JPH04139284A - Antifouling film composition - Google Patents
Antifouling film compositionInfo
- Publication number
- JPH04139284A JPH04139284A JP26353190A JP26353190A JPH04139284A JP H04139284 A JPH04139284 A JP H04139284A JP 26353190 A JP26353190 A JP 26353190A JP 26353190 A JP26353190 A JP 26353190A JP H04139284 A JPH04139284 A JP H04139284A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- chain acid
- antifouling
- acid anhydride
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 30
- 239000000203 mixture Substances 0.000 title claims abstract description 24
- 125000004018 acid anhydride group Chemical group 0.000 claims abstract description 21
- 150000008065 acid anhydrides Chemical group 0.000 claims abstract description 15
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 5
- 239000008199 coating composition Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 abstract description 15
- 239000011347 resin Substances 0.000 abstract description 15
- 229920002554 vinyl polymer Polymers 0.000 abstract description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 3
- 229920001225 polyester resin Polymers 0.000 abstract description 2
- 239000004645 polyester resin Substances 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 45
- 239000011248 coating agent Substances 0.000 description 24
- 238000000576 coating method Methods 0.000 description 24
- 239000003973 paint Substances 0.000 description 14
- 150000007513 acids Chemical class 0.000 description 13
- 239000002519 antifouling agent Substances 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- -1 benzoic acid Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 5
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 150000008064 anhydrides Chemical group 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Chemical group 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 239000003981 vehicle Substances 0.000 description 3
- YYNNRJWNBXEQTP-UHFFFAOYSA-N 2-[(4-bromophenyl)sulfonylamino]-3-phenylpropanoic acid Chemical compound C=1C=C(Br)C=CC=1S(=O)(=O)NC(C(=O)O)CC1=CC=CC=C1 YYNNRJWNBXEQTP-UHFFFAOYSA-N 0.000 description 2
- VBISQLWPGDULSX-UHFFFAOYSA-N 4-[3-(4-carboxyphenoxy)propoxy]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OCCCOC1=CC=C(C(O)=O)C=C1 VBISQLWPGDULSX-UHFFFAOYSA-N 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 238000009360 aquaculture Methods 0.000 description 2
- 244000144974 aquaculture Species 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 235000015170 shellfish Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- LKMDWARGXGFAGA-UHFFFAOYSA-N 1-methylcyclohex-2-ene-1,4-dicarboxylic acid Chemical compound OC(=O)C1(C)CCC(C(O)=O)C=C1 LKMDWARGXGFAGA-UHFFFAOYSA-N 0.000 description 1
- PMUPSYZVABJEKC-UHFFFAOYSA-N 1-methylcyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)CCCCC1C(O)=O PMUPSYZVABJEKC-UHFFFAOYSA-N 0.000 description 1
- NVRCFFIBPIEYQT-UHFFFAOYSA-N 1-methylcyclohexane-1,4-dicarboxylic acid Chemical compound OC(=O)C1(C)CCC(C(O)=O)CC1 NVRCFFIBPIEYQT-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 241000473391 Archosargus rhomboidalis Species 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000238586 Cirripedia Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
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- 241000251555 Tunicata Species 0.000 description 1
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- 239000012346 acetyl chloride Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
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- 125000002723 alicyclic group Chemical group 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
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- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
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- 239000000539 dimer Substances 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
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- 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
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- 239000007787 solid Substances 0.000 description 1
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- 230000002194 synthesizing effect Effects 0.000 description 1
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- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 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
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、新規な防汚性被膜組成物に関する。[Detailed description of the invention] (Industrial application field) The present invention relates to a novel antifouling coating composition.
（従来の技術）
従来、船舶や海上構造物の没水部には、フジッボ、フサ
コケムシ、ホヤ、藻類等の海中生物の付着による腐蝕や
船舶の航行速度の低下を防止するため、また養殖用の網
や金網への海中生物の付着による魚貝類の致死防止のた
め、タフナー、ロジン、可塑剤等のビヒクル成分に防汚
剤を配合してなる防汚塗料か、または例えば特公昭４０
−２１４２６号公報、特公昭４４−９５７９号公報、特
公昭５１−１２０４９号公報等に示される如く有機錫含
有不飽和単量体の重合体または共重合体を用いた防汚塗
料が、一般に塗装されている。(Prior art) Conventionally, submerged parts of ships and offshore structures have been used to prevent corrosion due to the adhesion of marine organisms such as barnacles, sea breams, sea squirts, and algae, as well as to prevent a reduction in the navigation speed of ships, and for aquaculture. In order to prevent the death of fish and shellfish due to the adhesion of marine organisms to nets and wire meshes, antifouling paints made by blending antifouling agents with vehicle components such as tougheners, rosin, and plasticizers, or for example,
As shown in Japanese Patent Publication No. 21426, Japanese Patent Publication No. 44-9579, Japanese Patent Publication No. 51-12049, etc., antifouling paints using polymers or copolymers of organotin-containing unsaturated monomers are generally used for coating. has been done.
しかしながら、前者の塗料は、それから得られる塗膜に
含まれるロジン及び防汚剤成分が溶出することによって
防汚効果を発揮するものであるが該塗膜は長時間の海水
浸漬において不溶性成分が多くなるとそれと共に塗面が
、凹凸状となり海中生物の付着を防止する効果が劣って
くる。また後者の塗料は、重合体にエステル結合を介し
て導入された有機錫化合物を含むｔＩ！膜が海水に浸漬
されて、該エステル結合の加水分解により、該有機錫化
合物が分離するとともに、カルボキシル基を含む重合体
が生成する。この重合体は、海水に溶解し、常に新鮮な
塗膜が露出し、防汚性を維持していくものである。しか
し、該塗膜の防汚性を有効に発揮させるため一般的には
多くの有機錫化合物が導入されており、魚貝類に対し、
悪影響をおよぼす欠点がある。However, although the former type of paint exhibits its antifouling effect by eluting the rosin and antifouling agent components contained in the resulting coating film, the coating film contains many insoluble components when immersed in seawater for a long time. At the same time, the painted surface becomes uneven and becomes less effective in preventing the adhesion of marine organisms. The latter coating also contains an organotin compound introduced into the polymer via an ester bond. When the membrane is immersed in seawater, the organotin compound is separated and a polymer containing carboxyl groups is produced by hydrolysis of the ester bonds. This polymer dissolves in seawater, always exposing a fresh coating film and maintaining antifouling properties. However, in order to effectively exhibit the antifouling properties of the coating film, many organic tin compounds are generally introduced, and they are harmful to fish and shellfish.
There are drawbacks that can have negative effects.
また、上記した欠点を改善するために、本出願人は特開
平２−９９５６７号公報に酸無水基を有する樹脂をビヒ
クル成分とする防汚性塗料を用いて防汚性塗膜を形成す
る方法について提案した。In addition, in order to improve the above-mentioned drawbacks, the present applicant has disclosed a method for forming an antifouling coating film using an antifouling paint containing a resin having an acid anhydride group as a vehicle component, as disclosed in Japanese Patent Application Laid-Open No. 2-99567. I proposed about.
該塗料で使用する樹脂は、具体的には無水イタコン酸又
は無水マレイン酸などの酸無水物を他の不飽和単量体と
ラジカル共重合反応させて得られる分子中に環状の酸無
水基を有する共重合体である。該共重合体によって形成
された塗膜は、加水分解により２個のカルボキシル基を
生成し水溶化されるが、共重合体中の酸無水基の数が多
いと長期間にわたる防汚保持性が悪（、また、逆に酸無
水基の数が少ないと短期間においても防汚性が十分に発
揮できないという欠点があった。Specifically, the resin used in the paint has a cyclic acid anhydride group in the molecule obtained by radical copolymerization of an acid anhydride such as itaconic anhydride or maleic anhydride with other unsaturated monomers. It is a copolymer with The coating film formed by the copolymer is water-solubilized by producing two carboxyl groups through hydrolysis, but if the number of acid anhydride groups in the copolymer is large, the antifouling property will be maintained for a long period of time. Conversely, if the number of acid anhydride groups is small, the antifouling property cannot be sufficiently exhibited even in a short period of time.
（発明が解決しようとする問題点）
本発明は、長期間防汚性に優れた効果を発揮し、しかも
毒性の低い防汚性被膜を提供することを目的としてなさ
れたものである。(Problems to be Solved by the Invention) The present invention has been made with the object of providing an antifouling coating that exhibits excellent antifouling properties for a long period of time and has low toxicity.
（問題点を解決するための手段）
本発明者等は、このような欠点を克服する組成物につい
て種々研究を重ねた結果、特定構造を有する鎖状酸無水
基をもつ樹脂組成物が、長期間防汚保持性を発揮する被
膜を提供できるものであることを見い出し、本発明を完
成するに至った。(Means for Solving the Problems) As a result of various studies on compositions that overcome these drawbacks, the present inventors have found that a resin composition having a chain acid anhydride group having a specific structure has a long The present inventors have discovered that it is possible to provide a coating that exhibits antifouling properties for a long period of time, and have completed the present invention.
即ち、本発明は１分子中に鎖状酸無水基を平均１．０個
以上有する化合物を含有することを特徴とする防汚性被
膜組成物に関する。That is, the present invention relates to an antifouling coating composition containing a compound having an average of 1.0 or more chain acid anhydride groups in one molecule.
本発明において、鎖状酸無水基は、式
酸素及び炭素と炭素とが結合して環状となった、−ＣＣ
−
酸無水基とは異なるものである。In the present invention, the chain acid anhydride group has the formula oxygen and carbon bonded to form a ring, -CC
- It is different from an acid anhydride group.
本発明組成物で用いる化合物は、
基を１分子中に平均１．０個以上、
該鎖状酸無水
好ましくは平
均２．０個以上有する、好ましくは数平均分子量５００
〜１００．０００の範囲、好ましくは数平均分子量７０
０〜５０．０００の範囲のものである。鎖状酸無水基が
平均１．０個未滴になると、化合物の水溶解性が悪くな
り十分な防汚性が得られない、また、数平均分子量が５
００より下回ると、長期防汚性が劣り、逆に、１００．
０００より上回ると十分な防汚性が得られない。The compound used in the composition of the present invention has an average of 1.0 or more groups in one molecule, preferably an average of 2.0 or more groups of the chain acid anhydride, and preferably a number average molecular weight of 500.
~100.000, preferably number average molecular weight 70
It is in the range of 0 to 50.000. If an average of 1.0 chain acid anhydride groups are left undropped, the water solubility of the compound will deteriorate and sufficient antifouling properties will not be obtained.
If it is less than 00, the long-term stain resistance will be poor;
If it exceeds 000, sufficient antifouling properties cannot be obtained.
本発明組成物で用いる化合物は上記した条件を満足する
ものであれば、特に制限なしに使用できる。具体的には
ビニル系樹脂、ポリエステル系樹脂、アルキド系樹脂、
シリコーン系樹脂、ポリウレタン系樹脂、フッ素系樹脂
などの樹脂中に鎖状酸無水基をもつもの：脂肪族塩基酸
を原料として得られる脂肪族鎖状酸無水物・芳香族・塩
基酸を原料として得られる芳香族鎖状酸無水物：複素環
酸から選ばれる少なくとも１種以上の塩基酸を原料とし
て得られる鎖状酸無水物などが挙げられる。The compounds used in the composition of the present invention can be used without particular limitations as long as they satisfy the above conditions. Specifically, vinyl resin, polyester resin, alkyd resin,
Resins with chain acid anhydride groups such as silicone resins, polyurethane resins, and fluorine resins: aliphatic chain acid anhydrides, aromatic, and basic acids obtained from aliphatic basic acids as raw materials. Obtainable aromatic chain acid anhydride: Examples include chain acid anhydrides obtained using at least one or more basic acids selected from heterocyclic acids as a raw material.
本発明において、分子中に鎖状酸無水基を導入する方法
については、従来から公知の鎖状酸無水基の合成方法に
従って実施できる。具体的にはビニル系、ポリエステル
系、アルキド系、シリコーン系、ポリウレタン系、フッ
素系などのカルボン酸樹脂又は上記塩基酸を無水酢酸又
はアセチルクロリドを作用させることにより、また、上
記カルボン酸樹脂の酸塩化樹脂又は上記塩基酸の酸塩化
物とピリジンとを反応させピリジン錯体を得たのち、こ
のものと上記カルボン酸樹脂又は上記塩基酸とを反応さ
せることにより、また、上記酸塩化樹脂又は上記塩基酸
の酸塩化物と該カルボン酸樹脂の塩（アルカリ金属、有
機）又は塩基酸の塩（アルカリ金属、有機）とを反応さ
せることにより実施できる。In the present invention, a method for introducing a chain acid anhydride group into a molecule can be carried out according to a conventionally known method for synthesizing a chain acid anhydride group. Specifically, by reacting vinyl-based, polyester-based, alkyd-based, silicone-based, polyurethane-based, fluorine-based, etc. carboxylic acid resins or the above basic acids with acetic anhydride or acetyl chloride; By reacting the chlorinated resin or the acid chloride of the above basic acid with pyridine to obtain a pyridine complex, and then reacting this complex with the above carboxylic acid resin or the above basic acid, the above acid chloride resin or the above base This can be carried out by reacting an acid chloride with a salt (alkali metal, organic) of the carboxylic acid resin or a salt (alkali metal, organic) of a basic acid.
上記塩基酸は、１分子中にカルボキシル基を平均１．０
個以上、好ましくは平均２．０個以上有する脂肪族、芳
香族又は複素環式の塩基酸である。該脂肪族塩基酸とし
ては、炭素が環状となった脂環族塩基酸、脂肪族環を構
成する炭素の一部が結合した有橋構造をもつ塩基品番族
環とカルボン酸との間が脂肪族鎖で結合した誘導体及び
脂肪族の炭素の一部が酸素、イ才つ、リン、盆素などの
電子で置換したものなども包含される。The above basic acid has an average of 1.0 carboxyl groups in one molecule.
It is an aliphatic, aromatic or heterocyclic basic acid having at least 2.0, preferably 2.0 or more on average. The aliphatic basic acids include alicyclic basic acids in which carbon is cyclic, and base products with a bridged structure in which some of the carbons constituting the aliphatic ring are bonded. Also included are derivatives bonded through group chains and derivatives in which a portion of aliphatic carbon is replaced with electrons such as oxygen, oxygen, phosphorus, and ions.
該塩基酸の具体例としては例えば酢酸、プロピオン酸、
酪酸、カプロン酸、カプリル酸、カプリン酸、ラウリン
酸、ミリスチン酸、パルミチン酸、バーサチック酸、ス
テアリン酸、オレイン酸、２−エチルヘキサン酸、ヤシ
油脂肪酸、オリーブ油脂肪酸、パーム油脂肪酸などの脂
肪族−塩基酸、ナフテン酸などの脂ｆｆｉ族酸、安思香
酸、ｐ −ｔｅｒｔ−安、ミ香酸、メチル安息香酸など
の芳香族−塩基酸、ロジンなどの多環式テルペン炭化水
素−塩基酸、アジピン酸、セバシン酸、コハク酸、マロ
ン酸、ドデカンニ酸、オクタデカンニ酸、ピメリン酸、
アゼライン酸、ダイマー酸ＨＯＯＣ（：Ｈ，ＳＣ，Ｈ，
ＳＣＨ，Ｃ０ＯＨ，ＨＯＯＣＣ，Ｈ，ＳＣ，Ｈ，ＳＣ，
Ｈ４Ｃ００Ｈ１Ｈ００ＣＣ！Ｈ４Ｓ０２ＣＪ、ＳＯ，Ｃ
Ｊ、Ｃ００Ｈ１などの脂肪族二塩基酸、
ヘキサヒドロフクル酸、ヘキサヒドロイソフタル酸、ヘ
キサヒドロテレフタル酸、ヘキサヒドロトリメリット酸
、メチルへキサヒドロフタル酸、メチルへキサヒドロテ
レフタル酸、△１−テトラヒドロフタル酸、△２−テト
ラヒドロフタル酸、△３−テトラヒドロフクル酸、△４
−テトラヒドロフタル酸、△１−テトラヒドロイソフタ
ル酸、△３−テトラヒドロイソフタル酸、△４−テトラ
ヒドロイソフタル酸、△１−テトラヒドロテレフタル酸
、△２−テトラヒドロテレフタル酸、メチルテトラヒド
ロテレフタル酸、イソフタル酸。Specific examples of the basic acid include acetic acid, propionic acid,
Aliphatic acids such as butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, versatic acid, stearic acid, oleic acid, 2-ethylhexanoic acid, coconut oil fatty acid, olive oil fatty acid, palm oil fatty acid - Basic acids, fatty acids such as naphthenic acid, aromatic basic acids such as benzoic acid, p-tert-amino acid, mymic acid, methylbenzoic acid, polycyclic terpene hydrocarbon basic acids such as rosin, etc. , adipic acid, sebacic acid, succinic acid, malonic acid, dodecanoic acid, octadecanniic acid, pimelic acid,
Azelaic acid, dimer acid HOOC (:H, SC, H,
SCH, C0OH, HOOCC, H, SC, H, SC,
H4C00H1H00CC! H4S02CJ, SO, C
J, aliphatic dibasic acids such as C00H1, hexahydrofucric acid, hexahydroisophthalic acid, hexahydroterephthalic acid, hexahydrotrimellitic acid, methylhexahydrophthalic acid, methylhexahydroterephthalic acid, △1- Tetrahydrophthalic acid, △2-tetrahydrophthalic acid, △3-tetrahydrofucric acid, △4
-tetrahydrophthalic acid, Δ1-tetrahydroisophthalic acid, Δ3-tetrahydroisophthalic acid, Δ4-tetrahydroisophthalic acid, Δ1-tetrahydroterephthalic acid, Δ2-tetrahydroterephthalic acid, methyltetrahydroterephthalic acid, isophthalic acid.
フクル酸、ジメチルイソフタル酸ナフタレンジカルボン
酸、４．４−ジフェニルメタンジカルボン酸、４．４−
ジフェニルメタンジカルボン酸、ＨＯＯＣＣ，Ｈ４−Ｌ
Ｌ ＪＬｃ、ｕ、ｃｏｏＨｌく
などが挙げられる。Fucric acid, dimethylisophthalic acid naphthalene dicarboxylic acid, 4.4-diphenylmethane dicarboxylic acid, 4.4-
diphenylmethane dicarboxylic acid, HOOCC, H4-L
Examples include L JLc, u, cooHlku, etc.
上記した塩基酸において、例えばＣ８以上程度の高級脂
肪族塩基酸を用いて、塗膜の疏水性を高め塗膜の溶出を
遅くしたり、また、Ｃ８未満程度の低級脂肪族塩基酸を
用いて塗膜の親水性を高め塗膜の溶出を早くしたりして
、即ち脂肪族塩基酸を適宜選択することにより、塗膜の
溶出速度を必要に応じて調整することができる。Among the above-mentioned basic acids, for example, a higher aliphatic basic acid of about C8 or higher may be used to increase the hydrophobicity of the coating film and slow down the elution of the coating film, or a lower aliphatic basic acid of about less than C8 may be used. The elution rate of the coating film can be adjusted as necessary by increasing the hydrophilicity of the coating film and speeding up the elution of the coating film, that is, by appropriately selecting the aliphatic basic acid.
また、芳香族塩基酸より生成される鎖状酸無水基は脂肪
族塩基酸より生成される該無水基よりも加水分解速度が
遅くなるので、両者を組合わせることにより、塗膜の溶
出速度を必要に応じて調整することができる。In addition, the hydrolysis rate of chain acid anhydride groups generated from aromatic basic acids is slower than that of the anhydride groups generated from aliphatic basic acids, so by combining the two, the elution rate of the coating film can be reduced. It can be adjusted as necessary.
本発明において、鎖状酸無水基を有する化合物は１分子
中に平均１．０個以上の鎖状酸無水基を有することがで
きる。該鎖状酸無水基を１分子中に平均２．０個以上含
有するポリ鎖状酸無水物は、例えば前記脂肪族二塩基酸
、芳香族多塩基酸又は複素環族多塩基酸を必須成分とす
ることにより得られる。In the present invention, the compound having a chain acid anhydride group can have an average of 1.0 or more chain acid anhydride groups in one molecule. The polychain acid anhydride containing an average of 2.0 or more chain acid anhydride groups in one molecule includes, for example, the aliphatic dibasic acid, aromatic polybasic acid, or heterocyclic polybasic acid as an essential component. It can be obtained by
本発明組成物には、要求される性能に応じて従来公知の
防汚剤１例えば、亜酸化銅、チオシアン銅、銅粉末など
の銅系防汚剤、トリフェニル錫フルオライド、トリフェ
ニル錫クロライド、トリブチル錫オキサイドなどの有機
錫防汚剤、エチレンビス（ジチオカルバミン酸）亜鉛、
テトラメチルチウラムジスルファイドなどの含チッ素４
才つ系防汚剤、酸化亜鉛等を配合することができる。The composition of the present invention may include conventionally known antifouling agents 1, such as copper-based antifouling agents such as cuprous oxide, copper thiocyanide, and copper powder, triphenyltin fluoride, triphenyltin chloride, etc., depending on the required performance. Organotin antifouling agents such as tributyltin oxide, zinc ethylene bis(dithiocarbamate),
Nitrogen-containing 4 such as tetramethylthiuram disulfide
Antifouling agents, zinc oxide, etc. can be added.
上記組成物には前記した防汚剤以外にも体質顔料、着色
顔料、可塑剤、塗料用添加剤、その他の樹脂等を必要に
応じて配合することができる。In addition to the above-mentioned antifouling agents, extender pigments, coloring pigments, plasticizers, paint additives, other resins, and the like may be blended into the composition as necessary.
更に本発明組成物は、従来の防汚性塗料に添加剤成分と
して配合することもできる。Furthermore, the composition of the present invention can also be incorporated into conventional antifouling paints as an additive component.
本発明組成物は、防汚性を必要とする建築物、水中構造
物等の基材に塗布することにより、実施される。即ち、
該組成物は、例えば住宅関連の諸施設やバイオクリーン
な環境が要求される病院、醸造工場、食品工場（例えば
製パン工場）、医薬品製造工場、電子機器製造工場等の
内装用として、微生物汚染から環境を守るのに有効であ
り、また水中構造物（例えば、船舶、港湾施設、ブイ、
パイプライン、橋梁、海底基地、養殖網、定置網等）に
塗装して、水中生物の付着生育の防止を行なうことがで
きる。該組成物を水中構造物に塗装することにより、長
期間にわたってすぐれた防汚性を有し、かつ人体に対し
極めて安全性の高い被覆物を捷供することができる。ま
た、該組成物を水中構造物に適用する場合、一般にはジ
ンクエポキシ系ショップブライマー、エポキシ系塩化ゴ
ム系下塗り防食塗料を塗装し、次いで該組成物を塗装す
るのが好ましい。The composition of the present invention is applied to base materials such as buildings and underwater structures that require antifouling properties. That is,
The composition can be used for the interior of housing-related facilities, hospitals that require a bio-clean environment, brewing factories, food factories (e.g., bakery factories), pharmaceutical manufacturing factories, electronic equipment manufacturing factories, etc., to prevent microbial contamination. It is effective in protecting the environment from water and underwater structures (e.g. ships, port facilities, buoys,
It can be applied to pipelines, bridges, submarine bases, aquaculture nets, fixed nets, etc. to prevent aquatic organisms from growing on them. By coating underwater structures with this composition, it is possible to provide a coating that has excellent antifouling properties over a long period of time and is extremely safe for the human body. When the composition is applied to an underwater structure, it is generally preferable to apply a zinc epoxy shop primer or an epoxy chloride rubber undercoat anticorrosive paint, and then apply the composition.
該組成物を塗布する場合、該組成物は、例えば刷毛塗り
、吹付は塗り、ローラー塗り、浸漬等の手段で基材表面
に塗布することができる。塗布量は、特に制限はないが
、一般には５〜４００ｇ／ばの範囲である。塗膜の乾燥
は、室温で行なうことができるが、必要に応じて約２０
０℃までの温度で加熱乾燥を行なってもよい。When applying the composition, the composition can be applied to the surface of the substrate by, for example, brushing, spraying, roller coating, dipping, or the like. The amount of coating is not particularly limited, but is generally in the range of 5 to 400 g/ba. Drying of the coating can be done at room temperature, but if necessary
Heat drying may be carried out at a temperature of up to 0°C.
（作用及び発明の効果）
本発明組成物は、従来の酸無水基を有する樹脂をビヒク
ル成分として用いた組成物と比較して長期防汚性に優れ
た性質を発揮する理由としては、次の様に推察される。(Actions and Effects of the Invention) The reason why the composition of the present invention exhibits superior long-term stain resistance compared to conventional compositions using resins having acid anhydride groups as vehicle components is as follows. It is inferred that
と、該酸無水基の加水分解により、塩基酸化合物が分離
するとともに、新たにカルボキシル基を含む化合物が生
成する。該塩基酸化合物の分離により、（海）水中生物
が被膜に付着するのを防止するとともに、カルボキシル
基を含む化合物が新鮮な塗膜を更新し防汚性を発揮する
。By hydrolysis of the acid anhydride group, the basic acid compound is separated and a new compound containing a carboxyl group is generated. Separation of the basic acid compound prevents (sea) aquatic organisms from adhering to the coating, and the carboxyl group-containing compound renews the fresh coating to exhibit antifouling properties.
（実施例） 次に実施例を掲げて本発明をさらに具体的に説明する。(Example) Next, the present invention will be explained in more detail with reference to Examples.
実施例１
セパチン酸１モルに無水酢酸２モルを混合し、窒素ガス
を流しながら還流させ脱水を行なったのち、続いて減圧
（１ｍｍＨｇ以上の減圧）下で２８０℃で３０分間反応
させて数平均分子量的５．０００のセパチン酸のポリ酸
無水物を得た。Example 1 1 mole of cepacic acid was mixed with 2 moles of acetic anhydride and dehydrated by refluxing the mixture while flowing nitrogen gas, followed by a reaction at 280°C for 30 minutes under reduced pressure (reduced pressure of 1 mmHg or more) to obtain a number average A polyanhydride of cepatic acid with a molecular weight of 5.000 was obtained.
次いで得られた該酸無水物２５ｇ、亜酸化ｗ４３０ｇ、
ベンガラ２ｇ、エロジル＃２００ （商標名、***デグ
サ社製、シリカ粉末、以下同様の意味を表わす、）０．
５ｇ、キシレン３６ｇをペイントコンディショナーで混
合分散して防汚性塗料を得た。Then, 25 g of the acid anhydride obtained, 430 g of suboxide w,
2g of Red Garla, Erosil #200 (Trade name, manufactured by West German Degussa, silica powder, hereinafter the same meaning) 0.
5 g of xylene and 36 g of xylene were mixed and dispersed with a paint conditioner to obtain an antifouling paint.
実施例２
実施例１において、セパチン酸に代えて１．３−ビス（
ｐ−カルボキシフェノキシ）プロパンを用いた以外は実
施例１と同様にして製造を行なって数平均分子量的５．
０００の１．３−ビス（ｐ−カルボキシフェノキシ）プ
ロパンのポリ酸無水物を得た６次いで、このものを用い
て実施例１と同様の配合で防汚塗料を得た。Example 2 In Example 1, 1,3-bis(
Production was carried out in the same manner as in Example 1 except that p-carboxyphenoxy)propane was used, and the number average molecular weight was 5.
A polyacid anhydride of 1.3-bis(p-carboxyphenoxy)propane of 0.000 was obtained.6 Next, using this product, an antifouling paint was obtained in the same formulation as in Example 1.
実施例３
実施例１において、セパチン酸１モルに代えてセパチン
酸０．５モル及び１．３−ビス（ｐ−カルボキシフェノ
キシ）プロパン０．５モルに置き代えた以外は実施例１
と同様にして製造を行なって数平均分子量的５，０００
のセパチン酸及び１．３−ビス（ｐ−カルボキシフェノ
キシ）プロパンのポリ酸無水物を得た０次いで、このも
のを用いて実施例１と同様の配合で防汚塗料を得た。Example 3 Example 1 except that 1 mole of sepathic acid in Example 1 was replaced with 0.5 mole of sepathic acid and 0.5 mole of 1,3-bis(p-carboxyphenoxy)propane.
The number average molecular weight was 5,000.
A polyacid anhydride of cepatic acid and 1,3-bis(p-carboxyphenoxy)propane was obtained. Then, using this product, an antifouling paint was obtained in the same formulation as in Example 1.
比較例１
塩化ビニル樹脂１０ｇ、ロジン１０ｇ、トリクレジルホ
スフェート４ｇ、トリフェニル錫フルオライド１０ｇ、
炭酸カルシウム５ｇ、弁柄５ｇ、キジロール２８ｇ、メ
チルイソブチルケトン２８ｇを実施例１と同様の方法で
調製した。Comparative Example 1 10 g of vinyl chloride resin, 10 g of rosin, 4 g of tricresyl phosphate, 10 g of triphenyltin fluoride,
5 g of calcium carbonate, 5 g of Bengara, 28 g of Kijirole, and 28 g of methyl isobutyl ketone were prepared in the same manner as in Example 1.
比較例２
塩化ゴム樹脂５ｇ、ロジン１５ｇ、トリクレジルホスフ
ェート４ｇ、亜塩化銅３０ｇ、炭酸カルク
シウム５ｇ、バリー５ｇ、弁柄４ｇ、キジロール３４ｇ
を実施例１と同様の方法で調製した。Comparative Example 2 Chlorinated rubber resin 5g, rosin 15g, tricresyl phosphate 4g, copper chloride 30g, calcium carbonate 5g, Barry 5g, Bengara 4g, Kijirole 34g
was prepared in the same manner as in Example 1.
比較例３
実施例１において、セパチン酸の無水ポリカルボン酸５
０ｇに代えて下記ビニル重合体溶液６２．５ｇを用いた
以外は実施例１と同様の配合及び製造方法で比較例３の
組成物を得た。Comparative Example 3 In Example 1, polycarboxylic anhydride 5 of cepacic acid
A composition of Comparative Example 3 was obtained using the same formulation and manufacturing method as in Example 1, except that 62.5 g of the following vinyl polymer solution was used instead of 0 g.
ビニル重合体溶液
無水マレイン酸２５ｇ、スチレン２５ｇ、メチルメタア
クリレート３０ｇ、エチルアクリレート２０ｇ、キシレ
ン４３ｇ及びベンゾイルパーオキサイド２．０ｇを混合
し、撹拌下９０〜１００℃で３時間反応させ、さらにベ
ンゾイルパーオキサイド１０ｇとキシレン１０７ｇを加
え、９０〜１００℃撹拌下２時間反応し、固形分４０重
量％の淡黄色粘稠液体を得た。Vinyl polymer solution 25 g of maleic anhydride, 25 g of styrene, 30 g of methyl methacrylate, 20 g of ethyl acrylate, 43 g of xylene and 2.0 g of benzoyl peroxide were mixed and reacted at 90 to 100°C for 3 hours with stirring, followed by benzoyl peroxide. 10 g and 107 g of xylene were added and reacted for 2 hours with stirring at 90 to 100°C to obtain a pale yellow viscous liquid with a solid content of 40% by weight.
実施例１〜３及び比較例１〜３の塗膜性能試験結果を後
記表−１にまとめて示す。The coating film performance test results of Examples 1 to 3 and Comparative Examples 1 to 3 are summarized in Table 1 below.
防汚性能試験結果
上記の実施例１〜３および比較例１〜３で得た塗料につ
いて大きさｌｏＯＸ３００Ｘ２ｍｍのサンドブラスト処
理鋼板にジンクエポキシ系ショップブライマー（乾燥膜
厚１５Ｐ）及びエポキシ系防ｉｌｌ塗料（同２００ｐ）
を予め塗装した塗板に乾燥膜厚が１００ＰＲになるよう
に塗装して試験塗板とし、７日間乾燥させて供試した６
表−１にこれら試験板を三重県鳥羽湾に２４ケ月浸漬し
て防汚性（数字は付着生物の付着面積を％で示す）を評
価
した結果を示した。Antifouling performance test results Regarding the paints obtained in Examples 1 to 3 and Comparative Examples 1 to 3 above, a zinc epoxy shop brusher (dry film thickness 15P) and an epoxy anti-ill paint (the same 200p)
A test coated plate was prepared by coating a pre-coated plate with a dry film thickness of 100PR, dried for 7 days, and then tested.
Table 1 shows the results of immersing these test plates in Toba Bay, Mie Prefecture for 24 months and evaluating their antifouling properties (numbers indicate the area of attached organisms in %).
表−１Table-1
Claims (2)
する化合物を含有することを特徴とする防汚性被膜組成
物。(1) An antifouling coating composition containing a compound having an average of 1.0 or more chain acid anhydride groups in one molecule.
芳香族鎖状酸無水物及び複素環式鎖状酸無水物から選ば
れる少なくとも１種の鎖状酸無水物であることを特徴と
する防汚性被膜組成物。(2) The compound according to claim 1 is an aliphatic chain acid anhydride,
An antifouling film composition comprising at least one type of chain acid anhydride selected from aromatic chain acid anhydrides and heterocyclic chain acid anhydrides.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26353190A JPH04139284A (en) | 1990-10-01 | 1990-10-01 | Antifouling film composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26353190A JPH04139284A (en) | 1990-10-01 | 1990-10-01 | Antifouling film composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04139284A true JPH04139284A (en) | 1992-05-13 |
Family
ID=17390831
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26353190A Pending JPH04139284A (en) | 1990-10-01 | 1990-10-01 | Antifouling film composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04139284A (en) |
-
1990
- 1990-10-01 JP JP26353190A patent/JPH04139284A/en active Pending
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