 3 ) In 100 parts by weight of the solid content of the binder component of the water-based antifouling paint composition, (B) the solid content of the resin emulsion is 0.1 to 99.9 parts by weight, and (C) the oxyalkylene group is contained The solid content of the chain organopolysiloxane emulsion is blended at 99 parts by weight or less . By doing in this way, the performance of the water-based antifouling paint composition according to the present invention is most effectively exhibited.
( 4 ) (A) The dialkyl sulfide compound is at least one dialkyl sulfide compound in which n in the general formula (I) is represented by 3 to 6. In this case, the excellent effect of the water-based antifouling paint composition of the present invention is exhibited well. Further, (A) the dialkyl sulfide compound is at least one di-tert-nonyl sulfide compound in which R 1 and R 2 in the general formula (I) are both tert-nonyl, and / or the general formula (I). R 1 and R 2 are preferably at least one di-tert-octyl sulfide compound in which both are tert-octyl. In this case, the adhesion of the water-based antifouling paint to the fishing net tool can be improved, and the elution of the marine organism repellent can be controlled, which is more preferable.
( 5 ) The active ingredient as a marine organism repellent is contained in an amount of 0.1 to 1000 parts by weight in terms of solid content with respect to 100 parts by weight of the solid content of the binder component of the water-based antifouling coating composition. By taking such a structure, the antifouling coating film which can exhibit the effect of this marine organism repellent effectively can be obtained.
( 6 ) As the marine organism repellent, (D) zinc component of bisdimethyldithiocarbamoylethylenebisdithiocarbamate dispersed in water so as to have an average particle diameter of 2 to 20 μm using a dispersant. 0.1 to 300 parts by weight is contained per 100 parts by weight of the solid content. By adopting this configuration, a water-based antifouling paint having a high anti-adhesion effect particularly on hydro-insects such as hydroworms and having no sedimentation and high storage stability can be obtained. Also, the dispersion of the aqueous dispersion of zinc bisdimethyldithiocarbamoylethylenebisdithiocarbamate in the coating composition can be performed by a method that is not different from that of the conventional organic solvent-type coating composition.
( 7 ) The active ingredient as a marine organism repellent is (E) bis (2-pyridinethiol-) in which the metal dispersed in water so as to have an average particle diameter of 2 to 20 μm using a dispersant is copper or zinc 1-oxide) At least one of the metal salts is an active ingredient. In particular, it is contained in an amount of 0.1 to 300 parts by weight per 100 parts by weight of the solid content of the binder component of the coating composition.
このようにすることによって、特に藻類・珪藻類などの付着防止効果が高く、全く沈降のない貯蔵安定性の高い水系防汚塗料が得られた。また、この分散についても従来の有機溶剤型塗料と何ら異なることのない方法で可能であることを見出した。
（８）海棲生物忌避剤として、水系防汚塗料組成物のバインダー構成成分の固形分１００重量部に対し、分散剤を用いて水に分散した平均粒子径が２〜２０μｍである（Ｄ）ビスジメチルジチオカルバモイルエチレンビスジチオカルバミン酸亜鉛と（Ｅ）金属が銅あるいは亜鉛であるビス（２−ピリジンチオール−１−オキシド）金属塩のうち少なくとも１種とを合計で０．１〜３００重量部含む。このようにすることによって、特にヒドロ虫などの腔腸動物と藻類・珪藻類などの双方に対し付着防止効果が高く、全く沈降のない貯蔵安定性の高い水系防汚塗料が得られる。また、この分散についても従来の有機溶剤型塗料と何ら異なることのない方法で可能であることを見出した。
（９） 水系防汚塗料組成物のバインダー構成成分の固形分１００重量部に対し、（Ｆ）分散剤を用いて水に分散した平均粒子径が２〜２０μｍである亜酸化銅を０．１〜１０００重量部含有する。亜酸化銅は広く一般的に用いられているが、従来水系防汚塗料としてはその比重の高さから非常に沈降しやすく、反応性の高さからも貯蔵安定性が悪いものしか得られていなかった。しかし、水系防汚塗料組成物のバインダー構成成分の固形分１００重量部に対し、（Ｆ）分散材を用いて水に分散した平均粒径が２〜２０μｍである亜酸化銅を０．１〜１０００重量部含有する水系防汚塗料組成物は、海棲生物全般に付着防止効果が高く、全く沈降のない貯蔵安定性の高い水系防汚塗料が得られる。また、本発明で用いられるいずれの海棲生物忌避剤と混合しても安定で防汚効果の高い水系防汚塗料が得られる。
（１０）上記いずれかの水系防汚組成物と、防汚剤中の水１００重量部に対して１〜２００重量部の水と共沸可能な有機溶剤とを含有する。このようにすることによって乾燥性が良好な水系防汚塗料組成物が得られる。
（１１）水と共沸可能な前記有機溶剤がイソブチルアルコール、エタノール、エチルベンゼン、エチルメチルケトン、キシレン、酢酸イソブチル、酢酸イソプロピル、酢酸エチル、酢酸ブチル、トルエン、１-ブタノール、２−ブタノール、１−プロパノール、２−プロパノールから選ばれる１種または２種以上の混合有機溶媒である。この場合に、特に乾燥性に優れた水系防汚塗料組成物が得られる。
By doing so, a water-based antifouling paint having a high anti-adhesion effect especially for algae and diatoms and having no sedimentation and high storage stability was obtained. It was also found that this dispersion can be achieved by a method that is not different from conventional organic solvent-type paints.
(8) As a marine organism repellent, the average particle size dispersed in water with a dispersant is 2 to 20 μm with respect to 100 parts by weight of the solid content of the binder component of the water-based antifouling coating composition (D) 0.1 to 300 parts by weight in total of zinc bisdimethyldithiocarbamoylethylenebisdithiocarbamate and (E) at least one of bis (2-pyridinethiol-1-oxide) metal salts in which the metal is copper or zinc . By doing so, a water-based antifouling paint having a high anti-adhesion effect on both coelenterates such as hydroworms and algae and diatoms, and having no sedimentation and high storage stability can be obtained. It was also found that this dispersion can be achieved by a method that is not different from conventional organic solvent-type paints.
(9) 0.1% of cuprous oxide having an average particle diameter of 2 to 20 μm dispersed in water using (F) a dispersant with respect to 100 parts by weight of the solid content of the binder component of the aqueous antifouling coating composition Contains ~ 1000 parts by weight. Cuprous oxide is widely used in general, but as water-based antifouling paints, it is very easy to settle due to its high specific gravity, and only those with poor storage stability are obtained due to their high reactivity. There wasn't. However, with respect to 100 parts by weight of the solid content of the binder component of the water-based antifouling coating composition, 0.1% of cuprous oxide having an average particle diameter of 2 to 20 μm dispersed in water using the (F) dispersing agent is 0.1 The water-based antifouling paint composition containing 1000 parts by weight has a high anti-adhesion effect on marine organisms in general, and a water-based antifouling paint having no sedimentation and high storage stability can be obtained. Further, even when mixed with any marine organism repellent used in the present invention, a water-based antifouling paint having a stable and high antifouling effect can be obtained.
(10) One of the above water-based antifouling compositions and 1 to 200 parts by weight of an organic solvent that can be azeotroped with water with respect to 100 parts by weight of water in the antifouling agent. By doing so, a water-based antifouling coating composition having good drying properties can be obtained.
(11) The organic solvent azeotropic with water is isobutyl alcohol, ethanol, ethylbenzene, ethyl methyl ketone, xylene, isobutyl acetate, isopropyl acetate, ethyl acetate, butyl acetate, toluene, 1-butanol, 2-butanol, 1- It is 1 type, or 2 or more types of mixed organic solvents chosen from a propanol and 2-propanol. In this case, a water-based antifouling coating composition having particularly excellent drying properties can be obtained.
本発明は、さらに前記水系防汚塗料組成物が漁網具用途に使用される防汚塗料組成物に関する。 The present invention further relates to an antifouling paint composition in which the water-based antifouling paint composition is used for fishing net equipment.
本発明は、さらに、前記水系防汚塗料組成物が施工された漁網具に関する。
The present invention further relates to fishing network device, wherein the water-based antifouling paint composition is construction.
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Delete
水系防汚塗料中のバインダー構成成分が、（Ａ）一般式（I）
Ｒ１−（Ｓ）ｎ−Ｒ２ （I）
（式中、Ｒ１、Ｒ２は炭素数１〜２０の直鎖または分岐状のアルキル基を、ｎは1〜２０の整数を示す)で表されるジアルキルサルファイド化合物と（Ｃ）親水性親油性バランス（ＨＬＢ）が１〜７であるオキシアルキレン基含有鎖状オルガノポリシロキサンとの水分散エマルジョンと、該水分散エマルジョン以外のバインダー構成成分として（Ｂ）樹脂エマルジョンとを必須成分として含有してなるものである。Ｒ1，Ｒ2は同一でも異なっていても良い。
The binder component in the water-based antifouling paint is: (A) General formula (I)
R 1 - (S) n- R 2 (I)
(Wherein R 1 and R 2 represent a linear or branched alkyl group having 1 to 20 carbon atoms, and n represents an integer of 1 to 20) and (C) a hydrophilic parent It contains an aqueous dispersion emulsion with an oxyalkylene group-containing chain organopolysiloxane having an oil balance (HLB) of 1 to 7, and (B) a resin emulsion as an essential component other than the aqueous dispersion emulsion. It will be. R 1 and R 2 may be the same or different.
一般式（I）において、Ｒ１およびＲ２で示される炭素数１〜２０の直鎖または分枝状のアルキル基としては、メチル、エチル、プロピル、イソプロピル、ブチル、ｔｅｒｔ−ブチル、ペンチル、ヘキシル、オクチル、ノニル、デシル、ドデシル、テトラデシル、ヘキサデシル、オクタデシルなどがあげられる。得られる塗膜の低温造膜性、付着性、柔軟性および塗料の貯蔵安定性の点から、とくに炭素数４〜１９のアルキル基が好ましい。一般式（I）において、ｎは１〜２０の整数であるが、得られる塗膜の低温造膜性、付着性、柔軟性および塗料の貯蔵安定性の点からｎが１〜１０、なかんずく３〜６であるのが好ましい。これらジアルキルサルファイド化合物は単独で用いてもよく、あるいは２種以上を組み合わせて用いてもよい。 In the general formula (I), the linear or branched alkyl group having 1 to 20 carbon atoms represented by R 1 and R 2 is methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl. Octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl and the like. An alkyl group having 4 to 19 carbon atoms is particularly preferable from the viewpoint of low-temperature film-forming properties, adhesion, flexibility, and coating storage stability of the resulting coating film. In the general formula (I), n is an integer of 1 to 20, and n is 1 to 10, especially 3 from the viewpoint of low-temperature film-forming property, adhesion, flexibility and paint storage stability of the resulting coating film. It is preferably ~ 6. These dialkyl sulfide compounds may be used alone or in combination of two or more.
得られる塗膜の低温造膜性、付着性、柔軟性および塗料の貯蔵安定性の点から好ましいジアルキルサルファイド化合物としては、ジ−ｔｅｒｔ−ブチルデカサルファイド、ジペンチルテトラサルファイド、ジペンチルペンタサルファイド、ジペンチルデカサルファイド、ジオクチルテトラサルファイド、ジオクチルペンタサルファイド、ジ−ｔｅｒｔ−オクチルペンタサルファイド、ジノニルテトラサルファイド、オクチルドデシルトリサルファイド、ジノニルペンタサルファイド、ジ−ｔｅｒｔ−ノニルテトラサルファイド、ジ−ｔｅｒｔ−ノニルペンタサルファイド、ジデシルテトラサルファイド、ジドデシルテトラサルファイド、ジオクタデシルテトラサルファイド、ジ−ｔｅｒｔ−ノニルヘキササルファイド、ジ−ｔｅｒｔ−オクチルヘキササルファイド、ジ−ｔｅｒｔ−ノニルヘプタサルファイド、ジ−ｔｅｒｔ−オクチルヘプタサルファイド、ジ−ｔｅｒｔ−ノニルオクタサルファイド、ジ−ｔｅｒｔ−オクチルオクタサルファイド、ジ−ｔｅｒｔ−ノニルノナサルファイド、ジ−ｔｅｒｔ−オクチルノナサルファイドなどがあげられる。 Preferred dialkyl sulfide compounds from the viewpoint of low-temperature film-forming properties, adhesion, flexibility and coating storage stability of the resulting coating film include di-tert-butyl decasulfide, dipentyl tetrasulfide, dipentyl pentasulfide, dipentyl decasulfide. , Dioctyltetrasulfide, dioctylpentasulfide, di-tert-octylpentasulfide, dinonyltetrasulfide, octyldodecyltrisulfide, dinonylpentasulfide, di-tert-nonyltetrasulfide, di-tert-nonylpentasulfide, didecyl Tetrasulfide, didodecyltetrasulfide, dioctadecyltetrasulfide, di-tert-nonylhexasulfide, di-tert-octi Hexasulfide, di-tert-nonylheptasulfide, di-tert-octylheptasulfide, di-tert-nonyloctasulfide, di-tert-octyloctasulfide, di-tert-nonylnonasulfide, di-tert-octylnonasulfide Etc.
例えば、ジアルキルサルファイド化合物の水分散エマルジョンは、例えば、前記ジアルキルサルファイド化合物をアニオン系界面活性剤、カチオン系界面活性剤、両性界面活性剤またはノニオン系界面活性剤から選ばれる１種または２種以上により水に分散、エマルジョン化したものを用いる。ジアルキルサルファイド化合物のエマルジョン化方法に特に制限はないが、例えば、（ａ）ジアルキルサルファイド化合物、（ｂ）界面活性剤をディスパー、ホモミキサーなどの分散機で混合、撹拌しながら（ｃ）水を徐々に添加していき、Ｗ／Ｏエマルジョンから相転換によってO／Ｗエマルジョンにするといった方法をとることにより、ジアルキルサルファイド化合物の安定な水分散エマルジョンを得ることが出来る。このエマルジョンの平均粒子径は０．１〜１μｍであることがより望ましい。 For example, a water-dispersed emulsion of a dialkyl sulfide compound is obtained by, for example, using the dialkyl sulfide compound as one or more selected from an anionic surfactant, a cationic surfactant, an amphoteric surfactant, or a nonionic surfactant. Dispersed in water and emulsified. There are no particular restrictions on the method for emulsifying the dialkyl sulfide compound. For example, (a) the dialkyl sulfide compound and (b) the surfactant are mixed with a disperser such as a disper or a homomixer, and (c) water is gradually added while stirring. A stable water-dispersed emulsion of a dialkyl sulfide compound can be obtained by adding to the solution and taking a method of converting the W / O emulsion into an O / W emulsion by phase conversion. The average particle size of this emulsion is more preferably 0.1 to 1 μm.
本発明による水系防汚塗料組成物のバインダー構成成分中(Ａ）該ジアルキルサルファイド化合物エマルジョン以外のバインダ構成成分として、塗膜形成化合物としてその他の樹脂エマルジョンを含有させることが出来る。このような他の樹脂エマルジョンとしては、例えば、アクリル樹脂エマルジョン、アクリルスチレン樹脂エマルジョン、酢酸ビニル樹脂エマルジョン、酢酸ビニルアクリル樹脂エマルジョン、酢酸ビニルベオバ樹脂エマルジョン、エチレン酢酸ビニル樹脂エマルジョン、合成ゴムラテックス、ウレタン樹脂エマルジョン、エポキシ樹脂エマルジョン、フェノール樹脂エマルジョン、アルキッド樹脂エマルジョン、ポリエステル樹脂エマルジョン、塩化ビニル樹脂エマルジョン、塩化ビニリデン樹脂エマルジョン、あるいはこれらの共重合樹脂エマルジョン、ハイブリッド樹脂エマルジョン、変性樹脂エマルジョン等があるが、これらに限るものではない。樹脂粒子の平均粒子径が０．１〜１μｍの樹脂エマルジョンがより好ましく用いられる。水系防汚塗料組成物のバインダー構成成分中(Ａ）該ジアルキルサルファイド化合物エマルジョン以外のバインダ構成成分として、これらのエマルジョンから選ばれた１種あるいは２種以上を用いることができる。 In the binder component of the water-based antifouling coating composition according to the present invention, (A) as a binder component other than the dialkyl sulfide compound emulsion, other resin emulsions can be contained as a coating film forming compound. Examples of such other resin emulsions include acrylic resin emulsions, acrylic styrene resin emulsions, vinyl acetate resin emulsions, vinyl acetate acrylic resin emulsions, vinyl acetate Veova resin emulsions, ethylene vinyl acetate resin emulsions, synthetic rubber latex, urethane resin emulsions. , Epoxy resin emulsions, phenol resin emulsions, alkyd resin emulsions, polyester resin emulsions, vinyl chloride resin emulsions, vinylidene chloride resin emulsions, or their copolymer resin emulsions, hybrid resin emulsions, modified resin emulsions, etc. It is not a thing. A resin emulsion having an average particle diameter of resin particles of 0.1 to 1 μm is more preferably used. One or two or more selected from these emulsions can be used as a binder constituent other than the (A) dialkyl sulfide compound emulsion in the binder constituent of the aqueous antifouling coating composition.
これらのうち、特にアクリル樹脂エマルジョンがより好ましい。アクリル樹脂エマルジョンとしては種々のものがあるが、たとえばボンコート４０−４１８（大日本インキ化学工業株式会社製：固形分５５％、ガラス転移点（Ｔｇ）１８℃、造膜温度（ＭＦＴ）１５℃）、ボンコートＢＣ−２８０（大日本インキ化学工業株式会社製：固形分５０％、ガラス転移点（Ｔｇ）２℃、造膜温度（ＭＦＴ）０〜３℃）、ボンコート９４２２（大日本インキ化学工業株式会社製：固形分４０％、ガラス転移点（Ｔｇ）４０℃、造膜温度（ＭＦＴ）４０℃）などがある。また、通常バインダーの造膜温度（ＭＦＴ）が設定されているものについては、その温度以上で乾燥させることが必要だが、本発明を用いることにより、その造膜温度以下で乾燥させても、有効な防汚効果を発揮することの出来る塗膜を得られ、また樹脂の性状に拠ることなく付着性の極めて良好な塗膜を得ることが出来る。 Of these, an acrylic resin emulsion is particularly preferable. There are various acrylic resin emulsions. For example, Boncoat 40-418 (Dainippon Ink & Chemicals, Inc .: solid content 55%, glass transition point (Tg) 18 ° C., film forming temperature (MFT) 15 ° C.) Boncoat BC-280 (manufactured by Dainippon Ink and Chemicals, Inc .: solid content 50%, glass transition point (Tg) 2 ° C., film forming temperature (MFT) 0 to 3 ° C.), Boncoat 9422 (Dainippon Ink Chemical Co., Ltd.) Company: 40% solid content, glass transition point (Tg) 40 ° C., film forming temperature (MFT) 40 ° C.) and the like. In addition, it is necessary to dry the binder film forming temperature (MFT) above that temperature, but it is effective even if it is dried below the film forming temperature by using the present invention. It is possible to obtain a coating film that can exhibit an excellent antifouling effect, and it is possible to obtain a coating film with extremely good adhesion without depending on the properties of the resin.
（Ａ）該ジアルキルサルファイド化合物エマルジョン以外のバインダー構成成分は、好ましくはバインダー構成成分の固形分１００重量部中１〜９９．９重量部であり、さらに好ましくは、１重量部〜９９重量部である。 (A) The binder component other than the dialkyl sulfide compound emulsion is preferably 1 to 99.9 parts by weight per 100 parts by weight of the solid content of the binder component, and more preferably 1 to 99 parts by weight. .
本発明に用いられる親水性親油性バランス（ＨＬＢ）が１から７の範囲にある（Ｃ）オキシアルキレン基含有鎖状オルガノポリシロキサンとしては、たとえばポリジメチルシロキサン、ポリメチルフェニルシロキサン、メチルフェニルシロキサン−ジメチルシロキサン、ポリエーテル変成ポリジメチルシロキサン、ポリエーテル変成ポリアルキル（メチル）シロキサン、ポリエステル変成ポリジメチルシロキサン、アルキル・ポリエーテル変性オルガノポリシロキサン、フロロシリコーンオイル、アミノ変成シリコーンオイル、その他各種官能基による変成シリコーンオイルなどがあげられるが、これらに限られるものではない。 Examples of the (C) oxyalkylene group-containing chain organopolysiloxane having a hydrophilic / lipophilic balance (HLB) in the range of 1 to 7 used in the present invention include polydimethylsiloxane, polymethylphenylsiloxane, methylphenylsiloxane- Dimethylsiloxane, polyether-modified polydimethylsiloxane, polyether-modified polyalkyl (methyl) siloxane, polyester-modified polydimethylsiloxane, alkyl-polyether-modified organopolysiloxane, fluorosilicone oil, amino-modified silicone oil, and other functional groups Examples include, but are not limited to, silicone oil.
これらのオキシアルキレン基含有鎖状オルガノポリシロキサンのうちで特に好ましいものは、親水性親油性バランス（ＨＬＢ）が１から７の範囲にある、ポリジメチルシロキサン、メチルフェニルシロキサン−ジメチルシロキサン共重合体、ポリエーテル変性ポリジメチルシロキサン、アルキル・ポリエーテル変性オルガノポリシロキサンである。これらのオキシアルキレン基含有鎖状オルガノポリシロキサンは、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。また本発明に用いるオキシアルキレン基含有鎖状オルガノポリシロキサンは、得られる塗膜の低温造膜性、付着性、柔軟性および塗料の貯蔵安定性ならび防汚性の点から、粘度が１〜１万ポイズ、なかんずく５０〜５００ポイズの範囲のものが好ましい。 Among these oxyalkylene group-containing chain organopolysiloxanes, particularly preferred are polydimethylsiloxane, methylphenylsiloxane-dimethylsiloxane copolymer having a hydrophilic / lipophilic balance (HLB) in the range of 1 to 7, Polyether-modified polydimethylsiloxane and alkyl-polyether-modified organopolysiloxane. These oxyalkylene group-containing chain organopolysiloxanes may be used alone or in combination of two or more. The oxyalkylene group-containing chain organopolysiloxane used in the present invention has a viscosity of 1 to 1 from the viewpoint of low-temperature film-forming properties, adhesion, flexibility, paint storage stability and antifouling properties of the resulting coating film. Those in the range of 10,000 poise, especially 50 to 500 poise are preferred.
本発明で使用される（Ｃ）オキシアルキレン基含有鎖状オルガノポリシロキサンの水分散エマルジョンは、前記オキシアルキレン基含有鎖状オルガノポリシロキサンをアニオン系界面活性剤、カチオン系界面活性剤、両性界面活性剤またはノニオン系界面活性剤から選ばれる１種または２種以上により水に分散、エマルジョン化したものを用いる。オキシアルキレン基含有鎖状オルガノポリシロキサンのエマルジョン化方法に特に制限はないが、例えば、（ａ）オキシアルキレン基含有鎖状オルガノポリシロキサン、（ｂ）界面活性剤をディスパー、ホモミキサーなどの分散機で混合、撹拌しながら（ｃ）水を徐々に添加していき、Ｗ／Ｏエマルジョンから相転換によってO／Ｗエマルジョンにするといった方法をとることにより、オキシアルキレン基含有鎖状オルガノポリシロキサンの安定な水分散エマルジョンを得ることが出来る。このエマルジョンの平均粒子径は０．１〜１μｍであることがより望ましい。また、前記（Ａ）ジアルキルサルファイド化合物のエマルジョンとの混合は、それぞれエマルジョン化したものを混合しても、予め混合したジアルキルサルファイド化合物とオキシアルキレン基含有鎖状オルガノポリシロキサンをエマルジョン化したものでも良い。 The water-dispersed emulsion of (C) oxyalkylene group-containing chain organopolysiloxane used in the present invention comprises the above oxyalkylene group-containing chain organopolysiloxane as an anionic surfactant, a cationic surfactant, an amphoteric surfactant. Used is one that is dispersed in water and emulsified with one or more selected from an agent or a nonionic surfactant. There are no particular restrictions on the method for emulsifying the oxyalkylene group-containing chain organopolysiloxane. For example, (a) an oxyalkylene group-containing chain organopolysiloxane, (b) a surfactant such as a disper or a homomixer (C) Stabilization of the oxyalkylene group-containing chain organopolysiloxane by gradually adding water while mixing and stirring in step (c) by adding water to the O / W emulsion by phase conversion. A water-dispersed emulsion can be obtained. The average particle size of this emulsion is more preferably 0.1 to 1 μm. In addition, the mixture of the dialkyl sulfide compound (A) with the emulsion may be a mixture of emulsions or an emulsion of a premixed dialkyl sulfide compound and an oxyalkylene group-containing chain organopolysiloxane. .
本発明で使用されるジアルキルサルファイド化合物エマルジョン、およびオキシアルキレン基含有鎖状オルガノポリシロキサンのエマルジョンを界面活性剤で分散する際、他の液状樹脂としてポリブテン、流動パラフィン、液状ポリオレフィンなどを添加することも可能である。 When the dialkyl sulfide compound emulsion and the oxyalkylene group-containing chain organopolysiloxane emulsion used in the present invention are dispersed with a surfactant, polybutene, liquid paraffin, liquid polyolefin or the like may be added as another liquid resin. Is possible.
前記バインダーエマルジョン中、（Ａ）ジアルキルサルファイド化合物エマルジョンの固形分１００重量部に対するその他のエマルジョンの配合割合は、造膜性、凍結融解安定性、付着性および防汚効果から判断して、（Ｃ）オキシアルキレン基含有鎖状オルガノポリシロキサンエマルジョンの固形分が０より多く１０００重量部以下、その他の樹脂エマルジョンの固形分が５０〜１０００重量部であり、好ましくは（Ｃ）オキシアルキレン基含有鎖状オルガノポリシロキサンエマルジョンの固形分が１０〜５００重量部、その他の（Ｂ）樹脂エマルジョンの固形分が８０〜８００重量部である。
In the binder emulsion, the blending ratio of the other emulsion with respect to 100 parts by weight of the solid content of the (A) dialkyl sulfide compound emulsion is judged from the film-forming property, freeze-thaw stability, adhesion and antifouling effect, (C) The solid content of the oxyalkylene group-containing chain organopolysiloxane emulsion is more than 0 and 1000 parts by weight or less , and the solid content of the other resin emulsion is 50 to 1000 parts by weight, preferably (C) the oxyalkylene group-containing chain organo The solid content of the polysiloxane emulsion is 10 to 500 parts by weight, and the solid content of the other (B) resin emulsion is 80 to 800 parts by weight.
上記水系防汚塗料組成物に配合される海棲生物忌避剤としての有効成分は、水系塗料防汚組成物中のバインダーの固形分１００重量部に対して、固形分換算で０．１〜１０００重量部含まれる。好ましくは、用いられる海棲生物忌避剤の比重に拠るが、比重が３以下の海棲生物忌避剤では固形分換算で１〜２００重量部、比重が３より大きな海棲生物忌避剤では固形分換算で１０〜４００重量部である。 The active ingredient as a marine organism repellent blended in the water-based antifouling paint composition is 0.1 to 1000 in terms of solid content with respect to 100 parts by weight of the solid content of the binder in the water-based paint antifouling composition. Part by weight is included. Preferably, depending on the specific gravity of the marine organism repellent used, the marine organism repellent with a specific gravity of 3 or less has a solid content of 1 to 200 parts by weight, and the marine organism repellent with a specific gravity greater than 3 has a solid content. It is 10 to 400 parts by weight in terms of conversion.
海棲生物忌避剤としては、亜酸化銅、銅粉、ロダン銅、ナフテン酸銅、亜鉛ピリチオン、銅ピリチオン、ビスジメチルジチオカルバモイルジンクエチレンビスジチオカーバメート、ジンクジメチルカーバメート、ジンクエチレンジチオカーバメート、マンガニーズエチレンビスジチオカーバメート、テトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、テトラブチルチウラムジスルフィド、２，４，５，６−テトラクロロイソフタロニトリル、２，３−ジクロロ−Ｎ−（２’，６’−ジエチルフェニル）マレイミド、２，３−ジクロロ−Ｎ−（２’−エチル−６’−メチルフェニル）マレイミド、４，５−ジクロロ−２−ｎ−オクチル−３（２Ｈ）−イソチアゾロン、２−メチルチオ−４−ｔ−ブチルアミノ−６−シクロプロピルアミノ−Ｓ−トリアジン、Ｎ−Ｎ’−ジメチルジクロロフェニル尿素、Ｎ−（フルオロジクロロメチルチオ）フタルイミド、Ｎ，Ｎ’−ジメチル−Ｎ’−フェニル−（Ｎ−フルオロジクロロメチルチオ）スルファミド、Ｎ−ジクロロフルオロメチルチオ−Ｎ’，Ｎ’−ジメチル−Ｎ−ｐ−トリスルファミド、ピリジン−トリフェニルボラン、トリフェニル（オクタデシルアミン）ボロン、トリフェニル（プロピルアミン）ボロン、トリフェニル[３−（２−エチルヘキシルオキシ）プロピルアミン]ボロン等の海棲生物忌避剤およびそのエマルジョンが挙げられ、このうちの１種もしくは２種以上を対象となる海棲生物により適宜選択して配合することが出来る。 Marine repellents include cuprous oxide, copper powder, rhodan copper, copper naphthenate, zinc pyrithione, copper pyrithione, bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate, zinc dimethylcarbamate, zinc ethylenedithiocarbamate, manganese ethylene Bisdithiocarbamate, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, 2,4,5,6-tetrachloroisophthalonitrile, 2,3-dichloro-N- (2 ', 6'-diethylphenyl) Maleimide, 2,3-dichloro-N- (2′-ethyl-6′-methylphenyl) maleimide, 4,5-dichloro-2-n-octyl-3 (2H) -isothiazolone, 2-methylthio-4-t -Butylamino-6-cycl Propylamino-S-triazine, NN'-dimethyldichlorophenylurea, N- (fluorodichloromethylthio) phthalimide, N, N'-dimethyl-N'-phenyl- (N-fluorodichloromethylthio) sulfamide, N-dichlorofluoro Methylthio-N ′, N′-dimethyl-Np-trisulfamide, pyridine-triphenylborane, triphenyl (octadecylamine) boron, triphenyl (propylamine) boron, triphenyl [3- (2-ethylhexyloxy) ) Propylamine] boron and other marine organism repellents and emulsions thereof, and one or more of them can be appropriately selected and blended depending on the marine organisms of interest.
この場合、（１）前記水系防汚塗料組成物のバインダー構成成分の固形分１００重量部に対し、前記海棲生物忌避剤として（Ｄ）分散剤を用いて水に分散した平均粒子径が２〜２０μｍであるビスジメチルジチオカルバモイルエチレンビスジチオカルバミン酸亜鉛を０.１〜３００重量部含有する場合、
（２）前記水系防汚塗料組成物のバインダー構成成分の固形分１００重量部に対し、前記海棲生物忌避剤として（Ｅ）分散剤を用いて水に分散した平均粒子径２〜２０μｍである金属が銅あるいは亜鉛であるビス（２−ピリジンチオール−１−オキシド）金属塩のうち少なくとも１種をとして０.１〜３００重量部含有する場合、
（３）前記水系防汚塗料組成物のバインダー構成成分の固形分１００重量部に対し、前記海棲生物忌避剤として、分散剤を用いて水に分散した平均粒子径が２〜２０μｍである（Ｄ）ビスジメチルジチオカルバモイルエチレンビスジチオカルバミン酸亜鉛と（Ｅ）金属が銅あるいは亜鉛であるビス（２−ピリジンチオール−１−オキシド）金属塩のうち少なくとも１種とを合計で０．１〜３００重量部含有する場合、あるいは
（４）前記水系防汚塗料組成物のバインダー構成成分の固形分1００重量部に対し、前記海棲生物忌避剤として（Ｆ）分散剤を用いて水に分散した平均粒子径が１〜２０μｍである亜酸化銅を０．１〜１０００重量部含有する場合が特に好ましい。
In this case, (1) The average particle size dispersed in water using (D) a dispersant as the marine organism repellent is 2 with respect to 100 parts by weight of the solid content of the binder component of the water-based antifouling coating composition. When 0.1 to 300 parts by weight of zinc bisdimethyldithiocarbamoylethylenebisdithiocarbamate that is ˜20 μm is contained,
(2) With respect to 100 parts by weight of the solid content of the binder component of the water-based antifouling coating composition, the average particle diameter is 2 to 20 μm dispersed in water using (E) a dispersant as the marine organism repellent. When containing 0.1 to 300 parts by weight of at least one of bis (2-pyridinethiol-1-oxide) metal salts in which the metal is copper or zinc,
(3) The average particle diameter dispersed in water using a dispersant as the marine organism repellent is 2 to 20 μm with respect to 100 parts by weight of the solid content of the binder component of the water-based antifouling coating composition ( D) 0.1 to 300 weights in total of zinc bisdimethyldithiocarbamoylethylenebisdithiocarbamate and (E) at least one of bis (2-pyridinethiol-1-oxide) metal salts in which the metal is copper or zinc Or (4) average particles dispersed in water using (F) a dispersant as a marine organism repellent with respect to 100 parts by weight of the solid content of the binder component of the aqueous antifouling coating composition The case of containing 0.1 to 1000 parts by weight of cuprous oxide having a diameter of 1 to 20 μm is particularly preferable.
塗料配合中の水に対して共沸可能な有機溶剤を添加することにより、良好な乾燥性が得られる。添加する共沸可能な有機溶剤は、塗料配合中の水１００重量部に対して１〜２００重量部である。 By adding an organic solvent which can be azeotroped with respect to water in the paint formulation, good drying properties can be obtained. The azeotropic organic solvent to be added is 1 to 200 parts by weight with respect to 100 parts by weight of water in the coating composition.
また、用いられる水に対して共沸可能な有機溶剤は、特に限定されないが、イソブチルアルコール、エタノール、エチルベンゼン、エチルメチルケトン、キシレン、酢酸イソブチル、酢酸イソプロピル、酢酸エチル、酢酸ブチル、トルエン、１-ブタノール、２−ブタノール、１−プロパノール、２−プロパノール、から選ばれる１種または２種以上の混合有機溶媒である場合が、特に好ましい。 The organic solvent that can be azeotroped with respect to water used is not particularly limited, but includes isobutyl alcohol, ethanol, ethylbenzene, ethyl methyl ketone, xylene, isobutyl acetate, isopropyl acetate, ethyl acetate, butyl acetate, toluene, 1- The case where it is 1 type, or 2 or more types of mixed organic solvents chosen from butanol, 2-butanol, 1-propanol, 2-propanol is especially preferable.
以下に実施例を示すが、本発明はこれら実施例に限定されるものではない。 Examples are shown below, but the present invention is not limited to these examples.
参考例及び本発明における塗料の作成は、まず、ジアルキルサルファイド化合物を含むオイルエマルジョン溶液あるいはジアルキルサルファイド化合物とオキシアルキレン基含有鎖状オルガノポリシロキサンを含むオイルエマルジョン溶液を作成し、その後、バインダー樹脂エマルジョンを加え、その溶液に、海棲生物忌避剤および他の薬剤を加え、水と有機溶剤および界面活性剤を加えて分散し水系防汚塗料組成物を得た。
In the preparation of the paint in the reference example and the present invention, first, an oil emulsion solution containing a dialkyl sulfide compound or an oil emulsion solution containing a dialkyl sulfide compound and an oxyalkylene group-containing chain organopolysiloxane was prepared, and then a binder resin emulsion was prepared. In addition, a marine organism repellent and other chemicals were added to the solution, and water, an organic solvent and a surfactant were added and dispersed to obtain an aqueous antifouling paint composition.
即ち、表１に記載の配合成分を添加攪拌してＯＥ１〜ＯＥ１０の水分散オイルエマルジョンを得た。さらに、これらの水分散オイルエマルジョンを用い、表２〜５に記載の配合成分を添加攪拌して試験例１〜３０（実施例は４、７、１１、１４、１６、１９〜３０、その他は参考例）と比較例１〜１０の塗料を得た。
That is, the blended components shown in Table 1 were added and stirred to obtain water-dispersed oil emulsions OE1 to OE10. Furthermore, using these water-dispersed oil emulsions, the ingredients listed in Tables 2 to 5 were added and stirred, and Test Examples 1 to 30 (Examples 4, 7, 11, 14, 16, 19 to 30 and others were The paints of Reference Example) and Comparative Examples 1 to 10 were obtained.
オイルエマルジョンの作成 （ＯＥ１溶液〜ＯＥ１０溶液）
実塗料配合（（試験例１〜３０（実施例は４、７、１１、１４、１６、１９〜３０、その他は参考例）、比較例１〜１０）
(試験例１)
付着性試験結果
試験例１〜３０（実施例は４、７、１１、１４、１６、１９〜３０、その他は参考例）と比較例１〜１０の水系防汚塗料組成物について安定性及び付着性の評価を行った。
Preparation of oil emulsion (OE1 solution to OE10 solution)
Actual paint formulation ( Test Examples 1 to 30 (Examples are 4, 7, 11, 14, 16, 19 to 30, others are reference examples) , Comparative Examples 1 to 10)
(Test Example 1)
Adhesion test results
Evaluation of stability and adhesiveness of the water-based antifouling paint compositions of Test Examples 1 to 30 (Examples are 4, 7, 11, 14, 16, 19 to 30 and others are reference examples) and Comparative Examples 1 to 10 went.
試験例１〜３０（実施例は４、７、１１、１４、１６、１９〜３０、その他は参考例）と比較例１〜１０の試験液を７８ｍｍ×１４６ｍｍのポリエチレン板に乾燥後の塗膜が均一になるように塗布した。その後、５℃、２０℃および５０℃にそれぞれ温度調整された恒温乾燥機中で１２時間乾燥した後、得られた塗装板を１．０ノットの流速になるように調整された回転ドラムに取り付け、２０℃海水中で１ヵ月間浸漬し、塗膜の状態を観察、残存状態について判定した（ロータリー試験）。さらに浸漬後の塗膜を乾いたカーゼを用いて、軽く指を添えて３回擦り、付着性の確認を行った（ラビング試験）。表６,７参照。
(試験例２)
貯蔵安定性試験結果および凍結融解（―２０℃−常温繰返し）安定性試験結果
試験例１〜３０（実施例は４、７、１１、１４、１６、１９〜３０、その他は参考例）および比較例1〜９の塗料組成物を直ちに２０℃に調整しイワタカップで粘度測定した。その後塗料組成物を３つの容器に移し変え一つは室温で３０日間放置し、一つは４０℃で４０日間放置した。もう一つは−２０℃にて凍結させた後、常温で解凍する操作を１０回繰り返した。それぞれの塗料中の沈殿状態および凝集状態を確認し、２０℃に調整してイワタカップにて粘度を測定した。その結果を表８,９に示す。
(試験例３)
防汚性試験
試験例１〜３０（実施例は４、７、１１、１４、１６、１９〜３０、その他は参考例）および比較例１〜１０で得られた塗料組成物を、テトロン製の漁網（２５０デニール、８４本、目合７５ｍｍ）に浸漬塗装し、室温にて乾燥した。このように塗料組成物を塗布した漁網を４０ｃｍ×６０ｃｍの鉄棒の枠に固定し、北海道斜里郡斜里町の定置網にて水深約１ｍに垂下浸漬し、その防汚性能を４ヵ月間にわたって定期的に観測した。結果を表１０、１１に示す。表中の数字は海棲生物の付着面積（％）を表す。
(試験例４)
乾燥性試験
上述で得られた実施例２８〜３０および比較例９の塗料組成物をポリエチレン製の漁網（４００デニール、４８本、目合６０ｍｍ）に浸漬塗装し２０℃室内で乾燥した。乾燥３０分後、指触にて乾燥を確認した。その結果を表１２に示す。
Test Examples 1 to 30 (Examples are 4, 7, 11, 14, 16, 19 to 30 and others are Reference Examples) and Comparative Examples 1 to 10 are dried onto a 78 mm × 146 mm polyethylene plate. Was applied so as to be uniform. Then, after drying for 12 hours in a thermostatic dryer adjusted to 5 ° C., 20 ° C. and 50 ° C., the obtained coated plate is attached to a rotating drum adjusted to a flow rate of 1.0 knots. Then, it was immersed in seawater at 20 ° C. for 1 month, the state of the coating film was observed, and the remaining state was determined (rotary test). Further, the coated film after immersion was lightly rubbed 3 times with a finger using a dry case to confirm adhesion (rubbing test). See Tables 6 and 7.
(Test Example 2)
Storage stability test results and freeze-thaw (-20 ° C-normal temperature repeat) stability test results
The coating compositions of Test Examples 1 to 30 (Examples are 4, 7, 11, 14, 16, 19 to 30 and others are reference examples) and Comparative Examples 1 to 9 are immediately adjusted to 20 ° C., and the viscosity is measured with an Iwata cup. did. Thereafter, the coating composition was transferred to three containers, one was left at room temperature for 30 days, and the other was left at 40 ° C. for 40 days. The other was the operation of freezing at −20 ° C. and then thawing at room temperature 10 times. The state of precipitation and aggregation in each paint was confirmed, adjusted to 20 ° C., and the viscosity was measured with an Iwata cup. The results are shown in Tables 8 and 9.
(Test Example 3)
Antifouling test
The coating compositions obtained in Test Examples 1 to 30 (Examples are 4, 7, 11, 14, 16, 19 to 30 and others are reference examples) and Comparative Examples 1 to 10 were used as Tetron fishing nets (250 denier). 84, 75 mm mesh) and dried at room temperature. The fishing net coated with the coating composition in this way is fixed to a 40cm x 60cm steel rod frame, and dipped in a stationary net in Shari-cho, Shari-gun, Hokkaido, at a depth of about 1m, and its antifouling performance is regularly monitored for 4 months. Observed at. The results are shown in Tables 10 and 11. The numbers in the table represent the marine organism attachment area (%).
(Test Example 4)
Drying Test The coating compositions of Examples 28 to 30 and Comparative Example 9 obtained above were dip-coated on a polyethylene fishing net (400 denier, 48, 60 mm mesh) and dried in a 20 ° C. room. After 30 minutes of drying, drying was confirmed by finger touch. The results are shown in Table 12.
なお、性能試験結果は総合評価がなされ、一部に悪い結果が出たとしても良好に使用できる環境に対して使用すればよい。例えば、表６の実施例７の５℃ラッピング試験は不可となっているが、実施例７の水系防汚塗料組成物は低温地帯で用いなければよい。 The performance test results are comprehensively evaluated and may be used in an environment where they can be used satisfactorily even if some results are bad. For example, the 5 ° C. wrapping test of Example 7 in Table 6 is not possible, but the water-based antifouling paint composition of Example 7 may not be used in a low temperature zone.
表６、表７より本願発明による防汚塗料は、優れた付着性を示し、その結果表１０、１１に示す防汚性結果においても良好な結果に結びついたと思われる。 From Tables 6 and 7, the antifouling paint according to the present invention showed excellent adhesion, and as a result, the antifouling results shown in Tables 10 and 11 are considered to have led to good results.
表６、表７より５℃において実施例２８、２９、３０の塗料が優れた付着性を示したのは、乾燥性が良好であったことに起因すると思われる。 From Tables 6 and 7, it is considered that the reason why the paints of Examples 28, 29 and 30 showed excellent adhesion at 5 ° C. was due to the good drying property.
表８，表９より本願発明による防汚塗料は、優れた貯蔵安定性を示した。特に低温−常温繰り返し試験において良好な結果を示した。 From Tables 8 and 9, the antifouling paint according to the present invention showed excellent storage stability. In particular, good results were shown in a low temperature-normal temperature repeated test.
以上の結果より本願発明は、環境や作業者に与える影響の少ない良好な貯蔵安定性と防汚性、低温に置ける造膜性や付着性能にも優れ、長期に安定化した防汚性能を発揮する防汚塗膜を形成する水系防汚塗料組成物を得られることが分かる。 Based on the above results, the present invention has excellent storage stability and antifouling properties with little impact on the environment and workers, excellent film-forming properties and adhesion performance at low temperatures, and exhibits stable antifouling performance over a long period of time. It turns out that the water-system antifouling paint composition which forms the antifouling coating film to be obtained can be obtained.
本発明の水系防汚塗料組成物は漁網等の漁具に対して有効に適用することができる。 The water-based antifouling paint composition of the present invention can be effectively applied to fishing gear such as fishing nets.
Claims (15)
Ｒ１−（Ｓ）ｎ−Ｒ２ （I）
（式中、Ｒ１、Ｒ２は炭素数１〜２０の直鎖または分岐状のアルキル基を、ｎは1〜２０の整数を示す)で表されるジアルキルサルファイド化合物と（Ｃ）親水性親油性バランス（ＨＬＢ）が１〜７であるオキシアルキレン基含有鎖状オルガノポリシロキサンとの水分散エマルジョンと、該水分散エマルジョン以外のバインダー構成成分として（Ｂ）樹脂エマルジョンとを含むことを特徴とし、下記化合物１［化１］、化合物２［化２］、化合物３を含有しない水系防汚塗料組成物。
（化合物３）
（Ａ）トリオルガノシリル基含有重合性不飽和モノマー及び（Ｂ）その他の重合性不飽和モノマーを含む混合物（Ｉ）を、水性媒体中に平均粒子径が５００ｎｍ以下となるように微分散させ、得られる乳化物を重合させることを特徴とするトリオルガノシリル基含有樹脂。 The binder component in the water-based antifouling paint is: (A) General formula (I)
R 1 - (S) n- R 2 (I)
(Wherein R 1 and R 2 represent a linear or branched alkyl group having 1 to 20 carbon atoms, and n represents an integer of 1 to 20) and (C) a hydrophilic parent and a water-dispersed emulsion of the oxyalkylene group-containing chain organopolysiloxane is an oily balance (HLB) is 1 to 7, characterized in that it comprises (B) a resin emulsion as a binder component other than the water-dispersible emulsion A water-based antifouling paint composition which does not contain the following compound 1 [Chemical Formula 1], Compound 2 [Chemical Formula 2] and Compound 3 .
(Compound 3)
(A) Mixture (I) containing a triorganosilyl group-containing polymerizable unsaturated monomer and (B) other polymerizable unsaturated monomer is finely dispersed in an aqueous medium so that the average particle size is 500 nm or less, A triorganosilyl group-containing resin obtained by polymerizing the obtained emulsion.
Fishing net instrument was constructed either aqueous antifouling coating composition according to claim 1 to 1 3, wherein.
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| JP5661766B2 (en) * | 2010-06-23 | 2015-01-28 | 中国塗料株式会社 | Antifouling paint composition, antifouling coating film and method for antifouling substrate |
| EP2468825A1 (en) | 2010-12-21 | 2012-06-27 | Akzo Nobel Coatings International B.V. | Antifouling coating composition |
| JP6907856B2 (en) | 2016-10-04 | 2021-07-21 | 信越化学工業株式会社 | Copolymer of (meth) acrylic acid triisopropylsilyl and (meth) acrylic acid derivative and method for producing the same |
| JP6967858B2 (en) * | 2017-02-28 | 2021-11-17 | 中国塗料株式会社 | Antifouling paint composition, its coating film, base material with antifouling coating, fishing net, antifouling method for base material and manufacturing method for base material with antifouling coating |
| CN115772256B (en) * | 2022-12-07 | 2023-09-29 | 珠海市耕海科技有限公司 | Environment-friendly antifouling emulsion and preparation method and application thereof |
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