JPS63168476A - Underwater antifouling coating agent - Google Patents
Underwater antifouling coating agentInfo
- Publication number
- JPS63168476A JPS63168476A JP61311221A JP31122186A JPS63168476A JP S63168476 A JPS63168476 A JP S63168476A JP 61311221 A JP61311221 A JP 61311221A JP 31122186 A JP31122186 A JP 31122186A JP S63168476 A JPS63168476 A JP S63168476A
- Authority
- JP
- Japan
- Prior art keywords
- antifouling
- polymer
- coating
- agent
- underwater
- 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 61
- 239000011248 coating agent Substances 0.000 title claims abstract description 55
- 239000002519 antifouling agent Substances 0.000 claims abstract description 36
- 229920001577 copolymer Polymers 0.000 claims abstract description 34
- 239000000178 monomer Substances 0.000 claims abstract description 31
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 9
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract 3
- 239000000314 lubricant Substances 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- 239000002904 solvent Substances 0.000 abstract description 12
- 238000001035 drying Methods 0.000 abstract description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 abstract description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012188 paraffin wax Substances 0.000 abstract description 3
- 239000008096 xylene Substances 0.000 abstract description 3
- BFWMWWXRWVJXSE-UHFFFAOYSA-M fentin hydroxide Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(O)C1=CC=CC=C1 BFWMWWXRWVJXSE-UHFFFAOYSA-M 0.000 abstract description 2
- 239000004605 External Lubricant Substances 0.000 abstract 1
- 239000003999 initiator Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 46
- 239000010408 film Substances 0.000 description 37
- 239000003973 paint Substances 0.000 description 37
- 229920000642 polymer Polymers 0.000 description 37
- -1 polydimethylsiloxane group Polymers 0.000 description 20
- 238000012360 testing method Methods 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 229920002379 silicone rubber Polymers 0.000 description 14
- 239000004945 silicone rubber Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 239000013535 sea water Substances 0.000 description 11
- 150000001875 compounds Chemical group 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 150000002894 organic compounds Chemical class 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229920002545 silicone oil Polymers 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
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- 238000010422 painting Methods 0.000 description 5
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- 239000003760 tallow Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
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- 150000002739 metals Chemical class 0.000 description 4
- 239000002685 polymerization catalyst Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000004264 Petrolatum Substances 0.000 description 3
- 150000003973 alkyl amines Chemical class 0.000 description 3
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- 238000004132 cross linking Methods 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229940057995 liquid paraffin Drugs 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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- 239000003960 organic solvent Substances 0.000 description 3
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- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- QHZLMUACJMDIAE-UHFFFAOYSA-N 1-monopalmitoylglycerol Chemical compound CCCCCCCCCCCCCCCC(=O)OCC(O)CO QHZLMUACJMDIAE-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 235000015278 beef Nutrition 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 150000001880 copper compounds Chemical class 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 150000002816 nickel compounds Chemical class 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- OQILCOQZDHPEAZ-UHFFFAOYSA-N octyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OCCCCCCCC OQILCOQZDHPEAZ-UHFFFAOYSA-N 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- 230000036314 physical performance Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000007665 sagging Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- KMEHEQFDWWYZIO-UHFFFAOYSA-N triacontyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCC KMEHEQFDWWYZIO-UHFFFAOYSA-N 0.000 description 2
- SBXWFLISHPUINY-UHFFFAOYSA-N triphenyltin Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)C1=CC=CC=C1 SBXWFLISHPUINY-UHFFFAOYSA-N 0.000 description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 2
- 239000010698 whale oil Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- UOZNXGJVAWDLQK-UHFFFAOYSA-N 1-(2,3-dimethylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC=CC(N2C(C=CC2=O)=O)=C1C UOZNXGJVAWDLQK-UHFFFAOYSA-N 0.000 description 1
- TUPMGRKCIDFTPF-UHFFFAOYSA-N 1-(2-anilinophenyl)pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1NC1=CC=CC=C1 TUPMGRKCIDFTPF-UHFFFAOYSA-N 0.000 description 1
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- YLJPMCJDTAPPRX-UHFFFAOYSA-N 1-(4-butylphenyl)pyrrole-2,5-dione Chemical compound C1=CC(CCCC)=CC=C1N1C(=O)C=CC1=O YLJPMCJDTAPPRX-UHFFFAOYSA-N 0.000 description 1
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- UGAGPNKCDRTDHP-UHFFFAOYSA-N 16-hydroxyhexadecanoic acid Chemical compound OCCCCCCCCCCCCCCCC(O)=O UGAGPNKCDRTDHP-UHFFFAOYSA-N 0.000 description 1
- FLPJVCMIKUWSDR-UHFFFAOYSA-N 2-(4-formylphenoxy)acetamide Chemical compound NC(=O)COC1=CC=C(C=O)C=C1 FLPJVCMIKUWSDR-UHFFFAOYSA-N 0.000 description 1
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- PHYFQTYBJUILEZ-UHFFFAOYSA-N Trioleoylglycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCCCCCCCC)COC(=O)CCCCCCCC=CCCCCCCCC PHYFQTYBJUILEZ-UHFFFAOYSA-N 0.000 description 1
- UWHZIFQPPBDJPM-FPLPWBNLSA-M Vaccenic acid Natural products CCCCCC\C=C/CCCCCCCCCC([O-])=O UWHZIFQPPBDJPM-FPLPWBNLSA-M 0.000 description 1
- 235000021322 Vaccenic acid Nutrition 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- FROZIYRKKUFAOC-UHFFFAOYSA-N amobam Chemical compound N.N.SC(=S)NCCNC(S)=S FROZIYRKKUFAOC-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- LVYAMPSKHSIFNV-UHFFFAOYSA-N azane;methylcarbamodithioic acid Chemical compound [NH4+].CNC([S-])=S LVYAMPSKHSIFNV-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000001046 cacaotero Nutrition 0.000 description 1
- 238000009924 canning Methods 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229940074979 cetyl palmitate Drugs 0.000 description 1
- XZJZNZATFHOMSJ-KTKRTIGZSA-N cis-3-dodecenoic acid Chemical compound CCCCCCCC\C=C/CC(O)=O XZJZNZATFHOMSJ-KTKRTIGZSA-N 0.000 description 1
- 239000003026 cod liver oil Substances 0.000 description 1
- 235000012716 cod liver oil Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- BQVVSSAWECGTRN-UHFFFAOYSA-L copper;dithiocyanate Chemical compound [Cu+2].[S-]C#N.[S-]C#N BQVVSSAWECGTRN-UHFFFAOYSA-L 0.000 description 1
- MMUFAGXJPKNAHT-UHFFFAOYSA-N copper;quinolin-8-ol Chemical compound [Cu].C1=CN=C2C(O)=CC=CC2=C1 MMUFAGXJPKNAHT-UHFFFAOYSA-N 0.000 description 1
- WCMMILVIRZAPLE-UHFFFAOYSA-M cyhexatin Chemical compound C1CCCCC1[Sn](C1CCCCC1)(O)C1CCCCC1 WCMMILVIRZAPLE-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- IEPRKVQEAMIZSS-AATRIKPKSA-N diethyl fumarate Chemical compound CCOC(=O)\C=C\C(=O)OCC IEPRKVQEAMIZSS-AATRIKPKSA-N 0.000 description 1
- NAPSCFZYZVSQHF-UHFFFAOYSA-N dimantine Chemical compound CCCCCCCCCCCCCCCCCCN(C)C NAPSCFZYZVSQHF-UHFFFAOYSA-N 0.000 description 1
- 229950010007 dimantine Drugs 0.000 description 1
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 1
- 229960004419 dimethyl fumarate Drugs 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
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- 235000013601 eggs Nutrition 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- WDQNIWFZKXZFAY-UHFFFAOYSA-M fentin acetate Chemical compound CC([O-])=O.C1=CC=CC=C1[Sn+](C=1C=CC=CC=1)C1=CC=CC=C1 WDQNIWFZKXZFAY-UHFFFAOYSA-M 0.000 description 1
- NJVOZLGKTAPUTQ-UHFFFAOYSA-M fentin chloride Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 NJVOZLGKTAPUTQ-UHFFFAOYSA-M 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- LQJBNNIYVWPHFW-QXMHVHEDSA-N gadoleic acid Chemical compound CCCCCCCCCC\C=C/CCCCCCCC(O)=O LQJBNNIYVWPHFW-QXMHVHEDSA-N 0.000 description 1
- UHUSDOQQWJGJQS-UHFFFAOYSA-N glycerol 1,2-dioctadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)OC(=O)CCCCCCCCCCCCCCCCC UHUSDOQQWJGJQS-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- PXDJXZJSCPSGGI-UHFFFAOYSA-N hexadecanoic acid hexadecyl ester Natural products CCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCC PXDJXZJSCPSGGI-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229940089456 isopropyl stearate Drugs 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- YKSNLCVSTHTHJA-UHFFFAOYSA-L maneb Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S YKSNLCVSTHTHJA-UHFFFAOYSA-L 0.000 description 1
- 229920000940 maneb Polymers 0.000 description 1
- 239000008268 mayonnaise Substances 0.000 description 1
- 235000010746 mayonnaise Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- YICRPERKKBDRSP-UHFFFAOYSA-N methyl 3-amino-4-methylthiophene-2-carboxylate Chemical compound COC(=O)C=1SC=C(C)C=1N YICRPERKKBDRSP-UHFFFAOYSA-N 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- BLCKKNLGFULNRC-UHFFFAOYSA-L n,n-dimethylcarbamodithioate;nickel(2+) Chemical compound [Ni+2].CN(C)C([S-])=S.CN(C)C([S-])=S BLCKKNLGFULNRC-UHFFFAOYSA-L 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- SFBHPFQSSDCYSL-UHFFFAOYSA-N n,n-dimethyltetradecan-1-amine Chemical compound CCCCCCCCCCCCCCN(C)C SFBHPFQSSDCYSL-UHFFFAOYSA-N 0.000 description 1
- MJCJUDJQDGGKOX-UHFFFAOYSA-N n-dodecyldodecan-1-amine Chemical compound CCCCCCCCCCCCNCCCCCCCCCCCC MJCJUDJQDGGKOX-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 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
- NKBWPOSQERPBFI-UHFFFAOYSA-N octadecyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC NKBWPOSQERPBFI-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000019809 paraffin wax Nutrition 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
- 150000002978 peroxides Chemical class 0.000 description 1
- YFMFSCRSAWIWOP-UHFFFAOYSA-N phenyl(trityl)diazene Chemical compound C1=CC=CC=C1N=NC(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 YFMFSCRSAWIWOP-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 description 1
- 235000015277 pork Nutrition 0.000 description 1
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- ZPWFUIUNWDIYCJ-UHFFFAOYSA-N propan-2-yl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC(C)C ZPWFUIUNWDIYCJ-UHFFFAOYSA-N 0.000 description 1
- KKMLIVYBGSAJPM-UHFFFAOYSA-L propineb Chemical compound [Zn+2].[S-]C(=S)NC(C)CNC([S-])=S KKMLIVYBGSAJPM-UHFFFAOYSA-L 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- KMQUXWFJALYLAL-UHFFFAOYSA-N pyridine-3-carboxylic acid;triphenyltin Chemical class OC(=O)C1=CC=CN=C1.C1=CC=CC=C1[Sn](C=1C=CC=CC=1)C1=CC=CC=C1 KMQUXWFJALYLAL-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000012177 spermaceti Substances 0.000 description 1
- 229940084106 spermaceti Drugs 0.000 description 1
- 235000019385 spermaceti wax Nutrition 0.000 description 1
- 238000007592 spray painting technique Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229930192474 thiophene Natural products 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
- 239000004408 titanium dioxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- UWHZIFQPPBDJPM-BQYQJAHWSA-N trans-vaccenic acid Chemical compound CCCCCC\C=C\CCCCCCCCCC(O)=O UWHZIFQPPBDJPM-BQYQJAHWSA-N 0.000 description 1
- DFNPRTKVCGZMMC-UHFFFAOYSA-M tributyl(fluoro)stannane Chemical compound CCCC[Sn](F)(CCCC)CCCC DFNPRTKVCGZMMC-UHFFFAOYSA-M 0.000 description 1
- PWBHRVGYSMBMIO-UHFFFAOYSA-M tributylstannanylium;acetate Chemical compound CCCC[Sn](CCCC)(CCCC)OC(C)=O PWBHRVGYSMBMIO-UHFFFAOYSA-M 0.000 description 1
- LPUCKLOWOWADAC-UHFFFAOYSA-M tributylstannyl 2-methylprop-2-enoate Chemical compound CCCC[Sn](CCCC)(CCCC)OC(=O)C(C)=C LPUCKLOWOWADAC-UHFFFAOYSA-M 0.000 description 1
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 1
- FOMOJHCBPYBMHJ-UHFFFAOYSA-N tricyclohexyl(tricyclohexylstannyloxy)stannane Chemical compound C1CCCCC1[Sn](C1CCCCC1)(C1CCCCC1)O[Sn](C1CCCCC1)(C1CCCCC1)C1CCCCC1 FOMOJHCBPYBMHJ-UHFFFAOYSA-N 0.000 description 1
- DVDWTXZYUHBOIX-UHFFFAOYSA-M tricyclohexylstannanylium;fluoride Chemical compound C1CCCCC1[Sn](C1CCCCC1)(F)C1CCCCC1 DVDWTXZYUHBOIX-UHFFFAOYSA-M 0.000 description 1
- FJEZLYTXQIEUAT-UHFFFAOYSA-M tricyclohexylstannyl acetate Chemical compound C1CCCCC1[Sn](C1CCCCC1)(OC(=O)C)C1CCCCC1 FJEZLYTXQIEUAT-UHFFFAOYSA-M 0.000 description 1
- RNVJQUPAEIQUTC-UHFFFAOYSA-N tricyclohexyltin Chemical compound C1CCCCC1[Sn](C1CCCCC1)C1CCCCC1 RNVJQUPAEIQUTC-UHFFFAOYSA-N 0.000 description 1
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
- 229940117972 triolein Drugs 0.000 description 1
- MUHFQLVFMFDJOK-UHFFFAOYSA-N triphenyl(triphenylstannyloxy)stannane Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(C=1C=CC=CC=1)O[Sn](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 MUHFQLVFMFDJOK-UHFFFAOYSA-N 0.000 description 1
- XOFYGTPELGZPLY-UHFFFAOYSA-M triphenylstannyl 2-chloroacetate Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(OC(=O)CCl)C1=CC=CC=C1 XOFYGTPELGZPLY-UHFFFAOYSA-M 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 239000011787 zinc oxide 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
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 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
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野］
本発明は側鎖にポリジメチルシロキサン基および／また
はトリメチルシリル基を有する重合体を含む水中防汚被
覆剤に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an underwater antifouling coating containing a polymer having a polydimethylsiloxane group and/or a trimethylsilyl group in its side chain.
〔従来の技術］
海水に浸漬されている船底、ブイ、漁網、冷却のための
各種吸排水管などの海中物体の表面には、フジッボ、セ
ルプラ、イガイ、藻類などの付着によって種々の支障が
起こる。これら生物の付着を防止するために、海水浸漬
物の表面に防汚塗料が塗布されることはよく知られてい
る。この防汚塗膜には大別して下記４２口のふたつの型
がある。[Prior Art] Various problems occur on the surfaces of underwater objects immersed in seawater, such as ship bottoms, buoys, fishing nets, and various intake and drainage pipes for cooling, due to adhesion of Fujibo, Serpura, mussels, algae, and the like. It is well known that antifouling paints are applied to the surfaces of objects immersed in seawater in order to prevent the attachment of these organisms. There are two types of antifouling coatings: 42 types as shown below.
イ）生物に対して付着防止効果を持ち、かつ海水中で微
溶解性のある有機錫共重合体、亜酸化銅などの防汚剤を
用いたもの。b) Products that use antifouling agents such as organic tin copolymers and cuprous oxide that have an anti-adhesion effect on living things and are slightly soluble in seawater.
たとえば、有機錫化合物を防汚剤として使用した塗料に
ついては、特公昭４０−２１４２６号公報、持公報４４
−９５７９号公報、特公昭４６−１３３９２号公報、特
公昭４９−２０４９１号公報、特公昭５１−１１６４７
号公報、特公昭５２−４８１７０号公報に開示されてい
る。For example, regarding paints using organic tin compounds as antifouling agents, Japanese Patent Publication No. 40-21426 and Publication No. 44 of
-9579 Publication, Japanese Patent Publication No. 13392/1972, Japanese Patent Publication No. 20491/1972, Japanese Patent Publication No. 11647/1977
It is disclosed in Japanese Patent Publication No. 52-48170.
口）防汚剤を用いず、海水へ溶解しない防汚塗料であっ
て、触媒、水分などの作用で加硫して三次元架橋し、膜
形成するシリコーンゴムを使ったもの。(Note) An antifouling paint that does not use antifouling agents and does not dissolve in seawater, and uses silicone rubber that is vulcanized and three-dimensionally crosslinked to form a film by the action of catalysts, moisture, etc.
たとえば、特公昭５３−３５９７４号公報には加硫シリ
コーンゴムを被覆剤として用いているものが開示されて
おり、また特開昭５１−９６８３０号公報にはヒドロキ
シル末端基を有するオリゴマー状シリコーンゴムとシリ
コーン油との混合物を使ったものが示されている。さら
に、特開昭５３−７９９８０号公報には加硫シリコーン
ゴムと金属を含まずかつシリコンを含まない流動性の有
機化合物との混合物が示されている。さらにまた、特公
昭６０−３４３３号公報にはオリゴマー状常温硬化形シ
リコーンゴム（たとえば信越化学工業株式会社の商品名
ＫＥ４５ＴＳ、ＫＥ４４ＲＴＶなど）と、流動パラフィ
ンまたはペトロラタムとを混合した海洋生物付着防止用
塗料が示されている。For example, Japanese Patent Publication No. 53-35974 discloses a coating using vulcanized silicone rubber, and Japanese Patent Application Publication No. 51-96830 discloses a coating using vulcanized silicone rubber as a coating material. A mixture with silicone oil is shown. Further, JP-A-53-79980 discloses a mixture of vulcanized silicone rubber and a fluid organic compound that does not contain metal or silicone. Furthermore, Japanese Patent Publication No. 60-3433 discloses a paint for preventing the adhesion of marine organisms, which is a mixture of oligomeric room-temperature curing silicone rubber (for example, Shin-Etsu Chemical Co., Ltd.'s product names KE45TS, KE44RTV, etc.) and liquid paraffin or petrolatum. It is shown.
〔発明が解決しようとする問題点１
これら従来公知の防汚塗料は、その型に応じた性能を発
揮できることから、用途目的に応じて使い分けられてい
るが、いずれも以下に記述する如き欠点を有しており、
これの改良が望まれている。[Problem to be solved by the invention 1 These conventionally known antifouling paints can exhibit performance depending on their type, so they are used depending on the purpose of use, but all of them have the following drawbacks. has,
Improvements in this are desired.
まず、前記のイの型の防汚塗料にはさらにふたつの型が
ある０ひとつは、塗膜を形成する樹脂は１毎水中へは溶
解せず、防ｔη剤だけが海水中へ溶解することによって
海中生物の付着を防止する型の防汚塗料である。この型
の防汚塗膜は初期の防汚効果はよい。しかしながら、塗
膜表面の防汚剤が溶出して失われたのちには、次第に塗
膜深部の防汚剤が溶出することになるが、防汚剤の溶出
速度としては塗膜深部になるにつれて遅いため、長期に
は防ｌり効果が不足していく欠点があった。First of all, there are two more types of antifouling paint of type A above.One is that the resin that forms the paint film does not dissolve in water, but only the antifouling agent dissolves in seawater. This is a type of antifouling paint that prevents the adhesion of marine organisms. This type of antifouling coating has a good initial antifouling effect. However, after the antifouling agent on the surface of the paint film is eluted and lost, the antifouling agent in the deeper part of the paint film gradually elutes. Because it is slow, it has the disadvantage that the prevention effect becomes insufficient in the long term.
いまひとつは、塗膜を形成する樹脂および防汚剤のいず
れもが海水中に溶解する型の防汚塗料である。この型の
塗料の防汚効果は防汚剤のみによる場合と防汚剤および
樹脂成分（有機錫共重合体など）の双方による場合があ
るが、いずれにおいても塗膜表面が溶出するため、常に
活性な防汚塗膜表面が維持されるから、前者よりも長期
の防汚効果を維持することができる。しかしながら、後
者においても、塗膜の消耗等に限界があり、満足な効果
を得ていないのが現状である。The other type is an antifouling paint in which both the resin that forms the coating film and the antifouling agent are dissolved in seawater. The antifouling effect of this type of paint may be due to the antifouling agent alone or to both the antifouling agent and the resin component (organic tin copolymer, etc.), but in either case, the paint surface is eluted, so Since the active antifouling coating surface is maintained, the antifouling effect can be maintained for a longer period of time than the former. However, even in the latter case, there are limits to the wear and tear of the coating film, and the current situation is that satisfactory effects have not been achieved.
また、前記口の防汚塗料は、いずれもシリコーンゴム被
覆表面の滑り性を利用して、上記表面への水中生物の付
着を防止するようにしたものであって、前記イの塗料の
ように水質汚染をきたすおそれのある溶出成分が無いと
いった利点を備えているものの、上記被膜を形成するた
めのシリコーンゴムは使用時に三次元架橋して膜形成を
行う点で以下の問題を有している。In addition, the antifouling paints for the mouth are all made to take advantage of the slipperiness of the silicone rubber coated surface to prevent aquatic organisms from adhering to the surface, and like the paint in A above, Although it has the advantage of not containing eluted components that may cause water pollution, the silicone rubber used to form the film has the following problems in that it undergoes three-dimensional crosslinking to form a film during use. .
第一には、塗装後の硬化性の問題がある。たとえば特公
昭６０−３４３３号公報に示されている空気中の湿分の
作用で硬化し皮膜を形成するオリゴマー状常温硬化形シ
リコーンゴムなどを用いた防汚塗料を被塗面に塗布した
とき、シリコーンゴムの硬化縮合反応を左右する架橋剤
が大気中の水分や温度によって活性化され、そのために
、１）塗膜表面の硬化が速く、それがかえって塗膜深部
の硬化を妨げて硬化不充分となり、その結果塗膜の被塗
面からの剥離、ふくれがおこる危険性が大きい。また、
水分の内部への浸透が遅いため硬化に要する時間も長く
なる。また、１１）高温、高湿な場所でこのような防汚
塗料が使用されたときは、架嬌剤の加水分解だけが優先
されて、架橋密度があがらず、塗膜物性の低下をきたす
ことになる。さらに、ＩＩ）乾燥地では大気中の水分が
少ないため架橋剤の加水分解が起こりにくく膜の硬化が
非常に遅くなる。それを防ぐために、硬化促進剤として
錫化合物、白金などの触媒が用いられる場合があるが、
低湿地ではそれらの触媒効果も不充分になりやすい。First, there is the problem of curing properties after painting. For example, when an antifouling paint using an oligomeric room-temperature curing silicone rubber that hardens under the action of moisture in the air to form a film, as shown in Japanese Patent Publication No. 60-3433, is applied to the surface to be coated. The cross-linking agent that controls the curing and condensation reaction of silicone rubber is activated by moisture and temperature in the air, and as a result, 1) the surface of the coating film hardens quickly, which actually prevents the deep part of the coating from curing, resulting in insufficient curing; As a result, there is a great risk that the paint film will peel off from the surface to be coated and blistering will occur. Also,
Since moisture penetrates slowly, the time required for curing becomes longer. In addition, 11) When such an antifouling paint is used in a high temperature and high humidity location, only the hydrolysis of the crosslinking agent takes priority, and the crosslinking density does not increase, resulting in a decrease in the physical properties of the paint film. become. Furthermore, II) In dry areas, there is little moisture in the atmosphere, so hydrolysis of the crosslinking agent is difficult to occur and the curing of the film is extremely slow. To prevent this, catalysts such as tin compounds and platinum are sometimes used as curing accelerators.
In low-lying wetlands, their catalytic effects tend to be insufficient.
第二に、上塗り性の問題がある。通常上塗り塗料の溶剤
が下塗り塗面を若干浸して層間密着性が良くなるが、下
地のシリコーンゴムが三次元架橋して硬化するため、上
塗り塗料の溶剤がシリコーンゴム表面を浸すことがなく
、そのため密着性が劣る。Second, there is the problem of overcoatability. Normally, the solvent in the top coat slightly soaks the surface of the undercoat, improving interlayer adhesion, but because the underlying silicone rubber cures through three-dimensional crosslinking, the solvent in the top coat does not soak the silicone rubber surface. Poor adhesion.
第三に、可使時間の問題がある。実際の塗装作業は、被
塗物の大きさ、構造の複雑さ、塗装中の降雨などによっ
て塗装が長引いたり中断されることがおこりつる。この
ような場合に可使時間の短い防汚塗料は塗装作業上はな
はだ不便である。Thirdly, there is the issue of pot life. In actual painting work, painting may take a long time or be interrupted due to factors such as the size of the object to be painted, the complexity of the structure, and rainfall during painting. In such cases, antifouling paints with a short pot life are extremely inconvenient in painting operations.
第四に、貯蔵安定性の問題があげられる。防汚塗料は製
造されてから使用されるまで長期保存されることがある
が、湿気などで硬化するものは製造時に乾燥窒素ガスを
封入する必要があり、また−変倍の蓋を開けると大気中
の湿気が入って塗料表面の硬化や増粘を起こし再使用す
ることが一種しくなるというような問題がある。Fourth, there is the issue of storage stability. Antifouling paints may be stored for a long time from the time they are manufactured until they are used, but those that harden due to moisture need to be filled with dry nitrogen gas during manufacture, and - when the lid of the variable magnification lens is opened, atmospheric air is released. There is a problem in that moisture gets inside and causes the surface of the paint to harden and thicken, making it difficult to reuse it.
そこで、本発明者らは、上記種々の問題点を回避できる
とともに、防汚性能にすぐれた水中防汚被覆剤を得るべ
く鋭意検討した結果、分子内にポリジメチルシロキサン
基および／またはトリメチルシリル基を有する溶剤揮発
形の特定の重合体を用いた水中防汚被覆剤を得ることに
成功し、すでに特願昭６０−２９８９１８号として提案
した。Therefore, the present inventors conducted intensive studies to obtain an underwater antifouling coating that can avoid the various problems mentioned above and has excellent antifouling performance. We have succeeded in obtaining an underwater antifouling coating using a specific solvent-volatile polymer, and have already proposed it in Japanese Patent Application No. 60-298918.
上記特定の重合体は、前記従来公知のシリコーンゴム系
のものとは異なり、溶剤揮発型であるために前述した硬
化性、上塗り性、可使時間、貯蔵安定性などの問題が本
質的になく、しかもこの重合体より形成される塗膜は表
面滑り性を発揮するために防汚性能の改善も認められる
ことが判明した。Unlike the conventionally known silicone rubber-based materials, the above-mentioned specific polymer is essentially free from the aforementioned problems such as curability, overcoatability, pot life, and storage stability because it is a solvent-volatile type. Moreover, it has been found that the coating film formed from this polymer has improved antifouling performance because it exhibits surface slipperiness.
また、本発明者らは、上記提案に係る特定の重合体に石
油ワックス、シリコーンオイル、油脂などの各線の表面
滑性剤を配合したときには、防汚性能がより改善された
ものとなることを知り、特願昭６１−１２６９８８号と
してすでに提案した。In addition, the present inventors have found that when a surface lubricant such as petroleum wax, silicone oil, or oil is added to the specific polymer proposed above, the antifouling performance is further improved. I learned of this and have already proposed it in Japanese Patent Application No. 126988/1983.
本発明は、これらの先行発明をベースとしてこの先行発
明をさらに改良すること、すなわち先行発明と同様に前
記従来公知の防汚塗料の問題点を解消できるとともに、
先行発明よりもさらに一段と改善された防汚性能が得ら
れる工業的により有用な水中防汚被覆剤を提供すること
を目的としている。The present invention further improves the prior invention based on these prior inventions, that is, it solves the problems of the conventionally known antifouling paints as well as the prior invention, and
It is an object of the present invention to provide an industrially more useful underwater antifouling coating that provides even more improved antifouling performance than the previous invention.
本発明者らは、上記目的を達成するために鋭意検討した
結果、先行発明に係る特定の重合体とともに防汚剤を用
いることにより、また上記防汚剤とさらに表面滑性剤を
用いることにより、上記重合体に基づく既述した利点を
失うことなく防汚性能を前記先行発明よりもさらに一段
と改善できることを知り、本発明を完成するに至った。As a result of intensive studies to achieve the above object, the present inventors have found that by using an antifouling agent together with the specific polymer according to the prior invention, and by using the above antifouling agent and a surface lubricating agent. The present invention was completed based on the knowledge that the antifouling performance can be further improved compared to the prior invention without losing the aforementioned advantages based on the polymer.
すなわち、本発明は、つぎの一般式；
％式％
（ただし、式中、Ｘは水素原子またはメチル基、ｎは２
〜４の整数、ｍは平均重合度で０〜７０を表わす）
で示される単量体Ａの一種または二種以上の重合体つま
り単独重合体または共重合体（以下、これらを重合体Ａ
という）、および／または上記単量体Ａの一種または二
種以上とこれらと共重合し得るビニル重合性単量体Ｂの
一種または二種以上とからなる共重合体（以下、これら
を共重合体ＡＢという）と、防汚剤とを必須成分として
含有する水中防汚被覆剤に係る第１の発明と、上記の共
重合体および防汚剤とともにさらに表面′滑性剤を必須
成分として含有する水中防ｔ１５被覆剤に係る第２の発
明とからなるものである。That is, the present invention is based on the following general formula;
An integer of ~4, m represents an average degree of polymerization of 0 to 70) (hereinafter referred to as polymer A).
), and/or a copolymer consisting of one or more of the above monomers A and one or more vinyl polymerizable monomers B that can be copolymerized with these monomers (hereinafter referred to as copolymerizable monomers). A first invention relating to an underwater antifouling coating agent containing a copolymer AB) and an antifouling agent as essential components; This invention consists of a second invention relating to an underwater waterproof T15 coating material.
本発明において使用する重合体Ａおよび共重合体Ａ Ｂ
を得るための前記一般式（１）で表わされる単ｉｊｔ体
Ａは、その分子内にポリジメチルシロキサン基（ｍ＝１
以上）またはトリメチルシリル基（ｍ＝０）を有する不
飽和カルボン酸モノエステルである。式ｆｉｌ中、ｍ＝
ｏ〜７０としているのは、ｍか７０より大きくなると、
単量体Ａの重合性ないし共重合性が低下し、均一に被膜
化しうる重合体Ａまたは共重合体ＡＢを得にくくなるた
めである。Polymer A and copolymer A B used in the present invention
The single ijt compound A represented by the general formula (1) for obtaining the formula (1) has a polydimethylsiloxane group (m=1) in its molecule.
above) or an unsaturated carboxylic acid monoester having a trimethylsilyl group (m=0). In the formula fil, m=
The reason why it is set as o~70 is that if it is larger than m or 70,
This is because the polymerizability or copolymerizability of monomer A decreases, making it difficult to obtain polymer A or copolymer AB that can be formed into a uniform film.
また、式ｔｌｌ中、ｎ ＝ ２〜４としているのは、ｎ
が２未満となると単量体Ａのエステル形成部の結合性か
弱くなり、重合段階あるいは′ｆｇｌ覆剤としての使用
時にエステル結合か解１碓して防汚性能およびその持続
性が低下するためであり、またｎが４を超えると重合体
が軟化するため、好ましくない。Also, in the formula tll, n = 2 to 4 is n
If it is less than 2, the bonding strength of the ester-forming moiety of monomer A will be weakened, and the ester bond will be dissolved during the polymerization stage or when used as a 'fgl covering agent, resulting in a decrease in the antifouling performance and its sustainability. However, if n exceeds 4, the polymer will soften, which is not preferable.
このような単量体Ａの具体的化合物芯を挙げれば、トリ
メチルシリル基を有するものとして（メタ）アクリル酸
トリメチルシリルエチル、（メタ）アクリル酸トリメチ
ルシリルプロピル、（メタ）アクリル酸トリメチルシリ
ルブチルがあり、またポリジメチルシロキサン基を有す
るものとしてｍ＝７０までの（メタ）アクリル酸ポリジ
メチルシロキサンエチル、（メタ）アクリル酸ポリジメ
チルシロキサンプロピル、（メタ）アクリル酸ポリジメ
チルシロキサンブチルがある。なお、上記の（メタ）と
はアクリル酸またはメタクリル酸のいずれであってもよ
いことを意味する。Specific compound cores of such monomer A include trimethylsilylethyl (meth)acrylate, trimethylsilylpropyl (meth)acrylate, and trimethylsilylbutyl (meth)acrylate as those having a trimethylsilyl group. Those having a dimethylsiloxane group include polydimethylsiloxaneethyl (meth)acrylate, polydimethylsiloxanepropyl (meth)acrylate, and polydimethylsiloxanebutyl (meth)acrylate in which m is up to 70. Note that the above (meth) means that it may be either acrylic acid or methacrylic acid.
このような単量体Ａは市販品として容易に入手可能なも
のであるが、その合成例を挙げれば、（メタ）アクリル
酸とアルキレングリコールとのエステルを得、これにト
リメチルシリル化合物ないしポリジメチルシロキサン化
合物を縮合反応させる方法、（メタ）アクリル酸とアリ
ルアルコールなどとのエステルを得、これにトリメチル
シリル化合物ないしポリジメチルシロキサン化合物を付
加反応させる方法などがある。Such monomer A is easily available as a commercial product, but to give an example of its synthesis, an ester of (meth)acrylic acid and alkylene glycol is obtained, and a trimethylsilyl compound or polydimethylsiloxane is added to this. Examples include a method of subjecting compounds to a condensation reaction, and a method of obtaining an ester of (meth)acrylic acid and allyl alcohol, and subjecting it to an addition reaction with a trimethylsilyl compound or a polydimethylsiloxane compound.
また、共重合体ＡＢを得るために上記の単量体Ａととも
に用いられるビニル重合性小壜体Ｂとしては、たとえば
メタクリル酸メチル、メタクリル酸エチル、メタクリル
酸ブチル、メタクリルＩｖ２−エチルヘキシル、メタク
リル酸２４ドロキシエチルなどのメタクリル酸エステル
類、アクリル酸エチル、アクリル酸ブチノペアクリル酸
２−エチルヘキシル、アクリル酸２−ヒドロキシエチル
などのアクリル酸エステル類、マレイン酸ジメチル、マ
レイン酸ジエチルなどのマレイン酸エステル類、フマー
ル酸ジメチル、フマール酸ジエチルなどのフマール酸エ
ステル類、スチレン、ビニルトルエン、α−メチルスチ
レン、塩化ビニル、酢酸ビニル、ブタジェン、アクリル
アミド、アクリロニトリル、メタクリル酸、アクリル酸
、マレイン酸などがあげられる。In addition, examples of the vinyl polymerizable small bottle B used together with the above-mentioned monomer A to obtain the copolymer AB include methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylic Iv2-ethylhexyl, methacrylic acid 24 Methacrylic esters such as droxyethyl, ethyl acrylate, butinope acrylate, acrylic esters such as 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, maleic esters such as dimethyl maleate, diethyl maleate, dimethyl fumarate , fumaric acid esters such as diethyl fumarate, styrene, vinyltoluene, α-methylstyrene, vinyl chloride, vinyl acetate, butadiene, acrylamide, acrylonitrile, methacrylic acid, acrylic acid, maleic acid, and the like.
このｎ１量体Ｂの使用ｌは、単量体Ａに基づく防汚効果
を勘案して、適宜の範囲に設定される。一般的には、単
量体Ａとの合計量中に占める単量体Ｂの割合が９０重量
％以下、特に７０重量％以下であるのがよい。すなわち
、共重合体ＡＢを構成する単１体Ａの割合が少なくとも
１０重１％、特に少なくとも３０ｉ１ｉ量％であれば、
この単量体Ａに基つく防汚効果を充分に発揮できるから
、上記範囲内で単量体Ｂの使用量を適宜設定すればよい
。The amount of n1mer B to be used is set within an appropriate range in consideration of the antifouling effect based on monomer A. Generally, the proportion of monomer B in the total amount of monomer A is preferably 90% by weight or less, particularly 70% by weight or less. That is, if the proportion of the monomer A constituting the copolymer AB is at least 10% by weight, especially at least 30% by weight,
Since the antifouling effect based on monomer A can be sufficiently exhibited, the amount of monomer B to be used may be appropriately set within the above range.
重合体Ａおよび共重合体ＡＢは、上述の如き単量体Ａま
たはこれと単１体Ｂとを、ビニル重合開始剤の存在下、
常法に準じて溶液重合、塊状重合、乳化重合、懸濁重合
などの各種方法で重合させるコトニより、得ることがで
きる。上記のビニル重合開始剤としては、アゾビスイソ
ブチロニトリル、トリフェニルメチルアゾベンゼンのよ
うなアゾ化合物、ベンゾイルペルオキシド、ジ【−ブチ
ルペルオキシドなどの過酸化物などがあげられる。Polymer A and copolymer AB are produced by combining monomer A as described above or monomer B thereof in the presence of a vinyl polymerization initiator.
It can be obtained from polymerization by various methods such as solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization according to conventional methods. Examples of the vinyl polymerization initiator include azo compounds such as azobisisobutyronitrile and triphenylmethylazobenzene, and peroxides such as benzoyl peroxide and di[-butyl peroxide].
上記の方法にて得られる重合体Ａおよび共重合体ＡＢの
重量平均分子量は、一般に１，０００〜１５０．０００
の範囲にあるのが望ましい。分子量が低すぎては、使用
に耐える被膜の形成が（碓しく、またあまりに高くなり
すぎると被覆剤用ワニスとしたとき粘度が高く、樹脂固
型分が低いため１回の塗装によって薄い被膜しか得られ
ず、一定以上の乾燥被膜厚を得るには数回の塗装を要す
るという不具合が出てくる。The weight average molecular weight of polymer A and copolymer AB obtained by the above method is generally 1,000 to 150.000.
It is desirable that it be within the range of . If the molecular weight is too low, it will be difficult to form a film that can withstand use, and if it is too high, the viscosity will be high when used as a coating varnish, and the resin solid content will be low, so only a thin film can be formed with one application. However, the problem arises that several coats of paint are required to obtain a dry film thickness above a certain level.
本発明において使用する防汚剤には、従来公知のものが
広く包含される。大別すれば、金属を含む有機化合物、
金属を含まない有機化合物および無機化合物がある。The antifouling agents used in the present invention include a wide range of conventionally known antifouling agents. Broadly divided, organic compounds containing metals,
There are organic and inorganic compounds that do not contain metals.
金属を含む有機化合物には、有機錫系化合物、有機銅系
化合物、有機ニッケル系化合物および有機亜鉛系化合物
などがあり、その曲マンネブ、マンセブ、プロピネブな
ども挙げられる。また、金１．４を含まない有機化合物
には、１・４−ナフトキノン、Ｎ−トリハロメチルチオ
フタルイミド、ジチオカルバミンＨ１Ｎ−アリールマレ
イミド、３−置換アミンート３−チンシリジン−２・４
−ジオン、ジチオシアノ系化合物などがある。さらに、
無機化合物としては、亜酸化銅、銅粉、チオシアン酸銅
、炭酸銅、塩化銅、硫「段調などの銅化合物、硫酸亜鉛
、酸化亜鉛、硫酸ニッケルなどが挙げられる。Examples of organic compounds containing metals include organotin compounds, organocopper compounds, organic nickel compounds, and organozinc compounds, and examples thereof include maneb, manseb, propineb, and the like. Organic compounds that do not contain gold 1.4 include 1,4-naphthoquinone, N-trihalomethylthiophthalimide, dithiocarbamine H1N-arylmaleimide, 3-substituted amine-3-tinsyridine-2,4
- Diones, dithiocyano compounds, etc. moreover,
Examples of inorganic compounds include cuprous oxide, copper powder, copper thiocyanate, copper carbonate, copper chloride, copper compounds such as sulfur, zinc sulfate, zinc oxide, nickel sulfate, and the like.
なお、上記の金属を含む有機化合物のうちの有機錫系化
合物としては、トリフェニル錫クロリド、トリフェニル
錫フルオリドなどのトリフェニル錫ハライド、トリシク
ロヘキシル錫クロリド、トリシクロヘキシル錫フルオリ
ドなどのトリシクロヘキシル錫ハライド、トリブチル錫
クロリド、トリブチル錫フルオリドなど゛のトリブチル
を易ハライド、トリフェニル錫ヒドロオキシド、トリシ
クロヘキシル錫ヒドロオキシド、ビス（トリフェニル８
）−α・α′−ジブロモサクシネート、ビス（トリシク
ロヘキシル錫）−α・α′−ジブロモサクシネート、ビ
ス（トリブチル錫）−α・α′−ジブロモサクシネート
、ビス−（トリフェニル錫）オキシド、ビス−（トリシ
クロヘキシル錫）オキシド、ビス−（トリブチル錫）オ
キシド、トリフェニル錫アセテート、トリシクロヘキシ
ル錫アセテート、トリブチル錫アセテート、トリフェニ
ル錫モノクロロアセテート、トリフェニル錫バーサチッ
ク酸エステル、トリフェニル錫ジメチルジチオカーバメ
ート、トリフェニル錫ニコチン酸エステルなどがある。Among the organic compounds containing the above metals, organotin compounds include triphenyltin halides such as triphenyltin chloride and triphenyltin fluoride, and tricyclohexyltin halides such as tricyclohexyltin chloride and tricyclohexyltin fluoride. , tributyltin chloride, tributyltin fluoride and other tributyl halides, triphenyltin hydroxide, tricyclohexyltin hydroxide, bis(triphenyltin 8
)-α・α′-dibromosuccinate, bis(tricyclohexyltin)-α・α′-dibromosuccinate, bis(tributyltin)-α・α′-dibromosuccinate, bis-(triphenyltin) oxide , bis-(tricyclohexyltin) oxide, bis-(tributyltin) oxide, triphenyltin acetate, tricyclohexyltin acetate, tributyltin acetate, triphenyltin monochloroacetate, triphenyltin versatate, triphenyltin dimethyldithio These include carbamates and triphenyltin nicotinic acid esters.
また、有機銅系化合物としては、オキシン銅、ノニルフ
ェノールスルホン階調、カッパービス（３−クロロ−１
・４−ナフトキノン−２−オレエート）、カッパービス
（１・４−ナフトキノン−２−オレエート）、カッパー
ビス（エチレンジアミン）−ビス（ドデシルベンゼンス
ルホネート）、酢酸銅、ナフテン酸銅、ビス（ペンタク
ロロフェノール酸）銅などがある。さらに、有機ニッケ
ル系化合物としては、酢酸ニッケル、ジメチルジチオカ
ルバミン酸ニッケルなどが、有機亜鉛系化合物としては
、酢酸亜鉛、カルバジン酸亜鉛、ジメチルジチオカルバ
ミン酸亜鉛などがある。In addition, organic copper compounds include oxine copper, nonylphenol sulfone gradation, kappa bis(3-chloro-1
・4-naphthoquinone-2-oleate), Kappabis(1,4-naphthoquinone-2-oleate), Kappabis(ethylenediamine)-bis(dodecylbenzenesulfonate), Copper acetate, Copper naphthenate, Bis(pentachlorophenolic acid) ) Copper, etc. Furthermore, examples of organic nickel compounds include nickel acetate and nickel dimethyldithiocarbamate, and examples of organic zinc compounds include zinc acetate, zinc carbazate, and zinc dimethyldithiocarbamate.
なおまた、上記の金属を含まない有機化合物のうちの１
・４−ナフトキノンとしては、２−アミ／−３−クロロ
−１・４−ナフトキノン、２・３−シクロロート４−ナ
フトキノン、５・１０−ジヒドロ−５・１０−ジオキサ
ナフト〔２・３−ｂｌ−１・４−ジチイン−２・３−ジ
カルボニトリルなどが、Ｎ−トリハロメチルチオフタル
イミドとしては、Ｎ−トリクロロメチルチオフタルイミ
ド、Ｎ−フルオロジクロロメチルチオフタルイミドなど
が、ジチオカルバミン酸としては、ビス（ジメチルチオ
カルバモイル）ジスルフィド、Ｎ−メチルジチオカルバ
ミン酸アンモニウム、エチレンビス（ジチオカルバミン
酸）アンモニウム、ミルネブなどが、それぞれ挙げられ
る。Furthermore, one of the above metal-free organic compounds
・4-naphthoquinone includes 2-ami/-3-chloro-1,4-naphthoquinone, 2,3-cycloroto-4-naphthoquinone, 5,10-dihydro-5,10-dioxanaphtho [2,3-bl-1・4-dithiin-2,3-dicarbonitrile, etc., N-trihalomethylthiophthalimide such as N-trichloromethylthiophthalimide, N-fluorodichloromethylthiophthalimide, etc., and dithiocarbamic acid such as bis(dimethylthiocarbamoyl) disulfide. , ammonium N-methyldithiocarbamate, ammonium ethylenebis(dithiocarbamate), milneb, and the like.
また、Ｎ−アリールマレイミドとしては、Ｎ−（２・４
・６４リクロ口フェニル）マレイミド、Ｎ−４−１−’
Ｊルマレイミド、Ｎ−３−クロロフェニルマレイミ）’
、Ｎ−（４−ｎ−ブチルフェニル）マレイミド、Ｎ−（
アニリノフェニル）マレイミド、Ｎ−（２・３−キシリ
ル）マレイミドなどが、３−置換アミノート３−チアゾ
リジン−２・４−ジオンとしては、３−ベンジリデンア
ミ７−１・３−チアゾリジン−２・４−ジオン、３−（
４−メチルベンジリデンアミ／）−１・３−チアゾリジ
ン−２・４−ジオン、３−（２−ヒドロキシベンジリデ
ンアミ／）−１・３−チアゾリジン−２・４−ジオン、
３−（４−ジメチルアミノベンジリデンアミノ）−１・
３−チアゾリン−２・４−ジオン、３−（２・４−ジク
ロロベンジリデンアミノ）−１・３−チアゾリジン−２
・４−ジオンなどが、ジチオシア／系化合物としては、
ジチオシアノメタン、ジチオシアノエタン、２・５−ジ
チオシア／チオフェンなどが、それぞれ挙げられる。In addition, as N-arylmaleimide, N-(2.4
・64 Licro-phenyl)maleimide, N-4-1-'
J lumaleimide, N-3-chlorophenylmaleimide)'
, N-(4-n-butylphenyl)maleimide, N-(
anilinophenyl)maleimide, N-(2,3-xylyl)maleimide, etc., and 3-substituted amino 3-thiazolidine-2,4-dione such as 3-benzylidene amide 7-1, 3-thiazolidine-2,4 -dione, 3-(
4-methylbenzylideneami/)-1,3-thiazolidine-2,4-dione, 3-(2-hydroxybenzylideneami/)-1,3-thiazolidine-2,4-dione,
3-(4-dimethylaminobenzylideneamino)-1.
3-Thiazoline-2,4-dione, 3-(2,4-dichlorobenzylideneamino)-1,3-thiazolidine-2
・4-dione etc. are dithiocya/based compounds,
Examples include dithiocyanomethane, dithiocyanoethane, 2,5-dithiocya/thiophene, and the like.
本発明においては、上述の如き各種の防汚剤の中からそ
の一種または二種以上を選択使用するが、その使用；旧
よ、重合体Ａおよび／または共重合体ＡＢの被膜が有す
る表面滑り性から期待される防汚効果と防汚剤の化学的
な防汚効果との相乗効果を勘案して適宜の範囲に設定さ
れる。一般的には、重合体Ａおよび／または共重合体Ａ
Ｂとの合計量中に占める防汚剤の割＆が０．１〜６５重
量％であるのが望ましい。防汚剤が過少では前記の相乗
効果を期待できず、過多では形成される水中防汚被膜に
クラック、剥Ｈ雅などの被膜欠陥が生じやすくなり、効
果的な防汚性が得られにくくなる。In the present invention, one or more antifouling agents are selected from among the various antifouling agents mentioned above. It is set within an appropriate range, taking into consideration the synergistic effect between the antifouling effect expected from the nature of the stain and the chemical antifouling effect of the antifouling agent. Generally, polymer A and/or copolymer A
It is desirable that the proportion of the antifouling agent in the total amount with B is 0.1 to 65% by weight. If the antifouling agent is too small, the synergistic effect described above cannot be expected, and if the antifouling agent is too large, film defects such as cracks and peeling will easily occur in the formed underwater antifouling film, making it difficult to obtain effective antifouling properties. .
本発明において使用する表面滑性剤としては、彼）漠に
表面？Ｐ１り性を付与するものとして知られる［ｎ々の
物質があり、その代表的な例を挙げれば、■ＪＩＳＫ２
２３５に規定される石油ワックス、■ＪＩＳ Ｋ ２２
３１ で規定される流動パラフィン、０２５℃において
５５，０００センチストークス以下の動粘度を有するシ
リコーンオイル、■−５℃以上の融点を有する炭素数８
以上の脂肪酸およびそのエステル、０炭素数１２〜２０
のアルキル基またはアルケニル基を有する有機アミンな
どがある。The surface lubricant used in the present invention may be vaguely referred to as surface lubricant. There are a number of substances that are known to impart P1 properties, and representative examples include ■JISK2
Petroleum wax specified in 235, ■JIS K 22
Liquid paraffin defined by 31, silicone oil having a kinematic viscosity of 55,000 centistokes or less at 025°C, ■ carbon number 8 having a melting point of -5°C or more
The above fatty acids and their esters, 0 carbon atoms 12-20
Examples include organic amines having an alkyl group or an alkenyl group.
上記■の具体例としては、パラフィンワックス、マイク
ロクリスタリンワックス、ペトロラタムなどが、上記■
の具体例としては、ｌ５ＯＶＧＩＯ１ＩＳＯＶＧ１５、
ｌ５ＯＶＧ３２、ｌ５ＯＶＧ６８、ｌ５ＯＶＧ１００の
各相当品が、上記■の具体例としては、たとえば信越化
学工業株式会社製の商品名ＫＦ９６Ｌ−０，８５、ＫＦ
９６Ｌ−２，０、ＫＦ９６−３０、ＫＦ９６Ｈ−５０，
０００、ＫＦ９６５、ＫＦ５０、ＫＦ５４、ＫＦ６９な
どが、それぞれあげられる。Specific examples of the above (■) include paraffin wax, microcrystalline wax, petrolatum, etc.
As a specific example, l5OVGIO1ISOVG15,
Specific examples of the above (■) include products equivalent to l5OVG32, l5OVG68, and l5OVG100, such as the product names KF96L-0,85 and KF manufactured by Shin-Etsu Chemical Co., Ltd.
96L-2,0, KF96-30, KF96H-50,
000, KF965, KF50, KF54, KF69, etc., respectively.
上記■のシリコーンオイルはジメチルシリコーンオイル
が最も一般的であるが、その他メチルフェニルシリコー
ンオイルなどの他のものであってもよい。The silicone oil mentioned in (2) above is most commonly dimethyl silicone oil, but other types such as methylphenyl silicone oil may also be used.
また、上記■の具体例としては、たとえばカプリル酸、
カプリン酸、ラウリン酸、ミリスチン酸、バルミチン酸
、ステアリン酸、セロチン酸、モンタン酸、メリシン酸
、ラウロレイン酸、オレイン酸、バクセン酸、ガドレイ
ン酸、鯨油酸、鯨油酸、ジュニペリン酸などがあげられ
る。また、これらカルボン酸のエステルとしては、ステ
アリルステアレート、ブチルラウレート、オクチルパル
ミテート、ブチルステアレート、イソプロピルステアレ
ート、セチルパルミテート、セリルセロテート、ミリシ
ルパルミテート、メリシルメリセート、鯨ろう、密ろう
、カルナウバろう、モンタンろう、蟲ろう、トリステア
リン、トルパルミチン、トリオレイン、ミリストジラウ
リン、カプリロラウロミリスチン、ステアロパルミトオ
レイン、モノステアリン、モノパルミチン、ジステアリ
ン、シバルミチン、牛脂、豚脂、馬脂、羊脂、鱈肝油、
ヤシ浦、パーム浦、木ろう、カポック油、カカオ脂、支
那脂、イリツペ脂などがあげられる。Further, as specific examples of the above (■), for example, caprylic acid,
Examples include capric acid, lauric acid, myristic acid, valmitic acid, stearic acid, cerotic acid, montanic acid, mellisic acid, lauroleic acid, oleic acid, vaccenic acid, gadoleic acid, whale oil acid, whale oil acid, and juniperic acid. In addition, esters of these carboxylic acids include stearyl stearate, butyl laurate, octyl palmitate, butyl stearate, isopropyl stearate, cetyl palmitate, seryl cerotate, myricyl palmitate, melysylmerisate, spermaceti, spermaceti Wax, carnauba wax, montan wax, wax wax, tristearin, tolpalmitin, triolein, myristodilaurin, caprylolauromyristin, stearopalmitolein, monostearin, monopalmitin, distearin, civalmitin, beef tallow, pork fat , horse tallow, mutton tallow, cod liver oil,
Examples include palm oil, palm oil, wood wax, kapok oil, cacao butter, China butter, and iritsupe butter.
さらに、上記■の具体例としては、たとえばドデシルア
ミン、テトラデシルアミン、ヘキサデシルアミン、オク
タデシルアミン、オレイルアミン、牛脂アルキルアミン
、ココアルキルアミン、大豆油アルキルアミン、ジドデ
シルアミン、ジ牛脂水素化アルキルアミン、ドデシルジ
メチルアミン、ココアルキルジメチルアミン、テトラデ
シルジメチルアミン、ヘキサメチルジメチルアミン、オ
クタデシルジメチルアミンなどが挙げられる。Furthermore, as specific examples of the above (1), for example, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, oleylamine, beef tallow alkylamine, cocoalkylamine, soybean oil alkylamine, didodecylamine, di-tallow hydrogenated alkylamine. , dodecyldimethylamine, cocoalkyldimethylamine, tetradecyldimethylamine, hexamethyldimethylamine, octadecyldimethylamine, and the like.
本発明においては、上述の如き各種の表面滑性剤の中か
らその一種または二種以上を選択使用するが、その使用
量は、前記の重合体Ａおよび／または共重合体ＡＢおよ
び防汚剤に基づく乾燥性。In the present invention, one or more of the above-mentioned surface lubricants are selected and used, and the amount used is determined by the amount of the above-mentioned polymer A and/or copolymer AB and the antifouling agent. Drying properties based on
密着性などの性能とさらに防汚性能とを勘案して、適宜
の範囲に設定される。一般的には、重合体Ａおよび／ま
たは共重合体ＡＢと表面滑性剤との合計量中に占める表
面滑性剤の割合が１〜７０重量％、特に５〜５０重量％
であるのが好ましい。It is set within an appropriate range, taking into consideration performance such as adhesion and antifouling performance. Generally, the proportion of the surface lubricant in the total amount of the polymer A and/or copolymer AB and the surface lubricant is 1 to 70% by weight, particularly 5 to 50% by weight.
It is preferable that
本発明の水中防汚被覆剤は、前記の重合体Ａおよび／ま
たは共重合体ＡＢを必須成分として含むか、あるいはこ
れらにさらに上述の表面滑性剤を必須成分として含ませ
てなるものであり、両被覆剤共通常は有機溶剤にて希釈
して用いられる。このため、重合体Ａおよび／または共
重合体ＡＢを得るにあたっての重合法として特に溶液重
合法または塊状重合法を採用するのが望ましい。The underwater antifouling coating of the present invention contains the above-mentioned polymer A and/or copolymer AB as an essential component, or further contains the above-mentioned surface lubricant as an essential component. Both coating materials are usually used after being diluted with an organic solvent. For this reason, it is particularly desirable to employ a solution polymerization method or a bulk polymerization method as the polymerization method for obtaining the polymer A and/or the copolymer AB.
上記目的で使用する有機溶剤としては、キシレン、トル
エンなどの芳香族炭化水素系溶剤、ヘキサン、ヘプタン
などの脂肪族炭化水素系溶剤、酢酸エチル、酢酸ブチル
などのエステル系溶剤、イソプロピルアルコール、ブチ
ルアルコールナトのアルコール系溶剤、ジオキサン、ジ
エチルエーテルなどのエーテル系溶剤、メチルエチルケ
トン、メチルイソブチルケトンなどのケトン系溶剤を単
独もしくはこれらの混合溶剤として用いられる。Organic solvents used for the above purpose include aromatic hydrocarbon solvents such as xylene and toluene, aliphatic hydrocarbon solvents such as hexane and heptane, ester solvents such as ethyl acetate and butyl acetate, isopropyl alcohol, and butyl alcohol. Alcohol solvents such as Nato, ether solvents such as dioxane and diethyl ether, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone can be used alone or as a mixed solvent.
有機溶剤の使用量は、溶液中の重合体Ａおよび／または
共重合体ＡＢの濃度が通常５〜８０重量％、特に３０〜
７０重量％の範囲となるようにするのが望ましい。この
ときの溶液の粘度は、被膜比が容易となる一般に２５ポ
イズ以下／２５°Ｃの範囲にあるのがよい。The amount of organic solvent used is such that the concentration of polymer A and/or copolymer AB in the solution is usually 5 to 80% by weight, particularly 30 to 80% by weight.
It is desirable that the content be in the range of 70% by weight. The viscosity of the solution at this time is generally preferably in the range of 25 poise or less/25°C, which facilitates the coating ratio.
このように構成される本発明の水中防汚被覆剤には、必
要に応じて弁柄、二酸化チタンなどの顔料や染料などの
着色剤を配合してもよい。また、通常のタレ止め剤、色
分れ防止剤、沈降防止剤、消泡剤などを加えても差し支
えない。The underwater antifouling coating of the present invention thus constructed may contain a coloring agent such as a pigment such as Bengara, titanium dioxide, or a dye, if necessary. Further, ordinary anti-sagging agents, anti-color separation agents, anti-settling agents, anti-foaming agents, etc. may be added.
本発明の水中防ｔｌｌ披Ｊ剤を用いて海水に浸漬される
べき物体の表面に防ｔη被膜を形成するには、溶剤を含
む分散体である上記波な剤を上記物体表面に適宜の手段
で塗布したのち、常６■下ないし加熱下で乾燥して溶剤
を揮散除去するだけでよい。In order to form an anti-teta film on the surface of an object to be immersed in seawater using the underwater anti-Tll agent of the present invention, the above-mentioned wave agent, which is a dispersion containing a solvent, is applied to the surface of the object by appropriate means. After coating, all you need to do is dry it for 6 minutes or under heat to volatilize and remove the solvent.
これにより表面滑り性の良好な、かつ防汚剤との相乗効
果のある防汚被膜が均一に形成される。As a result, an antifouling film with good surface slipperiness and a synergistic effect with the antifouling agent is uniformly formed.
本発明に用いられる前記の重合体Ａおよび／または共重
合体ＡＢは、いずれも単量体Ａに由来するポリジメチル
シロキサン基および／またはトリメチルシリル基を有す
るため、形成される塗膜に強力な表面滑り性を付与する
ものである。したがって該塗膜はそれ自体が海中生・吻
の付１−：ｔを物理的に防止する機能を有しているもの
である。The above-mentioned polymer A and/or copolymer AB used in the present invention both have polydimethylsiloxane groups and/or trimethylsilyl groups derived from monomer A, so the coating film formed has a strong surface. It imparts slipperiness. Therefore, the coating film itself has the function of physically preventing marine life and proboscis attachment.
また、ビニル重合性単量体Ｂは、共重合体ＡＢの塗膜に
必要により適度の表面滑り性を付与するため、また単量
体Ａ単独に比較してより高分子量の重合体を得るための
好都合な調節成分として作用するものである。In addition, vinyl polymerizable monomer B is used in order to impart appropriate surface slipperiness to the coating film of copolymer AB, and to obtain a polymer with a higher molecular weight than monomer A alone. It acts as a convenient regulatory component.
本発明に用いられる防汚剤は、海中生物の付着を化学的
に防止するものであって、重合体Ａおよび／または共重
合体ＡＢから得られる塗膜の強力な表面滑り性との相乗
効果によって防汚性を向上持続させる。ただし、防汚剤
の併用によって塗膜の表面滑り性は必ずしも向上すると
はかぎらない。The antifouling agent used in the present invention chemically prevents the adhesion of marine organisms, and has a synergistic effect with the strong surface slipperiness of the coating film obtained from Polymer A and/or Copolymer AB. Improves and sustains stain resistance. However, the combined use of an antifouling agent does not necessarily improve the surface slipperiness of the coating film.
以上の如く、第１の発明における重合体Ａおよび／また
は共重合体ＡＢと防汚剤の併用においては、重合体Ａお
よび／または共重合体ＡＢが防汚剤の過度の溶出および
溶出不足を適度に調節する機能を持ち、塗膜の防汚性能
は長期にわたって安定に維持されていると考えられる。As described above, when using the polymer A and/or copolymer AB in combination with an antifouling agent in the first invention, the polymer A and/or copolymer AB prevents excessive elution and insufficient elution of the antifouling agent. It has the ability to adjust appropriately, and it is thought that the antifouling performance of the paint film is maintained stably over a long period of time.
また、第２の発明に用いられる表面滑性剤は、前記の重
合体Ａおよび／または共重合体ＡＢおよび防汚剤と併用
することにより、海中生物の繁殖が旺盛な海域において
も防汚性能の一層の長期持続化がはかれる上で重要であ
る。上記事実についての本発明者らの推測では、該表面
滑性剤の使用に基づく表面滑性化効果、重合体Ａおよび
／または共重合体ＡＢと防汚剤とからなる塗膜への塗膜
劣化防止効果などにより、塗膜の表面滑り性が長期にわ
たって補強維持されることに起因すると考えられる。Furthermore, by using the surface lubricant used in the second invention in combination with the above-mentioned polymer A and/or copolymer AB and an antifouling agent, the antifouling agent can be used in combination with the above-mentioned polymer A and/or copolymer AB and an antifouling agent. This is important in achieving further long-term sustainability. According to the inventors' speculation regarding the above facts, the surface smoothening effect based on the use of the surface lubricant, the coating film made of the polymer A and/or copolymer AB and the antifouling agent, This is thought to be due to the fact that the surface slipperiness of the coating film is reinforced and maintained over a long period of time due to the deterioration prevention effect.
本発明の水中防汚被覆剤に用いられる前記した特定の重
合体は、それ自体が反応性を持たず溶剤揮発型の乾燥性
を有し海水に不溶な熱可塑性の塗膜を形成するため、本
発明の水中防汚被覆剤は従来の防汚塗料と比較して以下
の利点を備えている。The above-mentioned specific polymer used in the underwater antifouling coating of the present invention has no reactivity itself, has solvent-volatile drying properties, and forms a thermoplastic coating that is insoluble in seawater. The underwater antifouling coating of the present invention has the following advantages compared to conventional antifouling paints.
塗料の製造時に、防汚剤による変質の危険性がなく安定
である。また缶詰時に不活性ガスの封入を必要とせず可
使時間の制限がない。During the production of paint, there is no risk of deterioration due to antifouling agents and it is stable. Furthermore, there is no need to fill in inert gas when canning, and there is no limit on pot life.
速乾性であり、塗膜深部の硬化不良や乾燥時の湿度や温
度により左右されることがないため、ふくれやはくりが
起りにくい。It dries quickly and is not affected by poor curing in the deep parts of the paint film or by humidity or temperature during drying, so blistering and peeling are less likely to occur.
該塗膜上に同種または他の塗料を塗り重ねた時に居間密
着性にすぐれている。When the same type of paint or another paint is applied over the paint film, it has excellent adhesion to living rooms.
塗膜が海水に接した状態でも塗膜の消耗がないため、長
期にわたって防汚性能を維持することができる。また、
従来の架橋型シリコン系防汚塗料の表面滑り性に比較し
て明らかに低い値を示しておりずくれた防汚効果を裏つ
けている。Since the paint film does not wear out even when it comes into contact with seawater, it can maintain its antifouling performance over a long period of time. Also,
Compared to the surface slipperiness of conventional cross-linked silicone-based antifouling paints, this value is clearly lower, confirming the excellent antifouling effect.
［実施例１
以下に、本発明を重合体の製造例、実施例および比較例
によって具体的に説明する。例中の部は重量部、粘度は
２５゛Ｃにおける泡粘度測定値、分子量はＧＰＣ法によ
る重量平均分子竜を表わす。[Example 1] The present invention will be specifically explained below with reference to polymer production examples, examples, and comparative examples. In the examples, parts are parts by weight, viscosity is a foam viscosity measurement value at 25°C, and molecular weight is a weight average molecular weight measured by GPC method.
製造例１，２，４．５および７
ｉＱ ４シ幾付きのフラスコに第１表の配合に準じて溶
剤ａを仕込み反応温度に昇温させ、撹拌しながら単喰体
Ａ１単ｊｉ１体Ｂおよび重合触媒ａの混合液をフラスコ
の中へ２〜３時間で滴下し、滴下終了後同温度で３０分
間保持した。ついで溶剤すと重合触媒すとの混合物を２
０分間で滴下し、さらに同温度で３〜５時間撹拌を続け
て重合反応を完結させた。最後に希釈溶剤を加えて希釈
し各重合体（Ｈｅ Ｉ 、 ＩＩ 、 ＩＶ 、 Ｖオ
ヨびｖＩＩヲ得り。ナオ、第１表中の’ＪＡＭ体Ａの構
造式は、一般式＋１）におけるＸの構造およびｎ＋ Ｉ
ｎの数値で表わした。Production Examples 1, 2, 4.5 and 7 iQ Add solvent a according to the formulation in Table 1 to a flask with 4 holes, raise the temperature to the reaction temperature, and add monomer A1 monomer B and A mixed solution of polymerization catalyst a was dropped into the flask over a period of 2 to 3 hours, and after the dropwise addition was completed, the mixture was maintained at the same temperature for 30 minutes. Then, add 2 mixtures of solvent and polymerization catalyst.
The mixture was added dropwise over 0 minutes, and stirring was continued for 3 to 5 hours at the same temperature to complete the polymerization reaction. Finally, a diluting solvent was added to dilute to obtain each polymer (He I, II, IV, V and vII. In Table 1, the structural formula of 'JAM substance A is X in the general formula + 1). The structure of and n+ I
Expressed as a numerical value of n.
製造例３
耐熱耐圧の容器中に第１表の配合に仏じて単１体Ａ、単
量体Ｂおよび重合触媒ａを仕込み、完全に密封して振温
しながら反応温度に昇温させ、さらに同温度で２時間振
温を続けて反応を完結させた。つぎに希釈溶剤を加えて
３時間振温して溶解し重合体溶液Ｉｌｌを得た。Production Example 3 In a heat-resistant and pressure-resistant container, monomer A, monomer B, and polymerization catalyst a were charged according to the formulation shown in Table 1, the container was completely sealed, and the temperature was raised to the reaction temperature while shaking. Further shaking was continued at the same temperature for 2 hours to complete the reaction. Next, a diluting solvent was added and dissolved by shaking for 3 hours to obtain a polymer solution Ill.
製造例６
撹拌機付きのフラスコに第１表の配合に桑じて溶剤ａ、
単量体Ａおよび重合触媒ａを仕込み、撹拌しながら反応
温度に昇温させ、同温度で３時間撹拌を続けて重合体溶
液■１を得た。Production Example 6 In a flask equipped with a stirrer, add solvent a, according to the formulation in Table 1.
Monomer A and polymerization catalyst a were charged, the temperature was raised to the reaction temperature while stirring, and stirring was continued at the same temperature for 3 hours to obtain polymer solution 1.
実施例１〜５６
重合体溶液（Ｉ）〜（Ｖｌｌ）を用いて、後記の第２〜
４表に示す配合組成（表中の数値は重量％）により、２
．００ Ｏｒｐｍのホモミキサーで混合分散して、５６
種の水中防汚被覆剤を調製した。なお、配合成分中、パ
ラフィンワックス１２０Ｐおよびペトロラタム１号はＪ
ＩＳＫ２２３５の石油ワックスであり、ｌ５ＯＶＧＩＯ
はＪＩＳＫ２２３１の流動パラフィンである。また、商
品名がＫＦ−６９であるシリコーンオイルは信越化学工
業■製である。Examples 1 to 56 Using polymer solutions (I) to (Vll),
According to the formulation shown in Table 4 (values in the table are weight%), 2
．． Mix and disperse with a homo mixer of 00 Orpm to 56
An underwater antifouling coating for seeds was prepared. In addition, among the ingredients, paraffin wax 120P and petrolatum No. 1 are J
ISK2235 petroleum wax, l5OVGIO
is JISK2231 liquid paraffin. The silicone oil whose trade name is KF-69 is manufactured by Shin-Etsu Chemical Co., Ltd.
また、オイルブルー２Ｎ［オリエント化学［”Ｊの商品
名］は染料、デイスパロン６９００−２０Ｘ［楠本化成
■製の商品名〕およびアエロシール３００ ［日本アエ
ロシール■製の商品名］はいずれもタレ止め用添加剤で
ある。In addition, Oil Blue 2N [trade name of Orient Chemical ["J] is a dye, and Disparon 6900-20X [trade name of Kusumoto Kasei ■] and Aeroseal 300 [trade name of Nippon Aeroseal ■] are anti-sagging products. It is an additive for
比較例１〜４
重合体溶液（Ｉ）〜（［）を用いて実施例１〜５６と同
様にして、後記第５表に示す配合組成からなる水中防を
号被覆剤を調製した。Comparative Examples 1 to 4 In the same manner as in Examples 1 to 56, using polymer solutions (I) to ([), underwater protective coatings having the compositions shown in Table 5 below were prepared.
比較例５〜８
重合体溶液（Ｉ）〜（■１）の代わりに、ＫＥ４５ＴＳ
〔信越化学工業（ａ）製の商品名；オリゴマー状常温硬
化形シリコーンゴム５０Ｍ量％トルエン溶液］を用いた
以外は、実施例１〜５６と同様にして後記第５表コこ示
す配合組成からなる４種の水中防ｔｌテ彼覆剤を調製し
た。Comparative Examples 5 to 8 Instead of polymer solutions (I) to (■1), KE45TS
[Product name manufactured by Shin-Etsu Chemical Co., Ltd. (a); Oligomeric room-temperature curing silicone rubber 50 M% toluene solution] was used in the same manner as in Examples 1 to 56, from the formulation shown in Table 5 below. Four types of underwater anti-TL reversible agents were prepared.
比■咬例９〜１３
重合体溶液（Ｉ）〜（Ｖｌｌ）の代わりに有機錫共重合
体溶液を用いた以外は、実施例１〜５６と同様にして、
後記第５表に示す配合組成からなる水中防汚被覆剤を調
製した。Example 9 to 13 Same as Examples 1 to 56 except that organic tin copolymer solution was used instead of polymer solutions (I) to (Vll).
An underwater antifouling coating having a composition shown in Table 5 below was prepared.
なお、上記の有機錫共重合体溶液とは、メタクリル酸メ
チル４０部、アクリル酸オクチル２０部、メタクリル酸
トリブチル錫４０部を用いて重合した共重合体溶液で、
共重合体の重量平均分子量が９０．０００の透明なキシ
レン５０重量％溶液である。The above-mentioned organotin copolymer solution is a copolymer solution polymerized using 40 parts of methyl methacrylate, 20 parts of octyl acrylate, and 40 parts of tributyltin methacrylate.
The copolymer has a weight average molecular weight of 90.000 and is a transparent 50% by weight solution in xylene.
／′
以上の実施例１〜５６および比較例１〜１３の各被覆剤
につき、以下の物理性能試験、被膜の表面滑り角の測定
および防汚性能試験を行い、その性能を評価した。結果
は、後記の第６．７表に示されるとおりであった。/' Each of the coating materials of Examples 1 to 56 and Comparative Examples 1 to 13 was subjected to the following physical performance test, measurement of the surface slip angle of the coating, and antifouling performance test to evaluate the performance. The results were as shown in Table 6.7 below.
く物理性能試験〉
各被覆剤の貯蔵安定性、乾燥性および密着性を下記方法
にて測定した。Physical Performance Test> The storage stability, drying properties, and adhesion of each coating material were measured using the following methods.
Ａ）貯蔵安定性
各被覆剤を容量２５０ＣＣのマヨネーズビンに２００国
入れ、蓋をして密封した。これを温度７０°Ｃ１湿度７
５％の恒温恒湿器中に保存して、２週間後の各試料の増
粘度により、貯蔵安定性を判定した。A) Storage stability 200 pieces of each coating agent were placed in a mayonnaise bottle with a capacity of 250 cc, and the bottle was sealed with a lid. Temperature 70°C 1 Humidity 7
Storage stability was determined by the degree of viscosity increase of each sample after 2 weeks of storage in a 5% constant temperature and humidity chamber.
初期粘度より増加率が１０％未満のとき０１１０％以上
１００％未満のとき△、１００％以上のとき×と評価し
た。When the increase rate was less than 10% from the initial viscosity, it was evaluated as 0, when it was 10% or more and less than 100%, it was evaluated as Δ, and when it was 100% or more, it was evaluated as ×.
Ｂ）乾燥性
ＪＩＳ Ｋ ５４００，５．８の方法に準じて行っ
た。B) Drying property Drying was carried out according to the method of JIS K 5400, 5.8.
すなわち、各被覆剤をフィルムアプリケーターにてウェ
ット膜厚１００μの厚さでガラス板に塗布したものにつ
いて測定を行った。半硬化乾燥時間が１時間未満を０１
１時間以上３時間未満を△、３時間以上を×と評価した
。なお、各試験板は温度２０°Ｃ９湿度７５％の恒温恒
湿室にて乾燥を行った。That is, the measurement was performed on a glass plate coated with each coating agent to a wet film thickness of 100 μm using a film applicator. 01 if the semi-cured drying time is less than 1 hour
1 hour or more and less than 3 hours was evaluated as △, and 3 hours or more was evaluated as ×. Note that each test plate was dried in a constant temperature and humidity room at a temperature of 20° C. and a humidity of 75%.
Ｃ）密着性
ＪＩＳ Ｋ ５４００．６．１５の基盤目試験の方法に
準じて行った。すなわち、各被覆剤をフィルムアプリケ
ーターにてウェット膜厚１００戸の厚さで磨き鋼板（１
５０Ｘ７０Ｘ１ｆｌ）に塗布し、１週間、温度２０℃、
湿度７５％の恒温恒温室にて乾燥させた被膜にカッター
ナイフで２０ｔｘの長さに十字に下地まで達する切り傷
をつけた。その中心地の試験板裏面よりエリクセン試験
機にて１０卵の押し出しを行った。その際、被膜表面の
十字切り偏部の中心より剥離した長さによって密着性を
判定した。剥離０のとき○、５ｆ１未満のとき△、５ｆ
１以上のとき×と評価した。C) Adhesion The test was carried out according to the method of the substrate test of JIS K 5400.6.15. That is, each coating agent was applied to a polished steel plate (1
50 x 70 x 1 fl) for one week at a temperature of 20°C.
The coating was dried in a constant temperature room with a humidity of 75%, and a cut was made in a cross pattern reaching the base layer with a length of 20 tx using a cutter knife. Ten eggs were extruded from the back of the test plate at the center using an Erichsen tester. At that time, adhesion was determined by the length of peeling from the center of the cross-cut uneven portion of the coating surface. ○ when peeling is 0, △ when less than 5f1, 5f
When it was 1 or more, it was evaluated as ×.
〈被膜の表面滑り角の測定〉
前記乾燥性試験で用いた各試験板につき、第１図（５）
、 （１３）に示す滑り角測定機を用いて以下の要領で
被膜の表面滑り角を測定した。なお、上記測定機は、透
明ガラス板１と、このガラス板１上に一端Ａ側が固定治
具２により固定されかつ他端Ｂ側が支柱３により支えら
れてこの支柱３に沿って上方に移動しつるように設けら
れた可動板４とから構成されている。<Measurement of surface sliding angle of coating> For each test plate used in the drying test, see Figure 1 (5).
The surface slip angle of the coating was measured in the following manner using the slip angle measuring device shown in (13). The above-mentioned measuring device consists of a transparent glass plate 1, one end A side is fixed to the glass plate 1 by a fixing jig 2, the other end B side is supported by a column 3, and is moved upward along this column 3. It is composed of a movable plate 4 provided in a hanging manner.
まず、第１回置に示すように、透明ガラス板１上に、試
験板５をその被膜形成側が上方に位置するように、可動
板４を介して水平に置き、この試験板５上で可動板４の
一端Ａつまり固定治具２からの距離γが１８５調の位置
に注射器にて０．２ ｍｅの滅菌濾過海水を滴下して水
滴６を形成する。その後、第１図ＣＢ）に示すように、
可動板４の他端Ｂ側を支柱３に沿って１ｆｌ／秒の速度
で上方に移動させ、試験板５を傾斜させる。試験板５上
の水滴が滑り始めるときの傾斜角αを測定し、これを被
膜の表面滑り角とした。First, as shown in the first position, the test plate 5 is placed horizontally on the transparent glass plate 1 with the film forming side facing upward, and the test plate 5 is movable on the test plate 5. A water droplet 6 is formed by dropping 0.2 me of sterilized filtered seawater using a syringe at one end A of the plate 4, that is, at a position where the distance γ from the fixing jig 2 is 185 degrees. After that, as shown in Figure 1 CB),
The other end B side of the movable plate 4 is moved upward along the support column 3 at a speed of 1 fl/sec to tilt the test plate 5. The inclination angle α at which the water droplets on the test plate 5 begin to slide was measured, and this was taken as the surface slip angle of the coating.
なお、上記の測定は、温度２５°Ｃ１湿度７５％の恒温
恒湿室にて行い、各試験板につき３回の測定を行って、
その平均値で表わした。The above measurements were performed in a constant temperature and humidity room at a temperature of 25°C and a humidity of 75%, and each test plate was measured three times.
It was expressed as the average value.
〈防汚性能試験〉
各被覆剤を、サンドブラスト処理鋼板に予めタールビニ
ル系防錆塗料を塗布してなる塗装板（１００Ｘ ２００
Ｘ １ ｒｍ ）の両面に、乾燥膜厚が片面１２０声
となるようにスプレー塗りにより２回塗装して、試験板
を作製した。<Antifouling performance test> Each coating was applied to a sandblasted steel plate coated with tarvinyl anticorrosive paint (100 x 200
A test plate was prepared by spray painting on both sides of the sample (X 1 rm) twice so that the dry film thickness was 120 tones on one side.
この試験板につき、生物付着の激しい海域である兵庫県
相生市相生湾にて、２４ケ月の海水浸漬を行い、試験塗
膜上の付着生物の占有面積（付着面積）の割合を経時的
に測定した。This test board was immersed in seawater for 24 months in Aioi Bay, Aioi City, Hyogo Prefecture, which is a sea area with heavy biofouling, and the ratio of the area occupied by the biofouling organisms (adhesion area) on the test coating was measured over time. did.
上記第６，７表の結果から明らかなように、実施例１〜
５６については、貯蔵安定性、乾燥性、密着性のいずれ
についても良好であった。また、表面滑り角は７〜１１
度の範囲である。なお表面滑性剤を併用しない実施例１
〜４０においても１１度以下の範囲であり、このことは
本発明の前記特定の重合体の被膜自体が強力な表面滑り
性を有していることを示している。そして、防汚性能試
験における生物の付着は少なくとも２４力月経過後まで
は全く認められない。As is clear from the results in Tables 6 and 7 above, Examples 1-
Sample No. 56 had good storage stability, drying properties, and adhesion. In addition, the surface sliding angle is 7 to 11
range of degrees. Example 1 without using a surface lubricant
-40 is also in the range of 11 degrees or less, which indicates that the coating itself of the specific polymer of the present invention has strong surface slipping properties. Further, in the antifouling performance test, no biological attachment was observed at all until at least 24 months had passed.
これに対し、比較例１〜４は本発明の必須成分である防
汚剤が含まれていない塗料であり、１８〜２４力月で生
物の付着がみられた。また、比較例５〜８は、シリコン
ゴム系の塗料であり貯蔵安定性、乾燥性および密着性に
欠点がある。防汚性も不満足であり、表面滑り角におけ
る高い値がこれを裏付けている。さらに、比較例９〜１
３は有機錫共重合系の防汚塗料である。貯蔵安定性およ
び防汚性においてやや劣っている。塗膜表面がより親水
性であり表面滑り角は高い値を示した。On the other hand, Comparative Examples 1 to 4 were paints that did not contain the antifouling agent, which is an essential component of the present invention, and adhesion of living organisms was observed after 18 to 24 months. Moreover, Comparative Examples 5 to 8 are silicone rubber-based paints and have shortcomings in storage stability, drying properties, and adhesion. The antifouling properties are also unsatisfactory, as evidenced by the high value of the surface sliding angle. Furthermore, Comparative Examples 9 to 1
3 is an organic tin copolymer-based antifouling paint. Slightly inferior in storage stability and stain resistance. The coating surface was more hydrophilic and the surface slip angle showed a high value.
第１図（４）、（Ｂ）は水中防汚被覆剤から形成される
防汚被膜の表面滑り角を測定する方法を示す側面図であ
る。FIGS. 1(4) and 1(B) are side views showing a method for measuring the surface slip angle of an antifouling film formed from an underwater antifouling coating agent.
Claims (2)
〜４の整数、ｍは平均重合度で０〜７０を表わす） で示される単量体Ａの一種または二種以上の重合体、お
よび／または上記単量体Ａの一種または二種以上とこれ
らと共重合し得るビニル重合性単量体Ｂの一種または二
種以上とからなる共重合体と、防汚剤とを必須成分とし
て含有する水中防汚被覆剤。(1) The following general formula; ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) (However, in the formula, X is a hydrogen atom or a methyl group, and n is 2
an integer of ~4, m represents an average degree of polymerization of 0 to 70) and/or one or more of the above monomers A and these An underwater antifouling coating agent containing as essential components a copolymer consisting of one or more types of vinyl polymerizable monomer B that can be copolymerized with B, and an antifouling agent.
〜４の整数、ｍは平均重合度で０〜７０を表わす） で示される単量体Ａの一種または二種以上の重合体、お
よび／または上記単量体Ａの一種または二種以上とこれ
らと共重合し得るビニル重合性単量体Ｂの一種または二
種以上とからなる共重合体と、防汚剤と、表面滑性剤と
を必須成分として含有する水中防汚被覆剤。(2) The following general formula; ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) (However, in the formula, X is a hydrogen atom or a methyl group, and n is 2
an integer of ~4, m represents an average degree of polymerization of 0 to 70) and/or one or more of the above monomers A and these An underwater antifouling coating agent containing as essential components a copolymer consisting of one or more vinyl polymerizable monomers B that can be copolymerized with B, an antifouling agent, and a surface lubricant.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61311221A JPS63168476A (en) | 1986-12-30 | 1986-12-30 | Underwater antifouling coating agent |
| NO875462A NO173284C (en) | 1986-12-30 | 1987-12-29 | Antifouling paint |
| DK691487A DK171898B1 (en) | 1986-12-30 | 1987-12-29 | Antifouling paints containing an antifouling agent, a silicon-containing organic polymer and optionally an abrasive |
| DE8787119393T DE3780285T2 (en) | 1986-12-30 | 1987-12-30 | POLLUTION PREVENTING PAINT. |
| CA000555629A CA1310780C (en) | 1986-12-30 | 1987-12-30 | Antifouling paint |
| US07/139,541 US4898895A (en) | 1986-12-30 | 1987-12-30 | Antifouling pain having a polyacrylate component with pendent silyl or siloxane groups |
| EP87119393A EP0273457B1 (en) | 1986-12-30 | 1987-12-30 | Antifouling paint |
| KR1019870015407A KR960005430B1 (en) | 1986-12-30 | 1987-12-30 | Antifouling paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61311221A JPS63168476A (en) | 1986-12-30 | 1986-12-30 | Underwater antifouling coating agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63168476A true JPS63168476A (en) | 1988-07-12 |
Family
ID=18014555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61311221A Pending JPS63168476A (en) | 1986-12-30 | 1986-12-30 | Underwater antifouling coating agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63168476A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001072869A (en) * | 1999-09-06 | 2001-03-21 | Chugoku Marine Paints Ltd | Polysiloxane-acrylic resin block copolymer composition, antifouling agent composition, antifouling coated film, antifouling treatment base, and antifouling treatment of base |
| JP2021085027A (en) * | 2019-11-29 | 2021-06-03 | 日東化成株式会社 | Fishing net anti-fouling coating composition, fishing net having anti-fouling coating film formed using the composition on surface thereof, fishing net tool and underwater structure |
-
1986
- 1986-12-30 JP JP61311221A patent/JPS63168476A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001072869A (en) * | 1999-09-06 | 2001-03-21 | Chugoku Marine Paints Ltd | Polysiloxane-acrylic resin block copolymer composition, antifouling agent composition, antifouling coated film, antifouling treatment base, and antifouling treatment of base |
| JP2021085027A (en) * | 2019-11-29 | 2021-06-03 | 日東化成株式会社 | Fishing net anti-fouling coating composition, fishing net having anti-fouling coating film formed using the composition on surface thereof, fishing net tool and underwater structure |
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