WO2024029406A1 - Low-dielectric-constant insulating coating composition, cured product of same, and display device - Google Patents
Low-dielectric-constant insulating coating composition, cured product of same, and display device Download PDFInfo
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- WO2024029406A1 WO2024029406A1 PCT/JP2023/027213 JP2023027213W WO2024029406A1 WO 2024029406 A1 WO2024029406 A1 WO 2024029406A1 JP 2023027213 W JP2023027213 W JP 2023027213W WO 2024029406 A1 WO2024029406 A1 WO 2024029406A1
- Authority
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- WIPO (PCT)
- Prior art keywords
- dielectric constant
- coating composition
- insulating coating
- group
- low dielectric
- Prior art date
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- 239000008199 coating composition Substances 0.000 title claims abstract description 53
- -1 organosiloxane compound Chemical class 0.000 claims abstract description 30
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 27
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 14
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 12
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims description 64
- 150000001875 compounds Chemical class 0.000 claims description 38
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 19
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 18
- 238000007259 addition reaction Methods 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 13
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 150000003377 silicon compounds Chemical class 0.000 abstract 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 150000002430 hydrocarbons Chemical group 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 33
- 238000002156 mixing Methods 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 229920001296 polysiloxane Polymers 0.000 description 10
- 238000001723 curing Methods 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 239000003963 antioxidant agent Substances 0.000 description 8
- 230000003078 antioxidant effect Effects 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 229920002050 silicone resin Polymers 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- 125000005375 organosiloxane group Chemical group 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- CZNRFEXEPBITDS-UHFFFAOYSA-N 2,5-bis(2-methylbutan-2-yl)benzene-1,4-diol Chemical compound CCC(C)(C)C1=CC(O)=C(C(C)(C)CC)C=C1O CZNRFEXEPBITDS-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000008393 encapsulating agent Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229920005573 silicon-containing polymer Polymers 0.000 description 2
- 239000004447 silicone coating Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- UHXCHUWSQRLZJS-UHFFFAOYSA-N (4-dimethylsilylidenecyclohexa-2,5-dien-1-ylidene)-dimethylsilane Chemical compound C[Si](C)C1=CC=C([Si](C)C)C=C1 UHXCHUWSQRLZJS-UHFFFAOYSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 1
- QYXVDGZUXHFXTO-UHFFFAOYSA-L 3-oxobutanoate;platinum(2+) Chemical compound [Pt+2].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O QYXVDGZUXHFXTO-UHFFFAOYSA-L 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910004738 SiO1 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- 238000013006 addition curing Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 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
- 230000001588 bifunctional effect Effects 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 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
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- NYMPGSQKHIOWIO-UHFFFAOYSA-N hydroxy(diphenyl)silicon Chemical compound C=1C=CC=CC=1[Si](O)C1=CC=CC=C1 NYMPGSQKHIOWIO-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004957 naphthylene 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
- 229910052759 nickel Inorganic materials 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
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- ZPNJBTBYIHBSIG-UHFFFAOYSA-N phenyl-(2,2,6,6-tetramethylpiperidin-4-yl)methanone Chemical compound C1C(C)(C)NC(C)(C)CC1C(=O)C1=CC=CC=C1 ZPNJBTBYIHBSIG-UHFFFAOYSA-N 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000003566 sealing material Substances 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
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Silicon Polymers (AREA)
Abstract
The present invention is a low-dielectric-constant insulating coating composition containing: (A) a reaction adduct of an organic silicon compound represented by formula (1) and an organic silicon compound represented by formula (2), the reaction adduct having three or more SiH groups in a molecule; (B) an organosiloxane compound having two or more alkenyl groups in a molecule; and (C) a hydrosilylation reaction catalyst. A low-dielectric-constant insulating coating composition in which a cured product obtained by curing has a high mechanical strength and a low dielectric constant and dissipation tangent is thereby provided. (In the formulas, R1 is an independently substituted or unsubstituted divalent C1-12 hydrocarbon group, R2 is an independently substituted or unsubstituted monovalent C1-12 hydrocarbon group, and R3 is a single bond or an unsubstituted divalent C1-4 hydrocarbon group).
Description
本発明は、低誘電率絶縁性コーティング組成物、その硬化物および表示装置に関する。
The present invention relates to a low dielectric constant insulating coating composition, a cured product thereof, and a display device.
近年、情報通信機器は急激に進歩しており、映像情報などの大容量通信に伴い、伝送信号のデジタル化、高周波化が進んでいる。このためギガヘルツ高周波領域で伝送損失の少ない材料としてこれまで用いられてきたフッ素樹脂やセラミックスよりも加工性及び作業性に優れた樹脂材料が求められている。
In recent years, information and communication equipment has progressed rapidly, and along with large-capacity communications such as video information, the digitization and high frequency of transmission signals are progressing. For this reason, there is a need for resin materials that have better processability and workability than fluororesins and ceramics that have been used so far as materials with low transmission loss in the gigahertz high frequency range.
例えば、低誘電率、低誘電正接であり、耐熱性、強靭性に優れ、作業性も良好な硬化物を与えるビスマレイミド樹脂組成物が提案されている（特許文献１）。しかしながら、更なる改善が望まれている。
For example, a bismaleimide resin composition has been proposed that provides a cured product that has a low dielectric constant and a low dielectric loss tangent, has excellent heat resistance and toughness, and has good workability (Patent Document 1). However, further improvements are desired.
一方、耐熱性が要求される白色ＬＥＤ用封止材として利用できる硬化性組成物として、ケイ素原子に結合した水素原子を１分子中に３個以上有する化合物と、アルケニル基を１分子中に２個以上有するオルガノシロキサンと、ヒドロシリル化触媒とを必須成分として含む硬化性組成物が提案されている（特許文献２）。この硬化性組成物は、硬度、機械的強度、および耐クラック性が高く、短波長領域の光透過性、ガスバリア性に優れた硬化物を与えることができるとされている。しかし、硬化物の誘電特性についてこの文献は全く言及していない。
On the other hand, curable compositions that can be used as encapsulants for white LEDs that require heat resistance include compounds that have three or more silicon-bonded hydrogen atoms in one molecule and two alkenyl groups in one molecule. A curable composition containing as essential components an organosiloxane having one or more organosiloxanes and a hydrosilylation catalyst has been proposed (Patent Document 2). This curable composition is said to be able to provide a cured product with high hardness, mechanical strength, and crack resistance, and excellent light transmittance in a short wavelength region and gas barrier properties. However, this document makes no mention of the dielectric properties of the cured product.
従来技術では、低誘電特性（低誘電率及び低誘電正接）と、高い機械的強度とを両立できる硬化物を得られないといった問題がある。
従って、本発明は、上記問題を解決するためになされたものであり、硬化して得られる硬化物が、高い機械的強度ならびに低い比誘電率および誘電正接を有する低誘電率絶縁性コーティング組成物を提供することを目的とする。 The conventional technology has a problem in that it is not possible to obtain a cured product that has both low dielectric properties (low dielectric constant and low dielectric loss tangent) and high mechanical strength.
Therefore, the present invention has been made to solve the above problems, and provides a low dielectric constant insulating coating composition whose cured product has high mechanical strength and low dielectric constant and dielectric loss tangent. The purpose is to provide
従って、本発明は、上記問題を解決するためになされたものであり、硬化して得られる硬化物が、高い機械的強度ならびに低い比誘電率および誘電正接を有する低誘電率絶縁性コーティング組成物を提供することを目的とする。 The conventional technology has a problem in that it is not possible to obtain a cured product that has both low dielectric properties (low dielectric constant and low dielectric loss tangent) and high mechanical strength.
Therefore, the present invention has been made to solve the above problems, and provides a low dielectric constant insulating coating composition whose cured product has high mechanical strength and low dielectric constant and dielectric loss tangent. The purpose is to provide
上記課題を解決するために、本発明では、下記（Ａ）、（Ｂ）及び（Ｃ）を含む低誘電率絶縁性コーティング組成物を提供する。
（Ａ）下記式（１）で表される有機ケイ素化合物と、下記式（２）で表される有機ケイ素化合物との付加反応物であって、１分子中にＳｉＨ基を３個以上有する付加反応物、
（式中、Ｒ１は独立に置換または非置換の炭素数１～１２の２価炭化水素基である。）
（式中、Ｒ２は独立に置換または非置換の炭素数１～１２の１価炭化水素基であり、Ｒ３は単結合または非置換の炭素数１～４の２価炭化水素基である。）、
（Ｂ）アルケニル基を１分子中に２個以上有するオルガノシロキサン化合物、
（Ｃ）ヒドロシリル化反応触媒 In order to solve the above problems, the present invention provides a low dielectric constant insulating coating composition containing the following (A), (B) and (C).
(A) An addition reaction product of an organosilicon compound represented by the following formula (1) and an organosilicon compound represented by the following formula (2), which has three or more SiH groups in one molecule. reactant,
(In the formula, R 1 is independently a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms.)
(In the formula, R 2 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R 3 is a single bond or an unsubstituted divalent hydrocarbon group having 1 to 4 carbon atoms. ),
(B) an organosiloxane compound having two or more alkenyl groups in one molecule;
(C) Hydrosilylation reaction catalyst
（Ａ）下記式（１）で表される有機ケイ素化合物と、下記式（２）で表される有機ケイ素化合物との付加反応物であって、１分子中にＳｉＨ基を３個以上有する付加反応物、
（Ｂ）アルケニル基を１分子中に２個以上有するオルガノシロキサン化合物、
（Ｃ）ヒドロシリル化反応触媒 In order to solve the above problems, the present invention provides a low dielectric constant insulating coating composition containing the following (A), (B) and (C).
(A) An addition reaction product of an organosilicon compound represented by the following formula (1) and an organosilicon compound represented by the following formula (2), which has three or more SiH groups in one molecule. reactant,
(B) an organosiloxane compound having two or more alkenyl groups in one molecule;
(C) Hydrosilylation reaction catalyst
本発明の低誘電率絶縁性コーティング組成物であれば、機械的強度が高く、低い比誘電率および誘電正接を有する硬化物を与える低誘電率絶縁性コーティング組成物を提供できる。なお、本発明では比誘電率（真空の誘電率に対する比の値）を単に「誘電率」ともいう。
The low dielectric constant insulating coating composition of the present invention can provide a low dielectric constant insulating coating composition that provides a cured product with high mechanical strength and low dielectric constant and dielectric loss tangent. In the present invention, the relative dielectric constant (value of the ratio to the dielectric constant of vacuum) is also simply referred to as "permittivity."
本発明の低誘電率絶縁性コーティング組成物は、上記Ｒ１がフェニレン基、上記Ｒ２がメチル基又はフェニル基であることができる。
In the low dielectric constant insulating coating composition of the present invention, R 1 may be a phenylene group, and R 2 may be a methyl group or a phenyl group.
このような上記式（１）で表される有機ケイ素化合物と、上記式（２）で表される有機ケイ素化合物は入手し易く、これらの付加反応物である（Ａ）成分を効率良く得ることができる。
The organosilicon compound represented by the above formula (1) and the organosilicon compound represented by the above formula (2) are easily available, and component (A), which is an addition reaction product thereof, can be obtained efficiently. I can do it.
本発明の低誘電率絶縁性コーティング組成物は、さらに前記（Ｂ）が下記式（３）で表される化合物であることが好ましい。
（式中、Ｒ４は独立に非置換または置換の１価炭化水素基であり、Ｒ５は独立にメチル基又はフェニル基であり、ａは０～５０の整数であり、ｂは０～１００の整数である。ただし、ａが０のときＲ５はフェニル基であり、かつ、ｂは１～１００である。括弧が付されたシロキサン単位の配列順は任意である。）
In the low dielectric constant insulating coating composition of the present invention, it is further preferable that the above (B) is a compound represented by the following formula (3).
(In the formula, R 4 is independently an unsubstituted or substituted monovalent hydrocarbon group, R 5 is independently a methyl group or a phenyl group, a is an integer from 0 to 50, and b is an integer from 0 to 100. is an integer of. However, when a is 0, R 5 is a phenyl group, and b is 1 to 100. The arrangement order of the siloxane units in parentheses is arbitrary.)
このような（Ｂ）成分は容易に得ることができる。
Such component (B) can be easily obtained.
また本発明は、上記低誘電率絶縁性コーティング組成物を硬化してなることを特徴とする硬化物を提供する。
The present invention also provides a cured product obtained by curing the above-mentioned low dielectric constant insulating coating composition.
本発明の硬化物であれば、機械的強度に優れ、低い比誘電率および誘電正接を有する。
The cured product of the present invention has excellent mechanical strength, low dielectric constant and low dielectric loss tangent.
本発明の硬化物は、１０ＧＨｚにおける誘電率が３．０以下、かつ、誘電正接が０．０１以下のものであることが好ましい。
The cured product of the present invention preferably has a dielectric constant of 3.0 or less at 10 GHz and a dielectric loss tangent of 0.01 or less.
このような低誘電率絶縁性を有する硬化物であれば、高周波領域で伝送損失の少ない絶縁材料、コーティング材料、封止材として有用である。
A cured product with such low dielectric constant insulation is useful as an insulating material, coating material, or sealing material with low transmission loss in the high frequency range.
さらに本発明は、上記硬化物からなる層を有するものであることを特徴とする表示装置を提供する。
Furthermore, the present invention provides a display device characterized by having a layer made of the above-mentioned cured product.
本発明の表示装置であれば、使用する硬化物の機械的強度が高く、低い比誘電率および誘電正接を有することに加えて、透明性も有するため、高い信頼性を有する表示装置となる。
In the display device of the present invention, the cured product used has high mechanical strength, low dielectric constant and dielectric loss tangent, and also has transparency, so the display device has high reliability.
本発明の低誘電率絶縁性コーティング組成物は、得られる硬化物の機械的強度が高く、低い比誘電率および低い誘電正接を有することから、高周波領域で伝送損失の少ない電子デバイス及び電気デバイス用のコーティング材料として有用である。
The low dielectric constant insulating coating composition of the present invention has high mechanical strength, low dielectric constant, and low dielectric loss tangent of the obtained cured product, and therefore is suitable for electronic devices and electrical devices with low transmission loss in the high frequency range. It is useful as a coating material.
上述のように、高い機械的強度を有し、低い比誘電率および誘電正接を有する硬化物を与える低誘電率絶縁性コーティング組成物の開発が求められていた。
As mentioned above, there has been a need to develop a low dielectric constant insulating coating composition that provides a cured product with high mechanical strength and low dielectric constant and dielectric loss tangent.
本発明者は、上記課題について鋭意検討を重ねた結果、特定の成分を含む低誘電率絶縁性コーティング組成物であれば、上記課題を解決できることを見出し、本発明を完成させた。
As a result of intensive studies regarding the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using a low dielectric constant insulating coating composition containing specific components, and have completed the present invention.
即ち、本発明は、下記（Ａ）、（Ｂ）及び（Ｃ）を含む低誘電率絶縁性コーティング組成物である。
（Ａ）下記式（１）で表される有機ケイ素化合物と、下記式（２）で表される有機ケイ素化合物との付加反応物であって、１分子中にＳｉＨ基を３個以上有する付加反応物、
（式中、Ｒ１は独立に置換または非置換の炭素数１～１２の２価炭化水素基である。）
（式中、Ｒ２は独立に置換または非置換の炭素数１～１２の１価炭化水素基であり、Ｒ３は単結合または非置換の炭素数１～４の２価炭化水素基である。）、
（Ｂ）アルケニル基を１分子中に２個以上有するオルガノシロキサン化合物、
（Ｃ）ヒドロシリル化反応触媒 That is, the present invention is a low dielectric constant insulating coating composition containing the following (A), (B), and (C).
(A) An addition reaction product of an organosilicon compound represented by the following formula (1) and an organosilicon compound represented by the following formula (2), which has three or more SiH groups in one molecule. reactant,
(In the formula, R 1 is independently a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms.)
(In the formula, R 2 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R 3 is a single bond or an unsubstituted divalent hydrocarbon group having 1 to 4 carbon atoms. ),
(B) an organosiloxane compound having two or more alkenyl groups in one molecule;
(C) Hydrosilylation reaction catalyst
（Ａ）下記式（１）で表される有機ケイ素化合物と、下記式（２）で表される有機ケイ素化合物との付加反応物であって、１分子中にＳｉＨ基を３個以上有する付加反応物、
（Ｂ）アルケニル基を１分子中に２個以上有するオルガノシロキサン化合物、
（Ｃ）ヒドロシリル化反応触媒 That is, the present invention is a low dielectric constant insulating coating composition containing the following (A), (B), and (C).
(A) An addition reaction product of an organosilicon compound represented by the following formula (1) and an organosilicon compound represented by the following formula (2), which has three or more SiH groups in one molecule. reactant,
(B) an organosiloxane compound having two or more alkenyl groups in one molecule;
(C) Hydrosilylation reaction catalyst
以下、本発明について詳細に説明するが、本発明はこれらに限定されるものではない。
Hereinafter, the present invention will be explained in detail, but the present invention is not limited thereto.
［低誘電率絶縁性コーティング組成物］
本発明の低誘電率絶縁性コーティング組成物は下記（Ａ）～（Ｃ）成分を含有してなる付加硬化型シリコーン組成物である。本発明の低誘電率絶縁性コーティング組成物は、下記（Ａ）～（Ｃ）成分及び、必要に応じてその他の成分を、従来公知の方法で混合して調製することができる。
以下、各成分について詳細に説明する。 [Low dielectric constant insulating coating composition]
The low dielectric constant insulating coating composition of the present invention is an addition-curing silicone composition containing the following components (A) to (C). The low dielectric constant insulating coating composition of the present invention can be prepared by mixing the following components (A) to (C) and, if necessary, other components by a conventionally known method.
Each component will be explained in detail below.
本発明の低誘電率絶縁性コーティング組成物は下記（Ａ）～（Ｃ）成分を含有してなる付加硬化型シリコーン組成物である。本発明の低誘電率絶縁性コーティング組成物は、下記（Ａ）～（Ｃ）成分及び、必要に応じてその他の成分を、従来公知の方法で混合して調製することができる。
以下、各成分について詳細に説明する。 [Low dielectric constant insulating coating composition]
The low dielectric constant insulating coating composition of the present invention is an addition-curing silicone composition containing the following components (A) to (C). The low dielectric constant insulating coating composition of the present invention can be prepared by mixing the following components (A) to (C) and, if necessary, other components by a conventionally known method.
Each component will be explained in detail below.
［（Ａ）成分］
本発明の低誘電率絶縁性コーティング組成物における（Ａ）成分は、後述の（Ｂ）成分とヒドロシリル化反応を起こすことにより、架橋剤として機能する。 [(A) Component]
Component (A) in the low dielectric constant insulating coating composition of the present invention functions as a crosslinking agent by causing a hydrosilylation reaction with component (B) described below.
本発明の低誘電率絶縁性コーティング組成物における（Ａ）成分は、後述の（Ｂ）成分とヒドロシリル化反応を起こすことにより、架橋剤として機能する。 [(A) Component]
Component (A) in the low dielectric constant insulating coating composition of the present invention functions as a crosslinking agent by causing a hydrosilylation reaction with component (B) described below.
（Ａ）成分は、下記式（１）で表される有機ケイ素化合物と、下記式（２）で表される有機ケイ素化合物との付加反応物であって、１分子中にＳｉＨ基（ヒドロシリル基）を３個以上有する付加反応物である。
（式中、Ｒ１は独立に置換または非置換の炭素数１～１２の２価炭化水素基である。）
（式中、Ｒ２は独立に置換または非置換の炭素数１～１２の１価炭化水素基であり、Ｒ３は単結合または非置換の炭素数１～４の２価炭化水素基である。）
Component (A) is an addition reaction product of an organosilicon compound represented by the following formula (1) and an organosilicon compound represented by the following formula (2), and has an SiH group (hydrosilyl group) in one molecule. ) is an addition reaction product having three or more.
(In the formula, R 1 is independently a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms.)
(In the formula, R 2 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R 3 is a single bond or an unsubstituted divalent hydrocarbon group having 1 to 4 carbon atoms. .)
なお、上記式（２）で表される有機ケイ素化合物は、アルケニル基を１分子中に３個有すがシロキサン結合を持たないので、アルケニル基を１分子中に２個以上有するオルガノシロキサン化合物である（Ｂ）成分とは明確に区別される。
Note that the organosilicon compound represented by the above formula (2) has three alkenyl groups in one molecule but does not have a siloxane bond, so it is an organosiloxane compound having two or more alkenyl groups in one molecule. It is clearly distinguished from a certain component (B).
Ｒ１で表される炭素数１～１２の２価炭化水素基としては、メチレン基、エチレン基、ｎ－プロピレン基、ｎ－ブチレン基、ｎ－ペンチレン基、ｎ－ヘキシレン基、シクロヘキシレン基、ｎ－オクチレン基等のアルキレン基、フェニレン基、ナフチレン基等のアリーレン基等や、これらの基の水素原子の一部又は全部がフッ素、臭素、塩素等のハロゲン原子等で置換されたものが挙げられ、Ｒ１としては、フェニレン基が特に好ましい。
The divalent hydrocarbon group having 1 to 12 carbon atoms represented by R 1 includes methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, cyclohexylene group, Examples include alkylene groups such as n-octylene groups, arylene groups such as phenylene groups and naphthylene groups, and those in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, bromine, and chlorine. and R 1 is particularly preferably a phenylene group.
Ｒ２で表される炭素数１～１２の１価炭化水素基としては、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、ｔｅｒｔ－ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、オクチル基等のアルキル基、シクロヘキシル基等のシクロアルキル基、ビニル基、アリル基、プロペニル基等のアルケニル基、フェニル基、トリル基、キシリル基、ナフチル基等のアリール基、ベンジル基、フェニルエチル基、フェニルプロピル基等のアラルキル基等や、これらの基の水素原子の一部又は全部がフッ素、臭素、塩素等のハロゲン原子等で置換されたものが挙げられ、Ｒ２としてはメチル又はフェニル基が好ましく、フェニル基が特に好ましい。
The monovalent hydrocarbon group having 1 to 12 carbon atoms represented by R 2 includes methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group. alkyl groups such as octyl groups, cycloalkyl groups such as cyclohexyl groups, alkenyl groups such as vinyl groups, allyl groups, and propenyl groups, aryl groups such as phenyl groups, tolyl groups, xylyl groups, and naphthyl groups, benzyl groups, and phenyl groups. Examples include aralkyl groups such as ethyl group and phenylpropyl group, and those in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, bromine, chlorine, etc., and R 2 is methyl or A phenyl group is preferred, and a phenyl group is particularly preferred.
Ｒ３で表される非置換の炭素数１～４の２価炭化水素基としては、メチレン基、エチレン基、ｎ－プロピレン基、ｎ－ブチレン基等のアルキレン基が挙げられる。Ｒ３が単結合である場合は、ケイ素原子にビニル基が直接結合している有機ケイ素化合物を表す。Ｒ３としては単結合、メチレン基又はエチレン基が特に好ましい。
Examples of the unsubstituted divalent hydrocarbon group having 1 to 4 carbon atoms represented by R 3 include alkylene groups such as methylene group, ethylene group, n-propylene group, and n-butylene group. When R 3 is a single bond, it represents an organosilicon compound in which a vinyl group is directly bonded to a silicon atom. As R3 , a single bond, a methylene group, or an ethylene group is particularly preferable.
上記式（１）で表される有機ケイ素化合物の好適な具体例を下記に示すが、これらに限定されるものではない。また、上記式（１）で表される有機ケイ素化合物は１種単独でも２種以上を組み合わせても使用することができる。
Preferred specific examples of the organosilicon compound represented by the above formula (1) are shown below, but the invention is not limited thereto. Further, the organosilicon compounds represented by the above formula (1) can be used alone or in combination of two or more.
上記式（２）で表される化合物の好適な具体例を下記に示すが、これらに限定されるものではない。また、上記式（２）で表される化合物は１種単独でも２種以上を組み合わせても使用することができる。
Preferred specific examples of the compound represented by the above formula (2) are shown below, but the invention is not limited thereto. Furthermore, the compounds represented by the above formula (2) can be used alone or in combination of two or more.
上記式（１）で表される有機ケイ素化合物と、上記式（２）で表される有機ケイ素化合物との付加反応物である（Ａ）成分の好ましい例としては下記単位式で表される化合物が挙げられる。
（式中、ｎは１～１０の整数である。）
Preferred examples of component (A), which is an addition reaction product between the organosilicon compound represented by the above formula (1) and the organosilicon compound represented by the above formula (2), include a compound represented by the following unit formula: can be mentioned.
(In the formula, n is an integer from 1 to 10.)
前記単位式で表される化合物の具体例としては、下記式で表される化合物等が挙げられるが、これらに限定されるものではない。
Specific examples of the compound represented by the above unit formula include, but are not limited to, compounds represented by the following formula.
また、（Ａ）成分は上記単位式で表される化合物の１種単独でも２種以上の組み合わせでも使用することができる。
この場合、前記単位式で表される化合物であって、ｎが１のものを化合物Ｎ１、ｎが２のものを化合物Ｎ２、ｎが３のものを化合物Ｎ３、以下同様に、ｎがｋのものを化合物Ｎｋとすると、化合物Ｎ１、Ｎ２、Ｎ３、Ｎ４・・・Ｎｋからなる混合物における各化合物のモル分率（化合物Ｎ１、Ｎ２、Ｎ３、Ｎ４・・・Ｎｋの合計物質量を１モルとしたときの各化合物の物質量）は、以下の範囲とすることが好ましい。
ＦＮ１：ＦＮ２：ＦＮ３＝５０～６０：２０～３０：５～１５（モル％）
（式中、ＦＮｋは化合物Ｎｋのモル分率を表す。）
残りの化合物Ｎ４以上のもの（Ｎ４～Ｎｋ）の合計のモル分率は、５～１５（モル％）とすることができる。
このような（Ａ）成分を用いると、硬化物の機械的強度が向上するので好ましい。 In addition, component (A) can be used singly or in combination of two or more of the compounds represented by the above unit formula.
In this case, compounds represented by the above unit formula, where n is 1, are referred to as compound N 1 , those where n is 2 are referred to as compound N 2 , those where n is 3 are referred to as compound N 3 , and so on. If k is a compound N k , then the molar fraction of each compound in a mixture consisting of compounds N 1 , N 2 , N 3 , N 4 ...N k (compounds N 1 , N 2 , N 3 , N The amount of each compound when the total amount of 4 ...N k is 1 mole) is preferably in the following range.
F N1 :F N2 :F N3 =50-60:20-30:5-15 (mol%)
(In the formula, F Nk represents the molar fraction of compound N k .)
The total molar fraction of the remaining compounds N 4 or higher (N 4 to N k ) can be 5 to 15 (mol %).
It is preferable to use such component (A) because it improves the mechanical strength of the cured product.
この場合、前記単位式で表される化合物であって、ｎが１のものを化合物Ｎ１、ｎが２のものを化合物Ｎ２、ｎが３のものを化合物Ｎ３、以下同様に、ｎがｋのものを化合物Ｎｋとすると、化合物Ｎ１、Ｎ２、Ｎ３、Ｎ４・・・Ｎｋからなる混合物における各化合物のモル分率（化合物Ｎ１、Ｎ２、Ｎ３、Ｎ４・・・Ｎｋの合計物質量を１モルとしたときの各化合物の物質量）は、以下の範囲とすることが好ましい。
ＦＮ１：ＦＮ２：ＦＮ３＝５０～６０：２０～３０：５～１５（モル％）
（式中、ＦＮｋは化合物Ｎｋのモル分率を表す。）
残りの化合物Ｎ４以上のもの（Ｎ４～Ｎｋ）の合計のモル分率は、５～１５（モル％）とすることができる。
このような（Ａ）成分を用いると、硬化物の機械的強度が向上するので好ましい。 In addition, component (A) can be used singly or in combination of two or more of the compounds represented by the above unit formula.
In this case, compounds represented by the above unit formula, where n is 1, are referred to as compound N 1 , those where n is 2 are referred to as compound N 2 , those where n is 3 are referred to as compound N 3 , and so on. If k is a compound N k , then the molar fraction of each compound in a mixture consisting of compounds N 1 , N 2 , N 3 , N 4 ...N k (compounds N 1 , N 2 , N 3 , N The amount of each compound when the total amount of 4 ...N k is 1 mole) is preferably in the following range.
F N1 :F N2 :F N3 =50-60:20-30:5-15 (mol%)
(In the formula, F Nk represents the molar fraction of compound N k .)
The total molar fraction of the remaining compounds N 4 or higher (N 4 to N k ) can be 5 to 15 (mol %).
It is preferable to use such component (A) because it improves the mechanical strength of the cured product.
［（Ａ）成分の調製］
本発明の低誘電率絶縁性コーティング組成物における（Ａ）成分は、上記式（２）で表される化合物１モルに対して、上記式（１）で表される化合物を、過剰量、好ましくは３モルを越え３０モル以下、より好ましくは４．５モルを越え１５モル以下で混合して、両者を触媒の存在下でヒドロシリル化反応させることにより得ることができる。 [Preparation of component (A)]
Component (A) in the low dielectric constant insulating coating composition of the present invention preferably contains an excess amount of the compound represented by the above formula (1) with respect to 1 mole of the compound represented by the above formula (2). can be obtained by mixing more than 3 moles and less than 30 moles, more preferably more than 4.5 moles and less than 15 moles, and subjecting both to a hydrosilylation reaction in the presence of a catalyst.
本発明の低誘電率絶縁性コーティング組成物における（Ａ）成分は、上記式（２）で表される化合物１モルに対して、上記式（１）で表される化合物を、過剰量、好ましくは３モルを越え３０モル以下、より好ましくは４．５モルを越え１５モル以下で混合して、両者を触媒の存在下でヒドロシリル化反応させることにより得ることができる。 [Preparation of component (A)]
Component (A) in the low dielectric constant insulating coating composition of the present invention preferably contains an excess amount of the compound represented by the above formula (1) with respect to 1 mole of the compound represented by the above formula (2). can be obtained by mixing more than 3 moles and less than 30 moles, more preferably more than 4.5 moles and less than 15 moles, and subjecting both to a hydrosilylation reaction in the presence of a catalyst.
前記ヒドロシリル化反応に用いる触媒としては、公知のものを使用することができる。例えば、白金金属を担持したカーボン粉末、白金黒、塩化第２白金、塩化白金酸、塩化白金酸と一価アルコールとの反応生成物、塩化白金酸とオレフィン類との錯体、白金ビスアセトアセテート等の白金系触媒；パラジウム系触媒、ロジウム系触媒等の白金族金属系触媒が挙げられる。また、付加反応条件、精製条件、溶媒の使用等については特に限定されず、公知の方法を用いればよい。
As the catalyst used in the hydrosilylation reaction, any known catalyst can be used. For example, carbon powder supporting platinum metal, platinum black, platinum chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohol, complexes of chloroplatinic acid and olefins, platinum bisacetoacetate, etc. Platinum-based catalysts include platinum group metal catalysts such as palladium-based catalysts and rhodium-based catalysts. Further, addition reaction conditions, purification conditions, use of solvent, etc. are not particularly limited, and known methods may be used.
本発明の低誘電率絶縁性コーティング組成物における（Ａ）成分は、１種の化合物からなるものでも、２種以上の化合物の組み合わせ（混合物）からなるものでもよい。
The component (A) in the low dielectric constant insulating coating composition of the present invention may consist of one type of compound or a combination (mixture) of two or more types of compounds.
（Ａ）成分を構成する化合物１分子中にＳｉＨ基を３個以上有することは適切な測定手段を選択することにより確認できる。（Ａ）成分を構成する化合物が２種以上である場合には、適切な測定手段の組み合わせ（例えば、１Ｈ－ＮＭＲとＧＰＣなど）を選択することにより化合物ごとに１分子中にＳｉＨ基を３個以上有することを確認できる。
The presence of three or more SiH groups in one molecule of the compound constituting component (A) can be confirmed by selecting an appropriate measuring means. (A) When there are two or more types of compounds constituting the component, SiH groups can be added to one molecule for each compound by selecting an appropriate combination of measurement methods (for example, 1 H-NMR and GPC, etc.). It can be confirmed that there are three or more.
［（Ｂ）成分］
本発明の低誘電率絶縁性コーティング組成物における（Ｂ）成分は、アルケニル基を１分子中に２個以上有するオルガノシロキサン化合物である。（Ｂ）成分は、（Ａ）成分と、後述の（Ｃ）ヒドロシリル化反応触媒の存在下で付加反応する。前記オルガノシロキサン化合物としては、直鎖状、分岐状、環状のオルガノポリシロキサンを用いることができる。 [(B) Component]
Component (B) in the low dielectric constant insulating coating composition of the present invention is an organosiloxane compound having two or more alkenyl groups in one molecule. Component (B) undergoes an addition reaction with component (A) in the presence of (C) a hydrosilylation catalyst described below. As the organosiloxane compound, linear, branched, or cyclic organopolysiloxanes can be used.
本発明の低誘電率絶縁性コーティング組成物における（Ｂ）成分は、アルケニル基を１分子中に２個以上有するオルガノシロキサン化合物である。（Ｂ）成分は、（Ａ）成分と、後述の（Ｃ）ヒドロシリル化反応触媒の存在下で付加反応する。前記オルガノシロキサン化合物としては、直鎖状、分岐状、環状のオルガノポリシロキサンを用いることができる。 [(B) Component]
Component (B) in the low dielectric constant insulating coating composition of the present invention is an organosiloxane compound having two or more alkenyl groups in one molecule. Component (B) undergoes an addition reaction with component (A) in the presence of (C) a hydrosilylation catalyst described below. As the organosiloxane compound, linear, branched, or cyclic organopolysiloxanes can be used.
（Ｂ）成分の具体例としては、特に限定されないが、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・ジフェニルシロキサン・メチルビニルシロキサン共重合体、分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルシロキサン・ジフェニルシロキサン共重合体等が挙げられ、（Ｂ）成分は、１種単独でも２種以上を組み合わせても使用することができる。
Specific examples of component (B) include, but are not limited to, dimethylsiloxane/methylvinylsiloxane copolymer with trimethylsiloxy groups endblocked at both molecular chain ends, dimethylsiloxane/diphenylsiloxane/methylvinylsiloxane endblocked with trimethylsiloxy groups at both molecular chain ends. Examples include copolymers, dimethylsiloxane/diphenylsiloxane copolymers with dimethylvinylsiloxy groups endblocked at both molecular chain ends, and component (B) can be used alone or in combination of two or more.
（Ｂ）成分は、１００ｇあたりビニル基などのアルケニル基を、好ましくは０．１０～０．９０モル、より好ましくは０．２０～０．５０モル有する。このような（Ｂ）成分は、付加反応（架橋）し得るアルケニル基を十分に有するので、これが与える硬化物は、高硬度かつ高強度となる。
また、（Ｂ）成分は、２５℃における粘度が５～３０００ｍＰａ・ｓであることが好ましく、１０～２０００ｍＰａ・ｓであることがより好ましい。このような（Ｂ）成分は、室温で良好な流動性を示し、組成物の調製が容易で、基板に塗布する際に適度な粘度を有し、作業性に優れる。
本発明では、２５℃における粘度は、ＪＩＳ－Ｋ７１１７－１：１９９９に準拠しＢ型回転粘度計を用いて測定すればよい。 Component (B) preferably has 0.10 to 0.90 mol, more preferably 0.20 to 0.50 mol of alkenyl groups such as vinyl groups per 100 g. Since such component (B) has sufficient alkenyl groups capable of addition reaction (crosslinking), the cured product provided by this component has high hardness and high strength.
Furthermore, the viscosity of component (B) at 25° C. is preferably 5 to 3000 mPa·s, more preferably 10 to 2000 mPa·s. Component (B) exhibits good fluidity at room temperature, is easy to prepare as a composition, has appropriate viscosity when applied to a substrate, and has excellent workability.
In the present invention, the viscosity at 25° C. may be measured using a B-type rotational viscometer in accordance with JIS-K7117-1:1999.
また、（Ｂ）成分は、２５℃における粘度が５～３０００ｍＰａ・ｓであることが好ましく、１０～２０００ｍＰａ・ｓであることがより好ましい。このような（Ｂ）成分は、室温で良好な流動性を示し、組成物の調製が容易で、基板に塗布する際に適度な粘度を有し、作業性に優れる。
本発明では、２５℃における粘度は、ＪＩＳ－Ｋ７１１７－１：１９９９に準拠しＢ型回転粘度計を用いて測定すればよい。 Component (B) preferably has 0.10 to 0.90 mol, more preferably 0.20 to 0.50 mol of alkenyl groups such as vinyl groups per 100 g. Since such component (B) has sufficient alkenyl groups capable of addition reaction (crosslinking), the cured product provided by this component has high hardness and high strength.
Furthermore, the viscosity of component (B) at 25° C. is preferably 5 to 3000 mPa·s, more preferably 10 to 2000 mPa·s. Component (B) exhibits good fluidity at room temperature, is easy to prepare as a composition, has appropriate viscosity when applied to a substrate, and has excellent workability.
In the present invention, the viscosity at 25° C. may be measured using a B-type rotational viscometer in accordance with JIS-K7117-1:1999.
（Ｂ）成分としては、下記式（３）で表される化合物、即ち、直鎖状のオルガノポリシロキサンであることが好ましい。
（式中、Ｒ４は独立に非置換または置換の１価炭化水素基であり、Ｒ５は独立にメチル基又はフェニル基であり、ａは０～５０の整数であり、ｂは０～１００の整数である。ただし、ａが０のときＲ５はフェニル基であり、かつ、ｂは１～１００である。括弧が付されたシロキサン単位の配列順は任意である。）
Component (B) is preferably a compound represented by the following formula (3), that is, a linear organopolysiloxane.
(In the formula, R 4 is independently an unsubstituted or substituted monovalent hydrocarbon group, R 5 is independently a methyl group or a phenyl group, a is an integer from 0 to 50, and b is an integer from 0 to 100. is an integer of. However, when a is 0, R 5 is a phenyl group, and b is 1 to 100. The arrangement order of the siloxane units in parentheses is arbitrary.)
Ｒ４で表される非置換または置換の１価炭化水素基としては、脂肪族不飽和基、及び脂肪族不飽和基以外の１価炭化水素基が挙げられ、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、ｔ－ブチル基等の炭素原子数１～６のアルキル基；クロロメチル基、３，３，３－トリフルオロプロピル基等の炭素原子数１～４のハロアルキル基；フェニル基、トリル基等の炭素原子数６～１０のアリール基；ビニル基、アリル基などのアルケニル基が挙げられる。中でも、炭素原子数１～６のアルキル基、フェニル基、ビニル基が好ましく、特にメチル基が好ましい。
Examples of the unsubstituted or substituted monovalent hydrocarbon group represented by R 4 include aliphatic unsaturated groups and monovalent hydrocarbon groups other than aliphatic unsaturated groups, such as methyl group, ethyl group, Alkyl groups having 1 to 6 carbon atoms such as propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, t-butyl group; carbon atoms such as chloromethyl group and 3,3,3-trifluoropropyl group Examples include haloalkyl groups having 1 to 4 atoms; aryl groups having 6 to 10 carbon atoms such as phenyl and tolyl groups; alkenyl groups such as vinyl and allyl groups. Among these, alkyl groups having 1 to 6 carbon atoms, phenyl groups, and vinyl groups are preferred, and methyl groups are particularly preferred.
上記式（３）において、ａは０～５０の整数であり、１～１０であることが好ましく、１～７であることがより好ましく、２～４であることが更に好ましい。ｂは０～１００の整数であり、０～５０であることが好ましく、１～１０であることがより好ましく、２～４であることが更に好ましい。ただし、ａが０のときＲ５はフェニル基であり、かつ、ｂは１～１００である。括弧が付されたシロキサン単位の配列順は任意である。
In the above formula (3), a is an integer of 0 to 50, preferably 1 to 10, more preferably 1 to 7, and even more preferably 2 to 4. b is an integer from 0 to 100, preferably from 0 to 50, more preferably from 1 to 10, even more preferably from 2 to 4. However, when a is 0, R 5 is a phenyl group, and b is 1 to 100. The siloxane units in parentheses can be arranged in any order.
式（３）で表されるオルガノポリシロキサンは、例えば、ジクロロジフェニルシランやジアルコキシジフェニルシラン等の二官能性シランを加水分解・縮合させた後、または加水分解・縮合と同時に、脂肪族不飽和基を含有するシロキサン単位で末端を封鎖することにより得られる。
The organopolysiloxane represented by formula (3) can be produced by, for example, hydrolyzing and condensing a bifunctional silane such as dichlorodiphenylsilane or dialkoxydiphenylsilane, or simultaneously with aliphatic unsaturation. It is obtained by capping the ends with group-containing siloxane units.
（Ｂ）成分の配合量は、組成物中の脂肪族不飽和基に対するＳｉＨ基のモル比（ＳｉＨ基／脂肪族不飽和基）が０．５以上５以下であるようにすることができ、好ましくは０．８以上２以下となる量である。前記モル比（ＳｉＨ基／脂肪族不飽和基）が０．５以上５以下であれば、本発明の組成物を十分に硬化させることができる。
The blending amount of component (B) can be such that the molar ratio of SiH groups to aliphatic unsaturated groups in the composition (SiH groups/aliphatic unsaturated groups) is 0.5 or more and 5 or less, The amount is preferably 0.8 or more and 2 or less. When the molar ratio (SiH group/aliphatic unsaturated group) is 0.5 or more and 5 or less, the composition of the present invention can be sufficiently cured.
［（Ｃ）成分］
本発明の（Ｃ）成分であるヒドロシリル化反応触媒は、上記（Ａ）成分の調製に用いられるものと同様のものが使用できる。 [(C) Component]
The hydrosilylation reaction catalyst which is component (C) of the present invention can be the same as that used in the preparation of component (A) above.
本発明の（Ｃ）成分であるヒドロシリル化反応触媒は、上記（Ａ）成分の調製に用いられるものと同様のものが使用できる。 [(C) Component]
The hydrosilylation reaction catalyst which is component (C) of the present invention can be the same as that used in the preparation of component (A) above.
本発明の低誘電率絶縁性コーティング組成物への（Ｃ）成分の配合量は、反応促進および硬化物の着色防止の点から組成物全体の質量に対して、白金族金属原子として１～５００ｐｐｍが好ましく、より好ましくは１～１００ｐｐｍ程度、さらに好ましくは２～１２ｐｐｍとなる量である。
The amount of component (C) added to the low dielectric constant insulating coating composition of the present invention is 1 to 500 ppm as platinum group metal atoms based on the mass of the entire composition from the viewpoint of accelerating the reaction and preventing coloring of the cured product. The amount is preferably about 1 to 100 ppm, and even more preferably 2 to 12 ppm.
［その他の成分］
低誘電率絶縁性コーティング組成物には、上記（Ａ）～（Ｃ）成分に加え、必要に応じて酸化防止剤、無機充填剤等の成分を配合してもよい。 [Other ingredients]
In addition to the above-mentioned components (A) to (C), components such as an antioxidant and an inorganic filler may be added to the low dielectric constant insulating coating composition, if necessary.
低誘電率絶縁性コーティング組成物には、上記（Ａ）～（Ｃ）成分に加え、必要に応じて酸化防止剤、無機充填剤等の成分を配合してもよい。 [Other ingredients]
In addition to the above-mentioned components (A) to (C), components such as an antioxidant and an inorganic filler may be added to the low dielectric constant insulating coating composition, if necessary.
［酸化防止剤］
本発明の低誘電率絶縁性コーティング組成物の硬化物中には、上記（Ｂ）成分中の付加反応性炭素－炭素二重結合が未反応のまま残存している場合があり、それが大気中の酸素により酸化されることで硬化物が着色する原因となり得る。そこで、必要に応じ、本発明の低誘電率絶縁性コーティング組成物に酸化防止剤を配合することにより、このような着色を未然に防止することができる。 [Antioxidant]
In the cured product of the low dielectric constant insulating coating composition of the present invention, the addition-reactive carbon-carbon double bond in the component (B) may remain unreacted, and it may be exposed to the air. Oxidation due to the oxygen inside may cause the cured product to become discolored. Therefore, such coloring can be prevented by adding an antioxidant to the low dielectric constant insulating coating composition of the present invention, if necessary.
本発明の低誘電率絶縁性コーティング組成物の硬化物中には、上記（Ｂ）成分中の付加反応性炭素－炭素二重結合が未反応のまま残存している場合があり、それが大気中の酸素により酸化されることで硬化物が着色する原因となり得る。そこで、必要に応じ、本発明の低誘電率絶縁性コーティング組成物に酸化防止剤を配合することにより、このような着色を未然に防止することができる。 [Antioxidant]
In the cured product of the low dielectric constant insulating coating composition of the present invention, the addition-reactive carbon-carbon double bond in the component (B) may remain unreacted, and it may be exposed to the air. Oxidation due to the oxygen inside may cause the cured product to become discolored. Therefore, such coloring can be prevented by adding an antioxidant to the low dielectric constant insulating coating composition of the present invention, if necessary.
酸化防止剤としては、公知のものを使用することができ、例えば、２，６－ジ－ｔ－ブチル－４－メチルフェノール、２，５－ジ－ｔ－アミルヒドロキノン、２，５－ジ－ｔ－ブチルヒドロキノン、４，４’－ブチリデンビス（３－メチル－６－ｔ－ブチルフェノール）、２，２’－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、２，２’－メチレンビス（４－エチル－６－ｔ－ブチルフェノール）等が挙げられる。これらは、１種単独でも２種以上を組み合わせても使用することができる。
As the antioxidant, known antioxidants can be used, such as 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-amylhydroquinone, and 2,5-di-t-amylhydroquinone. t-Butylhydroquinone, 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4- ethyl-6-t-butylphenol) and the like. These can be used alone or in combination of two or more.
なお、この酸化防止剤を使用する場合、その配合量は特に制限されないが、上記（Ａ）成分と（Ｂ）成分との合計質量に対して、通常、１～１０，０００ｐｐｍ、特に、１０～１，０００ｐｐｍ程度配合することが好ましい。前記範囲内の配合量とすることによって、酸化防止能力が十分発揮され、着色、白濁、酸化劣化等の発生がなく光学的特性に優れた硬化物が得られる。
In addition, when using this antioxidant, its blending amount is not particularly limited, but it is usually 1 to 10,000 ppm, particularly 10 to 10,000 ppm, based on the total mass of components (A) and (B). It is preferable to add about 1,000 ppm. By incorporating the amount within the above range, the antioxidant ability is fully exhibited, and a cured product with excellent optical properties without coloration, cloudiness, oxidative deterioration, etc. can be obtained.
［無機充填剤］
本発明の低誘電率絶縁性コーティング組成物の粘度や、本発明の低誘電率絶縁性コーティング組成物から得られる硬化物の硬度等を調整したり、強度を向上させたり、蛍光体の分散を良くするために、ナノシリカや、溶融シリカ、結晶性シリカ、酸化チタン、ナノアルミナ、アルミナ等の無機充填剤を添加しても良い。 [Inorganic filler]
The viscosity of the low dielectric constant insulating coating composition of the present invention, the hardness of the cured product obtained from the low dielectric constant insulating coating composition of the present invention, etc. can be adjusted, the strength can be improved, and the dispersion of the phosphor can be controlled. To improve the quality, inorganic fillers such as nanosilica, fused silica, crystalline silica, titanium oxide, nanoalumina, alumina, etc. may be added.
本発明の低誘電率絶縁性コーティング組成物の粘度や、本発明の低誘電率絶縁性コーティング組成物から得られる硬化物の硬度等を調整したり、強度を向上させたり、蛍光体の分散を良くするために、ナノシリカや、溶融シリカ、結晶性シリカ、酸化チタン、ナノアルミナ、アルミナ等の無機充填剤を添加しても良い。 [Inorganic filler]
The viscosity of the low dielectric constant insulating coating composition of the present invention, the hardness of the cured product obtained from the low dielectric constant insulating coating composition of the present invention, etc. can be adjusted, the strength can be improved, and the dispersion of the phosphor can be controlled. To improve the quality, inorganic fillers such as nanosilica, fused silica, crystalline silica, titanium oxide, nanoalumina, alumina, etc. may be added.
無機充填剤を使用する場合の配合量は、上記（Ａ）成分と（Ｂ）の合計１００質量部に対し、好ましくは５～５００質量部であり、より好ましくは、１０～２００質量部である。このような配合量であると、本発明の低誘電率絶縁性コーティング組成物は取扱い易く、その硬化物の硬度や、強度は望ましいものとなる。
When using an inorganic filler, the blending amount is preferably 5 to 500 parts by mass, more preferably 10 to 200 parts by mass, based on the total of 100 parts by mass of components (A) and (B). . With such a blending amount, the low dielectric constant insulating coating composition of the present invention is easy to handle, and the hardness and strength of the cured product thereof are desirable.
［接着性向上剤］
本発明の低誘電率絶縁性コーティング組成物には、接着性向上剤を配合してもよい。接着性向上剤としては、シランカップリング剤やそのオリゴマー、シランカップリング剤と同様の反応性基を有するポリシロキサン等が例示される。 [Adhesion improver]
The low dielectric constant insulating coating composition of the present invention may contain an adhesion improver. Examples of the adhesion improver include a silane coupling agent, an oligomer thereof, and a polysiloxane having the same reactive group as the silane coupling agent.
本発明の低誘電率絶縁性コーティング組成物には、接着性向上剤を配合してもよい。接着性向上剤としては、シランカップリング剤やそのオリゴマー、シランカップリング剤と同様の反応性基を有するポリシロキサン等が例示される。 [Adhesion improver]
The low dielectric constant insulating coating composition of the present invention may contain an adhesion improver. Examples of the adhesion improver include a silane coupling agent, an oligomer thereof, and a polysiloxane having the same reactive group as the silane coupling agent.
接着性向上剤は、下記式（４）で表される化合物や、有機官能基としてアリルイソシアヌレート構造を有するシランカップリング剤が好ましい。
（式中、ｓは１～３の整数であり、ｔは０～３の整数であり、ｕは０～３の整数であり、但しｓ＋ｔ＋ｕは４～５の整数である。括弧が付されたシロキサン単位の配列順は任意である。）
The adhesion improver is preferably a compound represented by the following formula (4) or a silane coupling agent having an allyl isocyanurate structure as an organic functional group.
(In the formula, s is an integer from 1 to 3, t is an integer from 0 to 3, and u is an integer from 0 to 3, provided that s+t+u is an integer from 4 to 5. The arrangement order of the siloxane units is arbitrary.)
有機官能基としてアリルイソシアヌレート構造を有するシランカップリング剤としては以下の式（５）で表される化合物を挙げることができる。ただし、式中のＲ、Ｒ’は下記式においてのみ適用されるものとする。
（式中、少なくとも１つのＲ’はアリル基であり、その他は水素原子、アルキル基、シクロアルキル基、アリール基、ヘテロアリール基、非芳香族複素環式環、（ＣＨ２）３Ｓｉ（ＯＲ）３又はアリル基であり、Ｒは、アルキル基、シクロアルキル基、アリール基、ヘテロアリール基、非芳香族複素環式環、又はアリル基である。）
Examples of the silane coupling agent having an allyl isocyanurate structure as an organic functional group include a compound represented by the following formula (5). However, R and R' in the formula shall be applied only to the following formula.
(In the formula, at least one R' is an allyl group, and the others are hydrogen atoms, alkyl groups, cycloalkyl groups, aryl groups, heteroaryl groups, non-aromatic heterocyclic rings, (CH 2 ) 3 Si(OR ) 3 or an allyl group, and R is an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, a non-aromatic heterocyclic ring, or an allyl group.)
上記式中のＲは、Ｃ１～４のアルキル基が好ましく、メチル基又はエチル基がより好ましい。Ｒ’は、（ＣＨ２）３Ｓｉ（ＯＲ）３又はアリル基が好ましい。
R in the above formula is preferably a C1-4 alkyl group, more preferably a methyl group or an ethyl group. R' is preferably (CH 2 ) 3 Si(OR) 3 or an allyl group.
アリルイソシアヌレート構造を有するシランカップリング剤の具体例としては、Ｘ－１２－１２９０（信越化学工業株式会社製）や、下記式で表される化合物を挙げることができる。
Specific examples of the silane coupling agent having an allyl isocyanurate structure include X-12-1290 (manufactured by Shin-Etsu Chemical Co., Ltd.) and compounds represented by the following formula.
接着性向上剤の好適な具体例としては、下記式で表されるものが挙げられるが、これらに限定されるものではない。接着性向上剤は市販品であってもよい。
Preferred specific examples of the adhesion improver include those represented by the following formulas, but are not limited thereto. The adhesion improver may be a commercially available product.
接着性向上剤は、本発明の低誘電率絶縁性コーティング組成物及びその硬化物の基材に対する接着性を向上させるために組成物に配合される任意成分である。ここで、基材とは、金、銀、銅、ニッケルなどの金属材料、酸化アルミニウム、窒化アルミニウム、酸化チタンなどのセラミック材料、シリコーン樹脂、エポキシ樹脂などの高分子材料を指す。接着性向上剤は、１種単独でも２種以上を組み合わせても使用することができる。
The adhesion improver is an optional component that is added to the low dielectric constant insulating coating composition of the present invention and its cured product to improve the adhesion to the substrate. Here, the base material refers to metal materials such as gold, silver, copper, and nickel, ceramic materials such as aluminum oxide, aluminum nitride, and titanium oxide, and polymeric materials such as silicone resin and epoxy resin. The adhesion improvers can be used alone or in combination of two or more.
接着性向上剤を使用する場合の配合量は、上記（Ａ）成分と（Ｂ）の合計１００質量部に対し、好ましくは１～３０質量部であり、より好ましくは、１～１０質量部である。このような配合量であると、本発明の低誘電率絶縁性コーティング組成物及びその硬化物は、基材に対する接着性が効果的に向上し、また、着色が起こりにくい。
When using an adhesion improver, the blending amount is preferably 1 to 30 parts by mass, more preferably 1 to 10 parts by mass, based on the total of 100 parts by mass of components (A) and (B). be. With such a blending amount, the low dielectric constant insulating coating composition of the present invention and its cured product effectively improve the adhesion to the substrate, and are less likely to be colored.
［その他］
また、ポットライフを確保するために、１－エチニルシクロヘキサノール、３，５－ジメチル－１－ヘキシン－３－オール等の付加反応制御剤を配合することができる。 [others]
Further, in order to ensure pot life, addition reaction control agents such as 1-ethynylcyclohexanol and 3,5-dimethyl-1-hexyn-3-ol can be added.
また、ポットライフを確保するために、１－エチニルシクロヘキサノール、３，５－ジメチル－１－ヘキシン－３－オール等の付加反応制御剤を配合することができる。 [others]
Further, in order to ensure pot life, addition reaction control agents such as 1-ethynylcyclohexanol and 3,5-dimethyl-1-hexyn-3-ol can be added.
更に、太陽光線、蛍光灯等の光エネルギーによる光劣化に抵抗性を付与するため光安定剤を用いることも可能である。この光安定剤としては、光酸化劣化で生成するラジカルを捕捉するヒンダードアミン系安定剤が適しており、酸化防止剤と併用することで、酸化防止効果はより向上する。光安定剤の具体例としては、ビス（２，２，６，６－テトラメチル－４－ピペリジル）セバケート、４－ベンゾイル－２，２，６，６－テトラメチルピペリジン等が挙げられる。
Furthermore, it is also possible to use a light stabilizer to impart resistance to photodeterioration caused by light energy such as sunlight and fluorescent lamps. As this light stabilizer, a hindered amine stabilizer that captures radicals generated by photooxidative deterioration is suitable, and when used in combination with an antioxidant, the antioxidant effect is further improved. Specific examples of the light stabilizer include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, 4-benzoyl-2,2,6,6-tetramethylpiperidine, and the like.
本発明の低誘電率絶縁性コーティング組成物中、（Ａ）、（Ｂ）および（Ｃ）成分の合計量は５０～１００質量％であることが好ましく、８０～１００質量％であることがより好ましく、９０～１００質量％であることが更に好ましい。
また、本発明の低誘電率絶縁性コーティング組成物は、上述した各成分を均一になるよう混合することにより製造することができる。 In the low dielectric constant insulating coating composition of the present invention, the total amount of components (A), (B) and (C) is preferably 50 to 100% by mass, more preferably 80 to 100% by mass. It is preferably 90 to 100% by mass, and more preferably 90 to 100% by mass.
Further, the low dielectric constant insulating coating composition of the present invention can be produced by uniformly mixing the above-mentioned components.
また、本発明の低誘電率絶縁性コーティング組成物は、上述した各成分を均一になるよう混合することにより製造することができる。 In the low dielectric constant insulating coating composition of the present invention, the total amount of components (A), (B) and (C) is preferably 50 to 100% by mass, more preferably 80 to 100% by mass. It is preferably 90 to 100% by mass, and more preferably 90 to 100% by mass.
Further, the low dielectric constant insulating coating composition of the present invention can be produced by uniformly mixing the above-mentioned components.
本発明の低誘電率絶縁性コーティング組成物は、上記成分を含むものであるが、これまでこのような組成物が後述するような優れた機械的強度と低い誘電特性値（誘電率と誘電正接）を合わせ持つ硬化物を与えるとは全く知られておらず、予測もされていなかった。
例えば、上述したように特許文献２にはケイ素原子に結合した水素原子を１分子中に３個以上有する化合物と、アルケニル基を１分子中に２個以上有するオルガノシロキサンと、ヒドロシリル化触媒とを含む硬化性組成物が記載されているが、その用途は、耐熱性が要求される白色ＬＥＤ用封止材として利用できる硬化性組成物である。上記文献では、この硬化性組成物は、硬度、機械的強度、および耐クラック性が高く、短波長領域の光透過性、ガスバリア性に優れた硬化物を与えることができるとされているが、硬化物の誘電特性については全く言及していない。 The low dielectric constant insulating coating composition of the present invention contains the above components, but hitherto such compositions have shown excellent mechanical strength and low dielectric property values (permittivity and dielectric loss tangent) as described below. It was not known or predicted that it would give a cured product with this combination.
For example, as mentioned above, Patent Document 2 describes a compound having three or more hydrogen atoms bonded to a silicon atom in one molecule, an organosiloxane having two or more alkenyl groups in one molecule, and a hydrosilylation catalyst. A curable composition containing the above is described, and its use is as a curable composition that can be used as an encapsulant for white LEDs that require heat resistance. The above literature states that this curable composition has high hardness, mechanical strength, and crack resistance, and can provide a cured product with excellent light transmittance in the short wavelength region and gas barrier properties. No mention is made of the dielectric properties of the cured product.
例えば、上述したように特許文献２にはケイ素原子に結合した水素原子を１分子中に３個以上有する化合物と、アルケニル基を１分子中に２個以上有するオルガノシロキサンと、ヒドロシリル化触媒とを含む硬化性組成物が記載されているが、その用途は、耐熱性が要求される白色ＬＥＤ用封止材として利用できる硬化性組成物である。上記文献では、この硬化性組成物は、硬度、機械的強度、および耐クラック性が高く、短波長領域の光透過性、ガスバリア性に優れた硬化物を与えることができるとされているが、硬化物の誘電特性については全く言及していない。 The low dielectric constant insulating coating composition of the present invention contains the above components, but hitherto such compositions have shown excellent mechanical strength and low dielectric property values (permittivity and dielectric loss tangent) as described below. It was not known or predicted that it would give a cured product with this combination.
For example, as mentioned above, Patent Document 2 describes a compound having three or more hydrogen atoms bonded to a silicon atom in one molecule, an organosiloxane having two or more alkenyl groups in one molecule, and a hydrosilylation catalyst. A curable composition containing the above is described, and its use is as a curable composition that can be used as an encapsulant for white LEDs that require heat resistance. The above literature states that this curable composition has high hardness, mechanical strength, and crack resistance, and can provide a cured product with excellent light transmittance in the short wavelength region and gas barrier properties. No mention is made of the dielectric properties of the cured product.
低誘電率のシリコーンコーティングに関しては、以下のような技術が知られている。
１）メチルおよびフェニル基を有するシリコーン樹脂と、α，ω－ヒドロキシル化末端を有するポリジメチルシロキサンとを溶媒中に溶解したシリコーン組成物を、コーティングし、加熱することにより、シリコーン樹脂の残留－ＯＨ基の縮合によって、フィルムが架橋すると共に、「犠牲」シリコーンオイルの熱分解により、細孔が層の内部に生じることを利用する。フィルムのバルク全体に分布する細孔によってエポキシ基を有するシルセスキオキサンがもたらされる（特表２００９－５０５８１１号公報）。
２）エポキシ基を有するシルセスキオキサンと硬化剤を含む組成物を硬化することにより低誘電率の硬化物を得る（特開２００７－３３２２１１号公報）。
３）シリコーン系ポリマーに固形添加剤が分散されてなる低誘電率材料（シリコーン系ポリマーと固形添加剤との界面に空間が形成された構造を有する）により、硬化物は従来の材料に比べて低い誘電率を実現する（特開２０１０－００３７６１号公報）。 Regarding low dielectric constant silicone coatings, the following techniques are known.
1) By coating and heating a silicone composition in which a silicone resin having methyl and phenyl groups and polydimethylsiloxane having an α,ω-hydroxylated end are dissolved in a solvent, residual -OH of the silicone resin is removed. The condensation of the groups crosslinks the film, and the thermal decomposition of the "sacrificial" silicone oil takes advantage of the creation of pores inside the layer. Silsesquioxane having epoxy groups is produced by the pores distributed throughout the bulk of the film (Japanese Patent Publication No. 2009-505811).
2) A cured product with a low dielectric constant is obtained by curing a composition containing a silsesquioxane having an epoxy group and a curing agent (Japanese Unexamined Patent Publication No. 2007-332211).
3) Due to the low dielectric constant material made by dispersing a solid additive in a silicone polymer (having a structure in which a space is formed at the interface between the silicone polymer and the solid additive), the cured product has a higher dielectric strength than conventional materials. Realizes a low dielectric constant (Japanese Patent Application Laid-Open No. 2010-003761).
１）メチルおよびフェニル基を有するシリコーン樹脂と、α，ω－ヒドロキシル化末端を有するポリジメチルシロキサンとを溶媒中に溶解したシリコーン組成物を、コーティングし、加熱することにより、シリコーン樹脂の残留－ＯＨ基の縮合によって、フィルムが架橋すると共に、「犠牲」シリコーンオイルの熱分解により、細孔が層の内部に生じることを利用する。フィルムのバルク全体に分布する細孔によってエポキシ基を有するシルセスキオキサンがもたらされる（特表２００９－５０５８１１号公報）。
２）エポキシ基を有するシルセスキオキサンと硬化剤を含む組成物を硬化することにより低誘電率の硬化物を得る（特開２００７－３３２２１１号公報）。
３）シリコーン系ポリマーに固形添加剤が分散されてなる低誘電率材料（シリコーン系ポリマーと固形添加剤との界面に空間が形成された構造を有する）により、硬化物は従来の材料に比べて低い誘電率を実現する（特開２０１０－００３７６１号公報）。 Regarding low dielectric constant silicone coatings, the following techniques are known.
1) By coating and heating a silicone composition in which a silicone resin having methyl and phenyl groups and polydimethylsiloxane having an α,ω-hydroxylated end are dissolved in a solvent, residual -OH of the silicone resin is removed. The condensation of the groups crosslinks the film, and the thermal decomposition of the "sacrificial" silicone oil takes advantage of the creation of pores inside the layer. Silsesquioxane having epoxy groups is produced by the pores distributed throughout the bulk of the film (Japanese Patent Publication No. 2009-505811).
2) A cured product with a low dielectric constant is obtained by curing a composition containing a silsesquioxane having an epoxy group and a curing agent (Japanese Unexamined Patent Publication No. 2007-332211).
3) Due to the low dielectric constant material made by dispersing a solid additive in a silicone polymer (having a structure in which a space is formed at the interface between the silicone polymer and the solid additive), the cured product has a higher dielectric strength than conventional materials. Realizes a low dielectric constant (Japanese Patent Application Laid-Open No. 2010-003761).
このように、従来は、低誘電率のシリコーンコーティングを得るために、コーティング内の細孔（空隙）を設けたり、かご型構造のシルセスキオキサンを用いたりするため、コーティングそのものの密度が低下し、高硬度のコーティングは得られていなかった。そして、その誘電率及び誘電正接は、ギガヘルツ高周波領域で伝送損失の少ない材料として要求される特性を満足するものではなかった。
Conventionally, in order to obtain a silicone coating with a low dielectric constant, pores (voids) were created within the coating or silsesquioxane with a cage-like structure was used, which resulted in a decrease in the density of the coating itself. However, a coating with high hardness was not obtained. The dielectric constant and dielectric loss tangent did not satisfy the characteristics required as a material with low transmission loss in the gigahertz high frequency range.
一般に、ＧＨｚ帯では分極による双極子が電場に応答し誘電が引き起こされることが知られている。このため、ＧＨｚ帯における低誘電特性化には、構造中から分極を減らすことがポイントとなる。
誘電率は下記Ｃｌａｕｓｉｕｓ－Ｍｏｓｓｏｔｔｉの式で示され、モル分極率、モル容積が因子となる。このことから、分極を小さくすること、モル容積を大きくすることが低誘電率化においてポイントとなっている。 It is generally known that in the GHz band, dipoles due to polarization respond to an electric field, causing dielectricity. Therefore, the key to achieving low dielectric characteristics in the GHz band is to reduce polarization from within the structure.
The dielectric constant is expressed by the Clausius-Mossotti equation below, in which molar polarizability and molar volume are factors. For this reason, it is important to reduce the polarization and increase the molar volume in order to lower the dielectric constant.
誘電率は下記Ｃｌａｕｓｉｕｓ－Ｍｏｓｓｏｔｔｉの式で示され、モル分極率、モル容積が因子となる。このことから、分極を小さくすること、モル容積を大きくすることが低誘電率化においてポイントとなっている。 It is generally known that in the GHz band, dipoles due to polarization respond to an electric field, causing dielectricity. Therefore, the key to achieving low dielectric characteristics in the GHz band is to reduce polarization from within the structure.
The dielectric constant is expressed by the Clausius-Mossotti equation below, in which molar polarizability and molar volume are factors. For this reason, it is important to reduce the polarization and increase the molar volume in order to lower the dielectric constant.
誘電率＝［１＋２（ΣＰｍ／ΣＶｍ）］／［１－（ΣＰｍ／ΣＶｍ）］
（Ｐｍ：原子団のモル分極率，Ｖｍ：原子団のモル容積） Dielectric constant = [1+2(ΣPm/ΣVm)]/[1-(ΣPm/ΣVm)]
(Pm: molar polarizability of the atomic group, Vm: molar volume of the atomic group)
（Ｐｍ：原子団のモル分極率，Ｖｍ：原子団のモル容積） Dielectric constant = [1+2(ΣPm/ΣVm)]/[1-(ΣPm/ΣVm)]
(Pm: molar polarizability of the atomic group, Vm: molar volume of the atomic group)
また、誘電正接（ｔａｎδ）は交流電場に対する誘電応答の遅れであり、ＧＨｚ帯では双極子の配向緩和が主たる要因となる。このため、誘電正接を小さくするためには、双極子をなくす（無極性に近い構造とする）方法が考えられる。
従って、低誘電特性の観点からは、コーティングは、その構造中から分極を減らすと共に、双極子を可能な限り減らす（無極性に近い構造とする）ことが求められる。 Further, the dielectric loss tangent (tan δ) is a delay in dielectric response to an alternating current electric field, and in the GHz band, dipole orientation relaxation is the main factor. Therefore, in order to reduce the dielectric loss tangent, a method of eliminating the dipole (creating a nearly non-polar structure) can be considered.
Therefore, from the viewpoint of low dielectric properties, the coating is required to reduce polarization in its structure and to reduce dipoles as much as possible (to make the structure nearly non-polar).
従って、低誘電特性の観点からは、コーティングは、その構造中から分極を減らすと共に、双極子を可能な限り減らす（無極性に近い構造とする）ことが求められる。 Further, the dielectric loss tangent (tan δ) is a delay in dielectric response to an alternating current electric field, and in the GHz band, dipole orientation relaxation is the main factor. Therefore, in order to reduce the dielectric loss tangent, a method of eliminating the dipole (creating a nearly non-polar structure) can be considered.
Therefore, from the viewpoint of low dielectric properties, the coating is required to reduce polarization in its structure and to reduce dipoles as much as possible (to make the structure nearly non-polar).
この点、特許文献２に記載の付加硬化型硬化性組成物は、ＳｉＨ基に由来するシラノール基（分極をもたらす）が残留して、誘電正接を小さくする恐れがあるため、低誘電率絶縁性コーティング組成物が得られることは全く予測できなかった。また、上記硬化性組成物は、硬度、機械的強度、および耐クラック性が高い硬化物を与えることから、コーティングの密度が高く、誘電率が低くなるとは全く予測できなかった。
本発明は、このような予測に反して、硬化して得られる硬化物が、高い機械的強度ならびに低い比誘電率および誘電正接を両立できることを本発明者らが見出したことによって初めて達成された。 In this regard, the addition-curable curable composition described in Patent Document 2 has a low dielectric constant insulation property because silanol groups derived from SiH groups (which cause polarization) may remain and reduce the dielectric loss tangent. It was completely unexpected that a coating composition would be obtained. Moreover, since the above-mentioned curable composition provides a cured product with high hardness, mechanical strength, and crack resistance, it was completely unexpected that the coating would have a high density and a low dielectric constant.
The present invention was achieved for the first time when the present inventors discovered that, contrary to such predictions, the cured product obtained by curing can have both high mechanical strength and low relative dielectric constant and dielectric loss tangent. .
本発明は、このような予測に反して、硬化して得られる硬化物が、高い機械的強度ならびに低い比誘電率および誘電正接を両立できることを本発明者らが見出したことによって初めて達成された。 In this regard, the addition-curable curable composition described in Patent Document 2 has a low dielectric constant insulation property because silanol groups derived from SiH groups (which cause polarization) may remain and reduce the dielectric loss tangent. It was completely unexpected that a coating composition would be obtained. Moreover, since the above-mentioned curable composition provides a cured product with high hardness, mechanical strength, and crack resistance, it was completely unexpected that the coating would have a high density and a low dielectric constant.
The present invention was achieved for the first time when the present inventors discovered that, contrary to such predictions, the cured product obtained by curing can have both high mechanical strength and low relative dielectric constant and dielectric loss tangent. .
［硬化物］
本発明の低誘電率絶縁性コーティング組成物を硬化して本発明の硬化物とする。前記硬化物は、機械的強度に優れ、低い比誘電率および誘電正接を有する。なお、本発明の低誘電率絶縁性コーティング組成物の硬化条件については、特に制限されないが、６０～１８０℃、５～１８０分の条件とすることが好ましい。 [Cured product]
The low dielectric constant insulating coating composition of the present invention is cured to obtain the cured product of the present invention. The cured product has excellent mechanical strength, low dielectric constant, and low dielectric loss tangent. Note that the curing conditions for the low dielectric constant insulating coating composition of the present invention are not particularly limited, but preferably conditions are 60 to 180°C and 5 to 180 minutes.
本発明の低誘電率絶縁性コーティング組成物を硬化して本発明の硬化物とする。前記硬化物は、機械的強度に優れ、低い比誘電率および誘電正接を有する。なお、本発明の低誘電率絶縁性コーティング組成物の硬化条件については、特に制限されないが、６０～１８０℃、５～１８０分の条件とすることが好ましい。 [Cured product]
The low dielectric constant insulating coating composition of the present invention is cured to obtain the cured product of the present invention. The cured product has excellent mechanical strength, low dielectric constant, and low dielectric loss tangent. Note that the curing conditions for the low dielectric constant insulating coating composition of the present invention are not particularly limited, but preferably conditions are 60 to 180°C and 5 to 180 minutes.
本発明の低誘電率絶縁性コーティング組成物を硬化して得られる硬化物は、１０ＧＨｚにおける比誘電率が３．０以下、かつ、誘電正接が０．０１以下であることが好ましい。このような範囲であれば、高周波誘電特性に優れる。硬化物の１０ＧＨｚにおける比誘電率も誘電正接もその下限は低ければ低いほど良く、特に限定されないが、比誘電率は例えば１．５以上、誘電正接は例えば０．０００２以上であればよい。
なお、硬化物の１０ＧＨｚにおける比誘電率および誘電正接はＪＩＳ Ｃ２５６５に準拠して空洞共振器法により測定できる。例えば、空洞共振器誘電率測定装置（（株）ＡＥＴ社製）を用いて、０．３ｍｍ厚の硬化物の１０ＧＨｚにおける比誘電率および誘電正接を測定すればよい。 The cured product obtained by curing the low dielectric constant insulating coating composition of the present invention preferably has a dielectric constant of 3.0 or less at 10 GHz and a dielectric loss tangent of 0.01 or less. Within this range, high frequency dielectric properties are excellent. The lower the lower limits of the dielectric constant and the dielectric loss tangent at 10 GHz of the cured product, the better, and there are no particular limitations, but the dielectric constant may be, for example, 1.5 or more, and the dielectric loss tangent, for example, 0.0002 or more.
Note that the relative permittivity and dielectric loss tangent of the cured product at 10 GHz can be measured by the cavity resonator method in accordance with JIS C2565. For example, the dielectric constant and dielectric loss tangent of a 0.3 mm thick cured product at 10 GHz may be measured using a cavity resonator dielectric constant measuring device (manufactured by AET Co., Ltd.).
なお、硬化物の１０ＧＨｚにおける比誘電率および誘電正接はＪＩＳ Ｃ２５６５に準拠して空洞共振器法により測定できる。例えば、空洞共振器誘電率測定装置（（株）ＡＥＴ社製）を用いて、０．３ｍｍ厚の硬化物の１０ＧＨｚにおける比誘電率および誘電正接を測定すればよい。 The cured product obtained by curing the low dielectric constant insulating coating composition of the present invention preferably has a dielectric constant of 3.0 or less at 10 GHz and a dielectric loss tangent of 0.01 or less. Within this range, high frequency dielectric properties are excellent. The lower the lower limits of the dielectric constant and the dielectric loss tangent at 10 GHz of the cured product, the better, and there are no particular limitations, but the dielectric constant may be, for example, 1.5 or more, and the dielectric loss tangent, for example, 0.0002 or more.
Note that the relative permittivity and dielectric loss tangent of the cured product at 10 GHz can be measured by the cavity resonator method in accordance with JIS C2565. For example, the dielectric constant and dielectric loss tangent of a 0.3 mm thick cured product at 10 GHz may be measured using a cavity resonator dielectric constant measuring device (manufactured by AET Co., Ltd.).
硬化物の機械的強度（硬度、切断時伸び）については以下のように測定することができる。
（硬度）所定の厚さの硬化物を用いて、ＡＳＴＭ Ｄ ２２４０ に準じて硬度（ＳｈｏｒｅＤ）を２３℃で測定する。
（切断時伸び）所定の厚さの硬化物を用いて、ＪＩＳ－Ｋ－６２４９に準じて２３℃で測定する。 The mechanical strength (hardness, elongation at cutting) of the cured product can be measured as follows.
(Hardness) Using a cured product of a predetermined thickness, hardness (ShoreD) is measured at 23° C. according to ASTM D 2240.
(Elongation at cutting) Measure at 23°C using a cured product of a predetermined thickness according to JIS-K-6249.
（硬度）所定の厚さの硬化物を用いて、ＡＳＴＭ Ｄ ２２４０ に準じて硬度（ＳｈｏｒｅＤ）を２３℃で測定する。
（切断時伸び）所定の厚さの硬化物を用いて、ＪＩＳ－Ｋ－６２４９に準じて２３℃で測定する。 The mechanical strength (hardness, elongation at cutting) of the cured product can be measured as follows.
(Hardness) Using a cured product of a predetermined thickness, hardness (ShoreD) is measured at 23° C. according to ASTM D 2240.
(Elongation at cutting) Measure at 23°C using a cured product of a predetermined thickness according to JIS-K-6249.
本発明の低誘電率絶縁性コーティング組成物を各種基材、部品等に直接または他の層を介して塗布して該組成物を硬化させることにより、絶縁性コーティング層を形成することができる。また、本発明の低誘電率絶縁性コーティング組成物を硬化して得られる硬化物は透明性を有するため、表示装置としての用途に好適である。
An insulating coating layer can be formed by applying the low dielectric constant insulating coating composition of the present invention to various substrates, parts, etc. directly or via another layer and curing the composition. Further, since the cured product obtained by curing the low dielectric constant insulating coating composition of the present invention has transparency, it is suitable for use as a display device.
以下、実施例および比較例を示し、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、下記の例において、シロキサン単位を表す記号は以下のとおりである。
ＭＶｉ：（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２
ＭＶｉΦ：（ＣＨ２＝ＣＨ）（Ｃ６Ｈ５）（ＣＨ３）ＳｉＯ１／２
Ｄ２Φ：（Ｃ６Ｈ５）２ＳｉＯ２／２ EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples, but the present invention is not limited to the Examples below. In addition, in the following examples, the symbols representing siloxane units are as follows.
M Vi :( CH2 =CH)( CH3 )2SiO1 / 2
M ViΦ : ( CH2 =CH)( C6H5 )( CH3 ) SiO1 /2
D2Φ : ( C6H5 )2SiO2 / 2
ＭＶｉ：（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２
ＭＶｉΦ：（ＣＨ２＝ＣＨ）（Ｃ６Ｈ５）（ＣＨ３）ＳｉＯ１／２
Ｄ２Φ：（Ｃ６Ｈ５）２ＳｉＯ２／２ EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples, but the present invention is not limited to the Examples below. In addition, in the following examples, the symbols representing siloxane units are as follows.
M Vi :( CH2 =CH)( CH3 )2SiO1 / 2
M ViΦ : ( CH2 =CH)( C6H5 )( CH3 ) SiO1 /2
D2Φ : ( C6H5 )2SiO2 / 2
また、２５℃における粘度は、ＪＩＳ－Ｋ７１１７－１：１９９９に準拠しＢ型回転粘度計を用いて測定した。
Further, the viscosity at 25°C was measured using a B-type rotational viscometer in accordance with JIS-K7117-1:1999.
［合成例１］（Ａ）成分の調製
攪拌装置、冷却管、滴下ロートおよび温度計を備えた１Ｌの４つ口フラスコに、１，４－ビス（ジメチルシリル）ベンゼン（信越化学工業株式会社製）２６２．８ｇ（１．３５モル）、５％Ｐｔカーボン粉末（エヌ・イーケムキャット株式会社製）０．１２ｇを加え、オイルバスを用いて８５℃に加熱した。これにトリビニルフェニルシラン（信越化学工業株式会社製）を２８．０ｇ（０．１５モル）滴下した。滴下終了後、９０～１００℃の間で５時間撹拌した。撹拌後終了後２５℃に戻し、活性炭を２．９ｇ加え１時間撹拌した。撹拌後ろ過、減圧濃縮し、付加反応生成物９９．７ｇ（無色透明、収率８７％、２５℃における粘度：３０Ｐａ・ｓ）を得た。 [Synthesis Example 1] Preparation of component (A) 1,4-bis(dimethylsilyl)benzene (manufactured by Shin-Etsu Chemical Co., Ltd.) was placed in a 1L four-necked flask equipped with a stirrer, a cooling tube, a dropping funnel, and a thermometer. ) and 0.12 g of 5% Pt carbon powder (manufactured by N.E. Chemcat Co., Ltd.) were added, and the mixture was heated to 85° C. using an oil bath. To this, 28.0 g (0.15 mol) of trivinylphenylsilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise. After the addition was completed, the mixture was stirred at 90 to 100°C for 5 hours. After stirring, the temperature was returned to 25°C, 2.9 g of activated carbon was added, and the mixture was stirred for 1 hour. After stirring, the mixture was filtered and concentrated under reduced pressure to obtain 99.7 g of an addition reaction product (colorless and transparent, yield 87%, viscosity at 25°C: 30 Pa·s).
攪拌装置、冷却管、滴下ロートおよび温度計を備えた１Ｌの４つ口フラスコに、１，４－ビス（ジメチルシリル）ベンゼン（信越化学工業株式会社製）２６２．８ｇ（１．３５モル）、５％Ｐｔカーボン粉末（エヌ・イーケムキャット株式会社製）０．１２ｇを加え、オイルバスを用いて８５℃に加熱した。これにトリビニルフェニルシラン（信越化学工業株式会社製）を２８．０ｇ（０．１５モル）滴下した。滴下終了後、９０～１００℃の間で５時間撹拌した。撹拌後終了後２５℃に戻し、活性炭を２．９ｇ加え１時間撹拌した。撹拌後ろ過、減圧濃縮し、付加反応生成物９９．７ｇ（無色透明、収率８７％、２５℃における粘度：３０Ｐａ・ｓ）を得た。 [Synthesis Example 1] Preparation of component (A) 1,4-bis(dimethylsilyl)benzene (manufactured by Shin-Etsu Chemical Co., Ltd.) was placed in a 1L four-necked flask equipped with a stirrer, a cooling tube, a dropping funnel, and a thermometer. ) and 0.12 g of 5% Pt carbon powder (manufactured by N.E. Chemcat Co., Ltd.) were added, and the mixture was heated to 85° C. using an oil bath. To this, 28.0 g (0.15 mol) of trivinylphenylsilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise. After the addition was completed, the mixture was stirred at 90 to 100°C for 5 hours. After stirring, the temperature was returned to 25°C, 2.9 g of activated carbon was added, and the mixture was stirred for 1 hour. After stirring, the mixture was filtered and concentrated under reduced pressure to obtain 99.7 g of an addition reaction product (colorless and transparent, yield 87%, viscosity at 25°C: 30 Pa·s).
反応生成物を、１Ｈ－ＮＭＲ、ＧＰＣ等により分析した結果、このものは、下記式（ａ）～（ｃ）、（ｆ）で表される構造を有する化合物の混合物であり、各化合物の割合は（ａ）：（ｂ）：（ｃ）：（ｆ）＝５５：２５：１０：１０（ｍｏｌ％）であった。また、前記化合物はそれぞれ１分子中にＳｉＨ基を３個以上有する化合物であり、前記混合物全体としてＳｉＨ基の含有割合は、０．００３５モル／ｇであった。
As a result of analyzing the reaction product by 1 H-NMR, GPC, etc., it was found that this product is a mixture of compounds having structures represented by the following formulas (a) to (c) and (f). The ratio was (a):(b):(c):(f)=55:25:10:10 (mol%). Further, each of the compounds had three or more SiH groups in one molecule, and the content of SiH groups in the mixture as a whole was 0.0035 mol/g.
［実施例１］
（Ａ）合成例１で得られた反応生成物：７５質量部、
（Ｂ－１）平均単位式ＭＶｉΦ ２Ｄ２Φ ３で表される、１００ｇあたりビニル基を０．２２モル有する２５℃における粘度２，０００ｍＰａ・ｓのオルガノポリシロキサン：１１４質量部、
（Ｂ－２）平均単位式ＭＶｉ ２Ｄ２Φで表される、１００ｇあたりビニル基を０．５０モル有する２５℃における粘度１０ｍＰａ・ｓのオルガノポリシロキサン：９質量部、
（Ｃ）白金－ビニルシロキサン錯体：白金金属原子として（Ａ）、（Ｂ－１）および（Ｂ－２）の合計質量に対して３ｐｐｍとなる量、
接着性向上剤として、下記式（６）で表される化合物：２質量部、
ならびに
反応制御剤として、１－エチニルシクロヘキサノール：０．０７質量部
を混合して組成物を得た。この組成物を２ｍｍおよび０．３ｍｍ厚の金枠中に流し込み、１５０℃で４時間加熱して硬化物を得た。上記組成物におけるＳｉＨ／Ｖｉ比（ＳｉＨ基／脂肪族不飽和基）は０．８９であった。
[Example 1]
(A) Reaction product obtained in Synthesis Example 1: 75 parts by mass,
(B-1) Organopolysiloxane having 0.22 mol of vinyl groups per 100 g and having a viscosity of 2,000 mPa·s at 25°C, represented by the average unit formula M ViΦ 2 D 2Φ 3 : 114 parts by mass,
(B-2) Organopolysiloxane having a viscosity of 10 mPa·s at 25°C and having 0.50 mol of vinyl groups per 100 g, represented by the average unit formula M Vi 2 D 2Φ : 9 parts by mass,
(C) Platinum-vinylsiloxane complex: an amount of 3 ppm as platinum metal atoms based on the total mass of (A), (B-1) and (B-2),
As an adhesion improver, a compound represented by the following formula (6): 2 parts by mass,
A composition was obtained by mixing 0.07 parts by mass of 1-ethynylcyclohexanol as a reaction control agent. This composition was poured into metal frames with a thickness of 2 mm and 0.3 mm, and heated at 150° C. for 4 hours to obtain a cured product. The SiH/Vi ratio (SiH group/aliphatic unsaturated group) in the above composition was 0.89.
（Ａ）合成例１で得られた反応生成物：７５質量部、
（Ｂ－１）平均単位式ＭＶｉΦ ２Ｄ２Φ ３で表される、１００ｇあたりビニル基を０．２２モル有する２５℃における粘度２，０００ｍＰａ・ｓのオルガノポリシロキサン：１１４質量部、
（Ｂ－２）平均単位式ＭＶｉ ２Ｄ２Φで表される、１００ｇあたりビニル基を０．５０モル有する２５℃における粘度１０ｍＰａ・ｓのオルガノポリシロキサン：９質量部、
（Ｃ）白金－ビニルシロキサン錯体：白金金属原子として（Ａ）、（Ｂ－１）および（Ｂ－２）の合計質量に対して３ｐｐｍとなる量、
接着性向上剤として、下記式（６）で表される化合物：２質量部、
ならびに
反応制御剤として、１－エチニルシクロヘキサノール：０．０７質量部
を混合して組成物を得た。この組成物を２ｍｍおよび０．３ｍｍ厚の金枠中に流し込み、１５０℃で４時間加熱して硬化物を得た。上記組成物におけるＳｉＨ／Ｖｉ比（ＳｉＨ基／脂肪族不飽和基）は０．８９であった。
(A) Reaction product obtained in Synthesis Example 1: 75 parts by mass,
(B-1) Organopolysiloxane having 0.22 mol of vinyl groups per 100 g and having a viscosity of 2,000 mPa·s at 25°C, represented by the average unit formula M ViΦ 2 D 2Φ 3 : 114 parts by mass,
(B-2) Organopolysiloxane having a viscosity of 10 mPa·s at 25°C and having 0.50 mol of vinyl groups per 100 g, represented by the average unit formula M Vi 2 D 2Φ : 9 parts by mass,
(C) Platinum-vinylsiloxane complex: an amount of 3 ppm as platinum metal atoms based on the total mass of (A), (B-1) and (B-2),
As an adhesion improver, a compound represented by the following formula (6): 2 parts by mass,
A composition was obtained by mixing 0.07 parts by mass of 1-ethynylcyclohexanol as a reaction control agent. This composition was poured into metal frames with a thickness of 2 mm and 0.3 mm, and heated at 150° C. for 4 hours to obtain a cured product. The SiH/Vi ratio (SiH group/aliphatic unsaturated group) in the above composition was 0.89.
［実施例２］
（Ａ）合成例１で得られた反応生成物：７５質量部、
（Ｂ－１）平均単位式ＭＶｉΦ ２Ｄ２Φ ３で表される、１００ｇあたりビニル基を０．２２モル有する２５℃における粘度２，０００ｍＰａ・ｓのオルガノポリシロキサン：１２３質量部、
（Ｃ）白金－ビニルシロキサン錯体：白金金属原子として（Ａ）および（Ｂ－１）の合計質量に対して３ｐｐｍとなる量、
接着性向上剤として、上記式（６）で表される化合物：２質量部、
ならびに
反応制御剤として、１－エチニルシクロヘキサノール：０．０７質量部
を混合して組成物を得た。この組成物を２ｍｍおよび０．３ｍｍ厚の金枠中に流し込み、１５０℃で４時間加熱して硬化物を得た。上記組成物におけるＳｉＨ／Ｖｉ比は０．９７であった。 [Example 2]
(A) Reaction product obtained in Synthesis Example 1: 75 parts by mass,
(B-1) Organopolysiloxane having 0.22 mol of vinyl groups per 100 g and having a viscosity of 2,000 mPa·s at 25°C, represented by the average unit formula M ViΦ 2 D 2Φ 3 : 123 parts by mass,
(C) Platinum-vinylsiloxane complex: an amount of 3 ppm as platinum metal atoms based on the total mass of (A) and (B-1),
As an adhesion improver, a compound represented by the above formula (6): 2 parts by mass,
A composition was obtained by mixing 0.07 parts by mass of 1-ethynylcyclohexanol as a reaction control agent. This composition was poured into metal frames with a thickness of 2 mm and 0.3 mm, and heated at 150° C. for 4 hours to obtain a cured product. The SiH/Vi ratio in the above composition was 0.97.
（Ａ）合成例１で得られた反応生成物：７５質量部、
（Ｂ－１）平均単位式ＭＶｉΦ ２Ｄ２Φ ３で表される、１００ｇあたりビニル基を０．２２モル有する２５℃における粘度２，０００ｍＰａ・ｓのオルガノポリシロキサン：１２３質量部、
（Ｃ）白金－ビニルシロキサン錯体：白金金属原子として（Ａ）および（Ｂ－１）の合計質量に対して３ｐｐｍとなる量、
接着性向上剤として、上記式（６）で表される化合物：２質量部、
ならびに
反応制御剤として、１－エチニルシクロヘキサノール：０．０７質量部
を混合して組成物を得た。この組成物を２ｍｍおよび０．３ｍｍ厚の金枠中に流し込み、１５０℃で４時間加熱して硬化物を得た。上記組成物におけるＳｉＨ／Ｖｉ比は０．９７であった。 [Example 2]
(A) Reaction product obtained in Synthesis Example 1: 75 parts by mass,
(B-1) Organopolysiloxane having 0.22 mol of vinyl groups per 100 g and having a viscosity of 2,000 mPa·s at 25°C, represented by the average unit formula M ViΦ 2 D 2Φ 3 : 123 parts by mass,
(C) Platinum-vinylsiloxane complex: an amount of 3 ppm as platinum metal atoms based on the total mass of (A) and (B-1),
As an adhesion improver, a compound represented by the above formula (6): 2 parts by mass,
A composition was obtained by mixing 0.07 parts by mass of 1-ethynylcyclohexanol as a reaction control agent. This composition was poured into metal frames with a thickness of 2 mm and 0.3 mm, and heated at 150° C. for 4 hours to obtain a cured product. The SiH/Vi ratio in the above composition was 0.97.
［比較例１］
置換基がメチル基からなるシリコーン材料として、メチルシリコーンレジン系硬化性組成物（商品名：ＫＥＲ－２３００、信越化学工業社製、粘度（２５℃）：５，０００ｍＰａ・ｓ）を、実施例１と同様に２ｍｍおよび０．３ｍｍ厚の金枠中に流し込み、１５０℃で２時間加熱して硬化物を得た。 [Comparative example 1]
As a silicone material whose substituent is a methyl group, a methyl silicone resin curable composition (trade name: KER-2300, manufactured by Shin-Etsu Chemical Co., Ltd., viscosity (25°C): 5,000 mPa·s) was used in Example 1. Similarly, it was poured into metal frames of 2 mm and 0.3 mm thickness, and heated at 150° C. for 2 hours to obtain a cured product.
置換基がメチル基からなるシリコーン材料として、メチルシリコーンレジン系硬化性組成物（商品名：ＫＥＲ－２３００、信越化学工業社製、粘度（２５℃）：５，０００ｍＰａ・ｓ）を、実施例１と同様に２ｍｍおよび０．３ｍｍ厚の金枠中に流し込み、１５０℃で２時間加熱して硬化物を得た。 [Comparative example 1]
As a silicone material whose substituent is a methyl group, a methyl silicone resin curable composition (trade name: KER-2300, manufactured by Shin-Etsu Chemical Co., Ltd., viscosity (25°C): 5,000 mPa·s) was used in Example 1. Similarly, it was poured into metal frames of 2 mm and 0.3 mm thickness, and heated at 150° C. for 2 hours to obtain a cured product.
＜性能評価手法＞
上記各実施例および比較例で得られた硬化物について、下記手法に従い性能を評価した。評価結果を表１に示す。 <Performance evaluation method>
The performance of the cured products obtained in each of the above Examples and Comparative Examples was evaluated according to the following method. The evaluation results are shown in Table 1.
上記各実施例および比較例で得られた硬化物について、下記手法に従い性能を評価した。評価結果を表１に示す。 <Performance evaluation method>
The performance of the cured products obtained in each of the above Examples and Comparative Examples was evaluated according to the following method. The evaluation results are shown in Table 1.
（１）外観
２ｍｍ厚の硬化物の外観を目視により観察した。 (1) Appearance The appearance of the 2 mm thick cured product was visually observed.
２ｍｍ厚の硬化物の外観を目視により観察した。 (1) Appearance The appearance of the 2 mm thick cured product was visually observed.
（２）硬度
２ｍｍ厚の硬化物を３枚重ね６ｍｍとし、ＡＳＴＭ Ｄ ２２４０ に準じて硬度（ＳｈｏｒｅＤ）を２３℃で測定した。 (2) Hardness Three 2-mm-thick cured products were stacked to make a 6-mm layer, and the hardness (ShoreD) was measured at 23° C. according to ASTM D 2240.
２ｍｍ厚の硬化物を３枚重ね６ｍｍとし、ＡＳＴＭ Ｄ ２２４０ に準じて硬度（ＳｈｏｒｅＤ）を２３℃で測定した。 (2) Hardness Three 2-mm-thick cured products were stacked to make a 6-mm layer, and the hardness (ShoreD) was measured at 23° C. according to ASTM D 2240.
（３）伸び（切断時伸び）
２ｍｍ厚の硬化物を用いて、ＪＩＳ－Ｋ－６２４９に準じて２３℃で切断時伸びを測定した。 (3) Elongation (elongation at cutting)
Using a 2 mm thick cured product, elongation at break was measured at 23°C in accordance with JIS-K-6249.
２ｍｍ厚の硬化物を用いて、ＪＩＳ－Ｋ－６２４９に準じて２３℃で切断時伸びを測定した。 (3) Elongation (elongation at cutting)
Using a 2 mm thick cured product, elongation at break was measured at 23°C in accordance with JIS-K-6249.
（４）比誘電率および（５）誘電正接
空洞共振器誘電率測定装置（（株）ＡＥＴ社製）を用いて、０．３ｍｍ厚の硬化物の１０ＧＨｚにおける比誘電率および誘電正接を測定した。 (4) Relative permittivity and (5) Dielectric loss tangent The relative permittivity and dielectric loss tangent of a 0.3 mm thick cured product at 10 GHz were measured using a cavity resonator permittivity measuring device (manufactured by AET Co., Ltd.). .
空洞共振器誘電率測定装置（（株）ＡＥＴ社製）を用いて、０．３ｍｍ厚の硬化物の１０ＧＨｚにおける比誘電率および誘電正接を測定した。 (4) Relative permittivity and (5) Dielectric loss tangent The relative permittivity and dielectric loss tangent of a 0.3 mm thick cured product at 10 GHz were measured using a cavity resonator permittivity measuring device (manufactured by AET Co., Ltd.). .
以上の結果から、実施例１および２の組成物は、基板に塗布する際に適度な粘度を有する、作業性に優れるものであった。また、実施例１および２で得られた硬化物は、高硬度かつ高強度であり、１０ＧＨｚにおける比誘電率が３．０以下、かつ、誘電正接が０．０１以下であり高周波誘電特性に優れることが分かった。
From the above results, the compositions of Examples 1 and 2 had appropriate viscosity when applied to a substrate and were excellent in workability. In addition, the cured products obtained in Examples 1 and 2 have high hardness and high strength, have a relative dielectric constant of 3.0 or less at 10 GHz, and a dielectric loss tangent of 0.01 or less, and have excellent high-frequency dielectric properties. That's what I found out.
一方、比較例１のメチル系シリコーンレジン系硬化物は、強度が不足し、さらに誘電正接が大きく高周波特性を満たしていないことが分かった。
On the other hand, it was found that the methyl silicone resin cured product of Comparative Example 1 lacked strength, had a large dielectric loss tangent, and did not satisfy high frequency characteristics.
本明細書は、以下の態様を包含する。
［１］：下記（Ａ）、（Ｂ）及び（Ｃ）を含む低誘電率絶縁性コーティング組成物。
（Ａ）下記式（１）で表される有機ケイ素化合物と、下記式（２）で表される有機ケイ素化合物との付加反応物であって、１分子中にＳｉＨ基を３個以上有する付加反応物、
（式中、Ｒ１は独立に置換または非置換の炭素数１～１２の２価炭化水素基である。）
（式中、Ｒ２は独立に置換または非置換の炭素数１～１２の１価炭化水素基であり、Ｒ３は単結合または非置換の炭素数１～４の２価炭化水素基である。）、
（Ｂ）アルケニル基を１分子中に２個以上有するオルガノシロキサン化合物、
（Ｃ）ヒドロシリル化反応触媒
［２］：前記Ｒ１がフェニレン基、前記Ｒ２がメチル基又はフェニル基であることを特徴とする［１］に記載の低誘電率絶縁性コーティング組成物。
［３］：前記（Ｂ）が下記式（３）で表される化合物であることを特徴とする［１］又は［２］に記載の低誘電率絶縁性コーティング組成物。
（式中、Ｒ４は独立に非置換または置換の１価炭化水素基であり、Ｒ５は独立にメチル基又はフェニル基であり、ａは０～５０の整数であり、ｂは０～１００の整数である。ただし、ａが０のときＲ５はフェニル基であり、かつ、ｂは１～１００である。括弧が付されたシロキサン単位の配列順は任意である。）
［４］：［１］から［３］のいずれか１つに記載の低誘電率絶縁性コーティング組成物を硬化してなることを特徴とする硬化物。
［５］：１０ＧＨｚにおける誘電率が３．０以下、かつ、誘電正接が０．０１以下のものであることを特徴とする［４］に記載の硬化物。
［６］：［４］又は［５］に記載の硬化物からなる層を有するものであることを特徴とする表示装置。 The specification includes the following aspects.
[1]: A low dielectric constant insulating coating composition containing the following (A), (B) and (C).
(A) An addition reaction product of an organosilicon compound represented by the following formula (1) and an organosilicon compound represented by the following formula (2), which has three or more SiH groups in one molecule. reactant,
(In the formula, R 1 is independently a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms.)
(In the formula, R 2 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R 3 is a single bond or an unsubstituted divalent hydrocarbon group having 1 to 4 carbon atoms. ),
(B) an organosiloxane compound having two or more alkenyl groups in one molecule;
(C) Hydrosilylation reaction catalyst [2]: The low dielectric constant insulating coating composition according to [1], wherein R 1 is a phenylene group, and R 2 is a methyl group or a phenyl group.
[3]: The low dielectric constant insulating coating composition according to [1] or [2], wherein the (B) is a compound represented by the following formula (3).
(In the formula, R 4 is independently an unsubstituted or substituted monovalent hydrocarbon group, R 5 is independently a methyl group or a phenyl group, a is an integer from 0 to 50, and b is an integer from 0 to 100. is an integer of. However, when a is 0, R 5 is a phenyl group, and b is 1 to 100. The arrangement order of the siloxane units in parentheses is arbitrary.)
[4]: A cured product obtained by curing the low dielectric constant insulating coating composition according to any one of [1] to [3].
[5]: The cured product according to [4], which has a dielectric constant of 3.0 or less and a dielectric loss tangent of 0.01 or less at 10 GHz.
[6]: A display device comprising a layer made of the cured product according to [4] or [5].
［１］：下記（Ａ）、（Ｂ）及び（Ｃ）を含む低誘電率絶縁性コーティング組成物。
（Ａ）下記式（１）で表される有機ケイ素化合物と、下記式（２）で表される有機ケイ素化合物との付加反応物であって、１分子中にＳｉＨ基を３個以上有する付加反応物、
（Ｂ）アルケニル基を１分子中に２個以上有するオルガノシロキサン化合物、
（Ｃ）ヒドロシリル化反応触媒
［２］：前記Ｒ１がフェニレン基、前記Ｒ２がメチル基又はフェニル基であることを特徴とする［１］に記載の低誘電率絶縁性コーティング組成物。
［３］：前記（Ｂ）が下記式（３）で表される化合物であることを特徴とする［１］又は［２］に記載の低誘電率絶縁性コーティング組成物。
［４］：［１］から［３］のいずれか１つに記載の低誘電率絶縁性コーティング組成物を硬化してなることを特徴とする硬化物。
［５］：１０ＧＨｚにおける誘電率が３．０以下、かつ、誘電正接が０．０１以下のものであることを特徴とする［４］に記載の硬化物。
［６］：［４］又は［５］に記載の硬化物からなる層を有するものであることを特徴とする表示装置。 The specification includes the following aspects.
[1]: A low dielectric constant insulating coating composition containing the following (A), (B) and (C).
(A) An addition reaction product of an organosilicon compound represented by the following formula (1) and an organosilicon compound represented by the following formula (2), which has three or more SiH groups in one molecule. reactant,
(B) an organosiloxane compound having two or more alkenyl groups in one molecule;
(C) Hydrosilylation reaction catalyst [2]: The low dielectric constant insulating coating composition according to [1], wherein R 1 is a phenylene group, and R 2 is a methyl group or a phenyl group.
[3]: The low dielectric constant insulating coating composition according to [1] or [2], wherein the (B) is a compound represented by the following formula (3).
[4]: A cured product obtained by curing the low dielectric constant insulating coating composition according to any one of [1] to [3].
[5]: The cured product according to [4], which has a dielectric constant of 3.0 or less and a dielectric loss tangent of 0.01 or less at 10 GHz.
[6]: A display device comprising a layer made of the cured product according to [4] or [5].
なお、本発明は、上記実施形態に限定されるものではない。上記実施形態は例示であり、本発明の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本発明の技術的範囲に包含される。
Note that the present invention is not limited to the above embodiments. The above-mentioned embodiments are illustrative, and any embodiment that has substantially the same configuration as the technical idea stated in the claims of the present invention and has similar effects is the present invention. covered within the technical scope of
Claims (10)
- 下記（Ａ）、（Ｂ）及び（Ｃ）を含む低誘電率絶縁性コーティング組成物。
（Ａ）下記式（１）で表される有機ケイ素化合物と、下記式（２）で表される有機ケイ素化合物との付加反応物であって、１分子中にＳｉＨ基を３個以上有する付加反応物、
（Ｂ）アルケニル基を１分子中に２個以上有するオルガノシロキサン化合物、
（Ｃ）ヒドロシリル化反応触媒 A low dielectric constant insulating coating composition comprising the following (A), (B) and (C).
(A) An addition reaction product of an organosilicon compound represented by the following formula (1) and an organosilicon compound represented by the following formula (2), which has three or more SiH groups in one molecule. reactant,
(B) an organosiloxane compound having two or more alkenyl groups in one molecule;
(C) Hydrosilylation reaction catalyst - 前記Ｒ１がフェニレン基、前記Ｒ２がメチル基又はフェニル基であることを特徴とする請求項１に記載の低誘電率絶縁性コーティング組成物。 The low dielectric constant insulating coating composition according to claim 1 , wherein the R 1 is a phenylene group, and the R 2 is a methyl group or a phenyl group.
- 前記（Ｂ）が下記式（３）で表される化合物であることを特徴とする請求項１に記載の低誘電率絶縁性コーティング組成物。
- 前記（Ｂ）が下記式（３）で表される化合物であることを特徴とする請求項２に記載の低誘電率絶縁性コーティング組成物。
- 請求項１に記載の低誘電率絶縁性コーティング組成物を硬化してなることを特徴とする硬化物。 A cured product obtained by curing the low dielectric constant insulating coating composition according to claim 1.
- 請求項２に記載の低誘電率絶縁性コーティング組成物を硬化してなることを特徴とする硬化物。 A cured product obtained by curing the low dielectric constant insulating coating composition according to claim 2.
- 請求項３に記載の低誘電率絶縁性コーティング組成物を硬化してなることを特徴とする硬化物。 A cured product obtained by curing the low dielectric constant insulating coating composition according to claim 3.
- 請求項４に記載の低誘電率絶縁性コーティング組成物を硬化してなることを特徴とする硬化物。 A cured product obtained by curing the low dielectric constant insulating coating composition according to claim 4.
- １０ＧＨｚにおける誘電率が３．０以下、かつ、誘電正接が０．０１以下のものであることを特徴とする請求項５から請求項８のいずれか一項に記載の硬化物。 The cured product according to any one of claims 5 to 8, having a dielectric constant of 3.0 or less and a dielectric loss tangent of 0.01 or less at 10 GHz.
- 請求項９に記載の硬化物からなる層を有するものであることを特徴とする表示装置。 A display device comprising a layer made of the cured product according to claim 9.
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|---|---|---|---|---|
| JP2000080280A (en) * | 1998-09-07 | 2000-03-21 | Shin Etsu Chem Co Ltd | Zinc oxide-filled additional reaction curing type silicone rubber composition and its cured material |
| JP2006152063A (en) * | 2004-11-26 | 2006-06-15 | Jsr Corp | New polycarbosilane, method for producing the same, film-forming composition, film and method for forming the same |
| JP2020026502A (en) * | 2018-08-15 | 2020-02-20 | 信越化学工業株式会社 | Curable composition, cured product of the composition, and semiconductor device using the cured product |
| WO2021240302A2 (en) * | 2020-05-28 | 2021-12-02 | 3M Innovative Properties Company | Curable composition, reaction product therefrom, and electronic article including the same |
| JP2022084508A (en) * | 2020-11-26 | 2022-06-07 | 信越化学工業株式会社 | Dielectric property-lowering agent, low-dielectric resin composition containing the same, method for lowering dielectric properties of resin, and use as dielectric property-lowering agent |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000080280A (en) * | 1998-09-07 | 2000-03-21 | Shin Etsu Chem Co Ltd | Zinc oxide-filled additional reaction curing type silicone rubber composition and its cured material |
| JP2006152063A (en) * | 2004-11-26 | 2006-06-15 | Jsr Corp | New polycarbosilane, method for producing the same, film-forming composition, film and method for forming the same |
| JP2020026502A (en) * | 2018-08-15 | 2020-02-20 | 信越化学工業株式会社 | Curable composition, cured product of the composition, and semiconductor device using the cured product |
| WO2021240302A2 (en) * | 2020-05-28 | 2021-12-02 | 3M Innovative Properties Company | Curable composition, reaction product therefrom, and electronic article including the same |
| JP2022084508A (en) * | 2020-11-26 | 2022-06-07 | 信越化学工業株式会社 | Dielectric property-lowering agent, low-dielectric resin composition containing the same, method for lowering dielectric properties of resin, and use as dielectric property-lowering agent |
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