WO2023032724A1 - 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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- WO2023032724A1 WO2023032724A1 PCT/JP2022/031482 JP2022031482W WO2023032724A1 WO 2023032724 A1 WO2023032724 A1 WO 2023032724A1 JP 2022031482 W JP2022031482 W JP 2022031482W WO 2023032724 A1 WO2023032724 A1 WO 2023032724A1
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- WIPO (PCT)
- Prior art keywords
- dielectric constant
- insulating coating
- coating composition
- component
- low dielectric
- Prior art date
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- 239000008199 coating composition Substances 0.000 title claims abstract description 31
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 31
- 239000000047 product Substances 0.000 claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- -1 polycyclic hydrocarbon Chemical class 0.000 claims abstract description 25
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 24
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 17
- 238000007259 addition reaction Methods 0.000 claims abstract description 15
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 12
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 10
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 32
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 claims description 22
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 claims description 6
- PUNGSQUVTIDKNU-UHFFFAOYSA-N 2,4,6,8,10-pentamethyl-1,3,5,7,9,2$l^{3},4$l^{3},6$l^{3},8$l^{3},10$l^{3}-pentaoxapentasilecane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O[Si](C)O1 PUNGSQUVTIDKNU-UHFFFAOYSA-N 0.000 claims description 5
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 239000011247 coating layer Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 5
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 125000003342 alkenyl group Chemical group 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 7
- 230000003078 antioxidant effect Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- HGPDWMTUQRNTQT-UHFFFAOYSA-N 2,4,6,8,10-pentamethyl-1,3,5,7,9,2,4,6,8,10-pentaoxapentasilecane Chemical group C[SiH]1O[SiH](C)O[SiH](C)O[SiH](C)O[SiH](C)O1 HGPDWMTUQRNTQT-UHFFFAOYSA-N 0.000 description 5
- BQYPERTZJDZBIR-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical group C[SiH]1O[SiH](C)O[SiH](C)O[SiH](C)O1 BQYPERTZJDZBIR-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 125000003367 polycyclic group Chemical group 0.000 description 4
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000005024 alkenyl aryl group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 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 2
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- NWNPESVXYXCGLH-UHFFFAOYSA-N 4-ethenylbicyclo[2.2.1]hept-2-ene Chemical class C1CC2C=CC1(C=C)C2 NWNPESVXYXCGLH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 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 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 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 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([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
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- OQJPAHYVGNJBJK-UHFFFAOYSA-N (3-dimethylsilylphenyl)-dimethylsilane Chemical compound C[SiH](C)C1=CC=CC([SiH](C)C)=C1 OQJPAHYVGNJBJK-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000006039 1-hexenyl group Chemical group 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
- OTTZHAVKAVGASB-UHFFFAOYSA-N 2-heptene Natural products CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- MUUXBTFQEXVEEI-UHFFFAOYSA-N [2-(dimethyl-$l^{3}-silanyl)phenyl]-dimethylsilicon Chemical compound C[Si](C)C1=CC=CC=C1[Si](C)C MUUXBTFQEXVEEI-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 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
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- LJKNRSBEKUSSIE-UHFFFAOYSA-N hept-2-ene Chemical compound [CH2]CCCC=CC LJKNRSBEKUSSIE-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 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
- 238000001782 photodegradation Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/20—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances liquids, e.g. oils
- H01B3/22—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances liquids, e.g. oils hydrocarbons
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
Definitions
- the present invention relates to a low dielectric constant insulating coating composition, a cured product thereof, and a display device.
- Patent Document 1 a polycyclic hydrocarbon skeleton-containing compound having two addition-reactive carbon-carbon double bonds in one molecule and three or more silicon-bonded hydrogen atoms in one molecule. and a hydrosilylation catalyst as essential components.
- the present invention aims to provide a low dielectric constant insulating coating composition which has a low dielectric constant and a low dielectric loss tangent in a cured product obtained by curing, and has excellent workability when applied to a substrate. aim.
- the present inventors have conducted intensive studies to achieve the above object, and have found that a curable silicone composition containing a specific component containing a polycyclic hydrocarbon skeleton has excellent workability and a low dielectric constant.
- the present invention was completed by discovering that a cured product having a low dielectric constant and a low dielectric loss tangent can be obtained. That is, the present invention provides a low dielectric constant insulating coating composition, a cured product thereof, and a display device as described below.
- R is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
- a compound having two silicon-bonded hydrogen atoms in one molecule represented by (b) an addition reaction product with a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and an addition-reactive carbon-carbon double bond in one molecule; an addition reaction product having at least two in A low dielectric constant insulating coating composition comprising (B) a compound having 3 or more silicon-bonded hydrogen atoms in one molecule and (C) a hydrosilylation reaction catalyst.
- the polycyclic hydrocarbon of (b) is 5-vinylbicyclo[2.2.1]hept-2-ene, 6-vinylbicyclo[2.2.1]hept-2-ene, or a combination of the two.
- the low dielectric constant insulating coating composition according to [1].
- the component (B) contains 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, or a mixture of both [1] or [2 ].
- the component (B) is 5-vinylbicyclo[2.2.1]hept-2-ene, 6-vinylbicyclo[2.2.1]hept-2-ene or a mixture of both; including addition reaction products with 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, or mixtures of both [1]-[3]
- the low dielectric constant insulating coating composition according to any one of .
- [5] A cured product of the low dielectric constant insulating coating composition according to any one of [1] to [4].
- the low dielectric constant insulating coating composition of the present invention has a viscosity suitable for coating on a substrate, is excellent in workability, and the obtained cured product has a low dielectric constant and a low dielectric loss tangent. It is useful as a coating material for electronic and electrical devices with low transmission loss in the high frequency range.
- the component is (a) the following general formula (1):
- R is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
- a compound having two silicon-bonded hydrogen atoms in one molecule represented by (b) an addition reaction product with a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and an addition-reactive carbon-carbon double bond in one molecule; is an addition reaction product having at least two in
- ⁇ (a) component> (a) A compound having two silicon-bonded hydrogen atoms (hereinafter sometimes referred to as "SiH") represented by the above general formula (1) in one molecule is a reaction raw material for component (A). .
- SiH silicon-bonded hydrogen atoms
- R is the above monovalent hydrocarbon group, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl Alkyl groups such as group, sec-hexyl group; Cycloalkyl groups such as cyclopentyl group and cyclohexyl group; Aryl groups such as phenyl group and o-, m-, p-tolyl group; Aralkyl groups such as benzyl group and 2-phenylethyl group groups; alkenyl groups such as vinyl group, allyl group, 1-butenyl group and 1-hexenyl group; alkenylaryl groups such as p-vinylphenyl group; and one or more hydrogen atoms bonded to carbon atoms in these groups is substituted with a halogen atom, a cyano group, an epoxy
- R is the alkoxy group
- examples of the case where R is the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group.
- the above R is preferably a group other than an alkenyl group and an alkenylaryl group, and in particular, the component (a) in which all of the Rs are methyl groups is easy to industrially produce. is preferred due to its availability.
- addition-reactive means It means the ability to undergo the addition of a hydrogen atom (known as a hydrosilylation reaction).
- the component (b) is (i) those in which an addition-reactive carbon-carbon double bond is formed between two adjacent carbon atoms among the carbon atoms forming the polycyclic skeleton of the polycyclic hydrocarbon; (ii) hydrogen atoms bonded to carbon atoms forming the polycyclic skeleton of the polycyclic hydrocarbon are replaced by addition-reactive carbon-carbon double bond-containing groups, or (iii) of the carbon atoms forming the polycyclic skeleton of the polycyclic hydrocarbon, an addition-reactive carbon-carbon double bond is formed between two adjacent carbon atoms, and the polycyclic Any hydrogen atom bonded to a carbon atom forming the hydrocarbon polycyclic skeleton may be replaced by an addition-reactive carbon-carbon double bond-containing group.
- Structural formula (x) below: 5-vinylbicyclo[2.2.1]hept-2-ene represented by Structural formula (y) below: 6-vinylbicyclo[2.2.1]hept-2-ene represented by Combinations of both are included. (Hereinafter, when there is no need to distinguish between these three substances, they may be collectively referred to as "vinylnorbornene.")
- the substitution position of the vinyl group of the vinylnorbornene may be either cis configuration (exo type) or trans configuration (endo type). Since there is no difference between the two configurations, a combination of isomers of both configurations may be used.
- Component (A) is the above component (b) having two addition-reactive carbon-carbon double bonds in one molecule, per 1 mol of the component (a) having two SiH in one molecule.
- the (A) component thus obtained is derived from the component (a) in addition to the addition-reactive carbon-carbon double bond derived from the component (b) (specifically, R in the general formula (1) can contain addition-reactive carbon-carbon double bonds (derived from There are two. If there are too many addition-reactive carbon-carbon double bonds, the cured product obtained by curing the composition of the present invention tends to crack.
- hydrosilylation reaction catalyst all conventionally known catalysts can be used.
- platinum group metal catalysts such as palladium catalysts and rhodium catalysts.
- the addition reaction conditions, the use of solvents, etc. are not particularly limited, and may be as usual.
- component (A) As described above, in the preparation of component (A), an excess molar amount of component (b) is used with respect to component (a), so component (A) is derived from the structure of component (b). It has two addition-reactive carbon-carbon double bonds in one molecule. Furthermore, component (A) has a residue derived from component (a) above, which residue is derived from the structure of component (b) above but does not have an addition-reactive carbon-carbon double bond. It may also include structures joined by divalent residues of polycyclic hydrocarbons.
- component (A) for example, the following general formula (4): YX-(Y'-X) p -Y (4) (Wherein, X is the divalent residue of the compound of component (a) above, Y is the monovalent residue of the polycyclic hydrocarbon of component (b) above, and Y′ is the residue of the above (b ) is a divalent residue of the component and p is an integer from 0 to 10, preferably from 0 to 5)
- X is the divalent residue of the compound of component (a) above
- Y is the monovalent residue of the polycyclic hydrocarbon of component (b) above
- Y′ is the residue of the above (b ) is a divalent residue of the component
- p is an integer from 0 to 10, preferably from 0 to 5
- the value of p which is the number of repeating units represented by (Y'-X), can be adjusted by adjusting the excess molar amount of the component (b) to be reacted with respect to 1 mol of the component (a). can be set by
- Y in the general formula (4) includes, for example, the following structural formula: (hereinafter, if it is not necessary to distinguish between these six groups, they are collectively referred to as "NB groups", and the six types of structures are referred to as “NB” without distinguishing may be abbreviated).
- Y′ in the general formula (4) include the following structural formula: A bivalent residue represented by is included.
- the asymmetric divalent residue represented by the above structural formula is not limited to the left-right direction as described above, and the above structural formula substantially represents each of the above structures on paper. It also shows the structure rotated 180 degrees.
- Suitable specific examples of the component (A) represented by the general formula (4) are shown below, but are not limited thereto. (The meaning of "NB” is as described above, and “Me” in the formula represents a methyl group (the same applies hereinafter).)
- the (A) component of the present invention can be used singly or in combination of two or more.
- the component (B) is a compound having 3 or more SiH in one molecule.
- the SiH in the component (B) is added to the addition-reactive carbon-carbon double bond that the component (A) has at least two in one molecule by a hydrosilylation reaction to form a cured product with a three-dimensional network structure. give.
- the (B) component is, for example, the following general formula (5):
- R 1 is independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group other than an alkenyl group, having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and q is 3 to 10 , preferably an integer of 3 to 8, r is an integer of 0 to 7, preferably 0 to 2, and the sum of q + r is an integer of 3 to 10, preferably 3 to 6)
- a cyclic siloxane compound represented by is mentioned.
- R 1 in the general formula (5) is an unsubstituted or substituted monovalent hydrocarbon group other than an alkenyl group
- R 1 in the general formula (5) is an unsubstituted or substituted monovalent hydrocarbon group other than an alkenyl group
- R 1 in the general formula (5) is an unsubstituted or substituted monovalent hydrocarbon group other than an alkenyl group
- R 1 in the general formula (5) is an unsubstituted or substituted monovalent hydrocarbon group other than an alkenyl group
- R 1 in the general formula (5) examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert- Alkyl groups such as butyl group, pentyl group, isopentyl group, hexyl group and sec-hexyl group; Cycloalkyl groups such as cyclopentyl group and cyclohexyl group; Aryl groups such as phenyl group and
- R 1 is preferably a methyl group, and in particular, component (B) in which all R 1 are methyl groups is easy to industrially produce and readily available.
- component (B) for example, one or two of the above vinylnorbornenes and 1,3,5,7-tetramethylcyclotetrasiloxane are hydrosilylated to obtain SiH in one molecule.
- the component (B) can be used singly or in combination of two or more.
- the composition of the present invention contains a component having hydrogen atoms bonded to silicon atoms other than component (B) and/or an addition-reactive carbon-carbon dihydrogen atom bonded to silicon atoms other than component (A).
- a component with a double bond can be included. Therefore, the amount of hydrogen atoms bonded to silicon atoms in the present composition per mol of addition-reactive carbon-carbon double bonds bonded to silicon atoms in the present composition is usually 0.5 to 3.0. mol, preferably 0.8 to 2.0 mol.
- the amount of component (B) to be added to the low dielectric constant insulating coating composition of the present invention is the addition reactive carbon-carbon double bond in component (A).
- the amount of SiH in component (B) is generally 0.5 to 3.0 mol, preferably 0.8 to 2.0 mol, per 1 mol.
- the hydrosilylation reaction catalyst which is the component (C) of the present invention is the same as described in ⁇ Preparation of the component (A)> above.
- the amount of component (C) is not particularly limited as long as it is an effective amount as a catalyst. It is preferable to add an amount of about 1 to 500 ppm, particularly about 2 to 100 ppm. By setting the blending amount within the above range, the time required for the curing reaction becomes appropriate, and problems such as coloring of the cured product do not occur.
- the low dielectric constant insulating coating composition of the present invention may optionally contain other components within a range that does not impair the objects and effects of the present invention.
- the addition-reactive carbon-carbon double bond in the component (A) may remain unreacted.
- antioxidant all conventionally known ones can be used.
- the amount to be blended is not particularly limited as long as it is an effective amount as an antioxidant. , usually 10 to 10,000 ppm, preferably 100 to 1,000 ppm. By setting the blending amount within the above range, the antioxidant ability is fully exhibited, and a cured product having excellent optical properties without causing coloration, white turbidity, deterioration due to oxidation, etc., can be obtained.
- ⁇ Viscosity/hardness modifier> In order to adjust the viscosity of the low dielectric constant insulating coating composition of the present invention or the hardness of the cured product obtained from the low dielectric constant insulating coating composition of the present invention, it has an alkenyl group or SiH bonded to a silicon atom.
- the blending amount thereof is such that the alkenyl groups and the above (A) SiH in the above component (B) is usually 0.5 to 3.0 mol, preferably 0.8 to 2.0 mol, per 1 mol of the total amount of addition-reactive carbon-carbon double bonds possessed by the component. It is preferable to use a molar amount.
- the blending amounts thereof are the same as the above SiH and the SiH possessed by the component (B).
- the viscosity of the low dielectric constant insulating coating composition of the present invention at 25°C is preferably 10 to 10,000 mPa ⁇ s, more preferably 30 to 3,000 mPa ⁇ s. Within such a range, workability is excellent.
- the viscosity in the present invention indicates the viscosity measured at 25°C with a rotational viscometer according to JIS K 7117-1:1999.
- addition reaction controllers such as 1-ethynylcyclohexanol and 3,5-dimethyl-1-hexyn-3-ol can be blended.
- an inorganic filler such as fumed silica may be blended to improve strength within a range that does not affect transparency, and if necessary, dyes, pigments, flame retardants, etc. may be blended. good too.
- a light stabilizer to impart resistance to photodegradation due to light energy such as sunlight.
- Hindered amine-based stabilizers that capture radicals generated by photo-oxidative deterioration are suitable as the light stabilizer, and the antioxidant effect is further improved by using them together with antioxidants.
- Specific examples of light stabilizers include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate and 4-benzoyl-2,2,6,6-tetramethylpiperidine.
- the total amount of components (A), (B) and (C) is preferably 50 to 100% by mass, more preferably 80 to 100% by mass. Preferably, it is more preferably 90 to 100% by mass. Also, the low dielectric constant insulating coating composition of the present invention can be produced by uniformly mixing the components described above.
- the curing conditions for the low-dielectric-constant insulating coating composition of the present invention vary depending on the amount thereof, and are not particularly limited, but the conditions of 60 to 180° C. and 10 to 300 minutes are usually preferred.
- 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 such a range, high-frequency dielectric properties are excellent.
- 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.
- the cured product obtained by curing the low dielectric constant insulating coating composition of the present invention has transparency, it is suitable for use in display devices.
- platinum-vinylsiloxane complex an amount of 20 ppm relative to the total mass of (A) and (B) as platinum metal atoms
- 1-ethynylcyclohexanol 0.03 parts by mass were uniformly mixed
- a composition having a viscosity of 50 mPa ⁇ s was obtained. This composition was poured into a metal frame with a thickness of 0.3 mm and heated at 150° C. for 2 hours to obtain a cured product.
- a methyl silicone resin-based curable composition (trade name: KER-2300, manufactured by Shin-Etsu Chemical Co., Ltd., viscosity: 5,000 mPa s) was added to 0 in the same manner as in Example 1. It was poured into a metal frame with a thickness of 0.3 mm and heated at 150° C. for 2 hours to obtain a cured product.
- compositions of Examples 1 to 3 had suitable viscosities when applied to substrates and were excellent in workability.
- the cured products obtained in Examples 1 to 3 had a relative dielectric constant of 3.0 or less at 10 GHz and a dielectric loss tangent of 0.01 or less, indicating excellent high-frequency dielectric properties.
- the methyl-based silicone resin of Comparative Example 1 had a large dielectric loss tangent and did not satisfy the high frequency characteristics.
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Abstract
The present invention provides a low dielectric constant insulating coating composition, a cured product of which has a low relative dielectric constant and a low dielectric loss tangent, and which exhibits excellent workability when applied to a substrate. The present invention provides a low dielectric constant insulating coating composition that contains: (A) an addition reaction product of (a) a compound which is represented by formula (1) and has two hydrogen atoms in each molecule, each of the hydrogen atoms being bonded to a silicon atom, and (b) a polycyclic hydrocarbon which has two addition reactive carbon-carbon double bonds in each molecule; (B) a compound which has three or more hydrogen atoms in each molecule, each of the hydrogen atoms being bonded to a silicon atom; and (C) a hydrosilylation catalyst. (In formula (1), R independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.)
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.
先に、本発明者は、付加反応性炭素－炭素二重結合を１分子中に２個有する多環式炭化水素骨格含有化合物と、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、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を提案している（特許文献１）。
Previously, the present inventors have discovered a polycyclic hydrocarbon skeleton-containing compound having two addition-reactive carbon-carbon double bonds in one molecule and three or more silicon-bonded hydrogen atoms in one molecule. and a hydrosilylation catalyst as essential components (Patent Document 1).
一方、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。
On the other hand, in recent years, information communication equipment has progressed rapidly, and along with large-capacity communication such as video information, the digitization and higher frequency of transmission signals are progressing. For this reason, there is a demand for a resin material that is superior in processability and workability to fluororesins and ceramics that have been used so far as materials with less transmission loss in the gigahertz high frequency region.
従って、本発明は、硬化して得られる硬化物が低い比誘電率および誘電正接を有するとともに、基板に塗布する際に優れた作業性を併せ持つ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。
Accordingly, the present invention aims to provide a low dielectric constant insulating coating composition which has a low dielectric constant and a low dielectric loss tangent in a cured product obtained by curing, and has excellent workability when applied to a substrate. aim.
本発明者らは、上記目的を達成するために鋭意研究を行った結果、特定の多環式炭化水素骨格含有成分を含むシリコーン硬化性組成物が、優れた作業性を有し、低い比誘電率および低い誘電正接を有する硬化物を与えることを見出し、本発明を完成した。
即ち、本発明は、下記の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を提供するものである。 The present inventors have conducted intensive studies to achieve the above object, and have found that a curable silicone composition containing a specific component containing a polycyclic hydrocarbon skeleton has excellent workability and a low dielectric constant. The present invention was completed by discovering that a cured product having a low dielectric constant and a low dielectric loss tangent can be obtained.
That is, the present invention provides a low dielectric constant insulating coating composition, a cured product thereof, and a display device as described below.
即ち、本発明は、下記の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を提供するものである。 The present inventors have conducted intensive studies to achieve the above object, and have found that a curable silicone composition containing a specific component containing a polycyclic hydrocarbon skeleton has excellent workability and a low dielectric constant. The present invention was completed by discovering that a cured product having a low dielectric constant and a low dielectric loss tangent can be obtained.
That is, the present invention provides a low dielectric constant insulating coating composition, a cured product thereof, and a display device as described below.
［１］
（Ａ）
（ａ）下記式（１）：
（式（１）中、Ｒは、独立に非置換もしくは置換の炭素原子数１～１２の１価炭化水素基または炭素原子数１～６のアルコキシ基である。）
で表されるケイ素原子に結合した水素原子を１分子中に２個有する化合物と、
（ｂ）付加反応性炭素－炭素二重結合を１分子中に２個有する多環式炭化水素と
の付加反応生成物であって、かつ、付加反応性炭素－炭素二重結合を１分子中に少なくとも２個有する付加反応生成物、
（Ｂ）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、および
（Ｃ）ヒドロシリル化反応触媒
を含む低誘電率絶縁性コーティング組成物。
［２］
前記（ｂ）の多環式炭化水素が、５－ビニルビシクロ［２．２．１］ヘプト－２－エン、６－ビニルビシクロ［２．２．１］ヘプト－２－エンまたは前記両者の組み合わせである［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）成分が、１，３，５，７－テトラメチルシクロテトラシロキサン、１，３，５，７，９－ペンタメチルシクロペンタシロキサンまたはその両方の混合物を含むものである［１］または［２］に記載の低誘電率絶縁性コーティング組成物。
［４］
前記（Ｂ）成分が、
５－ビニルビシクロ［２．２．１］ヘプト－２－エン、６－ビニルビシクロ［２．２．１］ヘプト－２－エンまたはその両方の混合物と、
１，３，５，７－テトラメチルシクロテトラシロキサン、１，３，５，７，９－ペンタメチルシクロペンタシロキサンまたはその両方の混合物と
の付加反応生成物を含むものである［１］～［３］のいずれか１項に記載の低誘電率絶縁性コーティング組成物。
［５］
［１］～［４］のいずれか１項に記載の低誘電率絶縁性コーティング組成物の硬化物。
［６］
１０ＧＨｚにおける誘電率が３．０以下、かつ、誘電正接が０．０１以下である［５］に記載の硬化物。
［７］
［５］または［６］に記載の硬化物を絶縁性コーティング層として使用する方法。
［８］
［５］または［６］に記載の硬化物からなる層を有する表示装置。
[1]
(A)
(a) the following formula (1):
(In formula (1), R is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.)
A compound having two silicon-bonded hydrogen atoms in one molecule represented by
(b) an addition reaction product with a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and an addition-reactive carbon-carbon double bond in one molecule; an addition reaction product having at least two in
A low dielectric constant insulating coating composition comprising (B) a compound having 3 or more silicon-bonded hydrogen atoms in one molecule and (C) a hydrosilylation reaction catalyst.
[2]
The polycyclic hydrocarbon of (b) is 5-vinylbicyclo[2.2.1]hept-2-ene, 6-vinylbicyclo[2.2.1]hept-2-ene, or a combination of the two. The low dielectric constant insulating coating composition according to [1].
[3]
The component (B) contains 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, or a mixture of both [1] or [2 ].
[4]
The component (B) is
5-vinylbicyclo[2.2.1]hept-2-ene, 6-vinylbicyclo[2.2.1]hept-2-ene or a mixture of both;
including addition reaction products with 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, or mixtures of both [1]-[3] The low dielectric constant insulating coating composition according to any one of .
[5]
A cured product of the low dielectric constant insulating coating composition according to any one of [1] to [4].
[6]
The cured product according to [5], which has a dielectric constant of 3.0 or less at 10 GHz and a dielectric loss tangent of 0.01 or less.
[7]
A method of using the cured product according to [5] or [6] as an insulating coating layer.
[8]
A display device comprising a layer comprising the cured product of [5] or [6].
（Ａ）
（ａ）下記式（１）：
で表されるケイ素原子に結合した水素原子を１分子中に２個有する化合物と、
（ｂ）付加反応性炭素－炭素二重結合を１分子中に２個有する多環式炭化水素と
の付加反応生成物であって、かつ、付加反応性炭素－炭素二重結合を１分子中に少なくとも２個有する付加反応生成物、
（Ｂ）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、および
（Ｃ）ヒドロシリル化反応触媒
を含む低誘電率絶縁性コーティング組成物。
［２］
前記（ｂ）の多環式炭化水素が、５－ビニルビシクロ［２．２．１］ヘプト－２－エン、６－ビニルビシクロ［２．２．１］ヘプト－２－エンまたは前記両者の組み合わせである［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）成分が、１，３，５，７－テトラメチルシクロテトラシロキサン、１，３，５，７，９－ペンタメチルシクロペンタシロキサンまたはその両方の混合物を含むものである［１］または［２］に記載の低誘電率絶縁性コーティング組成物。
［４］
前記（Ｂ）成分が、
５－ビニルビシクロ［２．２．１］ヘプト－２－エン、６－ビニルビシクロ［２．２．１］ヘプト－２－エンまたはその両方の混合物と、
１，３，５，７－テトラメチルシクロテトラシロキサン、１，３，５，７，９－ペンタメチルシクロペンタシロキサンまたはその両方の混合物と
の付加反応生成物を含むものである［１］～［３］のいずれか１項に記載の低誘電率絶縁性コーティング組成物。
［５］
［１］～［４］のいずれか１項に記載の低誘電率絶縁性コーティング組成物の硬化物。
［６］
１０ＧＨｚにおける誘電率が３．０以下、かつ、誘電正接が０．０１以下である［５］に記載の硬化物。
［７］
［５］または［６］に記載の硬化物を絶縁性コーティング層として使用する方法。
［８］
［５］または［６］に記載の硬化物からなる層を有する表示装置。
[1]
(A)
(a) the following formula (1):
A compound having two silicon-bonded hydrogen atoms in one molecule represented by
(b) an addition reaction product with a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and an addition-reactive carbon-carbon double bond in one molecule; an addition reaction product having at least two in
A low dielectric constant insulating coating composition comprising (B) a compound having 3 or more silicon-bonded hydrogen atoms in one molecule and (C) a hydrosilylation reaction catalyst.
[2]
The polycyclic hydrocarbon of (b) is 5-vinylbicyclo[2.2.1]hept-2-ene, 6-vinylbicyclo[2.2.1]hept-2-ene, or a combination of the two. The low dielectric constant insulating coating composition according to [1].
[3]
The component (B) contains 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, or a mixture of both [1] or [2 ].
[4]
The component (B) is
5-vinylbicyclo[2.2.1]hept-2-ene, 6-vinylbicyclo[2.2.1]hept-2-ene or a mixture of both;
including addition reaction products with 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, or mixtures of both [1]-[3] The low dielectric constant insulating coating composition according to any one of .
[5]
A cured product of the low dielectric constant insulating coating composition according to any one of [1] to [4].
[6]
The cured product according to [5], which has a dielectric constant of 3.0 or less at 10 GHz and a dielectric loss tangent of 0.01 or less.
[7]
A method of using the cured product according to [5] or [6] as an insulating coating layer.
[8]
A display device comprising a layer comprising the cured product of [5] or [6].
本発明の低誘電率絶縁性コーティング組成物は、基板に塗布するのに適した粘度を有し、作業性に優れるとともに、得られる硬化物が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 a viscosity suitable for coating on a substrate, is excellent in workability, and the obtained cured product has a low dielectric constant and a low dielectric loss tangent. It is useful as a coating material for electronic and electrical devices with low transmission loss in the high frequency range.
以下、本発明をより詳細に説明する。
The present invention will be described in more detail below.
［（Ａ）成分］
（Ａ）成分は、
（ａ）下記一般式（１）：
（式（１）中、Ｒは、独立に非置換もしくは置換の炭素原子数１～１２の１価炭化水素基または炭素原子数１～６のアルコキシ基である。）
で表されるケイ素原子に結合した水素原子を１分子中に２個有する化合物と、
（ｂ）付加反応性炭素－炭素二重結合を１分子中に２個有する多環式炭化水素との付加反応生成物であって、かつ、付加反応性炭素－炭素二重結合を１分子中に少なくとも２個有する付加反応生成物である。 [(A) component]
(A) The component is
(a) the following general formula (1):
(In formula (1), R is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.)
A compound having two silicon-bonded hydrogen atoms in one molecule represented by
(b) an addition reaction product with a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and an addition-reactive carbon-carbon double bond in one molecule; is an addition reaction product having at least two in
（Ａ）成分は、
（ａ）下記一般式（１）：
で表されるケイ素原子に結合した水素原子を１分子中に２個有する化合物と、
（ｂ）付加反応性炭素－炭素二重結合を１分子中に２個有する多環式炭化水素との付加反応生成物であって、かつ、付加反応性炭素－炭素二重結合を１分子中に少なくとも２個有する付加反応生成物である。 [(A) component]
(A) The component is
(a) the following general formula (1):
A compound having two silicon-bonded hydrogen atoms in one molecule represented by
(b) an addition reaction product with a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and an addition-reactive carbon-carbon double bond in one molecule; is an addition reaction product having at least two in
＜（ａ）成分＞
（ａ）上記一般式（１）で表されるケイ素原子に結合した水素原子（以下、「ＳｉＨ」ということがある）を１分子中に２個有する化合物は（Ａ）成分の反応原料である。 <(a) component>
(a) A compound having two silicon-bonded hydrogen atoms (hereinafter sometimes referred to as "SiH") represented by the above general formula (1) in one molecule is a reaction raw material for component (A). .
（ａ）上記一般式（１）で表されるケイ素原子に結合した水素原子（以下、「ＳｉＨ」ということがある）を１分子中に２個有する化合物は（Ａ）成分の反応原料である。 <(a) component>
(a) A compound having two silicon-bonded hydrogen atoms (hereinafter sometimes referred to as "SiH") represented by the above general formula (1) in one molecule is a reaction raw material for component (A). .
上記式（１）中、Ｒが上記１価炭化水素基である場合としては、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、ｔｅｒｔ－ブチル基、ペンチル基、イソペンチル基、ヘキシル基、ｓｅｃ－ヘキシル基等のアルキル基；シクロペンチル基、シクロヘキシル基等のシクロアルキル基；フェニル基、ｏ－，ｍ－，ｐ－トリル等のアリール基；ベンジル基、２－フェニルエチル基等のアラルキル基；ビニル基、アリル基、１－ブテニル基、１－ヘキセニル基等のアルケニル基；ｐ－ビニルフェニル基等のアルケニルアリール基；およびこれらの基中の炭素原子に結合した１個以上の水素原子が、ハロゲン原子、シアノ基、エポキシ環含有基等で置換された、例えば、クロロメチル基、３－クロロプロピル基、３，３，３－トリフルオロプロピル基等のハロゲン化アルキル基；２－シアノエチル基；３－グリシドキシプロピル基等が挙げられる。
In the above formula (1), when R is the above monovalent hydrocarbon group, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl Alkyl groups such as group, sec-hexyl group; Cycloalkyl groups such as cyclopentyl group and cyclohexyl group; Aryl groups such as phenyl group and o-, m-, p-tolyl group; Aralkyl groups such as benzyl group and 2-phenylethyl group groups; alkenyl groups such as vinyl group, allyl group, 1-butenyl group and 1-hexenyl group; alkenylaryl groups such as p-vinylphenyl group; and one or more hydrogen atoms bonded to carbon atoms in these groups is substituted with a halogen atom, a cyano group, an epoxy ring-containing group, etc., for example, a halogenated alkyl group such as a chloromethyl group, a 3-chloropropyl group, a 3,3,3-trifluoropropyl group; 2-cyanoethyl group; 3-glycidoxypropyl group and the like.
また、Ｒが上記アルコキシ基である場合としては、例えば、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、ｓｅｃ－ブトキシ基、ｔｅｒｔ－ブトキシ基等が挙げられる。
Examples of the case where R is the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group.
上記の中でも、上記Ｒとしては、アルケニル基およびアルケニルアリール基以外のものが好ましく、特に、（ａ）成分としてはＲの全てがメチル基であるものが、工業的に製造することが容易であり、入手しやすいことから好ましい。
Among the above, the above R is preferably a group other than an alkenyl group and an alkenylaryl group, and in particular, the component (a) in which all of the Rs are methyl groups is easy to industrially produce. is preferred due to its availability.
この上記一般式（１）で表される化合物としては、例えば、
構造式：ＨＭｅ2Ｓｉ－ｐ－Ｃ6Ｈ4－ＳｉＭｅ2Ｈ
で表される １，４－ビス（ジメチルシリル）ベンゼン、
構造式：ＨＭｅ2Ｓｉ－ｍ－Ｃ6Ｈ4－ＳｉＭｅ2Ｈ
で表される １，３－ビス（ジメチルシリル）ベンゼン、
構造式：ＨＭｅ2Ｓｉ－ｏ－Ｃ6Ｈ4－ＳｉＭｅ2Ｈ
で表される １，２－ビス（ジメチルシリル）ベンゼン
等のシルフェニレン化合物が挙げられる。
この（Ａ）成分の反応原料である上記（ａ）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。 As the compound represented by the above general formula (1), for example,
Structural formula : HMe2Si -p- C6H4 - SiMe2H
1,4-bis(dimethylsilyl)benzene represented by
Structural formula: HMe2Si - m- C6H4 - SiMe2H
1,3-bis(dimethylsilyl)benzene represented by
Structural formula : HMe2Si -o- C6H4 - SiMe2H
Examples include silphenylene compounds such as 1,2-bis(dimethylsilyl)benzene represented by.
The above-mentioned component (a), which is a reaction raw material for component (A), can be used singly or in combination of two or more.
構造式：ＨＭｅ2Ｓｉ－ｐ－Ｃ6Ｈ4－ＳｉＭｅ2Ｈ
で表される １，４－ビス（ジメチルシリル）ベンゼン、
構造式：ＨＭｅ2Ｓｉ－ｍ－Ｃ6Ｈ4－ＳｉＭｅ2Ｈ
で表される １，３－ビス（ジメチルシリル）ベンゼン、
構造式：ＨＭｅ2Ｓｉ－ｏ－Ｃ6Ｈ4－ＳｉＭｅ2Ｈ
で表される １，２－ビス（ジメチルシリル）ベンゼン
等のシルフェニレン化合物が挙げられる。
この（Ａ）成分の反応原料である上記（ａ）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。 As the compound represented by the above general formula (1), for example,
Structural formula : HMe2Si -p- C6H4 - SiMe2H
1,4-bis(dimethylsilyl)benzene represented by
Structural formula: HMe2Si - m- C6H4 - SiMe2H
1,3-bis(dimethylsilyl)benzene represented by
Structural formula : HMe2Si -o- C6H4 - SiMe2H
Examples include silphenylene compounds such as 1,2-bis(dimethylsilyl)benzene represented by.
The above-mentioned component (a), which is a reaction raw material for component (A), can be used singly or in combination of two or more.
＜（ｂ）成分＞
（Ａ）成分の反応原料である（ｂ）付加反応性炭素－炭素二重結合を１分子中に２個有する多環式炭化水素において、前記「付加反応性」とは、ケイ素原子に結合した水素原子の付加（ヒドロシリル化反応として周知）を受け得る性質を意味する。 <(b) component>
In the (b) polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, which is the reaction raw material of component (A), the above-mentioned "addition-reactive" means It means the ability to undergo the addition of a hydrogen atom (known as a hydrosilylation reaction).
（Ａ）成分の反応原料である（ｂ）付加反応性炭素－炭素二重結合を１分子中に２個有する多環式炭化水素において、前記「付加反応性」とは、ケイ素原子に結合した水素原子の付加（ヒドロシリル化反応として周知）を受け得る性質を意味する。 <(b) component>
In the (b) polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, which is the reaction raw material of component (A), the above-mentioned "addition-reactive" means It means the ability to undergo the addition of a hydrogen atom (known as a hydrosilylation reaction).
また、該（ｂ）成分は、
（ｉ）多環式炭化水素の多環骨格を形成している炭素原子のうち、隣接する２つの炭素原子間に付加反応性炭素－炭素二重結合が形成されているもの、
（ｉｉ）多環式炭化水素の多環骨格を形成している炭素原子に結合した水素原子が、付加反応性炭素－炭素二重結合含有基によって置換されているもの、または、
（ｉｉｉ）多環式炭化水素の多環骨格を形成している炭素原子のうち、隣接する２つの炭素原子間に付加反応性炭素－炭素二重結合が形成されており、かつ、多環式炭化水素の多環骨格を形成している炭素原子に結合した水素原子が付加反応性炭素－炭素二重結合含有基によって置換されているものの何れであっても差し支えない。 In addition, the component (b) is
(i) those in which an addition-reactive carbon-carbon double bond is formed between two adjacent carbon atoms among the carbon atoms forming the polycyclic skeleton of the polycyclic hydrocarbon;
(ii) hydrogen atoms bonded to carbon atoms forming the polycyclic skeleton of the polycyclic hydrocarbon are replaced by addition-reactive carbon-carbon double bond-containing groups, or
(iii) of the carbon atoms forming the polycyclic skeleton of the polycyclic hydrocarbon, an addition-reactive carbon-carbon double bond is formed between two adjacent carbon atoms, and the polycyclic Any hydrogen atom bonded to a carbon atom forming the hydrocarbon polycyclic skeleton may be replaced by an addition-reactive carbon-carbon double bond-containing group.
（ｉ）多環式炭化水素の多環骨格を形成している炭素原子のうち、隣接する２つの炭素原子間に付加反応性炭素－炭素二重結合が形成されているもの、
（ｉｉ）多環式炭化水素の多環骨格を形成している炭素原子に結合した水素原子が、付加反応性炭素－炭素二重結合含有基によって置換されているもの、または、
（ｉｉｉ）多環式炭化水素の多環骨格を形成している炭素原子のうち、隣接する２つの炭素原子間に付加反応性炭素－炭素二重結合が形成されており、かつ、多環式炭化水素の多環骨格を形成している炭素原子に結合した水素原子が付加反応性炭素－炭素二重結合含有基によって置換されているものの何れであっても差し支えない。 In addition, the component (b) is
(i) those in which an addition-reactive carbon-carbon double bond is formed between two adjacent carbon atoms among the carbon atoms forming the polycyclic skeleton of the polycyclic hydrocarbon;
(ii) hydrogen atoms bonded to carbon atoms forming the polycyclic skeleton of the polycyclic hydrocarbon are replaced by addition-reactive carbon-carbon double bond-containing groups, or
(iii) of the carbon atoms forming the polycyclic skeleton of the polycyclic hydrocarbon, an addition-reactive carbon-carbon double bond is formed between two adjacent carbon atoms, and the polycyclic Any hydrogen atom bonded to a carbon atom forming the hydrocarbon polycyclic skeleton may be replaced by an addition-reactive carbon-carbon double bond-containing group.
この（ｂ）成分としては、例えば、
下記構造式（ｘ）：
で表される５－ビニルビシクロ［２．２．１］ヘプト－２－エン、
下記構造式（ｙ）：
で表される６－ビニルビシクロ［２．２．１］ヘプト－２－エン、
これら両者の組み合わせが挙げられる。（以下、これら３者を区別する必要がない場合は、「ビニルノルボルネン」と総称することがある。） As this component (b), for example,
Structural formula (x) below:
5-vinylbicyclo[2.2.1]hept-2-ene represented by
Structural formula (y) below:
6-vinylbicyclo[2.2.1]hept-2-ene represented by
Combinations of both are included. (Hereinafter, when there is no need to distinguish between these three substances, they may be collectively referred to as "vinylnorbornene.")
下記構造式（ｘ）：
下記構造式（ｙ）：
これら両者の組み合わせが挙げられる。（以下、これら３者を区別する必要がない場合は、「ビニルノルボルネン」と総称することがある。） As this component (b), for example,
Structural formula (x) below:
Structural formula (y) below:
Combinations of both are included. (Hereinafter, when there is no need to distinguish between these three substances, they may be collectively referred to as "vinylnorbornene.")
なお、前記ビニルノルボルネンのビニル基の置換位置は、シス配置（エキソ形）またはトランス配置（エンド形）のいずれであってもよく、また、前記配置の相違によって、該成分の反応性等に特段の差異がないことから、これら両配置の異性体の組み合わせであっても差し支えない。
The substitution position of the vinyl group of the vinylnorbornene may be either cis configuration (exo type) or trans configuration (endo type). Since there is no difference between the two configurations, a combination of isomers of both configurations may be used.
＜（Ａ）成分の調製＞
（Ａ）成分は、ＳｉＨを１分子中に２個有する上記（ａ）成分の１モルに対して、付加反応性炭素－炭素二重結合を１分子中に２個有する上記（ｂ）成分の１モルを越え１０モル以下、好ましくは１モルを越え５モル以下の過剰量を、ヒドロシリル化反応触媒の存在下で付加反応させることにより、ＳｉＨを有しない付加反応生成物として得ることができる。
こうして得られる（Ａ）成分は、（ｂ）成分由来の付加反応性炭素－炭素二重結合のほかに、（ａ）成分に由来する（具体的には、一般式（１）中のＲに由来する）付加反応性炭素－炭素二重結合を含み得るので、付加反応性炭素－炭素二重結合を１分子中に少なくとも２個含むが、この数は好ましくは２～６個、より好ましくは２個である。この付加反応性炭素－炭素二重結合が多すぎると、本発明の組成物を硬化させて得られる硬化物に割れが生じやすくなる。 <Preparation of component (A)>
Component (A) is the above component (b) having two addition-reactive carbon-carbon double bonds in one molecule, per 1 mol of the component (a) having two SiH in one molecule. An excess amount of more than 1 mol and 10 mol or less, preferably more than 1 mol and 5 mol or less, is subjected to an addition reaction in the presence of a hydrosilylation reaction catalyst to obtain an addition reaction product having no SiH.
The (A) component thus obtained is derived from the component (a) in addition to the addition-reactive carbon-carbon double bond derived from the component (b) (specifically, R in the general formula (1) can contain addition-reactive carbon-carbon double bonds (derived from There are two. If there are too many addition-reactive carbon-carbon double bonds, the cured product obtained by curing the composition of the present invention tends to crack.
（Ａ）成分は、ＳｉＨを１分子中に２個有する上記（ａ）成分の１モルに対して、付加反応性炭素－炭素二重結合を１分子中に２個有する上記（ｂ）成分の１モルを越え１０モル以下、好ましくは１モルを越え５モル以下の過剰量を、ヒドロシリル化反応触媒の存在下で付加反応させることにより、ＳｉＨを有しない付加反応生成物として得ることができる。
こうして得られる（Ａ）成分は、（ｂ）成分由来の付加反応性炭素－炭素二重結合のほかに、（ａ）成分に由来する（具体的には、一般式（１）中のＲに由来する）付加反応性炭素－炭素二重結合を含み得るので、付加反応性炭素－炭素二重結合を１分子中に少なくとも２個含むが、この数は好ましくは２～６個、より好ましくは２個である。この付加反応性炭素－炭素二重結合が多すぎると、本発明の組成物を硬化させて得られる硬化物に割れが生じやすくなる。 <Preparation of component (A)>
Component (A) is the above component (b) having two addition-reactive carbon-carbon double bonds in one molecule, per 1 mol of the component (a) having two SiH in one molecule. An excess amount of more than 1 mol and 10 mol or less, preferably more than 1 mol and 5 mol or less, is subjected to an addition reaction in the presence of a hydrosilylation reaction catalyst to obtain an addition reaction product having no SiH.
The (A) component thus obtained is derived from the component (a) in addition to the addition-reactive carbon-carbon double bond derived from the component (b) (specifically, R in the general formula (1) can contain addition-reactive carbon-carbon double bonds (derived from There are two. If there are too many addition-reactive carbon-carbon double bonds, the cured product obtained by curing the composition of the present invention tends to crack.
前記ヒドロシリル化反応触媒としては、従来から公知のものが全て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、溶媒の使用等については、特に限定されず通常のとおりとすればよい。
As the hydrosilylation reaction catalyst, all conventionally known catalysts can be used. For example, platinum metal-supported carbon powder, platinum black, diplatinum chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohols, complexes of chloroplatinic acid and olefins, platinum bisacetoacetate, etc. platinum group metal catalysts such as palladium catalysts and rhodium catalysts. Moreover, the addition reaction conditions, the use of solvents, etc. are not particularly limited, and may be as usual.
前記のとおり、（Ａ）成分の調製に際し、上記（ａ）成分に対して過剰モル量の上記（ｂ）成分を用いることから、該（Ａ）成分は、上記（ｂ）成分の構造に由来する付加反応性炭素－炭素二重結合を１分子中に２個有するものである。更に、（Ａ）成分は、上記（ａ）成分に由来する残基を有し、その残基が、上記（ｂ）成分の構造に由来するが付加反応性炭素－炭素二重結合を有しない多環式炭化水素の二価の残基によって結合されている構造を含むものであってもよい。
As described above, in the preparation of component (A), an excess molar amount of component (b) is used with respect to component (a), so component (A) is derived from the structure of component (b). It has two addition-reactive carbon-carbon double bonds in one molecule. Furthermore, component (A) has a residue derived from component (a) above, which residue is derived from the structure of component (b) above but does not have an addition-reactive carbon-carbon double bond. It may also include structures joined by divalent residues of polycyclic hydrocarbons.
即ち、（Ａ）成分としては、例えば、下記一般式（４）：
Ｙ－Ｘ－（Ｙ’－Ｘ）p－Ｙ （４）
（式中、Ｘは上記（ａ）成分の化合物の二価の残基であり、Ｙは上記（ｂ）成分の多環式炭化水素の一価の残基であり、Ｙ’は上記（ｂ）成分の二価の残基であり、ｐは０～１０、好ましくは０～５の整数である）
で表される化合物が挙げられる。 That is, as the component (A), for example, the following general formula (4):
YX-(Y'-X) p -Y (4)
(Wherein, X is the divalent residue of the compound of component (a) above, Y is the monovalent residue of the polycyclic hydrocarbon of component (b) above, and Y′ is the residue of the above (b ) is a divalent residue of the component and p is an integer from 0 to 10, preferably from 0 to 5)
The compound represented by is mentioned.
Ｙ－Ｘ－（Ｙ’－Ｘ）p－Ｙ （４）
（式中、Ｘは上記（ａ）成分の化合物の二価の残基であり、Ｙは上記（ｂ）成分の多環式炭化水素の一価の残基であり、Ｙ’は上記（ｂ）成分の二価の残基であり、ｐは０～１０、好ましくは０～５の整数である）
で表される化合物が挙げられる。 That is, as the component (A), for example, the following general formula (4):
YX-(Y'-X) p -Y (4)
(Wherein, X is the divalent residue of the compound of component (a) above, Y is the monovalent residue of the polycyclic hydrocarbon of component (b) above, and Y′ is the residue of the above (b ) is a divalent residue of the component and p is an integer from 0 to 10, preferably from 0 to 5)
The compound represented by is mentioned.
なお、上記（Ｙ’－Ｘ）で表される繰り返し単位の数であるｐの値については、上記（ａ）成分１モルに対して反応させる上記（ｂ）成分の過剰モル量を調整することにより設定することが可能である。
The value of p, which is the number of repeating units represented by (Y'-X), can be adjusted by adjusting the excess molar amount of the component (b) to be reacted with respect to 1 mol of the component (a). can be set by
上記一般式（４）中のＹとしては、具体的には、例えば、下記構造式：
で表される一価の残基（以下、これら６者を区別する必要がない場合は、これらを「ＮＢ基」と総称し、また、前記６種類の構造を区別せずに「ＮＢ」と略記することがある。）が挙げられる。
Specifically, Y in the general formula (4) includes, for example, the following structural formula:
(hereinafter, if it is not necessary to distinguish between these six groups, they are collectively referred to as "NB groups", and the six types of structures are referred to as "NB" without distinguishing may be abbreviated).
上記一般式（４）中のＹ’としては、具体的には、例えば、下記構造式：
で表される二価の残基が挙げられる。
Specific examples of Y′ in the general formula (4) include the following structural formula:
A bivalent residue represented by is included.
但し、上記構造式で表される非対称な二価の残基は、その左右方向が上記記載のとおりに限定されるものではなく、上記構造式は、実質上、個々の上記構造を紙面上で１８０度回転させた構造をも含めて示している。
However, the asymmetric divalent residue represented by the above structural formula is not limited to the left-right direction as described above, and the above structural formula substantially represents each of the above structures on paper. It also shows the structure rotated 180 degrees.
上記一般式（４）で表される（Ａ）成分の好適な具体例を、以下に示すが、これに限定されるものではない。（なお、「ＮＢ」の意味するところは、上記のとおりであり、式中の「Ｍｅ」はメチル基を示す（以下同様）。）
Suitable specific examples of the component (A) represented by the general formula (4) are shown below, but are not limited thereto. (The meaning of "NB" is as described above, and "Me" in the formula represents a methyl group (the same applies hereinafter).)
更に、本発明の（Ａ）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。
Furthermore, the (A) component of the present invention can be used singly or in combination of two or more.
［（Ｂ）成分］
（Ｂ）成分は、ＳｉＨを１分子中に３個以上有する化合物である。該（Ｂ）成分中のＳｉＨが、上記（Ａ）成分が１分子中に少なくとも２個有する付加反応性炭素－炭素二重結合とヒドロシリル化反応により付加して、３次元網状構造の硬化物を与える。 [(B) component]
The component (B) is a compound having 3 or more SiH in one molecule. The SiH in the component (B) is added to the addition-reactive carbon-carbon double bond that the component (A) has at least two in one molecule by a hydrosilylation reaction to form a cured product with a three-dimensional network structure. give.
（Ｂ）成分は、ＳｉＨを１分子中に３個以上有する化合物である。該（Ｂ）成分中のＳｉＨが、上記（Ａ）成分が１分子中に少なくとも２個有する付加反応性炭素－炭素二重結合とヒドロシリル化反応により付加して、３次元網状構造の硬化物を与える。 [(B) component]
The component (B) is a compound having 3 or more SiH in one molecule. The SiH in the component (B) is added to the addition-reactive carbon-carbon double bond that the component (A) has at least two in one molecule by a hydrosilylation reaction to form a cured product with a three-dimensional network structure. give.
該（Ｂ）成分としては、例えば、下記一般式（５）：
（式（５）中、Ｒ1は独立に水素原子またはアルケニル基以外の非置換もしくは置換の炭素原子数１～１２、好ましくは１～６の一価炭化水素基であり、ｑは３～１０、好ましくは３～８の整数、ｒは０～７、好ましくは０～２の整数であり、かつｑ＋ｒの和は３～１０、好ましくは３～６の整数である）
で表される環状シロキサン系化合物が挙げられる。 The (B) component is, for example, the following general formula (5):
(In formula (5), R 1 is independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group other than an alkenyl group, having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and q is 3 to 10 , preferably an integer of 3 to 8, r is an integer of 0 to 7, preferably 0 to 2, and the sum of q + r is an integer of 3 to 10, preferably 3 to 6)
A cyclic siloxane compound represented by is mentioned.
で表される環状シロキサン系化合物が挙げられる。 The (B) component is, for example, the following general formula (5):
A cyclic siloxane compound represented by is mentioned.
上記一般式（５）中のＲ1がアルケニル基以外の非置換もしくは置換の一価炭化水素基である場合としては、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、ｔｅｒｔ－ブチル基、ペンチル基、イソペンチル基、ヘキシル基、ｓｅｃ－ヘキシル基等のアルキル基；シクロペンチル基、シクロヘキシル基等のシクロアルキル基；フェニル基、ｏ－，ｍ－，ｐ－トリル等のアリール基；ベンジル基、２－フェニルエチル基等のアラルキル基；ｐ－ビニルフェニル基等のアルケニルアリール基；およびこれらの基中の炭素原子に結合した１個以上の水素原子が、ハロゲン原子、シアノ基、エポキシ環含有基等で置換された、例えば、クロロメチル基、３－クロロプロピル基、３，３，３－トリフルオロプロピル基等のハロゲン化アルキル基；２－シアノエチル基；３－グリシドキシプロピル基等が挙げられる。
Examples of the case where R 1 in the general formula (5) is an unsubstituted or substituted monovalent hydrocarbon group other than an alkenyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert- Alkyl groups such as butyl group, pentyl group, isopentyl group, hexyl group and sec-hexyl group; Cycloalkyl groups such as cyclopentyl group and cyclohexyl group; Aryl groups such as phenyl group and o-, m-, p-tolyl; aralkyl groups such as 2-phenylethyl groups; alkenylaryl groups such as p-vinylphenyl groups; and one or more hydrogen atoms bonded to carbon atoms in these groups are halogen atoms, cyano groups, epoxy rings halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group and 3,3,3-trifluoropropyl group; 2-cyanoethyl group; is mentioned.
上記の中でも、前記Ｒ1としては、メチル基が好ましく、特に、（Ｂ）成分としてはＲ1の全てがメチル基であるものが、工業的に製造することが容易であり、入手しやすいことから好ましい。
Among the above, R 1 is preferably a methyl group, and in particular, component (B) in which all R 1 are methyl groups is easy to industrially produce and readily available. preferred from
また、該（Ｂ）成分としては、例えば、上記ビニルノルボルネンの一種または二種と、１，３，５，７－テトラメチルシクロテトラシロキサンとをヒドロシリル化反応させて得られるＳｉＨを１分子中に３個以上有する付加反応生成物、例えば、下記一般式（６）：
（式（６）中、ｓは１～１００、好ましくは１～１０の整数である）
で表される化合物、および、上記ビニルノルボルネンの一種または二種と、１，３，５，７，９－ペンタメチルシクロペンタシロキサンとをヒドロシリル化反応させて得られるＳｉＨを１分子中に３個以上有する付加反応生成物、例えば、下記一般式（７）：
（式（７）中、ｔは１～１００、好ましくは１～１０の整数である）
で表される化合物が挙げられる。 Further, as the component (B), for example, one or two of the above vinylnorbornenes and 1,3,5,7-tetramethylcyclotetrasiloxane are hydrosilylated to obtain SiH in one molecule. An addition reaction product having 3 or more, for example, the following general formula (6):
(In formula (6), s is an integer of 1 to 100, preferably 1 to 10)
and one or two of the above vinylnorbornenes and 1,3,5,7,9-pentamethylcyclopentasiloxane are subjected to a hydrosilylation reaction to obtain 3 SiH in one molecule. The addition reaction product having the above, for example, the following general formula (7):
(In formula (7), t is an integer of 1 to 100, preferably 1 to 10)
The compound represented by is mentioned.
で表される化合物、および、上記ビニルノルボルネンの一種または二種と、１，３，５，７，９－ペンタメチルシクロペンタシロキサンとをヒドロシリル化反応させて得られるＳｉＨを１分子中に３個以上有する付加反応生成物、例えば、下記一般式（７）：
で表される化合物が挙げられる。 Further, as the component (B), for example, one or two of the above vinylnorbornenes and 1,3,5,7-tetramethylcyclotetrasiloxane are hydrosilylated to obtain SiH in one molecule. An addition reaction product having 3 or more, for example, the following general formula (6):
and one or two of the above vinylnorbornenes and 1,3,5,7,9-pentamethylcyclopentasiloxane are subjected to a hydrosilylation reaction to obtain 3 SiH in one molecule. The addition reaction product having the above, for example, the following general formula (7):
The compound represented by is mentioned.
上記(Ｂ)成分の好適な具体例を、以下に示すが、これに限定されるものではない。
Preferred specific examples of the component (B) are shown below, but are not limited thereto.
（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。
The component (B) can be used singly or in combination of two or more.
（Ｂ）成分の配合量は、次のように設定されることが好ましい。後述するように、本発明の組成物は、（Ｂ）成分以外のケイ素原子に結合した水素原子を有する成分、および／または（Ａ）成分以外のケイ素原子に結合した付加反応性炭素－炭素二重結合を有する成分を含有することができる。そこで、本組成物中のケイ素原子に結合した付加反応性炭素－炭素二重結合１モルに対して本組成物中のケイ素原子に結合した水素原子の量は、通常０．５～３．０モル、好ましくは０．８～２．０モルである。（Ｂ）成分の配合量がこのような条件を満たすようになされると、十分な硬度を有する硬化物を得ることができる。
上述の任意的成分を含まない場合には、本発明の低誘電率絶縁性コーティング組成物への（Ｂ）成分の配合量は、上記（Ａ）成分中の付加反応性炭素－炭素二重結合１モルに対して、該（Ｂ）成分中のＳｉＨが、通常、０．５～３．０モル、好ましくは０．８～２．０モルとなる量とするのがよい。 (B) It is preferable to set the compounding quantity of a component as follows. As will be described later, the composition of the present invention contains a component having hydrogen atoms bonded to silicon atoms other than component (B) and/or an addition-reactive carbon-carbon dihydrogen atom bonded to silicon atoms other than component (A). A component with a double bond can be included. Therefore, the amount of hydrogen atoms bonded to silicon atoms in the present composition per mol of addition-reactive carbon-carbon double bonds bonded to silicon atoms in the present composition is usually 0.5 to 3.0. mol, preferably 0.8 to 2.0 mol. When the blending amount of component (B) satisfies these conditions, a cured product having sufficient hardness can be obtained.
When the above optional components are not included, the amount of component (B) to be added to the low dielectric constant insulating coating composition of the present invention is the addition reactive carbon-carbon double bond in component (A). The amount of SiH in component (B) is generally 0.5 to 3.0 mol, preferably 0.8 to 2.0 mol, per 1 mol.
上述の任意的成分を含まない場合には、本発明の低誘電率絶縁性コーティング組成物への（Ｂ）成分の配合量は、上記（Ａ）成分中の付加反応性炭素－炭素二重結合１モルに対して、該（Ｂ）成分中のＳｉＨが、通常、０．５～３．０モル、好ましくは０．８～２．０モルとなる量とするのがよい。 (B) It is preferable to set the compounding quantity of a component as follows. As will be described later, the composition of the present invention contains a component having hydrogen atoms bonded to silicon atoms other than component (B) and/or an addition-reactive carbon-carbon dihydrogen atom bonded to silicon atoms other than component (A). A component with a double bond can be included. Therefore, the amount of hydrogen atoms bonded to silicon atoms in the present composition per mol of addition-reactive carbon-carbon double bonds bonded to silicon atoms in the present composition is usually 0.5 to 3.0. mol, preferably 0.8 to 2.0 mol. When the blending amount of component (B) satisfies these conditions, a cured product having sufficient hardness can be obtained.
When the above optional components are not included, the amount of component (B) to be added to the low dielectric constant insulating coating composition of the present invention is the addition reactive carbon-carbon double bond in component (A). The amount of SiH in component (B) is generally 0.5 to 3.0 mol, preferably 0.8 to 2.0 mol, per 1 mol.
［（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＞で記載したものと同じである。
（Ｃ）成分の配合量は、触媒としての有効量であればよく、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、白金族金属原子として、通常、１～５００ｐｐｍ、特に２～１００ｐｐｍ程度となる量を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で、硬化反応に要する時間が適度のものとなり、硬化物が着色する等の問題を生じることがない。 [(C) component]
The hydrosilylation reaction catalyst which is the component (C) of the present invention is the same as described in <Preparation of the component (A)> above.
The amount of component (C) is not particularly limited as long as it is an effective amount as a catalyst. It is preferable to add an amount of about 1 to 500 ppm, particularly about 2 to 100 ppm. By setting the blending amount within the above range, the time required for the curing reaction becomes appropriate, and problems such as coloring of the cured product do not occur.
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＞で記載したものと同じである。
（Ｃ）成分の配合量は、触媒としての有効量であればよく、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、白金族金属原子として、通常、１～５００ｐｐｍ、特に２～１００ｐｐｍ程度となる量を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で、硬化反応に要する時間が適度のものとなり、硬化物が着色する等の問題を生じることがない。 [(C) component]
The hydrosilylation reaction catalyst which is the component (C) of the present invention is the same as described in <Preparation of the component (A)> above.
The amount of component (C) is not particularly limited as long as it is an effective amount as a catalyst. It is preferable to add an amount of about 1 to 500 ppm, particularly about 2 to 100 ppm. By setting the blending amount within the above range, the time required for the curing reaction becomes appropriate, and problems such as coloring of the cured product do not occur.
［他の配合成分］
本発明の低誘電率絶縁性コーティング組成物には、上記（Ａ）～（Ｃ）成分に加えて、本発明の目的・効果を損なわない範囲で他の成分を配合することは任意である。 [Other ingredients]
In addition to the above components (A) to (C), the low dielectric constant insulating coating composition of the present invention may optionally contain other components within a range that does not impair the objects and effects of the present invention.
本発明の低誘電率絶縁性コーティング組成物には、上記（Ａ）～（Ｃ）成分に加えて、本発明の目的・効果を損なわない範囲で他の成分を配合することは任意である。 [Other ingredients]
In addition to the above components (A) to (C), the low dielectric constant insulating coating composition of the present invention may optionally contain other components within a range that does not impair the objects and effects of the present invention.
＜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（Ａ）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、
下記構造式（ｉ）：
で表される２－（ビシクロ［２．２．１］ヘプト－２－エン－５－イル）エチル基および／または
下記構造式（ｉｉ）：
で表される２－（ビシクロ［２．２．１］ヘプト－２－エン－６－イル）エチル基の炭素－炭素二重結合が含まれている場合がある。そして、前記炭素－炭素二重結合が含まれていると、大気中の酸素により酸化され前記硬化物が着色する原因となる。
そこで、本発明の低誘電率絶縁性コーティング組成物に、必要に応じ、酸化防止剤を配合することにより前記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 (A) may remain unreacted.
Structural formula (i) below:
and/or the following structural formula (ii):
The carbon-carbon double bond of the 2-(bicyclo[2.2.1]hept-2-en-6-yl)ethyl group represented by may be included. If the carbon-carbon double bond is included, it will be oxidized by oxygen in the air, causing the cured product to color.
Therefore, the 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（Ａ）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、
下記構造式（ｉ）：
下記構造式（ｉｉ）：
そこで、本発明の低誘電率絶縁性コーティング組成物に、必要に応じ、酸化防止剤を配合することにより前記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 (A) may remain unreacted.
Structural formula (i) below:
Therefore, the coloring can be prevented by adding an antioxidant to the low dielectric constant insulating coating composition of the present invention, if necessary.
この酸化防止剤としては、従来から公知のものが全て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 this antioxidant, all conventionally known ones can be used. 5-di-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 singly 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、酸化防止剤としての有効量であればよく、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、１０～１０，０００ｐｐｍ、特に１００～１，０００ｐｐｍ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。
When this antioxidant is used, the amount to be blended is not particularly limited as long as it is an effective amount as an antioxidant. , usually 10 to 10,000 ppm, preferably 100 to 1,000 ppm. By setting the blending amount within the above range, the antioxidant ability is fully exhibited, and a cured product having excellent optical properties without causing coloration, white turbidity, deterioration due to oxidation, etc., can be obtained.
＜粘度・硬度調整剤＞
本発明の低誘電率絶縁性コーティング組成物の粘度もしくは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するために、ケイ素原子に結合したアルケニル基またはＳｉＨを有する直鎖状ジオルガノポリシロキサンもしくは網状オルガノポリシロキサン；非反応性の（即ち、ケイ素原子に結合したアルケニル基およびＳｉＨを有しない）直鎖状もしくは環状ジオルガノポリシロキサン、シルフェニレン系化合物等を配合してもよい。 <Viscosity/hardness modifier>
In order to adjust the viscosity of the low dielectric constant insulating coating composition of the present invention or the hardness of the cured product obtained from the low dielectric constant insulating coating composition of the present invention, it has an alkenyl group or SiH bonded to a silicon atom. Linear diorganopolysiloxane or network organopolysiloxane; non-reactive (i.e., having no silicon-bonded alkenyl groups and SiH) linear or cyclic diorganopolysiloxane, silphenylene compounds, etc. You may
本発明の低誘電率絶縁性コーティング組成物の粘度もしくは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するために、ケイ素原子に結合したアルケニル基またはＳｉＨを有する直鎖状ジオルガノポリシロキサンもしくは網状オルガノポリシロキサン；非反応性の（即ち、ケイ素原子に結合したアルケニル基およびＳｉＨを有しない）直鎖状もしくは環状ジオルガノポリシロキサン、シルフェニレン系化合物等を配合してもよい。 <Viscosity/hardness modifier>
In order to adjust the viscosity of the low dielectric constant insulating coating composition of the present invention or the hardness of the cured product obtained from the low dielectric constant insulating coating composition of the present invention, it has an alkenyl group or SiH bonded to a silicon atom. Linear diorganopolysiloxane or network organopolysiloxane; non-reactive (i.e., having no silicon-bonded alkenyl groups and SiH) linear or cyclic diorganopolysiloxane, silphenylene compounds, etc. You may
本発明の低誘電率絶縁性コーティング組成物に、（Ｄ１）ケイ素原子に結合したアルケニル基を有する種々の構造のオルガノポリシロキサンを配合する場合、その配合量は、前記アルケニル基と上記（Ａ）成分が有する付加反応性炭素－炭素二重結合との合計量１モルに対する、上記（Ｂ）成分中のＳｉＨが、通常、０．５～３．０モル、好ましくは０．８～２．０モルとなる量とするのがよい。また、本発明の低誘電率絶縁性コーティング組成物に、（Ｄ２）ＳｉＨを有する種々の構造のオルガノポリシロキサンを配合する場合、その配合量は、前記ＳｉＨと上記（Ｂ）成分が有するＳｉＨとの合計量が、上記（Ａ）成分が有する付加反応性炭素－炭素二重結合１モルに対して、通常、０．５～３．０モル、好ましくは０．８～２．０モルとなる量とするのがよい。
When the low dielectric constant insulating coating composition of the present invention is blended with (D1) organopolysiloxanes having various structures having alkenyl groups bonded to silicon atoms, the blending amount thereof is such that the alkenyl groups and the above (A) SiH in the above component (B) is usually 0.5 to 3.0 mol, preferably 0.8 to 2.0 mol, per 1 mol of the total amount of addition-reactive carbon-carbon double bonds possessed by the component. It is preferable to use a molar amount. When the low dielectric constant insulating coating composition of the present invention is blended with (D2) organopolysiloxanes having various structures having SiH, the blending amounts thereof are the same as the above SiH and the SiH possessed by the component (B). is usually 0.5 to 3.0 mol, preferably 0.8 to 2.0 mol, per 1 mol of the addition-reactive carbon-carbon double bond of component (A). Quantity is better.
本発明の低誘電率絶縁性コーティング組成物の２５℃における粘度は、好ましくは１０～１０，０００ｍＰａ・ｓ、より好ましくは３０～３，０００ｍＰａ・ｓである。このような範囲であれば作業性に優れる。なお、本発明における粘度は、ＪＩＳ Ｋ ７１１７－１：１９９９に準じ回転粘度計によって２５℃で測定した粘度を示す。
The viscosity of the low dielectric constant insulating coating composition of the present invention at 25°C is preferably 10 to 10,000 mPa·s, more preferably 30 to 3,000 mPa·s. Within such a range, workability is excellent. The viscosity in the present invention indicates the viscosity measured at 25°C with a rotational viscometer according to JIS K 7117-1:1999.
＜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。更に、透明性に影響を与えない範囲で、強度を向上させるためにヒュームドシリカ等の無機質充填剤を配合してもよいし、必要に応じて、染料、顔料、難燃剤等を配合してもよい。 <Others>
Moreover, in order to ensure pot life, addition reaction controllers such as 1-ethynylcyclohexanol and 3,5-dimethyl-1-hexyn-3-ol can be blended. Furthermore, an inorganic filler such as fumed silica may be blended to improve strength within a range that does not affect transparency, and if necessary, dyes, pigments, flame retardants, etc. may be blended. good too.
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。更に、透明性に影響を与えない範囲で、強度を向上させるためにヒュームドシリカ等の無機質充填剤を配合してもよいし、必要に応じて、染料、顔料、難燃剤等を配合してもよい。 <Others>
Moreover, in order to ensure pot life, addition reaction controllers such as 1-ethynylcyclohexanol and 3,5-dimethyl-1-hexyn-3-ol can be blended. Furthermore, an inorganic filler such as fumed silica may be blended to improve strength within a range that does not affect transparency, and if necessary, dyes, pigments, flame retardants, etc. may be blended. good too.
更に、太陽光線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 photodegradation due to light energy such as sunlight. Hindered amine-based stabilizers that capture radicals generated by photo-oxidative deterioration are suitable as the light stabilizer, and the antioxidant effect is further improved by using them together with antioxidants. Specific examples of light stabilizers include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate and 4-benzoyl-2,2,6,6-tetramethylpiperidine.
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. Preferably, it is more preferably 90 to 100% by mass.
Also, the low dielectric constant insulating coating composition of the present invention can be produced by uniformly mixing the components described above.
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. Preferably, it is more preferably 90 to 100% by mass.
Also, the low dielectric constant insulating coating composition of the present invention can be produced by uniformly mixing the components described above.
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、その量により異なり、特に制限されないが、通常、６０～１８０℃、１０～３００分の条件とすることが好ましい。
The curing conditions for the low-dielectric-constant insulating coating composition of the present invention vary depending on the amount thereof, and are not particularly limited, but the conditions of 60 to 180° C. and 10 to 300 minutes are usually preferred.
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。
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 such a range, high-frequency dielectric properties are excellent.
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. In addition, 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 in display devices.
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。
Examples and comparative examples are shown below to specifically describe the present invention, but the present invention is not limited to the following examples.
［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５００ｍＬの４つ口フラスコに、ビニルノルボルネン（商品名：Ｖ００６２、東京化成社製；５－ビニルビシクロ［２．２．１］ヘプト－２－エンと６－ビニルビシクロ［２．２．１］ヘプト－２－エンとの略等モル量の異性体混合物）６０ｇ（０．５モル）を加え、オイルバスを用いて８５℃に加熱した。これに、５質量％の白金金属を担持したカーボン粉末０．０２ｇ添加し、攪拌しながら１，４－ビス（ジメチルシリル）ベンゼン３８．８ｇ（０．２モル）を２５分間かけて滴下した。滴下終了後、更に９０℃で加熱攪拌を２４時間行った後、室温まで冷却した。その後、白金金属担持カーボンをろ過して除去し、過剰のビニルノルボルネンを減圧留去して、無色透明なオイル状の反応生成物（２５℃における粘度：１，２００ｍＰａ・ｓ）７９ｇを得た。 [Synthesis Example 1] Preparation of component (A) In a 500 mL four-necked flask equipped with a stirrer, condenser, dropping funnel and thermometer, vinylnorbornene (trade name: V0062, manufactured by Tokyo Kasei Co.; 5-vinylbicyclo 60 g (0.5 mol) of an approximately equimolar isomer mixture of [2.2.1]hept-2-ene and 6-vinylbicyclo[2.2.1]hept-2-ene) was added, It was heated to 85° C. using an oil bath. To this, 0.02 g of carbon powder supporting 5% by mass of platinum metal was added, and 38.8 g (0.2 mol) of 1,4-bis(dimethylsilyl)benzene was added dropwise over 25 minutes while stirring. After completion of dropping, the mixture was further heated and stirred at 90° C. for 24 hours, and then cooled to room temperature. Thereafter, platinum metal-supporting carbon was removed by filtration, and excess vinylnorbornene was distilled off under reduced pressure to obtain 79 g of a colorless, transparent, oily reaction product (viscosity at 25°C: 1,200 mPa·s).
攪拌装置、冷却管、滴下ロートおよび温度計を備えた５００ｍＬの４つ口フラスコに、ビニルノルボルネン（商品名：Ｖ００６２、東京化成社製；５－ビニルビシクロ［２．２．１］ヘプト－２－エンと６－ビニルビシクロ［２．２．１］ヘプト－２－エンとの略等モル量の異性体混合物）６０ｇ（０．５モル）を加え、オイルバスを用いて８５℃に加熱した。これに、５質量％の白金金属を担持したカーボン粉末０．０２ｇ添加し、攪拌しながら１，４－ビス（ジメチルシリル）ベンゼン３８．８ｇ（０．２モル）を２５分間かけて滴下した。滴下終了後、更に９０℃で加熱攪拌を２４時間行った後、室温まで冷却した。その後、白金金属担持カーボンをろ過して除去し、過剰のビニルノルボルネンを減圧留去して、無色透明なオイル状の反応生成物（２５℃における粘度：１，２００ｍＰａ・ｓ）７９ｇを得た。 [Synthesis Example 1] Preparation of component (A) In a 500 mL four-necked flask equipped with a stirrer, condenser, dropping funnel and thermometer, vinylnorbornene (trade name: V0062, manufactured by Tokyo Kasei Co.; 5-vinylbicyclo 60 g (0.5 mol) of an approximately equimolar isomer mixture of [2.2.1]hept-2-ene and 6-vinylbicyclo[2.2.1]hept-2-ene) was added, It was heated to 85° C. using an oil bath. To this, 0.02 g of carbon powder supporting 5% by mass of platinum metal was added, and 38.8 g (0.2 mol) of 1,4-bis(dimethylsilyl)benzene was added dropwise over 25 minutes while stirring. After completion of dropping, the mixture was further heated and stirred at 90° C. for 24 hours, and then cooled to room temperature. Thereafter, platinum metal-supporting carbon was removed by filtration, and excess vinylnorbornene was distilled off under reduced pressure to obtain 79 g of a colorless, transparent, oily reaction product (viscosity at 25°C: 1,200 mPa·s).
反応生成物を、ＦＴ－ＩＲ、ＮＭＲ、ＧＰＣ等により分析した結果、このものは、
（１）ｐ－フェニレン基を１個有する化合物：ＮＢＭｅ2Ｓｉ－ｐ－Ｃ6Ｈ4－ＳｉＭｅ2ＮＢ ７２モル％、
（２）ｐ－フェニレン基を２個有する化合物：２４モル％（下記に代表的な構造式の一例を示す）、
および、
（３）ｐ－フェニレン基を３個有する化合物：４モル％（下記に代表的な構造式の一例を示す）
の混合物であった。また、前記混合物全体としての付加反応性炭素－炭素二重結合の含有割合は、０．４０モル／１００ｇであった。
As a result of analyzing the reaction product by FT-IR, NMR, GPC, etc.,
(1) Compound having one p-phenylene group: NBMe 2 Si-p-C 6 H 4 --SiMe 2 NB 72 mol %,
(2) a compound having two p-phenylene groups: 24 mol% (an example of a representative structural formula is shown below);
and,
(3) Compound having three p-phenylene groups: 4 mol% (an example of a typical structural formula is shown below)
was a mixture of Also, the content of the addition-reactive carbon-carbon double bonds in the mixture as a whole was 0.40 mol/100 g.
（１）ｐ－フェニレン基を１個有する化合物：ＮＢＭｅ2Ｓｉ－ｐ－Ｃ6Ｈ4－ＳｉＭｅ2ＮＢ ７２モル％、
（２）ｐ－フェニレン基を２個有する化合物：２４モル％（下記に代表的な構造式の一例を示す）、
（３）ｐ－フェニレン基を３個有する化合物：４モル％（下記に代表的な構造式の一例を示す）
(1) Compound having one p-phenylene group: NBMe 2 Si-p-C 6 H 4 --SiMe 2 NB 72 mol %,
(2) a compound having two p-phenylene groups: 24 mol% (an example of a representative structural formula is shown below);
(3) Compound having three p-phenylene groups: 4 mol% (an example of a typical structural formula is shown below)
［合成例２］（Ｂ）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５００ｍＬの４つ口フラスコに、トルエン８０ｇおよび１，３，５，７－テトラメチルシクロテトラシロキサン１１５．２ｇ（０．４８モル）を加え、オイルバスを用いて１１７℃に加熱した。これに、５質量％の白金金属を担持したカーボン粉末０．０５ｇ添加し、攪拌しながらビニルノルボルネン（商品名：Ｖ００６２、東京化成社製；５－ビニルビシクロ［２．２．１］ヘプト－２－エンと６－ビニルビシクロ［２．２．１］ヘプト－２－エンとの略等モル量の異性体混合物）４８ｇ（０．４モル）を１６分間かけて滴下した。滴下終了後、更に１２５℃で加熱攪拌を１６時間行った後、室温まで冷却した。その後、白金金属担持カーボンをろ過して除去し、トルエンを減圧留去して、無色透明なオイル状の反応生成物（２５℃における粘度：２，５００ｍＰａ・ｓ）１５２ｇを得た。 [Synthesis Example 2] Preparation of component (B) 80 g of toluene and 1,3,5,7-tetramethylcyclotetrasiloxane 115 were added to a 500 mL four-necked flask equipped with a stirrer, condenser, dropping funnel and thermometer. 0.2 g (0.48 mol) was added and heated to 117° C. using an oil bath. To this, 0.05 g of carbon powder supporting 5% by mass of platinum metal was added, and vinylnorbornene (trade name: V0062, manufactured by Tokyo Kasei Co., Ltd.; 5-vinylbicyclo[2.2.1]hept-2) was added while stirring. 48 g (0.4 mol) of an approximately equimolar isomer mixture of -ene and 6-vinylbicyclo[2.2.1]hept-2-ene) was added dropwise over 16 minutes. After completion of the dropwise addition, the mixture was heated and stirred at 125° C. for 16 hours, and then cooled to room temperature. Thereafter, platinum metal-supported carbon was removed by filtration, and toluene was distilled off under reduced pressure to obtain 152 g of a colorless, transparent, oily reaction product (viscosity at 25°C: 2,500 mPa·s).
攪拌装置、冷却管、滴下ロートおよび温度計を備えた５００ｍＬの４つ口フラスコに、トルエン８０ｇおよび１，３，５，７－テトラメチルシクロテトラシロキサン１１５．２ｇ（０．４８モル）を加え、オイルバスを用いて１１７℃に加熱した。これに、５質量％の白金金属を担持したカーボン粉末０．０５ｇ添加し、攪拌しながらビニルノルボルネン（商品名：Ｖ００６２、東京化成社製；５－ビニルビシクロ［２．２．１］ヘプト－２－エンと６－ビニルビシクロ［２．２．１］ヘプト－２－エンとの略等モル量の異性体混合物）４８ｇ（０．４モル）を１６分間かけて滴下した。滴下終了後、更に１２５℃で加熱攪拌を１６時間行った後、室温まで冷却した。その後、白金金属担持カーボンをろ過して除去し、トルエンを減圧留去して、無色透明なオイル状の反応生成物（２５℃における粘度：２，５００ｍＰａ・ｓ）１５２ｇを得た。 [Synthesis Example 2] Preparation of component (B) 80 g of toluene and 1,3,5,7-tetramethylcyclotetrasiloxane 115 were added to a 500 mL four-necked flask equipped with a stirrer, condenser, dropping funnel and thermometer. 0.2 g (0.48 mol) was added and heated to 117° C. using an oil bath. To this, 0.05 g of carbon powder supporting 5% by mass of platinum metal was added, and vinylnorbornene (trade name: V0062, manufactured by Tokyo Kasei Co., Ltd.; 5-vinylbicyclo[2.2.1]hept-2) was added while stirring. 48 g (0.4 mol) of an approximately equimolar isomer mixture of -ene and 6-vinylbicyclo[2.2.1]hept-2-ene) was added dropwise over 16 minutes. After completion of the dropwise addition, the mixture was heated and stirred at 125° C. for 16 hours, and then cooled to room temperature. Thereafter, platinum metal-supported carbon was removed by filtration, and toluene was distilled off under reduced pressure to obtain 152 g of a colorless, transparent, oily reaction product (viscosity at 25°C: 2,500 mPa·s).
反応生成物を、ＦＴ－ＩＲ、ＮＭＲ、ＧＰＣ等により分析した結果、このものは、
（１）テトラメチルシクロテトラシロキサン環を１個有する化合物：６モル％（下記に代表的な構造式の一例を示す）、
（２）テトラメチルシクロテトラシロキサン環を２個有する化合物：２５モル％（下記に代表的な構造式の一例を示す）、
（３）テトラメチルシクロテトラシロキサン環を３個有する化合物：１６モル％（下記に代表的な構造式の一例を示す）、
（４）テトラメチルシクロテトラシロキサン環を４個有する化合物：１１モル％（下記に代表的な構造式の一例を示す）、
および、
（５）テトラメチルシクロテトラシロキサン環を５～１２個有する化合物：４２モル％（下記に代表的な構造式の一例を示す）
（式中、ｎは４～１１の整数である。）
の混合物であった。なお、前記混合物全体としてのＳｉＨの含有割合は、０．６３モル／１００ｇであった。 As a result of analyzing the reaction product by FT-IR, NMR, GPC, etc.,
(1) a compound having one tetramethylcyclotetrasiloxane ring: 6 mol% (an example of a representative structural formula is shown below);
(2) a compound having two tetramethylcyclotetrasiloxane rings: 25 mol% (an example of a representative structural formula is shown below);
(3) a compound having three tetramethylcyclotetrasiloxane rings: 16 mol% (an example of a representative structural formula is shown below);
(4) a compound having four tetramethylcyclotetrasiloxane rings: 11 mol% (an example of a representative structural formula is shown below);
and,
(5) Compound having 5 to 12 tetramethylcyclotetrasiloxane rings: 42 mol% (an example of a representative structural formula is shown below)
(Wherein, n is an integer of 4 to 11.)
was a mixture of The content of SiH in the mixture as a whole was 0.63 mol/100 g.
（１）テトラメチルシクロテトラシロキサン環を１個有する化合物：６モル％（下記に代表的な構造式の一例を示す）、
（５）テトラメチルシクロテトラシロキサン環を５～１２個有する化合物：４２モル％（下記に代表的な構造式の一例を示す）
の混合物であった。なお、前記混合物全体としてのＳｉＨの含有割合は、０．６３モル／１００ｇであった。 As a result of analyzing the reaction product by FT-IR, NMR, GPC, etc.,
(1) a compound having one tetramethylcyclotetrasiloxane ring: 6 mol% (an example of a representative structural formula is shown below);
(5) Compound having 5 to 12 tetramethylcyclotetrasiloxane rings: 42 mol% (an example of a representative structural formula is shown below)
was a mixture of The content of SiH in the mixture as a whole was 0.63 mol/100 g.
［合成例３］（Ｂ）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５００ｍＬの４つ口フラスコに、トルエン８０ｇおよび１，３，５，７，９－ペンタメチルシクロペンタシロキサン１４４．０ｇ（０．４８モル）を加え、オイルバスを用いて１１７℃に加熱した。これに、５質量％の白金金属を担持したカーボン粉末０．０５ｇ添加し、攪拌しながらビニルノルボルネン（商品名：Ｖ００６２、東京化成社製；５－ビニルビシクロ［２．２．１］ヘプト－２－エンと６－ビニルビシクロ［２．２．１］ヘプト－２－エンとの略等モル量の異性体混合物）４８ｇ（０．４モル）を１６分間かけて滴下した。滴下終了後、更に１２５℃で加熱攪拌を１６時間行った後、室温まで冷却した。その後、白金金属担持カーボンをろ過して除去し、トルエンを減圧留去して、無色透明なオイル状の反応生成物（２５℃における粘度：３，５００ｍＰａ・ｓ）１７２ｇを得た。 [Synthesis Example 3] Preparation of component (B) 80 g of toluene and 1,3,5,7,9-pentamethylcyclopenta were placed in a 500 mL four-necked flask equipped with a stirrer, condenser, dropping funnel and thermometer. 144.0 g (0.48 mol) of siloxane was added and heated to 117° C. using an oil bath. To this, 0.05 g of carbon powder supporting 5% by mass of platinum metal was added, and vinylnorbornene (trade name: V0062, manufactured by Tokyo Kasei Co., Ltd.; 5-vinylbicyclo[2.2.1]hept-2) was added while stirring. 48 g (0.4 mol) of an approximately equimolar isomer mixture of -ene and 6-vinylbicyclo[2.2.1]hept-2-ene) was added dropwise over 16 minutes. After completion of the dropwise addition, the mixture was heated and stirred at 125° C. for 16 hours, and then cooled to room temperature. Thereafter, platinum metal-supporting carbon was removed by filtration, and toluene was distilled off under reduced pressure to obtain 172 g of a colorless and transparent oily reaction product (viscosity at 25° C.: 3,500 mPa·s).
攪拌装置、冷却管、滴下ロートおよび温度計を備えた５００ｍＬの４つ口フラスコに、トルエン８０ｇおよび１，３，５，７，９－ペンタメチルシクロペンタシロキサン１４４．０ｇ（０．４８モル）を加え、オイルバスを用いて１１７℃に加熱した。これに、５質量％の白金金属を担持したカーボン粉末０．０５ｇ添加し、攪拌しながらビニルノルボルネン（商品名：Ｖ００６２、東京化成社製；５－ビニルビシクロ［２．２．１］ヘプト－２－エンと６－ビニルビシクロ［２．２．１］ヘプト－２－エンとの略等モル量の異性体混合物）４８ｇ（０．４モル）を１６分間かけて滴下した。滴下終了後、更に１２５℃で加熱攪拌を１６時間行った後、室温まで冷却した。その後、白金金属担持カーボンをろ過して除去し、トルエンを減圧留去して、無色透明なオイル状の反応生成物（２５℃における粘度：３，５００ｍＰａ・ｓ）１７２ｇを得た。 [Synthesis Example 3] Preparation of component (B) 80 g of toluene and 1,3,5,7,9-pentamethylcyclopenta were placed in a 500 mL four-necked flask equipped with a stirrer, condenser, dropping funnel and thermometer. 144.0 g (0.48 mol) of siloxane was added and heated to 117° C. using an oil bath. To this, 0.05 g of carbon powder supporting 5% by mass of platinum metal was added, and vinylnorbornene (trade name: V0062, manufactured by Tokyo Kasei Co., Ltd.; 5-vinylbicyclo[2.2.1]hept-2) was added while stirring. 48 g (0.4 mol) of an approximately equimolar isomer mixture of -ene and 6-vinylbicyclo[2.2.1]hept-2-ene) was added dropwise over 16 minutes. After completion of the dropwise addition, the mixture was heated and stirred at 125° C. for 16 hours, and then cooled to room temperature. Thereafter, platinum metal-supporting carbon was removed by filtration, and toluene was distilled off under reduced pressure to obtain 172 g of a colorless and transparent oily reaction product (viscosity at 25° C.: 3,500 mPa·s).
反応生成物を、ＦＴ－ＩＲ、ＮＭＲ、ＧＰＣ等により分析した結果、このものは、
（１）ペンタメチルシクロペンタシロキサン環を１個有する化合物：５モル％（下記に代表的な構造式の一例を示す）、
（２）ペンタメチルシクロペンタシロキサン環を２個有する化合物：２８モル％（下記に代表的な構造式の一例を示す）、
（３）ペンタメチルシクロペンタシロキサン環を３個有する化合物：１４モル％（下記に代表的な構造式の一例を示す）、
（４）ペンタメチルシクロペンタシロキサン環を４個有する化合物：１０モル％（下記に代表的な構造式の一例を示す）、
および、
（５）ペンタメチルシクロペンタシロキサン環を５～１２個有する化合物：４３モル％（下記に代表的な構造式の一例を示す）
（式中、ｎは４～１１の整数である。）
の混合物であった。なお、前記混合物全体としてのＳｉＨの含有割合は、０．７８モル／１００ｇであった。 As a result of analyzing the reaction product by FT-IR, NMR, GPC, etc.,
(1) a compound having one pentamethylcyclopentasiloxane ring: 5 mol% (an example of a representative structural formula is shown below);
(2) a compound having two pentamethylcyclopentasiloxane rings: 28 mol% (an example of a representative structural formula is shown below);
(3) a compound having three pentamethylcyclopentasiloxane rings: 14 mol% (an example of a typical structural formula is shown below);
(4) a compound having four pentamethylcyclopentasiloxane rings: 10 mol% (an example of a representative structural formula is shown below);
and,
(5) Compound having 5 to 12 pentamethylcyclopentasiloxane rings: 43 mol% (an example of a representative structural formula is shown below)
(Wherein, n is an integer of 4 to 11.)
was a mixture of The content of SiH in the mixture as a whole was 0.78 mol/100 g.
（１）ペンタメチルシクロペンタシロキサン環を１個有する化合物：５モル％（下記に代表的な構造式の一例を示す）、
（５）ペンタメチルシクロペンタシロキサン環を５～１２個有する化合物：４３モル％（下記に代表的な構造式の一例を示す）
の混合物であった。なお、前記混合物全体としてのＳｉＨの含有割合は、０．７８モル／１００ｇであった。 As a result of analyzing the reaction product by FT-IR, NMR, GPC, etc.,
(1) a compound having one pentamethylcyclopentasiloxane ring: 5 mol% (an example of a representative structural formula is shown below);
(5) Compound having 5 to 12 pentamethylcyclopentasiloxane rings: 43 mol% (an example of a representative structural formula is shown below)
was a mixture of The content of SiH in the mixture as a whole was 0.78 mol/100 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）（ＭｅＨＳｉＯ）5：２５質量部（なお、（Ｂ）成分中の合計のＳｉＨ／前記（Ａ）成分中の合計の炭素－炭素二重結合（モル比）（ＳｉＨ／Ｃ＝Ｃ（モル比）＝１．３９ 以下、同様にしてＳｉＨ／炭素－炭素二重結合のモル比を「ＳｉＨ／Ｃ＝Ｃ（モル比）」と記載する。））、
（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）の合計質量に対して２０ｐｐｍとなる量、並びに
１－エチニルシクロヘキサノール：０．０３質量部
を均一に混合して、粘度が５０ｍＰａ・ｓの組成物を得た。この組成物を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。 [Example 1]
(A) the reaction product obtained in Synthesis Example 1: 75 parts by mass,
(B) (MeHSiO) 5 : 25 parts by mass (total SiH in component (B)/total carbon-carbon double bonds in component (A) (molar ratio) (SiH/C=C ( molar ratio) = 1.39 Hereinafter, the molar ratio of SiH/carbon-carbon double bonds is similarly described as “SiH/C=C (molar ratio)”)),
(C) platinum-vinylsiloxane complex: an amount of 20 ppm relative to the total mass of (A) and (B) as platinum metal atoms, and 1-ethynylcyclohexanol: 0.03 parts by mass were uniformly mixed, A composition having a viscosity of 50 mPa·s was obtained. This composition was poured into a metal frame with a thickness of 0.3 mm and heated at 150° C. for 2 hours to obtain a cured product.
（Ａ）合成例１で得られた反応生成物：７５質量部、
（Ｂ）（ＭｅＨＳｉＯ）5：２５質量部（なお、（Ｂ）成分中の合計のＳｉＨ／前記（Ａ）成分中の合計の炭素－炭素二重結合（モル比）（ＳｉＨ／Ｃ＝Ｃ（モル比）＝１．３９ 以下、同様にしてＳｉＨ／炭素－炭素二重結合のモル比を「ＳｉＨ／Ｃ＝Ｃ（モル比）」と記載する。））、
（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）の合計質量に対して２０ｐｐｍとなる量、並びに
１－エチニルシクロヘキサノール：０．０３質量部
を均一に混合して、粘度が５０ｍＰａ・ｓの組成物を得た。この組成物を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。 [Example 1]
(A) the reaction product obtained in Synthesis Example 1: 75 parts by mass,
(B) (MeHSiO) 5 : 25 parts by mass (total SiH in component (B)/total carbon-carbon double bonds in component (A) (molar ratio) (SiH/C=C ( molar ratio) = 1.39 Hereinafter, the molar ratio of SiH/carbon-carbon double bonds is similarly described as “SiH/C=C (molar ratio)”)),
(C) platinum-vinylsiloxane complex: an amount of 20 ppm relative to the total mass of (A) and (B) as platinum metal atoms, and 1-ethynylcyclohexanol: 0.03 parts by mass were uniformly mixed, A composition having a viscosity of 50 mPa·s was obtained. This composition was poured into a metal frame with a thickness of 0.3 mm and heated at 150° C. for 2 hours to obtain a cured product.
［実施例２］
（Ａ）合成例１で得られた反応生成物：６０質量部、
（Ｂ１）（ＭｅＨＳｉＯ）4：１０質量部、
（Ｂ２）合成例２で得られた反応生成物：３０質量部（ＳｉＨ／Ｃ＝Ｃ（モル比）＝１．４８）
（Ｃ）白金－ビニルシロキサン錯体：白金金属原子として（Ａ）、（Ｂ１）および（Ｂ２）の合計質量に対して２０ｐｐｍとなる量、並びに
１－エチニルシクロヘキサノール：０．０３質量部
を均一に混合して、粘度が１，０００ｍＰａ・ｓの組成物を得た。この組成物を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。 [Example 2]
(A) the reaction product obtained in Synthesis Example 1: 60 parts by mass,
(B1) (MeHSiO) 4 : 10 parts by mass,
(B2) Reaction product obtained in Synthesis Example 2: 30 parts by mass (SiH/C=C (molar ratio)=1.48)
(C) platinum-vinylsiloxane complex: an amount of 20 ppm with respect to the total mass of (A), (B1) and (B2) as platinum metal atoms, and 1-ethynylcyclohexanol: 0.03 parts by mass uniformly Mixing gave a composition with a viscosity of 1,000 mPa·s. This composition was poured into a metal frame with a thickness of 0.3 mm and heated at 150° C. for 2 hours to obtain a cured product.
（Ａ）合成例１で得られた反応生成物：６０質量部、
（Ｂ１）（ＭｅＨＳｉＯ）4：１０質量部、
（Ｂ２）合成例２で得られた反応生成物：３０質量部（ＳｉＨ／Ｃ＝Ｃ（モル比）＝１．４８）
（Ｃ）白金－ビニルシロキサン錯体：白金金属原子として（Ａ）、（Ｂ１）および（Ｂ２）の合計質量に対して２０ｐｐｍとなる量、並びに
１－エチニルシクロヘキサノール：０．０３質量部
を均一に混合して、粘度が１，０００ｍＰａ・ｓの組成物を得た。この組成物を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。 [Example 2]
(A) the reaction product obtained in Synthesis Example 1: 60 parts by mass,
(B1) (MeHSiO) 4 : 10 parts by mass,
(B2) Reaction product obtained in Synthesis Example 2: 30 parts by mass (SiH/C=C (molar ratio)=1.48)
(C) platinum-vinylsiloxane complex: an amount of 20 ppm with respect to the total mass of (A), (B1) and (B2) as platinum metal atoms, and 1-ethynylcyclohexanol: 0.03 parts by mass uniformly Mixing gave a composition with a viscosity of 1,000 mPa·s. This composition was poured into a metal frame with a thickness of 0.3 mm and heated at 150° C. for 2 hours to obtain a cured product.
［実施例３］
（Ａ）合成例１で得られた反応生成物：５８質量部、
（Ｂ）合成例３で得られた反応生成物：４２質量部（ＳｉＨ／Ｃ＝Ｃ（モル比）＝１．４１）
（Ｃ）白金－ビニルシロキサン錯体：白金金属原子として（Ａ１）および（Ｂ２）の合計質量に対して２０ｐｐｍとなる量、並びに
１－エチニルシクロヘキサノール：０．０３質量部
を均一に混合して、粘度が１，５００ｍＰａ・ｓの組成物を得た。この組成物を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。 [Example 3]
(A) the reaction product obtained in Synthesis Example 1: 58 parts by mass,
(B) Reaction product obtained in Synthesis Example 3: 42 parts by mass (SiH/C=C (molar ratio)=1.41)
(C) platinum-vinylsiloxane complex: an amount of 20 ppm relative to the total mass of (A1) and (B2) as platinum metal atoms, and 1-ethynylcyclohexanol: 0.03 parts by mass were uniformly mixed, A composition having a viscosity of 1,500 mPa·s was obtained. This composition was poured into a metal frame with a thickness of 0.3 mm and heated at 150° C. for 2 hours to obtain a cured product.
（Ａ）合成例１で得られた反応生成物：５８質量部、
（Ｂ）合成例３で得られた反応生成物：４２質量部（ＳｉＨ／Ｃ＝Ｃ（モル比）＝１．４１）
（Ｃ）白金－ビニルシロキサン錯体：白金金属原子として（Ａ１）および（Ｂ２）の合計質量に対して２０ｐｐｍとなる量、並びに
１－エチニルシクロヘキサノール：０．０３質量部
を均一に混合して、粘度が１，５００ｍＰａ・ｓの組成物を得た。この組成物を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。 [Example 3]
(A) the reaction product obtained in Synthesis Example 1: 58 parts by mass,
(B) Reaction product obtained in Synthesis Example 3: 42 parts by mass (SiH/C=C (molar ratio)=1.41)
(C) platinum-vinylsiloxane complex: an amount of 20 ppm relative to the total mass of (A1) and (B2) as platinum metal atoms, and 1-ethynylcyclohexanol: 0.03 parts by mass were uniformly mixed, A composition having a viscosity of 1,500 mPa·s was obtained. This composition was poured into a metal frame with a thickness of 0.3 mm and heated at 150° C. for 2 hours to obtain a cured product.
［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：５，０００ｍＰａ・ｓ）を、実施例１と同様に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 having a methyl group as a substituent, a methyl silicone resin-based curable composition (trade name: KER-2300, manufactured by Shin-Etsu Chemical Co., Ltd., viscosity: 5,000 mPa s) was added to 0 in the same manner as in Example 1. It was poured into a metal frame with a thickness of 0.3 mm 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：５，０００ｍＰａ・ｓ）を、実施例１と同様に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 having a methyl group as a substituent, a methyl silicone resin-based curable composition (trade name: KER-2300, manufactured by Shin-Etsu Chemical Co., Ltd., viscosity: 5,000 mPa s) was added to 0 in the same manner as in Example 1. It was poured into a metal frame with a thickness of 0.3 mm 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。観察結果を表１に示す。 <Performance evaluation method>
The properties of the cured products obtained in the above examples and comparative examples were evaluated according to the following methods. Observation 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。観察結果を表１に示す。 <Performance evaluation method>
The properties of the cured products obtained in the above examples and comparative examples were evaluated according to the following methods. Observation results are shown in Table 1.
－外観－
各硬化物の外観を目視により観察した。 -exterior-
The appearance of each cured product was visually observed.
各硬化物の外観を目視により観察した。 -exterior-
The appearance of each cured product was visually observed.
－比誘電率および誘電正接－
空洞共振器誘電率測定装置（（株）ＡＥＴ社製）を用いて、１０ＧＨｚにおける比誘電率および誘電正接を測定した。 －Relative permittivity and dielectric loss tangent－
Using a cavity resonator permittivity measuring device (manufactured by AET Co., Ltd.), the relative permittivity and dielectric loss tangent at 10 GHz were measured.
空洞共振器誘電率測定装置（（株）ＡＥＴ社製）を用いて、１０ＧＨｚにおける比誘電率および誘電正接を測定した。 －Relative permittivity and dielectric loss tangent－
Using a cavity resonator permittivity measuring device (manufactured by AET Co., Ltd.), the relative permittivity and dielectric loss tangent at 10 GHz were measured.
以上の結果から、実施例１～３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１～３で得られた硬化物は、１０ＧＨｚにおける比誘電率が３．０以下、かつ、誘電正接が０．０１以下であり高周波誘電特性に優れることが分かった。
一方、比較例１のメチル系シリコーンレジンは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。 From the above results, the compositions of Examples 1 to 3 had suitable viscosities when applied to substrates and were excellent in workability. In addition, the cured products obtained in Examples 1 to 3 had a relative dielectric constant of 3.0 or less at 10 GHz and a dielectric loss tangent of 0.01 or less, indicating excellent high-frequency dielectric properties.
On the other hand, it was found that the methyl-based silicone resin of Comparative Example 1 had a large dielectric loss tangent and did not satisfy the high frequency characteristics.
一方、比較例１のメチル系シリコーンレジンは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。 From the above results, the compositions of Examples 1 to 3 had suitable viscosities when applied to substrates and were excellent in workability. In addition, the cured products obtained in Examples 1 to 3 had a relative dielectric constant of 3.0 or less at 10 GHz and a dielectric loss tangent of 0.01 or less, indicating excellent high-frequency dielectric properties.
On the other hand, it was found that the methyl-based silicone resin of Comparative Example 1 had a large dielectric loss tangent and did not satisfy the high frequency characteristics.
Claims (8)
- （Ａ）
（ａ）下記式（１）：
で表されるケイ素原子に結合した水素原子を１分子中に２個有する化合物と、
（ｂ）付加反応性炭素－炭素二重結合を１分子中に２個有する多環式炭化水素と
の付加反応生成物であって、かつ、付加反応性炭素－炭素二重結合を１分子中に少なくとも２個有する付加反応生成物、
（Ｂ）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、および
（Ｃ）ヒドロシリル化反応触媒
を含む低誘電率絶縁性コーティング組成物。 (A)
(a) the following formula (1):
A compound having two silicon-bonded hydrogen atoms in one molecule represented by
(b) an addition reaction product with a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and an addition-reactive carbon-carbon double bond in one molecule; an addition reaction product having at least two in
A low dielectric constant insulating coating composition comprising (B) a compound having 3 or more silicon-bonded hydrogen atoms in one molecule and (C) a hydrosilylation reaction catalyst. - 前記（ｂ）の多環式炭化水素が、５－ビニルビシクロ［２．２．１］ヘプト－２－エン、６－ビニルビシクロ［２．２．１］ヘプト－２－エンまたは前記両者の組み合わせである請求項１に記載の低誘電率絶縁性コーティング組成物。 The polycyclic hydrocarbon of (b) is 5-vinylbicyclo[2.2.1]hept-2-ene, 6-vinylbicyclo[2.2.1]hept-2-ene, or a combination of the two. The low dielectric constant insulating coating composition according to claim 1, wherein
- 前記（Ｂ）成分が、１，３，５，７－テトラメチルシクロテトラシロキサン、１，３，５，７，９－ペンタメチルシクロペンタシロキサンまたはその両方の混合物を含むものである請求項１に記載の低誘電率絶縁性コーティング組成物。 2. The method of claim 1, wherein component (B) comprises 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, or a mixture of both. A low dielectric constant insulating coating composition.
- 前記（Ｂ）成分が、
５－ビニルビシクロ［２．２．１］ヘプト－２－エン、６－ビニルビシクロ［２．２．１］ヘプト－２－エンまたはその両方の混合物と、
１，３，５，７－テトラメチルシクロテトラシロキサン、１，３，５，７，９－ペンタメチルシクロペンタシロキサンまたはその両方の混合物と
の付加反応生成物を含むものである請求項１に記載の低誘電率絶縁性コーティング組成物。 The component (B) is
5-vinylbicyclo[2.2.1]hept-2-ene, 6-vinylbicyclo[2.2.1]hept-2-ene or a mixture of both;
2. The low molecular weight polymer of claim 1, comprising an addition reaction product with 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, or a mixture of both. A dielectric insulating coating composition. - 請求項１に記載の低誘電率絶縁性コーティング組成物の硬化物。 A cured product of the low dielectric constant insulating coating composition according to claim 1.
- １０ＧＨｚにおける誘電率が３．０以下、かつ、誘電正接が０．０１以下である請求項５に記載の硬化物。 The cured product according to claim 5, which has a dielectric constant of 3.0 or less at 10 GHz and a dielectric loss tangent of 0.01 or less.
- 請求項５または６に記載の硬化物を絶縁性コーティング層として使用する方法。 A method of using the cured product according to claim 5 or 6 as an insulating coating layer.
- 請求項５または６に記載の硬化物からなる層を有する表示装置。 A display device having a layer made of the cured product according to claim 5 or 6.
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| JP2005133073A (en) * | 2003-10-10 | 2005-05-26 | Shin Etsu Chem Co Ltd | Curing composition |
| JP2018523737A (en) * | 2015-08-31 | 2018-08-23 | サムスン エスディアイ カンパニー, リミテッドSamsung Sdi Co., Ltd. | Low temperature curing composition, cured film formed therefrom, and electronic device having said cured film |
| JP2020193243A (en) * | 2019-05-24 | 2020-12-03 | 信越化学工業株式会社 | Addition curing type silicone composition, cured product and optical semiconductor element |
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| JP2005133073A (en) * | 2003-10-10 | 2005-05-26 | Shin Etsu Chem Co Ltd | Curing composition |
| JP2018523737A (en) * | 2015-08-31 | 2018-08-23 | サムスン エスディアイ カンパニー, リミテッドSamsung Sdi Co., Ltd. | Low temperature curing composition, cured film formed therefrom, and electronic device having said cured film |
| JP2020193243A (en) * | 2019-05-24 | 2020-12-03 | 信越化学工業株式会社 | Addition curing type silicone composition, cured product and optical semiconductor element |
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