JP4178396B2 - Antifouling method and antifouling structure - Google Patents
Antifouling method and antifouling structure Download PDFInfo
- Publication number
- JP4178396B2 JP4178396B2 JP2003175860A JP2003175860A JP4178396B2 JP 4178396 B2 JP4178396 B2 JP 4178396B2 JP 2003175860 A JP2003175860 A JP 2003175860A JP 2003175860 A JP2003175860 A JP 2003175860A JP 4178396 B2 JP4178396 B2 JP 4178396B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- antifouling
- organohydrogenpolysiloxane
- mol
- cured
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 230000003373 anti-fouling effect Effects 0.000 title claims description 34
- 238000000034 method Methods 0.000 title claims description 16
- 239000000203 mixture Substances 0.000 claims description 51
- -1 polysiloxane Polymers 0.000 claims description 41
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 31
- 125000004432 carbon atom Chemical group C* 0.000 claims description 29
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 claims description 28
- 125000001424 substituent group Chemical group 0.000 claims description 25
- 125000003342 alkenyl group Chemical group 0.000 claims description 20
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 229920002379 silicone rubber Polymers 0.000 claims description 17
- 239000004945 silicone rubber Substances 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000009833 condensation Methods 0.000 claims description 13
- 230000005494 condensation Effects 0.000 claims description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 238000007259 addition reaction Methods 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 10
- 229920001296 polysiloxane Polymers 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 9
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 229910052799 carbon Chemical group 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- 229910000077 silane Inorganic materials 0.000 claims description 5
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 238000004880 explosion Methods 0.000 claims 1
- 238000005552 hardfacing Methods 0.000 claims 1
- 230000002209 hydrophobic effect Effects 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 28
- 150000002430 hydrocarbons Chemical group 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000010410 layer Substances 0.000 description 14
- 238000001723 curing Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 description 6
- 229920005601 base polymer Polymers 0.000 description 6
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 5
- 125000005388 dimethylhydrogensiloxy group Chemical group 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 239000002519 antifouling agent Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 238000013007 heat curing Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 229920002050 silicone resin Polymers 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000005046 Chlorosilane Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000004423 acyloxy group Chemical group 0.000 description 3
- 125000003302 alkenyloxy group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000009360 aquaculture Methods 0.000 description 3
- 244000144974 aquaculture Species 0.000 description 3
- DSVRVHYFPPQFTI-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane;platinum Chemical compound [Pt].C[Si](C)(C)O[Si](C)(C=C)C=C DSVRVHYFPPQFTI-UHFFFAOYSA-N 0.000 description 3
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000006459 hydrosilylation reaction Methods 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229910020388 SiO1/2 Inorganic materials 0.000 description 2
- 229910020447 SiO2/2 Inorganic materials 0.000 description 2
- 229910020487 SiO3/2 Inorganic materials 0.000 description 2
- 229910020485 SiO4/2 Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical group CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 2
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229940057995 liquid paraffin Drugs 0.000 description 2
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical group CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 125000006353 oxyethylene group Chemical group 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical class CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- FJYCQKNCFFNLAD-UHFFFAOYSA-N 1-propoxyoctane-1,8-diol Chemical compound CCCOC(O)CCCCCCCO FJYCQKNCFFNLAD-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
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- KTXWGMUMDPYXNN-UHFFFAOYSA-N 2-ethylhexan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-] KTXWGMUMDPYXNN-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 241000584629 Aosa Species 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 235000007516 Chrysanthemum Nutrition 0.000 description 1
- 244000189548 Chrysanthemum x morifolium Species 0.000 description 1
- 241000238586 Cirripedia Species 0.000 description 1
- 241001137251 Corvidae Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 241000237536 Mytilus edulis Species 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910019032 PtCl2 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 241000251555 Tunicata Species 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- KTOOYTYQCMCVKF-UHFFFAOYSA-N [SiH4].C(=C)C(C(C)(C)C)C(=NO)C(C(C)(C)C)C=C Chemical compound [SiH4].C(=C)C(C(C)(C)C)C(=NO)C(C(C)(C)C)C=C KTOOYTYQCMCVKF-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- NBJODVYWAQLZOC-UHFFFAOYSA-L [dibutyl(octanoyloxy)stannyl] octanoate Chemical compound CCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCC NBJODVYWAQLZOC-UHFFFAOYSA-L 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- WBQJELWEUDLTHA-UHFFFAOYSA-M benzyl(triethyl)azanium;acetate Chemical compound CC([O-])=O.CC[N+](CC)(CC)CC1=CC=CC=C1 WBQJELWEUDLTHA-UHFFFAOYSA-M 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- QAEKNCDIHIGLFI-UHFFFAOYSA-L cobalt(2+);2-ethylhexanoate Chemical compound [Co+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O QAEKNCDIHIGLFI-UHFFFAOYSA-L 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- VEVVRTWXUIWDAW-UHFFFAOYSA-N dodecan-1-amine;phosphoric acid Chemical class OP(O)(O)=O.CCCCCCCCCCCCN VEVVRTWXUIWDAW-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- GBFVZTUQONJGSL-UHFFFAOYSA-N ethenyl-tris(prop-1-en-2-yloxy)silane Chemical compound CC(=C)O[Si](OC(C)=C)(OC(C)=C)C=C GBFVZTUQONJGSL-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- VMESOKCXSYNAKD-UHFFFAOYSA-N n,n-dimethylhydroxylamine Chemical compound CN(C)O VMESOKCXSYNAKD-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-AZXPZELESA-N n-methylacetamide Chemical group C[15NH]C(C)=O OHLUUHNLEMFGTQ-AZXPZELESA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- IXSPLXSQNNZJJU-UHFFFAOYSA-N trimethyl(silyloxy)silane Chemical compound C[Si](C)(C)O[SiH3] IXSPLXSQNNZJJU-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011995 wilkinson's catalyst Substances 0.000 description 1
- UTODFRQBVUVYOB-UHFFFAOYSA-P wilkinson's catalyst Chemical compound [Cl-].C1=CC=CC=C1P(C=1C=CC=CC=1)(C=1C=CC=CC=1)[Rh+](P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 UTODFRQBVUVYOB-UHFFFAOYSA-P 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、特に、船舶、港湾施設、ブイ、パイプライン、橋梁、海底基地、海底油田掘削設備、発電所の導水路管、養殖網、定置網等（以下、「水中構造物」という）に塗装して、これらの表面への水生生物の付着・生育を防止するために好適な防汚塗膜を与える防汚方法及び防汚性構造物に関する。
【０００２】
【従来の技術】
室温でゴム状弾性体を与える室温硬化性シリコーンゴム組成物は種々のものが知られており、室温硬化性シリコーンゴム組成物（以下、「ＲＴＶ」という）から得られる硬化ゴムは、他の有機系ゴムに比較して優れた耐候性、耐久性、耐熱性、耐寒性等を具備することから種々の分野で使用され、建築分野においては、ガラス同士の接着用、金属とガラスとの接着用、コンクリート目地のシール用等に多用されており、近年では、建築物、プラント類、水中構造物等のコーティング材として広く利用されている。
【０００３】
ここで、水中構造物は、設置され又は就航すると、その飛沫部から没水部表面に亘って、海、河川等の水中に棲息しているフジツボ、ホヤ、セルプラ、ムラサキイガイ、カラスガイ、フサコケムシ、アオノリ、アオサ等の水生生物が付着・生育して種々の被害が発生する。例えば、船体に生物が付着した場合、水との摩擦抵抗が増大し、航行速度の低下が生じ、一定の速度を維持するためには燃料消費量が増加し、経済的に不利である。また、港湾施設等の水中又は水面に固定させておく構造物に生物が付着すると、これらが有する個々の機能を十分に発揮することが困難となり、基材を侵食することもある。更に、養殖網、定置網等に生物が付着すると網目が閉塞して魚類が死亡してしまうことがある。
【０００４】
水中構造物への水生生物の付着・生育の防止対策としては、有機錫化合物、亜酸化銅等の毒性防汚剤を配合した防汚塗料を構造物に塗装して対応していたが、水生生物の付着・生育はほぼ防止できたものの、毒性防汚剤を用いているために、塗料の製造や塗装時において環境安全衛生上好ましくなく、しかも水中において塗膜から毒性の防汚剤が徐々に溶出し、長期的にみれば水域を汚染するおそれがあることから、その使用が法的に禁止されることとなった。
【０００５】
一方、水生生物の付着・生育の防止効果があり、毒性防汚剤を含有しない塗料としては、塗膜の表面張力を低くして防汚性を付与させるものとして、ＲＴＶに流動パラフィン又はペトロラクタムを配合した無毒性防汚塗科が提案されている（例えば、特許文献１，２：特開昭５８−１３６７３号公報、特開昭６２−８４１６６号公報参照）。また、反応硬化型シリコーン樹脂の硬化に伴う体積収縮によって、相溶性が乏しく非反応性の極性基含有シリコーン樹脂が表面へ滲み出し、反応硬化型シリコーン樹脂のもつ低表面張力と相俟って防汚性を示す無毒性防汚塗料組成物（例えば、特許文献３，４：特許第２５０３９８６号公報、特許第２９５２３７５号公報参照）も提案されている。しかしながら、防汚性の持続性という面では十分な性能が得られず、溶出する化合物の安全性に関しても問題があった。
【０００６】
一方、構造体の表面防汚処理としては、防汚性反応性官能基を有する有機ポリマーを主成分とする前処理組成物を基材表面に処理し、その上に該反応性官能基と反応し得る反応性官能基を有する撥水性防汚剤を主成分とする防汚性組成物を前処理層と反応させる表面防汚処理構造体が記載され、更にアリル基含有アクリル樹脂を前処理し、その上に側鎖のみにＳｉＨ基を有するハイドロジェンポリシロキサン（ＫＦ−９９（信越化学工業（株）製））をハイドロシリレーション反応させることが例示されている（例えば、特許文献５：特開平５−１６９０１１号公報参照）。
【０００７】
しかし、この方法では前処理に使用しているアクリル樹脂と上層に使用しているシロキサンの濡れ性が悪いため、ハイドロシリレーションによる結合が十分ではなく、防汚性の持続性が不十分であった。
【０００８】
【特許文献１】
特開昭５８−１３６７３号公報
【特許文献２】
特開昭６２−８４１６６号公報
【特許文献３】
特許第２５０３９８６号公報
【特許文献４】
特許第２９５２３７５号公報
【特許文献５】
特開平５−１６９０１１号公報
【０００９】
【発明が解決しようとする課題】
従って、本発明は、特には水中構造物に塗装され、水中構造物の表面への水生生物の付着・生育を防止するために好適であり、その効果の持続性が良好な防汚塗膜を与える防汚方法及び防汚性構造物を提供することを目的とする。
【００１０】
【課題を解決するための手段及び発明の実施の形態】
本発明者らは、上記目的を達成するため鋭意検討を行った結果、縮合硬化型シリコーンゴム組成物において、ベースポリマーのジオルガノポリシロキサンの珪素原子に直結する全置換基のうち、２モル％以上が炭素数２以上の置換もしくは非置換の一価炭化水素基である特定のジオルガノポリシロキサンを用いた組成物の硬化被膜に、オルガノハイドロジェンポリシロキサンと白金族金属系触媒の混合物をコーティングし、硬化させること、この場合、より好ましくは、更にその上に脂肪族不飽和炭化水素基及びオキシアルキレン基を含有する化合物をコーティングし、硬化させることにより、著しい防汚性向上を達成でき、極めて良好な防汚性及びその持続性を得ることができ、更に安全性にも優れることを見出し、本発明をなすに至った。
【００１１】
従って、本発明は、
［Ｉ］基材、好ましくは水中構造物の表面に、（Ａ）分子中に少なくとも２個の珪素原子に結合した水酸基又は加水分解性基を有し、珪素原子に結合する全置換基の２モル％以上がアルケニル基であり、珪素原子に結合するその他の基がメチル基である下記一般式（１）又は（２）
【化７】
【化８】
で表されるジオルガノポリシロキサンをベースポリマーとし、加水分解性基を１分子中に２個以上有するシラン又はその部分加水分解物を配合してなる縮合硬化型シリコーンゴム組成物の硬化被膜を形成すると共に、この硬化被膜上に、（Ｂ）オルガノハイドロジェンポリシロキサンと白金族金属系触媒との混合物をこのオルガノハイドロジェンポリシロキサンが上記硬化被膜中のアルケニル基と付加反応した際に残存するような量で塗布し、上記硬化被膜中のアルケニル基とオルガノハイドロジェンポリシロキサンとを付加反応させて上記硬化被膜との間で第１の表面硬化層を形成し、更に、この第１の表面硬化層上に、（Ｃ）脂肪族不飽和炭化水素基及びオキシアルキレン基を含有する化合物を塗布し、上記第１の表面硬化層中の上記残存したオルガノハイドロジェンポリシロキサンと脂肪族不飽和炭化水素基とを付加反応させて、上記第１の表面硬化層との間で第２の表面硬化層を形成することを特徴とする基材の防汚方法、及び
［ＩＩ］上記防汚方法により防汚性被膜が形成された防汚性構造物
を提供する。
【００１２】
以下、本発明につき更に詳しく説明する。
本発明にかかる防汚方法及び防汚性構造物は、まず、構造物（基材）、特に水中構造物の表面に縮合硬化型シリコーンゴム組成物の硬化被膜が形成される。
この場合、このシリコーンゴム組成物の第一成分は、ジオルガノポリシロキサンであり、これをベースポリマーとするものである。
第一成分で使用されるベースポリマーのジオルガノポリシロキサンとしては、縮合反応で硬化するため、分子中に少なくとも２個の珪素原子に直結した水酸基又は加水分解性基を有し、全珪素原子に結合した置換基の２モル％以上が炭素数２以上の置換もしくは非置換の一価炭化水素基を有するものである。
【００１３】
従来使用されている縮合硬化型シリコーンゴム（ＲＴＶゴム）組成物のベースポリマーにおいて、縮合反応に関与する水酸基又は加水分解性基以外の置換基は、ほとんどがメチル基であるが、第一成分においては、この加水分解性基以外の置換基に縮合反応（架橋）に関与しない炭素数２以上の置換もしくは非置換の一価炭化水素基を特定量導入したものであり、硬化後は炭素数２以上の置換もしくは非置換の一価炭化水素基が硬化物に残存していることが必要である。
このジオルガノポリシロキサンは実質的に直鎖状であるが、ゲル化を起こさないあるいはゴム弾性を損なわない範囲において分岐していてもよい。分岐量は、通常１０モル％以下、好ましくは５モル％以下である。
具体的には下記一般式（１）又は（２）で表されるジオルガノポリシロキサシが好ましい。
【００１４】
【化３】
【００１５】
ここで、Ｒはメチル基、エチル基、プロピル基、ブチル基、２−エチルブチル基、オクチル基などのアルキル基、シクロヘキシル基、シクロペンチル基などのシクロアルキル基、ビニル基、プロペニル基、ブテニル基、ヘプテニル基、ヘキセニル基、アリル基などのアルケニル基、フェニル基、トリル基、キシリル基、ナフチル基、ジフェニル基などのアリール基、ベンジル基、フェニルエチル基などのアラルキル基あるいはこれらの基の炭素原子に結合している水素原子の一部又は全部をハロゲン原子、シアノ基などで置換したクロロメチル基、トリフロロプロピル基、２−シアノエチル基、３−シアノプロピル基などから選択される同一又は異種の非置換もしくは置換の好ましくは炭素数１〜１２、特に１〜１０の一価炭化水素基である。
【００１６】
また、Ｒのうち２モル％以上、好ましくは２．５モル％以上が炭素数２以上の置換もしくは非置換の一価炭化水素基であることが必要である。上限としては特に制限されないが、製造しやすさからすると５０モル％以下である。
【００１７】
炭素数２以上の置換もしくは非置換の一価炭化水素基としては、上述したＲのメチル基以外の一価炭化水素基が挙げられるが、ビニル基、アリル基、プロペニル基、ブテニル基、ヘプテニル基、へキセニル基等のアルケニル基、エチル基、プロピル基、フェニル基等が好ましく、中でも（Ｂ）成分のオルガノハイドロジェンポリシロキサンとヒドロシリル化反応可能なアルケニル基が好ましく、特にビニル基が好ましい。これらは２種以上であってもよい。
また、上記Ｒにおいて、炭素数２以上の一価炭化水素基以外の置換基としては、メチル基が好ましい。
【００１８】
Ｘは酸素原子又は炭素数１〜８の二価炭化水素基であり、二価炭化水素基としては−（ＣＨ2）m（ｍは１〜８を表す）で表される。これらの中でも酸素原子、−ＣＨ2ＣＨ2−が好ましい。ｎはジオルガノポリシロキサンの２５℃における粘度を１００〜１，０００，０００ｍＰａ・ｓ、好ましくは５００〜５００，０００ｍＰａ・ｓとする数である。
【００１９】
Ｙは加水分解性基であり、具体的には、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基などのアルコキシ基、ジメチルケトオキシム基、メチルエチルケトオキシム基などのケトオキシム基、アセトキシ基などのアシルオキシ基、イソプロペニルオキシ基、イソブテニルオキシ基などのアルケニルオキシ基等が挙げられ、アルコキシ基、ケトオキシム基が好ましく、特にメトキシ基、エトキシ基が好ましい。
【００２０】
このようなジオルガノポリシロキサンは、各種オルガノポリシロキサンの単量体である環状シロキサンもしくは線状オリゴマーを酸もしくは塩基触媒による平衡反応によって得る等の公知の方法により製造することができる。
また、このジオルガノポリシロキサンに分岐構造を導入する場合は、上記平衡化重合中にＳｉＯ3/2単位及び／又はＳｉＯ4/2単位を含むシランもしくはシロキサンをジオルガノポリシロキサンがゲル化しないレベルで添加するのが常法である。更に、このジオルガノポリシロキサンは、ストリップや洗浄等により低分子シロキサンを除去しておくことが望ましい。
【００２１】
上記縮合硬化型シリコーンゴム組成物には、架橋剤が使用される。架橋剤としては、加水分解性の基を１分子中に２個以上、好ましくは３個以上有するシランあるいはその部分加水分解縮合物が使用される。この場合、その加水分解性の基としては、メトキシ基、エトキシ基、ブトキシ基などのアルコキシ基、ジメチルケトオキシム基、メチルエチルケトオキシム基などのケトオキシム基、アセトキシ基などのアシルオキシ基、イソプロペニルオキシ基、イソブテニルオキシ基などのアルケニルオキシ基、Ｎ−ブチルアミノ基、Ｎ，Ｎ−ジエチルアミノ基などのアミノ基，Ｎ−メチルアセトアミド基などのアミド基等が挙げられる。これらの中でもアルコキシ基、ケトオキシム基、アシルオキシ基、アルケニルオキシ基が好ましい。
【００２２】
架橋剤の配合量は、上記ジオルガノポリシロキサン１００部（質量部、以下同様）に対して１〜５０部、好ましくは２〜３０部、より好ましくは５〜２０部とすることが望ましい。
【００２３】
また、縮合硬化型シリコーンゴム組成物には、基本的には硬化触媒を使用しないほうが好ましいが、硬化触媒を使用する場合は、以下のものが例示できる。ジブチル錫ジアセテート、ジブチル錫ジラウレート、ジブチル錫ジオクトエート等のアルキル錫エステル化合物、テトライソプロポキシチタン、テトラｎ−ブトキシチタン、テトラキス（２−エチルヘキソキシ）チタン、ジプロポキシビス（アセチルアセトナ）チタン、チタニウムイソプロポキシオクチレングリコール等のチタン酸エステル又はチタンキレート化合物、ナフテン酸亜鉛、ステアリン酸亜鉛、亜鉛−２−エチルオクトエート、鉄−２−エチルヘキソエート、コバルト−２−エチルヘキソエート、マンガン−２−エチルヘキソエート、ナフテン酸コバルト、アルコキシアルミニウム化合物等の有機金属化合物、３−アミノプロピルトリエトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン等のアミノアルキル基置換アルコキシシラン、ヘキシルアミン、リン酸ドデシルアミン等のアミン化合物及びその塩、ベンジルトリエチルアンモニウムアセテート等の第４級アンモニウム塩、酢酸カリウム、酢酸ナトリウム、蓚酸リチウム等のアルカリ金属の低級脂肪酸塩、ジメチルヒドロキシルアミン、ジエチルヒドロキシルアミン等のジアルキルヒドロキシルアミン、テトラメチルグアニジルプロピルトリメトキシシラン、テトラメチルグアニジルプロピルメチルジメトキシシラン、テトラメチルグアニジルプロピルトリス（トリメチルシロキシ）シラン等のグアニジル基を含有するシラン又はシロキサン等が例示され、これらはその１種に限定されず、２種もしくはそれ以上の混合物として使用してもよい。なお、これら硬化触媒の配合量は、上記ジオルガノポリシロキサン１００部に対して０〜２０部、好ましくは０．００１〜１０部、より好ましくは０．０１〜５部である。
【００２４】
また、縮合硬化型シリコーンゴム組成物には、上記成分以外に補強等の目的で１種以上の充填剤を用いることが好ましい。このような充填剤としては、例えば、煙霧質シリカ、沈降性シリカ、これらのシリカ表面を有機珪素化合物で疎水化処理したシリカ、石英粉末、カーボンブラック、タルク、ゼオライト及びベントナイト等の補強剤、アスベスト、ガラス繊維、炭素繊維及び有機繊維などの繊維質充填剤、炭酸カルシウム、炭酸亜鉛、珪酸カルシウム、酸化亜鉛、酸化マグネシウム、珪藻土等の塩基性充填剤、酸化チタンなどの光触媒活性を有する充填剤等が例示される。これらの充填剤のうち、炭酸カルシウム、珪酸カルシウム、表面を疎水化処理したシリカ、ゼオライト等が好ましく、特に表面を疎水化処理した煙霧質シリカ、炭酸カルシウムが好ましい。
【００２５】
上記充填剤の配合量は、目的や充填剤の種類により選択すればよいが、ベースポリマーのジオルガノポリシロキサン成分１００部に対して１〜５００部、特に５〜１００部であることが好ましい。
【００２６】
更に、縮合硬化型シリコーンゴム組成物には、防汚性を阻害しない範囲において種々の化合物を添加することは任意であり、例えばポリエチレングリコール又はその誘導体からなるチクソトロピー性付与剤、ベンガラ及び酸化セリウムなどの耐熱性向上剤、耐寒性向上剤、脱水剤、防錆剤、γ−アミノプロピルトリエトキシシランなどの接着性向上剤、トリオルガノシロキシ単位及びＳｉＯ2単位及び／又はモノオルガノシロキシ単位よりなる網状ポリシロキサンなどの液状補強剤などを必要に応じてその所定量を添加することができる。
上記縮合硬化型シリコーンゴム組成物は、室温で湿気により硬化するが、その成形方法、硬化条件などは、組成物の種類に応じた公知の方法、条件を採用することができる。
【００２７】
この場合、この組成物の硬化被膜の厚さは、基材の種類や用途により選択すればよいが、５０μｍ〜２ｍｍであることが好ましく、特に１００μｍ〜１ｍｍが好ましい。薄すぎると膜強度が不十分となることがあり、厚すぎるとコスト的に不利となることがある。
【００２８】
本発明においては、上記縮合硬化型シリコーンゴム組成物の硬化被膜上にオルガノハイドロジェンポリシロキサンと白金族金属系触媒との混合物を塗布し、上記硬化被膜との間で表面硬化層を形成する。
この場合、オルガノハイドロジェンポリシロキサンと白金族金属系触媒の混合物中のオルガノハイドロジェンポリシロキサンとしては、１分子中に１個以上、好ましくは１〜５０個の≡ＳｉＨ基を含有するものであり、直鎖状、分岐状、環状あるいは二次元網状構造の樹脂状物のいずれでもよい。このようなオルガノハイドロジェンポリシロキサンの代表例としては、例えば、下記式
ＨaＲ1 bＳｉＯ(4-a-b)/2
（式中、Ｒ1は独立に脂肪族不飽和結合を含有しない非置換又は置換の１価炭化水素基であり、ａ及びｂは、０＜ａ＜３、０≦ｂ＜３かつ０＜ａ＋ｂ≦３となる数であり、好ましくは０＜ａ＜２、０．８≦ｂ≦２かつ０．８＜ａ＋ｂ≦３となる数であり、特に好ましくは０．０５≦ａ≦１、１．５≦ｂ≦２かつ１．８≦ａ＋ｂ≦２．７となる数である。）
で表されるオルガノハイドロジェンポリシロキサンが挙げられる。
【００２９】
上記式中、Ｒ1の脂肪族不飽和結合を含有しない非置換又は置換の一価炭化水素基としては、炭素原子数が１〜１０、特に炭素原子数が１〜７のものであり、好ましくはメチル基等の炭素原子数１〜３の低級アルキル基、フェニル基、３，３，３−トリフルオロプロピル基である。
【００３０】
このようなオルガノハイドロジェンポリシロキサンの例としては、例えば、１，１，３，３−テトラメチルジシロキサン、１，３，５，７−テトラメチルテトラシクロシロキサン、１，３，５，７，８−ペンタメチルペンタシクロシロキサン等のシロキサンオリゴマー、分子鎖両末端トリメチルシロキシ基封鎖メチルハイドロジェンポリシロキサン、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、分子鎖両末端シラノール基封鎖メチルハイドロジェンポリシロキサン、分子鎖両末端シラノール基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルポリシロキサン、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖メチルハイドロジェンポリシロキサン、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体等、Ｒ’2（Ｈ）ＳｉＯ1/2単位とＳｉＯ4/2単位からなり、任意にＲ’3ＳｉＯ1/2単位、Ｒ’2ＳｉＯ2/2単位、Ｒ’（Ｈ）ＳｉＯ2/2単位、（Ｈ）ＳｉＯ3/2単位又はＲ’ＳｉＯ3/2単位を含み得るシリコーンレジン（但し、式中Ｒ’はＲ1と同様の一価炭化水素基である）などが挙げられる。
【００３１】
また、分子鎖片末端ジメチルハイドロジェンシロキシ基封鎖・片末端オキシアルキレン基含有ジメチルポリシロキサン、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖側鎖オキシアルキレン基含有ジメチルポリシロキサン等のオキシアルキレン基含有オルガノハイドロジェンポリシロキサンが挙げられる。これらは１種単独でも２種以上組み合わせても使用することができる。
【００３２】
本発明の組成物に用いるオルガノハイドロジェンポリシロキサンは、公知の方法で得ることができ、例えば、下記一般式：
Ｒ1ＳｉＨＣｌ2及びＲ1 2ＳｉＨＣｌ
（式中、Ｒ1は前記と同じである。）
から選ばれる少なくとも１種のクロロシランを（共）加水分解し、あるいは該クロロシランと下記一般式：
Ｒ1 3ＳｉＣｌ及びＲ1 2ＳｉＣｌ2
（式中、Ｒ1は前記と同様である。）
から選ばれる少なくとも１種のクロロシランを組み合わせて共加水分解して得ることができる。また、オルガノハイドロジェンポリシロキサンは、このように共加水分解して得られたポリシロキサンを平衡化したものでもよい。
【００３３】
なお、オルガノハイドロジェンポリシロキサンとしては、２５℃の粘度が１〜１，０００ｍＰａ・ｓ、特に５〜５００ｍＰａ・ｓであることが好ましい。
【００３４】
白金族金属系触媒としては、ヒドロシリル化反応に用いられる触媒として周知の触媒が挙げられる。その具体例としては、例えば、白金（白金黒を含む）、ロジウム、パラジウム等の白金族金属単体；
Ｈ2ＰｔＣｌ4・ｎＨ2Ｏ、Ｈ2ＰｔＣｌ6・ｎＨ2Ｏ、ＮａＨＰｔＣｌ6・ｎＨ2Ｏ、ＫＨＰｔＣｌ6・ｎＨ2Ｏ、Ｎａ2ＰｔＣｌ6・ｎＨ2Ｏ、Ｋ2ＰｔＣｌ4・ｎＨ2Ｏ、ＰｔＣｌ4・ｎＨ2Ｏ、ＰｔＣｌ2、Ｎａ2ＨＰｔＣｌ4・ｎＨ2Ｏ
（但し、式中、ｎは０〜６の整数であり、好ましくは０又は６である。）
等の塩化白金、塩化白金酸及び塩化白金酸塩、アルコール変性塩化白金酸（米国特許第３２２０９７２号明細書参照）、塩化白金酸とオレフィンとのコンプレックス（米国特許第３１５９６０１号明細書、同第３１５９６６２号明細書、同第３７７５４５２号明細書参照）、白金黒、パラジウム等の白金族金属をアルミナ、シリカ、カーボン等の担体に担持させたもの、ロジウム−オレフィンコンプレックス、クロロトリス（トリフェニルフォスフィン）ロジウム（ウィルキンソン触媒）、塩化白金、塩化白金酸又は塩化白金酸塩とビニル基含有シロキサン、特にビニル基含有環状シロキサンとのコンプレックスなどが挙げられる。また、白金微粉末やアルミナ、シリカゲル、アスベストなどの担体に白金粉末を担持させたもの、塩化白金酸あるいは塩化白金酸とアルコール、エーテル、アルデヒドなどとの錯体も例示される。この白金又は白金化合物は組成物中への分散をよくするためにイソプロパノール、エタノール、ベンゼン、トルエン、キシレンなどの有機溶媒あるいはオルガノポリシロキサンオイルに溶解乃至分散させて使用してもよい。使用量はオルガノハイドロジェンポリシロキサン１００部に対して白金金属として１〜１００，０００ｐｐｍであり、第一成分と第二成分を結合するために必須とされる成分である。
【００３５】
また、防汚性向上の目的で、従来から使用されているポリエーテル変性シリコーンオイル、ジメチルジフェニルシリコーンオイル、メチルフェニルシリコーンオイル等のシリコーンオイルや流動パラフィン、イソパラフィン等のパラフィンオイル等を本発明の目的を損なわない範囲で更に添加してもよい。
【００３６】
上記オルガノハイドロジェンポリシロキサンと白金族金属系触媒との混合物の層厚さは５０μｍ〜１ｍｍ、特に１００〜５００μｍであることが好ましい。薄すぎると膜強度が不十分となることがあり、厚すぎるとコスト的に不利となることがある。
また、この混合物の硬化は、（Ａ）成分の炭素数２以上の置換基がアルケニル基の場合は、室温硬化でも加熱硬化でもよく、それ以外の置換基の場合は加熱硬化が必要である。前者の加熱温度は５０〜２５０℃、特に８０〜２００℃であることが好ましく、後者の加熱温度は１００〜４００℃であることが好ましい。
この場合、縮合硬化型シリコーンゴム組成物のジオルガノポリシロキサンにおける炭素数２以上の一価炭化水素基がアルケニル基であると、上記混合物中の白金族金属系触媒の存在下にオルガノハイドロジェンポリシロキサンと付加反応し、付加反応硬化物が得られるものである。
【００３７】
更に、本発明においては、上記表面硬化層（第１の表面硬化層）上に、脂肪族不飽和炭化水素基及びオキシアルキレン基を含有する化合物を塗布し、第２の表面硬化層を形成することができる。この場合は、前の反応で（Ｂ）成分のオルガノハイドロジェンポリシロキサンが残存するようにしておく必要がある。脂肪族不飽和基としては、ビニル基、アリル基等の炭素数２〜６、特に２〜４のアルケニル基が好ましく、オキシアルキレン基としては、オキシエチレン基、オキシプロピレン基、オキシブチレン基等の炭素数２〜８、特に２〜４のオキシアルキレン基が好ましく、この場合、アルキレンオキシド付加モル数が１〜６０、特に３〜５０であることが好ましい。具体的にかかる化合物としては、
【化４】
この化合物による層厚さは５０μｍ〜１ｍｍ、特に１００〜５００μｍとすることが好ましい。
【００３８】
また、この層の硬化方法としては、室温硬化でも加熱硬化でもよいが、加熱硬化が好ましい。なお、この層は、上記オルガノハイドロジェンポリシロキサンと白金族金属系触媒との混合物による第１の表面硬化層のオルガノハイドロジェンポリシロキサンと上記化合物の脂肪族不飽和基とが白金族金属系触媒の存在下に付加反応し、付加反応硬化物が形成されるものである。
【００３９】
なお、本発明が適用される構造物（基材）としては、特に制限されないが、金属、セメント、ガラス等の無機材質や有機樹脂等が例示され、少なくとも一部が水中に没した水中構造物、例えば、船舶、港湾施設、ブイ、パイプライン、橋梁、海底基地、海底油田掘削設備、発電所の導水路管、養殖網、定置網等に好適に適用される。
【００４０】
【実施例】
以下、合成例及び実施例と比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。なお、粘度は２５℃での測定値を示す。また、部は質量部を示す。
【００４１】
［合成例１］
ポリマーＡの製造
温度計、撹拌機、冷却器を備えた内容積５リットルの三つロフラスコに２，４，６，８−テトラビニル−２，４，６，８−テトラメチルシクロテトラシロキサン２，７５２ｇ、蒸留水１．８ｇ、水酸化カリウム０．０８ｇを仕込み、１５０℃で５時間反応させた。反応後、８０℃まで冷却してエチレンクロロヒドリン４．０ｇを加え、更に８０℃で３時間反応させた後、減圧加熱により低揮発分を留去して、粘度１００，０００ｍＰａ・ｓ、不揮発分９５．８％の無色透明液体（両末端水酸基封鎖ポリメチルビニルシロキサン、珪素原子に結合した全置換基に対する炭素数２以上の置換基の割合：５０モル％）を２，４００ｇ得た。
【００４２】
［合成例２］
ポリマーＢの製造
合成例１の２，４，６，８−テトラビニル−２，４，６，８−テトラメチルシクロテトラシロキサン２，７５２ｇの代わりに、２，４，６，８−テトラビニル−２，４，６，８−テトラメチルシクロテトラシロキサン１，３７６ｇ、オクタメチルシクロテトラシロキサン１，１８４ｇを用いた以外は合成例１と同様にして、粘度６２，０００ｍＰａ・ｓ、不揮発分９６．８％の無色透明液体（両末端水酸基封鎖ポリメチルビニルシロキサン、珪素原子に結合した全置換基に対する炭素数２以上の置換基の割合：２５モル％）を２，３００ｇ得た。
【００４３】
［合成例３］
ポリマーＣの製造
合成例１の２，４，６，８−テトラビニル−２，４，６，８−テトラメチルシクロテトラシロキサン２，７５２ｇの代わりに、２，４，６，８−テトラビニル−２，４，６，８−テトラメチルシクロテトラシロキサン６８８ｇ、オクタメチルシクロテトラシロキサン１，７７６ｇを用いた以外は合成例１と同様にして、粘度５０，０００ｍＰａ・ｓ、不揮発分９６．６％の無色透明液体（両末端水酸基封鎖ポリメチルビニルシロキサン、珪素原子に結合した全置換基に対する炭素数２以上の置換基の割合：１２．５モル％）を２，２５０ｇ得た。
【００４４】
［合成例４］
ポリマーＤの製造
合成例１の２，４，６，８−テトラビニル−２，４，６，８−テトラメチルシクロテトラシロキサン２，７５２ｇの代わりに、２，４，６，８−テトラビニル−２，４，６，８−テトラメチルシクロテトラシロキサン２７５ｇ、オクタメチルシクロテトラシロキサン２，１３１ｇを用いた以外は合成例１と同様にして、粘度８０，０００ｍＰａ・ｓ、不揮発分９５．７％の無色透明液体（両末端水酸基封鎖ポリメチルビニルシロキサン、珪素原子に結合した全置換基に対する炭素数２以上の置換基の割合：５モル％）を２，１００ｇ得た。
【００４５】
［合成例５］
ポリマーＥの製造
合成例１の２，４，６，８−テトラビニル−２，４，６，８−テトラメチルシクロテトラシロキサシ２，７５２ｇの代わりに、２，４，６，８−テトラビニル−２，４，６，８−テトラメチルシクロテトラシロキサン１３８ｇ、オクタメチルシクロテトラシロキサン２，２５０ｇを用いた以外は合成例１と同様にして、粘度１５０，０００ｍＰａ・ｓ、不揮発分９９．２％の無色透明液体（両末端水酸基封鎖ポリメチルビニルシロキサン、珪素原子に結合した全置換基に対する炭素数２以上の置換基の割合：２．５モル％）を２，１５０ｇ得た。
【００４６】
［合成例６］
ポリマーＦの製造
合成例１の２，４，６，８−テトラビニル−２，４，６，８−テトラメチルシクロテトラシロキサン２，７５２ｇの代わりに、オクタメチルシクロテトラシロキサン２，３６８ｇを用いた以外は合成例１と同様にして、粘度８１，０００ｍＰａ・ｓ、不揮発分９６．３％の無色透明液体（両末端水酸基封鎖ポリメチルビニルシロキサン、珪素原子に結合した全置換基に対する炭素数２以上の置換基の割合：０モル％）を２，１００ｇ得た。
【００４７】
［合成例７］
ポリマーＧの製造
温度計、撹拌機、冷却器を備えた内容積２リットルの三つ口フラスコにポリマ−Ａを１，０００ｇ、テトラメトキシシランを７６ｇ仕込み、１２０℃で２４時間反応させた。反応後、減圧加熱によりメタノールと過剰のテトラメトキシシランを留去して、粘度１０８，０００ｍＰａ・ｓ、不揮発分９６．３％の無色透明液体（両末端トリメトキシ基封鎖ポリメチルビニルシロキサン、珪素原子に結合した全置換基に対する炭素数２以上の置換基の割合：５０モル％）を９７５ｇ得た。
【００４８】
［合成例８］
ポリマーＨの製造
合成例７のポリマーＡの代わりにポリマーＦを用いた以外は、合成例７と同様にして、粘度９０，０００ｍＰａ・ｓ、不揮発分９８．２％の無色透明液体（両末端トリメトキシ基封鎖ポリメチルビニルシロキサン、珪素原子に結合した全置換基に対する炭素数２以上の置換基の割合：０モル％）を９５０ｇ得た。
【００４９】
［処方例１］
ポリマーＡを１００部と表面がジメチルジクロロシランで処理された乾式シリカ（エロジルＲ９７２（日本アエロジル（株）製））５部を均一に混合し、これにビニルトリスメチルエチルケトオキシムシラン６部、γ−アミノプロピルトリエトキシシラン０．５部を減圧下で均一になるまで混合して、縮合硬化型シリコーンゴム組成物を調製した。
【００５０】
［処方例２］
処方例１において、ポリマーＡの代わりにポリマーＢを用いた以外は処方例１と同様の手法で組成物を調製した。
【００５１】
［処方例３］
処方例１において、ポリマーＡの代わりにポリマーＣを用いた以外は処方例１と同様の手法で組成物を調製した。
【００５２】
［処方例４］
処方例１において、ポリマーＡの代わりにポリマーＤを用いた以外は処方例１と同様の手法で組成物を調製した。
【００５３】
［処方例５］
処方例１において、ポリマーＡの代わりにポリマーＥを用いた以外は処方例１と同様の手法で組成物を調製した。
【００５４】
［処方例６］
ポリマーＡを１００部とコロイダル炭酸カルシウム５０部を均一に混合し、これにビニルトリスイソプロペノキシシラン８部、テトラメチルグアニジルプロピルトリメトキシシラン１．０部を減圧下で均一になるまで混合して、組成物を調製した。
【００５５】
［処方例７］
ポリマーＧを１００部とコロイダル炭酸カルシウム５０部を均一に混合し、これにメチルトリメトキシシラン６部、テトラブチルチタネート１．０部を減圧下で均一になるまで混合して、組成物を調製した。
【００５６】
［比較例１］
処方例１において、ポリマーＡの代わりにポリマーＦを用いた以外は処方例１と同様の手法で組成物を調製した。
【００５７】
［比較例２］
処方例６において、ポリマーＡの代わりにポリマーＦを用いた以外は処方例６と同様の手法で組成物を調製した。
【００５８】
［比較例３］
処方例７において、ポリマーＧの代わりにポリマーＨを用いた以外は処方例７と同様の手法で組成物を調製した。
【００５９】
次に、これら組成物を２３℃，５０％ＲＨの条件で７日間かけて硬化させた（初期）。更に、１００℃の乾燥機で１時間加熱した（加熱）。また、初期の硬化物表面に下記オルガノハイドロジェンポリシロキサン（Ｍ−ＤH 38−Ｍ）を厚さ２００μｍにコーティングし、１００℃の乾燥機で１時間加熱した（ＨＤＭ）。更に、初期の硬化物表面にオルガノハイドロジェンポリシロキサン（Ｍ−ＤH 38−Ｍ）１００ｇと白金−ジビニルテトラメチルジシロキサン錯体／トルエン溶液（白金元素含有量０．５ｗｔ％）１ｇの混合物を厚さ２００μｍにコーティングし、１００℃の乾燥機で１時間加熱した（ＨＤＭ（１）／Ｐｔ）。
【００６０】
【化５】
上記それぞれの条件で作製したシート表面の接触角を以下の通り測定した。結果を表１に示す。
＜初期接触角＞
水接触角：協和界面化学（株）製、接触角計ＣＡ−Ｘ１５０を使用（液滴量）して測定した。
＜耐久接触角＞
キシレンを浸した脱脂綿で１００往復ラビングした後の接触角を初期と同様に測定した。
【００６２】
【表１】
＜水滴転落角＞
シート表面に水滴を１滴たらし、シートの角度を０°（水平）から徐々に上げていき、９０°（垂直）に立てた時、水滴が流れ落ちた角度を読みとった。
初期の硬化物表面に下記に示すオルガノハイドロジェンポリシロキサン１００ｇと白金−ジビニルテトラメチルジシロキサン錯体／トルエン溶液（白金元素含有量０．５ｗｔ％）１ｇの混合物を厚さ２００μｍにコーティングし、１００℃の乾燥機で１時間加熱した（ＨＤＭ（１）〜（４）／Ｐｔ）。
また、初期の硬化物表面にオルガノハイドロジェンポリシロキサン（Ｍ−ＤH 38−Ｍ）１００ｇと白金−ジビニルテトラメチルジシロキサン錯体／トルエン溶液（白金元素含有量０．５ｗｔ％）１ｇの混合物を厚さ２００μｍにコーティングし、１００℃の乾燥機で１時間加熱した後、更に両末端にアリル基とＯＨ基を有する８個のオキシエチレン基を有する化合物（ＥＯ）１００ｇとジビニルテトラメチルジシロキサン錯体／トルエン溶液（白金元素含有量０．５ｗｔ％）１ｇの混合物を厚さ２００μｍにコーティングし、１００℃の乾燥機で１時間加熱した（ＨＤＭ（１）／Ｐｔ／ＥＯ）。
得られた結果を表２に示す。
【００６４】
【化６】
【表２】
＜防汚性能試験結果＞
上記の組成物を、エポキシ系防食塗料（膜厚２００μｍ）を用いて予め塗装した被塗板に、硬化膜厚が３００μｍになるように塗装して試験塗板とした。このように作製した試験塗板を、２３℃，５０％ＲＨの条件で７日間かけて硬化させた。
これらの硬化後の試験塗板につき、表３に示す硬化層処理を上記と同様にして行った後、三重県海岸の沖合いに１．５ｍの深さで１２ヶ月間にわたって懸垂試験を行い、フジツボ等の貝類、海藻類の付着状況を観察した。その結果を表３に示す。
【００６７】
【表３】
【発明の効果】
本発明の防汚方法によれば、無毒であり、環境面において何ら問題もなく、かつ長期間に亘って水生生物の付着・生育を防止し、優れた防汚性を示すものである。[0001]
BACKGROUND OF THE INVENTION
In particular, the present invention is applied to ships, harbor facilities, buoys, pipelines, bridges, submarine bases, submarine oil field drilling equipment, powerhouse conduit pipes, aquaculture nets, stationary nets, etc. (hereinafter referred to as “underwater structures”). The present invention also relates to an antifouling method and an antifouling structure that provide an antifouling coating film suitable for preventing adhesion and growth of aquatic organisms on these surfaces.
[0002]
[Prior art]
Various room temperature curable silicone rubber compositions that give rubbery elastic bodies at room temperature are known, and cured rubbers obtained from room temperature curable silicone rubber compositions (hereinafter referred to as “RTV”) are other organic materials. It is used in various fields because it has superior weather resistance, durability, heat resistance, cold resistance, etc. compared to rubber, and in the construction field, it is used for bonding between glasses and between metal and glass. In recent years, it is widely used as a coating material for buildings, plants, underwater structures and the like.
[0003]
Here, when an underwater structure is installed or put into service, barnacles, sea squirts, cell plastics, blue mussels, crows guys, chrysanthemum bugs, aonoris that live in the water of the sea, rivers, etc. from the splashed part to the surface of the submerged part Aquatic organisms such as Aosa attach and grow, causing various damage. For example, when organisms adhere to the hull, the frictional resistance with water increases, the navigation speed decreases, and fuel consumption increases to maintain a constant speed, which is economically disadvantageous. Moreover, if a living thing adheres to the structure fixed to the water or the water surface of a port facility etc., it will become difficult to fully exhibit each function which these have, and a base material may be eroded. Furthermore, if organisms adhere to aquaculture nets, stationary nets, etc., the nets may be blocked and fish may die.
[0004]
As measures to prevent the attachment and growth of aquatic organisms to underwater structures, antifouling paints containing toxic antifouling agents such as organotin compounds and cuprous oxide were applied to the structures. Although adherence and growth of living organisms were almost prevented, a toxic antifouling agent was used, which is undesirable for environmental safety and hygiene during the manufacture and painting of paints. In the long term, there is a risk of contaminating the water area, so its use is legally prohibited.
[0005]
On the other hand, as a paint which has an effect of preventing adhesion and growth of aquatic organisms and does not contain a toxic antifouling agent, RTV can be supplied with liquid paraffin or petrolactam as an antifouling property by lowering the surface tension of the coating film. Has been proposed (see, for example, Japanese Patent Application Laid-Open Nos. 58-13673 and 62-84166). In addition, volumetric shrinkage associated with the curing of the reactive curable silicone resin causes the poorly compatible and non-reactive polar group-containing silicone resin to ooze out to the surface, preventing the combination with the low surface tension of the reactive curable silicone resin. Non-toxic antifouling paint compositions exhibiting soiling properties (see, for example, Patent Documents 3 and 4: Patent Nos. 2503986 and 295375) have also been proposed. However, sufficient performance cannot be obtained in terms of sustainability of the antifouling property, and there is a problem with respect to the safety of the eluted compound.
[0006]
On the other hand, as the surface antifouling treatment of the structure, a pretreatment composition mainly composed of an organic polymer having an antifouling reactive functional group is treated on the surface of the substrate, and then reacted with the reactive functional group. A surface antifouling treatment structure is described in which an antifouling composition comprising a water-repellent antifouling agent having a reactive functional group as a main component is reacted with a pretreatment layer, and further an allyl group-containing acrylic resin is pretreated. Further, it is exemplified that hydrogen polysiloxane having a SiH group only on the side chain (KF-99 (manufactured by Shin-Etsu Chemical Co., Ltd.)) is subjected to a hydrosilylation reaction (for example, Patent Document 5: Special (See Kaihei 5-16901).
[0007]
However, this method has poor wettability between the acrylic resin used for the pretreatment and the siloxane used in the upper layer, so that the bonding by hydrosilylation is not sufficient, and the durability of the antifouling property is insufficient. It was.
[0008]
[Patent Document 1]
JP 58-13673 A
[Patent Document 2]
JP-A-62-84166
[Patent Document 3]
Japanese Patent No. 2503986
[Patent Document 4]
Japanese Patent No. 2952375
[Patent Document 5]
Japanese Patent Laid-Open No. 5-169011
[0009]
[Problems to be solved by the invention]
Therefore, the present invention is particularly suitable for preventing adhesion and growth of aquatic organisms on the surface of an underwater structure, which is coated on an underwater structure, and is a stain resistant coating film with good durability. An object is to provide an antifouling method and an antifouling structure.
[0010]
Means for Solving the Problem and Embodiment of the Invention
As a result of intensive studies to achieve the above object, the present inventors have found that in the condensation curable silicone rubber composition, 2 mol% of all substituents directly bonded to the silicon atom of the diorganopolysiloxane of the base polymer. Coated with a mixture of an organohydrogenpolysiloxane and a platinum group metal catalyst on a cured film of a composition using a specific diorganopolysiloxane which is a substituted or unsubstituted monovalent hydrocarbon group having 2 or more carbon atoms. And, in this case, more preferably, by further coating and curing a compound containing an aliphatic unsaturated hydrocarbon group and an oxyalkylene group thereon, a significant improvement in antifouling property can be achieved, It was found that it was possible to obtain extremely good antifouling properties and sustainability, and that it was also excellent in safety, leading to the present invention.
[0011]
Therefore, the present invention
[I] On the surface of a substrate, preferably an underwater structure, (A) 2 of all substituents having a hydroxyl group or hydrolyzable group bonded to a silicon atom in the molecule and bonded to a silicon atom More than mol%An alkenyl group in which the other group bonded to the silicon atom is a methyl groupIsThe following general formula (1) or (2)
[Chemical 7]
[Chemical 8]
Represented byIn addition to forming a cured film of a condensation curable silicone rubber composition comprising diorganopolysiloxane as a base polymer and blending a silane having two or more hydrolyzable groups in one molecule or a partial hydrolyzate thereof, (B) Mixture of organohydrogenpolysiloxane and platinum group metal catalyst on the cured coatingThe organohydrogenpolysiloxane is applied in such an amount that it remains when it undergoes an addition reaction with the alkenyl group in the cured coating, and the alkenyl group in the cured coating and the organohydrogenpolysiloxane are reacted by addition reaction. A first hardened layer is formed with the coating, and (C) a compound containing an aliphatic unsaturated hydrocarbon group and an oxyalkylene group is applied onto the first hardened layer, and The remaining organohydrogenpolysiloxane and the aliphatic unsaturated hydrocarbon group in the first hardened surface layer are subjected to an addition reaction to form a second between the first hardened surface layer and the first hardened surface layer.Antifouling method for base material characterized by forming a hardened surface layer, AndAnd
[II] An antifouling structure having an antifouling film formed by the above antifouling method
I will provide a.
[0012]
Hereinafter, the present invention will be described in more detail.
In the antifouling method and antifouling structure according to the present invention, first, a cured film of a condensation curable silicone rubber composition is formed on the surface of a structure (base material), particularly an underwater structure.
In this case, the first component of the silicone rubber composition is diorganopolysiloxane, which is a base polymer.
The diorganopolysiloxane of the base polymer used in the first component has a hydroxyl group or hydrolyzable group directly bonded to at least two silicon atoms in the molecule in order to be cured by a condensation reaction. 2 mol% or more of the bonded substituents have a substituted or unsubstituted monovalent hydrocarbon group having 2 or more carbon atoms.
[0013]
In the base polymer of the conventionally used condensation curable silicone rubber (RTV rubber) composition, most of the substituents other than the hydroxyl group or hydrolyzable group involved in the condensation reaction are methyl groups. Is obtained by introducing a specific amount of a substituted or unsubstituted monovalent hydrocarbon group having 2 or more carbon atoms that does not participate in the condensation reaction (crosslinking) to a substituent other than the hydrolyzable group, and has 2 carbon atoms after curing. It is necessary that the above substituted or unsubstituted monovalent hydrocarbon group remains in the cured product.
This diorganopolysiloxane is substantially linear, but may be branched as long as it does not cause gelation or impair rubber elasticity. The amount of branching is usually 10 mol% or less, preferably 5 mol% or less.
Specifically, diorganopolysiloxane represented by the following general formula (1) or (2) is preferable.
[0014]
[Chemical 3]
[0015]
Here, R is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a 2-ethylbutyl group or an octyl group, a cycloalkyl group such as a cyclohexyl group or a cyclopentyl group, a vinyl group, a propenyl group, a butenyl group, or a heptenyl. Group, hexenyl group, alkenyl group such as allyl group, phenyl group, tolyl group, xylyl group, naphthyl group, aryl group such as diphenyl group, aralkyl group such as benzyl group, phenylethyl group or the carbon atom of these groups The same or different unsubstituted selected from a chloromethyl group, a trifluoropropyl group, a 2-cyanoethyl group, a 3-cyanopropyl group, etc., in which some or all of the hydrogen atoms are substituted with a halogen atom, a cyano group, or the like Alternatively, the substitution is preferably a monovalent hydrocarbon group having 1 to 12 carbon atoms, particularly 1 to 10 carbon atoms.
[0016]
Further, 2 mol% or more, preferably 2.5 mol% or more of R is required to be a substituted or unsubstituted monovalent hydrocarbon group having 2 or more carbon atoms. Although it does not restrict | limit especially as an upper limit, From the ease of manufacture, it is 50 mol% or less.
[0017]
Examples of the substituted or unsubstituted monovalent hydrocarbon group having 2 or more carbon atoms include monovalent hydrocarbon groups other than the above-described methyl group of R, vinyl group, allyl group, propenyl group, butenyl group, heptenyl group. An alkenyl group such as a hexenyl group, an ethyl group, a propyl group, a phenyl group, and the like are preferable. Among them, an alkenyl group that can be hydrosilylated with the organohydrogenpolysiloxane of the component (B) is preferable, and a vinyl group is particularly preferable. Two or more of these may be used.
In R, a methyl group is preferable as the substituent other than the monovalent hydrocarbon group having 2 or more carbon atoms.
[0018]
X is an oxygen atom or a divalent hydrocarbon group having 1 to 8 carbon atoms. As the divalent hydrocarbon group, — (CH2)m(M represents 1 to 8). Among these, oxygen atom, -CH2CH2-Is preferred. n is a number that sets the viscosity of the diorganopolysiloxane at 25 ° C. to 100 to 1,000,000 mPa · s, preferably 500 to 500,000 mPa · s.
[0019]
Y is a hydrolyzable group, specifically, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group or a butoxy group, a ketoxime group such as a dimethyl ketoxime group or a methylethyl ketoxime group, an acyloxy group such as an acetoxy group, Examples thereof include alkenyloxy groups such as isopropenyloxy group and isobutenyloxy group, with alkoxy and ketoxime groups being preferred, and methoxy and ethoxy groups being particularly preferred.
[0020]
Such a diorganopolysiloxane can be produced by a known method such as obtaining a cyclic siloxane or linear oligomer which is a monomer of various organopolysiloxanes by an equilibrium reaction with an acid or base catalyst.
In addition, when a branched structure is introduced into the diorganopolysiloxane, SiO 2 is added during the equilibration polymerization.3/2Unit and / or SiO4/2It is usual to add silane or siloxane containing units at a level at which the diorganopolysiloxane does not gel. Further, it is desirable that the low molecular weight siloxane is removed from the diorganopolysiloxane by stripping or washing.
[0021]
A crosslinking agent is used in the condensation curable silicone rubber composition. As the crosslinking agent, a silane having 2 or more, preferably 3 or more hydrolyzable groups in one molecule, or a partially hydrolyzed condensate thereof is used. In this case, the hydrolyzable group includes an alkoxy group such as a methoxy group, an ethoxy group, and a butoxy group, a ketoxime group such as a dimethyl ketoxime group and a methyl ethyl ketoxime group, an acyloxy group such as an acetoxy group, an isopropenyloxy group, Examples include alkenyloxy groups such as isobutenyloxy group, amino groups such as N-butylamino group and N, N-diethylamino group, and amide groups such as N-methylacetamide group. Among these, an alkoxy group, a ketoxime group, an acyloxy group, and an alkenyloxy group are preferable.
[0022]
The blending amount of the crosslinking agent is desirably 1 to 50 parts, preferably 2 to 30 parts, more preferably 5 to 20 parts with respect to 100 parts (parts by mass, the same applies hereinafter) of the diorganopolysiloxane.
[0023]
In addition, it is preferable that the condensation curable silicone rubber composition basically does not use a curing catalyst, but when a curing catalyst is used, the following can be exemplified. Alkyl tin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, tetraisopropoxy titanium, tetra n-butoxy titanium, tetrakis (2-ethylhexoxy) titanium, dipropoxy bis (acetylacetona) titanium, titanium iso Titanic acid ester or titanium chelate compound such as propoxyoctylene glycol, zinc naphthenate, zinc stearate, zinc-2-ethyl octoate, iron-2-ethylhexoate, cobalt-2-ethylhexoate, manganese- Organometallic compounds such as 2-ethylhexoate, cobalt naphthenate and alkoxyaluminum compounds, amino acids such as 3-aminopropyltriethoxysilane and N-β (aminoethyl) γ-aminopropyltrimethoxysilane Amine compounds such as alkyl group-substituted alkoxysilanes, hexylamines, dodecylamine phosphates and salts thereof, quaternary ammonium salts such as benzyltriethylammonium acetate, lower fatty acid salts of alkali metals such as potassium acetate, sodium acetate, lithium oxalate, Dialkylhydroxylamine such as dimethylhydroxylamine and diethylhydroxylamine, guanidyl groups such as tetramethylguanidylpropyltrimethoxysilane, tetramethylguanidylpropylmethyldimethoxysilane and tetramethylguanidylpropyltris (trimethylsiloxy) silane Examples thereof include silane, siloxane and the like, which are not limited to one of them, and may be used as a mixture of two or more. In addition, the compounding quantity of these curing catalysts is 0-20 parts with respect to 100 parts of said diorganopolysiloxane, Preferably it is 0.001-10 parts, More preferably, it is 0.01-5 parts.
[0024]
In addition to the above components, it is preferable to use one or more fillers for the purpose of reinforcement in the condensation curable silicone rubber composition. Examples of such fillers include fumed silica, precipitated silica, silica whose surface is hydrophobized with an organosilicon compound, quartz powder, carbon black, talc, zeolite, bentonite and other reinforcing agents, asbestos Fiber fillers such as glass fiber, carbon fiber and organic fiber, basic fillers such as calcium carbonate, zinc carbonate, calcium silicate, zinc oxide, magnesium oxide and diatomaceous earth, fillers having photocatalytic activity such as titanium oxide, etc. Is exemplified. Of these fillers, calcium carbonate, calcium silicate, silica whose surface has been hydrophobized, zeolite, and the like are preferable, and fumed silica and calcium carbonate whose surface has been hydrophobized are particularly preferable.
[0025]
The blending amount of the filler may be selected depending on the purpose and the kind of the filler, but is preferably 1 to 500 parts, particularly preferably 5 to 100 parts with respect to 100 parts of the diorganopolysiloxane component of the base polymer.
[0026]
Furthermore, it is optional to add various compounds to the condensation curable silicone rubber composition as long as they do not inhibit the antifouling property. For example, thixotropy-imparting agents composed of polyethylene glycol or its derivatives, bengara, cerium oxide, etc. Heat resistance improver, cold resistance improver, dehydrating agent, rust preventive agent, adhesion improver such as γ-aminopropyltriethoxysilane, triorganosiloxy unit and SiO2A predetermined amount of a liquid reinforcing agent such as a reticulated polysiloxane composed of units and / or monoorganosiloxy units can be added as necessary.
The condensation curable silicone rubber composition is cured by moisture at room temperature, and a known method and conditions according to the type of the composition can be adopted as the molding method and curing conditions.
[0027]
In this case, the thickness of the cured coating film of this composition may be selected depending on the type and use of the substrate, but is preferably 50 μm to 2 mm, particularly preferably 100 μm to 1 mm. If it is too thin, the film strength may be insufficient, and if it is too thick, it may be disadvantageous in terms of cost.
[0028]
In the present invention, a mixture of an organohydrogenpolysiloxane and a platinum group metal catalyst is applied onto the cured film of the condensation curable silicone rubber composition, and a surface cured layer is formed between the cured film.
In this case, the organohydrogenpolysiloxane in the mixture of the organohydrogenpolysiloxane and the platinum group metal catalyst contains one or more, preferably 1 to 50 ≡SiH groups in one molecule. Any of linear, branched, cyclic, or two-dimensional network resinous materials may be used. Representative examples of such organohydrogenpolysiloxanes include, for example, the following formula:
HaR1 bSiO(4-ab) / 2
(Wherein R1Is an unsubstituted or substituted monovalent hydrocarbon group independently containing no aliphatic unsaturated bond, and a and b are numbers satisfying 0 <a <3, 0 ≦ b <3 and 0 <a + b ≦ 3 Yes, preferably 0 <a <2, 0.8 ≦ b ≦ 2, and 0.8 <a + b ≦ 3, particularly preferably 0.05 ≦ a ≦ 1, 1.5 ≦ b ≦ 2, and It is a number that satisfies 1.8 ≦ a + b ≦ 2.7. )
The organohydrogen polysiloxane represented by these is mentioned.
[0029]
In the above formula, R1The unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond is one having 1 to 10 carbon atoms, particularly 1 to 7 carbon atoms, preferably a carbon such as a methyl group. A lower alkyl group having 1 to 3 atoms, a phenyl group, and a 3,3,3-trifluoropropyl group.
[0030]
Examples of such organohydrogenpolysiloxanes include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyltetracyclosiloxane, 1,3,5,7, Siloxane oligomers such as 8-pentamethylpentacyclosiloxane, trimethylsiloxy group-capped methylhydrogen polysiloxane with molecular chain terminals, trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer with molecular chain terminals, and silanols with both molecular chains Blocked methyl hydrogen polysiloxane, Molecular chain both ends silanol group blocked dimethyl siloxane / methyl hydrogen siloxane copolymer, Molecular chain both ends dimethyl hydrogen siloxy group blocked dimethyl polysiloxane, Molecular chain both ends dimethyl hydrogen Siloxy group methylhydrogenpolysiloxane capped at both molecular chain terminals blocked with dimethylhydrogensiloxy groups dimethylsiloxane-methylhydrogensiloxane copolymer, R '2(H) SiO1/2Unit and SiO4/2Unit, optionally R 'ThreeSiO1/2Unit, R '2SiO2/2Unit, R '(H) SiO2/2Unit, (H) SiO3/2Unit or R'SiO3/2A silicone resin that can contain units, where R 'is R1And the same monovalent hydrocarbon group).
[0031]
In addition, oxyalkylene group-containing organohydrocarbons such as dimethylpolysiloxanes containing dimethylhydrogensiloxy group-blocked / single-end oxyalkylene groups and dimethylpolysiloxanes containing dimethylhydrogensiloxy group-blocked side-chain oxyalkylene groups are also included. Genpolysiloxane may be mentioned. These can be used singly or in combination of two or more.
[0032]
The organohydrogenpolysiloxane used in the composition of the present invention can be obtained by a known method, for example, the following general formula:
R1SiHCl2And R1 2SiHCl
(Wherein R1Is the same as above. )
(Co) hydrolysis of at least one chlorosilane selected from: or the chlorosilane and the following general formula:
R1 ThreeSiCl and R1 2SiCl2
(Wherein R1Is the same as described above. )
It can be obtained by combining and co-hydrolyzing at least one chlorosilane selected from. In addition, the organohydrogenpolysiloxane may be one obtained by equilibrating the polysiloxane obtained by cohydrolysis.
[0033]
The organohydrogenpolysiloxane preferably has a viscosity at 25 ° C. of 1 to 1,000 mPa · s, particularly 5 to 500 mPa · s.
[0034]
As the platinum group metal catalyst, a catalyst known as a catalyst used in the hydrosilylation reaction may be mentioned. Specific examples thereof include, for example, platinum group metals such as platinum (including platinum black), rhodium, and palladium;
H2PtClFour・ NH2O, H2PtCl6・ NH2O, NaHPtCl6・ NH2O, KHPtCl6・ NH2O, Na2PtCl6・ NH2O, K2PtClFour・ NH2O, PtClFour・ NH2O, PtCl2, Na2HPtClFour・ NH2O
(However, in the formula, n is an integer of 0 to 6, preferably 0 or 6.)
Platinum chloride, chloroplatinic acid and chloroplatinate, alcohol-modified chloroplatinic acid (see US Pat. No. 3,220,972), chloroplatinic acid and olefin complex (US Pat. Nos. 3,159,601 and 3,159,662) No. specification, see No. 3775452), a platinum group metal such as platinum black and palladium supported on a support such as alumina, silica, carbon, rhodium-olefin complex, chlorotris (triphenylphosphine) rhodium (Wilkinson's catalyst), platinum chloride, chloroplatinic acid, or a chloroplatinate and a vinyl group-containing siloxane, particularly a vinyl group-containing cyclic siloxane. Also exemplified are platinum fine powder, those obtained by supporting platinum powder on a carrier such as alumina, silica gel and asbestos, and chloroplatinic acid or a complex of chloroplatinic acid and alcohol, ether, aldehyde or the like. This platinum or platinum compound may be used by dissolving or dispersing in an organic solvent such as isopropanol, ethanol, benzene, toluene, xylene or an organopolysiloxane oil in order to improve dispersion in the composition. The amount used is 1 to 100,000 ppm as platinum metal with respect to 100 parts of the organohydrogenpolysiloxane, and is an essential component for bonding the first component and the second component.
[0035]
In addition, for the purpose of improving the antifouling property, conventionally used polyether-modified silicone oil, dimethyldiphenyl silicone oil, silicone oil such as methylphenyl silicone oil, paraffin oil such as liquid paraffin and isoparaffin, etc. You may add further in the range which does not impair.
[0036]
The layer thickness of the mixture of the organohydrogenpolysiloxane and the platinum group metal catalyst is preferably 50 μm to 1 mm, particularly preferably 100 to 500 μm. If it is too thin, the film strength may be insufficient, and if it is too thick, it may be disadvantageous in terms of cost.
In addition, the curing of the mixture may be room temperature curing or heat curing when the substituent having 2 or more carbon atoms of the component (A) is an alkenyl group, and heat curing is necessary in the case of other substituents. The former heating temperature is preferably 50 to 250 ° C., particularly preferably 80 to 200 ° C., and the latter heating temperature is preferably 100 to 400 ° C.
In this case, if the monovalent hydrocarbon group having 2 or more carbon atoms in the diorganopolysiloxane of the condensation curable silicone rubber composition is an alkenyl group, the organohydrogenpolysiloxane is present in the presence of the platinum group metal catalyst in the mixture. Addition reaction with siloxane gives an addition reaction cured product.
[0037]
Furthermore, in this invention, the compound containing an aliphatic unsaturated hydrocarbon group and an oxyalkylene group is apply | coated on the said surface hardening layer (1st surface hardening layer), and a 2nd surface hardening layer is formed. be able to. In this case, it is necessary that the organohydrogenpolysiloxane of the component (B) remains in the previous reaction. The aliphatic unsaturated group is preferably an alkenyl group having 2 to 6 carbon atoms, particularly 2 to 4 carbon atoms such as a vinyl group or an allyl group. The oxyalkylene group may be an oxyethylene group, an oxypropylene group, an oxybutylene group, or the like. An oxyalkylene group having 2 to 8 carbon atoms, particularly 2 to 4 carbon atoms is preferred. In this case, the number of added alkylene oxides is preferably 1 to 60, particularly 3 to 50. Specifically, as such a compound,
[Formula 4]
The layer thickness of this compound is preferably 50 μm to 1 mm, particularly preferably 100 to 500 μm.
[0038]
The curing method for this layer may be room temperature curing or heat curing, but heat curing is preferred. In this layer, the organohydrogenpolysiloxane of the first surface hardened layer by the mixture of the organohydrogenpolysiloxane and the platinum group metal catalyst and the aliphatic unsaturated group of the compound are a platinum group metal catalyst. In the presence of, an addition reaction is performed to form an addition reaction cured product.
[0039]
In addition, the structure (base material) to which the present invention is applied is not particularly limited, but examples thereof include inorganic materials such as metals, cement, and glass, organic resins, and the like, and at least a part of the structure is submerged in water. For example, it is suitably applied to ships, port facilities, buoys, pipelines, bridges, submarine bases, subsea oil field drilling equipment, waterway conduit pipes, aquaculture nets, stationary nets, and the like.
[0040]
【Example】
EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, a viscosity shows the measured value in 25 degreeC. Moreover, a part shows a mass part.
[0041]
[Synthesis Example 1]
Production of polymer A
2,752, g of 2,4,6,8-tetravinyl-2,4,6,8-tetramethylcyclotetrasiloxane, distilled water in a three-liter flask having an internal volume of 5 liters equipped with a thermometer, a stirrer and a condenser 1.8 g and 0.08 g of potassium hydroxide were charged and reacted at 150 ° C. for 5 hours. After the reaction, the mixture was cooled to 80 ° C., 4.0 g of ethylene chlorohydrin was added, and further reacted at 80 ° C. for 3 hours, and then the low volatile matter was distilled off by heating under reduced pressure to obtain a viscosity of 100,000 mPa · s, non-volatile. 2,400 g of 95.8% colorless transparent liquid (both end hydroxyl-blocked polymethylvinylsiloxane, ratio of substituents having 2 or more carbon atoms to all substituents bonded to silicon atoms: 50 mol%) was obtained.
[0042]
[Synthesis Example 2]
Production of polymer B
Instead of 2,752, g of 2,4,6,8-tetravinyl-2,4,6,8-tetramethylcyclotetrasiloxane in Synthesis Example 1, 2,4,6,8-tetravinyl-2,4, Colorless and transparent with a viscosity of 62,000 mPa · s and a non-volatile content of 96.8% in the same manner as in Synthesis Example 1 except that 1,376 g of 6,8-tetramethylcyclotetrasiloxane and 1,184 g of octamethylcyclotetrasiloxane were used. 2,300 g of liquid (both terminal hydroxyl-blocked polymethylvinylsiloxane, ratio of substituents having 2 or more carbon atoms to all substituents bonded to silicon atoms: 25 mol%) was obtained.
[0043]
[Synthesis Example 3]
Production of polymer C
Instead of 2,752, g of 2,4,6,8-tetravinyl-2,4,6,8-tetramethylcyclotetrasiloxane in Synthesis Example 1, 2,4,6,8-tetravinyl-2,4, A colorless transparent liquid having a viscosity of 50,000 mPa · s and a non-volatile content of 96.6% (similar to Synthesis Example 1 except that 688 g of 6,8-tetramethylcyclotetrasiloxane and 1,776 g of octamethylcyclotetrasiloxane were used) 2,250 g of polymethylvinylsiloxane blocked with hydroxyl groups at both ends and the ratio of substituents having 2 or more carbon atoms to all substituents bonded to silicon atoms (12.5 mol%) were obtained.
[0044]
[Synthesis Example 4]
Production of polymer D
Instead of 2,752, g of 2,4,6,8-tetravinyl-2,4,6,8-tetramethylcyclotetrasiloxane in Synthesis Example 1, 2,4,6,8-tetravinyl-2,4, A colorless transparent liquid having a viscosity of 80,000 mPa · s and a non-volatile content of 95.7% (similar to Synthesis Example 1 except that 275 g of 6,8-tetramethylcyclotetrasiloxane and 2,131 g of octamethylcyclotetrasiloxane were used) 2,100 g of hydroxyl group-blocked polymethylvinylsiloxane at both ends and the ratio of substituents having 2 or more carbon atoms to all substituents bonded to silicon atoms: 5 mol%) were obtained.
[0045]
[Synthesis Example 5]
Production of polymer E
Instead of 2,752, g of 2,4,6,8-tetravinyl-2,4,6,8-tetramethylcyclotetrasiloxaci of Synthesis Example 1, 2,4,6,8-tetravinyl-2,4 , 6,8-tetramethylcyclotetrasiloxane, colorless transparent liquid having a viscosity of 150,000 mPa · s and a non-volatile content of 99.2% in the same manner as in Synthesis Example 1 except for using 138 g of octamethylcyclotetrasiloxane and 2,250 g of octamethylcyclotetrasiloxane. 2,150 g of (both terminal hydroxyl-blocked polymethylvinylsiloxane, ratio of substituents having 2 or more carbon atoms to all substituents bonded to silicon atoms: 2.5 mol%) was obtained.
[0046]
[Synthesis Example 6]
Production of polymer F
Synthesis example except that 2,368 g of octamethylcyclotetrasiloxane was used instead of 2,752 g of 2,4,6,8-tetravinyl-2,4,6,8-tetramethylcyclotetrasiloxane in Synthesis Example 1 1, a colorless transparent liquid having a viscosity of 81,000 mPa · s and a non-volatile content of 96.3% (both end-terminated hydroxyl-blocked polymethylvinylsiloxane, a substituent having 2 or more carbon atoms with respect to all substituents bonded to silicon atoms) 2,100 g of a ratio: 0 mol%) was obtained.
[0047]
[Synthesis Example 7]
Production of polymer G
1,000 g of polymer A and 76 g of tetramethoxysilane were charged into a 2-neck three-necked flask equipped with a thermometer, a stirrer, and a condenser, and reacted at 120 ° C. for 24 hours. After the reaction, methanol and excess tetramethoxysilane are distilled off by heating under reduced pressure, and a colorless transparent liquid having a viscosity of 108,000 mPa · s and a non-volatile content of 96.3% (both end-terminated trimethoxy group-blocked polymethylvinylsiloxane, silicon atoms) 975 g of a ratio of substituents having 2 or more carbon atoms to all bonded substituents: 50 mol% was obtained.
[0048]
[Synthesis Example 8]
Production of polymer H
A colorless transparent liquid having a viscosity of 90,000 mPa · s and a non-volatile content of 98.2% (both end-terminated trimethoxy group-blocked polymethyl) except that the polymer F was used instead of the polymer A of Synthesis Example 7 950 g of vinyl siloxane and a ratio of substituents having 2 or more carbon atoms to all substituents bonded to silicon atoms (0 mol%) were obtained.
[0049]
[PrescriptionExample 1]
100 parts of polymer A and 5 parts of dry silica (EROSIL R972 (manufactured by Nippon Aerosil Co., Ltd.)), the surface of which was treated with dimethyldichlorosilane, were uniformly mixed, and this was mixed with 6 parts of vinyltrismethylethylketoxime silane and γ-amino. A condensation curable silicone rubber composition was prepared by mixing 0.5 parts of propyltriethoxysilane under reduced pressure until uniform.
[0050]
[PrescriptionExample 2]
PrescriptionIn Example 1, except that polymer B was used instead of polymer APrescriptionA composition was prepared in the same manner as in Example 1.
[0051]
[PrescriptionExample 3]
PrescriptionExample 1 except that polymer C was used instead of polymer APrescriptionA composition was prepared in the same manner as in Example 1.
[0052]
[PrescriptionExample 4]
PrescriptionIn Example 1, except that polymer D was used instead of polymer APrescriptionA composition was prepared in the same manner as in Example 1.
[0053]
[PrescriptionExample 5]
PrescriptionIn Example 1, except that polymer E was used instead of polymer A,PrescriptionA composition was prepared in the same manner as in Example 1.
[0054]
[PrescriptionExample 6]
100 parts of Polymer A and 50 parts of colloidal calcium carbonate are mixed uniformly, and 8 parts of vinyltrisisopropenoxysilane and 1.0 part of tetramethylguanidylpropyltrimethoxysilane are mixed under reduced pressure until uniform. Thus, a composition was prepared.
[0055]
[PrescriptionExample 7]
100 parts of polymer G and 50 parts of colloidal calcium carbonate were uniformly mixed, and 6 parts of methyltrimethoxysilane and 1.0 part of tetrabutyl titanate were mixed under reduced pressure until uniform, to prepare a composition. .
[0056]
[Comparative Example 1]
PrescriptionIn Example 1, except that polymer F was used instead of polymer A,PrescriptionA composition was prepared in the same manner as in Example 1.
[0057]
[ratioComparisonExample 2]
PrescriptionIn Example 6, except that polymer F was used instead of polymer APrescriptionA composition was prepared in the same manner as in Example 6.
[0058]
[Comparative Example 3]
PrescriptionIn Example 7, except that polymer H was used instead of polymer GPrescriptionA composition was prepared in the same manner as in Example 7.
[0059]
Next, these compositions were cured for 7 days under the conditions of 23 ° C. and 50% RH (initial stage). Furthermore, it heated for 1 hour with a 100 degreeC drying machine (heating). Further, the following organohydrogenpolysiloxane (MD) is formed on the surface of the initial cured product.H 38-M) was coated to a thickness of 200 μm and heated in a dryer at 100 ° C. for 1 hour (HDM). Furthermore, an organohydrogenpolysiloxane (MD) is formed on the surface of the initial cured product.H 38-M) A mixture of 100 g and 1 g of a platinum-divinyltetramethyldisiloxane complex / toluene solution (platinum element content 0.5 wt%) was coated to a thickness of 200 μm and heated in a dryer at 100 ° C. for 1 hour (HDM ( 1) / Pt).
[0060]
[Chemical formula 5]
The contact angle of the sheet surface produced under each of the above conditions was measured as follows. The results are shown in Table 1.
<Initial contact angle>
Water contact angle: Measured using a contact angle meter CA-X150 manufactured by Kyowa Interface Chemical Co., Ltd. (droplet amount).
<Durable contact angle>
The contact angle after 100 reciprocating rubs with absorbent cotton soaked in xylene was measured in the same manner as in the initial stage.
[0062]
[Table 1]
<Water drop falling angle>
One drop of water was dropped on the surface of the sheet, and the angle of the sheet was gradually increased from 0 ° (horizontal), and the angle at which the water droplets flowed down was read when the sheet was raised to 90 ° (vertical).
A mixture of 100 g of the organohydrogenpolysiloxane shown below and 1 g of a platinum-divinyltetramethyldisiloxane complex / toluene solution (platinum element content 0.5 wt%) as shown below was coated on the surface of the initial cured product to a thickness of 200 μm, and 100 ° C. For 1 hour (HDM (1) to (4) / Pt).
In addition, an organohydrogenpolysiloxane (MD) is formed on the surface of the initial cured product.H 38-M) A mixture of 100 g and a platinum-divinyltetramethyldisiloxane complex / toluene solution (platinum element content 0.5 wt%) 1 g was coated to a thickness of 200 μm, heated for 1 hour with a dryer at 100 ° C., and then further 200 μm thick mixture of 100 g of compound (EO) having 8 oxyethylene groups having allyl groups and OH groups at both ends and 1 g of divinyltetramethyldisiloxane complex / toluene solution (platinum element content 0.5 wt%) And heated in a dryer at 100 ° C. for 1 hour (HDM (1) / Pt / EO).
The obtained results are shown in Table 2.
[0064]
[Chemical 6]
[Table 2]
<Anti-fouling performance test results>
the aboveSet ofThe composition was applied to a coated plate previously coated with an epoxy anticorrosive paint (film thickness 200 μm) so as to have a cured film thickness of 300 μm to obtain a test coated plate. The test coated plate thus produced was cured for 7 days under the conditions of 23 ° C. and 50% RH.
About these test coating plates after hardening, after performing the hardened layer process shown in Table 3 in the same manner as described above, a suspension test was carried out for 12 months at a depth of 1.5 m off the coast of Mie Prefecture. The state of adhesion of shellfish and seaweed was observed. The results are shown in Table 3.
[0067]
[Table 3]
【The invention's effect】
According to the antifouling method of the present invention, it is non-toxic, has no environmental problems, prevents adhesion and growth of aquatic organisms over a long period of time, and exhibits excellent antifouling properties.
Claims (4)
で表されるジオルガノポリシロキサンをベースポリマーとし、加水分解性基を１分子中に２個以上有するシラン又はその部分加水分解物を配合してなる縮合硬化型シリコーンゴム組成物の硬化被膜を形成すると共に、この硬化被膜上に、（Ｂ）オルガノハイドロジェンポリシロキサンと白金族金属系触媒との混合物をこのオルガノハイドロジェンポリシロキサンが上記硬化被膜中のアルケニル基と付加反応した際に残存するような量で塗布し、上記硬化被膜中のアルケニル基とオルガノハイドロジェンポリシロキサンとを付加反応させて上記硬化被膜との間で第１の表面硬化層を形成し、更に、この第１の表面硬化層上に、（Ｃ）脂肪族不飽和炭化水素基及びオキシアルキレン基を含有する化合物を塗布し、上記第１の表面硬化層中の上記残存したオルガノハイドロジェンポリシロキサンと脂肪族不飽和炭化水素基とを付加反応させて、上記第１の表面硬化層との間で第２の表面硬化層を形成することを特徴とする基材の防汚方法。On the surface of the substrate, (A) the molecule has a hydroxyl group or hydrolyzable group bonded to at least two silicon atoms, and 2 mol% or more of all substituents bonded to the silicon atom are alkenyl groups, The following general formula (1) or (2), wherein the other group bonded to the silicon atom is a methyl group
A cured coating of a condensation curable silicone rubber composition comprising a diorganopolysiloxane represented by the formula, and a silane having two or more hydrolyzable groups in one molecule or a partial hydrolyzate thereof is formed. In addition, a mixture of (B) an organohydrogenpolysiloxane and a platinum group metal catalyst is left on the cured coating when the organohydrogenpolysiloxane undergoes an addition reaction with the alkenyl group in the cured coating. The first surface-cured layer is formed between the cured film and the alkenyl group in the cured film by addition reaction with the organohydrogenpolysiloxane. On the layer, (C) a compound containing an aliphatic unsaturated hydrocarbon group and an oxyalkylene group is applied, and the residue in the first surface hardened layer is applied. The organohydrogen with a polysiloxane and unsaturated aliphatic hydrocarbon groups by addition reaction, the first explosion of the substrate and forming a second hardfacing layer between the surface hardened layer Dirty way.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003175860A JP4178396B2 (en) | 2003-06-20 | 2003-06-20 | Antifouling method and antifouling structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003175860A JP4178396B2 (en) | 2003-06-20 | 2003-06-20 | Antifouling method and antifouling structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005007331A JP2005007331A (en) | 2005-01-13 |
| JP4178396B2 true JP4178396B2 (en) | 2008-11-12 |
Family
ID=34098890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003175860A Expired - Fee Related JP4178396B2 (en) | 2003-06-20 | 2003-06-20 | Antifouling method and antifouling structure |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4178396B2 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101246007B1 (en) * | 2008-05-29 | 2013-03-21 | 블루스타 실리콘즈 프랑스 에스에이에스 | Article having antifouling properties for aquatic and particularly sea use |
| JP4798396B2 (en) * | 2008-07-07 | 2011-10-19 | 信越化学工業株式会社 | Underwater biological adhesion prevention coating composition and underwater structure using the same |
| JP7419251B2 (en) | 2018-10-30 | 2024-01-22 | ダウ・東レ株式会社 | Curing reactive silicone compositions, cured products thereof, and their uses |
| JP7644604B2 (en) | 2018-12-27 | 2025-03-12 | ダウ・東レ株式会社 | Curable silicone composition, cured product thereof, and method for producing same |
| TWI843786B (en) | 2018-12-27 | 2024-06-01 | 日商陶氏東麗股份有限公司 | Curable silicone composition, its cured body and manufacturing process thereof |
| US12172357B2 (en) | 2018-12-27 | 2024-12-24 | Dow Toray Co., Ltd. | Method for producing curable silicone sheet having hot melt properties |
| CN113631659B (en) | 2019-03-29 | 2023-05-05 | 陶氏东丽株式会社 | Curable silicone composition, cured product thereof, and method for producing same |
| JP7599291B2 (en) | 2019-08-09 | 2024-12-13 | 中国塗料株式会社 | Underwater cable and method for protecting underwater cable |
| US12134697B2 (en) | 2019-12-27 | 2024-11-05 | Dow Toray Co., Ltd. | Curable hot-melt silicone composition, cured material thereof, and laminate containing curable hot-melt silicone composition or cured material thereof |
| EP4130157A4 (en) * | 2020-03-30 | 2024-01-17 | Dow Toray Co., Ltd. | CURABLE HOT-MELT SILICONE COMPOSITION, CURED PRODUCT BASED ON SAME, AND LAMINATE CONTAINING CURABLE HOT-MELT SILICONE COMPOSITION OR CURED PRODUCT BASED ON SAME |
-
2003
- 2003-06-20 JP JP2003175860A patent/JP4178396B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005007331A (en) | 2005-01-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3835796B2 (en) | Room temperature curable organopolysiloxane composition | |
| JP5997778B2 (en) | Novel alkoxysilyl-ethylene group-terminated silicon-containing compound, room temperature curable organopolysiloxane composition, and molded product obtained by curing the composition | |
| JP5432124B2 (en) | Antifouling coating composition based on curable polyorganosiloxane polyoxyalkylene copolymer | |
| DK2172523T3 (en) | PROCEDURE FOR THE PREPARATION OF ORGANOPOLYSILOXAN COMPOSITION VULCANIZABLE AT ROOM TEMPERATURE AND BASIC MATERIAL COATED WITH THE COMPOSITION OBTAINED IN THE PROCEDURE | |
| EP0467406B1 (en) | Film-forming organopolysiloxane composition | |
| JP4777591B2 (en) | Room temperature curable organopolysiloxane composition | |
| JP2009185169A (en) | Novel polyorganosiloxane and room temperature curable silicone composition containing it as a cross-linking agent | |
| JP2007238820A (en) | Organopolysiloxane hydrophilic composition, coating film thereof, cured product thereof, and use thereof | |
| EP3608367B1 (en) | Room-temperature-curable organopolysiloxane composition and base material | |
| EP2055750B1 (en) | Method of preparing an antifouling condensation curing organopolysiloxane composition | |
| JP2002241695A (en) | Water-repellent silicone coating agent composition | |
| CN102056996A (en) | Article having antisoiling properties and intended to be employed in aquatic uses, in particular marine uses | |
| JP2004531600A (en) | Anti-adhesion compositions containing fluorinated alkyl- or alkoxy-containing polymers or oligomers | |
| JP2011122156A (en) | Article comprising weather resistant silicone coating | |
| JP4178396B2 (en) | Antifouling method and antifouling structure | |
| JP2522854B2 (en) | Curable organopolysiloxane composition and cured product thereof | |
| EP1518905B1 (en) | Antifouling condensation curing organopolysiloxane composition and underwater structure | |
| TW202104439A (en) | Room-temperature curable organopolysiloxane composition and protective or adhesive composition for electric/electronic articles | |
| JP5186079B2 (en) | Organopolysiloxane composition, paint additive and antifouling paint composition | |
| JP3104545B2 (en) | Organopolysiloxane composition and rubber part | |
| CN114026186A (en) | Silicone elastomer coating | |
| JP4711072B2 (en) | Algae-proof condensation-curing organopolysiloxane composition, coating method thereof, and structure | |
| JP3179005B2 (en) | Room temperature foaming-curable silicone composition | |
| JP4386190B2 (en) | Antifouling condensation-curing organopolysiloxane composition and underwater structure | |
| JP3476368B2 (en) | Room temperature curable organopolysiloxane composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20050223 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20070514 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20070530 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20070726 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20080730 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20080812 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4178396 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110905 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140905 Year of fee payment: 6 |
|
| LAPS | Cancellation because of no payment of annual fees |