SG185477A1 - Antifouling paint composition, antifouling coating film, and method for controlling hydrolysis rate of antifouling coating film - Google Patents
Antifouling paint composition, antifouling coating film, and method for controlling hydrolysis rate of antifouling coating film Download PDFInfo
- Publication number
- SG185477A1 SG185477A1 SG2012082384A SG2012082384A SG185477A1 SG 185477 A1 SG185477 A1 SG 185477A1 SG 2012082384 A SG2012082384 A SG 2012082384A SG 2012082384 A SG2012082384 A SG 2012082384A SG 185477 A1 SG185477 A1 SG 185477A1
- Authority
- SG
- Singapore
- Prior art keywords
- antifouling
- coating film
- paint composition
- acid
- acrylic resin
- Prior art date
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- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 166
- 239000000203 mixture Substances 0.000 title claims abstract description 86
- 239000011248 coating agent Substances 0.000 title claims description 97
- 238000000576 coating method Methods 0.000 title claims description 97
- 239000003973 paint Substances 0.000 title claims description 76
- 230000007062 hydrolysis Effects 0.000 title claims description 31
- 238000006460 hydrolysis reaction Methods 0.000 title claims description 31
- 238000000034 method Methods 0.000 title claims description 25
- 239000002519 antifouling agent Substances 0.000 claims abstract description 101
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 77
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 77
- 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 claims abstract description 11
- 229940043810 zinc pyrithione Drugs 0.000 claims abstract description 10
- 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 claims abstract description 5
- 239000002253 acid Substances 0.000 claims description 50
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 32
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 32
- 229940112669 cuprous oxide Drugs 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- 150000007524 organic acids Chemical group 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 150000002430 hydrocarbons Chemical class 0.000 claims description 11
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
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- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 4
- 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 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- XOVSRHHCHKUFKM-UHFFFAOYSA-N s-methylthiohydroxylamine Chemical compound CSN XOVSRHHCHKUFKM-UHFFFAOYSA-N 0.000 claims description 2
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- XNFIRYXKTXAHAC-UHFFFAOYSA-N tralopyril Chemical group BrC1=C(C(F)(F)F)NC(C=2C=CC(Cl)=CC=2)=C1C#N XNFIRYXKTXAHAC-UHFFFAOYSA-N 0.000 abstract description 5
- 125000001424 substituent group Chemical group 0.000 abstract description 2
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- -1 cyclic organic acid Chemical class 0.000 description 36
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 28
- 239000000178 monomer Substances 0.000 description 28
- 239000011230 binding agent Substances 0.000 description 26
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 25
- 230000007774 longterm Effects 0.000 description 21
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- 241001465754 Metazoa Species 0.000 description 17
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- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 14
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- 238000005498 polishing Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
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- 239000010949 copper Substances 0.000 description 8
- 150000002736 metal compounds Chemical class 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 description 6
- 238000010828 elution Methods 0.000 description 6
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- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
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- 239000012188 paraffin wax Substances 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 238000007665 sagging Methods 0.000 description 5
- MHVJRKBZMUDEEV-UHFFFAOYSA-N (-)-ent-pimara-8(14),15-dien-19-oic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)C=C1CC2 MHVJRKBZMUDEEV-UHFFFAOYSA-N 0.000 description 4
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 4
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 4
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 4
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- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
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- 238000002360 preparation method Methods 0.000 description 4
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- SCDFWNDQCMAYQI-UHFFFAOYSA-N octadecan-1-amine;triphenylborane Chemical compound CCCCCCCCCCCCCCCCCCN.C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 SCDFWNDQCMAYQI-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- FIBARIGPBPUBHC-UHFFFAOYSA-N octyl 8-(3-octyloxiran-2-yl)octanoate Chemical compound CCCCCCCCOC(=O)CCCCCCCC1OC1CCCCCCCC FIBARIGPBPUBHC-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229960002969 oleic acid Drugs 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229930000776 pimarane Natural products 0.000 description 1
- GZHFBZCDMVGRTI-DIJYYDPMSA-N pimarane Chemical compound CC1(C)CCC[C@]2(C)[C@H]3CC[C@](CC)(C)C[C@@H]3CCC21 GZHFBZCDMVGRTI-DIJYYDPMSA-N 0.000 description 1
- 239000001739 pinus spp. Substances 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- MHVJRKBZMUDEEV-KRFUXDQASA-N sandaracopimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@@](C=C)(C)C=C2CC1 MHVJRKBZMUDEEV-KRFUXDQASA-N 0.000 description 1
- YZVSLDRKXBZOMY-KNOXWWKRSA-N sandaracopimaric acid Natural products CC(=C)[C@]1(C)CCC[C@]2(C)[C@H]3CC[C@](C)(C=C)C=C3CC[C@@H]12 YZVSLDRKXBZOMY-KNOXWWKRSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229960004274 stearic acid Drugs 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
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- HYVWIQDYBVKITD-UHFFFAOYSA-N tolylfluanid Chemical compound CN(C)S(=O)(=O)N(SC(F)(Cl)Cl)C1=CC=C(C)C=C1 HYVWIQDYBVKITD-UHFFFAOYSA-N 0.000 description 1
- PQSIXYSSKXAOFE-UHFFFAOYSA-N tri(propan-2-yl)silyl prop-2-enoate Chemical compound CC(C)[Si](C(C)C)(C(C)C)OC(=O)C=C PQSIXYSSKXAOFE-UHFFFAOYSA-N 0.000 description 1
- 125000002306 tributylsilyl group Chemical group C(CCC)[Si](CCCC)(CCCC)* 0.000 description 1
- 229960001147 triclofos Drugs 0.000 description 1
- ABVVEAHYODGCLZ-UHFFFAOYSA-N tridecan-1-amine Chemical compound CCCCCCCCCCCCCN ABVVEAHYODGCLZ-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl 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])[H] 0.000 description 1
- SWZDQOUHBYYPJD-UHFFFAOYSA-N tridodecylamine Chemical compound CCCCCCCCCCCCN(CCCCCCCCCCCC)CCCCCCCCCCCC SWZDQOUHBYYPJD-UHFFFAOYSA-N 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- AMHNZOICSMBGDH-UHFFFAOYSA-L zineb Chemical compound [Zn+2].[S-]C(=S)NCCNC([S-])=S AMHNZOICSMBGDH-UHFFFAOYSA-L 0.000 description 1
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1668—Vinyl-type polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1625—Non-macromolecular compounds organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1637—Macromolecular compounds
- C09D5/165—Macromolecular compounds containing hydrolysable groups
Abstract
Disclosed is an antifouling material composition that contains: an acrylic resin that has a predetermined substituent group at a side chain; and at least two types of antifouling agent including a first antifouling agent that is 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile. Further disclosed is an antifouling film formed from said antifouling material composition. Preferably, the antifouling agents include the first antifouling agent and a second antifouling agent selected from zinc pyrithione, copper pyrothione, pyridine triphenylborane, and the like.
Description
Antifouling Paint Composition, Antifouling Coating Film, and Method of
Controlling Hydrolysis Rate of Antifouling Coating Film
The present invention relates to an antifouling paint composition, and more specifically to an antifouling paint composition that allows formation of an antifouling coating film having a constant hydrolysis rate in water. Furthermore, the present invention relates to an antifouling coating film formed from the antifouling paint composition and a method of controlling a hydrolysis rate of the antifouling coating film in water.
Underwater structures such as marine vessels, various fishnets including those is for aquaculture, harbor facilities, oil fences, piping materials, bridges, buoyages, industrial water facilities, and sea bottom bases are exposed at all times in water where living organisms inhabit. Accordingly, as time passes, microorganisms such as bacteria adhere to these underwater structures while plants and animals such as acorn barnacles, sea mussels, sea lettuce, and diatoms that take Hves of these bacteria for food also adhere to these underwater structures, When the surface of the underwater structure is covered with these microorganisms and plants and animals, there occur damages such as corrosion of the covered area, a decrease in fuel efficiency of vessels due to an increase in frictional resistance of vessels to seawaier, massive death of fish and shellfishes due to clogging of fishnets, sinking of a buoyage due to reduced buoyancy, deterioration in operation efficiency, and the like,
In order to prevent adhesion of these harmful organisms, it is general to use a method of painting an antifouling paint containing one or more types of antifouling agents and a binder resin on the surface of the underwater structure to form an antifouling coating film on this surface. Various types of antifouling components each effective as an antifouling agent have been found so far and put into practical usc.
Among others, cuprous oxide (CuO) is known as an animal-resistant antifouling agent that can effectively prevent adhesion of animals such as acorn barnacles and regarded as one of frequently used antifouling agents. Various antifouling paints are proposed b that include cuprous oxide as an antifouling agent or include a combination of cuprous oxide and another antifouling agent having an antifouling effect against algae.
For example, Japanese Patent Laying-Open No. 10-298455 (PTL 1) discloses an antifouling paint composition containing cuprous oxide; bis(Z-pyridinethiol-1-oxide} copper salt; and one type of compounds selected from 2,4,5,6- tetrachloroisophthalonitrile, N,N-dimethyl-dichlorophenylurea, and zinc dimethyl dithiocarbamate. Furthermore, Japanese Patent Laying-Open No. 2001-342432 (PTL 2) discloses, as antifouling agents, a combination of cuprous oxide and 4,5-dichioro-2- n~octyl-3(2H)-isothiazoline; a combination of cuprous oxide and 2-pyridinethiol-1- oxide zinc salt; and a combination of cuprous oxide, 2-pyridinethicl-1-oxide copper salt and zinc ethylenebisdithiocarbamate, and the like.
On the other hand, as a binder resin used for an antifouling paint, a hydrolyzable resin having a hydrolyzable group such as, for example, a metal- containing group in a side chain of the resin has been used in recent years since an antifouling coating film of the hydrolyzable resin is self-polished by gradual! hydrolysis due fo immersion in water, which allows a long-term antifouling property to be exhibited (see PTL 1 and PTL 2 as described above).
PATENT LITERATURE
PTL 1: Japanese Patent Laying-Open No. 10-298455
PTL 2: Japanese Patent Laying-Open No. 2001-342432
Although cuprous oxide (CuO) is an effective antifouling component particularly as an animal-resistant antifouling agent, it is generally necessary to increase the blending amount of cuprous oxide in order to obtain an antifouling paint composition having a sufficiently high antifouling property by using cuprous oxide.
However, in the antifouling paint composition containing a large amount of cuprous oxide and a hydrolyzable resin as a binder resin, the hydrolysis rate of the formed antifouling coating film in water does not become constant, which causes a problem that a high antifouling property cannot be exhibited in a stable manner. Specifically, depending on the type of the hydrolyzable group contained in the hydrolyzable resin, even if the hydrolysis rate was relatively constant in the early stage of immersion in water, the hydrolysis rate sometimes rose rapidly after a lapse of a certain time period of immersion in water, or the hydrolysis rate was constant for a while after immersion in water, but the hydrolysis rate subsequently fell, and self-polishing of the coating film hardly progressed.
Accordingly, an object of the present invention is to provide an antifouling paint composition that allows formation of an antifouling coating film having a constant hydrolysis rate for a long period of time, thereby allowing a high antifouling property to be exhibited for a long period of time {for example, for the entire period during ship navigation) in a stable manner. Also, another object of the present invention is to provide an antifouling coating film formed from the antifouling paint composition, and a method of controlling the hydrolysis rate of the antifouling coating film in water by using the antifouling paint composition.
The present invention provides an antifouling paint composition containing two or more types of antifouling agents containing 4-bromo-2-(4-chlorophenyl}-5- (trifluoromethyl)-1H-pyrrole-3-carbonitrile; and an acrylic resin having a group expressed in a general formula (1) 0 —{Xj—C—O0—M—a (1) (where X is a group expressed in a general formula
Oo —O0— CY — kis QO or 1, Y is a hydrocarbon, M is a divalent metal, and A represents an organic acid residue of a monobasic acid) in a side chain.
It is preferable that the antifouling agents include a first antifouling agent that is a 4-bromo-2-{4-chlorophenyl)-S-{triflucromethyl}- 1 H-pyrrole-3-carbounitrile; and a second antifouling agent that is at least one type selected from the group consisting of zing pyrithione, copper pyrithione, pyridine-triphenyiborane, 1,1-dichloro-N- [(dimethylamino)sulfonyl}-1-fluoro-N-phenylmethanesulfenamide, |,1-dichloro-N- [(dimethylamino)sulfonyl]-1-fluoro-N-{4-methylphenyl) methanesulfenamide, N'-(3,4- dichlorophenyl)-N,N'-dimethylurea, N'-tert-butyl-N-cyclopropyi-6-(methyithio)-1,3,5- triazine-2, 4-diamine, and 4,5-dichlore-2-n-octyi-4-isothiazoling-3-one.
It is preferable that a ratio between a content of the first antifouling agent and a content of the second antifouling agent is within a range from 1/15 to 1/1 in a mass ratio.
The antifouling paint composition of the present invention does not need to contain cuprous oxide as the antifouling agent,
Furthermore, the acrylic resin may further have a group expressed in a general formula (2)
O Rr!
I ee = Oo GR? (2) , (where R', R? and R? are identical or different and each represent a hydrocarbon residue having a carbon number from 1 to 20) in a side chain.
Furthermore, the present invention provides an antifouling coating film formed using the antifouling paint composition of the present invention. Furthermore, the present invention provides a method of controlling a hydrolysis rate of an antifouling coating film in water that is formed on a surface of an object to be coated. The od -
controlling method of the present invention is characterized by using the antifouling paint composition of the present invention as a paint composition forming the antifouling coating film.
According to the antifouling paint composition of the present invention, it becomes possible to form an antifouling coating film that is hydrolyzed at a constant rate for a long period of time, thereby allowing a long-term antifouling performance to be exhibited in a stable manner. Furthermore, according to the antifouling paint composition of the present invention, it becomes possible to form an antifouling coating film that is excellent in long-term antifouling property and also excellent in resistance to cracking, The antifouling paint composition of the present invention can be suitably used as an antifouling paint for preventing fouling on the surface of underwater structures such as marine vessels, various fishnets including those for aquaculture, harbor facilities, oil fences, piping materials, bridges, buovages, industrial water facilities, and sea bottom bases.
Furthermore, according to the method of controlling the hydrolysis rate of the present invention, the hydrolysis rate of the antifouling coating film in water that is formed on the surface of an object to be coated can be rendered constant.
Fig. 1 is a photograph showing an example of the state of the surface of a test plate after an antifouling property test {organism adhesion test) (24 months after iumersion).
The antifouling paint composition of the present invention includes a hydrolyzable resin having a specific hydrolyzable group that is a binder resin, the first antifouling agent that is 4-bromo-2-(4-chlorophenyl}-S-(trifluoromethyl)-1 H-pyrrole- 3-carbonitrile, and one type or two or more types of antifouling agents different from the first antifouling agent. The antifouling coating film formed from such an antifouling paint composition hydrolyzes at a constant rate for a long period of time in water, especially in seawater. Therefore, according to the antifouling paint composition of the present invention, it becomes possible to obtain a coating film that exhibits a high antifouling performance for a long period of time in a stable manner.
Furthermore, the antifouling coating film formed from the antifouling paint composition of the present invention is excellent in long-term antifouling property and also in resistance to cracking. For example, when an antifouling paint composition is applied to a marine vessel and the like, an antifouling coating film is repeatedly exposed to a cycle of immersion in seawater for a certain time period and landing after this immersion in seawater. Therefore, the antifouling coating film is required to have flexibility sufficient to withstand such a condition. According to the present invention, it becomes possible to form an antifouling coating film that hardly undergoes cracking even after repetition of such a cycie. Each component contained in the antifouling paint composition of the present invention will be hereinafter described in detail. <Binder Resin>
The binder resin used for an antifouling paint composition of the present invention is an acrylic resin (hereinafter referred to as an acrylic resin (A)) having a group expressed in a general formula (1} below in a side chain.
OQ
—XF—C—0—N—A (1) k
Here, X is a group expressed in a general formula 0 ee Qe GY where kis 0 or 1, Y is a hydrocarbon, M is a divalent metal, and A represents an organic acid residue of a monobasic acid.
Generally, acrylic resin (A) exhibits such a property as being gradually hydrolyzed in water (particularly, in sea water), owing to hydrolyzability of metal ester bond included in the group expressed in the general formula (1) above. Therefore, the antifouling coating film formed from such an antifouling paint composition containing the acrylic resin as a binder resin has its surface self-polished by being immersed in water, thereby causing an antifouling component (antifouling agents, and a metal component and an organic acid component generated by hydrolysis of the metal ester bond) to be continuously released from the surface of the coating film. Therefore, antifouling performance is exhibited until the coating film is completely consumed.
However, the present inventors’ studies showed that the antifouling coating film formed from an antifouling paint composition containing acrylic resin (A) as a binder resin and cuprous oxide as a main component of the antifouling agent exhibits a constant hydrolysis rate for a while after immersion in water, but the hydrolysis rate subsequently falls and self-polishing of the coating film hardly progresses, with the result that sufficiently high antifouling performance cannot be exhibited for a long period of time. It is considered that such a phenomenon is caused by interaction between the metal ester portion of the group expressed in the general formula (1) above and cuprous oxide. In other words, it is considered specifically as follows. Even if hydrolysis of the metal esier portion smoothly progresses in the early stage of immersion in water, when self-polishing of the coating film progresses to some extent, the ionized cuprous oxide comes to show a certain interaction with the side chain expressed in the general formula (1) above. This causes a stronger interaction between the metal ester portion and cuprous oxide, thereby making it less likely to cause hydrolysis of the metal ester portion. Consequently, renewability of the coating film by hydrolysis becomes poor,
In the present invention, in order to solve the above-described problems, the antifouling agent described below in detail is used together with acrylic resin (A). By using this antifouling agent, even when acrylic resin (A) is used as a binder resin, the hydrolysis rate of the antifouling coating film can be kept constant for a long period of time, so that high antifouling performance can be exhibited for a long period of time in a stable manner.
Examples of acrylic resin (A) used in the present invention may include an acrylic resin having a group expressed in the general formula (1) above asa hydrolyzable group in a side chain and not having a group expressed in the general formula (2) below in a side chain (this acrylic resin will be hereinafter referred to as an acrylic resin (A1)); an acrylic resin having both of a group expressed in the general formula (1) above and a group expressed in the general formula (2) below as a hydrolyzable group in a side chain (this acrylic resin will be hereinafter referred to as an acrylic resin (A2)); and the like. Each of these resins may be used alone or in combination with two or more types of resins. Furthermore, acrylic resin (Al) and acrylic resin (A2) may be used together. In the present specification, the "acrylic resin” means a resin, at least a part of which is composed of a constitutional unit derived from a (meth)acrylic acid or a derivative thereof, or (meth)aerylic ester. The derivative of a (methacrylic acid also includes a (meth)acrylic acid metal sali. 1 rm Ge Gm SRE (2)
R3 (where R', R* and R” are identical or different and each represent a hydrocarbon residue having a carbon number from | to 20). [Acrylic Resin (A1)]
Acrylic resin (Al} is an acrylic resin having a group expressed in the general formula (1) above as a hydrolyzable group in a side chain and not having a group expressed in the general formula (2) above in a side chain, which is typically an acrylic resin having only a group expressed in the general formula (1) above as a hydrolyzable group in a side chain. In the general formula (1) above, M is a divalent metal and, for example, may be 3A to 7A, 8 and 1B to 7B group elements in the periodic table.
Among them, M is preferably copper or zinc.
In the general formula (1) above, A is an organic acid residue of a monobasic acid. Monobasic acid may be preferably, for example, a monobasic cyclic organic acid and the like. Monobasic cyclic organic acid is not particularly limited, but may be, for example, not only those having a cycloalkyl group such as naphthenic acid but also a resin acid such as a tricyclic resin acid, a salt thereof, and the like. Tricyelic resin acid is not particularly limited, which may be, for example, a monobasic acid having a diterpene-based hydrocarbon skeleton and the like, and examples thereof may be a compound having an abietane, pimarane, isopimarane, or labdane skeleton, and more specifically, examples thereof may be abietic acid, neoabietic acid, dehydroabietic acid, hydrogenated abietic acid, palustric acid, pimaric acid, isopimaric acid, levopimaric acid, dextropimaric acid, sandaracopimaric acid, and a salt thereof, and the like. Among these, abietic acid, hydrogenated abietic acid, and a salt thereof are preferred, because hydrolysis moderately oceurs, which leads to an excellent long- i0 term antifouling property and also excellent resistance to cracking of a coating film and availability, Furthermore, a monobasic cyelic organic acid may preferably have an acid value of 120 10 220 mgKOH/g. By using a monobasic cyclic organic acid having an acid value of not more than 220 mgKOH/g, the viscosity of the obtained binder resin (Al) can be lowered, thereby reducing the solvent content in the paint to be obtained.
This is because the viscosity of binder resin (Al) greatly depends on the interaction between functional groups expressed in general formula (1). Binder resin (Al) obtained by using a monobasic cyclic organic acid having an acid value of not more than 220 mgKOH/g tends to cause an increase in steric repulsion of the monobasic cyclic organic acid, In addition, it is considered that this steric repulsion acts to inhibit the interaction between the functional groups expressed in the general formula {1}, with the result that the viscosity of binder resin {Al) can be lowered. Furthermore, when the acid value is less than 120, the binder resin (Al) to be obtained becomes too hydrophobic, thereby preventing hydrolysis of the obtained coating film, which is not preferable.
The monobasic cyclic organic acid described above does not have to be highly purified, and for example, turpentine, a resin acid of a pine, or the like can also be employed. Examples thereof can include rosin, hydrogenated rosin, disproportionated rosin, and the like, as well as naphthenic acid. The rosin herein refers to gum rosin, wood rosin, tall oil rosin, and the like. The rosin, the hydrogenated rosin, and the digproportionated rosin are preferred because they are inexpensive and readily available and excellent in handleability, and they exhibit a long-term antifouling property. The above-described monobasic cyclic organic acid may be used alone or in combination of two or more types.
Monobasic acids that can be used in the present invention other than the above- described monobasic cyclic organic acids may be, for example, those having a carbon number from | to 20 such as acetic acid, propionic acid, butyric acid, lauryl acid, stearic acid, linolic acid, oleic acid, chloroacetic acid, fluoroacetic acid, and valeric acid.
These monobasic acids may be used alone or in combination of two or more types.
Y in the general formula (1) above is pot particularly limited as long as itis a hydrocarbon, and examples thereof may be a residue obtained when dibasic acid such as phthalic acid, succinic acid and maleic acid are added to a polymerizable unsaturated organic acid monomer.
A method of producing acrylic resin (Al} is not particularly Hmited, and examples thereof include (i) a method of causing reaction among a resin obtained by polymerization of a polymerizable unsaturated organic acid and another copolymerizable unsaturated monomer, a monobasic acid and a metal compound; and (ii) a method of causing reaction among a polymerizable unsaturated organic acid, a metal compound and a monobasic acid or causing reaction between a polymerizable unsaturated organic acid and a metal salt of a monobasic acid, and thereafter polymerizing the obtained metal containing unsaturated monomer and another copolymerizable unsaturated monomer; and the like. The same resin structure is provided in each of the resin oblained in the process of the method {i}, that is, the resin obtained by polymerization of a polymerizable unsaturated organic acid and another copolymerizable unsaturated monomer; and the resin obtained by causing reaction among a polymerizable unsaturated organic acid, a metal compound and a monobasic acid or causing reaction between a polymerizable unsaturated organic acid and a metal salt of a monobasic acid, and thereafter polymerizing the obtained metal containing unsaturated monomer and another copolymerizable unsaturated monomer in accordance with the method (ii), and further hydrolyzing its side chain expressed in the general formula (1). These resins are alse collectively referred to as a "base acrylic resin (al}" in the present specification.
Polymerizable unsaturated organic acid in the above-described methods (i) and (ii} is not particularly limited, and examples thereof include a polymerizable unsaturated organic acid having ene or more carboxy! groups, and the like. More specifically, examples of the polymerizable unsaturated organic acid include an unsaturated monobasic acid such as (methacrylic acid; an unsaturated dibasic acid and monoalkyl ester thereof such as maleic acid and monoalky! ester thereof, itaconic acid and monoalkyl ester thereof; a dibasic acid adduct of unsaturated-monobasic acid hydroxy alkyl ester such as a maleic acid adduct of 2-hydroxyethyl (methjacrylate, a phthalic acid adduct of 2-hydroxyethyl (meth)acrylate, a succinic acid adduct of 2- hydroxyethyl (methjacrylate. These polymerizable unsaturated organic acids may be used alone or in combination of two or more types. Furthermore, in the method (ii), a part or all of the metal containing unsaturated monomer may be replaced with a divalent metal di{meth)acrylate and then used, When divalent metal di{fmeth)acrylate is used, a resin has a cross-linking structure via the group expressed in the general formula (1), and this resin can also be used.
The above-described another copolymerizable unsaturated monomer is not particularly limited, and examples thereof may be, as (methacrylic esters, {methacrylic acid alky! ester with an ester portion having a carbon number from 1 to 20 such as methyl (meth)acrylate, ethy! (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, -buty] (methacrylate, t-butyl (meth)acrylate, 2-ethythexyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (methacrylate; hydroxy! group- containing {imeth)acrylic acid alkyl ester with an ester portion having a carbon number from 1 to 20 such as 2-hydroxypropy! {(methjacrylate and 2-hydroxyethyl {meth)acrylate; (meth)acrylic acid cyclic hydrocarbon ester such as phenyl (meth}acrylate and cyclohexyl (methacrylate; (methacrylic acid polyalkyleneglycol ester such as polyethyleneglycol mona(methjacrylate and polyethyleneglycol mono
{methacrylate representing a degree of polymerization of 2 to 10; alkoxyalkyl (meth)acrylate having a carbon number from 1 to 3; (meth)acrylamide; a vinyl compound such as styrene, a-methylstyrene, vinyl acetate, vinyl propionate, vinyl benzoate, vinyltoluene, and acrylonitrile; crotonic acid esters; diester of unsaturated 3 dibasic acid such as maleic acid diesters and itaconic acid diesters. The ester portion of (methacrylic esters described above is preferably an alkyl group having a carbon number from 1 to 8, and more preferably an alkyl group having a carbon number from 1 to 6, which is preferably methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and cyclohexyl (methacrylate. These may be used alone or in 16 combination of two or more types.
The above-described metal compound is not particularly limited, and examples thereof include metal oxide, metal hydroxide, metal chioride, metal sulfide, basic metal carbonate, acetic acid metal salt, and the like. Also, the monobasic acid described above is not particularly limited, and examples thereof may be those as described above.
Although the number average molecular weight (GPC, in terms of polystyrene) of base acrylic resin {al) described above is not particularly limited, it is preferably 2000 or more and 100000 or less, and more preferably 3000 or more and 40000 or less.
The number average molecular weight less than 2000 may cause deterioration in the film forming performance of the coating film while the number average molecular weight exceeding 100000 may cause deterioration in the storage stability of the obtained paint, which is not only suitable for practical use, but also not preferable in terms of public health and economical efficiency since a large amount of dilution solvents needs to be used during coating.
Acrylic resin (Al) contains at least one group expressed in general formula (1).
By adjusting the content of the group expressed in the general formula (1), the elution rate of the coating film into water (hydrolysis rate of the coating film) can be controlled at a desirable elution rate. The content of the group expressed in the general formula (1) above can be mainly adjusted by adjusting the acid value of base acrylic resin (al), and the acid value of base acrylic resin (al) is preferably 100 to 250 mgKOH/g.
When the acid value is less than 100 mgKOH/g, the amount of metal salt bonded to a side chain is decreased, which may deteriorate the antifouling property. When the acid value exceeds 250 mgKOH/g, the elution rate becomes too high, and accordingly, a long-term antifouling property tends to be hardly achieved. [Acrylic Resin (A2)]
Acrylic resin {A2) has hoth of a group expressed in the general formula (1) above and a group expressed in the general formula (2) above each as a hydrolyzable group in a side chain. In the general formula (2) above, R', R? and R® are identical or different and each represent a hydrocarbon residue having a carbon number from | to iG 20, and specific examples thereof include a linear or branched alkyl group having a carbon number not more than 20, such as a methyl] group, an ethyl group, an propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t- butyl group, a pentyl group, a hexyl group, a heptyl group, an octy! group, a nonyl group, a decyl group, an undecyi group, a dodecyl! group, a tridecyl group, and a tetradecy! group; a cyclic alkyl group such as a cyclohexyl group and a substituted cyclohexyl group; an aryl group, a substituted aryl group, and the like. Examples of the substituted aryl group include an aryl group substituted with halogen, an alkyl group having a carbon number up to around 18, an acyl group, a nitro group, an amino group, or the like, and the like. Among these, since a stable polishing rate (polishing speed) can be exhibited in the obtained coating film and antifouling performance can be maintained in a stable manner for a long period, an isopropyl group and the like are preferable.
A method of producing acrylic resin (A2) is not particularly limited, and examples thereof include a method (1) of causing reaction among a resin obtained by polymerization of a polymerizable unsaturated organic acid, a monomer component having a triorganosily! group and another copolymerizable unsaturated monomer, a monobasic acid and a metal compound; and a method (IT) of polymerization of a metal- containing unsaturated monomer obtained by causing reaction among a polymerizable unsaturated organic acid, a metal compound and a monobasic acid or reaction between a polymerizable unsaturated organic acid and a metal salt of a monobasic acid; a monomer component having a triorganosily] group; and another copolymerizable unsaturated monomer; and the like. The same resin structure is provided in each of the resin obtained in the process of the method (I), that is, the resin obtained by b polymerization of a polymerizable unsaturated organic acid, a monomer component having a triorganosily] group and another copolymerizable unsaturated monomer, and the resin obtained by polymerization of a metal-containing unsaturated monomer obtained by causing reaction among a polymerizable unsaturated organic acid, a metal compound and a monobasic acid or reaction between a polymerizable unsaturated organic acid and a metal salt of a monobasic acid; a monomer component having a triorganosilyl group; and another copolymerizable unsaturated monomer in accordance with the method (ID), and thereafter hydrolyzing its side chain expressed in the general formula (13. These resins are also collectively referred to as a "base acrylic resin (a2)" in the present specification.
As the monomer component having the triorganosilyl group described above, triorganosilyl (methjacrylate expressed in a general formula (3) below can be preferably used.
ZO R*
Ll
HC==C—C—0—S8i—R?® (3)
Re
In triorganosityl (meth)acrylate expressed in the general formula (3), Z represents a hydrogen atom or a methyl group. The above-described RY, R® and R® are identical or different and each represent a hydrocarbon residue having a carbon number from 1 to 20, and examples thereof may be a hydrocarbon residue similar to those of R',
R* and R® described above.
Specific examples of triorganosilyl (methacrylate expressed in the general formula (3) above are not particularly limited, and include trimethylsilyl(meth)acrylate, triethylsilyl (methacrylate, tri-n-propylsilyl (meth)acrylate, tri-i-propylsilyl
(meth)acrylate, tri-n-butylsilyl (methjacryiate, tri-i-butylsilyl (methjacrylate, tri-s- butylsilyl (methacrylate, tri-n-amylsilyl (meth)acrylate, tri-n-hexyl silyl (meth)acrylate, tri-n-octylsilyl (methacrylate, tri-n-dodecylsilyl (methacrylate, triphenylsilyl {meth)acrylate, tri-p-methyiphenylsilyl (methjacrylate, tribenzyisilyl (meth)acrylate, ethyldimethyisilyl (methacrylate, n-butyldimethylsilyl (methjacrylate, di-i-propyl-n- butylsilyl (meth)acrylate, n-octyldi-n-butylsilyl {(methjacrylate, di-i-propylstearylsiiyt (meth)acrylate, dicyclohexyl-phenylsilyl (meth)acrylate, t-butyldiphenylsilyl (meth)acrylate, lauryl-diphenylsilyl (methacrylate, t-butyl-m-nitrophenylmethylsilyl (methacrylate, and the like. Among them, tri-i-propylsilyl (methjacrylate is preferable since it can maintain a stable polishing rate (polishing speed) for a long period of time. These triorganosilyl {meth)acrylates may be used alone or in combination of two or more types.
Examples of polymerizable unsaturated organic acid, another copolymerizable unsaturated monomer, metal compound, and monobasic acid as described ahove may be those described with regard to acrylic resin (Al). These polymerizable unsaturated organic acid, another copolymerizable unsaturated monomer and the like may be used alone or in combination of two or more types.
The number average molecular weight (GPC, in terms of polystyrene) of the above-described base acrylic resin (a2) is not particularly limited, and is preferably 2000 or more and 100000 or less, and more preferably 3000 or more and 40000 or less.
The number average molecular weight less than 2000 may cause deterioration in the film forming performance of the coating film while the number average molecular weight exceeding 100000 may cause deterioration in the storage stability of the obtained paint, which is not only suitable for practical use, but also not preferable in terms of public health and economical efficiency since a large amount of dilution solvents needs to be used during coating.
Acrylic resin (A2) has af least one group expressed in the general formula (1) above and at least one side chain expressed in the general formula (2) above. By adjusting the total content of the groups expressed in the general formula (1) and the general formula (2), the elution rate of the coating film into water (hydrolysis rate of the coating film) can be controlled at a desirable elution rate. The total content of the groups expressed in the general formula (1) and the general formula (2) can be adjusted mainly by adjusting the acid value of base acrylic resin (a2), which is preferably set at 3 30 to 200 mgKOH/g. When the acid value is less than 30 mgKOH/g, the amount of metal salt to be bonded to a side chain is decreased, which may deteriorate the antifouling property. When the acid value exceeds 200 mgKOH/g, the elution rate becomes too high, and accordingly, a long-term antifouling property tends to be hardly achieved.
In the present invention, binder resins other than the above-described acrylic resin {A) may be used as a binder resin. By a combination use of other binder resins, the antifouling performance or resistance to cracking of a coating film may be further improved, and the physical properties and the consumption rate of the coating film can be more readily adjusted. Examples of other binder resins include chlorinated paraffin, 18 polyvinyl ether, polypropylene sebacate, partially hydrogenated terphenyl, polyvinyl acetate, poly (methjacrylic acid alkyl esters, polyether polyol, alkyd resin, polyester resin, polyvinyl chioride, silicone oil, wax; Vaseline; liquid paraffin, rosin, hydrogenated rosin, naphthenic acid, an aliphatic acid, a divalent metal salt thereof, and the like. Particularly, chlorinated paraffin, rosin and hydrogenated rosin are preferably used. Other binder resins may be used alone or in combination of two or more types.
The amount of use of other binder resins described above can be set at 0 to 150 parts by mass with respect to 100 parts by mass of acrylic resin {A} in a mass ratio based on the resin solid content. In consideration of improving effects for the antifouling performance and the resistance to cracking and the like, it is preferable to set the amount of use of other binder resins at 0 to 100 parts by mass with respect to 100 parts by mass of acrylic resin (A.
Furthermore, the antifouling paint composition of the present invention may contain a hydrolyzable resin other than acrylic resin (A) as a binder resin. Examples of hydrolyzable resins other than acrylic resin {A) include an acrylic resin (B) having a group expressed in the general formula (2) above in a side chain and not having a group expressed in the general formula (1) above. Although the coating film containing acrylic resin (BB) as a binder resin exhibits a relatively constant hydrolysis rate in the b carly stage of immersion in water, the hydrolysis rate tends to subsequently rise abruptly. Accordingly, in order to form an antifouling coating film that is hydrolyzed at a constant rate for a long period of time, the content of acrylic resin (B) is preferably not more than 50 parts by mass, and more preferably not more than 30 parts by mass, with respect to 100 parts by mass of acrylic resin (A) in a mass ratio based on the resin solid content.
In the antifouling paint composition of the present invention, the content of the binder resin is preferably 30 to 70 mass %, and more preferably 40 to 65 mass %, in the solid content contained in the antifouling paint composition. When the content is less than 30 mass %, defects such as cracks or peel-off may occur in the coating film.
Furthermore, when the content exceeds 70 mass %, a desirable antifouling effect tends to be hardly achieved. It is to be noted that the solid content contained in the antifouling paint composition means the total components contained in the antifouling paint composition other than the solvent. <Antifouling Agent>
The antifouling paint composition of the present invention contains two or more types of antifouling agents including 4-bromo-2-(4-chlorophenyl)-5-(trifiuoromethyl)- 1 H-pyrrole-3-carbonitrile (which will be hereinafter referred to as the first antifouling agent) expressed in the formula (4) below.
NC Br 7
NA p @
N ° aA H
The above-described first antifouling agent is an antifouling component that is effective as an animal-resistant antifouling agent. Therefore, by using the first antifouling agent, use of cuprous oxide conventionally frequently used can be completely eliminated or significantly reduced. Consequently, the hydrolysis rate of the antifouling coating film containing an acrylic resin (A) as a binder resin can be set at a constant rate for a long period of time. Furthermore, as cuprous oxide is not used or reduced, the specific gravity of the antifouling paint can be lowered while limitation on the material of the object to be coated can be alleviated. Since the antifouling paint containing cuprous oxide causes corrosion of an aluminum base material, it could not be used for an aluminum object to be coated. The antifouling paint composition of the present invention however can be used also for such an object to be coated without limitation. Furthermore, the blending amount of cuprous oxide that shows redness is reduced, it becomes possible to adjust the color of a coating film to be obtained.
The antifouling paint composition of the present invention contains at least one type of the second antifouling agents in addition to the above-described first antifouling agent. This allows formation of an antifouling coating film exhibiting a high antifouling property against not only aquatic animals but also plants such as algae, and having an excellent antifouling performance against the entire aquatic organisms. As the second antifouling agent, it is preferable to employ an antifouling component that exhibits a high antifouling property against aquatic plants such as algae, and examples thereof include zinc pyrithione (2-pyridinethiol-1-oxide zinc salt); copper pyrithione (2- pyridinethiol-1-oxide copper salt); triphenylborane-amine complexes such as pyridine- triphenylborane; 1,1-dichloro-N-[{dimethylamino)suifonyl]-1-fluoro-N- phenylmethanesulfenamide; 1,1-dichloro-N-[{dimethylamino)sulfonyl}-1-fluoro-N-{4- methylphenyl) methanesulfenamide; 4,5-dichloro-2-n-octyi-4-isothiazoline-3-one; N'- (3,4-dichlorophenyl)-N,N'-dimethylurea; and N'-tert-butyl-N-cyclopropyi-6- (methylthio)-1,3,5-triazine 2,4-diamine; and the like. These may be used alone or in combination of two or more types.
The triphenylborane-amine complex is a complex formed from triphenyliborane and an amine. The amine is not particularly limited, and examples thereof include primary amine such as n-propylamine, n-butylamine, n-hexylamine, n-octylamine, n-
decylamine, n-dedecylamine, n-tridecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine, aniline, and toluidine; secondary amine such as di-n-butylamine, di- n-hexylamine, di-n-octylamine, di-n-decylamine, di-n-dodecylamine, di-n- tridecylamine, di-n-tetradecylamine, di-n-hexadecylamine, di-n-octadecylamine, and diphenylamine; tertiary amine such as tri-n-propylamine, tri-n-hexylaroine, tri-n- octylamine, tri-n-decylamine, tri-n-dodecylamine, tri-n-tridecylamine, tri-n- tetradecylamine, tri-n-hexadecylamine, tri-n-octadecylamine, and triphenylamine; pyridines such as pyridine or pyridine with a substituent on the ring, such as pyridine, 2-picoline, 3-picoline, 4-picoline, 2-chloropyridine, 3-chloropyridine, and 4- i0 chloropyridine.
Among others, pyridine-triphenylborane containing pyridine as an amine is excellent in antifouling property, and therefore, preferably used.
The antifouling paint composition of the present invention can include, for example, cuprous oxide, cuprous thiocyanate {copper rhodanide) or the like as the second antifouling agent, in addition to the components described above, However, when cuprous oxide is used as a main component of the antifouling agent, the antifouling coating film that is hydrolyzed at a constant rate cannot be obtained as described above. Accordingly, when using cuprous oxide, it is preferable that the content of cuprous oxide is set at 15 mass % or less in the solid content contained in the 28 antifouling paint composition, and more preferable that cuprous oxide is not contained.
Furthermore, also when cuprous thiocyanate (copper rhodanide) is used in large amount, there occurs the same phenomenon as that in the case of cuprous oxide.
Accordingly, when using cuprous thiocyanate, it is preferable that the content of cuprous thiocyanate is set at 15 mass % or less in the solid content contained in the antifouling paint composition, and more preferable that cuprous thiocyanate is not contained.
The content of the first antifouling agent is preferably 1 to 60 mass %, and more preferably 3 to 50 mass %, in the solid content contained in the antifouling paint composition. When the content is less than 3 mass %, sufficient antifouling performance against aquatic animals tends to be hard to be achieved. When the content exceeds 60 mass %, defects such as cracks or peel-off may occur in the obtained coating film.
The content of the second antifouling agent (the total amount of antifouling agents other than the first antifouling agent) is preferably 5 to 60 mass %, and more preferably 10 to 55 mass %, in the solid content contained in the antifouling paint composition. When the content is less than 5 mass %, it is less likely to obtain an antifouling paint composition having excellent antifouling performance against the entire aquatic organisms. Furthermore, when the content exceeds 60 mass %, defects such as cracks or peel-off may occur in the obtained coating film.
The total content of the first antifouling agent and the second antifouling agent is preferably § to 70 mass %, and more preferably 10 to 60 mass %, in the solid content contained in the antifouling paint composition. When the total content is less than 5 mass %, it is less likely to obtain an antifouling paint composition excellent in long- i5 term antifouling property. Furthermore, when the total content exceeds 60 mass %, defects such as cracks or peel-off may occur in the coating film.
The ratio {mass ratio) between the content of the first antifouling agent and the content of the second antifouling agent (the total amount of antifouling agents other than the first antifouling agent) is preferably 1/15 to 1/1, and more preferably 1/12 to 1/2. When the mass ratio is less than 1/13, the animal-resistant antifouling property tends to deteriorate. Furthermore, when the mass ratio exceeds 1/1, the algae-resistant antifouling property tends to deteriorate. <Qther Additives>
The antifouling paint composition of the present invention may contain commonly used additives such as a plasticizer, a pigment and a solvent. Examples of plasticizers include phthalate-ester-based plasticizers such as dioctyl phthalate, dimethyl phthalate and dicyclohexyl phthalate; an aliphatic-dibasic-acid-ester-based plasticizer such as isobutyl adipate and dibutyl sebacate; glycol-ester-based plasticizers such as diethylene glyco! dibenzoate and pentaerythrito! alkyl ester; phosphoric-ester-
based plasticizers such as iricresyl phosphate and trichloroethyl phosphate; epoxy- based plasticizers such as epoxy soybean oil and octyl epoxy stearate; organic-tin-based plasticizers such as dioctyltin laurate and dibutyltin laurate; triocty] trimellitate, triacethylene, and the like. These plasticizers may be used alone or in combination of two or more types.
Examples of pigments include extenders such as precipitated barium, talc, clay, chalk, silica white, alumina white and bentonite; color pigments such as titanium oxide, zirconium oxide, basic lead sulfate, tin oxide, carbon black, graphite, red iron oxide (colcothar), chrome yellow, phthalocyanine green, phthalocyanine blue, and quinacridone. These pigments may be used alone or in combination of two or more types.
Examples of solvents include hydrocarbons such as toluene, xylene, ethylbenzene, eyclopentane, octane, heptane, cyclohexane, and white spirit; ethers such as dioxane, tetrahydrofuran, ethyleneglycol monomethyl! ether, ethyleneglyeol monoethy! ether, ethyleneglycol monobatyl ether, ethyleneglycol dibutyl ether, diethyleneglycol monomethyl ether, and diethyleneglycol monoethy! ether; esters such as butyl acetate, propy! acetate, benzyl acetate, ethyleneglycol monomethyl ether acetate, and ethyleneglycol monoethyl ether acetate; ketones such as ethyl isobutyl ketone and methyl isobutyl ketone; alechols such as n-butanol! and propyl alcohol; and the like. These solvents may be used alone or in combination of two or more types.
In addition to the above, for example, the following agents may be added, such as monoester of dicarboxylic acid such as monobutyl phthalate, monoocty! succinate, camphor, castor oil; a water binder, an anti-sagging agent, an anti-floating agent, an anti-settling agent, a defoaming agent, and the like.
The antifouling paint composition of the present invention can be prepared, for example, by adding, to the above-described binder resin, the above-described antifouling agent and, as required, commonly used additives such as a plasticizer, a coating film consumption control agent, a pigment, and a solvent, and mixing the resultant using a mixer such as a ball mill, a pebble mill, a roll mili, or a sand grind mill.
The antifouling coating film can be formed by applying the obtained antifouling paint composition to the surface of the object to be coated in accordance with an ordinary method, and then, volatilizing and removing a solvent at room temperature or under heating. Examples of objects to be coated are not particularly limited, but include underwater structures such as marine vessels, various fishnets, harbor facilities, oil fences, piping materials, bridges, and sea bottom bases. Since the antifouling coating film formed using the antifouling paint composition of the present invention is hydrolyzed at a constant rate for a long period of time, it can exhibit high antifouling performance for a long period of time in a stable manner. Furthermore, the antifouling coating film formed using the antifouling paint composition of the present invention has such an enhanced long-term antifouling property and is excellent in resistance to cracking.
Although the present invention will be hereinafter described in greater detail with reference to Examples and Comparative Examples, the present invention is not limited thereto. (Production Example 1) Preparation of Acrylic Resin Varnish
In a four-neck flask including a stirrer, a cooler, a temperature control device, a nitrogen introduction pipe, and a dropping funnel, 64 parts by mass of xylene and 16 parts by mass of n-butanol were added, and a temperature thereof was kept at 100°C.
In this solution, a mixture solution composed of monomers in accordance with a formulation (parts by mass) in Table 1 and 2 parts by mass of i-butylperoxy-2- ethylhexanoate was dropped at a constant velocity for 3 hours. After dropping ended, the temperature of the mixture solution was kept for 30 minutes. Thereafter, a mixture solution composed of 16 parts by mass of xylene, 4 parts by mass of n-butanol and 0.2 parts by mass of t-butylperoxy-2-ethylhexanocate was dropped at a constant velocity for 30 minutes. After dropping ended, the temperature of the mixture solution was kept for | hour and 30 minutes. A resin varnish I was thus obtained.
The solid content of the obtained resin varnish I was 49.8 mass % and viscosity was 4.4 _22.
poises. Furthermore, the acid value of resin in this resin varnish I was 130. Table 1 summarizes the acid value of the obtained resin and the solid content of resin varnish L
The abbreviations of monomers described in Table 1 shows the following compounds. {DY EA: ethyl acrylate 3 (2) CHMA: evclohexyl methacrylate {3} CHA: cyclohexyl acrylate {4) M-90G: methoxypolyethyleneglycol methacrylate ester (NK ester M-90G, manufactured by Shin-Nakamura Chemical Co., Ltd.) {5) MMA: methyl methacrylate 16 (6) AA: acrylic acid {7 MAA: methacrylic acid (8) TIPSA. tritsopropylsilyl acrylate
Then, in a similar reaction vessel, 100 parts by mass of resin varnish I, 25.4 parts by mass of zinc acetate, 39.2 parts by mass of naphthenic acid (NA-163, acid value of 165, manufactured by Daiwa Yushi Kogyo), and 110 parts by mass of xylene were added, and the mixture was heated to 130°C to thereby remove acetic acid together with the solvent. Thus, an acrylic resin varnish 1 having a solid content of 41.5 mass Yo was obtained. Viscosity was 12.3 poises. {Production Example 2) Preparation of Acrylic Resin Vamish 2
In the reaction vessel similar to that in production example 1 described above, 64 parts by mass of xylene and 16 parts by mass of n-butanol were added, and a temperature thereof was kept at 115°C. In this solution, a mixture solution composed of monomers in accordance with a formulation (parts by mass) in Table 1 and 3 parts by mass of t-butylperoxy-2-ethylhexanoate was dropped at a constant velocity for 3 hours. After dropping ended, the temperature of the mixture solution was kept for 30 minutes. Thereafter, a mixture solution composed of 16 parts by mass of xylene, 4 parts by mass of n-butanol and 0.2 parts by mass of t-butylperoxy-2-ethylhexanoate was dropped at a constant velocity for 30 minutes. After dropping ended, the temperature of the mixture solution was kept for 1 hour and 30 minutes. A resin varnish [1 was thus obtained. The solid content of the obtained resin vamish II was 49 7 mass % and viscosity was 9.5 poises. Furthermore, the number average molecular weight (GPC, in terms of polystyrene) of the resin contained in resin varnish
I was 6500 and the acid value was 160. Table 1 summarizes the acid value of the obtained resin and solid content of resin varnish IL
Then, reaction was conducted as in Production Example 1 above except that in a similar reaction vessel, 100 parts by mass of resin varnish II, 29.6 parts by mass of copper acetate, and 14.5 parts by mass of pivalic acid (acid value: 550 mgKOH/g) were added. Thus, an acrylic resin varnish 2 having a solid content of 45.2 mass % was obtained. (Production Example 3) Preparation of Acrylic Resin Varnish 3
In the reaction vessel similar to that in Production Example 1 described above, 64 parts by mass of xylene and 16 parts by mass of n-butanol were added, and a temperature thereof was kept at 115°C. In this solution, a mixture solution composed 13 of monomers in accordance with a formulation (parts by mass) in Table 1 and 2 parts by mass of t-butylperoxy-2-ethylhexancate was dropped at a constant velocity for 3 hours. After dropping ended, the temperature of the mixture solution was kept for 30 minutes. Thereafter, a mixture solution composed of 16 parts by mass of xylene, 4 parts by mass of n-butanol and 0.2 parts by mass of t-butylperoxy-2-ethylhexanoate was dropped at a constant velocity for 30 minutes. After dropping ended, the temperature of the mixture solution was kept for | hour and 30 minutes. A resin varnish TI was thus obtained. The solid content of the obtained resin varnish IIT was 49.6 mass % and viscosity was 6 poises. Furthermore, the number average molecular weight {GPC, in terms of polystyrene) of the resin contained in resin varnish II was 6000 and the acid value was 70 mgKOH/g. Table | summarizes the acid value of the obtained resin and solid content of resin varnish IIL
Then, reaction was conducted as in Production Example | above except that in a similar reaction vessel, {00 parts by mass of resin varnish I11, 12.9 parts by mass of copper acetate and 21.7 parts by mass of hydrogenated rosin (Hypale CH, acid value of
160, manufactured by Arskawa Chemical Industries, Ltd.) were added, and thus, an acrylic resin varnish 3 having a solid content of 50.6 mass % was obtained. (Production Example 4) Preparation of Acrylic Resin Varnish 4
In a reaction vessel as in Production Example | above, 50 parts by mass of xylol was added, and a temperature thereof was kept at 90°C. In this solution, a mixture solution composed of monomers in accordance with a formulation {parts by mass) in Table 1 and 1 part by mass of t-butylperoxy-2-ethylhexanoate was dropped at a constant velocity for 3 hours, After dropping ended, the temperature of the mixture solution was kept for 30 minutes. Thereafter, a mixture solution composed of 7 parts by mass of xylol and 0.2 parts by mass of t-butyiperoxy-2-ethylhexanoate was dropped at a constant velocity for 30 minutes. After dropping ended, the temperature of the mixture solution was kept for 1.5 hours, and cooled to 60 °C, to which 10 parts by mass of xylol was added. An acrylic resin varnish 4 was thus obtained. The solid content of the obtained acrylic resin varnish 4 was 60.0 mass % and viscosity was 7.5 poises.
Furthermore, the number average molecular weight (GPC, in terms of polystyrene) of the resin contained in acrylic resin varnish 4 was 8000, Table 1 summarizes the solid content of acrylic resin varnish 4. {Table 1]
TT } ! Production Production | Production Production
Example] | Example? | Example3 Example 4
Acrylic
Resin Varnish | I | i Itt | Resin
Varnish4
EA 583 | 16.30 2602 | .
CHMA 15.0 15.00 15.00 | -
CHA - | 15.00 . .
Monomer m0 006 00 | 2000 0.00 | - (Parts by | :
Massy | MMA : | 1.17 - 35.0
TAA 67 | 1027 | 898 -
MAA | 2 | : | .
Ts ; - 40.00 650
Acid Value (mgKOH/g) 130 160 | 70 -
Solid Content (Mass %) 49.8 | 49.7 49.6 60.6
<kExamples 1 to 41 and Comparative Examples 1 to 12>
Antifouling paint compositions were prepared by using acrylic resin varnishes 1 to 4 obtained in Production Examples 1 to 4 as described above and other components shown in Tables 2 to 6, and mixing the components with a high-speed disperser. Then, a long-term antifouling property, resistance to cracking, a state of the coating film, and a coating film consumption amount (polishing speed) were evaluated in accordance with the evaluation method below, Details of each component shown in Tables 2 to 6 are as follows. (1) Cuprous oxide: "NC-301" manufactured by NC Tech (2) Zinc white: "Zine Oxide Type 2" manufactured by Sakai Chemical Industry
Co., Ltd. (3) Red iron oxide: "Toda Color KN-R" manufactured by Toda Kogyo Corp. (4) Antifouling agent | (ECONEA): 4-bromo-2-{4~chlorophenyl)-5- (trifluoromethyl) 1 H-pyrrole-3-carbonitrile ("ECONEA" manufactured by Janssen
PMP) (5) Antifouling agent 2 (ZPT): ZPT (zinc pyrithione) ("Zinc OMADINE" manufactured by Arch Chemicals) (6) Antifouling agent 3 (CuPT): CuPT (copper pyrithione) "Copper
OMADINE" manufactured by Arch Chemicals) (7) Antifouling agent 4 (PK) : pyridine-triphenylborane ("PK" manufactured by
Hokko Chemical Industry Co., Ltd) (8) Antifouling agent 5 (YN-18-20} : triphenylborane-n-octadecylamine complex ("YN-18-20" manufactured by Benny Toyama Corporation) (9) Antifouling agent 6 (A4S): 1,1-dichlore-N-[{dimethylamino)sulfonyl]-1- fluoro-N-phenylmethanesulfenamide ("Preventol A4S" manufactured by Lanxess) (10) Antifouling agent 7 (ASS): 1, 1-dichloro-N-[(dimethylamino)sulfonyl}-1- fluoro-N-(4-methylphenylhimethanesulfenamide ("Preventol ASS" manufactured by
Lanxess} (11) Antifouling agent 8 (SN211): 4,5-dichloro-2-n-octyl-4-isothiazoline-3-
one(4,5-dichloro-2-n oetyl-3(2H)isothiazolone) ("SeaNine 211" manufactured by
Rohm and Haas Company) {12) Antifouling agent 9 (AG): N'-(3,4-dichloropheny!}-N N'-dimethylurea ("Preventol A6-AF" manufactured by Lanxess) 8 {13) Antifouling agent 10 (11051): N'-tert-butyl-N-cyclopropyl-6-(methylthio)- 1,3,5-triazine-2,4-diamine ("Irgarol 1051" manufactured by Ciba Specialty Chemicals inc. (14) Antifouling agent 11 (copper rhodanide): cuprous thiocyanate ("Copper
Rhodanide” manufactured by Nihon Kagaku Sangyo Co., Ltd.) 16 (15) Chlorinated paraffin: ("Toyoparax A50" manufactured by Tosoh
Corporation) (16) Wood rosin : ("WW Rosin” manufactured by Arakawa Chemical Industries,
Lid.) (17) Anti-sagging agent: "Disparlon A600-20X" manufactured by Kusumoto
Chemicals, Lid.
[Table 2] et | Example i Unit; Parts by Mass T 7 7 — = —— T
ENENERE
Acrylic Resin Varnish | | 38 | 49 | 38 | sI 37 | 38 | 36 | 38 | 37 3% | 36 | 37
Acrylic Resin Vamish 3 | i | i
Cuprous Oxide CC] | ; zineWite 120 13 lo] 2 [28 29 [29 | 30 | 28 29 | 28
Red fron Oxide To [ess 616 5565s
Antifouling Agent | (ECONEA) HE) 3 Jes | sf 3 4 3003 0 03 L343
TT TT oT menses nse nnn msn nsdn nnn
Antifouling Agent 2 (ZPT) | 9 ity 9 14 | | | | !
Antifouling Agent 3 (CuPT) | PIO | !
Antifouling Agent 4 (PK) CC | | 9 | ]
Antifouting Agent 5 (YN-18-20) | ur CL
Antifouling Agent 6 (A4S) Cl] 9
Antifouling Agent 7 (ASS) CC Te
Antifouling Agent 8 (SN211) | | | | Lo
Antifouling Agent 9 (AG) | Fo | | 10
Antifouling Agent 10 (11051) | | | RE | | | 1
Chiorinaied Paraffin vbr IEEE 1 Pod
Wood Rosin | i | '
Buiyl Cellosolve EE 2 12 12
Total {100 | 100 [ 100 [160 | 100 | 100 100 | 100 | 100 3Months 1 01 6 [0 [of 0 [ol 0 tol 0 [oo 0
Slime/Algae | 18Months | 0 | 0 | © RE ol 0 | 0 o lo io | oo 24Months | © | © | 0 | 0 | © 00 0 61 0 Lo 0 | 0 3 Months o lolol o ol 0 [oo 0 ! Long-Term Antifouling | 6 Months 0 0 0 0 | 0 0 0 a ; 0 0 | 0 0
Property | 2Months | © | 0 | © | 0 | 0 | 0 | © 6 f 0 {6 0 6
An { mal 5 | ot | i | i | i 1 TTT TTT TT TTT TTT TT TTT en {18 Months 6 0 1 0 | ot 0 | a 1 0 . ci ¢ {6 01 0C 24Months | 0 | 0 | 1 0 0 {0 0 fo 0 oo 0 0 Month oOo 0 0 | 0 o Lol o To 0 0 0] 0 3 Months C2 [17 20 | 17 Lie | we 26] 19 | 2 9
Months i8 N 22 17] 20 LATE LA ILL 18 | ©
Amount of | 6Months | 34 | 43 | 33 41 | 32 {34 | 35 136 | 34 | 36 | 37 | 35
Consumption of 9Months | SI | 60 | 49 | 59 | 50 4 56 | S3 | St | 54 | 56 | 58
Coating Film Eee ee — - {Total Amount of |_12 Months 7 BL 68 80 | 68 | 69 | 70 7 70 | | 7a EX 78
Decrease in Thickness | 1SMonths | 88 | 103 | 87 | 10i | 87 | 88 | 90 | 90 | 89 | 90 | 91 | 94 of Coating Film [wm]) | i18Months | 107 | 122 | 108 | 120 | 107 | 109 11i | 112 | 109 | 113 | 110 | 113 21 Months | 126 | 146 | 125 | 142 | 126 | 127 | 128 129 | 126 128 | 132 24 Months | 142 | 169 | 140 | 163 | 141 | 144 | 147 145 | 142 | 142 | 145 | 150
[Table 3] . Example
Unit: Parts by Mass | 7 T— 7 r TTT
Blas Le v7 | 18 ie [20 p21 | 22 | 23] 24
Acrylic Resin Varnish 1 38 | 3% | 3% | 3% | 39 | 38 | 38 | 40 | 38 | 39 | 37 | 38
Acrylic Resin Varnish 2 i | | | : | | i
Acrylic Resin Vamish3 BR A NN AN NN I I “uprous Oxide
Zinc White 20120 0 26 | 29 | 27 | 28 | 28 | 27 [29 | 27 | 29 | 28
Antifouling Agent 2 (ZPT) s | 6 | 5 | I 5s } Antifouling Agent 3 (CuPT) L4 BE
Antifouling Agent 4 (PK) 4 | | | | Co]
Antifouting Agent § (YN-18-20) 5 | | | | CT
Antifouling Agent 6 (A48) 5 i Antifouling Agent 7 (ASS) i EE | § | 5
Antifoufing Agent 8 (SN211) | | 6 Ps 6 | 6 ' : fers meee ee Lp — —
Antifouling Agent 9 (AG) | | | 5 5 i 4 1 5 eee rr rr { Antifouling Agent 10 (11051) i i LS i L414 {4
Anuti-sagging Agent 202) 2 2 2 0 2 2 12 200 02 12 0 2
Buty! Callosolve 2 12] 2 |2 2 jo 2124 2 [22 freee os ’ - rm ere rocco]
Xylene 1010] 9 | 10 we bg [or wun een ee |e or | or | 100 ied Too | 00 [To [100 3Momts | 0] 0 | 0 Jo 6 oo lolol 0 0olo
Long-Term Antifouting | 6 Months | © | 0 0 0 6 0 1 © 0 0 0 : e
Property | 12Months | 0 | 0 0 1061.0 | 0 1 © 0 0 0 0 10
StimefAlgse | asMonths | 0 0 | 0 joi 0 Jo Jo yo fol ojo]
Cl 24Mombs | 0 0 0 foi oo 0 Lo ela 0 0] 0
Months | 070 0 joj oo oto jo] 0 [0]o0
Long-Term Antifouling 6 Months | a 6 1 90 0 Lo to io 0
Property f2Months | 0 | © | © 0 | © 0 0 lo 0] © 6 | 0
Animals iSMontis | 0 | 0] 0 {0 | 0 | © EEE 0 | 0
Z4Months | 0 | 0, 0 0] o | 0 | 0 {06 6 o 0 Month 0 0 oo | ol eo | 0 | 0 [060i 0 0 | 0
Months | 17117] 18 Jas as | as |v lw TE TTT 0 7
Amount of OMonths 4 33 32 | 35 | 3 | 34 | 36 | 37 | 36 [34] 34 | 39 32
Consumptionof | g Months | SO | 55 | 50 | 49; S52 | SI | 54 | ss {so | Si | 5&5 SO
Coating Film TTT pI TTT oS = a ot Amouniof | 2Monts 60 [768 [70 eo Tro TT 0 Th Tan |e | 7s | 6
Decrease in Thickness | 15Months | 87 | 88 | 89 | 89 | 8 | 90 88 900 | 89 [92 | #7 { of Coating Film fpm]) | 18 Months | 109 { 109 | 111 | 110 111 | 109 | 107 | 111 | 109] 111 | 114 | 107 j ETE TT 1 lms mm 1m The Tee Te TI 21 Months | 127 128] 129 | 128 120 | 127 | 127 | 128 | 129] 129 | 131 | 126 “2aMonths | 142] 144 | 143 143 | 144 | 143 | 146 | 144 | 146] 144 | 148 | 147
[Table 4] . : Example i
Unit: Parts by Mass freer emp re p {2s | 26 | 27 | 28 | 29 [30] 31 | 32 | 33 | 34 | 35
Acrylic Resin Vamish bo] 34 B BN ERE Lo i
AcylieResinvamish2 1] 38 | 38 I [5 13s
Acrylic Resin Varnish 3 | | 40 1 39
Acrylic Resin Varnish 4 | | | i = ry ee ee : —
Cuprous Oxide i | i 9 0 | 11 i og
Zinc White [28 | 25 0 26 | 27 | 26 (| 9 | 10 110
Antifouling Agent 2 (ZPT) inl lw] ot] in| ww
Autifouling Agent 3 {CuPT) j -— Na a.
Antifouling Agent 4 (PK) | | i | | i
Antifouling Agent 5 (YN-18-20) i | !
Antifouling Agent 6 (A4S) | | | ;
Antifouling Agent 7 (A355) | i | i i | Lo
Antifouling A 9 (AB) i
Antiowling Agent JAAS) creeper eer ef
Antifouling Agent 10 (11051) | i | i i
Chlorinated Paraffin 2 | 2 2 2 1 Tz !
Wood Rosin 30 Po? P02 | 2 2
Anti-sagging Agent 2 02 2 22 EE 2 2
Butyl Cetlosolve ez Jv pv bn on Lon bor fr pn
Xylene V8 19 F100 | 8 | 10 8 1 1 9 | © 1 14
Total | 100 | 100 | 100 | 100 | 100 | 106 | 100 | 100 | 100 | 100 | 100 3 Months 0 0 1 0 ol oo | o 0 0 | 0 0 0! = momma =m mmmmmnmnrhennnnee i
Long-Term Antifouling 6 Months TL ~ ge 0. 0 0 1.0 oe 8 8
Property 2Months | 0 | 0 0 0 oO Lolo | oo oo 0
StimefAlgac Months | 0 | 6 | 0 oo | 0 oo | 0 | © | 0 | © 0 3 Months 6 ol 0 | 0 o | 0 | 0
Long-Term Antifouling 6 Months 0 | 0 UE epee se 0 +0 10
Property |_12 Months 0 ol oe 0 be o0 oO og 0 | 0
Animals | 18Monthis | 0 | 0 | 0 0 | © o 1 o | 0 — ; i Be Ee
State of Coating Film Al Al ATA A A | A | A : Resistance to Cracking A {ALA | A A Al A | A : © 0 Month 0 JoJo Teo lol0 0 0 | 0 | o : rrr eden : 3 Months 22 25 | 26 | 12 | 15 | 18 | 22 | 28 | 29 to} 15
Amountof ~~ 6Months | 43 49 | 53 | 25 | 3% | 35 | 42 51 | 55 24 | 3 i Consumptionof | 9 Months 63 | 74 | 78 | 36, 44 | 51 | 63 75 | 81 | 36 | 45
Coating Film Tae TT wa Too Tae 1 so 71 | ac - (Total Amount of 12 Moths | VB 98 100 | 49 | 60 | N | 85 j 100 162 |.as 5
Decrease in Thickness | 15 Months | 103 | 122 | 127 89 | 104 | 124 | 130 | 61 | 75 { of Coating Film [um]) | 18 Months | 122 | 349 | 15s | 71 | 92 l1o7 | 122 | 152 | 159 | 73 | 93 2¢ Months | 14] 1 1720 180 | 26 | 107 | i28 | 140 | 175 | 184 | 85 | 108 i 24 Months | 162 | 198 | 203 | 99 | 124 | 143 | 163 | 201 |, 208 | 98 | 126
[Table 5]
EE Emme i ; Example i
Unit: Parts by Mass } - 7 7
Acrylic Resin Varnish I hae a LL i i Acrylic Resin Varnish 2 42 | 40 i ~ { Acrylic Resin Varnish 3 i | 43 | 38
Acrylic Resin Vamish 4 CC
Zinc White NY no] 14 to wg
Red Iron Oxide 6 | 6 | 1 | 8 5
Antifouting Agent 2 (ZPT) in 9 | io
Antifouling Agent 3 (CuPT) | i
Antifouling Agent 4 (PK)
Antifouling Agent 4 (P%) SSS SUSU NUNS SU
Antifouling Agent § (YN-18-20) | i | i
Antifouling Agent 6 (A4S)
Antifouling Agent 7 {A5S) | !
Antifouling Agent 8 (SN211) | | | | i
Antifouling Agent 10 (T1051)
Antifouling Agent 11 (copper rhodanide) 10 | iro oo
Wood Resin | 3 | 2 | 2
Buryl Cellosolve B boro] 1 I 1
Xylene Boon nn
SMonths | 0 | 0 | 0 | 0 | 0
Long-Term Antifouling | _6 Months bo 08] LL 0 ;
Property | 12Months | 0 6 0 0 4 0 10
Slime/Algac | 18 Months | 0 o | © 6, 0 0 3 Months 0 lo | oo 6 | 0 | 0
Long-Term Antifouling | 6 Months UY : 8 6 1 a 0
Property {12 Months 0 | 0 | 0 | 0 0 | 0
An im a is | oon eee TT TTT
AHI | 18 Months g { 0 | 0 I 0 0 | 0 24 Months 0 | 0 0 loo 0 | 0
TA
0 Month 0 | 0 0 | 0 0 0 i 3 Months 12 1 22 28 | 29 11 15
Amount of _ 6Months | 36 | 41 51 [55 32
Consumptionaf ~~ ' 9 Months 52 | 63 74 8 | 35 45 ee _2Montls | 7 {Total Amount of |.12 Months A | se 5 | 118 43 60 of Coating Film fim} | 18 Months 18 74 | 91 21 Months 183 | 85 | 108 24 Months | 144 | 164 | 200 | 208 | 99 | 126
[Table 6] i Unit: Parts hy Mass EE ~ i TTT TTT TTT TNT TTY TTT -
Pol2 io 405 06 7 § 9 {10 arf o1z
Acrylic Resin Varnish 2 | | | 33 | :
Acrylic Resin amish IE EE 4
Acrylic Resin Varnish 4 | P| 4 | 32
Redboowd [7 [a sls 715 3 a 5 aa
AndfoutngAgau3(CubTy fl Ll gw jel 18
I Antifouling Agent 5 (YN-18-20} | | | i i
Antifouling Agent 6 (A485) | rT | | | CC
Antifouling Agent 7 (ASS) | i | BN
Antifouling Agent 10 (11051) | | CC
Anifouling Agent 11 {copper | | | | | | as]
Wood Rosin | Pg 2 4 | | PL 3 412 3
Amti-sagging Agent 2 42 2 02002 F202 2 42 2 02 2
Xylene 12 010 10 134 8 { 4 | 4 4 | 8 4 | 23 14
Long-Term |__6 Months ! | 33 4 8 . ! o | 1. !
Antifouling Property | 12 Months 3003 5 15 6 P01 2 03 0 0 | 3 2
Slime/Algae 2 5s | 5s soz 3 a4 2a Tas 24 Months | © 5 105 | 5 4] 3 4 IEEE EEE 1
Long-Term 6Months | 2 | © | © 0 0 | 3 10 6 | 2
Antifouling Property 3 Jo fo Tolo loo 2 40 2a
Animals 4 0 | o Jol ol 3 2 5 sd Ca | a4 24Months | 3 v0 [2 a | a2 Ts Ts 2 [55]
StawofCoaingFilm | A | A | A |B] A | A |B | B | A |B |BIA
Resistance to Cracking Ala Talal al alr Tals 3A
IC BC I
: 3Months | 19 | 16 | 18 [30 1 | #2 | 81 | 42 “Sl 27 | 12
Consumption of | 9 Months | 51 | 48 | 53 | 80133 | 33 | Is | 72 | 67 | 37 (rot Amountof _2Months | 71 1 67 1 73 101] 46 | 45 | 121 | 80 | 78
Decrease in Thickness |_15 Monts |.89 | 85 | 92 122] 71 | 59 | 136 6 | 120] 63 of Costing Film [umi) | 18 Months | 107 | 104 | 110 | 139] 111 103 129 | 88 | 87 | 72 | 135 | 7 21 Months | 127 | 122 | 330 | 155 195 | 184 | 133 | 90 | 89 | 85 | 148 | 36 24 Months | 144 149 1169 | 300 | 291 | 135 | 9)
(Evaluation) (1) Long-term Antifouling Property
The obtained antifouling paint composition was applied to a blast plate, to which a rustproof paint had been applied in advance so that a dry film thickness of a coating film 1s 300 pm, and the blast plate was left in a room for 2 days and nights for drying. The test plate having the antifouling coating film was thus obtained. The obtained test plate was subjected to an organism adhesion test by using an experimental raft installed in Marine Research Laboratory of Nippon Paint Marine Coatings Co., Ltd. in Tamano, Okayama Prefecture and an antifouling property was evaluated, The results are shown in Tables 2 to 6. The number of months in the tables shows a period during which the raft was immersed, In addition, numeric values in the tables cach show a proportion (%) of an organism adhering area to an area of the coating film (determination by visual inspection) and are rated based on the following criteria, and a ratio not higher than 1 was determined as pass. i5 Evaluation score 0: Proportion of the organism adhering area to the coating film area (0%
Evaluation score 1: Proportion of the organism adhering area to the coating film area more than 0% and less than 20%
Evaluation score 2: Proportion of the organism adhering area to the coating film area not less than 20% and less than 40%
Evaluation score 3: Proportion of the organism adhering area to the coating film areca not less than 40% and less than 60%
Evaluation score 4: Proportion of the organism adhering area to the coating film area not less than 60% and less than 80%
Evaluation score 5: Proportion of the organism adhering area to the coating film area 80% to 100%
Fig. 1 is a photograph showing an example of the state of the test plate surface after an antifouling property test (organism adhesion test) (24 months after immersion).
In Fig. 1, the left photograph shows an example in the case where the evaluation score of animal adhesion is § while the evaluation score of slime/algae adhesion is 0 (for example, Comparative Example 1}. The center photograph shows an example in the case where the evaluation score of animal adhesion is 0 while the evaluation score of slime/algae adhesion is 5 (for example, Comparative Example 3). The right 3 photograph shows an example in the case where both animals and slime/algae adhere, in which the evaluation score of animal adhesion is 3 while the evaluation score of slime/algae adhesion is 3. (2) State of Coating Film
A state of the coating film on the test plate after 6 months of a rafl immersion 16 period in the long-term antifouling property test above was observed visually and with rubbing, and then evaluated. The results thereof are shown in Tables 2t6 6. A coating film in which no crack was observed was evaluated as A and a coating film in which a crack was observed was evaluated as B.
Test for Resistance to Cracking (Dry and Wet Alternating Test)
A test plate having the antifouling coating film was obtained by applying the obtained antifouling paint composition (0 a blast plate, to which a rustproof paint had been applied in advance so that a dry film thickness of a coating film is 300 um and leaving the blast plate in a room for 2 days and nights for drying. The obtained test plate was immersed for | week in seawater at 40°C followed by drying in a room for 1 week, and a dry and wet alternating test with this procedure being defined as 1 cycle was conducted 20 cycles at the maximum. If a crack is generated in the coating {ilm during the test, the test was terminated at the time point of generation of a crack and the number of cycles at that time point is shown in the tables. A plate having no crack after 20 cycles was evaluated as A. (4) Coating Film Consumption Amount {Polishing Speed) Test
A test plate having the antifouling coating film was obtained by applying the obtained antifouling paint composition to a blast plate, to which a rustproof paint had been applied in advance so that a dry film thickness of a coating film is 300 yum and leaving the biast plate in a room for 2 days and nights for drying. This test plate was bonded to a side surface of 2 cylinder having a diameter of 750 mm and a length of 1200 mm, the cylinder was continuously turned in seawater for 24 months at a peripheral speed of 15 knots, and an amount of consumption of the coating film on the test plate (a total amount of decrease in thickness of the coating film {pum]) was 8 measured every three months, The test results are shown in Tables 2 to 6.
As shown in Tables 2 to 6, the hydrolysis rate (polishing speed) of the antifouling coating film obtained from the antifouling paint composition of cach
Example is almost constant for 24 months, so that a relatively high antifouling property can be exhibited against aquatic animals and slime/algae for a long period of time in a stable manner. Turthermore, it is also found that a long-term antifouling property and excellent resistance to cracking can be achieved. In addition, the state of the coating film is also excellent for a long period of time.
Claims (7)
1. An antifouling paint composition comprising: two or more types of antifouling agents containing 4-bromo-2-(4- chloropheny!l)-5-(trifluoromethyl)-1 H-pyrrole-3-carbonitrile; and an acrylic resin having a group expressed in a general formula (1) I —XF—C—O0—M—A (1) ER {where X is a group expressed in a general formula Q i oly kis 0 or 1, Vis a hydrocarbon, M is a divalent metal, and A represents an organic acid residue of a monobasic acid) in a side chain.
2. The antifouling paint composition according to claim 1, wherein said antifouling agents include a first antifouling agent that is 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyi)- I H-pyrrole-3-carbonitrile, and a second antifouling agent that is at least one type selected from the group consisting of zinc pyrithione, copper pyrithione, pyridine-triphenylborane, 1,1- dichloro-N-[{dimethylamino)suifonyl}-1-fluoro-N-phenylmethanesul fenamide, 1,1- dichloro-N-[{dimethylamino)sulfonyl}-1-fluoro-N-(4-methylpheny) methanesulfenamide, N'-(3,4-dichlorophenyl}-N,N'~dimethylurea, N'-tert-butyl-N- cyclopropyl-6-(methylthio}-1,3,5-triazine-2 4-diamine, and 4,5-dichloro-2-n-octyl-4- isothiazoline-3-one,
3. The antifouling paint composition according to claim 2, wherein a ratio between a content of said first antifouling agent and a content of said second antifouling agent is within a range from 1/15 to 1/1 in a mass ratio.
4. The antifouling paint composition according to claim 1, wherein said antifouling paint composition does not include cuprous oxide.
5. The antifouling paint composition according to claim 1, wherein said acrylic resin further has a group expressed in a general formula (2) eT eee TR 2) 3
2 . . . oe , y (where R!, R? and R? are identical or different and each represent a hydrocarbon residue having a carbon number from 1 to 20) in a side chain.
6. An antifouling coating film formed using the antifouling paint composition according to claim 1.
7. A method of controlling a hydrolysis rate of an antifouling coating film in water that is formed on a surface of an object to be coated, wherein the antifouling paint composition according to claim 1 is used as a paint composition forming said antifouling coating film.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2010/060277 WO2011158358A1 (en) | 2010-06-17 | 2010-06-17 | Antifouling material composition, antifouling film, and method for controlling hydrolysis rate of antifouling film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| SG185477A1 true SG185477A1 (en) | 2013-01-30 |
Family
ID=45347779
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SG2012082384A SG185477A1 (en) | 2010-06-17 | 2010-06-17 | Antifouling paint composition, antifouling coating film, and method for controlling hydrolysis rate of antifouling coating film |
Country Status (5)
| Country | Link |
|---|---|
| KR (1) | KR101464898B1 (en) |
| CN (1) | CN102933665B (en) |
| HK (1) | HK1178929A1 (en) |
| SG (1) | SG185477A1 (en) |
| WO (1) | WO2011158358A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9969892B2 (en) | 2013-05-22 | 2018-05-15 | Chugoku Marine Paints, Ltd. | Antifouling coating composition, antifouling coating film, substrate with antifouling coating film, and production process for the substrate |
| EP3330331B1 (en) | 2015-07-31 | 2020-09-02 | Chugoku Marine Paints, Ltd. | Antifouling coating material composition, antifouling coating film, antifouling substrate, rosin compound for antifouling coating material composition, and method for manufacturing antifouling coating material composition |
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|---|---|---|---|---|
| WO2016084769A1 (en) * | 2014-11-26 | 2016-06-02 | 中国塗料株式会社 | Antifouling coating composition, antifouling coating film, substrate having antifouling coating film, antifouling substrate, method for producing substrate having antifouling coating film, and method for preventing fouling of substrate |
| KR102626623B1 (en) * | 2015-04-09 | 2024-01-17 | 요툰 에이/에스 | Antifouling Composition |
| EP3291678B1 (en) * | 2015-05-05 | 2023-10-11 | Corning Incorporated | Antimicrobial materials exhibiting synergistic efficacy |
| JP6511944B2 (en) * | 2015-05-08 | 2019-05-15 | 三菱ケミカル株式会社 | Resin composition for antifouling paint and antifouling coating film |
| JP6717465B2 (en) * | 2016-07-01 | 2020-07-01 | 中国塗料株式会社 | Antifouling paint composition, antifouling coating film, substrate with antifouling coating film, method for producing the same, and antifouling method |
| KR102231192B1 (en) | 2016-07-05 | 2021-03-24 | 미쯔비시 케미컬 주식회사 | Polymer-containing composition and stainproof coating composition |
| WO2018221641A1 (en) | 2017-06-01 | 2018-12-06 | 中国塗料株式会社 | Multilayer antifouling coating, multilayer antifouling coating-equipped substrate and method for producing same, coating material kit for forming multilayer antifouling coating, top-layer antifouling coating material composition, and antifouling method |
| SG11201911459UA (en) | 2017-06-01 | 2020-01-30 | Chugoku Marine Paints | Multilayer antifouling coating film, substrate with multilayer antifouling coating film and method for producing same, coating material kit for forming multilayer antifouling coating film, upper-layer antifouling coating composition, and antifouling method |
| CN114908471A (en) * | 2022-04-13 | 2022-08-16 | 惠州市益晨网业科技有限公司 | Preparation method of novel anti-attachment net for marine ranch supporting facilities |
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| JPH051246A (en) * | 1991-06-26 | 1993-01-08 | Showa Highpolymer Co Ltd | Antifouling coating composition |
| JPH059414A (en) * | 1991-07-04 | 1993-01-19 | Showa Highpolymer Co Ltd | Antifouling coating composition |
| JPH07292280A (en) * | 1994-04-22 | 1995-11-07 | Nippon Chem Ind Co Ltd | Stable copper-containing pigment composition |
| GB9619573D0 (en) * | 1996-09-19 | 1996-10-30 | Zeneca Ltd | Monoazo inkjet dyes |
| EP0831134A1 (en) * | 1996-09-19 | 1998-03-25 | Sigma Coatings B.V. | Light- and bright-coloured antifouling paints |
| JP2004002819A (en) * | 2002-04-19 | 2004-01-08 | Nippon Paint Co Ltd | Antifouling paint |
| RU2420066C2 (en) * | 2006-02-01 | 2011-06-10 | Янссен Фармацевтика Н.В. | Combinations of 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1h-pyrrole-3-carbonitrile and metal compounds |
| US7893047B2 (en) * | 2006-03-03 | 2011-02-22 | Arch Chemicals, Inc. | Biocide composition comprising pyrithione and pyrrole derivatives |
| CA2647444A1 (en) * | 2006-04-10 | 2007-10-18 | Janssen Pharmaceutica N.V. | Combinations of 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1h-pyrrole-3-carbonitrile and biocidal compounds |
| EP2360214B1 (en) * | 2008-12-19 | 2013-07-17 | Nitto Kasei Co., Ltd. | Antifouling coating composition, antifouling coating film formed using the composition, coated article having the coating film on the surface, and antifouling treatment method to form the coating film |
| JP2010150355A (en) * | 2008-12-25 | 2010-07-08 | Nippon Paint Marine Kk | Anti-fouling coating composition, anti-fouling coating film, and method for controlling hydrolysis rate of anti-fouling coating film |
-
2010
- 2010-06-17 KR KR1020137001040A patent/KR101464898B1/en active IP Right Grant
- 2010-06-17 CN CN201080067300.1A patent/CN102933665B/en active Active
- 2010-06-17 WO PCT/JP2010/060277 patent/WO2011158358A1/en active Application Filing
- 2010-06-17 SG SG2012082384A patent/SG185477A1/en unknown
-
2013
- 2013-06-03 HK HK13106489.0A patent/HK1178929A1/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9969892B2 (en) | 2013-05-22 | 2018-05-15 | Chugoku Marine Paints, Ltd. | Antifouling coating composition, antifouling coating film, substrate with antifouling coating film, and production process for the substrate |
| EP3330331B1 (en) | 2015-07-31 | 2020-09-02 | Chugoku Marine Paints, Ltd. | Antifouling coating material composition, antifouling coating film, antifouling substrate, rosin compound for antifouling coating material composition, and method for manufacturing antifouling coating material composition |
| EP3783075A1 (en) | 2015-07-31 | 2021-02-24 | Chugoku Marine Paints, Ltd. | Antifouling coating composition, antifouling coating film, antifouling substrate, rosin compound for antifouling coating composition and method for producing antifouling coating composition |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20130045328A (en) | 2013-05-03 |
| KR101464898B1 (en) | 2014-11-24 |
| HK1178929A1 (en) | 2013-09-19 |
| CN102933665B (en) | 2015-12-02 |
| CN102933665A (en) | 2013-02-13 |
| WO2011158358A1 (en) | 2011-12-22 |
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