WO2022254901A1 - Novel organosilicon compound, novel crosslinking agent, curable composition, prepreg, laminate, metal-clad laminated board, and wiring board - Google Patents
Novel organosilicon compound, novel crosslinking agent, curable composition, prepreg, laminate, metal-clad laminated board, and wiring board Download PDFInfo
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- WO2022254901A1 WO2022254901A1 PCT/JP2022/013929 JP2022013929W WO2022254901A1 WO 2022254901 A1 WO2022254901 A1 WO 2022254901A1 JP 2022013929 W JP2022013929 W JP 2022013929W WO 2022254901 A1 WO2022254901 A1 WO 2022254901A1
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- Prior art keywords
- curable composition
- cross
- organosilicon compound
- group
- metal
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- 239000000203 mixture Substances 0.000 title claims abstract description 118
- 150000003961 organosilicon compounds Chemical class 0.000 title claims abstract description 68
- 239000003431 cross linking reagent Substances 0.000 title claims abstract description 44
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 23
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 20
- 125000004429 atom Chemical group 0.000 claims abstract description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 18
- 125000000962 organic group Chemical group 0.000 claims abstract description 11
- 125000001424 substituent group Chemical group 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- 125000005156 substituted alkylene group Chemical group 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims description 61
- 239000002184 metal Substances 0.000 claims description 61
- 239000011888 foil Substances 0.000 claims description 57
- 239000000463 material Substances 0.000 claims description 44
- 229920005989 resin Polymers 0.000 claims description 33
- 239000011347 resin Substances 0.000 claims description 33
- 239000000758 substrate Substances 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000000835 fiber Substances 0.000 claims description 12
- 238000004132 cross linking Methods 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 abstract description 8
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- 239000000047 product Substances 0.000 description 50
- 239000012074 organic phase Substances 0.000 description 39
- 239000002131 composite material Substances 0.000 description 34
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 26
- 238000000605 extraction Methods 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000000243 solution Substances 0.000 description 23
- 239000010410 layer Substances 0.000 description 21
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- 230000015572 biosynthetic process Effects 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
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- 239000011541 reaction mixture Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 14
- 239000000706 filtrate Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 239000012043 crude product Substances 0.000 description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 13
- -1 4-vinylphenyl groups Chemical group 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000006087 Silane Coupling Agent Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 11
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- 235000019341 magnesium sulphate Nutrition 0.000 description 10
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- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 6
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- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 4
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- 238000005259 measurement Methods 0.000 description 4
- LSEFCHWGJNHZNT-UHFFFAOYSA-M methyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 LSEFCHWGJNHZNT-UHFFFAOYSA-M 0.000 description 4
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- ISGYADUONBKLRG-UHFFFAOYSA-N 4-[(4-formylphenyl)-dimethylsilyl]benzaldehyde Chemical compound C=1C=C(C=O)C=CC=1[Si](C)(C)C1=CC=C(C=O)C=C1 ISGYADUONBKLRG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- NGMWFFYVXMMMPP-UHFFFAOYSA-N CCCCCCCCCCCC[Si](C1=CC(C=C)=CC=C1)(C1=CC(C=C)=CC=C1)C1=CC(C=C)=CC=C1 Chemical compound CCCCCCCCCCCC[Si](C1=CC(C=C)=CC=C1)(C1=CC(C=C)=CC=C1)C1=CC(C=C)=CC=C1 NGMWFFYVXMMMPP-UHFFFAOYSA-N 0.000 description 3
- ZLKKTCWSJLSGST-UHFFFAOYSA-N CCCCCCCCCCCC[Si](C1=CC(C=O)=CC=C1)(C1=CC(C=O)=CC=C1)C1=CC(C=O)=CC=C1 Chemical compound CCCCCCCCCCCC[Si](C1=CC(C=O)=CC=C1)(C1=CC(C=O)=CC=C1)C1=CC(C=O)=CC=C1 ZLKKTCWSJLSGST-UHFFFAOYSA-N 0.000 description 3
- ODTCBVRKRWJUGV-UHFFFAOYSA-N CCCCCCCCCCCC[Si](C1=CC=C(C=C)C=C1)(C1=CC=C(C=C)C=C1)C1=CC=C(C=C)C=C1 Chemical compound CCCCCCCCCCCC[Si](C1=CC=C(C=C)C=C1)(C1=CC=C(C=C)C=C1)C1=CC=C(C=C)C=C1 ODTCBVRKRWJUGV-UHFFFAOYSA-N 0.000 description 3
- MLVTUDXUNFRNSD-UHFFFAOYSA-N CCCCCCCCCCCC[Si](C1=CC=C(C=O)C=C1)(C1=CC=C(C=O)C=C1)C1=CC=C(C=O)C=C1 Chemical compound CCCCCCCCCCCC[Si](C1=CC=C(C=O)C=C1)(C1=CC=C(C=O)C=C1)C1=CC=C(C=O)C=C1 MLVTUDXUNFRNSD-UHFFFAOYSA-N 0.000 description 3
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- IDHKLYLHHJEBMA-UHFFFAOYSA-N bis(4-ethenylphenyl)-dimethylsilane Chemical compound C=1C=C(C=C)C=CC=1[Si](C)(C)C1=CC=C(C=C)C=C1 IDHKLYLHHJEBMA-UHFFFAOYSA-N 0.000 description 3
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- KDHRJLQXMOBXRV-UHFFFAOYSA-N 1-bromo-3-(diethoxymethyl)benzene Chemical compound CCOC(OCC)C1=CC=CC(Br)=C1 KDHRJLQXMOBXRV-UHFFFAOYSA-N 0.000 description 2
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- WHTKZGCDQCGCFG-UHFFFAOYSA-N [diphenyl-(2-trimethylsilylphenyl)silyl]peroxy-diphenyl-(2-trimethylsilylphenyl)silane Chemical compound C[Si](C)(C)C1=CC=CC=C1[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)OO[Si](C=1C(=CC=CC=1)[Si](C)(C)C)(C=1C=CC=CC=1)C1=CC=CC=C1 WHTKZGCDQCGCFG-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- ASUOLLHGALPRFK-UHFFFAOYSA-N phenylphosphonoylbenzene Chemical group C=1C=CC=CC=1P(=O)C1=CC=CC=C1 ASUOLLHGALPRFK-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JIYXDFNAPHIAFH-UHFFFAOYSA-N tert-butyl 3-tert-butylperoxycarbonylbenzoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC(C(=O)OC(C)(C)C)=C1 JIYXDFNAPHIAFH-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- XPEMYYBBHOILIJ-UHFFFAOYSA-N trimethyl(trimethylsilylperoxy)silane Chemical compound C[Si](C)(C)OO[Si](C)(C)C XPEMYYBBHOILIJ-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
Definitions
- the present invention relates to novel organosilicon compounds, novel cross-linking agents, curable compositions, prepregs, laminates, metal-clad laminates and wiring substrates.
- Wiring boards are used for applications such as electrical and electronic equipment.
- a wiring board can be manufactured, for example, as follows.
- a curable composition is impregnated into a fibrous base material and the curable composition is (semi) cured to produce a prepreg.
- One or more prepregs are sandwiched between a pair of metal foils, and the obtained first temporary laminate is heated and pressurized to produce a metal-clad laminate.
- a conductor pattern also referred to as a circuit pattern
- the outermost metal foil may be arranged only on one side of the first temporary laminate.
- a multilayer wiring board (also referred to as a multilayer printed wiring board) can be manufactured by forming a conductor pattern such as wiring.
- the outermost metal foil may be arranged only on one side of the second temporary laminate.
- a heated and pressurized prepreg contains a fiber base material, a resin, an inorganic filler (also referred to as a filler), and the like, and is also called a composite base material.
- the composite base material functions as an insulating layer.
- the resin contained in the prepreg is a (semi-)cured product of the curable composition, and the resin contained in the composite substrate is a cured product of the curable composition.
- a wiring board used for this purpose is required to reduce transmission loss in a high frequency region.
- Transmission loss includes conductor loss mainly caused by the surface resistance of the metal foil and dielectric loss caused by the dielectric loss tangent (D f ) of the composite base material. Therefore, the resin contained in the composite base material of the wiring board used for the above application is required to reduce the dielectric loss in the high frequency region.
- the dielectric loss tangent (D f ) depends on the frequency, and if the same material is used, the higher the frequency, the larger the dielectric loss tangent (D f ) tends to be.
- the resin contained in the composite base material preferably has a low dielectric loss tangent (D f ) under high frequency conditions.
- CTE coefficient of thermal expansion
- a first temporary laminate including the prepreg and the metal foil or a second temporary laminate including the composite base material, the prepreg and the metal foil will be produced.
- the temporary laminate is heated and pressurized, the metal foil may be displaced or peeled off.
- a smaller difference in coefficient of thermal expansion (CTE) between the prepreg or composite base material and the metal foil is preferred. Since resin generally has a higher coefficient of thermal expansion (CTE) than metal foil, it is preferable that the prepreg and composite base material have a lower coefficient of thermal expansion (CTE).
- a wiring board may be used in a relatively high-temperature environment.
- the resin contained in the prepreg and the composite base material preferably has a sufficiently high glass transition temperature (Tg) in order to ensure the reliability of the wiring board.
- Patent Document 1 discloses a polyphenylene oxide system consisting of polyphenylene oxide and trialkenyl isocyanurate.
- a wiring board resin composition containing a resin and a vinylsilane such as trimethoxyvinylsilane (TMVS) and triethoxyvinylsilane (TEVS) and a wiring board obtained using the same are disclosed (claims 1 to 4). .
- Vinylsilanes such as trimethoxyvinylsilane (TMVS) and triethoxyvinylsilane (TEVS) used in Patent Document 1 are silane coupling agents containing a bond between Si and a polar oxygen atom (O).
- TMVS trimethoxyvinylsilane
- TEVS triethoxyvinylsilane
- D f dielectric loss tangent
- organosilicon compounds having a specific chemical structure containing two or more reactive vinyl groups and free of Si-polar atom bonds can be used as cross-linking agents in curable compositions.
- the composite substrate obtained by using the curable composition comprising the dielectric loss tangent (D f ) under high frequency conditions is effectively reduced, the coefficient of thermal expansion (CTE) is sufficiently low, and the glass transition temperature (Tg) is It has been found to be sufficiently high and to have good characteristics for a wiring substrate used in a high frequency region.
- the adhesion between the composite base material and the metal foil is enhanced by using a silane coupling agent, and there is no description or suggestion regarding the use of an organosilicon compound as a cross-linking agent.
- Non-Patent Documents 1 and 2 and Patent Document 2 are cited as other related arts of the present invention.
- an organosilicon compound is synthesized in which two 4-vinylphenyl groups and two alkyl groups (specifically, —C 8 H 17 ) are bonded to Si.
- the reaction scheme is as follows.
- a synthesized organosilicon compound is polymerized, and the obtained linear polymer is evaluated for fluorescence properties.
- Non-Patent Document 1 uses an organosilicon compound as a monomer, does not describe or suggest its use as a cross-linking agent, and does not describe its dielectric properties.
- Non-Patent Document 2 an organosilicon compound is synthesized in which two 2-vinylphenyl groups and two alkyl groups (specifically, -Me, -Et or -Ph) are bonded to Si.
- a synthesized organosilicon compound is subjected to ring-closing metathesis to synthesize dibenzoheteropines.
- the reaction scheme is as follows.
- Non-Patent Document 2 does not describe the use of the organosilicon compound, neither describes nor suggests its use as a cross-linking agent, nor describes its dielectric properties.
- Patent Document 2 a plurality of organosilicon compounds in which Si is substituted with two 2-, 3- or 4-vinylphenyl groups and two alkyl groups are synthesized.
- An example of the organosilicon compound synthesized in Patent Document 2 is shown in [Chemical 3] below.
- the organosilicon compound is used for gas barrier applications, and there is no description or suggestion of its use as a cross-linking agent, nor is there any description of dielectric properties.
- organosilicon compounds in which all four atoms bonded to Si are non-polar atoms and have two or more reactive vinyl groups have been reported.
- organosilicon compounds having two or more reactive vinyl groups in which all four atoms bonded to Si are non-polar atoms are novel as crosslinkers.
- organosilicon compounds having specific structures are novel compounds. be.
- all four atoms bonded to Si are non-polar atoms, contain two or more reactive functional groups including a vinyl phenyl group, and the substituted position of the vinyl group on the benzene ring is the meta position.
- the organosilicon compound (the benzene ring contained in the organosilicon compound may have a substituent) is novel as a compound.
- the present invention has been made in view of the above circumstances, and an object thereof is to provide a novel organosilicon compound suitable for use as a cross-linking agent or the like.
- the present invention is also suitable for use in curable compositions having effectively reduced dielectric loss tangent (D f ) at high frequency conditions, sufficiently low coefficient of thermal expansion (CTE) and sufficiently low glass transition temperature (Tg).
- An object of the present invention is to provide a novel cross-linking agent capable of obtaining a (semi-)cured product with a high curing temperature and a curable composition using the same.
- the novel organosilicon compound and novel cross-linking agent of the present invention are suitable for use in curable compositions used in applications such as prepregs, metal-clad laminates and wiring boards, but can be used in any application. It is.
- the present invention provides the following novel organosilicon compounds, novel cross-linking agents, curable compositions, prepregs, laminates, metal-clad laminates and wiring substrates.
- M is a single bond or an optionally substituted alkylene group having 1 to 20 carbon atoms.
- the benzene ring may have a substituent.
- a vinyl group on the benzene ring is the meta position, n is an integer of 2 to 4, R is a hydrogen atom, a hydroxyl group or an organic group, and when R is an organic group, the atom bonded to Si is C.
- a curable composition comprising the cross-linking agent of [2] and a curable compound having two or more cross-linkable functional groups capable of cross-linking with the cross-linking agent.
- a prepreg comprising a fiber base material and a semi-cured or cured product of the curable composition of [3].
- a laminate comprising a substrate and a curable composition layer comprising the curable composition of [3].
- a laminate comprising a substrate and a semi-cured product of the curable composition of [3] or a (semi-)cured product-containing layer containing the cured product.
- the laminate of [5] or [6] wherein the substrate is a resin film or metal foil.
- a metal-clad laminate comprising an insulating layer containing a cured product of the curable composition of [3] and a metal foil.
- a wiring substrate comprising an insulating layer containing a cured product of the curable composition of [3] and wiring.
- a novel organosilicon compound suitable for use as a cross-linking agent or the like can be provided. According to the present invention, it is suitable for use in a curable composition, the dielectric loss tangent (D f ) under high frequency conditions is effectively reduced, the coefficient of thermal expansion (CTE) is sufficiently low, and the glass transition temperature (Tg) is A novel cross-linking agent capable of obtaining a sufficiently high (semi-) cured product and a curable composition using the same can be provided.
- FIG. 1 is a schematic cross-sectional view of a metal-clad laminate of a first embodiment according to the present invention
- FIG. FIG. 2 is a schematic cross-sectional view of a metal-clad laminate of a second embodiment according to the present invention
- 1 is a schematic cross-sectional view of a wiring board according to one embodiment of the present invention
- (semi-)curing is a generic term for semi-curing and curing.
- the term “wiring board” includes a multilayer wiring board.
- high frequency region is defined as a region with a frequency of 1 GHz or higher.
- number average molecular weight (Mn) is a polystyrene-equivalent number average molecular weight determined by a gel permeation chromatography (GPC) method.
- GPC gel permeation chromatography
- the organosilicon compound of the present invention is represented by the following formula (1m).
- the organosilicon compound of the present invention is suitable as a cross-linking agent and the like.
- the cross-linking agent of the present invention is represented by the following formula (1m).
- M is a single bond or an optionally substituted alkylene group having 1 to 20 carbon atoms.
- the benzene ring may have a substituent.
- a vinyl group on the benzene ring is the meta position, n is an integer of 2 to 4, R is a hydrogen atom, a hydroxyl group or an organic group, and when R is an organic group, the atom bonded to Si is C.
- the organosilicon compound and cross-linking agent of the present invention can be used for any purpose, and are suitable for curable compositions, prepregs, laminates, metal-clad laminates, wiring boards, and the like.
- the curable composition of the present invention comprises the cross-linking agent of the present invention and a curable compound having two or more cross-linkable functional groups capable of cross-linking with this cross-linking agent.
- the curable composition may be thermosetting or active energy ray curable.
- An active energy ray-curable composition is a composition that is cured by irradiation with active energy rays such as ultraviolet rays and electron beams. Thermosetting is preferred for applications such as metal-clad laminates and wiring boards.
- Curable compounds include monomers, oligomers, prepolymers, and the like. One or more of these can be used. Cured products of curable compounds include polyphenylene ether resins (PPE), bismaleimide resins, epoxy resins, fluorine resins, polyimide resins, olefin resins, polyester resins, polystyrene resins, hydrocarbon elastomers, benzoxazine resins, and active ester resins. , cyanate ester resins, butadiene resins, hydrogenated or non-hydrogenated styrene-butadiene resins, vinyl resins, cycloolefin polymers, aromatic polymers, divinyl aromatic polymers and combinations thereof.
- PPE polyphenylene ether resins
- bismaleimide resins epoxy resins, fluorine resins, polyimide resins, olefin resins, polyester resins, polystyrene resins, hydrocarbon elastomers, benzoxa
- the cured product of the curable compound preferably contains polyphenylene ether resin (PPE).
- PPE polyphenylene ether resin
- PPE polyphenylene ether resin
- the curable compound is preferably, for example, a polyphenylene ether oligomer represented by the following formula (P).
- X at both ends of formula (P) is each independently a group represented by the following formula (x1) or the following formula (x2).
- "*" indicates a bond with an oxygen atom.
- n is preferably 1-20, more preferably 3-15.
- the (semi-)cured product of the curable composition contains the reaction product of the curable compound and the cross-linking agent of the present invention.
- the number average molecular weight (Mn) of the oligomer is not particularly limited, preferably 1000-5000, more preferably 1000-4000.
- the curable composition preferably contains one or more polymerization initiators.
- the polymerization initiator organic peroxides, azo compounds, other known polymerization initiators, and combinations thereof can be used. Specific examples include dicumyl peroxide, benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(t-butyl peroxy)hexyne-3, di-t-butyl peroxide, t-butylcumyl peroxide, ⁇ , ⁇ '-di(t-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di( t-butylperoxy)hexane, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-but
- the curable composition may optionally contain one or more additives.
- additives include inorganic fillers (also referred to as fillers), compatibilizers and flame retardants.
- inorganic fillers include silica such as spherical silica, alumina, metal oxides such as titanium oxide and mica; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; talc; aluminum borate; barium sulfate; Calcium etc. are mentioned.
- silica, mica and talc are preferred, and spherical silica is more preferred, from the viewpoint of low thermal expansion.
- the inorganic filler may be surface treated with an epoxysilane-type, vinylsilane-type, methacrylsilane-type, or aminosilane-type silane coupling agent.
- the timing of surface treatment with a silane coupling agent is not particularly limited.
- An inorganic filler surface-treated with a silane coupling agent may be prepared in advance, or the silane coupling agent may be added by an integral blend method during preparation of the curable composition.
- flame retardants include halogen-based flame retardants and phosphorus-based flame retardants. One or more of these can be used.
- halogen-based flame retardants include brominated flame retardants such as pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A and hexabromocyclododecane; and chlorine-based flame retardants such as chlorinated paraffin. .
- phosphorus-based flame retardants include phosphoric acid esters such as condensed phosphoric acid esters and cyclic phosphoric acid esters; phosphazene compounds such as cyclic phosphazene compounds; phosphinate-based flame retardants such as aluminum dialkylphosphinate; melamine-based flame retardants such as melamine polyphosphate; and phosphine oxide compounds having a diphenylphosphine oxide group.
- the curable composition can contain one or more organic solvents, if necessary.
- the organic solvent is not particularly limited, and includes ketones such as methyl ethyl ketone; ethers such as dibutyl ether; esters such as ethyl acetate; amides such as dimethylformamide; aromatic hydrocarbons such as benzene, toluene and xylene; and chlorinated hydrocarbons such as
- the solid content concentration and composition can be designed according to the application.
- the solid content concentration is preferably 50 to 90% by mass.
- the prepreg of the present invention includes a fiber base material and a (semi-)cured product of the curable composition of the present invention.
- the (semi-)cured product may contain additives such as an inorganic filler (filler), if necessary.
- a prepreg can be produced by impregnating a fiber base material with a curable composition and (semi) curing the composition by heat curing or the like.
- the material of the fiber base material is not particularly limited, and includes inorganic fibers such as glass fiber, silica fiber and carbon fiber; organic fibers such as aramid fiber and polyester fiber; and combinations thereof.
- inorganic fibers such as glass fiber, silica fiber and carbon fiber
- organic fibers such as aramid fiber and polyester fiber
- combinations thereof for applications such as metal-clad laminates and wiring boards, glass fiber and the like are preferred.
- Examples of the form of the glass fiber substrate include glass cloth, glass paper and glass mat.
- the curing conditions of the curable composition can be set according to the composition of the curable composition, and semi-curing conditions (conditions under which complete curing is not performed) are preferred.
- semi-curing conditions conditions under which complete curing is not performed
- heat curing by heating at 80 to 180° C. for 1 to 10 minutes is preferred.
- it is preferable to adjust the composition and curing conditions of the curable composition so that the resin content in the resulting prepreg is within the range of 40 to 80% by mass.
- a first laminate of the present invention includes a substrate and a curable composition layer comprising the curable composition of the present invention.
- the second laminate of the present invention includes a base material and a (semi-)cured product-containing layer containing a (semi-)cured product of the curable composition of the present invention.
- the substrate is not particularly limited, and examples thereof include resin films, metal foils and combinations thereof.
- the resin film is not particularly limited, and known films can be used. Constituent resins of the resin film include polyimide, polyethylene terephthalate (PET), polyethylene naphthalate, cycloolefin polymer and polyether sulfide.
- PET polyethylene terephthalate
- the metal foil copper foil, silver foil, gold foil, aluminum foil, combinations thereof, and the like are preferable, and copper foil and the like are more preferable, because of their low electrical resistance.
- the metal-clad laminate of the present invention includes an insulating layer containing a cured product of the curable composition of the present invention and a metal foil.
- the insulating layer may be a layer containing a fiber base material and a cured product of the curable composition of the present invention.
- As the metal foil copper foil, silver foil, gold foil, aluminum foil, combinations thereof, and the like are preferable, and copper foil and the like are more preferable, because of their low electrical resistance.
- the metal foil may have a metal plating layer on its surface.
- the metal foil may be a carrier-attached metal foil that includes an ultra-thin metal foil and a carrier metal foil that supports it.
- At least one surface of the metal foil may be subjected to surface treatment such as rust prevention treatment, silane treatment, surface roughening treatment and barrier forming treatment.
- the thickness of the metal foil is not particularly limited, and is suitable for forming a conductor pattern (also called a circuit pattern) such as wiring. is 1.0 to 40 ⁇ m.
- the metal-clad laminate may be a single-sided metal-clad laminate having metal foil on one side, or a double-sided metal-clad laminate having metal foil on both sides, and may be a double-sided metal-clad laminate.
- a single-sided metal-clad laminate can be produced by stacking one or more of the above prepregs and a metal foil, and heating and pressurizing the resulting first temporary laminate.
- a double-sided metal-clad laminate can be produced by sandwiching one or more of the above prepregs between a pair of metal foils and heating and pressurizing the obtained first temporary laminate.
- a metal clad laminate using copper foil as the metal foil is called a copper clad laminate (CCL).
- the insulating layer preferably consists of a heat-pressed prepreg.
- the heat-pressed prepreg contains a fiber base material and a resin, and can optionally contain one or more additives such as inorganic fillers and flame retardants.
- a heat-pressed prepreg is also called a composite base material.
- the heating and pressurizing conditions for the first temporary laminate are not particularly limited, and are preferably, for example, a temperature of 170 to 250° C., a pressure of 0.3 to 30 MPa, and a time of 3 to 240 minutes.
- the metal-clad laminate 1 shown in FIG. It is a single-sided metal-clad laminate (laminate) in which layers) 12 are laminated.
- the metal-clad laminate 2 shown in FIG. 2 is made of a prepreg heated and pressed, and a metal foil (metal Layer) 12 is a double-sided metal-clad laminate laminated.
- the metal-clad laminates 1 and 2 may have layers other than those described above.
- the metal-clad laminates 1 and 2 may have an adhesive layer between the composite base material (cured material-containing layer) 11 and the metal foil (metal layer) 12 in order to enhance their adhesion.
- Known materials can be used for the adhesive layer, and examples thereof include epoxy resins, cyanate ester resins, acrylic resins, polyimide resins, maleimide resins, adhesive fluororesins, and combinations thereof.
- Commercially available adhesive fluororesins include "Fluon LM-ETFE LH-8000", “AH-5000", "AH-2000” and "EA-2000" manufactured by AGC.
- the thickness of the composite base material can be appropriately designed according to the application. From the viewpoint of preventing disconnection of the wiring board, the thickness is preferably 50 ⁇ m or more, more preferably 70 ⁇ m or more, and particularly preferably 100 ⁇ m or more. From the viewpoint of flexibility, miniaturization and weight reduction of the wiring board, the thickness is preferably 300 ⁇ m or less, more preferably 250 ⁇ m or less, and particularly preferably 200 ⁇ m or less.
- the wiring board of the present invention includes an insulating layer containing a cured product of the curable composition of the present invention, and wiring.
- the wiring board can be produced by forming a conductor pattern (circuit pattern) such as wiring using the metal foil on the outermost surface of the metal-clad laminate of the present invention.
- Methods for forming conductor patterns such as wiring include the subtractive method in which wiring is formed by etching metal foil, and the MSAP (Modified Semi-Additive Process) method in which wiring is formed by plating on metal foil. mentioned.
- FIG. 3 shows a schematic cross-sectional view of a wiring board according to one embodiment of the present invention.
- the wiring substrate 3 shown in FIG. 3 is formed by using the metal foil 12 on at least one of the outermost surfaces of the metal-clad laminate 2 of the second embodiment shown in FIG. is formed.
- the wiring board 3 is made of a prepreg heated and pressed, and a conductor pattern such as a wiring 22W is provided on at least one side of a composite base material (cured product-containing layer, insulating layer) 11 containing a cured product of the curable composition of the present invention.
- a (circuit pattern) 22 is formed.
- a multilayer wiring board (also referred to as a multilayer printed wiring board) may be manufactured by forming a conductor pattern such as a multilayer wiring board.
- the outermost metal foil may be arranged only on one side of the second temporary laminate.
- the wiring board of the present invention is suitable for use in a high frequency range (frequency range of 10 GHz or higher).
- the speed and capacity of communication have increased, and the frequency of signals has increased.
- a wiring board used for this purpose is required to reduce transmission loss in a high frequency region. Therefore, the resin contained in the composite base material of the wiring board used for the above application is required to reduce the dielectric loss in the high frequency region.
- the dielectric loss tangent (D f ) depends on the frequency, and if the same material is used, the higher the frequency, the larger the dielectric loss tangent (D f ) tends to be.
- the resin contained in the composite base material preferably has a low dielectric loss tangent (D f ) under high frequency conditions.
- CTE coefficient of thermal expansion
- a first temporary laminate including the prepreg and the metal foil or a second temporary laminate including the composite base material, the prepreg and the metal foil will be produced.
- the temporary laminate is heated and pressurized, the metal foil may be displaced or peeled off.
- a smaller difference in coefficient of thermal expansion (CTE) between the prepreg or composite base material and the metal foil is preferred. Since resin generally has a higher coefficient of thermal expansion (CTE) than metal foil, it is preferable that the prepreg and composite base material have a lower coefficient of thermal expansion (CTE).
- a wiring board may be used in a relatively high-temperature environment.
- the resin contained in the prepreg and the composite base material preferably has a sufficiently high glass transition temperature (Tg) in order to ensure the reliability of the wiring board.
- the organosilicon compound and cross-linking agent of the present invention unlike the silane coupling agent used in Patent Document 1 mentioned in the Background Art section, all four atoms bonded to Si are nonpolar atoms ( Specifically, it is a hydrogen atom or a carbon atom).
- the organosilicon compound of the present invention acts as a cross-linking agent that cross-links the curable compound having two or more cross-linkable functional groups. It was found that the dielectric loss tangent (D f ) of the (semi-)cured product of the curable composition can be effectively reduced.
- the (semi-)cured product of the curable composition containing the organosilicon compound of the present invention has a sufficiently low coefficient of thermal expansion (CTE) and a sufficiently high glass transition temperature (Tg). It was also found that the (semi-)cured product of the curable composition containing the organosilicon compound of the present invention has practically good adhesion to metals such as copper foil.
- the dielectric loss tangent (D f ) under high frequency conditions is effectively reduced, the coefficient of thermal expansion (CTE) is sufficiently low, and the glass transition A (semi-)cured product having a sufficiently high temperature (Tg) can be obtained.
- This (semi-)cured product is suitable for a composite base material, an insulating layer, and the like suitable for a wiring substrate used in a high frequency region.
- the (semi-)cured product of the curable composition of the present invention and the composite substrate containing the same preferably have a dielectric loss tangent (D f ) under high-frequency conditions, for example, within the following range.
- D f dielectric loss tangent
- a smaller dielectric loss tangent (D f ) at a frequency of 10 GHz is preferable, and is preferably 0.01 or less, more preferably 0.005 or less, and particularly preferably 0.003 or less.
- the lower limit is not particularly limited, and is, for example, 0.0001.
- the coefficient of thermal expansion (CTE) of the (semi-)cured product of the curable composition of the present invention and the composite substrate containing the same is preferably within the following range, for example.
- the coefficient of thermal expansion (CTE) is preferably as small as possible, preferably 70 ppm/°C or less, more preferably 50 ppm/°C or less, and particularly preferably 40 ppm/°C or less.
- the lower limit is not particularly limited, and is, for example, 1 ppm/°C.
- the glass transition temperature (Tg) of the (semi-)cured product of the curable composition of the present invention is preferably 150°C or higher, more preferably 180°C or higher, and particularly preferably 200°C or higher.
- the upper limit is not particularly limited, and is 300° C., for example.
- the dielectric loss tangent (D f ), coefficient of thermal expansion (CTE) and glass transition temperature (Tg) can be measured by the methods described in the section [Examples] below.
- the benzene ring may have a substituent.
- substituents that the benzene ring may have include alkyl groups and aryl groups having 1 to 18 carbon atoms, and from the viewpoint of raw material availability, methyl group, ethyl group, propyl group, butyl group, hexyl , octyl, phenyl and tolyl groups are preferred.
- the benzene ring preferably has no substituents.
- the substitution position of the vinyl group on the benzene ring may be ortho, meta or para positions.
- the substitution position of the vinyl group on the benzene ring is the meta position.
- the substitution position is the ortho position, steric hindrance between the vinyl group substituted on the organosilicon compound and the crosslinking reaction point of the curable compound may make it relatively difficult for the crosslinking reaction to progress compared to the meta position. . Therefore, physical properties such as the coefficient of thermal expansion (CTE) and the glass transition temperature (Tg) of the (semi-)cured product of the curable composition may relatively decrease.
- CTE coefficient of thermal expansion
- Tg glass transition temperature
- steric hindrance is greater than at the meta position, which may make it difficult to synthesize an organosilicon compound.
- the substitution position is the para position, unlike the meta position, the benzene ring tends to rotate about the axis connecting the silicon atom and the cross-linking point, especially under high frequency conditions, and the effect of reducing the dielectric loss tangent (D f ) is diminished. there is a possibility.
- the substitution position is the meta position, rotation of the benzene ring is unlikely to occur even under high frequency conditions, and the dielectric loss tangent (D f ) of the (semi) cured product of the curable composition under high frequency conditions can be more effectively reduced. .
- the organosilicon compound in which the substitution position is the meta position is easy to obtain raw materials and easy to synthesize. Since the positions of the central silicon atom of the organosilicon compound and the vinyl group are not too close, the effect of steric hindrance between the vinyl group and the cross-linking reaction point of the curable compound is small, and the cross-linking reaction of the curable composition proceeds easily.
- the (semi-)cured product of the curable composition also has a good coefficient of thermal expansion (CTE) and glass transition temperature (Tg).
- CTE coefficient of thermal expansion
- Tg glass transition temperature
- the number of reactive functional groups (also referred to simply as the number of functional groups) n is 2-4.
- the functional group number n can be two.
- the functionality n can be 3 or 4.
- R is a hydrogen atom, a hydroxyl group or an organic group, preferably an optionally substituted alkyl group having 1 to 18 carbon atoms.
- R preferably does not contain a polar atom such as an oxygen atom (O), since the dielectric loss tangent (D f ) of the (semi-)cured product of the curable composition can be more effectively reduced under high frequency conditions.
- R is preferably an unsubstituted alkyl group having 1 to 18 carbon atoms. More preferably, it is a straight-chain alkyl group having 1 to 18 carbon atoms.
- R preferably has a large number of carbon atoms because the polarity of the crosslinked structure is lowered, and the dielectric loss tangent (D f ) of the (semi-)cured product of the curable composition under high frequency conditions can be reduced more effectively.
- the upper limit of carbon number is 18.
- the number of carbon atoms in R is more preferably 3 to 18, particularly preferably 8 to 8. is 18.
- M is a single bond or an optionally substituted alkylene group having 1 to 20 carbon atoms.
- the upper limit of the number of carbon atoms is 20 from the viewpoint of ease of synthesis.
- M is preferably a single bond or an alkylene group having 1 to 4 carbon atoms, more preferably a single bond or a methylene group.
- the organosilicon compound of the present invention represented by formula (1m) can be synthesized by a known synthesis method. For specific synthesis examples, see the section "Examples”.
- a novel organosilicon compound suitable for use as a cross-linking agent or the like it is suitable for use in a curable composition, the dielectric loss tangent (D f ) under high frequency conditions is effectively reduced, the coefficient of thermal expansion (CTE) is sufficiently low, and the glass transition temperature (Tg) is A novel cross-linking agent capable of obtaining a sufficiently high (semi-) cured product and a curable composition using the same can be provided.
- the novel organosilicon compound and novel cross-linking agent of the present invention are suitable for use in curable compositions used in applications such as prepregs, metal-clad laminates and wiring boards, but can be used in any application. It is.
- the novel organosilicon compound of the present invention is suitable as a cross-linking agent and the like.
- the crosslinkers of the present invention are suitable for curable compositions containing curable compounds such as monomers, oligomers and prepolymers.
- the novel organosilicon compound and novel cross-linking agent of the present invention are suitable for curable compositions used in applications such as prepregs, metal-clad laminates and wiring boards.
- the curable composition containing the cross-linking agent of the present invention is suitable for use in applications such as prepregs, metal-clad laminates and wiring boards.
- INDUSTRIAL APPLICABILITY The metal-clad laminate of the present invention is suitable for wiring substrates and the like used in various electric devices and various electronic devices.
- the wiring board of the present invention is suitable for use in portable electronic devices such as mobile phones, smart phones, personal digital assistants and notebook computers; antennas for mobile phone base stations and automobiles; electronic devices such as servers, routers and backplanes; Radar for prevention, various sensors (for example, automotive sensors such as engine management sensors), and the like.
- the wiring board of the present invention is particularly suitable for communication using high-frequency signals, and is suitable for various applications requiring reduction of transmission loss in a high-frequency region.
- Examples 1 to 3 and 101 are working examples, and examples 21, 22, 31 and 32 are comparative examples. Unless otherwise specified, room temperature is around 25°C.
- the molecular weight of the synthesized organosilicon compound was determined by the electron impact method (EI) using a gas chromatograph mass spectrometer (GC-HRMS) (Agilent "7890A/JEOL JMS-T200 AccuTOF GCx-plus”). .
- EI electron impact method
- GC-HRMS gas chromatograph mass spectrometer
- SA9000 and OPE-2st are represented by the following formulas.
- the coating film After drying by heating at 80° C. for 30 minutes in an oven in an air atmosphere, the coating film is thermally cured (thermal cross-linking reaction) by heating at 200° C. for 2 hours in a nitrogen atmosphere to obtain a thickness of about 100 ⁇ m.
- a sample for evaluation (film-like cured product) was obtained. The evaluation samples obtained were evaluated as follows.
- Glass transition temperature Tg Glass transition temperature Tg
- DVA-200 dynamic viscoelasticity measuring device
- DMA dynamic viscoelasticity measurement
- Tg glass transition temperature
- CTE Coefficient of thermal expansion
- n-BuLi/n-hexane solution (2.6 mol/L, 35 mL, 91 mmol) was added dropwise thereto over 1 hour, and the mixture was stirred at ⁇ 70° C. or lower for 2 hours.
- Dichlorodimethylsilane (4.40 mL, 36.3 mmol) was added dropwise to the resulting reaction solution over 30 minutes, and the mixture was stirred at the same temperature as above for 2 hours. The flask was warmed to room temperature and stirred for 12 more hours. The reaction mixture was quenched with hydrochloric acid (2 mol/L, 120 mL), stirred at room temperature for 1 hour, and the organic phase was separated.
- n-BuLi/n-hexane solution (2.6 mol/L, 35 mL, 91 mmol) was added dropwise thereto over 1 hour. Stirred for hours.
- Dodecyltrichlorosilane (7.20 mL, 24.2 mmol) was added dropwise to the resulting reaction solution over 40 minutes, and the mixture was stirred at the same temperature as above for 2 hours. The flask was warmed to room temperature and stirred for 12 more hours. The reaction mixture was quenched with hydrochloric acid (2 mol/L, 120 mL), stirred at room temperature for 1 hour, and the organic phase was separated.
- Example 3 Synthesis of dodecyltris(vinylbenzyl)silane isomer mixture (C12-T-mp-Bn-Si) In a 50 mL four-necked flask under a nitrogen atmosphere, magnesium (cuttings, 0.898 g, 36.9 mmol) and diethyl ether (21.1 mL) were charged and cooled in an ice bath. The suspension was treated with a solution of 4-(chloromethyl)styrene/3-(chloromethyl)styrene mixture (1:1 (molar ratio), 5.12 g, 33.5 mmol) in diethyl ether (10.5 mL) for 1 hour. dripped over.
- the crude product was purified using silica gel column chromatography (mobile phase: n-hexane), and 0.319 g of dodecyltris(vinylbenzyl)silane isomer mixture (C12-T-mp-Bn-Si) was obtained as a colorless liquid. obtained (yield: 5.2%). From the results of NMR analysis, the molar ratio of 3-vinylbenzyl group and 4-vinylbenzyl group in the isomer mixture was estimated to be 1.4:1.6.
- Example 31 As a comparative organosilicon compound, a commercially available silane coupling agent, trimethoxyvinylsilane (TMVS, product of TCI) was prepared.
- TMVS trimethoxyvinylsilane
- Example 32 As a comparative organosilicon compound, a commercially available silane coupling agent, triethoxyvinylsilane (TEVS, product of TCI) was prepared.
- TEVS triethoxyvinylsilane
- the dielectric loss tangent (D f ) under high frequency conditions could be effectively reduced compared to Examples 31 and 32 using the silane coupling agent. From a comparison between Examples 1 and 21 and between Examples 2 and 22, by using an organosilicon compound in which the vinyl group on the benzene ring is substituted at the meta position as the cross-linking agent, under high frequency conditions, It has been found that the dissipation factor (D f ) can be reduced more effectively. In Examples 1 and 2, the dielectric loss tangent (D f ) under high frequency conditions is effectively reduced, the coefficient of thermal expansion (CTE) is sufficiently low, and the glass transition temperature (Tg) is sufficiently high to obtain a film-like cured product. was made.
- CTE coefficient of thermal expansion
- Tg glass transition temperature
- Example 101 Bifunctional chloromethylstyrene-modified PPE (OPE-2st), the organosilicon compound synthesized in Example 1, dicumyl peroxide as a radical polymerization initiator, spherical silica as an inorganic filler, and toluene were
- a curable composition (varnish) was prepared by mixing at a ratio of 7:3:0.1:10:10 and stirring at room temperature. After impregnating a glass cloth (E glass, #2116) as a fiber base material with the obtained curable composition (varnish), the curable composition is semi-cured by heating at 130 ° C. for 5 minutes, Got the prepreg. Two sheets of the obtained prepreg were laminated, sandwiched between a pair of copper foils, and the resulting temporary laminate was heated and pressed under conditions of 200° C., 1.5 hours, and 3 MPa to produce a metal-clad laminate. .
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Abstract
The present invention provides: a novel organosilicon compound suitable for use as a crosslinking agent or the like; a novel crosslinking agent; a curable composition; a prepreg; a laminate; a metal-clad laminated board; and a wiring board The organosilicon compound is represented by formula (1m). (In the formula, M is a single bond or an optionally substituted alkylene group having 1-20 carbon atoms. The benzene ring may have a substituent group. The position of substitution of the vinyl group on the benzene ring is a meta position. n is an integer between 2 and 4. R is a hydrogen atom, a hydroxyl group or an organic group, and if R is an organic group, an atom that bonds to Si is C.)
Description
本発明は、新規な有機ケイ素化合物、新規な架橋剤、硬化性組成物、プリプレグ、積層体、金属張積層板および配線基板に関する。
The present invention relates to novel organosilicon compounds, novel cross-linking agents, curable compositions, prepregs, laminates, metal-clad laminates and wiring substrates.
電気機器および電子機器等の用途に、配線基板(プリント配線板とも言う。)が使用される。配線基板は例えば、以下のようにして、製造できる。硬化性組成物を繊維基材に含浸させ、硬化性組成物を(半)硬化させて、プリプレグを作製する。1つ以上のプリプレグを一対の金属箔で挟み、得られた第1の仮積層体を加熱加圧して、金属張積層板を作製する。この金属張積層板の最表面にある金属箔を用いて、配線等の導体パターン(回路パターンとも言う。)を形成する。最表面の金属箔は、第1の仮積層体の片面側にのみ配置してもよい。
Wiring boards (also called printed wiring boards) are used for applications such as electrical and electronic equipment. A wiring board can be manufactured, for example, as follows. A curable composition is impregnated into a fibrous base material and the curable composition is (semi) cured to produce a prepreg. One or more prepregs are sandwiched between a pair of metal foils, and the obtained first temporary laminate is heated and pressurized to produce a metal-clad laminate. Using the metal foil on the outermost surface of this metal-clad laminate, a conductor pattern (also referred to as a circuit pattern) such as wiring is formed. The outermost metal foil may be arranged only on one side of the first temporary laminate.
得られた配線基板に対してさらに、1つ以上のプリプレグを重ね、これを一対の金属箔で挟み、得られた第2の仮積層体を加熱加圧し、最表面にある金属箔を用いて配線等の導体パターンを形成することで、多層配線基板(多層プリント配線板とも言う。)を製造できる。最表面の金属箔は、第2の仮積層体の片面側にのみ配置してもよい。
Further, one or more prepregs are superimposed on the obtained wiring board, sandwiched between a pair of metal foils, the obtained second temporary laminate is heated and pressed, and the metal foil on the outermost surface is used to A multilayer wiring board (also referred to as a multilayer printed wiring board) can be manufactured by forming a conductor pattern such as wiring. The outermost metal foil may be arranged only on one side of the second temporary laminate.
プリプレグの加熱加圧物は、繊維基材、樹脂および無機充填材(フィラーとも言う。)等を含み、コンポジット基材とも呼ばれる。配線基板において、コンポジット基材は、絶縁層として機能する。
プリプレグに含まれる樹脂は硬化性組成物の(半)硬化物であり、コンポジット基材に含まれる樹脂は硬化性組成物の硬化物である。 A heated and pressurized prepreg contains a fiber base material, a resin, an inorganic filler (also referred to as a filler), and the like, and is also called a composite base material. In the wiring board, the composite base material functions as an insulating layer.
The resin contained in the prepreg is a (semi-)cured product of the curable composition, and the resin contained in the composite substrate is a cured product of the curable composition.
プリプレグに含まれる樹脂は硬化性組成物の(半)硬化物であり、コンポジット基材に含まれる樹脂は硬化性組成物の硬化物である。 A heated and pressurized prepreg contains a fiber base material, a resin, an inorganic filler (also referred to as a filler), and the like, and is also called a composite base material. In the wiring board, the composite base material functions as an insulating layer.
The resin contained in the prepreg is a (semi-)cured product of the curable composition, and the resin contained in the composite substrate is a cured product of the curable composition.
近年、携帯用電子機器等の用途では、通信の高速化と大容量化が進み、信号の高周波化が進んでいる。この用途に用いられる配線基板には、高周波領域での伝送損失の低減が求められる。伝送損失には、主に金属箔の表面抵抗に起因する導体損失と、コンポジット基材の誘電正接(Df)に起因する誘電損失とがある。このため、上記用途に用いられる配線基板のコンポジット基材に含まれる樹脂には、高周波領域での誘電損失の低減が求められる。一般的に、誘電正接(Df)は周波数に依存し、同じ材料であれば、周波数が高くなる程、誘電正接(Df)が大きくなる傾向がある。コンポジット基材に含まれる樹脂は、高周波条件における誘電正接(Df)が低いことが好ましい。
2. Description of the Related Art In recent years, in applications such as portable electronic devices, the speed and capacity of communication have increased, and the frequency of signals has increased. A wiring board used for this purpose is required to reduce transmission loss in a high frequency region. Transmission loss includes conductor loss mainly caused by the surface resistance of the metal foil and dielectric loss caused by the dielectric loss tangent (D f ) of the composite base material. Therefore, the resin contained in the composite base material of the wiring board used for the above application is required to reduce the dielectric loss in the high frequency region. Generally, the dielectric loss tangent (D f ) depends on the frequency, and if the same material is used, the higher the frequency, the larger the dielectric loss tangent (D f ) tends to be. The resin contained in the composite base material preferably has a low dielectric loss tangent (D f ) under high frequency conditions.
プリプレグまたはコンポジット基材と金属箔との熱膨張係数(CTE)の差が大きいと、プリプレグと金属箔とを含む第1の仮積層体、またはコンポジット基材とプリプレグと金属箔とを含む第2の仮積層体を加熱加圧する際に、金属箔のずれまたは剥離が生じる恐れがある。プリプレグまたはコンポジット基材と金属箔との熱膨張係数(CTE)の差は、小さい方が好ましい。一般的に、樹脂は金属箔より熱膨張係数(CTE)が大きいので、プリプレグおよびコンポジット基材の熱膨張係数(CTE)は小さい方が好ましい。
If the difference in coefficient of thermal expansion (CTE) between the prepreg or composite base material and the metal foil is large, a first temporary laminate including the prepreg and the metal foil or a second temporary laminate including the composite base material, the prepreg and the metal foil will be produced. When the temporary laminate is heated and pressurized, the metal foil may be displaced or peeled off. A smaller difference in coefficient of thermal expansion (CTE) between the prepreg or composite base material and the metal foil is preferred. Since resin generally has a higher coefficient of thermal expansion (CTE) than metal foil, it is preferable that the prepreg and composite base material have a lower coefficient of thermal expansion (CTE).
配線基板は、比較的高温の環境下で使用される場合がある。この場合でも、配線基板の信頼性を確保するために、プリプレグおよびコンポジット基材に含まれる樹脂は、充分な高さのガラス転移温度(Tg)を有することが好ましい。
A wiring board may be used in a relatively high-temperature environment. Even in this case, the resin contained in the prepreg and the composite base material preferably has a sufficiently high glass transition temperature (Tg) in order to ensure the reliability of the wiring board.
配線基板においては、コンポジット基材と金属箔との密着性が重要である。従来、コンポジット基材と金属箔との密着性向上のために、金属箔のコンポジット基材側の表面を粗面化する技術がある。しかしながら、この技術では、高周波電流の損失が生じやすく、好ましくない。
金属箔のコンポジット基材側の表面を粗面化せずに、コンポジット基材と金属箔との密着性を高める技術として、特許文献1には、ポリフェニレンオキサイドおよびトリアルケニルイソシアヌレートからなるポリフェニレンオキサイド系樹脂と、トリメトキシビニルシラン(TMVS)およびトリエトキシビニルシラン(TEVS)等のビニルシランとを含む配線基板用樹脂組成物およびこれを用いて得られた配線基板が開示されている(請求項1~4)。 Adhesion between the composite base material and the metal foil is important in the wiring board. Conventionally, there is a technique for roughening the surface of the metal foil on the side of the composite base material in order to improve the adhesion between the composite base material and the metal foil. However, this technique is not preferable because high-frequency current loss is likely to occur.
As a technique for enhancing the adhesion between a composite substrate and a metal foil without roughening the surface of the metal foil on the composite substrate side,Patent Document 1 discloses a polyphenylene oxide system consisting of polyphenylene oxide and trialkenyl isocyanurate. A wiring board resin composition containing a resin and a vinylsilane such as trimethoxyvinylsilane (TMVS) and triethoxyvinylsilane (TEVS) and a wiring board obtained using the same are disclosed (claims 1 to 4). .
金属箔のコンポジット基材側の表面を粗面化せずに、コンポジット基材と金属箔との密着性を高める技術として、特許文献1には、ポリフェニレンオキサイドおよびトリアルケニルイソシアヌレートからなるポリフェニレンオキサイド系樹脂と、トリメトキシビニルシラン(TMVS)およびトリエトキシビニルシラン(TEVS)等のビニルシランとを含む配線基板用樹脂組成物およびこれを用いて得られた配線基板が開示されている(請求項1~4)。 Adhesion between the composite base material and the metal foil is important in the wiring board. Conventionally, there is a technique for roughening the surface of the metal foil on the side of the composite base material in order to improve the adhesion between the composite base material and the metal foil. However, this technique is not preferable because high-frequency current loss is likely to occur.
As a technique for enhancing the adhesion between a composite substrate and a metal foil without roughening the surface of the metal foil on the composite substrate side,
特許文献1で用いられているトリメトキシビニルシラン(TMVS)およびトリエトキシビニルシラン(TEVS)等のビニルシランは、Siと極性原子である酸素原子(O)との結合を含むシランカップリング剤である。
本発明者らが検討したところ、硬化性組成物に、Siと極性原子である酸素原子(O)との結合を含むシランカップリング剤を添加した場合、得られるコンポジット基材は誘電正接(Df)が増加する傾向があることが分かった。 Vinylsilanes such as trimethoxyvinylsilane (TMVS) and triethoxyvinylsilane (TEVS) used inPatent Document 1 are silane coupling agents containing a bond between Si and a polar oxygen atom (O).
As a result of studies by the present inventors, when a silane coupling agent containing a bond between Si and an oxygen atom (O), which is a polar atom, is added to the curable composition, the resulting composite substrate has a dielectric loss tangent (D f ) was found to tend to increase.
本発明者らが検討したところ、硬化性組成物に、Siと極性原子である酸素原子(O)との結合を含むシランカップリング剤を添加した場合、得られるコンポジット基材は誘電正接(Df)が増加する傾向があることが分かった。 Vinylsilanes such as trimethoxyvinylsilane (TMVS) and triethoxyvinylsilane (TEVS) used in
As a result of studies by the present inventors, when a silane coupling agent containing a bond between Si and an oxygen atom (O), which is a polar atom, is added to the curable composition, the resulting composite substrate has a dielectric loss tangent (D f ) was found to tend to increase.
本発明者らは、2つ以上の反応性ビニル基を含み、Siと極性原子との結合を含まない特定の化学構造を有する有機ケイ素化合物が、硬化性組成物の架橋剤として使用でき、これを含む硬化性組成物を用いて得られるコンポジット基材は、高周波条件における誘電正接(Df)が効果的に低減され、熱膨張係数(CTE)が充分に低く、ガラス転移温度(Tg)が充分に高く、高周波領域で用いられる配線基板用として良好な特性を有することを見出した。
なお、特許文献1では、シランカップリング剤を用いることで、コンポジット基材と金属箔との密着性を高めており、有機ケイ素化合物の架橋剤としての使用については、記載および示唆がない。 The inventors have discovered that organosilicon compounds having a specific chemical structure containing two or more reactive vinyl groups and free of Si-polar atom bonds can be used as cross-linking agents in curable compositions. The composite substrate obtained by using the curable composition comprising the dielectric loss tangent (D f ) under high frequency conditions is effectively reduced, the coefficient of thermal expansion (CTE) is sufficiently low, and the glass transition temperature (Tg) is It has been found to be sufficiently high and to have good characteristics for a wiring substrate used in a high frequency region.
InPatent Document 1, the adhesion between the composite base material and the metal foil is enhanced by using a silane coupling agent, and there is no description or suggestion regarding the use of an organosilicon compound as a cross-linking agent.
なお、特許文献1では、シランカップリング剤を用いることで、コンポジット基材と金属箔との密着性を高めており、有機ケイ素化合物の架橋剤としての使用については、記載および示唆がない。 The inventors have discovered that organosilicon compounds having a specific chemical structure containing two or more reactive vinyl groups and free of Si-polar atom bonds can be used as cross-linking agents in curable compositions. The composite substrate obtained by using the curable composition comprising the dielectric loss tangent (D f ) under high frequency conditions is effectively reduced, the coefficient of thermal expansion (CTE) is sufficiently low, and the glass transition temperature (Tg) is It has been found to be sufficiently high and to have good characteristics for a wiring substrate used in a high frequency region.
In
その他の本発明の本発明の関連技術として、非特許文献1、2および特許文献2が挙げられる。
非特許文献1では、Siに2つの4-ビニルフェニル基と2つのアルキル基(具体的には、-C8H17)とが結合した有機ケイ素化合物が合成されている。反応スキームは、以下の通りである。非特許文献1では、合成された有機ケイ素化合物を重合し、得られた直鎖ポリマーについて蛍光特性の評価が行われている。非特許文献1では、有機ケイ素化合物はモノマーとして使用されており、架橋剤としての使用について記載および示唆がなく、誘電特性についても記載がない。 Non-Patent Documents 1 and 2 and Patent Document 2 are cited as other related arts of the present invention.
InNon-Patent Document 1, an organosilicon compound is synthesized in which two 4-vinylphenyl groups and two alkyl groups (specifically, —C 8 H 17 ) are bonded to Si. The reaction scheme is as follows. In Non-Patent Document 1, a synthesized organosilicon compound is polymerized, and the obtained linear polymer is evaluated for fluorescence properties. Non-Patent Document 1 uses an organosilicon compound as a monomer, does not describe or suggest its use as a cross-linking agent, and does not describe its dielectric properties.
非特許文献1では、Siに2つの4-ビニルフェニル基と2つのアルキル基(具体的には、-C8H17)とが結合した有機ケイ素化合物が合成されている。反応スキームは、以下の通りである。非特許文献1では、合成された有機ケイ素化合物を重合し、得られた直鎖ポリマーについて蛍光特性の評価が行われている。非特許文献1では、有機ケイ素化合物はモノマーとして使用されており、架橋剤としての使用について記載および示唆がなく、誘電特性についても記載がない。
In
非特許文献2では、Siに2つの2-ビニルフェニル基と2つのアルキル基(具体的には、-Me、-Etまたは-Ph)とが結合した有機ケイ素化合物が合成されている。非特許文献2では、合成された有機ケイ素化合物を閉環メタセシス(Ring-closing metathesis)し、ジベンゾヘテロピン類を合成している。反応スキームは、以下の通りである。非特許文献2には、有機ケイ素化合物の用途について記載がなく、架橋剤としての使用について記載および示唆がなく、誘電特性についても記載がない。
In Non-Patent Document 2, an organosilicon compound is synthesized in which two 2-vinylphenyl groups and two alkyl groups (specifically, -Me, -Et or -Ph) are bonded to Si. In Non-Patent Document 2, a synthesized organosilicon compound is subjected to ring-closing metathesis to synthesize dibenzoheteropines. The reaction scheme is as follows. Non-Patent Document 2 does not describe the use of the organosilicon compound, neither describes nor suggests its use as a cross-linking agent, nor describes its dielectric properties.
特許文献2では、Siに2つの2-、3-または4-ビニルフェニル基および2つのアルキル基が置換した複数の有機ケイ素化合物が合成されている。以下の[化3]に、特許文献2で合成された有機ケイ素化合物の例を示す。特許文献2では、有機ケイ素化合物はガスバリア用途であり、架橋剤としての使用について記載および示唆がなく、誘電特性についても記載がない。
In Patent Document 2, a plurality of organosilicon compounds in which Si is substituted with two 2-, 3- or 4-vinylphenyl groups and two alkyl groups are synthesized. An example of the organosilicon compound synthesized in Patent Document 2 is shown in [Chemical 3] below. In Patent Document 2, the organosilicon compound is used for gas barrier applications, and there is no description or suggestion of its use as a cross-linking agent, nor is there any description of dielectric properties.
上記以外にも、Siと結合した4つの原子がすべて非極性原子であり、2つ以上の反応性ビニル基を有する有機ケイ素化合物はいくつか報告されている。しかしながら、過去には、Siと結合した4つの原子がすべて非極性原子であり、2つ以上の反応性ビニル基を有する有機ケイ素化合物の架橋剤としての使用について報告がない。Siと結合した4つの原子がすべて非極性原子であり、2つ以上の反応性ビニル基を有する有機ケイ素化合物はすべて、架橋剤として新規である。
さらに、Siと結合した4つの原子がすべて非極性原子であり、2つ以上の反応性ビニル基を有する有機ケイ素化合物のうち、特定の構造を有するいくつかの有機ケイ素化合物は、化合物として新規である。
具体的には、Siと結合した4つの原子がすべて非極性原子であり、ビニルフェニル基を含む2つ以上の反応性官能基を含み、ベンゼン環上のビニル基の置換位置がメタ位である有機ケイ素系化合物(有機ケイ素系化合物に含まれるベンゼン環は置換基を有していてもよい。)は、化合物として新規である。 In addition to the above, some organosilicon compounds in which all four atoms bonded to Si are non-polar atoms and have two or more reactive vinyl groups have been reported. However, in the past, there have been no reports on the use of organosilicon compounds having two or more reactive vinyl groups in which all four atoms bonded to Si are non-polar atoms as cross-linking agents. All organosilicon compounds having two or more reactive vinyl groups in which all four atoms bonded to Si are non-polar atoms are novel as crosslinkers.
Furthermore, among organosilicon compounds in which all four atoms bonded to Si are non-polar atoms and which have two or more reactive vinyl groups, some organosilicon compounds having specific structures are novel compounds. be.
Specifically, all four atoms bonded to Si are non-polar atoms, contain two or more reactive functional groups including a vinyl phenyl group, and the substituted position of the vinyl group on the benzene ring is the meta position. The organosilicon compound (the benzene ring contained in the organosilicon compound may have a substituent) is novel as a compound.
さらに、Siと結合した4つの原子がすべて非極性原子であり、2つ以上の反応性ビニル基を有する有機ケイ素化合物のうち、特定の構造を有するいくつかの有機ケイ素化合物は、化合物として新規である。
具体的には、Siと結合した4つの原子がすべて非極性原子であり、ビニルフェニル基を含む2つ以上の反応性官能基を含み、ベンゼン環上のビニル基の置換位置がメタ位である有機ケイ素系化合物(有機ケイ素系化合物に含まれるベンゼン環は置換基を有していてもよい。)は、化合物として新規である。 In addition to the above, some organosilicon compounds in which all four atoms bonded to Si are non-polar atoms and have two or more reactive vinyl groups have been reported. However, in the past, there have been no reports on the use of organosilicon compounds having two or more reactive vinyl groups in which all four atoms bonded to Si are non-polar atoms as cross-linking agents. All organosilicon compounds having two or more reactive vinyl groups in which all four atoms bonded to Si are non-polar atoms are novel as crosslinkers.
Furthermore, among organosilicon compounds in which all four atoms bonded to Si are non-polar atoms and which have two or more reactive vinyl groups, some organosilicon compounds having specific structures are novel compounds. be.
Specifically, all four atoms bonded to Si are non-polar atoms, contain two or more reactive functional groups including a vinyl phenyl group, and the substituted position of the vinyl group on the benzene ring is the meta position. The organosilicon compound (the benzene ring contained in the organosilicon compound may have a substituent) is novel as a compound.
本発明は上記事情に鑑みてなされたものであり、架橋剤等として用いて好適な新規な有機ケイ素化合物の提供を目的とする。
本発明はまた、硬化性組成物に用いて好適で、高周波条件における誘電正接(Df)が効果的に低減され、熱膨張係数(CTE)が充分に低く、ガラス転移温度(Tg)が充分に高い(半)硬化物を得ることが可能な新規な架橋剤およびこれを用いた硬化性組成物の提供を目的とする。
本発明の新規な有機ケイ素化合物および新規な架橋剤は、プリプレグ、金属張積層板および配線基板等の用途に用いられる硬化性組成物に用いて好適なものであるが、任意の用途に使用可能なものである。 The present invention has been made in view of the above circumstances, and an object thereof is to provide a novel organosilicon compound suitable for use as a cross-linking agent or the like.
The present invention is also suitable for use in curable compositions having effectively reduced dielectric loss tangent (D f ) at high frequency conditions, sufficiently low coefficient of thermal expansion (CTE) and sufficiently low glass transition temperature (Tg). An object of the present invention is to provide a novel cross-linking agent capable of obtaining a (semi-)cured product with a high curing temperature and a curable composition using the same.
The novel organosilicon compound and novel cross-linking agent of the present invention are suitable for use in curable compositions used in applications such as prepregs, metal-clad laminates and wiring boards, but can be used in any application. It is.
本発明はまた、硬化性組成物に用いて好適で、高周波条件における誘電正接(Df)が効果的に低減され、熱膨張係数(CTE)が充分に低く、ガラス転移温度(Tg)が充分に高い(半)硬化物を得ることが可能な新規な架橋剤およびこれを用いた硬化性組成物の提供を目的とする。
本発明の新規な有機ケイ素化合物および新規な架橋剤は、プリプレグ、金属張積層板および配線基板等の用途に用いられる硬化性組成物に用いて好適なものであるが、任意の用途に使用可能なものである。 The present invention has been made in view of the above circumstances, and an object thereof is to provide a novel organosilicon compound suitable for use as a cross-linking agent or the like.
The present invention is also suitable for use in curable compositions having effectively reduced dielectric loss tangent (D f ) at high frequency conditions, sufficiently low coefficient of thermal expansion (CTE) and sufficiently low glass transition temperature (Tg). An object of the present invention is to provide a novel cross-linking agent capable of obtaining a (semi-)cured product with a high curing temperature and a curable composition using the same.
The novel organosilicon compound and novel cross-linking agent of the present invention are suitable for use in curable compositions used in applications such as prepregs, metal-clad laminates and wiring boards, but can be used in any application. It is.
本発明は、以下の新規な有機ケイ素化合物、新規な架橋剤、硬化性組成物、プリプレグ、積層体、金属張積層板および配線基板を提供する。
The present invention provides the following novel organosilicon compounds, novel cross-linking agents, curable compositions, prepregs, laminates, metal-clad laminates and wiring substrates.
[1] 下式(1m)で表される有機ケイ素化合物。
[2] 下式(1m)で表される架橋剤。
(上式中、Mは、単結合または置換基を有していてもよい炭素数1~20のアルキレン基である。ベンゼン環は置換基を有していてもよい。ベンゼン環上のビニル基の置換位置はメタ位である。nは2~4の整数である。Rは水素原子、水酸基または有機基であり、Rが有機基であるとき、Siと結合した原子はCである。)
[1] An organosilicon compound represented by the following formula (1m).
[2] A cross-linking agent represented by the following formula (1m).
(In the above formula, M is a single bond or an optionally substituted alkylene group having 1 to 20 carbon atoms. The benzene ring may have a substituent. A vinyl group on the benzene ring is the meta position, n is an integer of 2 to 4, R is a hydrogen atom, a hydroxyl group or an organic group, and when R is an organic group, the atom bonded to Si is C.)
[2] 下式(1m)で表される架橋剤。
[2] A cross-linking agent represented by the following formula (1m).
[3] [2]の架橋剤と、当該架橋剤と架橋し得る2つ以上の架橋性官能基を有する硬化性化合物とを含む硬化性組成物。
[4] 繊維基材と、[3]の硬化性組成物の半硬化物または硬化物とを含む、プリプレグ。
[5] 基材と、[3]の硬化性組成物からなる硬化性組成物層とを含む、積層体。
[6] 基材と、[3]の硬化性組成物の半硬化物または硬化物を含む(半)硬化物含有層とを含む、積層体。
[7] 前記基材が樹脂フィルムまたは金属箔である、[5]または[6]の積層体。
[8] [3]の硬化性組成物の硬化物を含む絶縁層と、金属箔とを含む、金属張積層板。
[9] [3]の硬化性組成物の硬化物を含む絶縁層と、配線とを含む、配線基板。 [3] A curable composition comprising the cross-linking agent of [2] and a curable compound having two or more cross-linkable functional groups capable of cross-linking with the cross-linking agent.
[4] A prepreg comprising a fiber base material and a semi-cured or cured product of the curable composition of [3].
[5] A laminate comprising a substrate and a curable composition layer comprising the curable composition of [3].
[6] A laminate comprising a substrate and a semi-cured product of the curable composition of [3] or a (semi-)cured product-containing layer containing the cured product.
[7] The laminate of [5] or [6], wherein the substrate is a resin film or metal foil.
[8] A metal-clad laminate comprising an insulating layer containing a cured product of the curable composition of [3] and a metal foil.
[9] A wiring substrate comprising an insulating layer containing a cured product of the curable composition of [3] and wiring.
[4] 繊維基材と、[3]の硬化性組成物の半硬化物または硬化物とを含む、プリプレグ。
[5] 基材と、[3]の硬化性組成物からなる硬化性組成物層とを含む、積層体。
[6] 基材と、[3]の硬化性組成物の半硬化物または硬化物を含む(半)硬化物含有層とを含む、積層体。
[7] 前記基材が樹脂フィルムまたは金属箔である、[5]または[6]の積層体。
[8] [3]の硬化性組成物の硬化物を含む絶縁層と、金属箔とを含む、金属張積層板。
[9] [3]の硬化性組成物の硬化物を含む絶縁層と、配線とを含む、配線基板。 [3] A curable composition comprising the cross-linking agent of [2] and a curable compound having two or more cross-linkable functional groups capable of cross-linking with the cross-linking agent.
[4] A prepreg comprising a fiber base material and a semi-cured or cured product of the curable composition of [3].
[5] A laminate comprising a substrate and a curable composition layer comprising the curable composition of [3].
[6] A laminate comprising a substrate and a semi-cured product of the curable composition of [3] or a (semi-)cured product-containing layer containing the cured product.
[7] The laminate of [5] or [6], wherein the substrate is a resin film or metal foil.
[8] A metal-clad laminate comprising an insulating layer containing a cured product of the curable composition of [3] and a metal foil.
[9] A wiring substrate comprising an insulating layer containing a cured product of the curable composition of [3] and wiring.
本発明によれば、架橋剤等として用いて好適な新規な有機ケイ素化合物を提供できる。本発明によれば、硬化性組成物に用いて好適で、高周波条件における誘電正接(Df)が効果的に低減され、熱膨張係数(CTE)が充分に低く、ガラス転移温度(Tg)が充分に高い(半)硬化物を得ることが可能な新規な架橋剤およびこれを用いた硬化性組成物を提供できる。
INDUSTRIAL APPLICABILITY According to the present invention, a novel organosilicon compound suitable for use as a cross-linking agent or the like can be provided. According to the present invention, it is suitable for use in a curable composition, the dielectric loss tangent (D f ) under high frequency conditions is effectively reduced, the coefficient of thermal expansion (CTE) is sufficiently low, and the glass transition temperature (Tg) is A novel cross-linking agent capable of obtaining a sufficiently high (semi-) cured product and a curable composition using the same can be provided.
本明細書において、(半)硬化は、半硬化および硬化の総称である。
本明細書において、特に分けて記載しない限り、「配線基板」は、多層配線基板を含むものとする。
本明細書において、「高周波領域」は、周波数1GHz以上の領域と定義する。
本明細書において、特に明記しない限り、「数平均分子量(Mn)」はゲル浸透クロマトグラフィ(GPC)法により求められるポリスチレン換算の数平均分子量である。
本明細書において、特に明記しない限り、数値範囲を示す「~」は、その前後に記載された数値を下限値および上限値として含む意味で使用される。
以下、本発明の実施の形態を説明する。 As used herein, (semi-)curing is a generic term for semi-curing and curing.
In this specification, unless otherwise specified, the term "wiring board" includes a multilayer wiring board.
In this specification, "high frequency region" is defined as a region with a frequency of 1 GHz or higher.
In the present specification, unless otherwise specified, "number average molecular weight (Mn)" is a polystyrene-equivalent number average molecular weight determined by a gel permeation chromatography (GPC) method.
In this specification, unless otherwise specified, the numerical range "to" is used to include the numerical values before and after it as lower and upper limits.
Embodiments of the present invention will be described below.
本明細書において、特に分けて記載しない限り、「配線基板」は、多層配線基板を含むものとする。
本明細書において、「高周波領域」は、周波数1GHz以上の領域と定義する。
本明細書において、特に明記しない限り、「数平均分子量(Mn)」はゲル浸透クロマトグラフィ(GPC)法により求められるポリスチレン換算の数平均分子量である。
本明細書において、特に明記しない限り、数値範囲を示す「~」は、その前後に記載された数値を下限値および上限値として含む意味で使用される。
以下、本発明の実施の形態を説明する。 As used herein, (semi-)curing is a generic term for semi-curing and curing.
In this specification, unless otherwise specified, the term "wiring board" includes a multilayer wiring board.
In this specification, "high frequency region" is defined as a region with a frequency of 1 GHz or higher.
In the present specification, unless otherwise specified, "number average molecular weight (Mn)" is a polystyrene-equivalent number average molecular weight determined by a gel permeation chromatography (GPC) method.
In this specification, unless otherwise specified, the numerical range "to" is used to include the numerical values before and after it as lower and upper limits.
Embodiments of the present invention will be described below.
[新規な有機ケイ素化合物、新規な架橋剤]
本発明の有機ケイ素化合物は、下式(1m)で表される。
本発明の有機ケイ素化合物は、架橋剤等として好適である。
本発明の架橋剤は、下式(1m)で表される。
(上式中、Mは、単結合または置換基を有していてもよい炭素数1~20のアルキレン基である。ベンゼン環は置換基を有していてもよい。ベンゼン環上のビニル基の置換位置はメタ位である。nは2~4の整数である。Rは水素原子、水酸基または有機基であり、Rが有機基であるとき、Siと結合した原子はCである。)
[Novel organosilicon compound, novel cross-linking agent]
The organosilicon compound of the present invention is represented by the following formula (1m).
The organosilicon compound of the present invention is suitable as a cross-linking agent and the like.
The cross-linking agent of the present invention is represented by the following formula (1m).
(In the above formula, M is a single bond or an optionally substituted alkylene group having 1 to 20 carbon atoms. The benzene ring may have a substituent. A vinyl group on the benzene ring is the meta position, n is an integer of 2 to 4, R is a hydrogen atom, a hydroxyl group or an organic group, and when R is an organic group, the atom bonded to Si is C.)
本発明の有機ケイ素化合物は、下式(1m)で表される。
本発明の有機ケイ素化合物は、架橋剤等として好適である。
本発明の架橋剤は、下式(1m)で表される。
The organosilicon compound of the present invention is represented by the following formula (1m).
The organosilicon compound of the present invention is suitable as a cross-linking agent and the like.
The cross-linking agent of the present invention is represented by the following formula (1m).
本発明の有機ケイ素化合物および架橋剤は任意の用途に使用でき、硬化性組成物、プリプレグ、積層体、金属張積層板および配線基板等に好適である。
The organosilicon compound and cross-linking agent of the present invention can be used for any purpose, and are suitable for curable compositions, prepregs, laminates, metal-clad laminates, wiring boards, and the like.
[硬化性組成物]
本発明の硬化性組成物は、本発明の架橋剤と、この架橋剤と架橋し得る2つ以上の架橋性官能基を有する硬化性化合物とを含む。
硬化性組成物は、熱硬化性でも活性エネルギー線硬化性でもよい。活性エネルギー線硬化性組成物は、紫外線および電子線等の活性エネルギー線の照射によって硬化する組成物である。金属張積層板および配線基板等の用途では、熱硬化性が好ましい。 [Curable composition]
The curable composition of the present invention comprises the cross-linking agent of the present invention and a curable compound having two or more cross-linkable functional groups capable of cross-linking with this cross-linking agent.
The curable composition may be thermosetting or active energy ray curable. An active energy ray-curable composition is a composition that is cured by irradiation with active energy rays such as ultraviolet rays and electron beams. Thermosetting is preferred for applications such as metal-clad laminates and wiring boards.
本発明の硬化性組成物は、本発明の架橋剤と、この架橋剤と架橋し得る2つ以上の架橋性官能基を有する硬化性化合物とを含む。
硬化性組成物は、熱硬化性でも活性エネルギー線硬化性でもよい。活性エネルギー線硬化性組成物は、紫外線および電子線等の活性エネルギー線の照射によって硬化する組成物である。金属張積層板および配線基板等の用途では、熱硬化性が好ましい。 [Curable composition]
The curable composition of the present invention comprises the cross-linking agent of the present invention and a curable compound having two or more cross-linkable functional groups capable of cross-linking with this cross-linking agent.
The curable composition may be thermosetting or active energy ray curable. An active energy ray-curable composition is a composition that is cured by irradiation with active energy rays such as ultraviolet rays and electron beams. Thermosetting is preferred for applications such as metal-clad laminates and wiring boards.
硬化性化合物としては、モノマー、オリゴマーおよびプレポリマー等が挙げられる。これらは、1種以上用いることができる。
硬化性化合物の硬化物としては、ポリフェニレンエーテル樹脂(PPE)、ビスマレイミド樹脂、エポキシ樹脂、フッ素樹脂、ポリイミド樹脂、オレフィン系樹脂、ポリエステル樹脂、ポリスチレン樹脂、炭化水素エラストマー、ベンゾオキサジン樹脂、活性エステル樹脂、シアネートエステル樹脂、ブタジエン樹脂、水添または非水添スチレンブタジエン樹脂、ビニル系樹脂、シクロオレフィンポリマー、芳香族重合体、ジビニル芳香族重合体およびこれらの組合せ等が挙げられる。 Curable compounds include monomers, oligomers, prepolymers, and the like. One or more of these can be used.
Cured products of curable compounds include polyphenylene ether resins (PPE), bismaleimide resins, epoxy resins, fluorine resins, polyimide resins, olefin resins, polyester resins, polystyrene resins, hydrocarbon elastomers, benzoxazine resins, and active ester resins. , cyanate ester resins, butadiene resins, hydrogenated or non-hydrogenated styrene-butadiene resins, vinyl resins, cycloolefin polymers, aromatic polymers, divinyl aromatic polymers and combinations thereof.
硬化性化合物の硬化物としては、ポリフェニレンエーテル樹脂(PPE)、ビスマレイミド樹脂、エポキシ樹脂、フッ素樹脂、ポリイミド樹脂、オレフィン系樹脂、ポリエステル樹脂、ポリスチレン樹脂、炭化水素エラストマー、ベンゾオキサジン樹脂、活性エステル樹脂、シアネートエステル樹脂、ブタジエン樹脂、水添または非水添スチレンブタジエン樹脂、ビニル系樹脂、シクロオレフィンポリマー、芳香族重合体、ジビニル芳香族重合体およびこれらの組合せ等が挙げられる。 Curable compounds include monomers, oligomers, prepolymers, and the like. One or more of these can be used.
Cured products of curable compounds include polyphenylene ether resins (PPE), bismaleimide resins, epoxy resins, fluorine resins, polyimide resins, olefin resins, polyester resins, polystyrene resins, hydrocarbon elastomers, benzoxazine resins, and active ester resins. , cyanate ester resins, butadiene resins, hydrogenated or non-hydrogenated styrene-butadiene resins, vinyl resins, cycloolefin polymers, aromatic polymers, divinyl aromatic polymers and combinations thereof.
金属張積層板および配線基板等の用途では、硬化性化合物の硬化物は、ポリフェニレンエーテル樹脂(PPE)を含むことが好ましい。
本明細書において、「ポリフェニレンエーテル樹脂(PPE)」は、特に明記しない限り、非変性ポリフェニレンエーテル樹脂および変性ポリフェニレンエーテル樹脂を含むものとする。 For applications such as metal-clad laminates and wiring boards, the cured product of the curable compound preferably contains polyphenylene ether resin (PPE).
As used herein, "polyphenylene ether resin (PPE)" is intended to include unmodified polyphenylene ether resins and modified polyphenylene ether resins, unless otherwise specified.
本明細書において、「ポリフェニレンエーテル樹脂(PPE)」は、特に明記しない限り、非変性ポリフェニレンエーテル樹脂および変性ポリフェニレンエーテル樹脂を含むものとする。 For applications such as metal-clad laminates and wiring boards, the cured product of the curable compound preferably contains polyphenylene ether resin (PPE).
As used herein, "polyphenylene ether resin (PPE)" is intended to include unmodified polyphenylene ether resins and modified polyphenylene ether resins, unless otherwise specified.
上記用途において、硬化性化合物としては例えば、下式(P)で表されるポリフェニレンエーテルオリゴマーが好ましい。
In the above applications, the curable compound is preferably, for example, a polyphenylene ether oligomer represented by the following formula (P).
式(P)の両端のXはそれぞれ独立に、下式(x1)または下式(x2)で表される基である。これら式中、「*」は酸素原子との結合手を示す。
X at both ends of formula (P) is each independently a group represented by the following formula (x1) or the following formula (x2). In these formulas, "*" indicates a bond with an oxygen atom.
mは、好ましくは1~20、より好ましくは3~15である。
nは、好ましくは1~20、より好ましくは3~15である。 m is preferably 1-20, more preferably 3-15.
n is preferably 1-20, more preferably 3-15.
nは、好ましくは1~20、より好ましくは3~15である。 m is preferably 1-20, more preferably 3-15.
n is preferably 1-20, more preferably 3-15.
硬化性組成物の(半)硬化物は、硬化性化合物と本発明の架橋剤との反応生成物を含む。
The (semi-)cured product of the curable composition contains the reaction product of the curable compound and the cross-linking agent of the present invention.
オリゴマーの数平均分子量(Mn)は特に制限されず、好ましくは1000~5000、より好ましくは1000~4000である。
The number average molecular weight (Mn) of the oligomer is not particularly limited, preferably 1000-5000, more preferably 1000-4000.
硬化性組成物は、1種以上の重合開始剤を含むことが好ましい。重合開始剤としては、有機過酸化物、アゾ系化合物、その他の公知の重合開始剤、およびこれらの組合せを用いることができる。具体例としては、ジクミルパーオキサイド、ベンゾイルパーオキサイド、クメンハイドロパーオキサイド、2,5-ジメチルヘキサン-2,5-ジハイドロパーオキサイド、2,5-ジメチル-2,5-ジ(t-ブチルパーオキシ)ヘキシン-3、ジ-t-ブチルパーオキサイド、t-ブチルクミルパーオキサイド、α,α’-ジ(t-ブチルパーオキシ)ジイソプロピルベンゼン、2,5-ジメチル-2,5-ジ(t-ブチルパーオキシ)ヘキサン、ジ-t-ブチルパーオキシイソフタレート、t-ブチルパーオキシベンゾエート、2,2-ビス(t-ブチルパーオキシ)ブタン、2,2-ビス(t-ブチルパーオキシ)オクタン、2,5-ジメチル-2,5-ジ(ベンゾイルパーオキシ)ヘキサン、ジ(トリメチルシリル)パーオキサイド、トリメチルシリルトリフェニルシリルパーオキサイドおよびアゾビスイソブチロニトリル等が挙げられる。
The curable composition preferably contains one or more polymerization initiators. As the polymerization initiator, organic peroxides, azo compounds, other known polymerization initiators, and combinations thereof can be used. Specific examples include dicumyl peroxide, benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(t-butyl peroxy)hexyne-3, di-t-butyl peroxide, t-butylcumyl peroxide, α,α'-di(t-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di( t-butylperoxy)hexane, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy ) octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, di(trimethylsilyl)peroxide, trimethylsilyltriphenylsilylperoxide and azobisisobutyronitrile.
硬化性組成物は必要に応じて、1種以上の添加剤を含むことができる。添加剤としては、無機充填材(フィラーとも言う。)、相溶化剤および難燃剤等が挙げられる。
無機充填材としては、例えば、球状シリカ等のシリカ、アルミナ、酸化チタンおよびマイカ等の金属酸化物;水酸化アルミニウムおよび水酸化マグネシウム等の金属水酸化物;タルク;ホウ酸アルミニウム;硫酸バリウム;炭酸カルシウム等が挙げられる。これらは、1種以上用いることができる。中でも、低熱膨張性の観点から、シリカ、マイカおよびタルク等が好ましく、球状シリカがより好ましい。
無機充填材は、エポキシシランタイプ、ビニルシランタイプ、メタクリルシランタイプ、またはアミノシランタイプのシランカップリング剤で表面処理されたものでもよい。シランカップリング剤による表面処理のタイミングは、特に制限されない。予め、シランカップリング剤で表面処理された無機充填材を用意してもよいし、硬化性組成物の調製時にインテグラルブレンド法でシランカップリング剤を添加してもよい。 The curable composition may optionally contain one or more additives. Examples of additives include inorganic fillers (also referred to as fillers), compatibilizers and flame retardants.
Examples of inorganic fillers include silica such as spherical silica, alumina, metal oxides such as titanium oxide and mica; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; talc; aluminum borate; barium sulfate; Calcium etc. are mentioned. One or more of these can be used. Among them, silica, mica and talc are preferred, and spherical silica is more preferred, from the viewpoint of low thermal expansion.
The inorganic filler may be surface treated with an epoxysilane-type, vinylsilane-type, methacrylsilane-type, or aminosilane-type silane coupling agent. The timing of surface treatment with a silane coupling agent is not particularly limited. An inorganic filler surface-treated with a silane coupling agent may be prepared in advance, or the silane coupling agent may be added by an integral blend method during preparation of the curable composition.
無機充填材としては、例えば、球状シリカ等のシリカ、アルミナ、酸化チタンおよびマイカ等の金属酸化物;水酸化アルミニウムおよび水酸化マグネシウム等の金属水酸化物;タルク;ホウ酸アルミニウム;硫酸バリウム;炭酸カルシウム等が挙げられる。これらは、1種以上用いることができる。中でも、低熱膨張性の観点から、シリカ、マイカおよびタルク等が好ましく、球状シリカがより好ましい。
無機充填材は、エポキシシランタイプ、ビニルシランタイプ、メタクリルシランタイプ、またはアミノシランタイプのシランカップリング剤で表面処理されたものでもよい。シランカップリング剤による表面処理のタイミングは、特に制限されない。予め、シランカップリング剤で表面処理された無機充填材を用意してもよいし、硬化性組成物の調製時にインテグラルブレンド法でシランカップリング剤を添加してもよい。 The curable composition may optionally contain one or more additives. Examples of additives include inorganic fillers (also referred to as fillers), compatibilizers and flame retardants.
Examples of inorganic fillers include silica such as spherical silica, alumina, metal oxides such as titanium oxide and mica; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; talc; aluminum borate; barium sulfate; Calcium etc. are mentioned. One or more of these can be used. Among them, silica, mica and talc are preferred, and spherical silica is more preferred, from the viewpoint of low thermal expansion.
The inorganic filler may be surface treated with an epoxysilane-type, vinylsilane-type, methacrylsilane-type, or aminosilane-type silane coupling agent. The timing of surface treatment with a silane coupling agent is not particularly limited. An inorganic filler surface-treated with a silane coupling agent may be prepared in advance, or the silane coupling agent may be added by an integral blend method during preparation of the curable composition.
難燃剤としては、例えば、ハロゲン系難燃剤およびリン系難燃剤等が挙げられる。これらは、1種以上用いることができる。ハロゲン系難燃剤としては、例えば、ペンタブロモジフェニルエーテル、オクタブロモジフェニルエーテル、デカブロモジフェニルエーテル、テトラブロモビスフェノールAおよびヘキサブロモシクロドデカン等の臭素系難燃剤;塩素化パラフィン等の塩素系難燃剤等が挙げられる。リン系難燃剤としては、例えば、縮合リン酸エステルおよび環状リン酸エステル等のリン酸エステル;環状ホスファゼン化合物等のホスファゼン化合物;ジアルキルホスフィン酸アルミニウム塩等のホスフィン酸塩系難燃剤;リン酸メラミンおよびポリリン酸メラミン等のメラミン系難燃剤;ジフェニルホスフィンオキサイド基を有するホスフィンオキサイド化合物等が挙げられる。
Examples of flame retardants include halogen-based flame retardants and phosphorus-based flame retardants. One or more of these can be used. Examples of halogen-based flame retardants include brominated flame retardants such as pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A and hexabromocyclododecane; and chlorine-based flame retardants such as chlorinated paraffin. . Examples of phosphorus-based flame retardants include phosphoric acid esters such as condensed phosphoric acid esters and cyclic phosphoric acid esters; phosphazene compounds such as cyclic phosphazene compounds; phosphinate-based flame retardants such as aluminum dialkylphosphinate; melamine-based flame retardants such as melamine polyphosphate; and phosphine oxide compounds having a diphenylphosphine oxide group.
硬化性組成物は必要に応じて、1種以上の有機溶媒を含むことができる。有機溶媒としては特に制限されず、メチルエチルケトン等のケトン類;ジブチルエーテル等のエーテル類;酢酸エチル等のエステル類;ジメチルホルムアミド等のアミド類;ベンゼン、トルエンおよびキシレン等の芳香族炭化水素類;トリクロロエチレン等の塩素化炭化水素等が挙げられる。
The curable composition can contain one or more organic solvents, if necessary. The organic solvent is not particularly limited, and includes ketones such as methyl ethyl ketone; ethers such as dibutyl ether; esters such as ethyl acetate; amides such as dimethylformamide; aromatic hydrocarbons such as benzene, toluene and xylene; and chlorinated hydrocarbons such as
硬化性組成物において、固形分濃度および配合組成は、用途等に応じて設計できる。
プリプレグ等の用途では、固形分濃度は、好ましくは50~90質量%である。 In the curable composition, the solid content concentration and composition can be designed according to the application.
For applications such as prepreg, the solid content concentration is preferably 50 to 90% by mass.
プリプレグ等の用途では、固形分濃度は、好ましくは50~90質量%である。 In the curable composition, the solid content concentration and composition can be designed according to the application.
For applications such as prepreg, the solid content concentration is preferably 50 to 90% by mass.
[プリプレグ]
本発明のプリプレグは、繊維基材と、本発明の硬化性組成物の(半)硬化物とを含む。(半)硬化物は必要に応じて、無機充填材(フィラー)等の添加剤を含むことができる。
プリプレグは、硬化性組成物を繊維基材に含浸させ、熱硬化等により(半)硬化させることで、製造できる。 [Prepreg]
The prepreg of the present invention includes a fiber base material and a (semi-)cured product of the curable composition of the present invention. The (semi-)cured product may contain additives such as an inorganic filler (filler), if necessary.
A prepreg can be produced by impregnating a fiber base material with a curable composition and (semi) curing the composition by heat curing or the like.
本発明のプリプレグは、繊維基材と、本発明の硬化性組成物の(半)硬化物とを含む。(半)硬化物は必要に応じて、無機充填材(フィラー)等の添加剤を含むことができる。
プリプレグは、硬化性組成物を繊維基材に含浸させ、熱硬化等により(半)硬化させることで、製造できる。 [Prepreg]
The prepreg of the present invention includes a fiber base material and a (semi-)cured product of the curable composition of the present invention. The (semi-)cured product may contain additives such as an inorganic filler (filler), if necessary.
A prepreg can be produced by impregnating a fiber base material with a curable composition and (semi) curing the composition by heat curing or the like.
繊維基材の材料としては特に制限されず、ガラス繊維、シリカ繊維および炭素繊維等の無機繊維;アラミド繊維およびポリエステル繊維等の有機繊維;これらの組合せ等が挙げられる。金属張積層板および配線基板等の用途では、ガラス繊維等が好ましい。ガラス繊維基材の形態としては、ガラスクロス、ガラスペーパーおよびガラスマット等が挙げられる。
The material of the fiber base material is not particularly limited, and includes inorganic fibers such as glass fiber, silica fiber and carbon fiber; organic fibers such as aramid fiber and polyester fiber; and combinations thereof. For applications such as metal-clad laminates and wiring boards, glass fiber and the like are preferred. Examples of the form of the glass fiber substrate include glass cloth, glass paper and glass mat.
硬化性組成物の硬化条件は、硬化性組成物の組成に応じて設定でき、半硬化条件(完全硬化しない条件)が好ましい。
上式(P)で表されるポリフェニレンエーテルオリゴマーを含む硬化性組成物を用いる場合、例えば、80~180℃で1~10分間加熱する熱硬化が好ましい。
金属張積層板および配線基板等の用途では、得られるプリプレグ中の樹脂含有量が40~80質量%の範囲内となるように、硬化性組成物の組成および硬化条件を調整することが好ましい。 The curing conditions of the curable composition can be set according to the composition of the curable composition, and semi-curing conditions (conditions under which complete curing is not performed) are preferred.
When using a curable composition containing a polyphenylene ether oligomer represented by the above formula (P), for example, heat curing by heating at 80 to 180° C. for 1 to 10 minutes is preferred.
For applications such as metal-clad laminates and wiring boards, it is preferable to adjust the composition and curing conditions of the curable composition so that the resin content in the resulting prepreg is within the range of 40 to 80% by mass.
上式(P)で表されるポリフェニレンエーテルオリゴマーを含む硬化性組成物を用いる場合、例えば、80~180℃で1~10分間加熱する熱硬化が好ましい。
金属張積層板および配線基板等の用途では、得られるプリプレグ中の樹脂含有量が40~80質量%の範囲内となるように、硬化性組成物の組成および硬化条件を調整することが好ましい。 The curing conditions of the curable composition can be set according to the composition of the curable composition, and semi-curing conditions (conditions under which complete curing is not performed) are preferred.
When using a curable composition containing a polyphenylene ether oligomer represented by the above formula (P), for example, heat curing by heating at 80 to 180° C. for 1 to 10 minutes is preferred.
For applications such as metal-clad laminates and wiring boards, it is preferable to adjust the composition and curing conditions of the curable composition so that the resin content in the resulting prepreg is within the range of 40 to 80% by mass.
[積層体]
本発明の第1の積層体は、基材と、上記の本発明の硬化性組成物からなる硬化性組成物層とを含む。
本発明の第2の積層体は、基材と、上記の本発明の硬化性組成物の(半)硬化物を含む(半)硬化物含有層とを含む。
本発明の第1、第2の積層体において、基材としては特に制限されず、樹脂フィルム、金属箔およびこれらの組合せ等が挙げられる。
樹脂フィルムとしては特に制限されず、公知のものを用いることができる。樹脂フィルムの構成樹脂としては、ポリイミド、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート、シクロオレフィンポリマーおよびポリエーテルサルファイド等が挙げられる。
電気抵抗が低いことから、金属箔としては、銅箔、銀箔、金箔、アルミニウム箔およびこれらの組合せ等が好ましく、銅箔等がより好ましい。 [Laminate]
A first laminate of the present invention includes a substrate and a curable composition layer comprising the curable composition of the present invention.
The second laminate of the present invention includes a base material and a (semi-)cured product-containing layer containing a (semi-)cured product of the curable composition of the present invention.
In the first and second laminates of the present invention, the substrate is not particularly limited, and examples thereof include resin films, metal foils and combinations thereof.
The resin film is not particularly limited, and known films can be used. Constituent resins of the resin film include polyimide, polyethylene terephthalate (PET), polyethylene naphthalate, cycloolefin polymer and polyether sulfide.
As the metal foil, copper foil, silver foil, gold foil, aluminum foil, combinations thereof, and the like are preferable, and copper foil and the like are more preferable, because of their low electrical resistance.
本発明の第1の積層体は、基材と、上記の本発明の硬化性組成物からなる硬化性組成物層とを含む。
本発明の第2の積層体は、基材と、上記の本発明の硬化性組成物の(半)硬化物を含む(半)硬化物含有層とを含む。
本発明の第1、第2の積層体において、基材としては特に制限されず、樹脂フィルム、金属箔およびこれらの組合せ等が挙げられる。
樹脂フィルムとしては特に制限されず、公知のものを用いることができる。樹脂フィルムの構成樹脂としては、ポリイミド、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート、シクロオレフィンポリマーおよびポリエーテルサルファイド等が挙げられる。
電気抵抗が低いことから、金属箔としては、銅箔、銀箔、金箔、アルミニウム箔およびこれらの組合せ等が好ましく、銅箔等がより好ましい。 [Laminate]
A first laminate of the present invention includes a substrate and a curable composition layer comprising the curable composition of the present invention.
The second laminate of the present invention includes a base material and a (semi-)cured product-containing layer containing a (semi-)cured product of the curable composition of the present invention.
In the first and second laminates of the present invention, the substrate is not particularly limited, and examples thereof include resin films, metal foils and combinations thereof.
The resin film is not particularly limited, and known films can be used. Constituent resins of the resin film include polyimide, polyethylene terephthalate (PET), polyethylene naphthalate, cycloolefin polymer and polyether sulfide.
As the metal foil, copper foil, silver foil, gold foil, aluminum foil, combinations thereof, and the like are preferable, and copper foil and the like are more preferable, because of their low electrical resistance.
[金属張積層板]
本発明の金属張積層板は、本発明の硬化性組成物の硬化物を含む絶縁層と、金属箔とを含む。
絶縁層は、繊維基材と本発明の硬化性組成物の硬化物とを含む層であってもよい。
電気抵抗が低いことから、金属箔としては、銅箔、銀箔、金箔、アルミニウム箔およびこれらの組合せ等が好ましく、銅箔等がより好ましい。金属箔は、表面に金属メッキ層を有するものでもよい。金属箔は、極薄金属箔とそれを支持するキャリア金属箔とを含むキャリア付き金属箔であってもよい。金属箔は、少なくとも一方の表面に、防錆処理、シラン処理、粗面化処理およびバリア形成処理等の表面処理が施されたものでもよい。
金属箔の厚みは特に制限されず、配線等の導体パターン(回路パターンとも言う。)の形成に好適であることから、好ましくは0.1~100μm、より好ましくは0.2~50μm、特に好ましくは1.0~40μmである。 [Metal clad laminate]
The metal-clad laminate of the present invention includes an insulating layer containing a cured product of the curable composition of the present invention and a metal foil.
The insulating layer may be a layer containing a fiber base material and a cured product of the curable composition of the present invention.
As the metal foil, copper foil, silver foil, gold foil, aluminum foil, combinations thereof, and the like are preferable, and copper foil and the like are more preferable, because of their low electrical resistance. The metal foil may have a metal plating layer on its surface. The metal foil may be a carrier-attached metal foil that includes an ultra-thin metal foil and a carrier metal foil that supports it. At least one surface of the metal foil may be subjected to surface treatment such as rust prevention treatment, silane treatment, surface roughening treatment and barrier forming treatment.
The thickness of the metal foil is not particularly limited, and is suitable for forming a conductor pattern (also called a circuit pattern) such as wiring. is 1.0 to 40 μm.
本発明の金属張積層板は、本発明の硬化性組成物の硬化物を含む絶縁層と、金属箔とを含む。
絶縁層は、繊維基材と本発明の硬化性組成物の硬化物とを含む層であってもよい。
電気抵抗が低いことから、金属箔としては、銅箔、銀箔、金箔、アルミニウム箔およびこれらの組合せ等が好ましく、銅箔等がより好ましい。金属箔は、表面に金属メッキ層を有するものでもよい。金属箔は、極薄金属箔とそれを支持するキャリア金属箔とを含むキャリア付き金属箔であってもよい。金属箔は、少なくとも一方の表面に、防錆処理、シラン処理、粗面化処理およびバリア形成処理等の表面処理が施されたものでもよい。
金属箔の厚みは特に制限されず、配線等の導体パターン(回路パターンとも言う。)の形成に好適であることから、好ましくは0.1~100μm、より好ましくは0.2~50μm、特に好ましくは1.0~40μmである。 [Metal clad laminate]
The metal-clad laminate of the present invention includes an insulating layer containing a cured product of the curable composition of the present invention and a metal foil.
The insulating layer may be a layer containing a fiber base material and a cured product of the curable composition of the present invention.
As the metal foil, copper foil, silver foil, gold foil, aluminum foil, combinations thereof, and the like are preferable, and copper foil and the like are more preferable, because of their low electrical resistance. The metal foil may have a metal plating layer on its surface. The metal foil may be a carrier-attached metal foil that includes an ultra-thin metal foil and a carrier metal foil that supports it. At least one surface of the metal foil may be subjected to surface treatment such as rust prevention treatment, silane treatment, surface roughening treatment and barrier forming treatment.
The thickness of the metal foil is not particularly limited, and is suitable for forming a conductor pattern (also called a circuit pattern) such as wiring. is 1.0 to 40 μm.
金属張積層板は、片面に金属箔を有する片面金属張積層板であってもよいし、両面に金属箔を有する両面金属張積層板であってもよく、両面金属張積層板であることが好ましい。
片面金属張積層板は、1つ以上の上記のプリプレグと金属箔とを重ね、得られた第1の仮積層体を加熱加圧することで、製造できる。
両面金属張積層板は、1つ以上の上記のプリプレグを一対の金属箔で挟み、得られた第1の仮積層体を加熱加圧することで、製造できる。
金属箔として銅箔を使用した金属張積層板は、銅張積層板(Copper Clad Laminate:CCL)と呼ばれる。 The metal-clad laminate may be a single-sided metal-clad laminate having metal foil on one side, or a double-sided metal-clad laminate having metal foil on both sides, and may be a double-sided metal-clad laminate. preferable.
A single-sided metal-clad laminate can be produced by stacking one or more of the above prepregs and a metal foil, and heating and pressurizing the resulting first temporary laminate.
A double-sided metal-clad laminate can be produced by sandwiching one or more of the above prepregs between a pair of metal foils and heating and pressurizing the obtained first temporary laminate.
A metal clad laminate using copper foil as the metal foil is called a copper clad laminate (CCL).
片面金属張積層板は、1つ以上の上記のプリプレグと金属箔とを重ね、得られた第1の仮積層体を加熱加圧することで、製造できる。
両面金属張積層板は、1つ以上の上記のプリプレグを一対の金属箔で挟み、得られた第1の仮積層体を加熱加圧することで、製造できる。
金属箔として銅箔を使用した金属張積層板は、銅張積層板(Copper Clad Laminate:CCL)と呼ばれる。 The metal-clad laminate may be a single-sided metal-clad laminate having metal foil on one side, or a double-sided metal-clad laminate having metal foil on both sides, and may be a double-sided metal-clad laminate. preferable.
A single-sided metal-clad laminate can be produced by stacking one or more of the above prepregs and a metal foil, and heating and pressurizing the resulting first temporary laminate.
A double-sided metal-clad laminate can be produced by sandwiching one or more of the above prepregs between a pair of metal foils and heating and pressurizing the obtained first temporary laminate.
A metal clad laminate using copper foil as the metal foil is called a copper clad laminate (CCL).
絶縁層は好ましくは、プリプレグの加熱加圧物からなる。プリプレグの加熱加圧物は、繊維基材と樹脂とを含み、必要に応じて無機充填材および難燃剤等の1種以上の添加剤を含むことができる。プリプレグの加熱加圧物は、コンポジット基材とも呼ばれる。
第1の仮積層体の加熱加圧条件は特に制限されず、例えば、温度170~250℃、圧力0.3~30MPa、時間3~240分間が好ましい。 The insulating layer preferably consists of a heat-pressed prepreg. The heat-pressed prepreg contains a fiber base material and a resin, and can optionally contain one or more additives such as inorganic fillers and flame retardants. A heat-pressed prepreg is also called a composite base material.
The heating and pressurizing conditions for the first temporary laminate are not particularly limited, and are preferably, for example, a temperature of 170 to 250° C., a pressure of 0.3 to 30 MPa, and a time of 3 to 240 minutes.
第1の仮積層体の加熱加圧条件は特に制限されず、例えば、温度170~250℃、圧力0.3~30MPa、時間3~240分間が好ましい。 The insulating layer preferably consists of a heat-pressed prepreg. The heat-pressed prepreg contains a fiber base material and a resin, and can optionally contain one or more additives such as inorganic fillers and flame retardants. A heat-pressed prepreg is also called a composite base material.
The heating and pressurizing conditions for the first temporary laminate are not particularly limited, and are preferably, for example, a temperature of 170 to 250° C., a pressure of 0.3 to 30 MPa, and a time of 3 to 240 minutes.
図1および図2に、本発明に係る第1、第2の実施形態の金属張積層板の模式断面図を示す。
図1に示す金属張積層板1は、プリプレグの加熱加圧物からなり、本発明の硬化性組成物の硬化物を含むコンポジット基材(硬化物含有層)11の片面に、金属箔(金属層)12が積層された片面金属張積層板(積層体)である。
図2に示す金属張積層板2は、プリプレグの加熱加圧物からなり、本発明の硬化性組成物の硬化物を含むコンポジット基材(硬化物含有層)11の両面に、金属箔(金属層)12が積層された両面金属張積層板である。 1 and 2 show schematic cross-sectional views of metal-clad laminates of first and second embodiments according to the present invention.
The metal-cladlaminate 1 shown in FIG. It is a single-sided metal-clad laminate (laminate) in which layers) 12 are laminated.
The metal-cladlaminate 2 shown in FIG. 2 is made of a prepreg heated and pressed, and a metal foil (metal Layer) 12 is a double-sided metal-clad laminate laminated.
図1に示す金属張積層板1は、プリプレグの加熱加圧物からなり、本発明の硬化性組成物の硬化物を含むコンポジット基材(硬化物含有層)11の片面に、金属箔(金属層)12が積層された片面金属張積層板(積層体)である。
図2に示す金属張積層板2は、プリプレグの加熱加圧物からなり、本発明の硬化性組成物の硬化物を含むコンポジット基材(硬化物含有層)11の両面に、金属箔(金属層)12が積層された両面金属張積層板である。 1 and 2 show schematic cross-sectional views of metal-clad laminates of first and second embodiments according to the present invention.
The metal-clad
The metal-clad
金属張積層板1、2は、上記以外の層を有していてもよい。
金属張積層板1、2は、コンポジット基材(硬化物含有層)11と金属箔(金属層)12との間に、これらの接着性を高めるために、接着層を有することができる。接着層の材料としては公知のものを用いることができ、エポキシ樹脂、シアネートエステル樹脂、アクリル樹脂、ポリイミド樹脂、マレイミド樹脂、接着性フッ素樹脂およびこれらの組合せ等が挙げられる。市販の接着性フッ素樹脂としては、AGC社製の「Fluon LM‐ETFE LH-8000」、「AH-5000」、「AH-2000」および「EA-2000」等が挙げられる。 The metal-clad laminates 1 and 2 may have layers other than those described above.
The metal-clad laminates 1 and 2 may have an adhesive layer between the composite base material (cured material-containing layer) 11 and the metal foil (metal layer) 12 in order to enhance their adhesion. Known materials can be used for the adhesive layer, and examples thereof include epoxy resins, cyanate ester resins, acrylic resins, polyimide resins, maleimide resins, adhesive fluororesins, and combinations thereof. Commercially available adhesive fluororesins include "Fluon LM-ETFE LH-8000", "AH-5000", "AH-2000" and "EA-2000" manufactured by AGC.
金属張積層板1、2は、コンポジット基材(硬化物含有層)11と金属箔(金属層)12との間に、これらの接着性を高めるために、接着層を有することができる。接着層の材料としては公知のものを用いることができ、エポキシ樹脂、シアネートエステル樹脂、アクリル樹脂、ポリイミド樹脂、マレイミド樹脂、接着性フッ素樹脂およびこれらの組合せ等が挙げられる。市販の接着性フッ素樹脂としては、AGC社製の「Fluon LM‐ETFE LH-8000」、「AH-5000」、「AH-2000」および「EA-2000」等が挙げられる。 The metal-clad
The metal-clad
コンポジット基材の厚みは、用途に応じて適宜設計できる。配線基板の断線予防の観点から、好ましくは50μm以上、より好ましくは70μm以上、特に好ましくは100μm以上である。配線基板の柔軟性、小型化および軽量化の観点から、好ましくは、300μm以下、より好ましくは250μm以下、特に好ましくは200μm以下である。
The thickness of the composite base material can be appropriately designed according to the application. From the viewpoint of preventing disconnection of the wiring board, the thickness is preferably 50 μm or more, more preferably 70 μm or more, and particularly preferably 100 μm or more. From the viewpoint of flexibility, miniaturization and weight reduction of the wiring board, the thickness is preferably 300 μm or less, more preferably 250 μm or less, and particularly preferably 200 μm or less.
[配線基板]
本発明の配線基板は、本発明の硬化性組成物の硬化物を含む絶縁層と、配線とを含む。
配線基板は、上記の本発明の金属張積層板の最表面にある金属箔を用いて配線等の導体パターン(回路パターン)を形成することで、製造できる。配線等の導体パターンを形成する方法としては、金属箔をエッチングして配線等を形成するサブトラクティブ法、および、金属箔の上にメッキで配線を形成するMSAP(Modified Semi Additive Process)法等が挙げられる。 [Wiring board]
The wiring board of the present invention includes an insulating layer containing a cured product of the curable composition of the present invention, and wiring.
The wiring board can be produced by forming a conductor pattern (circuit pattern) such as wiring using the metal foil on the outermost surface of the metal-clad laminate of the present invention. Methods for forming conductor patterns such as wiring include the subtractive method in which wiring is formed by etching metal foil, and the MSAP (Modified Semi-Additive Process) method in which wiring is formed by plating on metal foil. mentioned.
本発明の配線基板は、本発明の硬化性組成物の硬化物を含む絶縁層と、配線とを含む。
配線基板は、上記の本発明の金属張積層板の最表面にある金属箔を用いて配線等の導体パターン(回路パターン)を形成することで、製造できる。配線等の導体パターンを形成する方法としては、金属箔をエッチングして配線等を形成するサブトラクティブ法、および、金属箔の上にメッキで配線を形成するMSAP(Modified Semi Additive Process)法等が挙げられる。 [Wiring board]
The wiring board of the present invention includes an insulating layer containing a cured product of the curable composition of the present invention, and wiring.
The wiring board can be produced by forming a conductor pattern (circuit pattern) such as wiring using the metal foil on the outermost surface of the metal-clad laminate of the present invention. Methods for forming conductor patterns such as wiring include the subtractive method in which wiring is formed by etching metal foil, and the MSAP (Modified Semi-Additive Process) method in which wiring is formed by plating on metal foil. mentioned.
図3に、本発明に係る一実施形態の配線基板の模式断面図を示す。図3に示す配線基板3は、図2に示した第2の実施形態の金属張積層板2の少なくとも一方の最表面にある金属箔12を用いて配線22W等の導体パターン(回路パターン)22を形成したものである。
配線基板3は、プリプレグの加熱加圧物からなり、本発明の硬化性組成物の硬化物を含むコンポジット基材(硬化物含有層、絶縁層)11の少なくとも片面に、配線22W等の導体パターン(回路パターン)22が形成されたものである。 FIG. 3 shows a schematic cross-sectional view of a wiring board according to one embodiment of the present invention. The wiring substrate 3 shown in FIG. 3 is formed by using themetal foil 12 on at least one of the outermost surfaces of the metal-clad laminate 2 of the second embodiment shown in FIG. is formed.
The wiring board 3 is made of a prepreg heated and pressed, and a conductor pattern such as awiring 22W is provided on at least one side of a composite base material (cured product-containing layer, insulating layer) 11 containing a cured product of the curable composition of the present invention. A (circuit pattern) 22 is formed.
配線基板3は、プリプレグの加熱加圧物からなり、本発明の硬化性組成物の硬化物を含むコンポジット基材(硬化物含有層、絶縁層)11の少なくとも片面に、配線22W等の導体パターン(回路パターン)22が形成されたものである。 FIG. 3 shows a schematic cross-sectional view of a wiring board according to one embodiment of the present invention. The wiring substrate 3 shown in FIG. 3 is formed by using the
The wiring board 3 is made of a prepreg heated and pressed, and a conductor pattern such as a
得られた配線基板に対してさらに、1つ以上のプリプレグを重ね、これを一対の金属箔で挟み、得られた第2の仮積層体を加熱加圧し、最表面の金属箔を用いて配線等の導体パターンを形成することで、多層配線基板(多層プリント配線板とも言う。)を製造してもよい。最表面の金属箔は、第2の仮積層体の片面側にのみ配置してもよい。
本発明の配線基板は、高周波領域(周波数10GHz以上の領域)で用いて好適である。 Further, one or more prepregs are superimposed on the obtained wiring board, sandwiched between a pair of metal foils, the obtained second temporary laminate is heated and pressed, and wiring is performed using the outermost metal foil. A multilayer wiring board (also referred to as a multilayer printed wiring board) may be manufactured by forming a conductor pattern such as a multilayer wiring board. The outermost metal foil may be arranged only on one side of the second temporary laminate.
The wiring board of the present invention is suitable for use in a high frequency range (frequency range of 10 GHz or higher).
本発明の配線基板は、高周波領域(周波数10GHz以上の領域)で用いて好適である。 Further, one or more prepregs are superimposed on the obtained wiring board, sandwiched between a pair of metal foils, the obtained second temporary laminate is heated and pressed, and wiring is performed using the outermost metal foil. A multilayer wiring board (also referred to as a multilayer printed wiring board) may be manufactured by forming a conductor pattern such as a multilayer wiring board. The outermost metal foil may be arranged only on one side of the second temporary laminate.
The wiring board of the present invention is suitable for use in a high frequency range (frequency range of 10 GHz or higher).
近年、携帯用電子機器等の用途では、通信の高速化と大容量化が進み、信号の高周波化が進んでいる。この用途に用いられる配線基板には、高周波領域での伝送損失の低減が求められる。このため、上記用途に用いられる配線基板のコンポジット基材に含まれる樹脂には、高周波領域での誘電損失の低減が求められる。一般的に、誘電正接(Df)は周波数に依存し、同じ材料であれば、周波数が高くなる程、誘電正接(Df)が大きくなる傾向がある。コンポジット基材に含まれる樹脂は、高周波条件における誘電正接(Df)が低いことが好ましい。
2. Description of the Related Art In recent years, in applications such as portable electronic devices, the speed and capacity of communication have increased, and the frequency of signals has increased. A wiring board used for this purpose is required to reduce transmission loss in a high frequency region. Therefore, the resin contained in the composite base material of the wiring board used for the above application is required to reduce the dielectric loss in the high frequency region. Generally, the dielectric loss tangent (D f ) depends on the frequency, and if the same material is used, the higher the frequency, the larger the dielectric loss tangent (D f ) tends to be. The resin contained in the composite base material preferably has a low dielectric loss tangent (D f ) under high frequency conditions.
プリプレグまたはコンポジット基材と金属箔との熱膨張係数(CTE)の差が大きいと、プリプレグと金属箔とを含む第1の仮積層体、またはコンポジット基材とプリプレグと金属箔とを含む第2の仮積層体を加熱加圧する際に、金属箔のずれまたは剥離が生じる恐れがある。プリプレグまたはコンポジット基材と金属箔との熱膨張係数(CTE)の差は、小さい方が好ましい。一般的に、樹脂は金属箔より熱膨張係数(CTE)が大きいので、プリプレグおよびコンポジット基材の熱膨張係数(CTE)は小さい方が好ましい。
If the difference in coefficient of thermal expansion (CTE) between the prepreg or composite base material and the metal foil is large, a first temporary laminate including the prepreg and the metal foil or a second temporary laminate including the composite base material, the prepreg and the metal foil will be produced. When the temporary laminate is heated and pressurized, the metal foil may be displaced or peeled off. A smaller difference in coefficient of thermal expansion (CTE) between the prepreg or composite base material and the metal foil is preferred. Since resin generally has a higher coefficient of thermal expansion (CTE) than metal foil, it is preferable that the prepreg and composite base material have a lower coefficient of thermal expansion (CTE).
配線基板は、比較的高温の環境下で使用される場合がある。この場合でも、配線基板の信頼性を確保するために、プリプレグおよびコンポジット基材に含まれる樹脂は、充分な高さのガラス転移温度(Tg)を有することが好ましい。
A wiring board may be used in a relatively high-temperature environment. Even in this case, the resin contained in the prepreg and the composite base material preferably has a sufficiently high glass transition temperature (Tg) in order to ensure the reliability of the wiring board.
本発明の有機ケイ素化合物および架橋剤は、[背景技術]の項で挙げた特許文献1で使用されているシランカップリング剤とは異なり、Siと結合した4つの原子はすべて、非極性原子(具体的には、水素原子または炭素原子)である。
本発明者らが検討したところ、硬化性組成物に本発明の有機ケイ素化合物を添加した場合、この有機ケイ素化合物は、2つ以上の架橋性官能基を有する硬化性化合物を架橋する架橋剤として機能し、かつ、硬化性組成物の(半)硬化物の誘電正接(Df)を効果的に低減できることが分かった。
また、本発明の有機ケイ素化合物を含む硬化性組成物の(半)硬化物は、熱膨張係数(CTE)が充分に低く、ガラス転移温度(Tg)が充分に高いことが分かった。
また、本発明の有機ケイ素化合物を含む硬化性組成物の(半)硬化物は、銅箔等の金属との密着性も実用的に良好であることが分かった。 In the organosilicon compound and cross-linking agent of the present invention, unlike the silane coupling agent used inPatent Document 1 mentioned in the Background Art section, all four atoms bonded to Si are nonpolar atoms ( Specifically, it is a hydrogen atom or a carbon atom).
As a result of studies by the present inventors, when the organosilicon compound of the present invention is added to a curable composition, the organosilicon compound acts as a cross-linking agent that cross-links the curable compound having two or more cross-linkable functional groups. It was found that the dielectric loss tangent (D f ) of the (semi-)cured product of the curable composition can be effectively reduced.
It was also found that the (semi-)cured product of the curable composition containing the organosilicon compound of the present invention has a sufficiently low coefficient of thermal expansion (CTE) and a sufficiently high glass transition temperature (Tg).
It was also found that the (semi-)cured product of the curable composition containing the organosilicon compound of the present invention has practically good adhesion to metals such as copper foil.
本発明者らが検討したところ、硬化性組成物に本発明の有機ケイ素化合物を添加した場合、この有機ケイ素化合物は、2つ以上の架橋性官能基を有する硬化性化合物を架橋する架橋剤として機能し、かつ、硬化性組成物の(半)硬化物の誘電正接(Df)を効果的に低減できることが分かった。
また、本発明の有機ケイ素化合物を含む硬化性組成物の(半)硬化物は、熱膨張係数(CTE)が充分に低く、ガラス転移温度(Tg)が充分に高いことが分かった。
また、本発明の有機ケイ素化合物を含む硬化性組成物の(半)硬化物は、銅箔等の金属との密着性も実用的に良好であることが分かった。 In the organosilicon compound and cross-linking agent of the present invention, unlike the silane coupling agent used in
As a result of studies by the present inventors, when the organosilicon compound of the present invention is added to a curable composition, the organosilicon compound acts as a cross-linking agent that cross-links the curable compound having two or more cross-linkable functional groups. It was found that the dielectric loss tangent (D f ) of the (semi-)cured product of the curable composition can be effectively reduced.
It was also found that the (semi-)cured product of the curable composition containing the organosilicon compound of the present invention has a sufficiently low coefficient of thermal expansion (CTE) and a sufficiently high glass transition temperature (Tg).
It was also found that the (semi-)cured product of the curable composition containing the organosilicon compound of the present invention has practically good adhesion to metals such as copper foil.
硬化性組成物に、架橋剤として本発明の有機ケイ素化合物を添加することで、高周波条件における誘電正接(Df)が効果的に低減され、熱膨張係数(CTE)が充分に低く、ガラス転移温度(Tg)が充分に高い(半)硬化物を得ることができる。この(半)硬化物は、高周波領域で用いられる配線基板用として好適なコンポジット基材および絶縁層等に好適である。
By adding the organosilicon compound of the present invention as a cross-linking agent to the curable composition, the dielectric loss tangent (D f ) under high frequency conditions is effectively reduced, the coefficient of thermal expansion (CTE) is sufficiently low, and the glass transition A (semi-)cured product having a sufficiently high temperature (Tg) can be obtained. This (semi-)cured product is suitable for a composite base material, an insulating layer, and the like suitable for a wiring substrate used in a high frequency region.
本発明の硬化性組成物の(半)硬化物およびこれを含むコンポジット基材の高周波条件における誘電正接(Df)は、例えば、以下のような範囲内であることが好ましい。
周波数10GHzにおける誘電正接(Df)は小さい方が好ましく、好ましくは0.01以下、より好ましくは0.005以下、特に好ましくは0.003以下である。下限値は特に制限されず、例えば0.0001である。 The (semi-)cured product of the curable composition of the present invention and the composite substrate containing the same preferably have a dielectric loss tangent (D f ) under high-frequency conditions, for example, within the following range.
A smaller dielectric loss tangent (D f ) at a frequency of 10 GHz is preferable, and is preferably 0.01 or less, more preferably 0.005 or less, and particularly preferably 0.003 or less. The lower limit is not particularly limited, and is, for example, 0.0001.
周波数10GHzにおける誘電正接(Df)は小さい方が好ましく、好ましくは0.01以下、より好ましくは0.005以下、特に好ましくは0.003以下である。下限値は特に制限されず、例えば0.0001である。 The (semi-)cured product of the curable composition of the present invention and the composite substrate containing the same preferably have a dielectric loss tangent (D f ) under high-frequency conditions, for example, within the following range.
A smaller dielectric loss tangent (D f ) at a frequency of 10 GHz is preferable, and is preferably 0.01 or less, more preferably 0.005 or less, and particularly preferably 0.003 or less. The lower limit is not particularly limited, and is, for example, 0.0001.
本発明の硬化性組成物の(半)硬化物およびこれを含むコンポジット基材の熱膨張係数(CTE)は、例えば、以下のような範囲内であることが好ましい。
熱膨張係数(CTE)は小さい方が好ましく、好ましくは70ppm/℃以下、より好ましくは50ppm/℃以下、特に好ましくは40ppm/℃以下である。下限値は特に制限されず、例えば1ppm/℃である。 The coefficient of thermal expansion (CTE) of the (semi-)cured product of the curable composition of the present invention and the composite substrate containing the same is preferably within the following range, for example.
The coefficient of thermal expansion (CTE) is preferably as small as possible, preferably 70 ppm/°C or less, more preferably 50 ppm/°C or less, and particularly preferably 40 ppm/°C or less. The lower limit is not particularly limited, and is, for example, 1 ppm/°C.
熱膨張係数(CTE)は小さい方が好ましく、好ましくは70ppm/℃以下、より好ましくは50ppm/℃以下、特に好ましくは40ppm/℃以下である。下限値は特に制限されず、例えば1ppm/℃である。 The coefficient of thermal expansion (CTE) of the (semi-)cured product of the curable composition of the present invention and the composite substrate containing the same is preferably within the following range, for example.
The coefficient of thermal expansion (CTE) is preferably as small as possible, preferably 70 ppm/°C or less, more preferably 50 ppm/°C or less, and particularly preferably 40 ppm/°C or less. The lower limit is not particularly limited, and is, for example, 1 ppm/°C.
本発明の硬化性組成物の(半)硬化物のガラス転移温度(Tg)は、好ましくは150℃以上、より好ましくは180℃以上、特に好ましくは200℃以上である。上限値は特に制限されず、例えば300℃である。
The glass transition temperature (Tg) of the (semi-)cured product of the curable composition of the present invention is preferably 150°C or higher, more preferably 180°C or higher, and particularly preferably 200°C or higher. The upper limit is not particularly limited, and is 300° C., for example.
誘電正接(Df)、熱膨張係数(CTE)およびガラス転移温度(Tg)は、後記[実施例]の項に記載の方法にて測定することができる。
The dielectric loss tangent (D f ), coefficient of thermal expansion (CTE) and glass transition temperature (Tg) can be measured by the methods described in the section [Examples] below.
式(1m)で表される本発明の有機ケイ素化合物において、ベンゼン環は置換基を有していてもよい。ベンゼン環が有していてもよい置換基としては例えば、炭素数1~18のアルキル基およびアリール基が挙げられ、原料入手性の観点から、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、オクチル基、フェニル基およびトリル基が好ましい。ベンゼン環は、置換基を有さないことが好ましい。
In the organosilicon compound of the present invention represented by formula (1m), the benzene ring may have a substituent. Examples of substituents that the benzene ring may have include alkyl groups and aryl groups having 1 to 18 carbon atoms, and from the viewpoint of raw material availability, methyl group, ethyl group, propyl group, butyl group, hexyl , octyl, phenyl and tolyl groups are preferred. The benzene ring preferably has no substituents.
式(1m)で表される本発明の有機ケイ素化合物において、ベンゼン環上のビニル基の置換位置としては、オルト位、メタ位およびパラ位があり得る。本発明では、ベンゼン環上のビニル基の置換位置は、メタ位である。
上記置換位置がオルト位の場合、有機ケイ素化合物に置換したビニル基と硬化性化合物の架橋反応点との立体障害により、メタ位に比較して、架橋反応が相対的に進みにくい可能性がある。そのため、硬化性組成物の(半)硬化物の熱膨張係数(CTE)およびガラス転移温度(Tg)等の物性が相対的に低下する可能性がある。また、メタ位に比較して、立体障害が大きくなるため、有機ケイ素化合物の合成が難しい可能性がある。
上記置換位置がパラ位の場合、メタ位と異なり、特に高周波条件で、ケイ素原子と架橋点とを結ぶ軸に対してベンゼン環の回転が起こりやすく、誘電正接(Df)の低減効果が薄れる可能性がある。
上記置換位置がメタ位である場合、高周波条件においてもベンゼン環の回転が起こりにくく、硬化性組成物の(半)硬化物の高周波条件での誘電正接(Df)をより効果的に低減できる。上記置換位置がメタ位である有機ケイ素化合物は、原料が入手しやすく、合成もしやすい。有機ケイ素化合物の中心ケイ素原子とビニル基との位置が近すぎないため、ビニル基と硬化性化合物の架橋反応点との立体障害の影響が小さく、硬化性組成物の架橋反応も進みやすい。硬化性組成物の(半)硬化物は、熱膨張係数(CTE)およびガラス転移温度(Tg)も良好である。
なお、上記置換位置がメタ位である場合に、硬化性組成物の(半)硬化物の高周波条件での誘電正接(Df)をより効果的に低減できる理由は、必ずしも明らかではなく、上記説明は本発明者らの推測を含む。 In the organosilicon compound of the present invention represented by formula (1m), the substitution position of the vinyl group on the benzene ring may be ortho, meta or para positions. In the present invention, the substitution position of the vinyl group on the benzene ring is the meta position.
When the substitution position is the ortho position, steric hindrance between the vinyl group substituted on the organosilicon compound and the crosslinking reaction point of the curable compound may make it relatively difficult for the crosslinking reaction to progress compared to the meta position. . Therefore, physical properties such as the coefficient of thermal expansion (CTE) and the glass transition temperature (Tg) of the (semi-)cured product of the curable composition may relatively decrease. In addition, steric hindrance is greater than at the meta position, which may make it difficult to synthesize an organosilicon compound.
When the above substitution position is the para position, unlike the meta position, the benzene ring tends to rotate about the axis connecting the silicon atom and the cross-linking point, especially under high frequency conditions, and the effect of reducing the dielectric loss tangent (D f ) is diminished. there is a possibility.
When the substitution position is the meta position, rotation of the benzene ring is unlikely to occur even under high frequency conditions, and the dielectric loss tangent (D f ) of the (semi) cured product of the curable composition under high frequency conditions can be more effectively reduced. . The organosilicon compound in which the substitution position is the meta position is easy to obtain raw materials and easy to synthesize. Since the positions of the central silicon atom of the organosilicon compound and the vinyl group are not too close, the effect of steric hindrance between the vinyl group and the cross-linking reaction point of the curable compound is small, and the cross-linking reaction of the curable composition proceeds easily. The (semi-)cured product of the curable composition also has a good coefficient of thermal expansion (CTE) and glass transition temperature (Tg).
The reason why the dielectric loss tangent (D f ) under high frequency conditions of the (semi-)cured product of the curable composition can be more effectively reduced when the substitution position is the meta position is not necessarily clear. The description includes speculations of the inventors.
上記置換位置がオルト位の場合、有機ケイ素化合物に置換したビニル基と硬化性化合物の架橋反応点との立体障害により、メタ位に比較して、架橋反応が相対的に進みにくい可能性がある。そのため、硬化性組成物の(半)硬化物の熱膨張係数(CTE)およびガラス転移温度(Tg)等の物性が相対的に低下する可能性がある。また、メタ位に比較して、立体障害が大きくなるため、有機ケイ素化合物の合成が難しい可能性がある。
上記置換位置がパラ位の場合、メタ位と異なり、特に高周波条件で、ケイ素原子と架橋点とを結ぶ軸に対してベンゼン環の回転が起こりやすく、誘電正接(Df)の低減効果が薄れる可能性がある。
上記置換位置がメタ位である場合、高周波条件においてもベンゼン環の回転が起こりにくく、硬化性組成物の(半)硬化物の高周波条件での誘電正接(Df)をより効果的に低減できる。上記置換位置がメタ位である有機ケイ素化合物は、原料が入手しやすく、合成もしやすい。有機ケイ素化合物の中心ケイ素原子とビニル基との位置が近すぎないため、ビニル基と硬化性化合物の架橋反応点との立体障害の影響が小さく、硬化性組成物の架橋反応も進みやすい。硬化性組成物の(半)硬化物は、熱膨張係数(CTE)およびガラス転移温度(Tg)も良好である。
なお、上記置換位置がメタ位である場合に、硬化性組成物の(半)硬化物の高周波条件での誘電正接(Df)をより効果的に低減できる理由は、必ずしも明らかではなく、上記説明は本発明者らの推測を含む。 In the organosilicon compound of the present invention represented by formula (1m), the substitution position of the vinyl group on the benzene ring may be ortho, meta or para positions. In the present invention, the substitution position of the vinyl group on the benzene ring is the meta position.
When the substitution position is the ortho position, steric hindrance between the vinyl group substituted on the organosilicon compound and the crosslinking reaction point of the curable compound may make it relatively difficult for the crosslinking reaction to progress compared to the meta position. . Therefore, physical properties such as the coefficient of thermal expansion (CTE) and the glass transition temperature (Tg) of the (semi-)cured product of the curable composition may relatively decrease. In addition, steric hindrance is greater than at the meta position, which may make it difficult to synthesize an organosilicon compound.
When the above substitution position is the para position, unlike the meta position, the benzene ring tends to rotate about the axis connecting the silicon atom and the cross-linking point, especially under high frequency conditions, and the effect of reducing the dielectric loss tangent (D f ) is diminished. there is a possibility.
When the substitution position is the meta position, rotation of the benzene ring is unlikely to occur even under high frequency conditions, and the dielectric loss tangent (D f ) of the (semi) cured product of the curable composition under high frequency conditions can be more effectively reduced. . The organosilicon compound in which the substitution position is the meta position is easy to obtain raw materials and easy to synthesize. Since the positions of the central silicon atom of the organosilicon compound and the vinyl group are not too close, the effect of steric hindrance between the vinyl group and the cross-linking reaction point of the curable compound is small, and the cross-linking reaction of the curable composition proceeds easily. The (semi-)cured product of the curable composition also has a good coefficient of thermal expansion (CTE) and glass transition temperature (Tg).
The reason why the dielectric loss tangent (D f ) under high frequency conditions of the (semi-)cured product of the curable composition can be more effectively reduced when the substitution position is the meta position is not necessarily clear. The description includes speculations of the inventors.
式(1m)で表される本発明の有機ケイ素化合物において、反応性官能基の数(単に、官能基数とも言う。)nは、2~4である。
官能基数nは、2であることができる。
官能基数nは、3または4であることができる。 In the organosilicon compound of the present invention represented by formula (1m), the number of reactive functional groups (also referred to simply as the number of functional groups) n is 2-4.
The functional group number n can be two.
The functionality n can be 3 or 4.
官能基数nは、2であることができる。
官能基数nは、3または4であることができる。 In the organosilicon compound of the present invention represented by formula (1m), the number of reactive functional groups (also referred to simply as the number of functional groups) n is 2-4.
The functional group number n can be two.
The functionality n can be 3 or 4.
式(1m)で表される本発明の有機ケイ素化合物において、Rは水素原子、水酸基または有機基であり、好ましくは置換基を有していてもよい炭素数1~18のアルキル基である。硬化性組成物の(半)硬化物の高周波条件での誘電正接(Df)をより効果的に低減できることから、Rは、酸素原子(O)等の極性原子を含まないことが好ましい。Rは、置換基を有さない炭素数1~18のアルキル基であることが好ましい。より好ましくは炭素数1~18の直鎖のアルキル基である。
Rは、炭素数が多い方が、架橋構造の極性が低下し、硬化性組成物の(半)硬化物の高周波条件での誘電正接(Df)をより効果的に低減でき、好ましい。合成容易性の観点から、炭素数の上限は、18である。硬化性組成物の(半)硬化物の高周波条件での誘電正接(Df)の低減効果および合成容易性の観点から、Rの炭素数は、より好ましくは3~18、特に好ましくは8~18である。 In the organosilicon compound of the present invention represented by formula (1m), R is a hydrogen atom, a hydroxyl group or an organic group, preferably an optionally substituted alkyl group having 1 to 18 carbon atoms. R preferably does not contain a polar atom such as an oxygen atom (O), since the dielectric loss tangent (D f ) of the (semi-)cured product of the curable composition can be more effectively reduced under high frequency conditions. R is preferably an unsubstituted alkyl group having 1 to 18 carbon atoms. More preferably, it is a straight-chain alkyl group having 1 to 18 carbon atoms.
R preferably has a large number of carbon atoms because the polarity of the crosslinked structure is lowered, and the dielectric loss tangent (D f ) of the (semi-)cured product of the curable composition under high frequency conditions can be reduced more effectively. From the viewpoint of ease of synthesis, the upper limit of carbon number is 18. From the viewpoint of the effect of reducing the dielectric loss tangent (D f ) of the (semi-)cured product of the curable composition under high frequency conditions and the ease of synthesis, the number of carbon atoms in R is more preferably 3 to 18, particularly preferably 8 to 8. is 18.
Rは、炭素数が多い方が、架橋構造の極性が低下し、硬化性組成物の(半)硬化物の高周波条件での誘電正接(Df)をより効果的に低減でき、好ましい。合成容易性の観点から、炭素数の上限は、18である。硬化性組成物の(半)硬化物の高周波条件での誘電正接(Df)の低減効果および合成容易性の観点から、Rの炭素数は、より好ましくは3~18、特に好ましくは8~18である。 In the organosilicon compound of the present invention represented by formula (1m), R is a hydrogen atom, a hydroxyl group or an organic group, preferably an optionally substituted alkyl group having 1 to 18 carbon atoms. R preferably does not contain a polar atom such as an oxygen atom (O), since the dielectric loss tangent (D f ) of the (semi-)cured product of the curable composition can be more effectively reduced under high frequency conditions. R is preferably an unsubstituted alkyl group having 1 to 18 carbon atoms. More preferably, it is a straight-chain alkyl group having 1 to 18 carbon atoms.
R preferably has a large number of carbon atoms because the polarity of the crosslinked structure is lowered, and the dielectric loss tangent (D f ) of the (semi-)cured product of the curable composition under high frequency conditions can be reduced more effectively. From the viewpoint of ease of synthesis, the upper limit of carbon number is 18. From the viewpoint of the effect of reducing the dielectric loss tangent (D f ) of the (semi-)cured product of the curable composition under high frequency conditions and the ease of synthesis, the number of carbon atoms in R is more preferably 3 to 18, particularly preferably 8 to 8. is 18.
式(1m)で表される本発明の有機ケイ素化合物において、Mは、単結合または置換基を有していてもよい炭素数1~20のアルキレン基である。合成容易性の観点から、炭素数の上限は、20である。有機ケイ素化合物の合成容易性の観点から、Mは、好ましくは単結合または炭素数1~4のアルキレン基であり、より好ましくは単結合またはメチレン基である。
In the organosilicon compound of the present invention represented by formula (1m), M is a single bond or an optionally substituted alkylene group having 1 to 20 carbon atoms. The upper limit of the number of carbon atoms is 20 from the viewpoint of ease of synthesis. From the viewpoint of ease of synthesizing the organosilicon compound, M is preferably a single bond or an alkylene group having 1 to 4 carbon atoms, more preferably a single bond or a methylene group.
式(1m)で表される本発明の有機ケイ素化合物は、公知の合成法により、合成することができる。具体的な合成例については、[実施例]の項を参照されたい。
The organosilicon compound of the present invention represented by formula (1m) can be synthesized by a known synthesis method. For specific synthesis examples, see the section "Examples".
以上説明したように、本発明によれば、架橋剤等として用いて好適な新規な有機ケイ素化合物を提供できる。本発明によれば、硬化性組成物に用いて好適で、高周波条件における誘電正接(Df)が効果的に低減され、熱膨張係数(CTE)が充分に低く、ガラス転移温度(Tg)が充分に高い(半)硬化物を得ることが可能な新規な架橋剤およびこれを用いた硬化性組成物を提供できる。
本発明の新規な有機ケイ素化合物および新規な架橋剤は、プリプレグ、金属張積層板および配線基板等の用途に用いられる硬化性組成物に用いて好適なものであるが、任意の用途に使用可能なものである。 As explained above, according to the present invention, it is possible to provide a novel organosilicon compound suitable for use as a cross-linking agent or the like. According to the present invention, it is suitable for use in a curable composition, the dielectric loss tangent (D f ) under high frequency conditions is effectively reduced, the coefficient of thermal expansion (CTE) is sufficiently low, and the glass transition temperature (Tg) is A novel cross-linking agent capable of obtaining a sufficiently high (semi-) cured product and a curable composition using the same can be provided.
The novel organosilicon compound and novel cross-linking agent of the present invention are suitable for use in curable compositions used in applications such as prepregs, metal-clad laminates and wiring boards, but can be used in any application. It is.
本発明の新規な有機ケイ素化合物および新規な架橋剤は、プリプレグ、金属張積層板および配線基板等の用途に用いられる硬化性組成物に用いて好適なものであるが、任意の用途に使用可能なものである。 As explained above, according to the present invention, it is possible to provide a novel organosilicon compound suitable for use as a cross-linking agent or the like. According to the present invention, it is suitable for use in a curable composition, the dielectric loss tangent (D f ) under high frequency conditions is effectively reduced, the coefficient of thermal expansion (CTE) is sufficiently low, and the glass transition temperature (Tg) is A novel cross-linking agent capable of obtaining a sufficiently high (semi-) cured product and a curable composition using the same can be provided.
The novel organosilicon compound and novel cross-linking agent of the present invention are suitable for use in curable compositions used in applications such as prepregs, metal-clad laminates and wiring boards, but can be used in any application. It is.
[用途]
本発明の新規な有機ケイ素化合物は、架橋剤等として好適である。
本発明の架橋剤は、モノマー、オリゴマーおよびプレポリマー等の硬化性化合物を含む硬化性組成物に好適である。
本発明の新規な有機ケイ素化合物および新規な架橋剤は、プリプレグ、金属張積層板および配線基板等の用途に用いられる硬化性組成物に好適である。
本発明の架橋剤を含む硬化性組成物は、プリプレグ、金属張積層板および配線基板等の用途に用いられる硬化性組成物に好適である。
本発明の金属張積層板は、各種電気機器および各種電子機器等に使用される配線基板等に好適である。
本発明の配線基板は、携帯電話、スマートフォン、携帯情報端末およびノートパソコン等の携帯用電子機器;携帯電話基地局および自動車等のアンテナ;サーバー、ルーターおよびバックプレーン等の電子機器;無線インフラ;衝突防止用等のレーダー;各種センサ(例えば、エンジンマネージメントセンサ等の自動車用センサ)等に好適である。
本発明の配線基板は特に、高周波信号を用いて通信を行う用途に好適であり、高周波領域において伝送損失の低減が求められる様々な用途に好適である。 [Use]
The novel organosilicon compound of the present invention is suitable as a cross-linking agent and the like.
The crosslinkers of the present invention are suitable for curable compositions containing curable compounds such as monomers, oligomers and prepolymers.
The novel organosilicon compound and novel cross-linking agent of the present invention are suitable for curable compositions used in applications such as prepregs, metal-clad laminates and wiring boards.
The curable composition containing the cross-linking agent of the present invention is suitable for use in applications such as prepregs, metal-clad laminates and wiring boards.
INDUSTRIAL APPLICABILITY The metal-clad laminate of the present invention is suitable for wiring substrates and the like used in various electric devices and various electronic devices.
The wiring board of the present invention is suitable for use in portable electronic devices such as mobile phones, smart phones, personal digital assistants and notebook computers; antennas for mobile phone base stations and automobiles; electronic devices such as servers, routers and backplanes; Radar for prevention, various sensors (for example, automotive sensors such as engine management sensors), and the like.
The wiring board of the present invention is particularly suitable for communication using high-frequency signals, and is suitable for various applications requiring reduction of transmission loss in a high-frequency region.
本発明の新規な有機ケイ素化合物は、架橋剤等として好適である。
本発明の架橋剤は、モノマー、オリゴマーおよびプレポリマー等の硬化性化合物を含む硬化性組成物に好適である。
本発明の新規な有機ケイ素化合物および新規な架橋剤は、プリプレグ、金属張積層板および配線基板等の用途に用いられる硬化性組成物に好適である。
本発明の架橋剤を含む硬化性組成物は、プリプレグ、金属張積層板および配線基板等の用途に用いられる硬化性組成物に好適である。
本発明の金属張積層板は、各種電気機器および各種電子機器等に使用される配線基板等に好適である。
本発明の配線基板は、携帯電話、スマートフォン、携帯情報端末およびノートパソコン等の携帯用電子機器;携帯電話基地局および自動車等のアンテナ;サーバー、ルーターおよびバックプレーン等の電子機器;無線インフラ;衝突防止用等のレーダー;各種センサ(例えば、エンジンマネージメントセンサ等の自動車用センサ)等に好適である。
本発明の配線基板は特に、高周波信号を用いて通信を行う用途に好適であり、高周波領域において伝送損失の低減が求められる様々な用途に好適である。 [Use]
The novel organosilicon compound of the present invention is suitable as a cross-linking agent and the like.
The crosslinkers of the present invention are suitable for curable compositions containing curable compounds such as monomers, oligomers and prepolymers.
The novel organosilicon compound and novel cross-linking agent of the present invention are suitable for curable compositions used in applications such as prepregs, metal-clad laminates and wiring boards.
The curable composition containing the cross-linking agent of the present invention is suitable for use in applications such as prepregs, metal-clad laminates and wiring boards.
INDUSTRIAL APPLICABILITY The metal-clad laminate of the present invention is suitable for wiring substrates and the like used in various electric devices and various electronic devices.
The wiring board of the present invention is suitable for use in portable electronic devices such as mobile phones, smart phones, personal digital assistants and notebook computers; antennas for mobile phone base stations and automobiles; electronic devices such as servers, routers and backplanes; Radar for prevention, various sensors (for example, automotive sensors such as engine management sensors), and the like.
The wiring board of the present invention is particularly suitable for communication using high-frequency signals, and is suitable for various applications requiring reduction of transmission loss in a high-frequency region.
以下に実施例を挙げて本発明を具体的に説明するが、本発明はこれらに限定されない。例1~3、101が実施例であり、例21、22、31、32が比較例である。特に明記しない限り、室温は25℃程度である。
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these. Examples 1 to 3 and 101 are working examples, and examples 21, 22, 31 and 32 are comparative examples. Unless otherwise specified, room temperature is around 25°C.
[市販試薬]
[実施例]の項において、触媒および試薬は、特に明記しない限り、市販品をそのまま反応に用いた。溶媒は、脱水および脱酸素された市販品を用いた。 [Commercial reagent]
Unless otherwise specified, commercially available catalysts and reagents were used as they were in the [Examples] section. Dehydrated and deoxygenated commercial products were used as solvents.
[実施例]の項において、触媒および試薬は、特に明記しない限り、市販品をそのまま反応に用いた。溶媒は、脱水および脱酸素された市販品を用いた。 [Commercial reagent]
Unless otherwise specified, commercially available catalysts and reagents were used as they were in the [Examples] section. Dehydrated and deoxygenated commercial products were used as solvents.
[有機ケイ素化合物の評価項目と評価方法]
(構造)
合成した有機ケイ素化合物の構造は、核磁気共鳴装置(日本電子株式会社製「JNM-AL300」)を用い、1H-NMR測定を行うことで同定した。 [Evaluation items and evaluation methods of organosilicon compounds]
(structure)
The structure of the synthesized organosilicon compound was identified by 1 H-NMR measurement using a nuclear magnetic resonance apparatus (“JNM-AL300” manufactured by JEOL Ltd.).
(構造)
合成した有機ケイ素化合物の構造は、核磁気共鳴装置(日本電子株式会社製「JNM-AL300」)を用い、1H-NMR測定を行うことで同定した。 [Evaluation items and evaluation methods of organosilicon compounds]
(structure)
The structure of the synthesized organosilicon compound was identified by 1 H-NMR measurement using a nuclear magnetic resonance apparatus (“JNM-AL300” manufactured by JEOL Ltd.).
(分子量)
合成した有機ケイ素化合物の分子量は、ガスクロマトグラフ質量分析計(GC-HRMS)(Agilent社製「7890A/JEOL社JMS-T200 AccuTOF GCx-plus」)を用いて、電子衝撃法(EI)により求めた。 (molecular weight)
The molecular weight of the synthesized organosilicon compound was determined by the electron impact method (EI) using a gas chromatograph mass spectrometer (GC-HRMS) (Agilent "7890A/JEOL JMS-T200 AccuTOF GCx-plus"). .
合成した有機ケイ素化合物の分子量は、ガスクロマトグラフ質量分析計(GC-HRMS)(Agilent社製「7890A/JEOL社JMS-T200 AccuTOF GCx-plus」)を用いて、電子衝撃法(EI)により求めた。 (molecular weight)
The molecular weight of the synthesized organosilicon compound was determined by the electron impact method (EI) using a gas chromatograph mass spectrometer (GC-HRMS) (Agilent "7890A/JEOL JMS-T200 AccuTOF GCx-plus"). .
[評価用サンプル(フィルム状硬化物)の作製方法]
硬化性化合物として、以下の2種類のポリフェニレンエーテルオリゴマーを用意した。
(SA9000
)2官能メタクリル変性PPE(SABIC社製「SA9000」)、
(OPE-2st)2官能クロロメチルスチレン変性PPE(三菱ガス化学社製「OPE-2st」)。 [Method for preparing evaluation sample (film-like cured product)]
As curable compounds, the following two types of polyphenylene ether oligomers were prepared.
(SA9000
) Bifunctional methacrylic-modified PPE ("SA9000" manufactured by SABIC),
(OPE-2st) Bifunctional chloromethylstyrene-modified PPE ("OPE-2st" manufactured by Mitsubishi Gas Chemical Company).
硬化性化合物として、以下の2種類のポリフェニレンエーテルオリゴマーを用意した。
(SA9000
)2官能メタクリル変性PPE(SABIC社製「SA9000」)、
(OPE-2st)2官能クロロメチルスチレン変性PPE(三菱ガス化学社製「OPE-2st」)。 [Method for preparing evaluation sample (film-like cured product)]
As curable compounds, the following two types of polyphenylene ether oligomers were prepared.
(SA9000
) Bifunctional methacrylic-modified PPE ("SA9000" manufactured by SABIC),
(OPE-2st) Bifunctional chloromethylstyrene-modified PPE ("OPE-2st" manufactured by Mitsubishi Gas Chemical Company).
上記の2官能メタクリル変性PPE(SA9000)または2官能クロロメチルスチレン変性PPE(OPE-2st)と、各例で合成または用意した有機ケイ素化合物と、ラジカル重合開始剤としてのジクミルパーオキサイドと、トルエンとを、質量比7:3:0.1:7で混合し、室温で攪拌して、トルエン溶液(硬化性組成物)を調製した。
次に、アプリケータ(ヨシミツ精機社製)を用いて、厚み125μmのポリイミドフィルム上に、上記トルエン溶液を塗布して、厚さ250μmの塗布膜を形成した。
オーブンにて、空気雰囲気下、80℃で30分間加熱乾燥させた後、窒素雰囲気下、200℃で2時間加熱することで、塗布膜を熱硬化(熱架橋反応)させて、厚み約100μmの評価用サンプル(フィルム状硬化物)を得た。得られた評価用サンプルに対して、下記の評価を行った。 The above bifunctional methacrylic-modified PPE (SA9000) or bifunctional chloromethylstyrene-modified PPE (OPE-2st), the organosilicon compound synthesized or prepared in each example, dicumyl peroxide as a radical polymerization initiator, and toluene were mixed at a mass ratio of 7:3:0.1:7 and stirred at room temperature to prepare a toluene solution (curable composition).
Next, using an applicator (manufactured by Yoshimitsu Seiki Co., Ltd.), the toluene solution was applied onto a polyimide film having a thickness of 125 μm to form a coating film having a thickness of 250 μm.
After drying by heating at 80° C. for 30 minutes in an oven in an air atmosphere, the coating film is thermally cured (thermal cross-linking reaction) by heating at 200° C. for 2 hours in a nitrogen atmosphere to obtain a thickness of about 100 μm. A sample for evaluation (film-like cured product) was obtained. The evaluation samples obtained were evaluated as follows.
次に、アプリケータ(ヨシミツ精機社製)を用いて、厚み125μmのポリイミドフィルム上に、上記トルエン溶液を塗布して、厚さ250μmの塗布膜を形成した。
オーブンにて、空気雰囲気下、80℃で30分間加熱乾燥させた後、窒素雰囲気下、200℃で2時間加熱することで、塗布膜を熱硬化(熱架橋反応)させて、厚み約100μmの評価用サンプル(フィルム状硬化物)を得た。得られた評価用サンプルに対して、下記の評価を行った。 The above bifunctional methacrylic-modified PPE (SA9000) or bifunctional chloromethylstyrene-modified PPE (OPE-2st), the organosilicon compound synthesized or prepared in each example, dicumyl peroxide as a radical polymerization initiator, and toluene were mixed at a mass ratio of 7:3:0.1:7 and stirred at room temperature to prepare a toluene solution (curable composition).
Next, using an applicator (manufactured by Yoshimitsu Seiki Co., Ltd.), the toluene solution was applied onto a polyimide film having a thickness of 125 μm to form a coating film having a thickness of 250 μm.
After drying by heating at 80° C. for 30 minutes in an oven in an air atmosphere, the coating film is thermally cured (thermal cross-linking reaction) by heating at 200° C. for 2 hours in a nitrogen atmosphere to obtain a thickness of about 100 μm. A sample for evaluation (film-like cured product) was obtained. The evaluation samples obtained were evaluated as follows.
[フィルム状硬化物の評価項目と評価方法]
(比誘電率(Dk)および誘電正接(Df))
評価用サンプル(フィルム状硬化物)の10GHzにおける比誘電率(Dk)および誘電正接(Df)を、室温で、ベクトルネットワークアナライザ(アジレントテクノロジー社製「E8361C」)を用い、SPDR法により測定した。 [Evaluation items and evaluation methods of film-like cured product]
(Relative permittivity (D k ) and dissipation factor (D f ))
The dielectric constant (D k ) and dielectric loss tangent (D f ) of the evaluation sample (cured film) at 10 GHz are measured at room temperature by the SPDR method using a vector network analyzer ("E8361C" manufactured by Agilent Technologies). did.
(比誘電率(Dk)および誘電正接(Df))
評価用サンプル(フィルム状硬化物)の10GHzにおける比誘電率(Dk)および誘電正接(Df)を、室温で、ベクトルネットワークアナライザ(アジレントテクノロジー社製「E8361C」)を用い、SPDR法により測定した。 [Evaluation items and evaluation methods of film-like cured product]
(Relative permittivity (D k ) and dissipation factor (D f ))
The dielectric constant (D k ) and dielectric loss tangent (D f ) of the evaluation sample (cured film) at 10 GHz are measured at room temperature by the SPDR method using a vector network analyzer ("E8361C" manufactured by Agilent Technologies). did.
(ガラス転移温度Tg)
動的粘弾性測定装置(アイティー計測制御株式会社製「DVA-200」)を用いて、評価用サンプル(フィルム状硬化物)の動的粘弾性測定(DMA)を行い、ガラス転移温度(Tg)(℃)を測定した。測定は、周波数10Hz、昇温速度2℃/min、温度範囲25~300℃の条件で行った。 (Glass transition temperature Tg)
Using a dynamic viscoelasticity measuring device (“DVA-200” manufactured by IT Keisoku Co., Ltd.), dynamic viscoelasticity measurement (DMA) of the evaluation sample (film-like cured product) was performed, and the glass transition temperature (Tg ) (°C) was measured. The measurement was performed under the conditions of a frequency of 10 Hz, a heating rate of 2°C/min, and a temperature range of 25 to 300°C.
動的粘弾性測定装置(アイティー計測制御株式会社製「DVA-200」)を用いて、評価用サンプル(フィルム状硬化物)の動的粘弾性測定(DMA)を行い、ガラス転移温度(Tg)(℃)を測定した。測定は、周波数10Hz、昇温速度2℃/min、温度範囲25~300℃の条件で行った。 (Glass transition temperature Tg)
Using a dynamic viscoelasticity measuring device (“DVA-200” manufactured by IT Keisoku Co., Ltd.), dynamic viscoelasticity measurement (DMA) of the evaluation sample (film-like cured product) was performed, and the glass transition temperature (Tg ) (°C) was measured. The measurement was performed under the conditions of a frequency of 10 Hz, a heating rate of 2°C/min, and a temperature range of 25 to 300°C.
(熱膨張係数(CTE))
熱機械分析装置(エスアイアイ・ナノテクノロジー株式会社製「TMA/SS7100」)を用い、ガラス転移温度(Tg)未満における、評価用サンプル(フィルム状硬化物)の熱膨張係数(CTE)を測定した。測定は、昇温速度5℃/min、温度範囲-50~340℃の条件で行った。 (Coefficient of thermal expansion (CTE))
Using a thermomechanical analyzer ("TMA/SS7100" manufactured by SII Nanotechnology Co., Ltd.), the thermal expansion coefficient (CTE) of the evaluation sample (film-like cured product) below the glass transition temperature (Tg) was measured. . The measurement was carried out under the conditions of a temperature increase rate of 5°C/min and a temperature range of -50 to 340°C.
熱機械分析装置(エスアイアイ・ナノテクノロジー株式会社製「TMA/SS7100」)を用い、ガラス転移温度(Tg)未満における、評価用サンプル(フィルム状硬化物)の熱膨張係数(CTE)を測定した。測定は、昇温速度5℃/min、温度範囲-50~340℃の条件で行った。 (Coefficient of thermal expansion (CTE))
Using a thermomechanical analyzer ("TMA/SS7100" manufactured by SII Nanotechnology Co., Ltd.), the thermal expansion coefficient (CTE) of the evaluation sample (film-like cured product) below the glass transition temperature (Tg) was measured. . The measurement was carried out under the conditions of a temperature increase rate of 5°C/min and a temperature range of -50 to 340°C.
[例1]ジメチルビス(3-ビニルフェニル)シラン(C1-D-m-St-Si)の合成
<ビス(3-ホルミルフェニル)ジメチルシランの合成>
窒素雰囲気下、500mLの四ツ口フラスコに、3-ブロモベンズアルデヒドジエチルアセタール(24.0g、90.8mmol)とテトラヒドロフラン(300mL)を仕込んだ。この溶液を-65℃以下に冷却し、これに、n-BuLi/n-ヘキサン溶液(2.6mol/L、35mL、91mmol)を1時間かけて滴下し、-70℃以下で2時間攪拌した。得られた反応溶液に、ジクロロジメチルシラン(4.40mL、36.3mmol)を30分かけて滴下し、上記と同じ温度で2時間攪拌した。フラスコを室温まで加温し、12時間以上攪拌した。反応混合物を塩酸(2mol/L、120mL)でクエンチし、室温で1時間攪拌し、有機相を分離した。さらに、水相に酢酸エチル(100mL)を加え、有機相を分離する抽出を2回行った。これら抽出で得られた有機相を合わせた。合わせた有機相を飽和食塩水(100mL)で洗浄し、硫酸マグネシウムを用いて乾燥し、ろ過し、ろ液を減圧下で濃縮して、粗物を得た。粗物をシリカゲルカラムクロマトグラフィー(移動相:クロロホルム/n-ヘキサン=1:2(体積比))を用いて精製し、淡黄色液体のビス(3-ホルミルフェニル)ジメチルシランを8.61g得た(収率:88%)。 [Example 1] Synthesis of dimethylbis(3-vinylphenyl)silane (C1-D-m-St-Si) <Synthesis of bis(3-formylphenyl)dimethylsilane>
A 500 mL four-necked flask was charged with 3-bromobenzaldehyde diethyl acetal (24.0 g, 90.8 mmol) and tetrahydrofuran (300 mL) under a nitrogen atmosphere. This solution was cooled to −65° C. or lower, n-BuLi/n-hexane solution (2.6 mol/L, 35 mL, 91 mmol) was added dropwise thereto over 1 hour, and the mixture was stirred at −70° C. or lower for 2 hours. . Dichlorodimethylsilane (4.40 mL, 36.3 mmol) was added dropwise to the resulting reaction solution over 30 minutes, and the mixture was stirred at the same temperature as above for 2 hours. The flask was warmed to room temperature and stirred for 12 more hours. The reaction mixture was quenched with hydrochloric acid (2 mol/L, 120 mL), stirred at room temperature for 1 hour, and the organic phase was separated. Furthermore, ethyl acetate (100 mL) was added to the aqueous phase and extraction was performed twice to separate the organic phase. The organic phases from these extractions were combined. The combined organic phase was washed with saturated brine (100 mL), dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure to give crude material. The crude product was purified using silica gel column chromatography (mobile phase: chloroform/n-hexane=1:2 (volume ratio)) to obtain 8.61 g of pale yellow liquid bis(3-formylphenyl)dimethylsilane. (Yield: 88%).
<ビス(3-ホルミルフェニル)ジメチルシランの合成>
窒素雰囲気下、500mLの四ツ口フラスコに、3-ブロモベンズアルデヒドジエチルアセタール(24.0g、90.8mmol)とテトラヒドロフラン(300mL)を仕込んだ。この溶液を-65℃以下に冷却し、これに、n-BuLi/n-ヘキサン溶液(2.6mol/L、35mL、91mmol)を1時間かけて滴下し、-70℃以下で2時間攪拌した。得られた反応溶液に、ジクロロジメチルシラン(4.40mL、36.3mmol)を30分かけて滴下し、上記と同じ温度で2時間攪拌した。フラスコを室温まで加温し、12時間以上攪拌した。反応混合物を塩酸(2mol/L、120mL)でクエンチし、室温で1時間攪拌し、有機相を分離した。さらに、水相に酢酸エチル(100mL)を加え、有機相を分離する抽出を2回行った。これら抽出で得られた有機相を合わせた。合わせた有機相を飽和食塩水(100mL)で洗浄し、硫酸マグネシウムを用いて乾燥し、ろ過し、ろ液を減圧下で濃縮して、粗物を得た。粗物をシリカゲルカラムクロマトグラフィー(移動相:クロロホルム/n-ヘキサン=1:2(体積比))を用いて精製し、淡黄色液体のビス(3-ホルミルフェニル)ジメチルシランを8.61g得た(収率:88%)。 [Example 1] Synthesis of dimethylbis(3-vinylphenyl)silane (C1-D-m-St-Si) <Synthesis of bis(3-formylphenyl)dimethylsilane>
A 500 mL four-necked flask was charged with 3-bromobenzaldehyde diethyl acetal (24.0 g, 90.8 mmol) and tetrahydrofuran (300 mL) under a nitrogen atmosphere. This solution was cooled to −65° C. or lower, n-BuLi/n-hexane solution (2.6 mol/L, 35 mL, 91 mmol) was added dropwise thereto over 1 hour, and the mixture was stirred at −70° C. or lower for 2 hours. . Dichlorodimethylsilane (4.40 mL, 36.3 mmol) was added dropwise to the resulting reaction solution over 30 minutes, and the mixture was stirred at the same temperature as above for 2 hours. The flask was warmed to room temperature and stirred for 12 more hours. The reaction mixture was quenched with hydrochloric acid (2 mol/L, 120 mL), stirred at room temperature for 1 hour, and the organic phase was separated. Furthermore, ethyl acetate (100 mL) was added to the aqueous phase and extraction was performed twice to separate the organic phase. The organic phases from these extractions were combined. The combined organic phase was washed with saturated brine (100 mL), dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure to give crude material. The crude product was purified using silica gel column chromatography (mobile phase: chloroform/n-hexane=1:2 (volume ratio)) to obtain 8.61 g of pale yellow liquid bis(3-formylphenyl)dimethylsilane. (Yield: 88%).
1H-NMR(CDCl3):δ(ppm)10.02(s,2H,CHO),8.02(s,2H,Ar-H),7.90(td,2H,J=7.68,1.71Hz,Ar-H),7.76(d,2H,J=7.68Hz,Ar-H),7.54(t,2H,J=7.68Hz,Ar-H),0.66(s,6H,Si-CH3).
1 H-NMR (CDCl 3 ): δ (ppm) 10.02 (s, 2H, CHO), 8.02 (s, 2H, Ar—H), 7.90 (td, 2H, J=7.68 , 1.71 Hz, Ar-H), 7.76 (d, 2H, J=7.68 Hz, Ar-H), 7.54 (t, 2H, J=7.68 Hz, Ar-H), 0. 66(s, 6H, Si—CH 3 ).
<ジメチルビス(3-ビニルフェニル)シランの合成>
500mLの四ツ口フラスコに、窒素雰囲気下で、メチルトリフェニルホスホニウムブロミド(25.6g、71.1mmol)とテトラヒドロフラン(128mL)とを仕込んだ。フラスコを0℃に冷却し、懸濁液にカリウムtert-ブトキシド(9.03g、80.5mmol)を加えた。反応混合物を上記と同じ温度で5分以上攪拌した。反応混合物に、ビス(3-ホルミルフェニル)ジメチルシラン(8.00g、29.8mmol)のテトラヒドロフラン(128mL)溶液を20分かけて滴下した。フラスコを室温まで加温し、7時間攪拌した。反応混合物に4-tert-ブチルピロカテコール(0.60mg)を加えた後、30℃、減圧下で濃縮した。得られた混合物に水(200mL)とジエチルエーテル(200mL)とを加え、有機相を分離する抽出を行った。さらに、水相にジエチルエーテル(200mL)を加え、有機相を分離する抽出を2回行った。これら抽出で得られた有機相を合わせた。合わせた有機相を硫酸マグネシウムを用いて乾燥し、ろ過し、ろ液を減圧下で濃縮して、粗混合物を得た。粗混合物にn-ヘキサン(160mL)とジエチルエーテル(40mL)とを加え、30分間攪拌した。混合物をろ紙を用いてろ過し、ろ液を減圧下で濃縮して、粗物(オイル)を得た。粗物をシリカゲルカラムクロマトグラフィー(移動相:n-ヘキサン)を用いて精製し、無色液体のジメチルビス(3-ビニルフェニル)シラン(C1-D-m-St-Si)を7.39g得た(収率:94%)。 <Synthesis of dimethylbis(3-vinylphenyl)silane>
A 500 mL four-necked flask was charged with methyltriphenylphosphonium bromide (25.6 g, 71.1 mmol) and tetrahydrofuran (128 mL) under a nitrogen atmosphere. The flask was cooled to 0° C. and potassium tert-butoxide (9.03 g, 80.5 mmol) was added to the suspension. The reaction mixture was stirred at the same temperature as above for 5 minutes longer. A solution of bis(3-formylphenyl)dimethylsilane (8.00 g, 29.8 mmol) in tetrahydrofuran (128 mL) was added dropwise to the reaction mixture over 20 minutes. The flask was warmed to room temperature and stirred for 7 hours. After adding 4-tert-butylpyrocatechol (0.60 mg) to the reaction mixture, the mixture was concentrated at 30° C. under reduced pressure. Water (200 mL) and diethyl ether (200 mL) were added to the resulting mixture and extraction was performed to separate the organic phase. Furthermore, diethyl ether (200 mL) was added to the aqueous phase and extraction was performed twice to separate the organic phase. The organic phases from these extractions were combined. The combined organic phases were dried using magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure to give a crude mixture. n-Hexane (160 mL) and diethyl ether (40 mL) were added to the crude mixture and stirred for 30 minutes. The mixture was filtered using filter paper, and the filtrate was concentrated under reduced pressure to obtain a crude product (oil). The crude product was purified using silica gel column chromatography (mobile phase: n-hexane) to obtain 7.39 g of colorless liquid dimethylbis(3-vinylphenyl)silane (C1-Dm-St-Si). (Yield: 94%).
500mLの四ツ口フラスコに、窒素雰囲気下で、メチルトリフェニルホスホニウムブロミド(25.6g、71.1mmol)とテトラヒドロフラン(128mL)とを仕込んだ。フラスコを0℃に冷却し、懸濁液にカリウムtert-ブトキシド(9.03g、80.5mmol)を加えた。反応混合物を上記と同じ温度で5分以上攪拌した。反応混合物に、ビス(3-ホルミルフェニル)ジメチルシラン(8.00g、29.8mmol)のテトラヒドロフラン(128mL)溶液を20分かけて滴下した。フラスコを室温まで加温し、7時間攪拌した。反応混合物に4-tert-ブチルピロカテコール(0.60mg)を加えた後、30℃、減圧下で濃縮した。得られた混合物に水(200mL)とジエチルエーテル(200mL)とを加え、有機相を分離する抽出を行った。さらに、水相にジエチルエーテル(200mL)を加え、有機相を分離する抽出を2回行った。これら抽出で得られた有機相を合わせた。合わせた有機相を硫酸マグネシウムを用いて乾燥し、ろ過し、ろ液を減圧下で濃縮して、粗混合物を得た。粗混合物にn-ヘキサン(160mL)とジエチルエーテル(40mL)とを加え、30分間攪拌した。混合物をろ紙を用いてろ過し、ろ液を減圧下で濃縮して、粗物(オイル)を得た。粗物をシリカゲルカラムクロマトグラフィー(移動相:n-ヘキサン)を用いて精製し、無色液体のジメチルビス(3-ビニルフェニル)シラン(C1-D-m-St-Si)を7.39g得た(収率:94%)。 <Synthesis of dimethylbis(3-vinylphenyl)silane>
A 500 mL four-necked flask was charged with methyltriphenylphosphonium bromide (25.6 g, 71.1 mmol) and tetrahydrofuran (128 mL) under a nitrogen atmosphere. The flask was cooled to 0° C. and potassium tert-butoxide (9.03 g, 80.5 mmol) was added to the suspension. The reaction mixture was stirred at the same temperature as above for 5 minutes longer. A solution of bis(3-formylphenyl)dimethylsilane (8.00 g, 29.8 mmol) in tetrahydrofuran (128 mL) was added dropwise to the reaction mixture over 20 minutes. The flask was warmed to room temperature and stirred for 7 hours. After adding 4-tert-butylpyrocatechol (0.60 mg) to the reaction mixture, the mixture was concentrated at 30° C. under reduced pressure. Water (200 mL) and diethyl ether (200 mL) were added to the resulting mixture and extraction was performed to separate the organic phase. Furthermore, diethyl ether (200 mL) was added to the aqueous phase and extraction was performed twice to separate the organic phase. The organic phases from these extractions were combined. The combined organic phases were dried using magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure to give a crude mixture. n-Hexane (160 mL) and diethyl ether (40 mL) were added to the crude mixture and stirred for 30 minutes. The mixture was filtered using filter paper, and the filtrate was concentrated under reduced pressure to obtain a crude product (oil). The crude product was purified using silica gel column chromatography (mobile phase: n-hexane) to obtain 7.39 g of colorless liquid dimethylbis(3-vinylphenyl)silane (C1-Dm-St-Si). (Yield: 94%).
反応スキーム、NMR分析結果およびHRMS分析結果は、以下の通りである。
The reaction scheme, NMR analysis results and HRMS analysis results are as follows.
1H-NMR(CDCl3):δ(ppm)8.53(brs,2H,Ar-H),7.46-7.37(m,4H,Ar-H),7.32(t,2H,J=7.68Hz,Ar-H),6.71(dd,2H,J=11.10,17.07Hz,-CH=CH2),5.73(d,2H,J=17.07Hz,-CH=CH2),5.23(d,2H,J=11.10Hz,-CH=CH2),0.56(s,6H,Si-CH3).
HRMS(EI):m/z Calcd for C18H20Si:(M+)264.133,found 264.130. 1 H-NMR (CDCl 3 ): δ (ppm) 8.53 (brs, 2H, Ar-H), 7.46-7.37 (m, 4H, Ar-H), 7.32 (t, 2H , J = 7.68 Hz, Ar-H), 6.71 (dd, 2H, J = 11.10, 17.07 Hz, -CH = CH 2 ), 5.73 (d, 2H, J = 17.07 Hz , -CH=CH 2 ), 5.23 (d, 2H, J=11.10 Hz, -CH=CH 2 ), 0.56 (s, 6H, Si-CH 3 ).
HRMS (EI): m/z Calcd for C18H20Si : (M + ) 264.133 , found 264.130.
HRMS(EI):m/z Calcd for C18H20Si:(M+)264.133,found 264.130. 1 H-NMR (CDCl 3 ): δ (ppm) 8.53 (brs, 2H, Ar-H), 7.46-7.37 (m, 4H, Ar-H), 7.32 (t, 2H , J = 7.68 Hz, Ar-H), 6.71 (dd, 2H, J = 11.10, 17.07 Hz, -CH = CH 2 ), 5.73 (d, 2H, J = 17.07 Hz , -CH=CH 2 ), 5.23 (d, 2H, J=11.10 Hz, -CH=CH 2 ), 0.56 (s, 6H, Si-CH 3 ).
HRMS (EI): m/z Calcd for C18H20Si : (M + ) 264.133 , found 264.130.
[例2]ドデシルトリス(3-ビニルフェニル)シラン(C12-T-m-St-Si)の合成
<ドデシルトリス(3-ホルミルフェニル)シランの合成>
500mLの四ツ口フラスコに、窒素雰囲気下で、3-ブロモベンズアルデヒドジエチルアセタール(24.0g、90.8mmol)とテトラヒドロフラン(300mL)とを仕込んだ。この溶液を-65℃以下に冷却し、これに、n-BuLi/n-ヘキサン溶液(2.6mol/L、35mL、91mmol)を1時間かけて滴下し、反応溶液を-70℃以下で2時間攪拌した。得られた反応溶液にドデシルトリクロロシラン(7.20mL、24.2mmol)を40分かけて滴下し、上記と同じ温度で2時間攪拌した。フラスコを室温まで加温し、12時間以上攪拌した。反応混合物を塩酸(2mol/L、120mL)でクエンチし、室温で1時間攪拌し、有機相を分離した。さらに、水相に酢酸エチル(100mL)を加え、有機相を分離する抽出を2回行った。これら抽出で得られた有機相を合わせた。合わせた有機相を飽和食塩水(100mL)で洗浄し、硫酸マグネシウムを用いて乾燥し、ろ過し、ろ液を減圧下で濃縮して、粗物を得た。粗物をシリカゲルカラムクロマトグラフィー(移動相:クロロホルム/n-ヘキサン=1:1(体積比))を用いて精製し、無色液体のドデシルトリス(3-ホルミルフェニル)シランを10.5g得た(収率:85%)。 [Example 2] Synthesis of dodecyltris(3-vinylphenyl)silane (C12-Tm-St-Si) <Synthesis of dodecyltris(3-formylphenyl)silane>
A 500 mL four-necked flask was charged with 3-bromobenzaldehyde diethyl acetal (24.0 g, 90.8 mmol) and tetrahydrofuran (300 mL) under a nitrogen atmosphere. This solution was cooled to −65° C. or lower, and n-BuLi/n-hexane solution (2.6 mol/L, 35 mL, 91 mmol) was added dropwise thereto over 1 hour. Stirred for hours. Dodecyltrichlorosilane (7.20 mL, 24.2 mmol) was added dropwise to the resulting reaction solution over 40 minutes, and the mixture was stirred at the same temperature as above for 2 hours. The flask was warmed to room temperature and stirred for 12 more hours. The reaction mixture was quenched with hydrochloric acid (2 mol/L, 120 mL), stirred at room temperature for 1 hour, and the organic phase was separated. Furthermore, ethyl acetate (100 mL) was added to the aqueous phase and extraction was performed twice to separate the organic phase. The organic phases from these extractions were combined. The combined organic phase was washed with saturated brine (100 mL), dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure to give crude material. The crude product was purified using silica gel column chromatography (mobile phase: chloroform/n-hexane=1:1 (volume ratio)) to obtain 10.5 g of colorless liquid dodecyltris(3-formylphenyl)silane ( Yield: 85%).
<ドデシルトリス(3-ホルミルフェニル)シランの合成>
500mLの四ツ口フラスコに、窒素雰囲気下で、3-ブロモベンズアルデヒドジエチルアセタール(24.0g、90.8mmol)とテトラヒドロフラン(300mL)とを仕込んだ。この溶液を-65℃以下に冷却し、これに、n-BuLi/n-ヘキサン溶液(2.6mol/L、35mL、91mmol)を1時間かけて滴下し、反応溶液を-70℃以下で2時間攪拌した。得られた反応溶液にドデシルトリクロロシラン(7.20mL、24.2mmol)を40分かけて滴下し、上記と同じ温度で2時間攪拌した。フラスコを室温まで加温し、12時間以上攪拌した。反応混合物を塩酸(2mol/L、120mL)でクエンチし、室温で1時間攪拌し、有機相を分離した。さらに、水相に酢酸エチル(100mL)を加え、有機相を分離する抽出を2回行った。これら抽出で得られた有機相を合わせた。合わせた有機相を飽和食塩水(100mL)で洗浄し、硫酸マグネシウムを用いて乾燥し、ろ過し、ろ液を減圧下で濃縮して、粗物を得た。粗物をシリカゲルカラムクロマトグラフィー(移動相:クロロホルム/n-ヘキサン=1:1(体積比))を用いて精製し、無色液体のドデシルトリス(3-ホルミルフェニル)シランを10.5g得た(収率:85%)。 [Example 2] Synthesis of dodecyltris(3-vinylphenyl)silane (C12-Tm-St-Si) <Synthesis of dodecyltris(3-formylphenyl)silane>
A 500 mL four-necked flask was charged with 3-bromobenzaldehyde diethyl acetal (24.0 g, 90.8 mmol) and tetrahydrofuran (300 mL) under a nitrogen atmosphere. This solution was cooled to −65° C. or lower, and n-BuLi/n-hexane solution (2.6 mol/L, 35 mL, 91 mmol) was added dropwise thereto over 1 hour. Stirred for hours. Dodecyltrichlorosilane (7.20 mL, 24.2 mmol) was added dropwise to the resulting reaction solution over 40 minutes, and the mixture was stirred at the same temperature as above for 2 hours. The flask was warmed to room temperature and stirred for 12 more hours. The reaction mixture was quenched with hydrochloric acid (2 mol/L, 120 mL), stirred at room temperature for 1 hour, and the organic phase was separated. Furthermore, ethyl acetate (100 mL) was added to the aqueous phase and extraction was performed twice to separate the organic phase. The organic phases from these extractions were combined. The combined organic phase was washed with saturated brine (100 mL), dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure to give crude material. The crude product was purified using silica gel column chromatography (mobile phase: chloroform/n-hexane=1:1 (volume ratio)) to obtain 10.5 g of colorless liquid dodecyltris(3-formylphenyl)silane ( Yield: 85%).
1H-NMR(CDCl3):δ(ppm)10.01(s,3H,CHO),8.00(brs,3H,s,Ar-H), 7.97(td,3H,J=7.68,1.71 Hz,Ar-H),7.76(d,3H,J=7.68Hz,Ar-H),7.58(t,3H,J=7.68Hz,Ar-H),1.56~1.33(m,6H,-CH2-),1.22(brs,16H,-CH2-),0.87(t,3H,J=6.83 Hz,CH3).
1 H-NMR (CDCl 3 ): δ (ppm) 10.01 (s, 3H, CHO), 8.00 (brs, 3H, s, Ar—H), 7.97 (td, 3H, J=7 .68, 1.71 Hz, Ar-H), 7.76 (d, 3H, J = 7.68 Hz, Ar-H), 7.58 (t, 3H, J = 7.68 Hz, Ar-H) , 1.56-1.33 (m, 6H, —CH 2 —), 1.22 (brs, 16H, —CH 2 —), 0.87 (t, 3H, J=6.83 Hz, CH 3 ).
<ドデシルトリス(3-ビニルフェニル)シランの合成>
500mLの四ツ口フラスコに、窒素雰囲気下で、メチルトリフェニルホスホニウムブロミド(22.6g、63.3mmol)とテトラヒドロフラン(144mL)とを仕込んだ。フラスコを0℃に冷却し、懸濁液にカリウムtert-ブトキシド(7.98g、71.1mmol)を加えた。反応混合物を上記と同じ温度で5分以上攪拌した。反応混合物に、ドデシルトリス(3-ホルミルフェニル)シラン(9.00g、17.6mmol)のテトラヒドロフラン(144mL)溶液を20分かけて滴下した。フラスコを室温まで加温し、1時間攪拌した。反応混合物に4-tert-ブチルピロカテコール(2.55mg)を加えた後、30℃、減圧下で濃縮した。得られた混合物に水(200mL)とジエチルエーテル(200mL)とを加え、有機相を分離する抽出を行った。さらに、水相にジエチルエーテル(200mL)を加え、有機相を分離する抽出を行った。これら抽出で得られた有機相を合わせた。合わせた有機相を硫酸マグネシウムを用いて乾燥し、ろ過し、ろ液を減圧下で濃縮して、粗混合物を得た。粗混合物にn-ヘキサン(160mL)とジエチルエーテル(40mL)とを加え、30分間攪拌した。混合物をろ紙を用いてろ過し、ろ液を減圧下で濃縮して、粗物(赤色のオイル)を得た。粗物をシリカゲルカラムクロマトグラフィー(移動相:n-ヘキサン)を用いて精製し、淡黄色液体のドデシルトリス(3-ビニルフェニル)シラン(C12-T-m-St-Si)を6.32gを得た(収率:71%)。 <Synthesis of dodecyltris(3-vinylphenyl)silane>
A 500 mL four-necked flask was charged with methyltriphenylphosphonium bromide (22.6 g, 63.3 mmol) and tetrahydrofuran (144 mL) under a nitrogen atmosphere. The flask was cooled to 0° C. and potassium tert-butoxide (7.98 g, 71.1 mmol) was added to the suspension. The reaction mixture was stirred at the same temperature as above for 5 minutes longer. A solution of dodecyltris(3-formylphenyl)silane (9.00 g, 17.6 mmol) in tetrahydrofuran (144 mL) was added dropwise to the reaction mixture over 20 minutes. The flask was warmed to room temperature and stirred for 1 hour. After adding 4-tert-butylpyrocatechol (2.55 mg) to the reaction mixture, it was concentrated at 30° C. under reduced pressure. Water (200 mL) and diethyl ether (200 mL) were added to the resulting mixture and extraction was performed to separate the organic phase. Furthermore, diethyl ether (200 mL) was added to the aqueous phase, and extraction was performed to separate the organic phase. The organic phases from these extractions were combined. The combined organic phases were dried using magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure to give a crude mixture. n-Hexane (160 mL) and diethyl ether (40 mL) were added to the crude mixture and stirred for 30 minutes. The mixture was filtered using filter paper and the filtrate was concentrated under reduced pressure to obtain a crude product (red oil). The crude product was purified using silica gel column chromatography (mobile phase: n-hexane), and 6.32 g of pale yellow liquid dodecyltris(3-vinylphenyl)silane (C12-Tm-St-Si) was added. obtained (yield: 71%).
500mLの四ツ口フラスコに、窒素雰囲気下で、メチルトリフェニルホスホニウムブロミド(22.6g、63.3mmol)とテトラヒドロフラン(144mL)とを仕込んだ。フラスコを0℃に冷却し、懸濁液にカリウムtert-ブトキシド(7.98g、71.1mmol)を加えた。反応混合物を上記と同じ温度で5分以上攪拌した。反応混合物に、ドデシルトリス(3-ホルミルフェニル)シラン(9.00g、17.6mmol)のテトラヒドロフラン(144mL)溶液を20分かけて滴下した。フラスコを室温まで加温し、1時間攪拌した。反応混合物に4-tert-ブチルピロカテコール(2.55mg)を加えた後、30℃、減圧下で濃縮した。得られた混合物に水(200mL)とジエチルエーテル(200mL)とを加え、有機相を分離する抽出を行った。さらに、水相にジエチルエーテル(200mL)を加え、有機相を分離する抽出を行った。これら抽出で得られた有機相を合わせた。合わせた有機相を硫酸マグネシウムを用いて乾燥し、ろ過し、ろ液を減圧下で濃縮して、粗混合物を得た。粗混合物にn-ヘキサン(160mL)とジエチルエーテル(40mL)とを加え、30分間攪拌した。混合物をろ紙を用いてろ過し、ろ液を減圧下で濃縮して、粗物(赤色のオイル)を得た。粗物をシリカゲルカラムクロマトグラフィー(移動相:n-ヘキサン)を用いて精製し、淡黄色液体のドデシルトリス(3-ビニルフェニル)シラン(C12-T-m-St-Si)を6.32gを得た(収率:71%)。 <Synthesis of dodecyltris(3-vinylphenyl)silane>
A 500 mL four-necked flask was charged with methyltriphenylphosphonium bromide (22.6 g, 63.3 mmol) and tetrahydrofuran (144 mL) under a nitrogen atmosphere. The flask was cooled to 0° C. and potassium tert-butoxide (7.98 g, 71.1 mmol) was added to the suspension. The reaction mixture was stirred at the same temperature as above for 5 minutes longer. A solution of dodecyltris(3-formylphenyl)silane (9.00 g, 17.6 mmol) in tetrahydrofuran (144 mL) was added dropwise to the reaction mixture over 20 minutes. The flask was warmed to room temperature and stirred for 1 hour. After adding 4-tert-butylpyrocatechol (2.55 mg) to the reaction mixture, it was concentrated at 30° C. under reduced pressure. Water (200 mL) and diethyl ether (200 mL) were added to the resulting mixture and extraction was performed to separate the organic phase. Furthermore, diethyl ether (200 mL) was added to the aqueous phase, and extraction was performed to separate the organic phase. The organic phases from these extractions were combined. The combined organic phases were dried using magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure to give a crude mixture. n-Hexane (160 mL) and diethyl ether (40 mL) were added to the crude mixture and stirred for 30 minutes. The mixture was filtered using filter paper and the filtrate was concentrated under reduced pressure to obtain a crude product (red oil). The crude product was purified using silica gel column chromatography (mobile phase: n-hexane), and 6.32 g of pale yellow liquid dodecyltris(3-vinylphenyl)silane (C12-Tm-St-Si) was added. obtained (yield: 71%).
反応スキーム、NMR分析結果およびHRMS分析結果は、以下の通りである。
The reaction scheme, NMR analysis results and HRMS analysis results are as follows.
1H-NMR(CDCl3):δ(ppm)7.54(brs,3H,Ar-H),7.48(d,3H,J=6.83Hz,Ar-H),7.40(d,3H,J=6.83Hz,Ar-H),7.32(t,3H,J=6.83Hz,Ar-H),6.69(dd,3H,J=11.10,17.93Hz,-CH=CH2),5.69(d,3H,J=17.93Hz,-CH=CH2),5.21(d,3H,J=11.10Hz,-CH=CH2),1.52-1.42(m,2H,-CH2-),1.42-1.32(m,4H,-CH2-),1.32-1.11(m,16H,-CH2-),0.87(t,3H,J=6.83Hz,CH3).
HRMS(EI):m/z Calcd for C36H46Si:(M+)506.337,found 506.329. 1 H-NMR (CDCl 3 ): δ (ppm) 7.54 (brs, 3H, Ar-H), 7.48 (d, 3H, J = 6.83 Hz, Ar-H), 7.40 (d , 3H, J = 6.83 Hz, Ar-H), 7.32 (t, 3H, J = 6.83 Hz, Ar-H), 6.69 (dd, 3H, J = 11.10, 17.93 Hz , —CH=CH 2 ), 5.69 (d, 3H, J=17.93 Hz, —CH=CH 2 ), 5.21 (d, 3H, J=11.10 Hz, —CH=CH 2 ), 1.52-1.42 (m, 2H, —CH 2 —), 1.42-1.32 (m, 4H, —CH 2 —), 1.32-1.11 (m, 16H, —CH 2- ), 0.87(t, 3H, J=6.83Hz, CH3 ).
HRMS (EI): m/z Calcd for C36H46Si : (M + ) 506.337 , found 506.329.
HRMS(EI):m/z Calcd for C36H46Si:(M+)506.337,found 506.329. 1 H-NMR (CDCl 3 ): δ (ppm) 7.54 (brs, 3H, Ar-H), 7.48 (d, 3H, J = 6.83 Hz, Ar-H), 7.40 (d , 3H, J = 6.83 Hz, Ar-H), 7.32 (t, 3H, J = 6.83 Hz, Ar-H), 6.69 (dd, 3H, J = 11.10, 17.93 Hz , —CH=CH 2 ), 5.69 (d, 3H, J=17.93 Hz, —CH=CH 2 ), 5.21 (d, 3H, J=11.10 Hz, —CH=CH 2 ), 1.52-1.42 (m, 2H, —CH 2 —), 1.42-1.32 (m, 4H, —CH 2 —), 1.32-1.11 (m, 16H, —CH 2- ), 0.87(t, 3H, J=6.83Hz, CH3 ).
HRMS (EI): m/z Calcd for C36H46Si : (M + ) 506.337 , found 506.329.
[例3]ドデシルトリス(ビニルベンジル)シラン異性体混合物(C12-T-mp-Bn-Si)の合成
50mLの四ツ口フラスコに、窒素雰囲気下で、マグネシウム(切削片状、0.898g、36.9mmol)とジエチルエーテル(21.1mL)を仕込み、氷浴で冷却した。懸濁液に、4-(クロロメチル)スチレン/3-(クロロメチル)スチレン混合物(1:1(モル比)、5.12g、33.5mmol)のジエチルエーテル(10.5mL)溶液を1時間かけて滴下した。上記と同じ温度で1時間攪拌した後、ドデシルトリクロロシラン(3.33mL、11.2mmol)を20分かけて滴下した。フラスコを室温まで加温し、12時間以上攪拌した。反応液に水(15mL)を加え10分間以上攪拌し、有機相を分離した。さらに、水相にジエチルエーテル(30mL)を加え、有機相を分離する抽出を2回行った。これら抽出で得られた有機相を合わせた。合わせた有機相を硫酸マグネシウムを用いて乾燥し、ろ過し、ろ液を減圧下で濃縮して、粗物を得た。粗物をシリカゲルカラムクロマトグラフィー(移動相:n-ヘキサン)を用いて精製し、無色の液体としてドデシルトリス(ビニルベンジル)シラン異性体混合物(C12-T-mp-Bn-Si)を0.319g得た(収率:5.2%)。NMRの分析結果から、異性体混合物中の3-ビニルベンジル基と4-ビニルベンジル基のモル比は1.4:1.6と推算された。 [Example 3] Synthesis of dodecyltris(vinylbenzyl)silane isomer mixture (C12-T-mp-Bn-Si) In a 50 mL four-necked flask under a nitrogen atmosphere, magnesium (cuttings, 0.898 g, 36.9 mmol) and diethyl ether (21.1 mL) were charged and cooled in an ice bath. The suspension was treated with a solution of 4-(chloromethyl)styrene/3-(chloromethyl)styrene mixture (1:1 (molar ratio), 5.12 g, 33.5 mmol) in diethyl ether (10.5 mL) for 1 hour. dripped over. After stirring for 1 hour at the same temperature as above, dodecyltrichlorosilane (3.33 mL, 11.2 mmol) was added dropwise over 20 minutes. The flask was warmed to room temperature and stirred for 12 more hours. Water (15 mL) was added to the reaction solution, and the mixture was stirred for 10 minutes or longer, and the organic phase was separated. Furthermore, diethyl ether (30 mL) was added to the aqueous phase and extraction was performed twice to separate the organic phase. The organic phases from these extractions were combined. The combined organic phase was dried with magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure to give crude material. The crude product was purified using silica gel column chromatography (mobile phase: n-hexane), and 0.319 g of dodecyltris(vinylbenzyl)silane isomer mixture (C12-T-mp-Bn-Si) was obtained as a colorless liquid. obtained (yield: 5.2%). From the results of NMR analysis, the molar ratio of 3-vinylbenzyl group and 4-vinylbenzyl group in the isomer mixture was estimated to be 1.4:1.6.
50mLの四ツ口フラスコに、窒素雰囲気下で、マグネシウム(切削片状、0.898g、36.9mmol)とジエチルエーテル(21.1mL)を仕込み、氷浴で冷却した。懸濁液に、4-(クロロメチル)スチレン/3-(クロロメチル)スチレン混合物(1:1(モル比)、5.12g、33.5mmol)のジエチルエーテル(10.5mL)溶液を1時間かけて滴下した。上記と同じ温度で1時間攪拌した後、ドデシルトリクロロシラン(3.33mL、11.2mmol)を20分かけて滴下した。フラスコを室温まで加温し、12時間以上攪拌した。反応液に水(15mL)を加え10分間以上攪拌し、有機相を分離した。さらに、水相にジエチルエーテル(30mL)を加え、有機相を分離する抽出を2回行った。これら抽出で得られた有機相を合わせた。合わせた有機相を硫酸マグネシウムを用いて乾燥し、ろ過し、ろ液を減圧下で濃縮して、粗物を得た。粗物をシリカゲルカラムクロマトグラフィー(移動相:n-ヘキサン)を用いて精製し、無色の液体としてドデシルトリス(ビニルベンジル)シラン異性体混合物(C12-T-mp-Bn-Si)を0.319g得た(収率:5.2%)。NMRの分析結果から、異性体混合物中の3-ビニルベンジル基と4-ビニルベンジル基のモル比は1.4:1.6と推算された。 [Example 3] Synthesis of dodecyltris(vinylbenzyl)silane isomer mixture (C12-T-mp-Bn-Si) In a 50 mL four-necked flask under a nitrogen atmosphere, magnesium (cuttings, 0.898 g, 36.9 mmol) and diethyl ether (21.1 mL) were charged and cooled in an ice bath. The suspension was treated with a solution of 4-(chloromethyl)styrene/3-(chloromethyl)styrene mixture (1:1 (molar ratio), 5.12 g, 33.5 mmol) in diethyl ether (10.5 mL) for 1 hour. dripped over. After stirring for 1 hour at the same temperature as above, dodecyltrichlorosilane (3.33 mL, 11.2 mmol) was added dropwise over 20 minutes. The flask was warmed to room temperature and stirred for 12 more hours. Water (15 mL) was added to the reaction solution, and the mixture was stirred for 10 minutes or longer, and the organic phase was separated. Furthermore, diethyl ether (30 mL) was added to the aqueous phase and extraction was performed twice to separate the organic phase. The organic phases from these extractions were combined. The combined organic phase was dried with magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure to give crude material. The crude product was purified using silica gel column chromatography (mobile phase: n-hexane), and 0.319 g of dodecyltris(vinylbenzyl)silane isomer mixture (C12-T-mp-Bn-Si) was obtained as a colorless liquid. obtained (yield: 5.2%). From the results of NMR analysis, the molar ratio of 3-vinylbenzyl group and 4-vinylbenzyl group in the isomer mixture was estimated to be 1.4:1.6.
反応スキーム、NMR分析結果およびHRMS分析結果は、以下の通りである。
The reaction scheme, NMR analysis results and HRMS analysis results are as follows.
1H-NMR(CDCl3):δ(ppm)7.35~6.81(m,12H,Ar-H),6.74~6.55(m,3H,H-5,-CH=CH2),5.68(d,3H,J=17.1Hz,-CH=CH2),5.20(d,1.36H,J=10.2Hz,-CH=CH2,m-体),5.17(d,1.64H,J=11.1Hz,-CH=CH2,o-体),2.10(s,6H,Si-CH2-Ar),1.38-1.06(m,20H,-CH2-),0.88(t,3H,J=6.83Hz,CH3),0.56-0.39(m,2H,-CH2-).
HRMS(EI):m/z Calcd for C39H52Si:(M+)548.384,found 548.376. 1 H-NMR (CDCl 3 ): δ (ppm) 7.35-6.81 (m, 12H, Ar—H), 6.74-6.55 (m, 3H, H-5, —CH═CH 2 ), 5.68 (d, 3H, J=17.1Hz, -CH=CH 2 ), 5.20 (d, 1.36H, J=10.2Hz, -CH=CH 2, m-body) , 5.17 (d, 1.64H, J=11.1 Hz, —CH=CH 2 , o-form), 2.10 (s, 6H, Si—CH 2 —Ar), 1.38-1. 06 (m, 20H, —CH 2 —), 0.88 (t, 3H, J=6.83 Hz, CH 3 ), 0.56-0.39 (m, 2H, —CH 2 —).
HRMS (EI): m/z Calcd for C39H52Si : (M <+ >) 548.384, found 548.376 .
HRMS(EI):m/z Calcd for C39H52Si:(M+)548.384,found 548.376. 1 H-NMR (CDCl 3 ): δ (ppm) 7.35-6.81 (m, 12H, Ar—H), 6.74-6.55 (m, 3H, H-5, —CH═CH 2 ), 5.68 (d, 3H, J=17.1Hz, -CH=CH 2 ), 5.20 (d, 1.36H, J=10.2Hz, -CH=CH 2, m-body) , 5.17 (d, 1.64H, J=11.1 Hz, —CH=CH 2 , o-form), 2.10 (s, 6H, Si—CH 2 —Ar), 1.38-1. 06 (m, 20H, —CH 2 —), 0.88 (t, 3H, J=6.83 Hz, CH 3 ), 0.56-0.39 (m, 2H, —CH 2 —).
HRMS (EI): m/z Calcd for C39H52Si : (M <+ >) 548.384, found 548.376 .
[例21]ジメチルビス(4-ビニルフェニル)シラン(C1-D-p-St-Si)の合成
<ビス(4-ホルミルフェニル)ジメチルシランの合成>
500mLの四ツ口フラスコに、窒素雰囲気下で、4-ブロモベンズアルデヒドジメチルアセタール(24.0g、102mmol)とテトラヒドロフラン(300mL)とを仕込んだ。この溶液を-65℃以下に冷却し、これに、n-BuLi/n-ヘキサン溶液(2.6mol/L、39mL、100mmol)を1時間かけて滴下し、反応溶液を-70℃以下で2時間攪拌した。得られた反応溶液にジクロロジメチルシラン(4.93mL、40.7mmol)を40分かけて滴下し、上記と同じ温度で2時間攪拌した。フラスコを室温まで加温し、12時間以上攪拌した。反応混合物を塩酸(2mol/L、120mL)でクエンチし、ジエチルエーテル(100mL)を加え、有機相を分離する抽出を行った。さらに、水相にジエチルエーテル(100mL)を加え、有機相を分離する抽出を2回行った。これら抽出で得られた有機相を合わせた。合わせた有機相を飽和食塩水(100mL)で洗浄し、硫酸マグネシウムを用いて乾燥し、ろ過し、ろ液を減圧下で濃縮して、アセタール/アルデヒドの粗混合物を得た。粗混合物にテトラヒドロフラン(100mL)と塩酸(2mol/L、100mL)とを加え、2時間加熱還流した。室温まで冷却した後、反応液に飽和炭酸水素ナトリウム水溶液(240mL)を滴下した。反応液にジエチルエーテル(100mL)を加え、有機相を分離する抽出を3回行った。これら抽出で得られた有機相を合わせた。合わせた有機相を飽和食塩水(100mL)で洗浄し、硫酸マグネシウムを用いて乾燥し、ろ過し、ろ液を減圧下で濃縮して、粗物(淡黄色のオイル)を得た。粗物に酢酸エチル/n-ヘキサン混合溶液(1:7(体積比)、120mL)を加え、加熱還流させた後、0℃までゆっくりと冷却した。懸濁液をろ過し、得られた固体を減圧下で乾燥して、ビス(4-ホルミルフェニル)ジメチルシランを8.40g得た(収率:77%)。 [Example 21] Synthesis of dimethylbis(4-vinylphenyl)silane (C1-D-p-St-Si) <Synthesis of bis(4-formylphenyl)dimethylsilane>
A 500 mL four-necked flask was charged with 4-bromobenzaldehyde dimethylacetal (24.0 g, 102 mmol) and tetrahydrofuran (300 mL) under a nitrogen atmosphere. This solution was cooled to −65° C. or lower, and n-BuLi/n-hexane solution (2.6 mol/L, 39 mL, 100 mmol) was added dropwise thereto over 1 hour. Stirred for hours. Dichlorodimethylsilane (4.93 mL, 40.7 mmol) was added dropwise to the resulting reaction solution over 40 minutes, and the mixture was stirred at the same temperature as above for 2 hours. The flask was warmed to room temperature and stirred for 12 more hours. The reaction mixture was quenched with hydrochloric acid (2 mol/L, 120 mL), diethyl ether (100 mL) was added and extraction was performed to separate the organic phase. Furthermore, diethyl ether (100 mL) was added to the aqueous phase and extraction was performed twice to separate the organic phase. The organic phases from these extractions were combined. The combined organic phase was washed with saturated brine (100 mL), dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure to give a crude acetal/aldehyde mixture. Tetrahydrofuran (100 mL) and hydrochloric acid (2 mol/L, 100 mL) were added to the crude mixture, and the mixture was heated under reflux for 2 hours. After cooling to room temperature, saturated aqueous sodium hydrogencarbonate solution (240 mL) was added dropwise to the reaction solution. Diethyl ether (100 mL) was added to the reaction solution, and extraction was performed three times to separate the organic phase. The organic phases from these extractions were combined. The combined organic phase was washed with saturated brine (100 mL), dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure to give a crude material (pale yellow oil). A mixed solution of ethyl acetate/n-hexane (1:7 (volume ratio), 120 mL) was added to the crude product, heated to reflux, and then slowly cooled to 0°C. The suspension was filtered, and the obtained solid was dried under reduced pressure to obtain 8.40 g of bis(4-formylphenyl)dimethylsilane (yield: 77%).
<ビス(4-ホルミルフェニル)ジメチルシランの合成>
500mLの四ツ口フラスコに、窒素雰囲気下で、4-ブロモベンズアルデヒドジメチルアセタール(24.0g、102mmol)とテトラヒドロフラン(300mL)とを仕込んだ。この溶液を-65℃以下に冷却し、これに、n-BuLi/n-ヘキサン溶液(2.6mol/L、39mL、100mmol)を1時間かけて滴下し、反応溶液を-70℃以下で2時間攪拌した。得られた反応溶液にジクロロジメチルシラン(4.93mL、40.7mmol)を40分かけて滴下し、上記と同じ温度で2時間攪拌した。フラスコを室温まで加温し、12時間以上攪拌した。反応混合物を塩酸(2mol/L、120mL)でクエンチし、ジエチルエーテル(100mL)を加え、有機相を分離する抽出を行った。さらに、水相にジエチルエーテル(100mL)を加え、有機相を分離する抽出を2回行った。これら抽出で得られた有機相を合わせた。合わせた有機相を飽和食塩水(100mL)で洗浄し、硫酸マグネシウムを用いて乾燥し、ろ過し、ろ液を減圧下で濃縮して、アセタール/アルデヒドの粗混合物を得た。粗混合物にテトラヒドロフラン(100mL)と塩酸(2mol/L、100mL)とを加え、2時間加熱還流した。室温まで冷却した後、反応液に飽和炭酸水素ナトリウム水溶液(240mL)を滴下した。反応液にジエチルエーテル(100mL)を加え、有機相を分離する抽出を3回行った。これら抽出で得られた有機相を合わせた。合わせた有機相を飽和食塩水(100mL)で洗浄し、硫酸マグネシウムを用いて乾燥し、ろ過し、ろ液を減圧下で濃縮して、粗物(淡黄色のオイル)を得た。粗物に酢酸エチル/n-ヘキサン混合溶液(1:7(体積比)、120mL)を加え、加熱還流させた後、0℃までゆっくりと冷却した。懸濁液をろ過し、得られた固体を減圧下で乾燥して、ビス(4-ホルミルフェニル)ジメチルシランを8.40g得た(収率:77%)。 [Example 21] Synthesis of dimethylbis(4-vinylphenyl)silane (C1-D-p-St-Si) <Synthesis of bis(4-formylphenyl)dimethylsilane>
A 500 mL four-necked flask was charged with 4-bromobenzaldehyde dimethylacetal (24.0 g, 102 mmol) and tetrahydrofuran (300 mL) under a nitrogen atmosphere. This solution was cooled to −65° C. or lower, and n-BuLi/n-hexane solution (2.6 mol/L, 39 mL, 100 mmol) was added dropwise thereto over 1 hour. Stirred for hours. Dichlorodimethylsilane (4.93 mL, 40.7 mmol) was added dropwise to the resulting reaction solution over 40 minutes, and the mixture was stirred at the same temperature as above for 2 hours. The flask was warmed to room temperature and stirred for 12 more hours. The reaction mixture was quenched with hydrochloric acid (2 mol/L, 120 mL), diethyl ether (100 mL) was added and extraction was performed to separate the organic phase. Furthermore, diethyl ether (100 mL) was added to the aqueous phase and extraction was performed twice to separate the organic phase. The organic phases from these extractions were combined. The combined organic phase was washed with saturated brine (100 mL), dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure to give a crude acetal/aldehyde mixture. Tetrahydrofuran (100 mL) and hydrochloric acid (2 mol/L, 100 mL) were added to the crude mixture, and the mixture was heated under reflux for 2 hours. After cooling to room temperature, saturated aqueous sodium hydrogencarbonate solution (240 mL) was added dropwise to the reaction solution. Diethyl ether (100 mL) was added to the reaction solution, and extraction was performed three times to separate the organic phase. The organic phases from these extractions were combined. The combined organic phase was washed with saturated brine (100 mL), dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure to give a crude material (pale yellow oil). A mixed solution of ethyl acetate/n-hexane (1:7 (volume ratio), 120 mL) was added to the crude product, heated to reflux, and then slowly cooled to 0°C. The suspension was filtered, and the obtained solid was dried under reduced pressure to obtain 8.40 g of bis(4-formylphenyl)dimethylsilane (yield: 77%).
1H-NMR(CDCl3):δ(ppm)10.03(s,2H,CHO),7.86(d,4H,J=7.68Hz,Ar-H),7.68(d,4H,J=8.54Hz,Ar-H),0.64(s,6H,Si-CH3).
1 H-NMR (CDCl 3 ): δ (ppm) 10.03 (s, 2H, CHO), 7.86 (d, 4H, J = 7.68 Hz, Ar-H), 7.68 (d, 4H , J=8.54 Hz, Ar—H), 0.64 (s, 6H, Si—CH 3 ).
<ジメチルビス(4-ビニルフェニル)シランの合成>
500mLの四ツ口フラスコに、窒素雰囲気下で、メチルトリフェニルホスホニウムブロミド(25.6g、71.7mmol)とテトラヒドロフラン(128mL)とを仕込んだ。フラスコを0℃に冷却し、懸濁液にカリウムtert-ブトキシド(9.03g、80.5mmol)を加えた。反応混合物を上記と同じ温度で5分以上攪拌した。反応混合物に、ビス(4-ホルミルフェニル)ジメチルシラン(8.00g、29.8mmol)のテトラヒドロフラン(128mL)溶液を20分かけて滴下した。フラスコを室温まで加温し、2時間攪拌した。反応混合物に4-tert-ブチルピロカテコール(0.60mg)を加えた後、30℃、減圧下で濃縮した。得られた混合物に水(200mL)とジエチルエーテル(200mL)とを加え、有機相を分離する抽出を行った。さらに、水相にジエチルエーテル(200mL)を加え、有機相を分離する抽出を行った。これら抽出で得られた有機相を合わせた。合わせた有機相を硫酸マグネシウムを用いて乾燥し、ろ過し、ろ液を減圧下で濃縮して、粗混合物を得た。粗混合物にn-ヘキサン(160mL)とジエチルエーテル(40mL)とを加え、30分間攪拌した。混合物をろ紙を用いてろ過し、ろ液を減圧下で濃縮して、粗物を得た。粗物をシリカゲルカラムクロマトグラフィー(移動相:n-ヘキサン)を用いて精製し、無色液体のジメチルビス(4-ビニルフェニル)シラン(C1-D-p-St-Si)を7.27g得た(収率:92%)。 <Synthesis of dimethylbis(4-vinylphenyl)silane>
A 500 mL four-necked flask was charged with methyltriphenylphosphonium bromide (25.6 g, 71.7 mmol) and tetrahydrofuran (128 mL) under a nitrogen atmosphere. The flask was cooled to 0° C. and potassium tert-butoxide (9.03 g, 80.5 mmol) was added to the suspension. The reaction mixture was stirred at the same temperature as above for 5 minutes longer. A solution of bis(4-formylphenyl)dimethylsilane (8.00 g, 29.8 mmol) in tetrahydrofuran (128 mL) was added dropwise to the reaction mixture over 20 minutes. The flask was warmed to room temperature and stirred for 2 hours. After adding 4-tert-butylpyrocatechol (0.60 mg) to the reaction mixture, the mixture was concentrated at 30° C. under reduced pressure. Water (200 mL) and diethyl ether (200 mL) were added to the resulting mixture and extraction was performed to separate the organic phase. Furthermore, diethyl ether (200 mL) was added to the aqueous phase, and extraction was performed to separate the organic phase. The organic phases from these extractions were combined. The combined organic phases were dried using magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure to give a crude mixture. n-Hexane (160 mL) and diethyl ether (40 mL) were added to the crude mixture and stirred for 30 minutes. The mixture was filtered using filter paper, and the filtrate was concentrated under reduced pressure to obtain a crude product. The crude product was purified using silica gel column chromatography (mobile phase: n-hexane) to obtain 7.27 g of colorless liquid dimethylbis(4-vinylphenyl)silane (C1-D-p-St-Si). (Yield: 92%).
500mLの四ツ口フラスコに、窒素雰囲気下で、メチルトリフェニルホスホニウムブロミド(25.6g、71.7mmol)とテトラヒドロフラン(128mL)とを仕込んだ。フラスコを0℃に冷却し、懸濁液にカリウムtert-ブトキシド(9.03g、80.5mmol)を加えた。反応混合物を上記と同じ温度で5分以上攪拌した。反応混合物に、ビス(4-ホルミルフェニル)ジメチルシラン(8.00g、29.8mmol)のテトラヒドロフラン(128mL)溶液を20分かけて滴下した。フラスコを室温まで加温し、2時間攪拌した。反応混合物に4-tert-ブチルピロカテコール(0.60mg)を加えた後、30℃、減圧下で濃縮した。得られた混合物に水(200mL)とジエチルエーテル(200mL)とを加え、有機相を分離する抽出を行った。さらに、水相にジエチルエーテル(200mL)を加え、有機相を分離する抽出を行った。これら抽出で得られた有機相を合わせた。合わせた有機相を硫酸マグネシウムを用いて乾燥し、ろ過し、ろ液を減圧下で濃縮して、粗混合物を得た。粗混合物にn-ヘキサン(160mL)とジエチルエーテル(40mL)とを加え、30分間攪拌した。混合物をろ紙を用いてろ過し、ろ液を減圧下で濃縮して、粗物を得た。粗物をシリカゲルカラムクロマトグラフィー(移動相:n-ヘキサン)を用いて精製し、無色液体のジメチルビス(4-ビニルフェニル)シラン(C1-D-p-St-Si)を7.27g得た(収率:92%)。 <Synthesis of dimethylbis(4-vinylphenyl)silane>
A 500 mL four-necked flask was charged with methyltriphenylphosphonium bromide (25.6 g, 71.7 mmol) and tetrahydrofuran (128 mL) under a nitrogen atmosphere. The flask was cooled to 0° C. and potassium tert-butoxide (9.03 g, 80.5 mmol) was added to the suspension. The reaction mixture was stirred at the same temperature as above for 5 minutes longer. A solution of bis(4-formylphenyl)dimethylsilane (8.00 g, 29.8 mmol) in tetrahydrofuran (128 mL) was added dropwise to the reaction mixture over 20 minutes. The flask was warmed to room temperature and stirred for 2 hours. After adding 4-tert-butylpyrocatechol (0.60 mg) to the reaction mixture, the mixture was concentrated at 30° C. under reduced pressure. Water (200 mL) and diethyl ether (200 mL) were added to the resulting mixture and extraction was performed to separate the organic phase. Furthermore, diethyl ether (200 mL) was added to the aqueous phase, and extraction was performed to separate the organic phase. The organic phases from these extractions were combined. The combined organic phases were dried using magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure to give a crude mixture. n-Hexane (160 mL) and diethyl ether (40 mL) were added to the crude mixture and stirred for 30 minutes. The mixture was filtered using filter paper, and the filtrate was concentrated under reduced pressure to obtain a crude product. The crude product was purified using silica gel column chromatography (mobile phase: n-hexane) to obtain 7.27 g of colorless liquid dimethylbis(4-vinylphenyl)silane (C1-D-p-St-Si). (Yield: 92%).
反応スキーム、NMR分析結果およびHRMS分析結果は、以下の通りである。
The reaction scheme, NMR analysis results and HRMS analysis results are as follows.
1H-NMR(CDCl3):δ(ppm)7.48(d,4H,J=8.54Hz,Ar-H),7.38(d,4H,J=7.68Hz,Ar-H),6.71(dd,2H,J=11.1,17.9Hz,-CH=CH2),5.77(d,2H,J=17.1Hz,-CH=CH2),5.25(d,2H,J=10.2Hz,-CH=CH2),0.54(s,6H,Si-CH3).
HRMS(EI):m/z Calcd for C18H20Si:(M+)264.133,found 264.131. 1 H-NMR (CDCl 3 ): δ (ppm) 7.48 (d, 4H, J = 8.54 Hz, Ar-H), 7.38 (d, 4H, J = 7.68 Hz, Ar-H) , 6.71 (dd, 2H, J=11.1, 17.9 Hz, -CH=CH 2 ), 5.77 (d, 2H, J=17.1 Hz, -CH=CH 2 ), 5.25 (d, 2H, J=10.2 Hz, -CH=CH 2 ), 0.54 (s, 6H, Si-CH 3 ).
HRMS (EI): m/z Calcd for C18H20Si : (M + ) 264.133 , found 264.131.
HRMS(EI):m/z Calcd for C18H20Si:(M+)264.133,found 264.131. 1 H-NMR (CDCl 3 ): δ (ppm) 7.48 (d, 4H, J = 8.54 Hz, Ar-H), 7.38 (d, 4H, J = 7.68 Hz, Ar-H) , 6.71 (dd, 2H, J=11.1, 17.9 Hz, -CH=CH 2 ), 5.77 (d, 2H, J=17.1 Hz, -CH=CH 2 ), 5.25 (d, 2H, J=10.2 Hz, -CH=CH 2 ), 0.54 (s, 6H, Si-CH 3 ).
HRMS (EI): m/z Calcd for C18H20Si : (M + ) 264.133 , found 264.131.
[例22]ドデシルトリス(4-ビニルフェニル)シラン(C12-T-p-St-Si)の合成
<ドデシルトリス(4-ホルミルフェニル)シランの合成>
500mLの四ツ口フラスコに、窒素雰囲気下で、4-ブロモベンズアルデヒドジメチルアセタール(24.0g、102mmol)とテトラヒドロフラン(300mL)とを仕込んだ。この溶液を-66℃以下に冷却し、これに、n-BuLi/n-ヘキサン溶液(2.6mol/L、39mL、100mmol)を1時間かけて滴下し、反応溶液を-70℃以下で2時間攪拌した。得られた反応溶液にドデシルトリクロロシラン(8.08mL、27.2mmol)を40分かけて滴下し、上記と同じ温度で2時間攪拌した。フラスコを室温まで加温し、12時間以上攪拌した。反応混合物を塩酸(2mol/L、120mL)でクエンチし、ジエチルエーテル(100mL)を加え、有機相を分離する抽出を行った。さらに、水相にジエチルエーテル(100mL)を加え、有機相を分離する抽出を行った。これら抽出で得られた有機相を合わせた。合わせた有機相を飽和食塩水(100mL)で洗浄し、硫酸マグネシウムを用いて乾燥し、ろ過し、ろ液を減圧下で濃縮して、粗物を得た。粗物をシリカゲルカラムクロマトグラフィー(移動相:クロロホルム/n-ヘキサン=1:1(体積比))を用いて精製し、無色液体のドデシルトリス(4-ホルミルフェニル)シランを9.53g得た(収率:68%)。 [Example 22] Synthesis of dodecyltris(4-vinylphenyl)silane (C12-T-p-St-Si) <Synthesis of dodecyltris(4-formylphenyl)silane>
A 500 mL four-necked flask was charged with 4-bromobenzaldehyde dimethylacetal (24.0 g, 102 mmol) and tetrahydrofuran (300 mL) under a nitrogen atmosphere. This solution was cooled to −66° C. or lower, and n-BuLi/n-hexane solution (2.6 mol/L, 39 mL, 100 mmol) was added dropwise thereto over 1 hour. Stirred for hours. Dodecyltrichlorosilane (8.08 mL, 27.2 mmol) was added dropwise to the resulting reaction solution over 40 minutes, and the mixture was stirred at the same temperature as above for 2 hours. The flask was warmed to room temperature and stirred for 12 more hours. The reaction mixture was quenched with hydrochloric acid (2 mol/L, 120 mL), diethyl ether (100 mL) was added and extraction was performed to separate the organic phase. Furthermore, diethyl ether (100 mL) was added to the aqueous phase, and extraction was performed to separate the organic phase. The organic phases from these extractions were combined. The combined organic phase was washed with saturated brine (100 mL), dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure to give crude material. The crude product was purified using silica gel column chromatography (mobile phase: chloroform/n-hexane=1:1 (volume ratio)) to obtain 9.53 g of colorless liquid dodecyltris(4-formylphenyl)silane ( Yield: 68%).
<ドデシルトリス(4-ホルミルフェニル)シランの合成>
500mLの四ツ口フラスコに、窒素雰囲気下で、4-ブロモベンズアルデヒドジメチルアセタール(24.0g、102mmol)とテトラヒドロフラン(300mL)とを仕込んだ。この溶液を-66℃以下に冷却し、これに、n-BuLi/n-ヘキサン溶液(2.6mol/L、39mL、100mmol)を1時間かけて滴下し、反応溶液を-70℃以下で2時間攪拌した。得られた反応溶液にドデシルトリクロロシラン(8.08mL、27.2mmol)を40分かけて滴下し、上記と同じ温度で2時間攪拌した。フラスコを室温まで加温し、12時間以上攪拌した。反応混合物を塩酸(2mol/L、120mL)でクエンチし、ジエチルエーテル(100mL)を加え、有機相を分離する抽出を行った。さらに、水相にジエチルエーテル(100mL)を加え、有機相を分離する抽出を行った。これら抽出で得られた有機相を合わせた。合わせた有機相を飽和食塩水(100mL)で洗浄し、硫酸マグネシウムを用いて乾燥し、ろ過し、ろ液を減圧下で濃縮して、粗物を得た。粗物をシリカゲルカラムクロマトグラフィー(移動相:クロロホルム/n-ヘキサン=1:1(体積比))を用いて精製し、無色液体のドデシルトリス(4-ホルミルフェニル)シランを9.53g得た(収率:68%)。 [Example 22] Synthesis of dodecyltris(4-vinylphenyl)silane (C12-T-p-St-Si) <Synthesis of dodecyltris(4-formylphenyl)silane>
A 500 mL four-necked flask was charged with 4-bromobenzaldehyde dimethylacetal (24.0 g, 102 mmol) and tetrahydrofuran (300 mL) under a nitrogen atmosphere. This solution was cooled to −66° C. or lower, and n-BuLi/n-hexane solution (2.6 mol/L, 39 mL, 100 mmol) was added dropwise thereto over 1 hour. Stirred for hours. Dodecyltrichlorosilane (8.08 mL, 27.2 mmol) was added dropwise to the resulting reaction solution over 40 minutes, and the mixture was stirred at the same temperature as above for 2 hours. The flask was warmed to room temperature and stirred for 12 more hours. The reaction mixture was quenched with hydrochloric acid (2 mol/L, 120 mL), diethyl ether (100 mL) was added and extraction was performed to separate the organic phase. Furthermore, diethyl ether (100 mL) was added to the aqueous phase, and extraction was performed to separate the organic phase. The organic phases from these extractions were combined. The combined organic phase was washed with saturated brine (100 mL), dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure to give crude material. The crude product was purified using silica gel column chromatography (mobile phase: chloroform/n-hexane=1:1 (volume ratio)) to obtain 9.53 g of colorless liquid dodecyltris(4-formylphenyl)silane ( Yield: 68%).
1H-NMR(CDCl3):δ(ppm)10.06(s,3H,CHO),7.89(d,6H,J=8.54Hz,Ar-H),7.67(d,6H,J=8.54Hz,Ar-H),1.47~1.39(m,6H,-CH2-),1.23(brs,16H,-CH2-),0.87(t,3H,J=6.83 Hz,Si-CH3).
1 H-NMR (CDCl 3 ): δ (ppm) 10.06 (s, 3H, CHO), 7.89 (d, 6H, J = 8.54 Hz, Ar-H), 7.67 (d, 6H , J=8.54 Hz, Ar-H), 1.47-1.39 (m, 6H, -CH 2 -), 1.23 (brs, 16H, -CH 2 -), 0.87 (t, 3H, J=6.83 Hz, Si—CH 3 ).
<ドデシルトリス(4-ビニルフェニル)シランの合成>
500mLの四ツ口フラスコに、窒素雰囲気下で、メチルトリフェニルホスホニウムブロミド(21.3g、59.6mmol)とテトラヒドロフラン(136mL)とを仕込んだ。フラスコを0℃に冷却し、懸濁液にカリウムtert-ブトキシド(7.53g、67.1mmol)を加えた。反応混合物を上記と同じ温度で5分以上攪拌した。反応混合物に、ドデシルトリス(4-ホルミルフェニル)シラン(8.50g、16.6mmol)のテトラヒドロフラン(136mL)溶液を20分かけて滴下した。フラスコを室温まで加温し、1時間攪拌した。反応混合物に4-tert-ブチルピロカテコール(2.55mg)を加えた後、30℃、減圧下で濃縮した。得られた混合物に水(200mL)とジエチルエーテル(200mL)とを加え、有機相を分離する抽出を行った。さらに、水相にジエチルエーテル(200mL)を加え、有機相を分離する抽出を行った。これら抽出で得られた有機相を合わせた。合わせた有機相を硫酸マグネシウムを用いて乾燥し、ろ過し、ろ液を減圧下で濃縮して、粗混合物を得た。粗混合物にn-ヘキサン(160mL)とジエチルエーテル(40mL)とを加え、30分間攪拌した。混合物をろ紙を用いてろ過し、ろ液を減圧下で濃縮して、粗物(黄色のオイル)を得た。粗物をシリカゲルカラムクロマトグラフィー(移動相:n-ヘキサン)を用いて精製し、淡黄色液体のドデシルトリス(4-ビニルフェニル)シラン(C12-T-p-St-Si)を4.73g得た(収率:56%)。 <Synthesis of dodecyltris(4-vinylphenyl)silane>
A 500 mL four-necked flask was charged with methyltriphenylphosphonium bromide (21.3 g, 59.6 mmol) and tetrahydrofuran (136 mL) under a nitrogen atmosphere. The flask was cooled to 0° C. and potassium tert-butoxide (7.53 g, 67.1 mmol) was added to the suspension. The reaction mixture was stirred at the same temperature as above for 5 minutes longer. A solution of dodecyltris(4-formylphenyl)silane (8.50 g, 16.6 mmol) in tetrahydrofuran (136 mL) was added dropwise to the reaction mixture over 20 minutes. The flask was warmed to room temperature and stirred for 1 hour. After adding 4-tert-butylpyrocatechol (2.55 mg) to the reaction mixture, it was concentrated at 30° C. under reduced pressure. Water (200 mL) and diethyl ether (200 mL) were added to the resulting mixture and extraction was performed to separate the organic phase. Furthermore, diethyl ether (200 mL) was added to the aqueous phase, and extraction was performed to separate the organic phase. The organic phases from these extractions were combined. The combined organic phases were dried using magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure to give a crude mixture. n-Hexane (160 mL) and diethyl ether (40 mL) were added to the crude mixture and stirred for 30 minutes. The mixture was filtered using filter paper and the filtrate was concentrated under reduced pressure to give a crude product (yellow oil). The crude product was purified using silica gel column chromatography (mobile phase: n-hexane) to obtain 4.73 g of pale yellow liquid dodecyltris(4-vinylphenyl)silane (C12-Tp-St-Si). (Yield: 56%).
500mLの四ツ口フラスコに、窒素雰囲気下で、メチルトリフェニルホスホニウムブロミド(21.3g、59.6mmol)とテトラヒドロフラン(136mL)とを仕込んだ。フラスコを0℃に冷却し、懸濁液にカリウムtert-ブトキシド(7.53g、67.1mmol)を加えた。反応混合物を上記と同じ温度で5分以上攪拌した。反応混合物に、ドデシルトリス(4-ホルミルフェニル)シラン(8.50g、16.6mmol)のテトラヒドロフラン(136mL)溶液を20分かけて滴下した。フラスコを室温まで加温し、1時間攪拌した。反応混合物に4-tert-ブチルピロカテコール(2.55mg)を加えた後、30℃、減圧下で濃縮した。得られた混合物に水(200mL)とジエチルエーテル(200mL)とを加え、有機相を分離する抽出を行った。さらに、水相にジエチルエーテル(200mL)を加え、有機相を分離する抽出を行った。これら抽出で得られた有機相を合わせた。合わせた有機相を硫酸マグネシウムを用いて乾燥し、ろ過し、ろ液を減圧下で濃縮して、粗混合物を得た。粗混合物にn-ヘキサン(160mL)とジエチルエーテル(40mL)とを加え、30分間攪拌した。混合物をろ紙を用いてろ過し、ろ液を減圧下で濃縮して、粗物(黄色のオイル)を得た。粗物をシリカゲルカラムクロマトグラフィー(移動相:n-ヘキサン)を用いて精製し、淡黄色液体のドデシルトリス(4-ビニルフェニル)シラン(C12-T-p-St-Si)を4.73g得た(収率:56%)。 <Synthesis of dodecyltris(4-vinylphenyl)silane>
A 500 mL four-necked flask was charged with methyltriphenylphosphonium bromide (21.3 g, 59.6 mmol) and tetrahydrofuran (136 mL) under a nitrogen atmosphere. The flask was cooled to 0° C. and potassium tert-butoxide (7.53 g, 67.1 mmol) was added to the suspension. The reaction mixture was stirred at the same temperature as above for 5 minutes longer. A solution of dodecyltris(4-formylphenyl)silane (8.50 g, 16.6 mmol) in tetrahydrofuran (136 mL) was added dropwise to the reaction mixture over 20 minutes. The flask was warmed to room temperature and stirred for 1 hour. After adding 4-tert-butylpyrocatechol (2.55 mg) to the reaction mixture, it was concentrated at 30° C. under reduced pressure. Water (200 mL) and diethyl ether (200 mL) were added to the resulting mixture and extraction was performed to separate the organic phase. Furthermore, diethyl ether (200 mL) was added to the aqueous phase, and extraction was performed to separate the organic phase. The organic phases from these extractions were combined. The combined organic phases were dried using magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure to give a crude mixture. n-Hexane (160 mL) and diethyl ether (40 mL) were added to the crude mixture and stirred for 30 minutes. The mixture was filtered using filter paper and the filtrate was concentrated under reduced pressure to give a crude product (yellow oil). The crude product was purified using silica gel column chromatography (mobile phase: n-hexane) to obtain 4.73 g of pale yellow liquid dodecyltris(4-vinylphenyl)silane (C12-Tp-St-Si). (Yield: 56%).
反応スキーム、NMR分析結果およびHRMS分析結果は、以下の通りである。
The reaction scheme, NMR analysis results and HRMS analysis results are as follows.
1H-NMR(CDCl3):δ(ppm)7.47(d,6H,J=7.68Hz,Ar-H),7.39(d,6H,J=8.54Hz,Ar-H),6.72(dd,3H,J=10.7,17.5Hz,-CH=CH2),5.79(d,3H,J=17.9Hz,-CH=CH2),5.27(d,3H,J=11.1Hz,-CH=CH2),1.49~1.22(m,22H,-CH2-),0.86(t,3H,J=6.40Hz,CH3).
HRMS(EI):m/z Calcd for C36H46Si:(M+)506.337,found 506.331. 1 H-NMR (CDCl 3 ): δ (ppm) 7.47 (d, 6H, J = 7.68 Hz, Ar-H), 7.39 (d, 6H, J = 8.54 Hz, Ar-H) , 6.72 (dd, 3H, J=10.7, 17.5 Hz, —CH=CH 2 ), 5.79 (d, 3H, J=17.9 Hz, —CH=CH 2 ), 5.27 (d, 3H, J=11.1 Hz, -CH=CH 2 ), 1.49 to 1.22 (m, 22H, -CH 2 -), 0.86 (t, 3H, J=6.40 Hz, CH3 ).
HRMS (EI): m/z Calcd for C36H46Si : (M + ) 506.337 , found 506.331.
HRMS(EI):m/z Calcd for C36H46Si:(M+)506.337,found 506.331. 1 H-NMR (CDCl 3 ): δ (ppm) 7.47 (d, 6H, J = 7.68 Hz, Ar-H), 7.39 (d, 6H, J = 8.54 Hz, Ar-H) , 6.72 (dd, 3H, J=10.7, 17.5 Hz, —CH=CH 2 ), 5.79 (d, 3H, J=17.9 Hz, —CH=CH 2 ), 5.27 (d, 3H, J=11.1 Hz, -CH=CH 2 ), 1.49 to 1.22 (m, 22H, -CH 2 -), 0.86 (t, 3H, J=6.40 Hz, CH3 ).
HRMS (EI): m/z Calcd for C36H46Si : (M + ) 506.337 , found 506.331.
[例31]
比較用の有機ケイ素化合物として、市販のシランカップリング剤であるトリメトキシビニルシラン(TMVS、TCI社商品)を用意した。 [Example 31]
As a comparative organosilicon compound, a commercially available silane coupling agent, trimethoxyvinylsilane (TMVS, product of TCI) was prepared.
比較用の有機ケイ素化合物として、市販のシランカップリング剤であるトリメトキシビニルシラン(TMVS、TCI社商品)を用意した。 [Example 31]
As a comparative organosilicon compound, a commercially available silane coupling agent, trimethoxyvinylsilane (TMVS, product of TCI) was prepared.
[例32]
比較用の有機ケイ素化合物として、市販のシランカップリング剤であるトリエトキシビニルシラン(TEVS、TCI社商品)を用意した。 [Example 32]
As a comparative organosilicon compound, a commercially available silane coupling agent, triethoxyvinylsilane (TEVS, product of TCI) was prepared.
比較用の有機ケイ素化合物として、市販のシランカップリング剤であるトリエトキシビニルシラン(TEVS、TCI社商品)を用意した。 [Example 32]
As a comparative organosilicon compound, a commercially available silane coupling agent, triethoxyvinylsilane (TEVS, product of TCI) was prepared.
[評価と結果]
例1、2、21、22、31、32において、得られたまたは用意した有機ケイ素化合物を用い、上記の[評価用サンプル(フィルム状硬化物)の作製方法]に従って評価用サンプルを作製し、評価した。評価結果を表1~表3に示す。 [Evaluation and results]
Using the organosilicon compound obtained or prepared in Examples 1, 2, 21, 22, 31, and 32, an evaluation sample was prepared according to the above [Method for preparing evaluation sample (film-like cured product)], evaluated. Evaluation results are shown in Tables 1 to 3.
例1、2、21、22、31、32において、得られたまたは用意した有機ケイ素化合物を用い、上記の[評価用サンプル(フィルム状硬化物)の作製方法]に従って評価用サンプルを作製し、評価した。評価結果を表1~表3に示す。 [Evaluation and results]
Using the organosilicon compound obtained or prepared in Examples 1, 2, 21, 22, 31, and 32, an evaluation sample was prepared according to the above [Method for preparing evaluation sample (film-like cured product)], evaluated. Evaluation results are shown in Tables 1 to 3.
[結果のまとめ]
例1、2では、架橋剤としてベンゼン環上のビニル基の置換位置がメタ位である有機ケイ素化合物(式(1m)で表される有機ケイ素化合物)を用いて、フィルム状硬化物を得た。
例21、22では、架橋剤としてベンゼン環上のビニル基の置換位置がパラ位である比較用の有機ケイ素化合物を用いて、フィルム状硬化物を得た。
例31、32では、比較用の有機ケイ素化合物であるシランカップリング剤を用いて、フィルム状硬化物を得た。
例1、2、21、22では、シランカップリング剤を用いた例31、32に対して、高周波条件における誘電正接(Df)を効果的に低減できた。
例1と例21との比較、および、例2と例22との比較から、架橋剤として、ベンゼン環上のビニル基の置換位置がメタ位である有機ケイ素化合物を用いることで、高周波条件における誘電正接(Df)をより効果的に低減できることが分かった。
例1、2では、高周波条件における誘電正接(Df)が効果的に低減され、熱膨張係数(CTE)が充分に低く、ガラス転移温度(Tg)が充分に高いフィルム状硬化物を得ることができた。 [Summary of results]
In Examples 1 and 2, an organosilicon compound (an organosilicon compound represented by formula (1m)) in which the vinyl group on the benzene ring is substituted at the meta position was used as a cross-linking agent to obtain a cured film. .
In Examples 21 and 22, a film-like cured product was obtained using a comparative organosilicon compound in which the vinyl group on the benzene ring was substituted at the para-position as a cross-linking agent.
In Examples 31 and 32, a film-like cured product was obtained using a silane coupling agent which is an organosilicon compound for comparison.
In Examples 1, 2, 21 and 22, the dielectric loss tangent (D f ) under high frequency conditions could be effectively reduced compared to Examples 31 and 32 using the silane coupling agent.
From a comparison between Examples 1 and 21 and between Examples 2 and 22, by using an organosilicon compound in which the vinyl group on the benzene ring is substituted at the meta position as the cross-linking agent, under high frequency conditions, It has been found that the dissipation factor (D f ) can be reduced more effectively.
In Examples 1 and 2, the dielectric loss tangent (D f ) under high frequency conditions is effectively reduced, the coefficient of thermal expansion (CTE) is sufficiently low, and the glass transition temperature (Tg) is sufficiently high to obtain a film-like cured product. was made.
例1、2では、架橋剤としてベンゼン環上のビニル基の置換位置がメタ位である有機ケイ素化合物(式(1m)で表される有機ケイ素化合物)を用いて、フィルム状硬化物を得た。
例21、22では、架橋剤としてベンゼン環上のビニル基の置換位置がパラ位である比較用の有機ケイ素化合物を用いて、フィルム状硬化物を得た。
例31、32では、比較用の有機ケイ素化合物であるシランカップリング剤を用いて、フィルム状硬化物を得た。
例1、2、21、22では、シランカップリング剤を用いた例31、32に対して、高周波条件における誘電正接(Df)を効果的に低減できた。
例1と例21との比較、および、例2と例22との比較から、架橋剤として、ベンゼン環上のビニル基の置換位置がメタ位である有機ケイ素化合物を用いることで、高周波条件における誘電正接(Df)をより効果的に低減できることが分かった。
例1、2では、高周波条件における誘電正接(Df)が効果的に低減され、熱膨張係数(CTE)が充分に低く、ガラス転移温度(Tg)が充分に高いフィルム状硬化物を得ることができた。 [Summary of results]
In Examples 1 and 2, an organosilicon compound (an organosilicon compound represented by formula (1m)) in which the vinyl group on the benzene ring is substituted at the meta position was used as a cross-linking agent to obtain a cured film. .
In Examples 21 and 22, a film-like cured product was obtained using a comparative organosilicon compound in which the vinyl group on the benzene ring was substituted at the para-position as a cross-linking agent.
In Examples 31 and 32, a film-like cured product was obtained using a silane coupling agent which is an organosilicon compound for comparison.
In Examples 1, 2, 21 and 22, the dielectric loss tangent (D f ) under high frequency conditions could be effectively reduced compared to Examples 31 and 32 using the silane coupling agent.
From a comparison between Examples 1 and 21 and between Examples 2 and 22, by using an organosilicon compound in which the vinyl group on the benzene ring is substituted at the meta position as the cross-linking agent, under high frequency conditions, It has been found that the dissipation factor (D f ) can be reduced more effectively.
In Examples 1 and 2, the dielectric loss tangent (D f ) under high frequency conditions is effectively reduced, the coefficient of thermal expansion (CTE) is sufficiently low, and the glass transition temperature (Tg) is sufficiently high to obtain a film-like cured product. was made.
[例101]
2官能クロロメチルスチレン変性PPE(OPE-2st)と、例1で合成した有機ケイ素化合物と、ラジカル重合開始剤としてのジクミルパーオキサイドと、無機充填材としての球状シリカと、トルエンとを、質量比7:3:0.1:10:10で混合し、室温で攪拌して、硬化性組成物(ワニス)を調製した。
得られた硬化性組成物(ワニス)を繊維基材としてのガラスクロス(Eガラス、#2116)に含浸させた後、130℃で5分間加熱して、硬化性組成物を半硬化させて、プリプレグを得た。
得られたプリプレグを2枚重ね、これらを一対の銅箔で挟み、得られた仮積層体を、200℃、1.5時間、3MPaの条件で加熱加圧して、金属張積層板を作製した。 [Example 101]
Bifunctional chloromethylstyrene-modified PPE (OPE-2st), the organosilicon compound synthesized in Example 1, dicumyl peroxide as a radical polymerization initiator, spherical silica as an inorganic filler, and toluene were A curable composition (varnish) was prepared by mixing at a ratio of 7:3:0.1:10:10 and stirring at room temperature.
After impregnating a glass cloth (E glass, #2116) as a fiber base material with the obtained curable composition (varnish), the curable composition is semi-cured by heating at 130 ° C. for 5 minutes, Got the prepreg.
Two sheets of the obtained prepreg were laminated, sandwiched between a pair of copper foils, and the resulting temporary laminate was heated and pressed under conditions of 200° C., 1.5 hours, and 3 MPa to produce a metal-clad laminate. .
2官能クロロメチルスチレン変性PPE(OPE-2st)と、例1で合成した有機ケイ素化合物と、ラジカル重合開始剤としてのジクミルパーオキサイドと、無機充填材としての球状シリカと、トルエンとを、質量比7:3:0.1:10:10で混合し、室温で攪拌して、硬化性組成物(ワニス)を調製した。
得られた硬化性組成物(ワニス)を繊維基材としてのガラスクロス(Eガラス、#2116)に含浸させた後、130℃で5分間加熱して、硬化性組成物を半硬化させて、プリプレグを得た。
得られたプリプレグを2枚重ね、これらを一対の銅箔で挟み、得られた仮積層体を、200℃、1.5時間、3MPaの条件で加熱加圧して、金属張積層板を作製した。 [Example 101]
Bifunctional chloromethylstyrene-modified PPE (OPE-2st), the organosilicon compound synthesized in Example 1, dicumyl peroxide as a radical polymerization initiator, spherical silica as an inorganic filler, and toluene were A curable composition (varnish) was prepared by mixing at a ratio of 7:3:0.1:10:10 and stirring at room temperature.
After impregnating a glass cloth (E glass, #2116) as a fiber base material with the obtained curable composition (varnish), the curable composition is semi-cured by heating at 130 ° C. for 5 minutes, Got the prepreg.
Two sheets of the obtained prepreg were laminated, sandwiched between a pair of copper foils, and the resulting temporary laminate was heated and pressed under conditions of 200° C., 1.5 hours, and 3 MPa to produce a metal-clad laminate. .
本発明は上記実施形態及び実施例に限定されるものではなく、本発明の趣旨を逸脱しない限りにおいて、適宜設計変更できる。
The present invention is not limited to the above embodiments and examples, and design modifications can be made as appropriate without departing from the gist of the present invention.
この出願は、2021年6月4日に出願された日本出願特願2021-094309号を基礎とする優先権を主張し、その開示の全てをここに取り込む。
This application claims priority based on Japanese Patent Application No. 2021-094309 filed on June 4, 2021, and the entire disclosure thereof is incorporated herein.
1、2:金属張積層板、3:配線基板、11:コンポジット基材、12:金属箔、22:導体パターン(回路パターン)、22W:配線。
1, 2: Metal-clad laminate, 3: Wiring board, 11: Composite base material, 12: Metal foil, 22: Conductor pattern (circuit pattern), 22W: Wiring.
Claims (14)
- 下式(1m)で表される有機ケイ素化合物。
- Rは、置換基を有していてもよい炭素数1~18のアルキル基である、請求項1に記載の有機ケイ素化合物。 The organosilicon compound according to claim 1, wherein R is an optionally substituted alkyl group having 1 to 18 carbon atoms.
- Mは、単結合または炭素数1~4のアルキレン基である、請求項1または2に記載の有機ケイ素化合物。 The organosilicon compound according to claim 1 or 2, wherein M is a single bond or an alkylene group having 1 to 4 carbon atoms.
- 下式(1m)で表される架橋剤。
- Rは、置換基を有していてもよい炭素数1~18のアルキル基である、請求項4に記載の架橋剤。 The cross-linking agent according to claim 4, wherein R is an optionally substituted alkyl group having 1 to 18 carbon atoms.
- Mは、単結合または炭素数1~4のアルキレン基である、請求項4または5に記載の架橋剤。 The cross-linking agent according to claim 4 or 5, wherein M is a single bond or an alkylene group having 1 to 4 carbon atoms.
- プリプレグ、金属張積層板または配線基板の製造に用いられる硬化性組成物用である、請求項4~6のいずれか1項に記載の架橋剤。 The cross-linking agent according to any one of claims 4 to 6, which is used for curable compositions used in the production of prepregs, metal-clad laminates or wiring boards.
- 請求項4~7のいずれか1項に記載の架橋剤と、当該架橋剤と架橋し得る2つ以上の架橋性官能基を有する硬化性化合物とを含む、硬化性組成物。 A curable composition comprising the cross-linking agent according to any one of claims 4 to 7 and a curable compound having two or more cross-linkable functional groups capable of cross-linking with the cross-linking agent.
- 繊維基材と、請求項8に記載の硬化性組成物の半硬化物または硬化物とを含む、プリプレグ。 A prepreg comprising a fiber base material and a semi-cured or cured product of the curable composition according to claim 8.
- 基材と、請求項8に記載の硬化性組成物からなる硬化性組成物層とを含む、積層体。 A laminate comprising a substrate and a curable composition layer made of the curable composition according to claim 8.
- 基材と、請求項8に記載の硬化性組成物の半硬化物または硬化物を含む(半)硬化物含有層とを含む、積層体。 A laminate comprising a substrate and a semi-cured product of the curable composition according to claim 8 or a (semi-)cured product-containing layer containing the cured product.
- 前記基材が樹脂フィルムまたは金属箔である、請求項10または11に記載の積層体。 The laminate according to claim 10 or 11, wherein the base material is a resin film or a metal foil.
- 請求項8に記載の硬化性組成物の硬化物を含む絶縁層と、金属箔とを含む、金属張積層板。 A metal-clad laminate comprising an insulating layer containing the cured product of the curable composition according to claim 8 and a metal foil.
- 請求項8に記載の硬化性組成物の硬化物を含む絶縁層と、配線とを含む、配線基板。 A wiring substrate comprising an insulating layer containing the cured product of the curable composition according to claim 8 and wiring.
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JP2004259899A (en) * | 2003-02-25 | 2004-09-16 | Matsushita Electric Works Ltd | Printed circuit board, resin composition therefor, and multilayer printed circuit board |
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2022
- 2022-03-24 WO PCT/JP2022/013929 patent/WO2022254901A1/en active Application Filing
- 2022-04-27 TW TW111115961A patent/TW202313636A/en unknown
Patent Citations (1)
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JP2004259899A (en) * | 2003-02-25 | 2004-09-16 | Matsushita Electric Works Ltd | Printed circuit board, resin composition therefor, and multilayer printed circuit board |
Non-Patent Citations (1)
Title |
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STÖVER H. D. H., FRÉCHET J. M. J.: "NMR characterization of cross-linked polystyrene gels", MACROMOLECULES, AMERICAN CHEMICAL SOCIETY, US, vol. 24, no. 4, 1 January 1991 (1991-01-01), US , pages 883 - 888, XP093009855, ISSN: 0024-9297, DOI: 10.1021/ma00004a012 * |
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