JP7468399B2 - Silicone coating composition and article - Google Patents
Silicone coating composition and article Download PDFInfo
- Publication number
- JP7468399B2 JP7468399B2 JP2021024731A JP2021024731A JP7468399B2 JP 7468399 B2 JP7468399 B2 JP 7468399B2 JP 2021024731 A JP2021024731 A JP 2021024731A JP 2021024731 A JP2021024731 A JP 2021024731A JP 7468399 B2 JP7468399 B2 JP 7468399B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- groups
- coating composition
- silicone coating
- substituted
- 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.)
- Active
Links
- 239000000203 mixture Substances 0.000 title claims description 62
- 239000004447 silicone coating Substances 0.000 title claims description 46
- -1 isopropenyloxy group Chemical group 0.000 claims description 49
- 150000001875 compounds Chemical class 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 22
- 238000006482 condensation reaction Methods 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 9
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 125000004423 acyloxy group Chemical group 0.000 claims description 6
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 description 28
- 238000000576 coating method Methods 0.000 description 26
- 239000007789 gas Substances 0.000 description 22
- 239000000758 substrate Substances 0.000 description 20
- 238000001723 curing Methods 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000005260 corrosion Methods 0.000 description 16
- 230000007797 corrosion Effects 0.000 description 16
- 230000035699 permeability Effects 0.000 description 11
- 239000013522 chelant Substances 0.000 description 10
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 7
- 229920001296 polysiloxane Polymers 0.000 description 7
- 125000005372 silanol group Chemical group 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 238000005452 bending Methods 0.000 description 6
- 239000007809 chemical reaction catalyst Substances 0.000 description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920002050 silicone resin Polymers 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229910052784 alkaline earth metal Chemical class 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- 239000010953 base metal Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920002379 silicone rubber Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000000068 chlorophenyl group Chemical group 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 238000005536 corrosion prevention Methods 0.000 description 3
- 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 3
- 125000001207 fluorophenyl group Chemical group 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000005062 perfluorophenyl group Chemical group FC1=C(C(=C(C(=C1F)F)F)F)* 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000004945 silicone rubber Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 3
- 125000005023 xylyl group Chemical group 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- RBSBUSKLSKHTBA-UHFFFAOYSA-N dihydroxy-methyl-phenylsilane Chemical compound C[Si](O)(O)C1=CC=CC=C1 RBSBUSKLSKHTBA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical group CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- 125000005999 2-bromoethyl group Chemical group 0.000 description 1
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 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
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- SOYBEXQHNURCGE-UHFFFAOYSA-N 3-ethoxypropan-1-amine Chemical compound CCOCCCN SOYBEXQHNURCGE-UHFFFAOYSA-N 0.000 description 1
- FAXDZWQIWUSWJH-UHFFFAOYSA-N 3-methoxypropan-1-amine Chemical compound COCCCN FAXDZWQIWUSWJH-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- TUXYZHVUPGXXQG-UHFFFAOYSA-M 4-bromobenzoate Chemical compound [O-]C(=O)C1=CC=C(Br)C=C1 TUXYZHVUPGXXQG-UHFFFAOYSA-M 0.000 description 1
- KMQLIDDEQAJAGJ-UHFFFAOYSA-N 4-oxo-4-phenylbutyric acid Chemical compound OC(=O)CCC(=O)C1=CC=CC=C1 KMQLIDDEQAJAGJ-UHFFFAOYSA-N 0.000 description 1
- LDNHMLRKFLFPIV-UHFFFAOYSA-N 4-trimethylsilyloxybutan-1-amine Chemical compound C[Si](C)(C)OCCCCN LDNHMLRKFLFPIV-UHFFFAOYSA-N 0.000 description 1
- SAIKULLUBZKPDA-UHFFFAOYSA-N Bis(2-ethylhexyl) amine Chemical compound CCCCC(CC)CNCC(CC)CCCC SAIKULLUBZKPDA-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004965 Silica aerogel Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 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
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-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
- 239000006096 absorbing agent Substances 0.000 description 1
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical group CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
- KEBBHXFLBGHGMA-UHFFFAOYSA-K aluminum;4-ethyl-3-oxohexanoate Chemical compound [Al+3].CCC(CC)C(=O)CC([O-])=O.CCC(CC)C(=O)CC([O-])=O.CCC(CC)C(=O)CC([O-])=O KEBBHXFLBGHGMA-UHFFFAOYSA-K 0.000 description 1
- YNCDEEFMDXHURQ-UHFFFAOYSA-N aluminum;ethyl 3-oxobutanoate Chemical compound [Al].CCOC(=O)CC(C)=O YNCDEEFMDXHURQ-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-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
- 239000011230 binding agent Substances 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
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 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
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 229940114081 cinnamate Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 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
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- WPCPXPTZTOMGRF-UHFFFAOYSA-K di(butanoyloxy)alumanyl butanoate Chemical compound [Al+3].CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O WPCPXPTZTOMGRF-UHFFFAOYSA-K 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XCLIHDJZGPCUBT-UHFFFAOYSA-N dimethylsilanediol Chemical compound C[Si](C)(O)O XCLIHDJZGPCUBT-UHFFFAOYSA-N 0.000 description 1
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- AVHQYNBSFNOKCT-UHFFFAOYSA-N ethyl-dihydroxy-phenylsilane Chemical compound CC[Si](O)(O)C1=CC=CC=C1 AVHQYNBSFNOKCT-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient 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
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 229940049918 linoleate Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- ZWXYOPPJTRVTST-UHFFFAOYSA-N methyl-tris(prop-1-en-2-yloxy)silane Chemical compound CC(=C)O[Si](C)(OC(C)=C)OC(C)=C ZWXYOPPJTRVTST-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- KYCGURZGBKFEQB-UHFFFAOYSA-N n',n'-dibutylpropane-1,3-diamine Chemical compound CCCCN(CCCC)CCCN KYCGURZGBKFEQB-UHFFFAOYSA-N 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- QIOYHIUHPGORLS-UHFFFAOYSA-N n,n-dimethyl-3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN(C)C QIOYHIUHPGORLS-UHFFFAOYSA-N 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- NAQQTJZRCYNBRX-UHFFFAOYSA-N n-pentan-3-ylidenehydroxylamine Chemical group CCC(CC)=NO NAQQTJZRCYNBRX-UHFFFAOYSA-N 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- CYCFYXLDTSNTGP-UHFFFAOYSA-L octadecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CYCFYXLDTSNTGP-UHFFFAOYSA-L 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
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 1
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- XGIZTLFJCDBRDD-UHFFFAOYSA-N phenyl-tris(prop-1-en-2-yloxy)silane Chemical compound CC(=C)O[Si](OC(C)=C)(OC(C)=C)C1=CC=CC=C1 XGIZTLFJCDBRDD-UHFFFAOYSA-N 0.000 description 1
- 229940049953 phenylacetate Drugs 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 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
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 239000004408 titanium dioxide Substances 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
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical compound [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- JACRWUWPXAESPB-UHFFFAOYSA-M tropate Chemical compound OCC(C([O-])=O)C1=CC=CC=C1 JACRWUWPXAESPB-UHFFFAOYSA-M 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
Description
本発明は、室温（２３℃±１５℃）において大気中の湿気（水分）で加水分解・縮合反応により架橋・硬化する湿気硬化型の室温硬化性シリコーンコーティング剤組成物等に関し、特には、電気・電子部品、構造材部品等に使用されるシリコーンコーティング剤組成物等に関する。本発明のシリコーンコーティング剤組成物は、保存安定性に優れ、各種の基材に塗工した後は室温で速やかに硬化して、透明性、可撓性（基材の屈曲に対する追従性）、密着性（基材との接着性）、低ガス透過性等に優れる硬化被膜を得ることができることから、各種基材に対する表面保護、撥水性、防錆性、耐水性、耐候性、耐薬品性、耐汚染性等の各種の機能性付与が可能なシリコーンコーティング剤組成物とすることができる。 The present invention relates to a moisture-curable room-temperature curable silicone coating composition that crosslinks and cures by hydrolysis and condensation reactions with atmospheric moisture (water) at room temperature (23°C ± 15°C), and in particular to a silicone coating composition used for electrical and electronic components, structural material components, etc. The silicone coating composition of the present invention has excellent storage stability, and after being applied to various substrates, it cures quickly at room temperature to obtain a cured coating that is excellent in transparency, flexibility (ability to follow the bending of the substrate), adhesion (adhesion to the substrate), low gas permeability, etc., and therefore can be a silicone coating composition that can impart various functionalities to various substrates, such as surface protection, water repellency, rust prevention, water resistance, weather resistance, chemical resistance, and contamination resistance.
シリコーン樹脂（オルガノポリシロキサン樹脂）は、炭化水素系の他の有機樹脂とは異なり、耐熱性、耐候性、耐水性、難燃性等に優れ、高硬度の表面を有する硬化被膜を形成し得ることから、分子内にケイ素原子に結合したアルコキシ基やシラノール基などの架橋性基を有する硬化性シリコーンゴム組成物（シリコーンエラストマー組成物）や、シリコーンレジン系樹脂（三次元網状構造を有するポリオルガノシルセルキオキサン樹脂等）が、各種基材の表面保護材、耐熱塗料、耐候性塗料、撥水剤、各種バインダー等の用途、分野に広く使用されている。中でも、シリコーン樹脂の耐熱性、電気絶縁性が良好であることから家電製品、電子部品などの電子基板のコンフォーマルコートに使用される。また、樹脂組成物の工夫により、希釈有機溶媒を必要としないコーティング組成物も可能となり、ＶＯＣ（揮発性有機化合物）問題／安全性に優れたコーティング剤が上市されている。ところが、一般的なシリコーンゴム系やシリコーンレジン系のコーティング剤組成物は、硫化水素などの腐食性ガスに対して電極金属（特に銀電極）の保護効果が低く、解決が望まれていた。 Unlike other hydrocarbon-based organic resins, silicone resins (organopolysiloxane resins) have excellent heat resistance, weather resistance, water resistance, and flame retardancy, and can form cured coatings with high surface hardness. Therefore, curable silicone rubber compositions (silicone elastomer compositions) having crosslinkable groups such as alkoxy groups and silanol groups bonded to silicon atoms in the molecule, and silicone resin-based resins (polyorganosilxelquioxane resins having a three-dimensional network structure, etc.) are widely used in applications and fields such as surface protection materials for various substrates, heat-resistant paints, weather-resistant paints, water repellents, and various binders. In particular, silicone resins are used for conformal coating of electronic substrates such as home appliances and electronic components because of their good heat resistance and electrical insulation. In addition, by devising resin compositions, it is possible to create coating compositions that do not require dilution with organic solvents, and coating agents with excellent VOC (volatile organic compound) issues and safety are on the market. However, typical silicone rubber and silicone resin coating compositions have poor protection for electrode metals (especially silver electrodes) against corrosive gases such as hydrogen sulfide, and a solution was needed.
従来、硫化水素などの腐食性ガスによる金属腐食を低減させるためには、アクリル樹脂系、ウレタン樹脂系のコーティング剤を使用せざるを得なかったが、このような有機樹脂コーティング材料は一般的には有機溶媒で希釈された状態で使用され、ＶＯＣ、安全性の問題を抱えていた。また、耐熱性、電気特性の問題からアクリル系、ウレタン系のコーティング剤には使用範囲に限界がある。
以上のようなことから、耐熱性、電気特性に加え、硫化水素等の腐食性ガスによる金属腐食を防ぐ能力に優れた無溶剤型シリコーン系コーティング剤が望まれていた。
In the past, in order to reduce metal corrosion caused by corrosive gases such as hydrogen sulfide, it was necessary to use acrylic resin-based and urethane resin-based coating agents, but such organic resin coating materials are generally used in a diluted state with an organic solvent, which poses problems with VOCs and safety.In addition, there are limitations to the range of use of acrylic and urethane coating agents due to problems with heat resistance and electrical properties.
For these reasons, there has been a demand for a solventless silicone coating agent that is excellent in heat resistance, electrical properties, and in addition, in its ability to prevent metal corrosion caused by corrosive gases such as hydrogen sulfide.
本発明は、シリコーン系コーティング剤の中でも、硬化後に硬質被膜を形成するタイプの材料であるが、このようなシリコーンコーティング剤組成物としては、従来より末端シラノール基を有する平均分子量が約３，０００～２，０００，０００の硬化性シリコーン樹脂を、トルエン、キシレン等の有機溶剤に溶解させた、いわゆるシリコーンワニス溶液が多用されてきた。このものを使用すれば、表面硬度、密着性、耐熱性、耐候性、耐水性等に優れた被膜を得ることができるが、有機溶剤を必須成分とすることや、シラノール基同士の脱水縮合架橋反応を利用するため、一般的に被膜形成には１５０℃以上で長時間の加熱硬化が必要とされる。 The present invention is a silicone-based coating material that forms a hard film after curing. Conventionally, the silicone coating composition used is a silicone varnish solution in which a curable silicone resin with an average molecular weight of about 3,000 to 2,000,000 and terminal silanol groups is dissolved in an organic solvent such as toluene or xylene. By using this, a coating excellent in surface hardness, adhesion, heat resistance, weather resistance, water resistance, etc. can be obtained. However, since the organic solvent is an essential component and the dehydration condensation crosslinking reaction between silanol groups is utilized, heat curing at 150°C or higher for a long period of time is generally required to form the coating.
これに対し、有機溶剤を含有せず、常温硬化が可能で、保存安定性に優れる一液タイプの無溶剤常温硬化型シリコーンコーティング剤組成物が求められており、オルガノアルコキシシランを部分（共）加水分解縮合した比較的低分子量のシリコーンアルコキシオリゴマーの利用が検討され、同時にこのシリコーンアルコキシオリゴマーの湿気による加水分解反応と脱アルコール縮合反応を効果的に促進して、シロキサン結合による架橋被膜を形成させる硬化触媒の研究も盛んに行われ、引用の技術が提案されている（特許文献１、２：特開昭６０－２３３１６４号公報、特許第４１１０４０２号公報）。
ただし、いずれの技術も、得られる硬化被膜は剛直で可撓性に劣るため基材の屈曲に対する追従性に劣ったものであり、また、硫化水素による金属腐食を防ぐことはできなかった。
In response to this, there is a demand for one-part, solventless, room temperature curing silicone coating agent compositions that do not contain organic solvents, can be cured at room temperature, and have excellent storage stability. The use of relatively low molecular weight silicone alkoxy oligomers obtained by partial (co)hydrolysis and condensation of organoalkoxysilanes has been examined, and at the same time, active research has been conducted into curing catalysts that effectively promote the moisture-induced hydrolysis reaction and dealcoholization condensation reaction of these silicone alkoxy oligomers to form crosslinked coatings through siloxane bonds, and the following technologies have been proposed (Patent Documents 1 and 2: JP-A-60-233164, JP-A-4110402).
However, in both techniques, the resulting cured coating is rigid and has poor flexibility, and is therefore poor at conforming to the bending of the substrate, and furthermore, it is not possible to prevent metal corrosion caused by hydrogen sulfide.
一方、無溶剤シリコーン組成物において、硫黄性腐食性ガスによる基材金属の腐食防止を目的とした技術の例として、銀や銅等の金属粉を組成物中に添加し、金属粉の犠牲的腐食により基材金属の腐食を低減する技術（特許文献３、４：特許第４１１４０３７号公報、特許第４５３０１３７号公報）や、有機添加物によって基材金属の腐食を低減する技術（特許文献５：特許第６４１８１１５号公報）が挙げられる。いずれも優れた技術であるが、シリコーン被膜中に侵入する腐食性ガス種を被膜内部の反応によって無害化する手段であり、腐食性ガスの種類によっては効果が不十分であった。 On the other hand, examples of techniques aimed at preventing corrosion of base metals by sulfurous corrosive gases in solventless silicone compositions include techniques in which metal powders such as silver or copper are added to the composition and the sacrificial corrosion of the metal powder reduces corrosion of the base metal (Patent Documents 3 and 4: Japanese Patent Nos. 4114037 and 4530137), and techniques in which organic additives reduce corrosion of the base metal (Patent Document 5: Japanese Patent No. 6418115). Both are excellent techniques, but they are means of neutralizing corrosive gas species that penetrate into the silicone coating through reactions inside the coating, and the effects are insufficient depending on the type of corrosive gas.
本発明は、上記欠点を解決するためになされたもので、有機溶剤を含有せず、硬化性有機ケイ素化合物本来の特性を損なうことなく、コーティング剤組成物としての保存安定性に優れ、基材に塗工した後は常温で速やかに硬化して、透明性、密着性等に優れ、基材の屈曲に対する追従性（可撓性）に優れた硬化被膜を与えることができ、かつ低ガス透過性であるため基材の腐食防止性、特に硫黄性ガスである硫化水素による硫化を低減することが可能であるシリコーンコーティング剤組成物を提供することを目的とするものである。 The present invention has been made to solve the above-mentioned problems, and aims to provide a silicone coating composition that does not contain organic solvents, does not impair the inherent properties of the curable organosilicon compound, has excellent storage stability as a coating composition, cures quickly at room temperature after application to a substrate, and can give a cured coating that is excellent in transparency, adhesion, etc., and has excellent conformity (flexibility) to bending of the substrate, and has low gas permeability, thereby preventing corrosion of the substrate, and in particular reducing sulfurization caused by hydrogen sulfide, a sulfurous gas.
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、下記一般式（１）で表される分子中に非置換又は置換のフェニル基を少なくとも１個有し、かつ分子中に少なくとも４個、好ましくは４～６個の加水分解性基を含有する特定分子構造のオルガノトリシロキサン化合物を主剤とし、硬化触媒を含有した縮合反応硬化性のシリコーンコーティング剤組成物を用いることによって、密閉化での優れた保存性を示し、かつ開放雰囲気下では気中水分による加水分解縮合反応により速やかに硬化し、透明性、密着性等に優れ、基材の屈曲に対する追従性（可撓性）に優れた硬化被膜を与えることができ、かつ低ガス透過性であるため硬化被膜が硫化水素による硫化を低減することが可能であることを知見し、本発明を完成させた。 As a result of intensive research conducted by the present inventors to achieve the above object, it was discovered that by using a condensation reaction curable silicone coating composition containing a curing catalyst and an organotrisiloxane compound of a specific molecular structure, represented by the following general formula (1), which has at least one unsubstituted or substituted phenyl group in the molecule and at least four, preferably four to six hydrolyzable groups in the molecule, as the main component, it is possible to give a cured coating that exhibits excellent storage stability in a sealed environment, cures quickly in an open atmosphere by a hydrolysis condensation reaction caused by moisture in the air, and has excellent transparency, adhesion, etc., and excellent conformability (flexibility) to bending of the substrate, and that has low gas permeability, making it possible to reduce sulfurization of the cured coating caused by hydrogen sulfide, and thus completed the present invention.
即ち、本発明は、下記のシリコーンコーティング剤組成物及び該組成物の硬化物で封止、コーティング、固定又は接着された物品を与えるものである。
［１］
（Ａ）下記一般式（１）で表される加水分解性基含有オルガノトリシロキサン化合物：
１００質量部、
（Ｂ）硬化触媒： ０．０１～１０質量部
を含有するシリコーンコーティング剤組成物。
［２］
上記一般式（１）において、Ｒ3が非置換、ハロゲン置換又はアルキル置換のフェニル基である［１］に記載のシリコーンコーティング剤組成物。
［３］
上記一般式（１）において、Ｘがメトキシ基、エトキシ基、イソプロペニルオキシ基又はケトオキシム基である［１］又は［２］に記載のシリコーンコーティング剤組成物。
［４］
上記一般式（１）において、Ｒ
1
が非置換、ハロゲン置換又はアルキル置換のフェニル基である［１］～［３］のいずれかに記載のシリコーンコーティング剤組成物。
［５］
（Ａ）成分１００質量部に対して、更に、（Ａ）成分以外の下記一般式（２）で示される加水分解性オルガノシラン化合物及び／又はその部分加水分解縮合物（Ｃ）を０．１～１００質量部含有する［１］～［４］のいずれかに記載のシリコーンコーティング剤組成物。
（Ｒ1）aＳｉ（Ｘ）(4-a) （２）
（式中、Ｒ1、Ｘ、ａは、それぞれ上記と同じ。）
［６］
有機溶剤を含まないものである［１］～［５］のいずれかに記載のシリコーンコーティング剤組成物。
［７］
（Ａ）成分が、下記一般式（２）
（Ｒ1）aＳｉ（Ｘ）(4-a) （２）
（式中、Ｒ1、Ｘ、ａは、それぞれ上記と同じ。）
で示される加水分解性オルガノシラン化合物と、下記一般式（３）
で示されるジオルガノシランジオールとの加水分解・縮合反応物である［１］～［６］のいずれかに記載のシリコーンコーティング剤組成物。
［８］
［１］～［７］のいずれかに記載のシリコーンコーティング剤組成物の硬化物で封止、コーティング、固定又は接着された物品。
That is, the present invention provides the following silicone coating composition and an article which is sealed, coated, fixed or adhered with the cured product of said composition.
[1]
(A) A hydrolyzable group-containing organotrisiloxane compound represented by the following general formula (1):
100 parts by weight,
(B) A silicone coating composition containing a curing catalyst: 0.01 to 10 parts by mass.
[2]
The silicone coating composition according to [1], wherein in the above general formula (1), R 3 is an unsubstituted, halogen-substituted or alkyl-substituted phenyl group.
[3]
The silicone coating composition according to [1] or [2], wherein in the above general formula (1), X is a methoxy group, an ethoxy group, an isopropenyloxy group, or a ketoxime group.
[4]
The silicone coating composition according to any one of [1] to [3], wherein in the above general formula (1), R 1 is an unsubstituted, halogen-substituted or alkyl-substituted phenyl group.
［ ５ ］
The silicone coating composition according to any one of [1] to [4] further contains, per 100 parts by mass of component (A), 0.1 to 100 parts by mass of a hydrolyzable organosilane compound other than component (A) and/or a partial hydrolysis condensate thereof (C) represented by the following general formula ( 2 ):
( R1 ) aSi (X) (4-a) (2)
(In the formula, R 1 , X, and a are the same as above.)
［ ６ ］
The silicone coating composition according to any one of [1] to [ 5 ], which does not contain an organic solvent.
［ ７ ］
The component (A) is represented by the following general formula (2):
( R1 ) aSi (X) (4-a) (2)
(In the formula, R 1 , X, and a are the same as above.)
and a hydrolyzable organosilane compound represented by the following general formula (3):
The silicone coating composition according to any one of [1] to [ 6 ], which is a hydrolysis/condensation reaction product with a diorganosilanediol represented by the following formula:
［ 8 ］
An article that is sealed, coated, fixed or adhered with a cured product of the silicone coating composition according to any one of [1] to [ 7 ].
本発明によれば、保存安定性に優れ、有機溶剤を含有しなくても基材に塗工可能であり、塗工後に常温で速やかに硬化被膜を形成し、該硬化被膜は透明性、密着性等に優れ、基材の屈曲に対する追従性（可撓性）に優れた硬化被膜を与えることができ、かつ低ガス透過性であるため基材の腐食防止性、特に硫黄性ガスである硫化水素による硫化を低減することが可能であるシリコーンコーティング剤組成物が得られる。 According to the present invention, a silicone coating composition is obtained which has excellent storage stability, can be applied to a substrate without containing an organic solvent, quickly forms a cured film at room temperature after application, and can provide a cured film with excellent transparency, adhesion, etc., and excellent conformability (flexibility) to bending of the substrate. In addition, the composition has low gas permeability, and therefore can prevent corrosion of the substrate, and in particular can reduce sulfurization caused by hydrogen sulfide, a sulfurous gas.
以下、本発明を詳細に説明する。 The present invention is described in detail below.
［（Ａ）成分］
（Ａ）成分は、本発明のシリコーンコーティング剤組成物の主剤となるものであり、下記一般式（１）で表される、分子中に非置換又は置換のフェニル基を少なくとも１個有し、かつ分子中に少なくとも４個、好ましくは４～６個の加水分解性基を含有する特定分子構造のオルガノトリシロキサン化合物である。
（Ａ）成分の加水分解性基含有オルガノトリシロキサン化合物は、後述する（Ｂ）成分の硬化触媒の存在下に、室温（２３℃±１５℃、以下同じ）において大気中の湿気（水分）で加水分解・縮合反応により速やかに架橋・硬化して、透明性、密着性等に優れ、基材の屈曲に対する追従性（可撓性）に優れると共に、ガス透過性が抑制された硬化被膜を与えることができる。
[Component (A)]
Component (A) is the main component of the silicone coating composition of the present invention, and is an organotrisiloxane compound of a specific molecular structure represented by general formula (1) below, which has at least one unsubstituted or substituted phenyl group in the molecule and at least four, and preferably four to six, hydrolyzable groups in the molecule.
The hydrolyzable group-containing organotrisiloxane compound of component (A) in the presence of a curing catalyst, component (B), described below, undergoes a hydrolysis and condensation reaction in the presence of atmospheric moisture (water) at room temperature (23°C±15°C, the same applies hereinafter) to rapidly crosslink and cure to provide a cured coating that has excellent transparency, adhesion, and the like, excellent conformability to bending of the substrate (flexibility), and which also has reduced gas permeability.
上記式（１）において、Ｒ1、Ｒ3はそれぞれ独立に、炭素数１～１０の非置換又はハロゲン置換の一価炭化水素基であり、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、シクロヘキシル基、ヘプチル基、オクチル基、２－エチルヘキシル基、ノニル基、デシル基等の、炭素数１～１０の直鎖状、分岐状又は環状のアルキル基、ビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基、イソブテニル基、ペンテニル基、ヘキセニル基、シクロヘキセニル基等の、炭素数２～１０の直鎖状、分岐状又は環状のアルケニル基、フェニル基、トリル基、キシリル基、ナフチル基等の炭素数６～１０のアリール基、メシチル基等の炭素数７～１０のアルキルアリール基、ベンジル基、フェニルエチル基等の炭素数７～１０のアラルキル基や、これらの基の水素原子の一部がハロゲン原子等で置換されたクロロメチル基、２－ブロモエチル基、３，３，３－トリフルオロプロピル基、３，３，４，４，５，５，５－ヘプタフルオロペンチル基、２，３，３－トリフルオロ－２－クロロシクロブチル基、３，４－ジブロモ－１－クロロヘキシル基、ジフルオロモノクロロビニル基、２－ヨードシクロヘキセニル基、クロロフェニル基、パークロロフェニル基、フルオロフェニル基、パーフルオロフェニル基、２，２，２－トリフルオロトリル基、２，４－ジブロモベンジル基等のハロゲン置換一価炭化水素基が挙げられる。 In the above formula (1), R 1 and R 3 are each independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, such as a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, such as a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group or decyl group; a linear, branched or cyclic alkenyl group having 2 to 10 carbon atoms, such as a vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, hexenyl group or cyclohexenyl group; an aryl group having 6 to 10 carbon atoms, such as a phenyl group, tolyl group, xylyl group or naphthyl group; and alkylaryl groups having 7 to 10 carbon atoms, such as a mesityl group; aralkyl groups having 7 to 10 carbon atoms, such as a benzyl group and a phenylethyl group; and halogen-substituted monovalent hydrocarbon groups in which some of the hydrogen atoms of these groups have been substituted with halogen atoms, such as a chloromethyl group, a 2-bromoethyl group, a 3,3,3-trifluoropropyl group, a 3,3,4,4,5,5,5-heptafluoropentyl group, a 2,3,3-trifluoro-2-chlorocyclobutyl group, a 3,4-dibromo-1-chlorohexyl group, a difluoromonochlorovinyl group, a 2-iodocyclohexenyl group, a chlorophenyl group, a perchlorophenyl group, a fluorophenyl group, a perfluorophenyl group, a 2,2,2-trifluorotolyl group, and a 2,4-dibromobenzyl group.
これらのうち、Ｒ1としては、メチル基、エチル基、プロピル基、ビニル基、フェニル基が好ましく、また、後述するＲ2の項でも説明するように、得られる硬化被膜の低ガス透過性が重要となる場合には非置換、ハロゲン置換又はアルキル置換のフェニル基であることが好ましいが、本発明の組成物の加水分解・縮合反応による硬化速度の設計上の理由で、その他の各種の一価有機基を選択することができる。 Of these, R1 is preferably a methyl group, an ethyl group, a propyl group, a vinyl group or a phenyl group, and, as will be explained in the section on R2 below, when low gas permeability of the resulting cured coating is important, an unsubstituted, halogen-substituted or alkyl-substituted phenyl group is preferred. However, various other monovalent organic groups can be selected for reasons of designing the curing speed due to the hydrolysis and condensation reactions of the composition of the present invention.
Ｒ3としては、得られる硬化被膜のガス透過性低減の観点から、フェニル基、トリル基、キシリル基、クロロフェニル基、パークロロフェニル基、フルオロフェニル基、パーフルオロフェニル基、２，２，２－トリフルオロトリル基等の非置換、ハロゲン置換又はアルキル置換のフェニル基であることが好ましい。
また、Ｒ3としては、上記した非置換、ハロゲン置換又はアルキル置換のフェニル基以外の一価炭化水素基とすることによって、硬化被膜のＴｇをコントロールすることができ、目的の低ガス透過性とＴｇに合わせてＲ3を種々設計することができる。これらの中でも、得られる硬化被膜の離型性、撥水性が良好なことから、アルキル基、アリル基、フルオロアルキル基が好ましい。
From the viewpoint of reducing the gas permeability of the resulting cured coating, R3 is preferably an unsubstituted, halogen-substituted or alkyl-substituted phenyl group, such as a phenyl group, a tolyl group, a xylyl group, a chlorophenyl group, a perchlorophenyl group, a fluorophenyl group, a perfluorophenyl group or a 2,2,2-trifluorotolyl group.
Furthermore, by using a monovalent hydrocarbon group other than the above-mentioned unsubstituted, halogen-substituted or alkyl-substituted phenyl group as R3 , the Tg of the cured coating can be controlled, and R3 can be variously designed according to the desired low gas permeability and Tg. Among these, alkyl groups, allyl groups and fluoroalkyl groups are preferred because the resulting cured coating has good releasability and water repellency.
上記式（１）において、Ｒ2は、非置換、ハロゲン置換又はアルキル置換のフェニル基であり、（Ａ）成分の式（１）で示されるオルガノトリシロキサン化合物は１分子中に少なくとも１個の非置換、ハロゲン置換又はアルキル置換のフェニル基（例えば、上記で例示したフェニル基、トリル基、キシリル基、クロロフェニル基、パークロロフェニル基、フルオロフェニル基、パーフルオロフェニル基、２，２，２－トリフルオロトリル基等）を有する必要がある。低ガス透過性を重視する場合、好ましくは分子中に２個（即ち、Ｒ2とＲ3の両方）の非置換、ハロゲン置換又はアルキル置換のフェニル基を有することが望ましい。 In the above formula (1), R2 is an unsubstituted, halogen-substituted or alkyl-substituted phenyl group, and the organotrisiloxane compound of component (A) represented by formula (1) must have at least one unsubstituted, halogen-substituted or alkyl-substituted phenyl group per molecule (for example, the phenyl, tolyl, xylyl, chlorophenyl, perchlorophenyl, fluorophenyl, perfluorophenyl, 2,2,2-trifluorotolyl groups exemplified above). When low gas permeability is important, it is preferable to have two unsubstituted, halogen-substituted or alkyl-substituted phenyl groups per molecule (i.e., both R2 and R3 ).
この非置換又は置換のフェニル基によって硬化被膜のガス透過性が低減されるものであり、分子中に非置換又は置換のフェニル基を有さないオルガノトリシロキサン化合物では、硬化被膜はガス透過性が高くなり、基材金属の腐食性ガスによる腐食を低減できなくなる。 These unsubstituted or substituted phenyl groups reduce the gas permeability of the cured coating. With organotrisiloxane compounds that do not have unsubstituted or substituted phenyl groups in the molecule, the cured coating has high gas permeability and is unable to reduce corrosion of the base metal due to corrosive gases.
上記式（１）において、Ｘはそれぞれ独立に非置換又はアルコキシ置換のアルコキシ基、アリールオキシ基、アルケニルオキシ基、アシルオキシ基及びケトオキシム基から選ばれる少なくとも１種の加水分解性基である。Ｘとして、具体的には、好ましくは炭素数１～７の、非置換又はアルコキシ置換のアルコキシ基、アリールオキシ基、アルケニルオキシ基、アシルオキシ基及びケトオキシム基から選ばれる少なくとも１種の加水分解性基が挙げられ、例えば、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、イソブトキシ基、ｓｅｃ－ブトキシ基、ｔｅｒｔ－ブトキシ基等の炭素数１～６、好ましくは炭素数１～４のアルコキシ基、メトキシ置換メトキシ基、メトキシ置換エトキシ基、エトキシ置換メトキシ基、エトキシ置換エトキシ基等の炭素数２～４のアルコキシ置換のアルコキシ基、ビニルオキシ基、アリルオキシ基、プロペニルオキシ基、イソプロペニルオキシ基、ブテニルオキシ基等の炭素数２～４のアルケニルオキシ基、フェニルオキシ基等の炭素数６～１０のアリールオキシ基、アセトキシ基、プロピオノキシ基等の炭素数２～４のアシルオキシ基、ジメチルケトオキシム基、メチルエチルケトオキシム基、ジエチルケトオキシム基等の炭素数３～６のケトオキシム基等が挙げられる。好ましくはメトキシ基、エトキシ基、イソプロペニルオキシ基、メチルエチルケトオキシム基等である。 In the above formula (1), X is independently at least one hydrolyzable group selected from unsubstituted or alkoxy-substituted alkoxy groups, aryloxy groups, alkenyloxy groups, acyloxy groups, and ketoxime groups. Specific examples of X include at least one hydrolyzable group selected from unsubstituted or alkoxy-substituted alkoxy groups, aryloxy groups, alkenyloxy groups, acyloxy groups, and ketoxime groups, preferably having 1 to 7 carbon atoms, such as methoxy groups, ethoxy groups, propoxy groups, isopropoxy groups, butoxy groups, isobutoxy groups, sec-butoxy groups, tert-butoxy groups, and other alkoxy groups having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, methoxy-substituted methoxy groups, methoxy-substituted ethoxy groups, ethoxy groups, etc. Examples of the alkoxy groups include alkoxy-substituted alkoxy groups having 2 to 4 carbon atoms, such as substituted methoxy groups and ethoxy-substituted ethoxy groups; alkenyloxy groups having 2 to 4 carbon atoms, such as vinyloxy groups, allyloxy groups, propenyloxy groups, isopropenyloxy groups, and butenyloxy groups; aryloxy groups having 6 to 10 carbon atoms, such as phenyloxy groups; acyloxy groups having 2 to 4 carbon atoms, such as acetoxy groups and propionoxy groups; and ketoxime groups having 3 to 6 carbon atoms, such as dimethylketoxime groups, methylethylketoxime groups, and diethylketoxime groups. Preferred are methoxy groups, ethoxy groups, isopropenyloxy groups, and methylethylketoxime groups.
ａは結合するケイ素原子毎に独立に０又は１であり、好ましくは１である。
（Ａ）成分の加水分解性基含有オルガノトリシロキサン化合物は、上記式（１）において、加水分解性基Ｘを１分子中に少なくとも４個、好ましくは４～６個、より好ましくは４個有するものであり、所望の硬化速度、保存性特性を達成するために適した脱離基を選択することができる。
a is independently 0 or 1 for each silicon atom to which it is bonded, and is preferably 1.
The hydrolyzable group-containing organotrisiloxane compound of component (A) has at least four, preferably 4 to 6, and more preferably 4 hydrolyzable groups X per molecule in the above formula (1), and a leaving group appropriate for achieving the desired curing rate and storage properties can be selected.
式（１）で表される加水分解性基含有オルガノトリシロキサン化合物として、具体的には、下記に示す化合物が例示できる。
なお、（Ａ）成分の上記一般式（１）で示される加水分解性基含有オルガノトリシロキサン化合物は、下記一般式（２）で示されるケイ素原子に結合した１価炭化水素基として上記したＲ1と加水分解性基Ｘとを有する加水分解性オルガノシラン化合物と、下記一般式（３）で示されるケイ素原子に結合した１価炭化水素基として上記したＲ2とＲ3とを１個ずつ有する分子中に非置換、ハロゲン置換又はアルキル置換のフェニル基を少なくとも１個、好ましくは２個有するジオルガノシランジオール（ジオルガノジヒドロキシシラン）とを縮合反応触媒の存在下に従来公知の条件で加水分解・縮合反応させることによって、容易に製造することができる。
（Ｒ1）aＳｉ（Ｘ）(4-a) （２）
( R1 ) aSi (X) (4-a) (2)
上記式（２）で示される加水分解性オルガノシラン化合物として、具体的には、ビニルトリメトキシシラン、フェニルトリメトキシシラン、メチルトリメトキシシラン、ビニルトリエトキシシラン、フェニルトリエトキシシラン、メチルトリエトキシシラン、ビニルトリイソプロペノキシシラン、フェニルトリイソプロペノキシシラン、メチルトリイソプロペノキシシラン等が例示できる。 Specific examples of hydrolyzable organosilane compounds represented by the above formula (2) include vinyltrimethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, vinyltriisopropenoxysilane, phenyltriisopropenoxysilane, and methyltriisopropenoxysilane.
上記式（３）で示されるジオルガノシランジオールとして、具体的には、ジフェニルシランジオール、メチルフェニルシランジオール、エチルフェニルシランジオール等が例示できる。 Specific examples of diorganosilanediols represented by the above formula (3) include diphenylsilanediol, methylphenylsilanediol, and ethylphenylsilanediol.
式（２）で示される加水分解性オルガノシラン化合物と式（３）で示されるジオルガノシランジオールの反応割合は、式（３）で示されるジオルガノシランジオール中のシラノール基１モルに対して式（２）で示される加水分解性オルガノシラン化合物が１モル以上であることが好ましいが、反応生成物中の残存シラノール基を低減させるために該シラノール基１モルに対して該加水分解性オルガノシラン化合物が２モル以上であることがより好ましい。式（２）で示される加水分解性オルガノシラン化合物の反応モル比の上限は５モル程度以下でよい。反応生成物中に残存シラノール基が多い場合には、その後の組成物の硬化反応速度を低下させることがある。 The reaction ratio of the hydrolyzable organosilane compound represented by formula (2) and the diorganosilanediol represented by formula (3) is preferably 1 mole or more of the hydrolyzable organosilane compound represented by formula (2) per mole of silanol groups in the diorganosilanediol represented by formula (3), but more preferably 2 moles or more of the hydrolyzable organosilane compound per mole of the silanol groups in order to reduce the remaining silanol groups in the reaction product. The upper limit of the reaction molar ratio of the hydrolyzable organosilane compound represented by formula (2) may be about 5 moles or less. If there are many remaining silanol groups in the reaction product, the curing reaction speed of the subsequent composition may be reduced.
上記反応に用いる縮合反応触媒としては、チタンキレート化合物、テトラメチルグアニジルプロピルトリメトキシシラン等のグアニジル基含有シラン化合物、アルミニウムキレート化合物、有機ジルコニウム化合物等が例示できる。
縮合反応触媒の添加量は、上記式（３）で示されるジオルガノシランジオールと上記式（２）で示される加水分解性オルガノシラン化合物が室温下～加熱下での縮合反応が進行するのに十分な量であればよく、通常、上記ジオルガノシランジオールと加水分解性オルガノシラン化合物との合計１００質量部に対して０．０１～１０質量部、特には０．１～５質量部程度が好ましい。
Examples of the condensation reaction catalyst used in the above reaction include titanium chelate compounds, guanidyl group-containing silane compounds such as tetramethylguanidylpropyltrimethoxysilane, aluminum chelate compounds, and organic zirconium compounds.
The amount of the condensation reaction catalyst added may be an amount sufficient for the condensation reaction of the diorganosilanediol represented by formula (3) above and the hydrolyzable organosilane compound represented by formula (2) above to proceed at room temperature to under heating, and is usually preferably about 0.01 to 10 parts by mass, and particularly preferably about 0.1 to 5 parts by mass, per 100 parts by mass of the total of the diorganosilanediol and the hydrolyzable organosilane compound.
反応条件としては、０～１５０℃、特には２５～１００℃程度の温度で、５～１２０分、特には１０～６０分程度の条件で、好ましくは、縮合反応により副生するアルコール等を除去しながら反応させることで反応生成物（（Ａ）成分）を得ることができる。 The reaction conditions are a temperature of 0 to 150°C, particularly 25 to 100°C, and a time of 5 to 120 minutes, particularly 10 to 60 minutes, preferably while removing by-products such as alcohol produced by the condensation reaction, to obtain a reaction product (component (A)).
本発明のシリコーンコーティング剤組成物において、（Ａ）成分の加水分解性基含有オルガノトリシロキサン化合物は、１種単独で又は２種以上を併用して使用できる。 In the silicone coating composition of the present invention, the hydrolyzable group-containing organotrisiloxane compound of component (A) can be used alone or in combination of two or more.
［（Ｂ）成分］
（Ｂ）成分の硬化触媒は、上記一般式（１）で示される（Ａ）成分の加水分解性基含有オルガノトリシロキサン化合物が硬化工程中において、大気中の湿気（水分）と加水分解・縮合反応して本発明の組成物が速やかに硬化被膜にいたるのに必要な縮合反応触媒であり、有機錫化合物、有機アルミニウム化合物、有機チタン化合物、有機ジルコニウム化合物、有機塩基化合物から選択されるものであり、（Ａ）成分の上記一般式（１）において選択された加水分解性基Ｘの反応性に合わせて、適した触媒が選択される。
[Component (B)]
The curing catalyst of component (B) is a condensation reaction catalyst necessary for the composition of the present invention to rapidly form a cured coating by hydrolysis and condensation reaction of the hydrolyzable group-containing organotrisiloxane compound of component (A) represented by general formula (1) above with moisture (water) in the atmosphere during the curing step, and is selected from organotin compounds, organoaluminum compounds, organotitanium compounds, organozirconium compounds, and organic base compounds, with an appropriate catalyst being selected according to the reactivity of the hydrolyzable group X selected in the general formula (1) of component (A) above.
このような縮合反応触媒としては、アルカリ金属又はアルカリ土類金属の水酸化物、酸化物、あるいは塩基性金属塩類が例示され、具体的には、水酸化カルシウム、水酸化マグネシウムなどのアルカリ土類金属の水酸化物、塩化カルシウム、塩化マグネシウムなどのアルカリ土類金属の塩化物、酸化カルシウム、酸化マグネシウムなどのアルカリ土類金属の酸化物、塩基性炭酸亜鉛、塩基性炭酸マグネシウムなどの塩基性金属塩を例示することができる。 Examples of such condensation reaction catalysts include hydroxides, oxides, or basic metal salts of alkali metals or alkaline earth metals. Specific examples include hydroxides of alkaline earth metals such as calcium hydroxide and magnesium hydroxide, chlorides of alkaline earth metals such as calcium chloride and magnesium chloride, oxides of alkaline earth metals such as calcium oxide and magnesium oxide, and basic metal salts such as basic zinc carbonate and basic magnesium carbonate.
また、その他の縮合反応触媒として、アルミニウムキレート化合物、有機チタン化合物、有機錫化合物、アミノアルキルアルコキシシラン、アンモニウム塩なども使用できる。アルミニウムキレート化合物としては、アルミニウムエチルアセトアセテートジイソプロピレート、アルミニウムトリス（エチルアセテート）、アルミニウムトリス（エチルアセトネート）、アルミニウムビスエチルアセトアセテートモノアセチルアセトネートなどが例示される。有機チタン化合物としては、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）チタンなどが例示される。有機錫化合物としては、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、オクトエ酸第一錫、ナフテン酸第一錫、オレイン酸第一錫、イソ酪酸第一錫、リノール酸第一錫、ステアリン酸第一錫、ベンゾール酸第一錫、ナフトエ酸第一錫、ラウリン酸第一錫、ｏ－チム酸第一錫、β－ベンゾイルプロピオン酸第一錫、クロトン酸第一錫、トロパ酸第一錫、ｐ－ブロモ安息香酸第一錫、パルミトオレイン酸第一錫、桂皮酸第一錫、及びフェニル酢酸第一錫のようなカルボン酸の錫塩などが例示される。アミノアルキルアルコキシシランとしては、γ－アミノプロピルトリメチルメトキシシラン、γ－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、γ－アミノプロピルメチルジメトキシシラン、Ｎ－（β－アミノエチル）－γ－アミノプロピルメチルジメトキシシラン、γ－（ジメチルアミノ）プロピルトリメトキシシランなどが例示される。アンモニウム塩としては、酸とアミンの塩が例示され、酸としては酢酸、ギ酸などが、またアミンとしてはアリルアミン、２－エチルヘキシルアミン、３－エトキシプロピルアミン、ジイソブチルアミン、３－ジエチルアミノプロピルアミン、ジ－２－エチルヘキシルアミン、ジブチルアミノプロピルアミン、トリ－ｎ－オクチルアミン、ｔｅｒｔ－ブチルアミン、ｓｅｃ－ブチルアミン、プロピルアミン、３－メトキシプロピルアミンなどが例示される。 Other condensation reaction catalysts that can be used include aluminum chelate compounds, organic titanium compounds, organic tin compounds, aminoalkylalkoxysilanes, and ammonium salts. Examples of aluminum chelate compounds include aluminum ethylacetoacetate diisopropylate, aluminum tris(ethyl acetate), aluminum tris(ethyl acetonate), and aluminum bisethylacetoacetate monoacetylacetonate. Examples of organic titanium compounds include tetraisopropoxytitanium, tetra-n-butoxytitanium, and tetrakis(2-ethylhexoxy)titanium. Examples of organotin compounds include tin salts of carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, stannous octoate, stannous naphthenate, stannous oleate, stannous isobutyrate, stannous linoleate, stannous stearate, stannous benzoate, stannous naphthoate, stannous laurate, o-stannous thymate, stannous β-benzoylpropionate, stannous crotonate, stannous tropate, stannous p-bromobenzoate, stannous palmitoleate, stannous cinnamate, and stannous phenylacetate. Examples of aminoalkylalkoxysilanes include γ-aminopropyltrimethylmethoxysilane, γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, and γ-(dimethylamino)propyltrimethoxysilane. Examples of ammonium salts include salts of acids and amines, and examples of acids include acetic acid and formic acid, and examples of amines include allylamine, 2-ethylhexylamine, 3-ethoxypropylamine, diisobutylamine, 3-diethylaminopropylamine, di-2-ethylhexylamine, dibutylaminopropylamine, tri-n-octylamine, tert-butylamine, sec-butylamine, propylamine, and 3-methoxypropylamine.
（Ｂ）成分の硬化触媒の配合量は、反応が良好に進行し、また得られるシリコーンコーティング剤組成物の硬化性が良好なものとなることから、（Ａ）成分の加水分解性基含有オルガノトリシロキサン化合物１００質量部に対して、０．０１～１０質量部であり、特に０．０２～５質量部が好ましい。 The amount of the curing catalyst (B) to be blended is 0.01 to 10 parts by weight, and preferably 0.02 to 5 parts by weight, per 100 parts by weight of the hydrolyzable group-containing organotrisiloxane compound (A), in order to ensure that the reaction proceeds smoothly and that the resulting silicone coating composition has good curing properties.
［（Ｃ）成分］
本発明のシリコーンコーティング剤組成物は、上記（Ａ）成分、（Ｂ）成分の他に、上記（Ａ）成分の製造に用いたのと同様の、上記式（２）で示される加水分解性オルガノシラン化合物（Ｃ）を更に含有するものであってもよい。該（Ｃ）成分を配合すると、組成物の保存性を向上させることができ、また組成物の硬化時間（可使時間）を制御できるという効果が得られる。
なお、上記式（２）で示される加水分解性オルガノシラン化合物と上記式（３）で示されるジオルガノシランジオールを反応させて（Ａ）成分を得る際に、式（２）で示される加水分解性オルガノシラン化合物を過剰量にて反応させ、反応後の余剰の式（２）で示される加水分解性オルガノシラン化合物をそのまま用いてもよい。
[Component (C)]
The silicone coating composition of the present invention may further contain, in addition to the above components (A) and (B), a hydrolyzable organosilane compound (C) represented by the above formula (2) which is the same as that used in the production of the above component (A). By adding the component (C), the shelf life of the composition can be improved, and the curing time (pot life) of the composition can be controlled.
When the hydrolyzable organosilane compound represented by the above formula (2) is reacted with the diorganosilanediol represented by the above formula (3) to obtain component (A), the hydrolyzable organosilane compound represented by formula (2) may be reacted in an excess amount, and the excess hydrolyzable organosilane compound represented by formula (2) remaining after the reaction may be used as is.
この上記式（２）で示される加水分解性オルガノシラン化合物の含有量は、（Ａ）成分１００質量部に対して１００質量部以下（０～１００質量部）であればよく、好ましくは０．１～５０質量部程度であればよい。 The content of the hydrolyzable organosilane compound represented by the above formula (2) may be 100 parts by mass or less (0 to 100 parts by mass) per 100 parts by mass of component (A), and is preferably about 0.1 to 50 parts by mass.
［その他の成分］
本発明のシリコーンコーティング剤組成物には、更に必要に応じて、少量の各種添加剤、例えば可塑剤、剥離剤、難燃剤、酸化防止剤、紫外線吸収剤や二酸化チタン、カーボンブラック又は酸化鉄などの顔料や染料を本発明の目的を損なわない範囲で配合してもよい。また同様に煙霧質シリカ、シリカエアロゲル、シリカゲル、及びこれらを有機シラン類、有機シロキサン類あるいは有機シラザン類で処理した補強性シリカ充填剤、更にアスベスト、粉砕溶融石英、酸化アルミニウム、珪酸アルミニウム、珪酸ジルコニウム、酸化マグネシウム、酸化亜鉛、タルク、珪藻土、雲母、炭酸カルシウム、クレー、ジルコニア、ガラス、砂、黒鉛、硫酸バリウム、硫酸亜鉛、アルミニウム粉末、おがくず、コルク、フルオロカーボンの重合体粉末、シリコーンゴム粉末、シリコーン樹脂粉末などの充填剤を本発明の目的を損なわない範囲で配合してもよい。
[Other ingredients]
The silicone coating composition of the present invention may further contain small amounts of various additives, such as plasticizers, release agents, flame retardants, antioxidants, ultraviolet absorbers, and pigments and dyes such as titanium dioxide, carbon black, or iron oxide, as long as the objects of the present invention are not impaired.Furthermore, fumed silica, silica aerogel, silica gel, and reinforcing silica fillers obtained by treating these with organic silanes, organic siloxanes, or organic silazanes, as well as asbestos, crushed fused quartz, aluminum oxide, aluminum silicate, zirconium silicate, magnesium oxide, zinc oxide, talc, diatomaceous earth, mica, calcium carbonate, clay, zirconia, glass, sand, graphite, barium sulfate, zinc sulfate, aluminum powder, sawdust, cork, fluorocarbon polymer powder, silicone rubber powder, silicone resin powder, and other fillers may also be contained within the scope of the present invention.
更に必要に応じて有機溶剤を配合することも構わないが、ＶＯＣ、安全上への配慮から、組成物が工程上使用可能な粘度であるかぎり、有機溶剤は含まないか、少ない方が好ましい。 Organic solvents may also be added if necessary, but in consideration of VOCs and safety, it is preferable for the composition to contain no or little organic solvents as long as the composition has a viscosity that can be used in the process.
本発明のシリコーンコーティング剤組成物を製造するにあたっては、前記した（Ａ）、（Ｂ）成分の所定量を単純に混合すればよく、この場合、混合時の温度は限定されないが、特に加熱等の操作を行う必要はなく、室温下で１０分間以上、好ましくは１０～６０分間の撹拌混合を行うのみで容易に得ることができる。なお、この混合の際には、水分の混入によってアルコキシ基等の加水分解性基が加水分解してしまうのを防ぐ目的で、窒素雰囲気下にて行うことが好ましい。 In producing the silicone coating composition of the present invention, the above-mentioned (A) and (B) components are simply mixed in the prescribed amounts. In this case, the temperature during mixing is not limited, but there is no need to perform any particular operation such as heating. The composition can be easily obtained by simply stirring and mixing at room temperature for 10 minutes or more, preferably 10 to 60 minutes. It is preferable to carry out this mixing in a nitrogen atmosphere in order to prevent hydrolyzable groups such as alkoxy groups from being hydrolyzed due to the inclusion of moisture.
このようにして、本発明のシリコーンコーティング剤組成物は、該組成物の硬化物で封止、コーティング、固定又は接着した物品を提供することができる。
本発明のシリコーンコーティング剤組成物は、各種の金属基材、木材、石材、モルタル板、スレート板、瓦、コンクリート、ガラス、セラミックス類、プラスチック製品、有機樹脂塗膜製品等に対し、従来公知の方法によって塗布硬化させてコーティング被膜とすることができる。この場合、塗布方法としては、具体的には刷毛塗り、スプレー塗布、浸漬、フローコーター、ナイフコーター、スピンコーター等の方法を挙げることができ、更に現場塗装を行うことも可能である。また、塗布量としては、基材の種類や塗工を行う目的によって異なるが、一般的には硬化後の被膜厚さが０．１～２００μｍの範囲となるようにすればよく、好ましくは１～１００μｍの範囲である。
In this manner, the silicone coating composition of the present invention can provide articles that are sealed, coated, fixed or adhered with the cured product of the composition.
The silicone coating composition of the present invention can be applied to various metal substrates, wood, stone, mortar boards, slate boards, roof tiles, concrete, glass, ceramics, plastic products, organic resin coated products, etc., by a conventionally known method, and cured to form a coating film. In this case, specific examples of the application method include brush application, spray application, immersion, flow coater, knife coater, spin coater, etc., and on-site painting is also possible. The amount of application varies depending on the type of substrate and the purpose of coating, but generally, it is sufficient to apply the coating film so that the thickness after curing is in the range of 0.1 to 200 μm, and preferably in the range of 1 to 100 μm.
本発明のシリコーンコーティング剤組成物の硬化条件としては、特に限定されないが、空気中の湿分によって硬化して被膜を形成するものであるため、室温～８０℃の温度範囲で１分間～２時間程度放置することにより乾燥し（タックフリー状態）、更に数時間～数日間の放置によって硬化反応を完結させることができる。 The curing conditions for the silicone coating composition of the present invention are not particularly limited, but since it cures and forms a coating due to moisture in the air, it will dry (tack-free state) when left at room temperature to 80°C for about 1 minute to 2 hours, and the curing reaction can be completed by leaving it for a few hours to several days.
このようにして、本発明のシリコーンコーティング剤組成物は、該組成物の硬化物で封止、コーティング、固定又は接着した物品を提供することができる。 In this way, the silicone coating composition of the present invention can provide articles that are sealed, coated, fixed or adhered with the cured product of the composition.
以下、調製例、及び実施例、参考例と比較例を示し、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、各例において、室温は２５℃を示し、粘度は２５℃における回転粘度計による測定値を示す。
The present invention will be specifically described below with reference to Preparation Examples, Examples , Reference Examples and Comparative Examples, but the present invention is not limited to the following Examples. In each Example, the room temperature is 25° C., and the viscosity is measured by a rotational viscometer at 25° C.
［調製例］
（Ａ）成分
（Ａ－１）
１００ｍｌフラスコに、ジフェニルシランジオール（１６．２ｇ）、ビニルトリメトキシシラン（２５ｇ）、チタンキレート触媒（０．２ｇ、マツモトファインケミカル（株）製、オルガチックスＴＣ－４０１）を添加し、１００℃下で６０分間反応させた後、発生するメタノールと余剰ビニルトリメトキシシランを窒素ガスフローにて除去することで、下記式で示されるオルガノトリシロキサン化合物（Ａ－１）を得た。
Component (A)
(A-1)
Diphenylsilanediol (16.2 g), vinyltrimethoxysilane (25 g), and a titanium chelate catalyst (0.2 g, Orgatix TC-401, manufactured by Matsumoto Fine Chemical Co., Ltd.) were added to a 100 ml flask and reacted for 60 minutes at 100° C. After that, the generated methanol and excess vinyltrimethoxysilane were removed with a nitrogen gas flow, yielding organotrisiloxane compound (A-1) represented by the following formula.
（Ａ－２）
１００ｍｌフラスコに、ジフェニルシランジオール（１６．２ｇ）、フェニルトリメトキシシラン（２５ｇ）、チタンキレート触媒（０．２ｇ、マツモトファインケミカル（株）製、オルガチックスＴＣ－４０１）を添加し、１００℃下で６０分間反応させた後、発生するメタノールを窒素ガスフローにて除去、その後、余剰フェニルトリメトキシシランを減圧下加熱で除去することで、下記式で示されるオルガノトリシロキサン化合物（Ａ－２）を得た。
Diphenylsilanediol (16.2 g), phenyltrimethoxysilane (25 g), and a titanium chelate catalyst (0.2 g, Orgatix TC-401, manufactured by Matsumoto Fine Chemical Co., Ltd.) were added to a 100 ml flask and reacted for 60 minutes at 100° C. After that, the generated methanol was removed with a nitrogen gas flow, and then the excess phenyltrimethoxysilane was removed by heating under reduced pressure to obtain organotrisiloxane compound (A-2) represented by the following formula.
（Ａ－３）
１００ｍｌフラスコに、ジフェニルシランジオール（１６．２ｇ）、メチルトリメトキシシラン（２５ｇ）、チタンキレート触媒（０．２ｇ、マツモトファインケミカル（株）製、オルガチックスＴＣ－４０１）を添加し、１００℃下で６０分間反応させた後、発生するメタノールと余剰メチルトリメトキシシランを窒素ガスフローにて除去することで、下記式で示されるオルガノトリシロキサン化合物（Ａ－３）を得た。
Diphenylsilanediol (16.2 g), methyltrimethoxysilane (25 g), and a titanium chelate catalyst (0.2 g, Orgatix TC-401, manufactured by Matsumoto Fine Chemical Co., Ltd.) were added to a 100 ml flask and reacted for 60 minutes at 100° C. After that, the generated methanol and excess methyltrimethoxysilane were removed with a nitrogen gas flow, yielding organotrisiloxane compound (A-3) represented by the following formula.
（Ａ－４）
１００ｍｌフラスコに、ジフェニルシランジオール（１６．２ｇ）、ビニルトリイソプロペノキシシラン（２５ｇ）、テトラメチルグアニジルプロピルトリメトキシシラン（０．２ｇ）を添加し、１００℃下で６０分間反応させた後、発生するアセトンを窒素ガスフローにて除去、その後、余剰ビニルトリイソプロペノキシシランを減圧下加熱で除去することで、下記式で示されるオルガノトリシロキサン化合物（Ａ－４）を得た。
Diphenylsilanediol (16.2 g), vinyltriisopropenoxysilane (25 g), and tetramethylguanidylpropyltrimethoxysilane (0.2 g) were added to a 100 ml flask and reacted for 60 minutes at 100° C. After that, the acetone that was generated was removed with a nitrogen gas flow, and then the excess vinyltriisopropenoxysilane was removed by heating under reduced pressure, yielding organotrisiloxane compound (A-4) represented by the following formula.
（Ａ－５）
１００ｍｌフラスコに、メチルフェニルシランジオール（１６．２ｇ、一部は二量化している）、ビニルトリメトキシシラン（２５ｇ）、チタンキレート触媒（０．２ｇ、マツモトファインケミカル（株）製、オルガチックスＴＣ－４０１）を添加し、１００℃下で６０分間反応させた後、発生するメタノールと余剰ビニルトリメトキシシランを窒素ガスフローにて除去することで、下記式で示されるオルガノトリシロキサン化合物（Ａ－５）を得た。
Methylphenylsilanediol (16.2 g, partially dimerized), vinyltrimethoxysilane (25 g), and a titanium chelate catalyst (0.2 g, Orgatix TC-401, manufactured by Matsumoto Fine Chemical Co., Ltd.) were added to a 100 ml flask and reacted for 60 minutes at 100° C. After that, the generated methanol and excess vinyltrimethoxysilane were removed with a nitrogen gas flow, yielding organotrisiloxane compound (A-5) represented by the following formula.
（Ａ）成分（比較用）
（ａ－１）
１００ｍｌフラスコに、ジメチルシランジオール（１２．３ｇ、一部は二量化している）、メチルトリメトキシシラン（２０ｇ）、チタンキレート触媒（０．２ｇ、マツモトファインケミカル（株）製、オルガチックスＴＣ－４０１）を添加し、１００℃下で６０分間反応させた後、発生するメタノールと余剰メチルトリメトキシシランを窒素ガスフローにて除去することで、下記式で示されるオルガノトリシロキサン化合物（ａ－１）を得た。
(a-1)
Dimethylsilanediol (12.3 g, partially dimerized), methyltrimethoxysilane (20 g), and a titanium chelate catalyst (0.2 g, Orgatix TC-401, manufactured by Matsumoto Fine Chemical Co., Ltd.) were added to a 100 ml flask and reacted for 60 minutes at 100° C., after which the generated methanol and excess methyltrimethoxysilane were removed with a nitrogen gas flow to obtain organotrisiloxane compound (a-1) represented by the following formula.
（ａ－２）
１００ｍｌフラスコに、末端水酸基型ジメチルシリコーンポリマー（７００ｍＰａ．ｓ、３００ｇ）、メチルトリメトキシシラン（２５ｇ）、チタンキレート触媒（０．２ｇ、マツモトファインケミカル（株）製、オルガチックスＴＣ－４０１）を添加し、１００℃下で６０分間反応させた後、発生するメタノールを窒素ガスフローにて除去、その後、余剰メチルトリメトキシシランを減圧下加熱で除去することで、下記式で示されるオルガノポリシロキサン化合物（ａ－２）を得た。
A hydroxyl-terminated dimethyl silicone polymer (700 mPa.s, 300 g), methyltrimethoxysilane (25 g), and a titanium chelate catalyst (0.2 g, Orgatix TC-401, manufactured by Matsumoto Fine Chemical Co., Ltd.) were added to a 100 ml flask and reacted for 60 minutes at 100° C., after which the generated methanol was removed with a nitrogen gas flow, and then the excess methyltrimethoxysilane was removed by heating under reduced pressure, thereby obtaining an organopolysiloxane compound (a-2) represented by the following formula:
［実施例１～４、参考例１、比較例１～３］
１０ｍｌガラスカップ内に、表１、２に示す各成分を各配合量にて配合し、手混合にて、室温下、１０分間撹拌し、シリコーンコーティング剤組成物を得た。なお、（Ａ－１）～（Ａ－５）、（ａ－１）、（ａ－２）は溶剤成分無しである。得られたシリコーンコーティング剤組成物の外観及び性状を目視にて確認し、表１、２に併記した。
また、上記で得られたシリコーンコーティング剤組成物を、２３℃／５０％Ｒｈ×７日の硬化条件で硬化させた。得られた硬化物の外観及び性状を目視にて確認し、表１、２に併記した。
[Examples 1 to 4, Reference Example 1 , Comparative Examples 1 to 3]
The components shown in Tables 1 and 2 were mixed in the respective amounts in a 10 ml glass cup and stirred by hand at room temperature for 10 minutes to obtain silicone coating compositions. Note that (A-1) to (A-5), (a-1), and (a-2) do not contain a solvent component. The appearance and properties of the obtained silicone coating compositions were visually inspected and are also shown in Tables 1 and 2.
The silicone coating composition obtained above was cured under the conditions of 23° C./50% Rh for 7 days. The appearance and properties of the resulting cured product were visually inspected and the results are shown in Tables 1 and 2.
上記調製例で得られた（Ａ）成分以外に使用した原料を以下に示す。
（Ｂ）成分
（Ｂ－１）
錫触媒：Ｕ－８３０（日東化成（株）製、ジオクチル錫）
（Ｂ－２）
アミン触媒：テトラメチルグアニジルプロピルトリメトキシシラン
（Ｃ）成分
（Ｃ－１）
ビニルトリメトキシシラン
The raw materials used in addition to the component (A) obtained in the above Preparation Example are shown below.
Component (B)
(B-1)
Tin catalyst: U-830 (manufactured by Nitto Kasei Co., Ltd., dioctyl tin)
(B-2)
Amine catalyst: Tetramethylguanidylpropyltrimethoxysilane
Component (C)
(C-1)
Vinyltrimethoxysilane
（Ａ）成分（比較用）
（ａ－３）
アクリル樹脂成分を主体とする、溶剤型コーティング剤：Ｈｕｍｉｓｅａｌ（登録商標）－１Ｂ６６ＮＳを準備した。固形分３５質量％（溶媒成分６５質量％）であるが、薄膜塗布とするため、追加溶媒（希釈材 Ｈｕｍｉｓｅａｌ（登録商標）シンナー９０１）で倍希釈とした。
(A) Component (for comparison)
(a-3)
A solvent-based coating agent, Humiseal (registered trademark)-1B66NS, mainly composed of acrylic resin, was prepared. The solid content was 35% by mass (solvent content 65% by mass), but in order to apply a thin film, it was diluted 2x with an additional solvent (diluent: Humiseal (registered trademark) Thinner 901).
次に、上記実施例、参考例及び比較例のシリコーンコーティング剤組成物、及び上記（ａ－３）成分を用いた比較例３を用いて、硬化物外観、タックフリータイム、腐食防止性試験、及び可撓性を評価した。これらの結果を表３に示す。
Next, the silicone coating agent compositions of the above Examples , Reference Examples , and Comparative Examples, as well as Comparative Example 3 using the above component (a-3), were evaluated for cured product appearance, tack-free time, corrosion prevention properties, and flexibility. The results are shown in Table 3.
（硬化物外観）
下記タックフリータイムの評価で作製したアルミシャーレ上で硬化した被膜を、目視により、透明性、着色程度の評価を行った。
(Appearance of the cured product)
The coating film cured on the aluminum petri dish prepared in the tack-free time evaluation described below was visually evaluated for transparency and degree of coloration.
（タックフリータイム）
アルミシャーレ上に各組成物（液体）を０．２０ｇ採取し、２ｃｍ×２ｃｍ（４ｃｍ2）の正方形状に塗り広げ、指触により各組成物表面の粘着性がなくなるまでの時間を硬化時間（タックフリータイム）として評価した。
(Tuck free time)
0.20 g of each composition (liquid) was placed on an aluminum dish and spread over a 2 cm x 2 cm ( 4 cm2) square. The time until the surface of each composition became tacky when touched with a finger was recorded as the curing time (tack-free time).
（腐食防止性試験）
各材料（シリコーンコーティング剤組成物）を、銀メッキアルミニウム板の表面に硬化被膜が約２００μｍとなるように、０．０８ｇの各組成物（液体）を２ｃｍ×２ｃｍ（４ｃｍ2）の正方形状に塗り広げ、２３℃／５０％Ｒｈ×７日の硬化条件で硬化させ、硫化水素ガス腐食試験機を使用して、銀メッキ面腐食状態を経時（初期、１日後、３日後、７日後、１４日後）で観察した。腐食条件は以下の通り。
硫化水素濃度 ：２ｐｐｍ
温度 ：２３℃
湿度 ：５０％Ｒｈ
腐食試験前後の銀メッキ面を観察し、初期の銀光沢から変化（黒色化、灰色化）した時点で腐食したと判断した。
(Corrosion prevention test)
0.08 g of each material (silicone coating composition) was spread onto the surface of a silver-plated aluminum plate in a 2 cm x 2 cm ( 4 cm2) square shape so that the cured film was about 200 μm thick, and cured under the conditions of 23°C/50% Rh x 7 days, and the silver-plated surface corrosion state was observed over time (initial, 1 day, 3 days, 7 days, 14 days) using a hydrogen sulfide gas corrosion tester. The corrosion conditions were as follows:
Hydrogen sulfide concentration: 2 ppm
Temperature: 23℃
Humidity: 50% Rh
The silver-plated surface was observed before and after the corrosion test, and it was determined that corrosion had occurred when the initial silver luster changed (turned black or gray).
（可撓性）
上記腐食防止性試験終了後のコート済み（シリコーンコーティング剤組成物の硬化被膜を有する）銀メッキアルミニウム板を折り曲げた際に、コート層が割れずに基材に追従できるかを評価した。
(Flexibility)
After the above corrosion prevention test, the coated silver-plated aluminum plate (having a cured film of the silicone coating composition) was bent, and an evaluation was made as to whether the coating layer could conform to the substrate without cracking.
（結果）
以上の結果から、本発明のシリコーンコーティング剤組成物は、常温における硬化性、透明性に優れ、かつ腐食性ガスから金属基材の腐食を防ぐ効果と、基材追従性（可撓性）に優れることが確認された。
(result)
From the above results, it was confirmed that the silicone coating agent composition of the present invention has excellent curing properties and transparency at room temperature, as well as the effect of preventing corrosion of metal substrates from corrosive gases and excellent substrate conformability (flexibility).
Claims (8)
（Ｂ）硬化触媒： ０．０１～１０質量部
を含有するシリコーンコーティング剤組成物。 (A) a hydrolyzable group-containing organotrisiloxane compound represented by the following general formula (1): 100 parts by mass,
(B) A silicone coating composition containing a curing catalyst: 0.01 to 10 parts by mass.
（Ｒ1）aＳｉ（Ｘ）(4-a) （２）
（式中、Ｒ1、Ｘ、ａは、それぞれ上記と同じ。） The silicone coating composition according to any one of claims 1 to 4, further comprising, per 100 parts by mass of component (A), 0.1 to 100 parts by mass of a hydrolyzable organosilane compound represented by the following general formula ( 2 ) and/or a partial hydrolyzed condensate thereof (C), other than component (A):
( R1 ) aSi (X) (4-a) (2)
(In the formula, R 1 , X, and a are the same as above.)
（Ｒ1）aＳｉ（Ｘ）(4-a) （２）
（式中、Ｒ1、Ｘ、ａは、それぞれ上記と同じ。）
で示される加水分解性オルガノシラン化合物と、下記一般式（３）
で示されるジオルガノシランジオールとの加水分解・縮合反応物である請求項１～６のいずれか１項に記載のシリコーンコーティング剤組成物。 The component (A) is represented by the following general formula (2):
( R1 ) aSi (X) (4-a) (2)
(In the formula, R 1 , X, and a are the same as above.)
and a hydrolyzable organosilane compound represented by the following general formula (3):
7. The silicone coating composition according to claim 1, which is a hydrolysis/condensation reaction product with a diorganosilanediol represented by the formula:
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW110107446A TW202140702A (en) | 2020-03-17 | 2021-03-03 | Silicone coating agent composition and article particularly reducing sulfurization due to hydrogen sulfide which is a sulfur gas |
| KR1020210033230A KR20210116331A (en) | 2020-03-17 | 2021-03-15 | Silicone Coating Composition and Article |
| CN202110280617.3A CN113402911B (en) | 2020-03-17 | 2021-03-16 | Silicone coating agent composition and article |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020045945 | 2020-03-17 | ||
| JP2020045945 | 2020-03-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2021147608A JP2021147608A (en) | 2021-09-27 |
| JP7468399B2 true JP7468399B2 (en) | 2024-04-16 |
Family
ID=77847917
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2021024731A Active JP7468399B2 (en) | 2020-03-17 | 2021-02-19 | Silicone coating composition and article |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP7468399B2 (en) |
| KR (1) | KR20210116331A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4299683A1 (en) * | 2021-02-24 | 2024-01-03 | Shin-Etsu Chemical Co., Ltd. | Silicone coating agent composition and article |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002363539A (en) | 2001-06-07 | 2002-12-18 | Chuo Rika Kogyo Corp | Pore sealing agent |
| JP2003253208A (en) | 2002-03-01 | 2003-09-10 | Chuo Rika Kogyo Corp | Permeable inorganic anticorrosive coating composition and method for repair coating of metal structure using the same |
| JP2008050490A (en) | 2006-08-25 | 2008-03-06 | Nard Inst Ltd | Method for producing siloxane-based surface coating agent |
| JP2010270276A (en) | 2009-05-25 | 2010-12-02 | D & D:Kk | One component normal temperature-curable coating material |
| WO2011087073A1 (en) | 2010-01-18 | 2011-07-21 | 日本ジッコウ株式会社 | Silicone resin composition and protective coating method using silicone resin composition |
| JP2017057433A (en) | 2015-09-14 | 2017-03-23 | 信越化学工業株式会社 | Method for preventing sulfurization of metal base material, method for evaluating sulfurization preventability, and package circuit board |
| JP2018184395A (en) | 2017-04-24 | 2018-11-22 | 国立研究開発法人産業技術総合研究所 | Method for producing siloxane compound, novel siloxane compound, and use thereof |
| US20190225756A1 (en) | 2016-07-14 | 2019-07-25 | Inkron Oy | Siloxane monomers, their polymerization and uses thereof |
| WO2020036074A1 (en) | 2018-08-17 | 2020-02-20 | 信越化学工業株式会社 | Composition including organopolysiloxane compound, production method therefor, coating material, and coated article |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60233164A (en) | 1984-05-07 | 1985-11-19 | Shin Etsu Chem Co Ltd | Coating organopolysiloxane composition |
| JPS6139018U (en) | 1984-08-16 | 1986-03-12 | 釜屋化学工業株式会社 | Portable storage container for cosmetics, etc. |
| JP4114037B2 (en) | 2001-09-25 | 2008-07-09 | 信越化学工業株式会社 | Silicone rubber sealing / sealing material for preventing or delaying sulfidation of electric / electronic parts and sulfidation preventing or delaying method |
| JP4110402B2 (en) | 2003-06-19 | 2008-07-02 | 信越化学工業株式会社 | Silicone coating composition |
| JP4530137B2 (en) | 2003-09-17 | 2010-08-25 | 信越化学工業株式会社 | Organopolysiloxane composition for sealing and sealing precision electronic parts, corrosion prevention or delay method for precision electronic parts, and silver-containing precision electronic parts |
-
2021
- 2021-02-19 JP JP2021024731A patent/JP7468399B2/en active Active
- 2021-03-15 KR KR1020210033230A patent/KR20210116331A/en active Search and Examination
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002363539A (en) | 2001-06-07 | 2002-12-18 | Chuo Rika Kogyo Corp | Pore sealing agent |
| JP2003253208A (en) | 2002-03-01 | 2003-09-10 | Chuo Rika Kogyo Corp | Permeable inorganic anticorrosive coating composition and method for repair coating of metal structure using the same |
| JP2008050490A (en) | 2006-08-25 | 2008-03-06 | Nard Inst Ltd | Method for producing siloxane-based surface coating agent |
| JP2010270276A (en) | 2009-05-25 | 2010-12-02 | D & D:Kk | One component normal temperature-curable coating material |
| WO2011087073A1 (en) | 2010-01-18 | 2011-07-21 | 日本ジッコウ株式会社 | Silicone resin composition and protective coating method using silicone resin composition |
| JP2017057433A (en) | 2015-09-14 | 2017-03-23 | 信越化学工業株式会社 | Method for preventing sulfurization of metal base material, method for evaluating sulfurization preventability, and package circuit board |
| US20190225756A1 (en) | 2016-07-14 | 2019-07-25 | Inkron Oy | Siloxane monomers, their polymerization and uses thereof |
| JP2019528246A (en) | 2016-07-14 | 2019-10-10 | インクロン オサケユキチュアＩｎｋｒｏｎ Ｏｙ | Siloxane monomers, their polymerization and their use |
| JP2018184395A (en) | 2017-04-24 | 2018-11-22 | 国立研究開発法人産業技術総合研究所 | Method for producing siloxane compound, novel siloxane compound, and use thereof |
| WO2020036074A1 (en) | 2018-08-17 | 2020-02-20 | 信越化学工業株式会社 | Composition including organopolysiloxane compound, production method therefor, coating material, and coated article |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2021147608A (en) | 2021-09-27 |
| KR20210116331A (en) | 2021-09-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100363126B1 (en) | An epoxy-functional organopolysiloxane resin and An epoxy-functional organopoly silioxane coating composition | |
| JP3445831B2 (en) | Silicone resin composition | |
| TWI457373B (en) | Organopolysilmethylenesiloxane and a cured product thereof | |
| KR102093273B1 (en) | Novel ethynyl-group-containing organopolysiloxane compound, method for producing straight-chain organopolysiloxane compound containing ethynyl group at both molecular chain ends, method for producing alkoxysilyl-ethynyl-group-terminated organosiloxane polymer, room-temperature-curable composition, and molded article that is cured product of same | |
| TWI424027B (en) | Room temperature hardening organopolysiloxane composition | |
| CN107429061B (en) | Room temperature curable organopolysiloxane composition and molded article that is cured product of the composition | |
| KR101865547B1 (en) | Moisture-curable, elastomeric, translucent silicone waterproofing coating and method of making the same | |
| JP5006600B2 (en) | Production method of siloxane surface coating agent | |
| JP7468399B2 (en) | Silicone coating composition and article | |
| JPS6325024B2 (en) | ||
| JPH07278497A (en) | Coating composition for covering | |
| JP2004331704A (en) | Primer composition | |
| JPH0645755B2 (en) | Material that crosslinks to an elastomer at room temperature, method for producing the same, and paint-compatible sealant containing the material | |
| JPH04214764A (en) | Cold-curing organopolysiloxane composition | |
| JP6402690B2 (en) | Organopolysilmethylenesiloxane composition | |
| JP6319168B2 (en) | Method for producing condensation reaction product, method for producing room temperature curable organopolysiloxane composition containing the condensation reaction product | |
| US3694427A (en) | Curable silox anol-silacyclobutane composition | |
| TWI389979B (en) | Room temperature hardened organopolysiloxane composition | |
| CN113402911B (en) | Silicone coating agent composition and article | |
| JP3162301B2 (en) | Silicone resin composition and coating method for preventing dirt | |
| CN116917427A (en) | Silicone coating agent composition and article | |
| JP7211494B2 (en) | Room temperature curable organopolysiloxane composition and method for producing the same | |
| JPH0343310B2 (en) | ||
| CN109689814B (en) | Primer composition and curtain wall unit | |
| JP2001262051A (en) | Primer composition and adhesion process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20230125 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20231011 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20231024 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20231219 |
|
| 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: 20240305 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20240318 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7468399 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |