JP2020132764A - Polyphenylene ether-containing resin composition - Google Patents
Polyphenylene ether-containing resin composition Download PDFInfo
- Publication number
- JP2020132764A JP2020132764A JP2019028391A JP2019028391A JP2020132764A JP 2020132764 A JP2020132764 A JP 2020132764A JP 2019028391 A JP2019028391 A JP 2019028391A JP 2019028391 A JP2019028391 A JP 2019028391A JP 2020132764 A JP2020132764 A JP 2020132764A
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- JP
- Japan
- Prior art keywords
- group
- resin composition
- mass
- methyl
- polyphenylene ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001955 polyphenylene ether Polymers 0.000 title claims abstract description 99
- 239000011342 resin composition Substances 0.000 title claims abstract description 91
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000011347 resin Substances 0.000 claims abstract description 25
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 23
- -1 vinyl aromatic compound Chemical class 0.000 claims description 260
- 239000004744 fabric Substances 0.000 claims description 21
- 229920005992 thermoplastic resin Polymers 0.000 claims description 21
- 239000003063 flame retardant Substances 0.000 claims description 18
- 239000011521 glass Substances 0.000 claims description 18
- 125000001424 substituent group Chemical group 0.000 claims description 18
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 17
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 16
- 239000011888 foil Substances 0.000 claims description 16
- 229920001400 block copolymer Polymers 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 229920002554 vinyl polymer Polymers 0.000 claims description 13
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 11
- 125000005647 linker group Chemical group 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 9
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 6
- 239000005062 Polybutadiene Substances 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 229920002857 polybutadiene Polymers 0.000 claims description 6
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 4
- 239000004971 Cross linker Substances 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- 229910052727 yttrium Inorganic materials 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 150000002430 hydrocarbons Chemical group 0.000 description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 20
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 239000002966 varnish Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 12
- 125000000524 functional group Chemical group 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 9
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 9
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 9
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 239000004793 Polystyrene Substances 0.000 description 8
- 239000000945 filler Substances 0.000 description 8
- 229920002223 polystyrene Polymers 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 5
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 description 4
- 125000005838 1,3-cyclopentylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:2])C([H])([H])C1([H])[*:1] 0.000 description 4
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 description 4
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 4
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical group C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000005395 methacrylic acid group Chemical group 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- CTPYJEXTTINDEM-UHFFFAOYSA-N 1,2-bis(1-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOCC(C)C1=CC=CC=C1C(C)COOC(C)(C)C CTPYJEXTTINDEM-UHFFFAOYSA-N 0.000 description 3
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 3
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 3
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 2
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000006219 1-ethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000005916 2-methylpentyl group Chemical group 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 2
- 125000004337 3-ethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003469 3-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 238000004925 denaturation Methods 0.000 description 2
- 230000036425 denaturation Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000006166 lysate Substances 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 125000005641 methacryl group Chemical group 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 1
- NLBJAOHLJABDAU-UHFFFAOYSA-N (3-methylbenzoyl) 3-methylbenzenecarboperoxoate Chemical compound CC1=CC=CC(C(=O)OOC(=O)C=2C=C(C)C=CC=2)=C1 NLBJAOHLJABDAU-UHFFFAOYSA-N 0.000 description 1
- CCNDOQHYOIISTA-UHFFFAOYSA-N 1,2-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1C(C)(C)OOC(C)(C)C CCNDOQHYOIISTA-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
Description
本発明は、ポリフェニレンエーテル含有樹脂組成物等に関する。 The present invention relates to a polyphenylene ether-containing resin composition and the like.
近年、情報ネットワーク技術の著しい進歩、又は情報ネットワークを活用したサービスの拡大に伴い、電子機器には情報量の大容量化及び処理速度の高速化が求められている。これらの要求に応えるために、プリント配線板等の基板用材料には、従来から求められていた難燃性、耐熱性、銅箔とのピール強度等の特性に加え、低誘電率化・低誘電正接化が求められている。このため、プリント配線板等の基板用材料に用いられる樹脂組成物の更なる改良が検討されている。 In recent years, with the remarkable progress of information network technology or the expansion of services utilizing information networks, electronic devices are required to have a large amount of information and a high processing speed. In order to meet these demands, substrate materials such as printed wiring boards have low dielectric constant and low dielectric constant in addition to the characteristics such as flame retardancy, heat resistance, and peel strength with copper foil that have been conventionally required. Dielectric loss tangent is required. Therefore, further improvement of the resin composition used for the material for the substrate such as the printed wiring board is being studied.
基板用材料の中でも、ポリフェニレンエーテル（ＰＰＥ）が、比較的低い誘電率及び比較的低い誘電正接を有するため、上述した要求に応えられるプリント配線板用材料として好適である。例えば、特許文献１に記載のポリフェニレンエーテル含有樹脂組成物は、ポリフェニレンエーテル１分子当たりの平均フェノール性水酸基数を特定の範囲内に制御したり、互いに分子量の異なる複数のポリフェニレンエーテルの含有量を特定したりすることによって、成形性、耐熱性、接着性及び電気特性の改良を図るものである。 Among the materials for substrates, polyphenylene ether (PPE) has a relatively low dielectric constant and a relatively low dielectric loss tangent, and is therefore suitable as a material for printed wiring boards that can meet the above-mentioned requirements. For example, the polyphenylene ether-containing resin composition described in Patent Document 1 controls the average number of phenolic hydroxyl groups per molecule of polyphenylene ether within a specific range, and specifies the content of a plurality of polyphenylene ethers having different molecular weights from each other. By doing so, the moldability, heat resistance, adhesiveness and electrical properties are improved.
特許文献１に記載のポリフェニレンエーテル含有樹脂組成物には、電気特性について、例えば誘電率及び誘電正接の低減について、未だに検討の余地がある。 The polyphenylene ether-containing resin composition described in Patent Document 1 still has room for study on electrical properties, for example, reduction of dielectric constant and dielectric loss tangent.
したがって、本発明は、電気特性に優れるポリフェニレンエーテル含有樹脂組成物、並びにそれを用いて形成された電子回路基板材料、樹脂フィルム、プリプレグ及び積層体を提供することを目的とする。 Therefore, an object of the present invention is to provide a polyphenylene ether-containing resin composition having excellent electrical properties, and an electronic circuit substrate material, a resin film, a prepreg, and a laminate formed by using the polyphenylene ether-containing resin composition.
本発明者らは、上記課題を解決すべく鋭意研究を重ねた結果、ポリフェニレンエーテル、架橋剤、及び有機過酸化物を含む樹脂組成物においてポリフェニレンエーテルの構造及び分子量を特定することによって、樹脂組成物の硬化物の電気特性を向上させられることを見出し、本発明の完成に至った。すなわち、本発明は、以下のとおりである。
［１］
（ａ）下記式（１）：
Ｘは、ａ価の任意の連結基であり、ａは２．５以上の数であり、
Ｒ５は、各々独立に任意の置換基であり、ｋは各々独立に１〜４の整数であり、ｋ個あるＲ５のうちの少なくとも１つは、下記式（２）：
で表される部分構造を含み、
Ｙは、各々独立に下記式（３）：
で表される構造を有する２価の連結基であり、ｎはＹの繰り返し数を表し、各々独立に１〜２００の整数であり、
Ｌは、任意の２価の連結基、又は単結合であり、かつ
Ａは、各々独立に、炭素−炭素二重結合及び／又はエポキシ結合を含有する置換基を示す｝
で表される構造を有し、かつ数平均分子量が５００〜８，０００であるポリフェニレンエーテル成分Ａ；
（ｂ）架橋剤；及び
（ｃ）有機過酸化物；
を含む樹脂組成物。
［２］
前記架橋剤が、炭素−炭素不飽和二重結合を１分子中に平均２個以上有し、前記架橋剤の数平均分子量が４，０００以下であり、かつ前記ポリフェニレンエーテル成分Ａ：前記架橋剤の重量比が、２５：７５〜９５：５である、項目１に記載の樹脂組成物。
［３］
前記架橋剤が、トリアリルシアヌレート、トリアリルイソシアヌレート、及びポリブタジエンから成る群より選択される少なくとも一種の化合物を含む、項目１又は２に記載の樹脂組成物。
［４］
前記有機過酸化物の１分間半減期温度が、１５５℃〜１８５℃である、項目１〜３のいずれか１項に記載の樹脂組成物。
［５］
前記有機過酸化物の含有量が、前記ポリフェニレンエーテル成分Ａと前記架橋剤の合計質量１００質量部を基準として、０．０５質量部〜５質量部である、項目１〜４のいずれか１項に記載の樹脂組成物。
［６］
前記樹脂組成物が、熱可塑性樹脂をさらに含み、前記熱可塑性樹脂が、ビニル芳香族化合物とオレフィン系アルケン化合物とのブロック共重合体及びその水素添加物、並びにビニル芳香族化合物の単独重合体から成る群より選択される少なくとも１種であり、かつ前記ブロック共重合体又はその水素添加物の前記ビニル芳香族化合物由来の単位の含有率が２０質量％以上である、項目１〜５のいずれか１項に記載の樹脂組成物。
［７］
前記熱可塑性樹脂の重量平均分子量が、１０，０００〜３００，０００である、項目６に記載の樹脂組成物。
［８］
前記熱可塑性樹脂の含有量が、前記ポリフェニレンエーテル成分Ａ及び前記架橋剤の合計質量１００質量部を基準として、２質量部〜２０質量部である、項目６又は７に記載の樹脂組成物。
［９］
前記樹脂組成物が、難燃剤をさらに含み、かつ前記難燃剤が、前記樹脂組成物の硬化後に前記樹脂組成物中で他の含有成分と相溶しない、項目１〜８のいずれか１項に記載の樹脂組成物。
［１０］
項目１〜９のいずれか１項に記載の樹脂組成物を含む、電子回路基板材料。
［１１］
項目１〜９のいずれか１項に記載の樹脂組成物を含む、樹脂フィルム。
［１２］
基材と、項目１〜９のいずれか１項に記載の樹脂組成物との複合体である、プリプレグ。
［１３］
前記基材がガラスクロスである、項目１２に記載のプリプレグ。
［１４］
項目１１に記載の樹脂フィルム、又は項目１２若しくは１３に記載のプリプレグの硬化物と、金属箔との積層体。
As a result of intensive studies to solve the above problems, the present inventors have identified the structure and molecular weight of the polyphenylene ether in the resin composition containing the polyphenylene ether, a cross-linking agent, and an organic peroxide to determine the resin composition. We have found that the electrical properties of a cured product can be improved, and have completed the present invention. That is, the present invention is as follows.
[1]
(A) The following formula (1):
X is an arbitrary linking group of a value, and a is a number of 2.5 or more.
R 5 is any substituent independently, k are each independently 1 to 4 integer, at least one of the k is R 5 is represented by the following formula (2):
Including the partial structure represented by
Y is independently expressed by the following equation (3):
It is a divalent linking group having a structure represented by, n represents the number of repetitions of Y, and each is an integer of 1 to 200 independently.
L is an arbitrary divalent linking group or a single bond, and A is a substituent containing a carbon-carbon double bond and / or an epoxy bond, respectively}.
Polyphenylene ether component A having a structure represented by and having a number average molecular weight of 500 to 8,000;
(B) Crosslinker; and (c) Organic peroxide;
Resin composition containing.
[2]
The cross-linking agent has an average of two or more carbon-carbon unsaturated double bonds in one molecule, the number average molecular weight of the cross-linking agent is 4,000 or less, and the polyphenylene ether component A: the cross-linking agent. The resin composition according to item 1, wherein the weight ratio of the resin composition is 25:75 to 95: 5.
[3]
The resin composition according to item 1 or 2, wherein the cross-linking agent comprises at least one compound selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, and polybutadiene.
[4]
The resin composition according to any one of items 1 to 3, wherein the one-minute half-life temperature of the organic peroxide is 155 ° C to 185 ° C.
[5]
Item 1 of item 1 to 4, wherein the content of the organic peroxide is 0.05 parts by mass to 5 parts by mass based on the total mass of 100 parts by mass of the polyphenylene ether component A and the cross-linking agent. The resin composition according to.
[6]
The resin composition further comprises a thermoplastic resin, and the thermoplastic resin is derived from a block copolymer of a vinyl aromatic compound and an olefin-based alkene compound and a hydrogenated product thereof, and a homopolymer of the vinyl aromatic compound. Any one of items 1 to 5, which is at least one selected from the group consisting of, and has a content of 20% by mass or more of the unit derived from the vinyl aromatic compound of the block copolymer or its hydrogenated product. The resin composition according to item 1.
[7]
The resin composition according to item 6, wherein the thermoplastic resin has a weight average molecular weight of 10,000 to 300,000.
[8]
The resin composition according to item 6 or 7, wherein the content of the thermoplastic resin is 2 parts by mass to 20 parts by mass based on the total mass of 100 parts by mass of the polyphenylene ether component A and the cross-linking agent.
[9]
Item 1 to any one of items 1 to 8, wherein the resin composition further contains a flame retardant, and the flame retardant is incompatible with other contained components in the resin composition after curing of the resin composition. The resin composition described.
[10]
An electronic circuit board material containing the resin composition according to any one of items 1 to 9.
[11]
A resin film containing the resin composition according to any one of items 1 to 9.
[12]
A prepreg that is a composite of a base material and the resin composition according to any one of items 1 to 9.
[13]
The prepreg according to item 12, wherein the base material is glass cloth.
[14]
A laminate of the resin film according to item 11 or the cured product of the prepreg according to item 12 or 13 and a metal foil.
本発明によれば、ポリフェニレンエーテル含有樹脂組成物の電気特性に優れ、それを用いて電子回路基板材料、樹脂フィルム、プリプレグ及び積層体を提供することができる。 According to the present invention, the polyphenylene ether-containing resin composition has excellent electrical properties, and it is possible to provide an electronic circuit substrate material, a resin film, a prepreg, and a laminate by using the same.
以下、本発明を実施するための形態（以下、単に「本実施形態」という）について詳細に説明する。なお、本発明は、以下の本実施形態に限定されるものではなく、その要旨の範囲内で種々変形して実施することができる。 Hereinafter, embodiments for carrying out the present invention (hereinafter, simply referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.
樹脂組成物
本実施形態に係る樹脂組成物は、ポリフェニレンエーテル（ＰＰＥ）と、架橋剤と、有機過酸化物とを含み、所望により、難燃剤、その他の添加剤、熱可塑性樹脂、シリカフィラー、溶剤などをさらに含むことができる。本実施形態に係る樹脂組成物の構成要素について以下に説明する。
Resin Composition The resin composition according to the present embodiment contains a polyphenylene ether (PPE), a cross-linking agent, and an organic peroxide, and if desired, a flame retardant, other additives, a thermoplastic resin, a silica filler, and the like. It can further contain a solvent and the like. The components of the resin composition according to this embodiment will be described below.
ポリフェニレンエーテル（ＰＰＥ）
一般に、ポリフェニレンエーテル（ＰＰＥ）は、置換又は非置換のフェニレンエーテル単位から構成される繰り返し構造を有する。本明細書では、用語「ポリフェニレンエーテル」は、ダイマー、トリマー、オリゴマー及びポリマーを含むものとする。ＰＰＥは、フェニレンエーテル単位以外の共重合成分単位を含んでよいが、このような共重合成分単位の量は、全単位構造の数に対して、典型的には、０％以上又は０％超、かつ３０％以下、２５％以下、２０％以下、１５％以下、１０％以下、又は５％以下である。
Polyphenylene ether (PPE)
In general, polyphenylene ethers (PPEs) have a repeating structure composed of substituted or unsubstituted phenylene ether units. As used herein, the term "polyphenylene ether" is intended to include dimers, trimmers, oligomers and polymers. The PPE may contain a copolymerization component unit other than the phenylene ether unit, but the amount of such a copolymerization component unit is typically 0% or more or more than 0% with respect to the number of all unit structures. And 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, or 5% or less.
典型的なＰＰＥとしては、例えば、ポリ（２，６−ジメチル−１，４−フェニレンエーテル）、ポリ（２−メチル−６−エチル−１，４−フェニレンエーテル）、ポリ（２−メチル−６−フェニル−１，４−フェニレンエーテル）、ポリ（２，６−ジクロロ−１，４−フェニレンエーテル）等、更に、２，６−ジメチルフェノールと他のフェノール類（例えば、２，３，６−トリメチルフェノール、２−メチル−６−ブチルフェノール等）との共重合体、及び、２，６−ジメチルフェノールとビフェノール類又はビスフェノール類とをカップリングさせて得られるＰＰＥ共重合体、等が挙げられる。 Typical PPEs include, for example, poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6). −Phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), etc., as well as 2,6-dimethylphenol and other phenols (eg, 2,3,6- Examples thereof include a copolymer with trimethylphenol, 2-methyl-6-butylphenol, etc., and a PPE copolymer obtained by coupling 2,6-dimethylphenol with biphenols or bisphenols.
ポリフェニレンエーテル成分Ａ（ＰＰＥ−Ａ）
本実施形態に係る樹脂組成物は、ポリフェニレンエーテル成分として、下記式（１）：
The resin composition according to this embodiment has the following formula (1): as a polyphenylene ether component.
式（１）中、Ｘはａ価の任意の連結基であり、ａは、２．５以上の数であり、好ましくは３以上の整数、より好ましくは３〜６の整数である。Ｘの具体例としては、例えば、炭化水素基；窒素、リン、ケイ素若しくは酸素から選ばれる、一つ又は複数の元素を含有する炭化水素基；又は窒素、リン、ケイ素等の元素若しくはこれらを含む基などが挙げられる。 In the formula (1), X is an arbitrary linking group of a value, and a is a number of 2.5 or more, preferably an integer of 3 or more, and more preferably an integer of 3 to 6. Specific examples of X include, for example, a hydrocarbon group; a hydrocarbon group containing one or more elements selected from nitrogen, phosphorus, silicon or oxygen; or an element such as nitrogen, phosphorus, silicon or these. Group etc. can be mentioned.
また、Ｒ５は、任意の置換基であり、ｋは１〜４の整数であり、ｋが２以上である場合には、２個のＲ５が連結して環を形成していてよく、ｋ個あるＲ５のうちの少なくとも１つは、下記式（２）：
式（２）中、Ｒ１１は、各々独立に、Ｃ１−８アルキル基であり、Ｒ１２は、各々独立にＣ１−８アルキレン基であり、ｂは独立に０又は１であり、Ｒ１３は、水素原子、Ｃ１−８アルキル基又はフェニル基のいずれかを示し、これらのアルキル基、アルキレン基及びフェニル基は、Ｃ１−８の条件を満たす限度で置換基を有していてもよい。 In formula (2), R 11 is an independently C 1-8 alkyl group, R 12 is an independent C 1-8 alkylene group, b is independently 0 or 1, and R is. Reference numeral 13 denotes a hydrogen atom, a C 1-8 alkyl group, or a phenyl group, and these alkyl groups, alkylene groups, and phenyl groups have substituents to the extent that the conditions of C 1-8 are satisfied. May be good.
式（２）で表される部分構造は、好ましくは、２級及び／又は３級炭素を有し、例えば、イソプロピル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｔｅｒｔ−アミル基、２，２−ジメチルプロピル基、又はこれらの末端にフェニル基を有する構造などを有することができる。式（２）で表される部分構造は、式（１）中のＲ５が結合しているベンゼン環に直接結合していることが好ましい。また、式（２）で表される部分構造は、式（１）中のＲ５が結合しているベンゼン環の２位及び／又は６位（−Ｏ−に対してオルト位）に結合していることが好ましい。 The partial structure represented by the formula (2) preferably has secondary and / or tertiary carbons, for example, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a tert-amyl group, and the like. It can have a structure having a 2,2-dimethylpropyl group or a phenyl group at the end thereof. Partial structure represented by formula (2) is preferably directly bonded to the benzene ring to which R 5 in the formula (1) is attached. The partial structure represented by formula (2) is attached to the formula 2-position of the benzene ring (1) R 5 in is bonded and / or 6-position (ortho to -O-) Is preferable.
式（１）で表される構造のうちの下記：
４，６−ジｔｅｒｔ−ブチルベンゼン１，２，３−トリオール、２，６−ビス（３−ｔｅｒｔ−ブチル−２−ヒドロキシ−５−メチルベンジル）−４−メチルフェノール、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔｅｒｔ−ブチルフェニル）ブタン、２，４，６−トリス（３’，５’−ジ−ｔｅｒｔ−ブチル−４’−ヒドロキシベンジル）メシチレン、ペンタエリトリトールテトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオナート］、１，３，５−トリス［［３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシフェニル］メチル］−１，３，５−トリアジン−２，４，６（１Ｈ，３Ｈ，５Ｈ）−トリオン、１，３，５−トリス［［４−（１，１−ジメチルエチル）−３−ヒドロキシ−２，６−ジメチルフェニル］メチル］−１，３，５−トリアジン−２，４，６（１Ｈ，３Ｈ，５Ｈ）−トリオン。
The following of the structures represented by the formula (1):
4,6-ditert-butylbenzene 1,2,3-triol, 2,6-bis (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenol, 1,1,3- Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 2,4,6-tris (3', 5'-di-tert-butyl-4'-hydroxybenzyl) mecitylene, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] Methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris [[4- (1,1-dimethylethyl) -3-hydroxy- 2,6-Dimethylphenyl] Methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione.
式（１）におけるＹは、各々独立に、下記式（３）：
式（３）において、Ｒ２１は、独立にＣ１−６の飽和又は不飽和の炭化水素基であり、好ましくはメチル、エチル基、ｎ−プロピル基、ビニル基、アリル基、エチニル基、プロパルギル基などであり、より好ましくはメチル基、エチル基であり、さらに好ましくはメチル基である。Ｒ２２は、独立に水素原子又はＣ１−６の飽和又は不飽和の炭化水素基であり、好ましくは水素原子、メチル基、エチル基、ｎ−プロピル基などであり、より好ましくは水素原子、メチル基であり、さらに好ましくは水素原子である。ここで、飽和又は不飽和の炭化水素基はＣ１−６の条件を満たす限度で置換基を有していてもよい。 In formula (3), R 21 is an independently saturated or unsaturated hydrocarbon group of C 1-6 , preferably a methyl, ethyl group, n-propyl group, vinyl group, allyl group, ethynyl group, propargyl. It is a group or the like, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. R 22 is independently a hydrogen atom or a saturated or unsaturated hydrocarbon group of C 1-6 , preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or the like, and more preferably a hydrogen atom. It is a methyl group, more preferably a hydrogen atom. Here, the saturated or unsaturated hydrocarbon group may have a substituent as long as the condition of C 1-6 is satisfied.
式（１）におけるＡは、炭素−炭素二重結合及び／又はエポキシ結合を含有する置換基であり、Ａの具体例は、下記式（４）〜（８）：
式（４）〜（８）において、Ｒ３１は、それぞれ独立に、水素、水酸基、又はＣ１−３０の炭化水素基、アリール基、アルコキシ基、アリロキシ基、アミノ基若しくはヒドロキシアルキル基である。Ｒ３２は、それぞれ独立に、Ｃ１−３０の炭化水素基である。Ｒ３３は、それぞれ独立に、水素、水酸基、又はＣ１−３０の炭化水素基、アリール基、アルコキシ基、アリロキシ基、アミノ基、ヒドロキシアルキル基、ビニル基若しくはイソプロペニル基であり、Ｒ３３のうち少なくとも一つは、ビニル基又はイソプロペニル基である。ｓとｔは、０〜５の整数である。 In formulas (4) to (8), R 31 is independently a hydrogen, a hydroxyl group, or a C 1-30 hydrocarbon group, an aryl group, an alkoxy group, an allyloxy group, an amino group or a hydroxyalkyl group. R 32 is an independent C 1-30 hydrocarbon group. R 33 is independently a hydrogen, a hydroxyl group, or a C 1-30 hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a hydroxyalkyl group, a vinyl group or an isopropenyl group, and is a R 33 . At least one of them is a vinyl group or an isopropenyl group. s and t are integers from 0 to 5.
Ｒ３１の炭化水素基の具体例としては、メチル、エチル、ｎ−プロピル、２−プロピル、ｎ−ブチル、イソブチル、ｔ−ブチル、ｎ−ペンチル、１−エチルプロピル、１−メチルブチル、２−メチルブチル、３−メチルブチル、アミル、シクロペンチル、２，２−ジメチルプロピル、１，１−ジメチルプロピル、ｎ−へキシル、シクロヘキシル、１−エチルブチル、２−エチルブチル、３−エチルブチル、１−メチルペンチル、２−メチルペンチル、３−メチルペンチレン、４−メチルペンチレン、１，１−ジメチルブチレン、２，２−ジメチルブチレン、３，３−ジメチルブチル、１，２−ジメチルブチル、１，３−ジメチルブチル、２，３−ジメチルブチル、ｎ−ヘプチル、１−メチルへキシル、２−メチルへキシル、３−メチルへキシル、４−メチルへキシル、５−メチルへキシル、１−エチルペンチル、２−エチルペンチル、３−エチルペンチル、１，１−ジメチルペンチル、２，２−ジメチルペンチル、３，３−ジメチルペンチル、４，４−ジメチルペンチル、１，２−ジメチルペンチル、１，３−ジメチルペンチル、１，４−ジメチルペンチル、２，３−ジメチルペンチル、２，４−ジメチルペンチル、３，４−ジメチルペンチル、２−メチル−３，３−ジメチルブチル、１−メチル−３，３−ジメチルブチル、１，２，３−トリメチルブチル、１，３−ジメチル−２−ペンチル、２−イソプロピルブチル、２−メチルシクロヘキシル、３−メチルシクロヘキシル、４−メチルシクロヘキシル、１−シクロヘキシルメチル、２−エチルシクロペンチル、３−エチルシクロペンチル、２，３−ジメチルシクロペンチル、２，４−ジメチルシクロペンチル、２−メチルシクロペンチルメチル、２−シクロペンチルエチル、１−シクロペンチルエチル、ｎ−オクチル、２−オクチル、３−オクチル、４−オクチル、２−メチルヘプチル、３−メチルヘプチル、４−メチルヘプチル、５−メチルヘプチル、６−メチルヘプチル、２−エチルへキシル、３−エチルへキシル、４−エチルへキシル、５−エチルへキシル、１，１−ジメチルへキシル、２，２−ジメチルへキシル、３，３−ジメチルへキシル、４，４−ジメチルへキシル、５，５−ジメチルへキシル、１，２−ジメチルへキシル、１，３−ジメチルへキシル、１，４−ジメチルへキシル、１，５−ジメチルへキシル、２，３−ジメチルへキシル、２，４−ジメチルへキシル、２，５−ジメチルへキシル、１，１−エチルメチルペンチル、２，２−エチルメチルペンチル、３，３−エチルメチルペンチル、４，４−エチルメチルペンチル、１−エチル−２−メチルペンチル、１−エチル−３−メチルペンチル、１−エチル−４−メチルペンチル、２−エチル−１−メチルペンチル、３−エチル−１−メチルペンチル、４−エチル−１−メチルペンチル、２−エチル−３−メチルペンチル、２−エチル−４−メチルペンチル、３−エチル−２−メチルペンチル、４−エチル−３−メチルペンチル、３−エチル−４−メチルペンチル、４−エチル−３−メチルペンチル、１−（２−メチルプロピル）ブチル、１−（２−メチルプロピル）−２−メチルブチル、１，１−（２−メチルプロピル）エチル、１，１−（２−メチルプロピル）エチルプロピル、１，１−ジエチルプロピル、２，２−ジエチルプロピル、１，１−エチルメチル−２，２−ジメチルプロピル、２，２−エチルメチル−１，１−ジメチルプロピル、２−エチル−１，１−ジメチルブチル、２，３−ジメチルシクロヘキシル、２，３−ジメチルシクロヘキシル、２，５−ジメチルシクロヘキシル、２，６−ジメチルシクロヘキシル、３，５−ジメチルシクロヘキシル、２−メチルシクロヘキシルメチル、３−メチルシクロヘキシルメチル、４−メチルシクロヘキシルメチル、２−エチルシクロヘキシル、３−エチルシクロヘキシル、４−エチルシクロヘキシル、２−シクロヘキシルエチル、１−シクロヘキシルエチル、１−シクロヘキシル−２−エチレン、ノニル、イソノニル、デシル、イソデシル、ウンデシル、ドデシル、ベンジル、２−フェニルエチル等が挙げられる。 Specific examples of the hydrocarbon group of R 31 include methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-ethylpropyl, 1-methylbutyl and 2-methylbutyl. , 3-Methylbutyl, Amil, Cyclopentyl, 2,2-dimethylpropyl, 1,1-dimethylpropyl, n-hexyl, Cyclohexyl, 1-ethylbutyl, 2-ethylbutyl, 3-ethylbutyl, 1-methylpentyl, 2-methyl Pentyl, 3-methylpentylene, 4-methylpentylene, 1,1-dimethylbutylene, 2,2-dimethylbutylene, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2 , 3-Dimethylbutyl, n-Heptyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-Ethylpentyl, 1,1-dimethylpentyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4 -Dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,4-dimethylpentyl, 2-methyl-3,3-dimethylbutyl, 1-methyl-3,3-dimethylbutyl, 1,2 , 3-trimethylbutyl, 1,3-dimethyl-2-pentyl, 2-isopropylbutyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1-cyclohexylmethyl, 2-ethylcyclopentyl, 3-ethylcyclopentyl , 2,3-Dimethylcyclopentyl, 2,4-dimethylcyclopentyl, 2-methylcyclopentylmethyl, 2-cyclopentylethyl, 1-cyclopentylethyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methyl Heptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, 1,1- To dimethylhexyl, 2,2-dimethylhexyl, 3,3-dimethylhexyl, 4,4-dimethylhexyl, 5,5-dimethylhexyl, 1,2-dimethylhexyl, 1,3-dimethyl Xyl, 1,4-dimethylhexyl, 1,5-dimethylhexyl, 2,3-dimethylhexyl, 2,4-di Methylhexyl, 2,5-dimethylhexyl, 1,1-ethylmethylpentyl, 2,2-ethylmethylpentyl, 3,3-ethylmethylpentyl, 4,4-ethylmethylpentyl, 1-ethyl-2- Methylpentyl, 1-ethyl-3-methylpentyl, 1-ethyl-4-methylpentyl, 2-ethyl-1-methylpentyl, 3-ethyl-1-methylpentyl, 4-ethyl-1-methylpentyl, 2- Ethyl-3-methylpentyl, 2-ethyl-4-methylpentyl, 3-ethyl-2-methylpentyl, 4-ethyl-3-methylpentyl, 3-ethyl-4-methylpentyl, 4-ethyl-3-methyl Pentyl, 1- (2-methylpropyl) butyl, 1- (2-methylpropyl) -2-methylbutyl, 1,1- (2-methylpropyl) ethyl, 1,1- (2-methylpropyl) ethylpropyl, 1,1-diethylpropyl, 2,2-diethylpropyl, 1,1-ethylmethyl-2,2-dimethylpropyl, 2,2-ethylmethyl-1,1-dimethylpropyl, 2-ethyl-1,1- Dimethylbutyl, 2,3-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2-methylcyclohexylmethyl, 3-methylcyclohexylmethyl, 4-Methylcyclohexylmethyl, 2-ethylcyclohexyl, 3-ethylcyclohexyl, 4-ethylcyclohexyl, 2-cyclohexylethyl, 1-cyclohexylethyl, 1-cyclohexyl-2-ethylene, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl , Benzyl, 2-phenylethyl and the like.
Ｒ３１の炭化水素基は、好ましくは、メチル、エチル、ｎ−プロピル、２−プロピル、ｎ−ブチル、イソブチル、ｔ−ブチル、ｎ−ペンチル、１−エチルプロピル、１−メチルブチル、２−メチルブチル、３−メチルブチル、アミル、シクロペンチル、ｎ−へキシルル、シクロヘキシル、１−エチルブチル、２−エチルブチル、３−エチルブチル、１−メチルペンチル、２−メチルペンチル、３−メチルペンチル、４−メチルペンチル、ｎ−ヘプチル、１−メチルへキシル、２−メチルへキシル、３−メチルへキシル、４−メチルへキシル、５−メチルへキシル、１−エチルペンチル、２−エチルペンチル、３−エチルペンチル、２−メチルシクロヘキシル、３−メチルシクロヘキシル、４−メチルシクロヘキシル、ｎ−オクチル、２−オクチル、３−オクチル、４−オクチル、２−メチルヘプチル、３−メチルヘプチル、４−メチルヘプチル、５−メチルヘプチル、６−メチルヘプチル、２−エチルへキシル、３−エチルへキシル、４−エチルへキシル、５−エチルへキシル、ノニル、イソノニル、デシル、イソデシル、ウンデシル、ドデシル、ベンジル等であり、より好ましくは、メチル、エチル、ｎ−プロピル、２−プロピル、ｎ−ブチル、イソブチル、ｔ−ブチル、ｎ−ペンチル、１−エチルプロピル、１−メチルブチル、２−メチルブチル、３−メチルブチル、アミル、シクロペンチル、ｎ−へキシル、シクロヘキシル、ｎ−ヘプチル、ｎ−オクチル、２−オクチル、３−オクチル、４−オクチル、２−メチルヘプチル、３−メチルヘプチル、４−メチルヘプチル、５−メチルヘプチル、６−メチルヘプチル、２−エチルへキシル、３−エチルへキシル、４−エチルへキシル、５−エチルへキシル、ノニル、イソノニル、デシル、イソデシル、ウンデシル、ドデシル、ベンジル等であり、さらに好ましくは、メチル、エチル、ｎ−プロピル、２−プロピル、ｎ−ブチル、イソブチル、ｔ−ブチル、ｎ−ペンチル、アミル、シクロペンチル、ｎ−へキシル、シクロヘキシル、ｎ−ヘプチル、ｎ−オクチル、２−オクチル、３−オクチル、４−オクチル、２−メチルヘプチル、３−メチルヘプチル、４−メチルヘプチル、５−メチルヘプチル、６−メチルヘプチル、２−エチルへキシル、３−エチルへキシル、４−エチルへキシル、５−エチルへキシル、ノニル、イソノニル、デシル、イソデシル、ウンデシル、ドデシル、ベンジル等である。 The hydrocarbon group of R 31 is preferably methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-Methylbutyl, amyl, cyclopentyl, n-hexyl, cyclohexyl, 1-ethylbutyl, 2-ethylbutyl, 3-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, n-heptyl , 1-Methylhexyl, 2-Methylhexyl, 3-Methylhexyl, 4-Methylhexyl, 5-Methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 2-methylcyclohexyl , 3-Methylcyclohexyl, 4-Methylcyclohexyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methyl Heptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, benzyl and the like, more preferably methyl and ethyl. , N-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, amyl, cyclopentyl, n-hexyl, cyclohexyl , N-Heptyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethyl Xyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, benzyl and the like, more preferably methyl, ethyl, n-propyl, 2 -Propyl, n-butyl, isobutyl, t-butyl, n-pentyl, amyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2- Methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, nonyl, isononyl , Decyl, Isodecyl, Undecyl, De Decyl, benzyl, etc.
Ｒ３２の炭化水素基の具体例としては、メチレン、エチレン、トリメチレン、１，２−プロピレン、テトラメチレン、２−メチル−１，３−トリメチレン、１，１−ジメチルエチレン、ペンタメチレン、１−エチル−１，３−プロピレン、１−メチル−１，４−ブチレン、２−メチル−１，４−ブチルレン、３−メチル−１，４−ブチレン、２，２−ジメチル−１，３−プロピレン、１，２−シクロペンチレン、１，３−シクロペンチレン、２，２−ジメチル−１，３−プロピレン、１，１−ジメチル−１，３−プロピレン、３，３−ジメチル−１，３−プロピレン、ヘキサメチレン、１，２−シクロヘキシレン、１，３−シクロヘキシレン、１，４−シクロヘキシレン、１−エチル−１，４−ブチレン、２−エチル−１，４−ブチレン、３−エチル−１，４−ブチレン、１−メチル−１，５−ペンチレン、２−メチル−１，５−ペンチレン、３−メチル−１，５−ペンチレン、４−メチルペンチレン、１，１−ジメチル−１，４−ブチレン、２，２−ジメチル−１，４−ブチレン、３，３−ジメチル−１，４−ブチレン、１，２−ジメチル−１，４−ブチレン、１，３−ジメチル−１，４−ブチレン、２，３−ジメチル−１，４−ブチレン、ヘプタメチレン、１−メチル−１，６−へキシレン、２−メチル−１，６−ヘキシレン、３−メチル−１，６−ヘキシレン、４−メチル−１，６−ヘキシレン、５−メチル−１，６−ヘキシレン、１−エチル−１，５−ペンチレン、２−エチル−１，５−ペンチレン、３−エチル−１，５−ペンチレン、１，１−ジメチル−１，５−ペンチレン、２，２−ジメチル−１，５−ペンチレン、３，３−ジメチル−１，５−ペンチレン、４，４−ジメチル−１，５−ペンチレン、１，２−ジメチル−１，５−ペンチレン、１，３−ジメチル−１，５−ペンチレン、１，４−ジメチル−１，５−ペンチレン、２，３−ジメチル−１，５−ペンチレン、２，４−ジメチル−１，５−ペンチレン、３，４−ジメチル−１，５−ペンチレン、２−メチル−３，３−ジメチル−１，４−ブチレン、１−メチル−３，３−ジメチル−１，４−ブチレン、１，２，３−トリメチルー１，４−ブチレン等が挙げられる。 Specific examples of the hydrocarbon group for R 32 include methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,3-trimethylene, 1,1-dimethylethylene, pentamethylene, 1-ethyl -1,3-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, 3-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1 , 2-Cyclopentylene, 1,3-Cyclopentylene, 2,2-dimethyl-1,3-propylene, 1,1-dimethyl-1,3-propylene, 3,3-dimethyl-1,3-propylene , Hexamethylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, 1-ethyl-1,4-butylene, 2-ethyl-1,4-butylene, 3-ethyl-1 , 4-butylene, 1-methyl-1,5-pentylene, 2-methyl-1,5-pentylene, 3-methyl-1,5-pentylene, 4-methylpentylene, 1,1-dimethyl-1,4 -Butylene, 2,2-dimethyl-1,4-butylene, 3,3-dimethyl-1,4-butylene, 1,2-dimethyl-1,4-butylene, 1,3-dimethyl-1,4-butylene , 2,3-Dimethyl-1,4-butylene, heptamethylene, 1-methyl-1,6-hexylene, 2-methyl-1,6-hexylene, 3-methyl-1,6-hexylene, 4-methyl -1,6-hexylene, 5-methyl-1,6-hexylene, 1-ethyl-1,5-pentylene, 2-ethyl-1,5-pentylene, 3-ethyl-1,5-pentylene, 1,1 -Dimethyl-1,5-pentylene, 2,2-dimethyl-1,5-pentylene, 3,3-dimethyl-1,5-pentylene, 4,4-dimethyl-1,5-pentylene, 1,2-dimethyl -1,5-pentylene, 1,3-dimethyl-1,5-pentylene, 1,4-dimethyl-1,5-pentylene, 2,3-dimethyl-1,5-pentylene, 2,4-dimethyl-1 , 5-Pentylene, 3,4-Dimethyl-1,5-Pentylene, 2-Methyl-3,3-Dimethyl-1,4-butylene, 1-Methyl-3,3-dimethyl-1,4-butylene, 1 , 2,3-Trimethyl-1,4-butylene and the like.
また、Ｒ３２の炭化水素基の具体例としては、１，３−ジメチル−１，４−ペンチレン、２−イソプロピル−１，４−ブチレン、２−メチル−１，４−シクロヘキシレン、３−メチル−１，４−シクロヘキシレン、４−メチル−１，４−シクロヘキシレン、１−シクロヘキシルメチレン、２−エチル−１，３−シクロペンチレン、３−エチル−１，３−シクロペンチレン、２，３−ジメチル−１，３−シクロペンチレン、２，４−ジメチル−１，３−シクロペンチレン、２−メチル−１，３−シクロペンチルメチレン、２−シクロペンチルエチレン、１−シクロペンチルエチレン、オクタメチレン、１−メチル−１，７−ヘプチレン、１−エチル１，６−へキシレン、１−プロピル−１，５−ペンチレン、２−メチル−１，７−ヘプチレン、３−メチル−１，７−ヘプチレン、４−メチル−１，７−ヘプチレン、５−メチル−１，７−ヘプチレン、６−メチル−１，７−ヘプチレン、２−エチル−１，６−ヘキシレン、３−エチル−１，６−ヘキシレン、４−エチル−１，６−ヘキシレン、５−エチル−１，６−ヘキシレン、１，１−ジメチル−１，６−ヘキシレン、２，２−ジメチル−１，６−ヘキシレン、３，３−ジメチル−１，６−ヘキシレン、４，４−ジメチル−１，６−ヘキシレン、５，５−ジメチル−１，６−ヘキシレン、１，２−ジメチル−１，６−ヘキシレン、１，３−ジメチル−１，６−ヘキシレン、１，４−ジメチル−１，６−ヘキシレン、１，５−ジメチル−１，６−ヘキシレン、２，３−ジメチル−１，６−ヘキシレン、２，４−ジメチル−１，６−ヘキシレン、２，５−ジメチル−１，６−ヘキシレン、１，１−エチルメチル−１，５−ペンチレン、２，２−エチルメチル−１，５−ペンチレン、３，３−エチルメチル−１，５−ペンチレン、４，４−エチルメチル−１，５−ペンチレン、１−エチル−２−メチル−１，５−ペンチレン、１−エチル−３−メチル−１，５−ペンチレン、１−エチル−４−メチル−１，５−ペンチレン、２−エチル−１−メチル−１，５−ペンチレン、３−エチル−１−メチル−１，５−ペンチレン、４−エチル−１−メチル−１，５−ペンチレン、２−エチル−３−メチル−１，５−ペンチレン、２−エチル−４−メチル−１，５−ペンチレン、３−エチル−２−メチル−１，５−ペンチレン、４−エチル−３−メチル−１，５−ペンチレン、３−エチル−４−メチル−１，５−ペンチレン、４−エチル−３−メチル−１，５−ペンチレン等が挙げられる。 Specific examples of the hydrocarbon group for R 32, 1,3-dimethyl-1,4-pentylene, 2-isopropyl-1,4-butylene, 2-methyl-1,4-cyclohexylene, 3-methyl -1,4-Cyclohexylene, 4-methyl-1,4-cyclohexylene, 1-cyclohexylmethylene, 2-ethyl-1,3-cyclopentylene, 3-ethyl-1,3-cyclopentylene, 2, 3-Dimethyl-1,3-cyclopentylene, 2,4-dimethyl-1,3-cyclopentylene, 2-methyl-1,3-cyclopentylmethylene, 2-cyclopentylethylene, 1-cyclopentylethylene, octamethylene, 1-Methyl-1,7-Heptylene, 1-Ethyl 1,6-Hexylene, 1-propyl-1,5-Pentylene, 2-Methyl-1,7-Heptylene, 3-Methyl-1,7-Heptylene, 4-Methyl-1,7-Heptylene, 5-Methyl-1,7-Heptylene, 6-Methyl-1,7-Heptylene, 2-Ethyl-1,6-Hexylene, 3-Ethyl-1,6-Hexylene, 4-Ethyl-1,6-hexylene, 5-ethyl-1,6-hexylene, 1,1-dimethyl-1,6-hexylene, 2,2-dimethyl-1,6-hexylene, 3,3-dimethyl- 1,6-Hexylene, 4,4-dimethyl-1,6-hexylene, 5,5-dimethyl-1,6-hexylene, 1,2-dimethyl-1,6-hexylene, 1,3-dimethyl-1, 6-Hexylene, 1,4-dimethyl-1,6-hexylene, 1,5-dimethyl-1,6-hexylene, 2,3-dimethyl-1,6-hexylene, 2,4-dimethyl-1,6-- Hexylene, 2,5-dimethyl-1,6-hexylene, 1,1-ethylmethyl-1,5-pentylene, 2,2-ethylmethyl-1,5-pentylene, 3,3-ethylmethyl-1,5 -Pentylene, 4,4-ethylmethyl-1,5-pentylene, 1-ethyl-2-methyl-1,5-pentylene, 1-ethyl-3-methyl-1,5-pentylene, 1-ethyl-4- Methyl-1,5-pentylene, 2-ethyl-1-methyl-1,5-pentylene, 3-ethyl-1-methyl-1,5-pentylene, 4-ethyl-1-methyl-1,5-pentylene, 2-Ethyl-3-methyl-1,5-pentylene, 2-ethyl-4-methyl-1,5-pentylene, 3-ethyl-2-methyl-1,5-pentylene, 4-ethyl-3-methyl- 1,5-pentylene, 3-ethyl- Examples thereof include 4-methyl-1,5-pentylene and 4-ethyl-3-methyl-1,5-pentylene.
さらに、Ｒ３２の炭化水素基の具体例としては、１−（２−メチルプロピル）−１，４−ブチレン、１−（２−メチルプロピル）−２−メチル−１，４−ブチレン、１，１−（２−メチルプロピル）エチレン、１，１−（２−メチルプロピル）エチル−１，３−プロピレン、１，１−ジエチル−１，３−プロピレン、２，２−ジエチル−１，３−プロピレン、１，１−エチルメチル−２，２−ジメチル−１，３−プロピレン、２，２−エチルメチル−１，１−ジメチル−１，３−プロピレン、２−エチル−１，１−ジメチル−１，４−ブチレン、２，３−ジメチル−１，４−シクロヘキシレン、２，３−ジメチル−１，４−シクロヘキシレン、２，５−ジメチル−１，４−シクロヘキシレン、２，６−ジメチル−１，４−シクロヘキシレン、３，５−ジメチル−１，４−シクロヘキシレン、２−メチル−１，４−シクロヘキシル−１−メチレン、３−メチル−１，４−シクロヘキシル−１−メチレン、４−メチル−１，４−シクロヘキシル−１−メチレン、２−エチル−１，４−シクロヘキシレン、３−エチル−１，４−シクロヘキシレン、４−エチル−１，４−シクロヘキシレン、２−シクロヘキシルエチレン、１−シクロヘキシルエチレン、１−シクロヘキシル−２−エチレン、ノニルメチレン、１−メチル−１，８−オクチレン、デシルメチレン、１−メチル−１，８−ノニレン、ウンデシルメチレン、ドデシルメチレン、１，４−フェニレン、１，３−フェニレン、１，２−フェニレン、メチレン−１，４−フェニレン−メチレン、エチレン−１，４−フェニレン−エチレン等が挙げられる。 Further, specific examples of the hydrocarbon group for R 32, 1- (2-methylpropyl) -1,4-butylene, 1- (2-methylpropyl) -2-methyl-1,4-butylene, 1, 1- (2-methylpropyl) ethylene, 1,1- (2-methylpropyl) ethyl-1,3-propylene, 1,1-diethyl-1,3-propylene, 2,2-diethyl-1,3- Ethylene, 1,1-ethylmethyl-2,2-dimethyl-1,3-propylene, 2,2-ethylmethyl-1,1-dimethyl-1,3-propylene, 2-ethyl-1,1-dimethyl- 1,4-butylene, 2,3-dimethyl-1,4-cyclohexylene, 2,3-dimethyl-1,4-cyclohexylene, 2,5-dimethyl-1,4-cyclohexylene, 2,6-dimethyl -1,4-Cyclohexylene, 3,5-dimethyl-1,4-cyclohexylene, 2-methyl-1,4-cyclohexyl-1-ethylene, 3-methyl-1,4-cyclohexyl-1-methylene, 4 -Methyl-1,4-cyclohexyl-1-methylene, 2-ethyl-1,4-cyclohexylene, 3-ethyl-1,4-cyclohexylene, 4-ethyl-1,4-cyclohexylene, 2-cyclohexylethylene , 1-Cyclohexylethylene, 1-Cyclohexyl-2-ethylene, nonylmethylene, 1-methyl-1,8-octylene, decylmethylene, 1-methyl-1,8-nonylene, undecylmethylene, dodecylmethylene, 1,4 Examples thereof include −phenylene, 1,3-phenylene, 1,2-phenylene, methylene-1,4-phenylene-methylene, ethylene-1,4-phenylene-ethylene and the like.
Ｒ３２の炭化水素基は、好ましくは、メチレン、エチレン、トリメチレン、１，２−プロピレン、テトラメチレン、２−メチル−１，２−プロピレン、１，１−ジメチルエチレン、ペンタメチレン、１−エチル−１，３−プロピレン、１−メチル−１，４−ブチレン、２−メチル−１，４−ブチレン、３−メチル−１，４−ブチレン、２，２−ジメチル−１，３−プロピレン、１，３−シクロペンチレン、１，６−へキサメチレン、１，４−シクロヘキシレン、１−エチル−１，４−ブチレン、２−エチル−１，４−ブチレン、３−エチル−１，４−ブチレン、１−メチル−１，５−ペンチレン、２−メチル−１，５−ペンチレン、３−メチル−１，５−ペンチレン、４−メチル−１，５−ペンチレン、ヘプタメチチレン、１−メチル−１，６−ヘキシレン、２−メチル−１，６−ヘキシレン、３−メチル−１，６−ヘキシレン、４−メチル−１，６−ヘキシレン、５−メチル−１，６−ヘキシレン、１−エチル−１，５−ペンチレン、２−エチル−１，５−ペンチレン、３−エチル−１，５−ペンチレン、２−メチル−１，４−シクロヘキシレン、３−メチル−１，４−シクロヘキシレン、４−メチル−１，４−シクロヘキシレン、オクタメチレン、１−メチル−１，７−ヘプチレン、３−メチル−１，７−ヘプチレン、４−メチル−１，７−ヘプチレン、２−メチル−１，７−ヘプチレン、５−メチル−１，７−ヘプチレン、６−メチル−１，７−ヘプチレン、２−エチル−１，６−ヘキシレン、３−エチル−１，６−ヘキシレン、４−エチル−１，６−ヘキシレン、５−エチル−１，６−ヘキシレン、ノニルメチレン、デシルメチレン、ウンデシルメチレン、ドデシルメチレン等であり、より好ましくは、メチレン、エチレン、トリメチレン、１，２−プロピレン、テトラメチレン、２−メチル−１，２−プロピレン、１，１−ジメチルエチレン、ペンタメチレン、１−エチル−１，３−プロピレン、１−メチル−１，４−ブチレン、２−メチル−１，４−ブチレン、３−メチル−１，４−ブチレン、２，２−ジメチル−１，３−プロピレン、１，３−シクロペンチレン、１，６−へキサメチレン、１，４−シクロヘキシレン、ヘプタメチチレン、オクタメチレン、１−メチル−１，７−ヘプチレン、３−メチル−１，７−ヘプチレン、４−メチル−１，７−ヘプチレン、２−メチル−１，７−ヘプチレン、５−メチル−１，７−ヘプチレン、６−メチル−１，７−ヘプチレン、２−エチル−１，６−ヘキシレン、３−エチル−１，６−ヘキシレン、４−エチル−１，６−ヘキシレン、５−エチル−１，６−ヘキシレン、ノニルメチレン、デシルメチレン、ウンデシルメチレン、ドデシルメチレン等であり、さらに好ましくは、メチレン、エチレン、トリメチレン、１，２−プロピレン、テトラメチレン、２−メチル−１，２−プロピレン、１，１−ジメチルエチレン、ペンタメチレン、２，２−ジメチル−１，３−プロピレン、１，３−シクロペンチレン、１，６−へキサメチレン、１，４−シクロヘキシレン、ヘプタメチレン、オクタメチレン、１−メチル−１，７−ヘプチレン、３−メチル−１，７−ヘプチレン、４−メチル−１，７−ヘプチレン、２−メチル−１，７−ヘプチレン、５−メチル−１，７−ヘプチレン、６−メチル−１，７−ヘプチレン、２−エチル−１，６−ヘキシレン、３−エチル−１，６−ヘキシレン、４−エチル−１，６−ヘキシレン、５−エチル−１，６−ヘキシレン、ノニルメチレン、デシルメチレン、ウンデシルメチレン、ドデシルメチレン等である。 The hydrocarbon group of R 32 is preferably methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,2-propylene, 1,1-dimethylethylene, pentamethylene, 1-ethyl-. 1,3-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, 3-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1, 3-Cyclopentylene, 1,6-hexamethylene, 1,4-cyclohexylene, 1-ethyl-1,4-butylene, 2-ethyl-1,4-butylene, 3-ethyl-1,4-butylene, 1-Methyl-1,5-pentylene, 2-methyl-1,5-pentylene, 3-methyl-1,5-pentylene, 4-methyl-1,5-pentylene, heptamethylylene, 1-methyl-1,6- Hexylene, 2-methyl-1,6-hexylene, 3-methyl-1,6-hexylene, 4-methyl-1,6-hexylene, 5-methyl-1,6-hexylene, 1-ethyl-1,5- Pentylene, 2-ethyl-1,5-pentylene, 3-ethyl-1,5-pentylene, 2-methyl-1,4-cyclohexylene, 3-methyl-1,4-cyclohexylene, 4-methyl-1, 4-Cyclohexylene, Octamethylene, 1-Methyl-1,7-Heptylene, 3-Methyl-1,7-Heptylene, 4-Methyl-1,7-Heptylene, 2-Methyl-1,7-Heptylene, 5- Methyl-1,7-Heptylene, 6-Methyl-1,7-Heptylene, 2-Ethyl-1,6-Hexylene, 3-Ethyl-1,6-Hexylene, 4-Ethyl-1,6-Hexylene, 5- Ethyl-1,6-hexylene, nonylmethylene, decylmethylene, undecylmethylene, dodecylmethylene and the like, more preferably methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,2. -Propylene, 1,1-dimethylethylene, pentamethylene, 1-ethyl-1,3-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, 3-methyl-1,4 -Butylene, 2,2-dimethyl-1,3-propylene, 1,3-cyclopentylene, 1,6-hexamethylene, 1,4-cyclohexylene, heptamethylylene, octamethylene, 1-methyl-1,7- Heptylene, 3-Methyl-1,7-Heptylene, 4-Methyl-1,7-Heptylene, 2-Methyl-1,7-Heptylene, 5-Methyl Chill-1,7-heptylene, 6-methyl-1,7-heptyrene, 2-ethyl-1,6-hexylene, 3-ethyl-1,6-hexylene, 4-ethyl-1,6-hexylene, 5- Ethyl-1,6-hexylene, nonylmethylene, decylmethylene, undecylmethylene, dodecylmethylene and the like, more preferably methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,2. -Propylene, 1,1-dimethylethylene, pentamethylene, 2,2-dimethyl-1,3-propylene, 1,3-cyclopentylene, 1,6-hexamethylene, 1,4-cyclohexylene, heptamethylene, Octamethylene, 1-methyl-1,7-heptylene, 3-methyl-1,7-heptylene, 4-methyl-1,7-heptylene, 2-methyl-1,7-heptylene, 5-methyl-1,7 -Heptylene, 6-Methyl-1,7-Heptylene, 2-Ethyl-1,6-Hexylene, 3-Ethyl-1,6-Hexylene, 4-Ethyl-1,6-Hexylene, 5-Ethyl-1,6 -Hexylene, nonylmethylene, decylmethylene, undecylmethylene, dodecylmethylene, etc.
式（１）中のＡについて、炭素−炭素二重結合を含有する置換基の具体例としては、ビニル基、アリル基、イソプロペニル基、１−ブテニル基、１−ペンテニル基、ｐ−ビニルフェニル基、ｐ−イソプロペニルフェニル基、ｍ−ビニルフェニル基、ｍ−イソプロペニルフェニル基、ｏ−ビニルフェニル基、ｏ−イソプロペニルフェニル基、ｐ−ビニルベンジル基、ｐ−イソプロペニルベンジル基、ｍ−ビニルベンジル基、ｍ−イソプロペニルベンジル基、ｏ−ビニルベンジル基、ｏ−イソプロペニルベンジル基、ｐ−ビニルフェニルエテニル基、ｐ−ビニルフェニルプロペニル基、ｐ−ビニルフェニルブテニル基、ｍ−ビニルフェニルエテニル基、ｍ−ビニルフェニルプロペニル基、ｍ−ビニルフェニルブテニル基、ｏ−ビニルフェニルエテニル基、ｏ−ビニルフェニルプロペニル基、ｏ−ビニルフェニルブテニル基、メタクリル基、アクリル基、２−エチルアクリル基、２−ヒドロキシメチルアクリル基等が挙げられる。 Regarding A in the formula (1), specific examples of the substituent containing a carbon-carbon double bond include a vinyl group, an allyl group, an isopropenyl group, a 1-butenyl group, a 1-pentenyl group, and a p-vinylphenyl. Group, p-isopropenylphenyl group, m-vinylphenyl group, m-isopropenylphenyl group, o-vinylphenyl group, o-isopropenylphenyl group, p-vinylbenzyl group, p-isopropenylbenzyl group, m- Vinylbenzyl group, m-isopropenylbenzyl group, o-vinylbenzyl group, o-isopropenylbenzyl group, p-vinylphenylethenyl group, p-vinylphenylpropenyl group, p-vinylphenylbutenyl group, m-vinyl Phenylethenyl group, m-vinylphenylpropenyl group, m-vinylphenylbutenyl group, o-vinylphenylethenyl group, o-vinylphenylpropenyl group, o-vinylphenylbutenyl group, methacryl group, acrylic group, 2 -Ethyl acrylic group, 2-hydroxymethyl acrylic group and the like can be mentioned.
式（１）におけるＬは、任意の２価の連結基又は単結合（直接結合）である。Ｌが単結合である場合、式（１）で表される構造は、下記式：
で表される構造を有する。
L in the formula (1) is an arbitrary divalent linking group or a single bond (direct bond). When L is a single bond, the structure represented by the formula (1) is as follows:
It has a structure represented by.
式（１）で表される構造は、Ｘの価数ａの値に応じて様々な分岐構造を取り得る。例えば、式（１）においてａ＝３の場合には、以下の式：
で表される分岐構造などが挙げられる。
The structure represented by the formula (1) can have various branched structures depending on the value of the valence a of X. For example, when a = 3 in the equation (1), the following equation:
The branch structure represented by is mentioned.
式（１）で表される構造としては、具体的には下記に示すような構造が挙げられる。
上記の式中、Ｚは、式（１）におけるＸに相当する任意の連結基である。Ｒ１は、式（２）で表される置換基であり、ｂは１〜４の整数である。なお、Ｒ１の位置に限定はなく、Ｒ１は、任意の位置を取ってよい。また、ｂが２以上の場合には、複数あるＲ１のそれぞれが、同じ構造を取っても、異なった構造を取ってもよい。Ｒ１としては、例えば、イソプロピル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｔｅｒｔ−アミル基、２，２−ジメチルプロピル基、又はこれらの末端にフェニル基を有する構造などが挙げられる。Ａは、炭素−炭素二重結合及び／又はエポキシ結合を含有する置換基である。Ｒ２は、水素、又は炭素数１〜８の鎖状若しくは環状構造を有する炭化水素基である。Ｒ２が複数ある場合には、それぞれの置換基は同じでも異なっていてもよい。Ｒ２の具体例としては、例えば、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、ｎ−ペンチル基、シクロペンチル基、ｎ−ヘキシル基、シクロヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基、フェニル基、ベンジル基、２−エチルヘキシル基等が挙げられ、合成時の反応性等の観点から、水素、メチル、エチル、ｎ−プロピル基、ｎ−ブチル基、ｎ−ペンチル基、シクロペンチル基、ｎ−ヘキシル基、シクロヘキシル基、ｎ−ヘプチル基、及びｎ−オクチル基が好ましい。しかしながら、合成時の反応性が、Ｒ２の位置又は合成時の反応条件を適切に設定することによってもコントロールできる場合には、Ｒ２の構造に制限はなく、Ｃ１−８の条件を満たす範囲内で任意の構造でよい。Ｚは、炭化水素基；窒素、リン、ケイ素、酸素から選ばれる、一つ又は複数の元素を含有する炭化水素基；又は窒素、リン、ケイ素等の元素若しくはこれらを含む基である。 In the above formula, Z is an arbitrary linking group corresponding to X in the formula (1). R 1 is a substituent represented by the formula (2), and b is an integer of 1 to 4. The position of R 1 is not limited, and R 1 may take any position. Also, if b is 2 or more, each of the plurality of R 1 is, take the same structure may take a different structure. Examples of R 1 include an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a tert-amyl group, a 2,2-dimethylpropyl group, or a structure having a phenyl group at the terminal thereof. .. A is a substituent containing a carbon-carbon double bond and / or an epoxy bond. R 2 is hydrogen or a hydrocarbon group having a chain or cyclic structure having 1 to 8 carbon atoms. If the R 2 there are a plurality, each of the substituents may be the same or different. Specific examples of R 2 include, for example, a methyl group, an ethyl group, n- propyl group, n- butyl group, n- pentyl group, a cyclopentyl group, n- hexyl group, a cyclohexyl group, n- heptyl, n- octyl Examples include a group, a phenyl group, a benzyl group, a 2-ethylhexyl group, and the like, and from the viewpoint of reactivity during synthesis, hydrogen, methyl, ethyl, n-propyl group, n-butyl group, n-pentyl group, cyclopentyl group and the like. , N-hexyl group, cyclohexyl group, n-heptyl group, and n-octyl group are preferable. However, if the reactivity at the time of synthesis can be controlled by appropriately setting the position of R 2 or the reaction conditions at the time of synthesis, the structure of R 2 is not limited and the condition of C 1-8 is satisfied. Any structure may be used within the range. Z is a hydrocarbon group; a hydrocarbon group selected from nitrogen, phosphorus, silicon, oxygen and containing one or more elements; or an element such as nitrogen, phosphorus, silicon or a group containing these.
Ｚとしての炭化水素基の具体例は、例えば、下記式で表される構造などである。
また、Ｚとして、窒素、リン、ケイ素及び酸素から成る群から選ばれる、一つ又は複数の元素を含有する炭化水素基の具体例は、下記式で表されるものである。
また、Ｚとして、窒素、リン、酸素等を含む基の具体例は、以下のとおりである。
上記具体例のうち、一つ目のものについてＡの構造を具体的にすると、下記式のような構造になる。なお、４〜６分岐の場合も同様であり、また下記式中のＲ３１、Ｒ３２、ｓ及びｔは、Ａの具体例において定義したとおりである。
ポリフェニレンエーテル成分Ａの数平均分子量（Ｍｎ）は、ＧＰＣを用いたポリスチレン換算分子量において、５００〜８，０００であり、流動性、他の成分との相溶性などの観点から、好ましくは７００〜６，０００、より好ましくは９００〜４，５００である。また、同様の観点から、ポリフェニレンエーテル成分Ａの分子量分布は、Ｍｗ（重量平均分子量）／Ｍｎとして、好ましくは、１．１〜５、１．４〜４、又は１．５〜３の範囲内である。 The number average molecular weight (Mn) of the polyphenylene ether component A is 500 to 8,000 in terms of polystyrene-equivalent molecular weight using GPC, and is preferably 700 to 6 from the viewpoint of fluidity and compatibility with other components. 000, more preferably 900-4,500. From the same viewpoint, the molecular weight distribution of the polyphenylene ether component A is preferably in the range of 1.1 to 5, 1.4 to 4, or 1.5 to 3 in terms of Mw (weight average molecular weight) / Mn. Is.
本実施形態における式（１）の構造を有する変性ポリフェニレンエーテルは、例えば、より高分子量のフェニレンエーテルポリマーを用いた再分配反応法によりポリフェニレンエーテルを調製し、その末端に基Ａを導入することにより製造することができる。再分配反応によるポリフェニレンエーテルの製造の場合は、公知の反応条件に定められた条件に従い製造することが可能である。この場合、得られるポリマーは、原料となるフェニレンエーテルポリマーよりも分子量が低くなるため、目的の分子量に合わせ、原料ポリフェニレンエーテルと多官能フェノール化合物の比率を調整してよい。 The modified polyphenylene ether having the structure of the formula (1) in the present embodiment is prepared by, for example, preparing a polyphenylene ether by a redistribution reaction method using a higher molecular weight phenylene ether polymer and introducing a group A at the terminal thereof. Can be manufactured. In the case of producing polyphenylene ether by a redistribution reaction, it can be produced according to the conditions specified in the known reaction conditions. In this case, since the obtained polymer has a lower molecular weight than the raw material phenylene ether polymer, the ratio of the raw material polyphenylene ether to the polyfunctional phenol compound may be adjusted according to the target molecular weight.
また、式（１）中の置換基Ａを、例えば、式（４）〜（７）で表される官能基を、得られたポリフェニレンエーテルポリマー末端へ導入する方法に限定はなく、官能基の種類に応じて公知の様々な方法を採用してよい。例えば、式（４）、（６）又は（７）の構造を有する官能基の導入は、一般的には、Ｗｉｌｌｉａｍｓｏｎ合成法によるエーテル結合の形成に従うことができる。式（５）の構造を有する官能基の導入は、ポリフェニレンエーテルポリマー末端の水酸基と、炭素−炭素二重結合を有するカルボン酸（以下カルボン酸）とのエステル結合の形成反応であり、公知のエステル結合形成方法を利用することができる。 Further, the method for introducing the substituent A in the formula (1) into, for example, the functional group represented by the formulas (4) to (7) into the terminal of the obtained polyphenylene ether polymer is not limited, and the functional group is not limited. Various known methods may be adopted depending on the type. For example, the introduction of a functional group having the structure of the formula (4), (6) or (7) can generally follow the formation of an ether bond by the Williamson synthetic method. The introduction of a functional group having the structure of the formula (5) is a reaction of forming an ester bond between a hydroxyl group at the terminal of a polyphenylene ether polymer and a carboxylic acid having a carbon-carbon double bond (hereinafter referred to as carboxylic acid), and is a known ester. A bond forming method can be used.
ポリフェニレンエーテル成分Ａ（ＰＰＥ−Ａ）は、高硬化反応性及び低誘電特性、並びに良好な流動性・成形性を有し、耐熱性に優れるので、各種電気・電子機器用の材料として好適に使用でき、特に、電気・電子部品（プリント配線板基材等）用のプリプレグの製造に好適に使用できる。ＰＰＥ−Ａは、樹脂組成物において、単独の樹脂として使用してもよいし、他の構造を有するポリフェニレンエーテルと併用してもよいし、公知の各種添加剤と組み合わせて使用することもできる。樹脂組成物中のＰＰＥ−Ａの含有量は、例えば、０．５質量％〜９５質量％とすることができる。 Polyphenylene ether component A (PPE-A) has high curing reactivity and low dielectric properties, as well as good fluidity and moldability, and is excellent in heat resistance, and is therefore suitably used as a material for various electric and electronic devices. In particular, it can be suitably used for manufacturing prepregs for electrical / electronic parts (printed wiring board base materials, etc.). In the resin composition, PPE-A may be used as a single resin, may be used in combination with polyphenylene ether having another structure, or may be used in combination with various known additives. The content of PPE-A in the resin composition can be, for example, 0.5% by mass to 95% by mass.
ポリフェニレンエーテル成分Ｂ（ＰＰＥ−Ｂ）
本実施形態に係る樹脂組成物は、上記で説明された数平均分子量５００〜８，０００のポリフェニレンエーテル成分Ａに加えて、１分子当たりの平均フェノール性水酸基数が１．２個以上、かつ数平均分子量が８，０００以上５０，０００以下のポリフェニレンエーテル成分Ｂを含むことが好ましい。ポリフェニレンエーテル成分Ｂは、その生産プロセスにおいて安定であり、かつ誘電特性及び耐熱性に優れているため、ポリフェニレンエーテル成分Ａを阻害することなく、樹脂組成物の硬化物の電気特性を向上させる傾向にある。
Polyphenylene ether component B (PPE-B)
In the resin composition according to the present embodiment, in addition to the polyphenylene ether component A having a number average molecular weight of 500 to 8,000 described above, the average number of phenolic hydroxyl groups per molecule is 1.2 or more and the number is large. It preferably contains a polyphenylene ether component B having an average molecular weight of 8,000 or more and 50,000 or less. Since the polyphenylene ether component B is stable in the production process and has excellent dielectric properties and heat resistance, it tends to improve the electrical properties of the cured product of the resin composition without inhibiting the polyphenylene ether component A. is there.
ポリフェニレンエーテル成分Ｂ（ＰＰＥ−Ｂ）は、ポリフェニレンエーテル成分Ａ（ＰＰＥ−Ａ）と区別されることができ、かつ１分子当たりの平均フェノール性水酸基数１．２個以上と数平均分子量８，０００〜５０，０００を満たすのであれば、任意のポリフェニレンエーテル（ＰＰＥ）でよい。ＰＰＥ−Ａとの併用の観点から、ＰＰＥ−Ｂの数平均分子量は、好ましくは、８，０００を超え、かつ５０，０００以下である。樹脂組成物においてＰＰＥ−ＡとＰＰＥ−Ｂを併用する場合には、樹脂組成物の安定性及び耐熱性の観点から、ＰＰＥ−ＡとＰＰＥ−Ｂとの合計質量１００質量％を基準として、ＰＰＥ−Ａの含有量が１質量％〜９９．９質量％であり、かつＰＰＥ−Ｂの含有量が０．１質量％〜９９質量％であることが好ましく、より好ましくは、ＰＰＥ−Ａの含有量が２０質量％〜９８質量％であり、かつＰＰＥ−Ｂの含有量が２質量％〜８０質量％、さらに好ましくはＰＰＥ−Ａの含有量が４０質量％〜９５質量％であり、かつＰＰＥ−Ｂの含有量が５質量％〜６０質量％である。 The polyphenylene ether component B (PPE-B) can be distinguished from the polyphenylene ether component A (PPE-A), and the average number of phenolic hydroxyl groups per molecule is 1.2 or more, and the number average molecular weight is 8,000. Any polyphenylene ether (PPE) may be used as long as it satisfies ~ 50,000. From the viewpoint of combined use with PPE-A, the number average molecular weight of PPE-B is preferably more than 8,000 and less than 50,000. When PPE-A and PPE-B are used in combination in the resin composition, PPE is based on a total mass of 100% by mass of PPE-A and PPE-B from the viewpoint of stability and heat resistance of the resin composition. The content of −A is preferably 1% by mass to 99.9% by mass, and the content of PPE-B is preferably 0.1% by mass to 99% by mass, and more preferably the content of PPE-A. The amount is 20% by mass to 98% by mass, and the content of PPE-B is 2% by mass to 80% by mass, more preferably the content of PPE-A is 40% by mass to 95% by mass, and PPE. The content of −B is 5% by mass to 60% by mass.
架橋剤
本実施形態では、架橋反応を起こすか、又は促進する能力を有する任意の架橋剤を使用することができる。架橋剤は、数平均分子量が４，０００以下であることが好ましい。架橋剤の数平均分子量が４，０００以下であると、樹脂組成物の粘度の増大を抑制でき、また加熱成型時の良好な樹脂流動性が得られる。数平均分子量は、一般的な分子量測定方法で測定したものであればよく、具体的には、ＧＰＣを用いて測定した値等が挙げられる。
Crosslinking Agent In this embodiment, any crosslinking agent having the ability to cause or promote a crosslinking reaction can be used. The cross-linking agent preferably has a number average molecular weight of 4,000 or less. When the number average molecular weight of the cross-linking agent is 4,000 or less, an increase in the viscosity of the resin composition can be suppressed, and good resin fluidity during heat molding can be obtained. The number average molecular weight may be any one measured by a general molecular weight measuring method, and specific examples thereof include a value measured by using GPC.
架橋剤は、架橋反応の観点から、炭素−炭素不飽和二重結合を１分子中に平均２個以上有することが好ましい。架橋剤は、１種類の化合物で構成されてもよく、２種類以上の化合物で構成されてもよい。本明細書にいう「炭素−炭素不飽和二重結合」とは、架橋剤がポリマー又はオリゴマーである場合、主鎖より分岐した末端に位置する二重結合をいう。炭素−炭素不飽和二重結合としては、例えば、ポリブタジエンにおける１，２−ビニル結合が挙げられる。 From the viewpoint of the cross-linking reaction, the cross-linking agent preferably has two or more carbon-carbon unsaturated double bonds in one molecule on average. The cross-linking agent may be composed of one kind of compound or two or more kinds of compounds. As used herein, the term "carbon-carbon unsaturated double bond" refers to a double bond located at the end branched from the main chain when the cross-linking agent is a polymer or oligomer. Examples of the carbon-carbon unsaturated double bond include a 1,2-vinyl bond in polybutadiene.
架橋剤の数平均分子量が６００未満である場合、架橋剤の１分子当たりの炭素−炭素不飽和二重結合の数（平均値）は、２〜４であることが好ましい。架橋剤の数平均分子量が６００〜１５００の場合には、架橋剤の１分子当たりの炭素−炭素不飽和二重結合の数（平均値）は、４〜２６であることが好ましい。架橋剤の数平均分子量が１，５００〜４，０００の場合には、架橋剤の１分子当たりの炭素−炭素不飽和二重結合の数（平均値）は、２６〜６０であることが好ましい。架橋剤の数平均分子量が上記範囲内にある場合に、炭素−炭素不飽和二重結合の数が特定値以上であることにより、本実施形態に係る樹脂組成物は、架橋剤の反応性が一層高まり、樹脂組成物の硬化物の架橋密度が一層向上し、その結果、一層優れた耐熱性を付与できる。一方で、架橋剤の数平均分子量が上記範囲内にある場合に、炭素−炭素不飽和二重結合の数が、特定値以下であることにより、加熱成形時に一層優れた樹脂流動性を付与できる。 When the number average molecular weight of the cross-linking agent is less than 600, the number of carbon-carbon unsaturated double bonds (average value) per molecule of the cross-linking agent is preferably 2 to 4. When the number average molecular weight of the cross-linking agent is 600 to 1500, the number of carbon-carbon unsaturated double bonds (average value) per molecule of the cross-linking agent is preferably 4 to 26. Number of cross-linking agents When the average molecular weight is 1,500 to 4,000, the number of carbon-carbon unsaturated double bonds (average value) per molecule of the cross-linking agent is preferably 26 to 60. .. When the number average molecular weight of the cross-linking agent is within the above range, the number of carbon-carbon unsaturated double bonds is equal to or more than a specific value, so that the resin composition according to the present embodiment has the reactivity of the cross-linking agent. Further, the crosslink density of the cured product of the resin composition is further improved, and as a result, more excellent heat resistance can be imparted. On the other hand, when the number average molecular weight of the cross-linking agent is within the above range, the number of carbon-carbon unsaturated double bonds is not more than a specific value, so that more excellent resin fluidity can be imparted during heat molding. ..
架橋剤としては、例えば、トリアリルイソシアヌレート（ＴＡＩＣ）等のトリアルケニルイソシアヌレート化合物、トリアリルシアヌレート（ＴＡＣ）等のトリアルケニルシアヌレート化合物、分子中にメタクリル基を２個以上有する多官能メタクリレート化合物、分子中にアクリル基を２個以上有する多官能アクリレート化合物、ポリブタジエン等の分子中にビニル基を２個以上有する多官能ビニル化合物、分子中にビニルベンジル基を有するジビニルベンゼン等のビニルベンジル化合物、４，４’−ビスマレイミドジフェニルメタン等の分子中にマレイミド基を２個以上有する多官能マレイミド化合物等が挙げられる。これらの架橋剤は、１種を単独で、又は２種以上を組み合わせて用いられる。架橋剤は、これらの中でも、トリアリルシアヌレート、トリアリルイソシアヌレート、及びポリブタジエンから成る群より選択される少なくとも１種の化合物を含むことが好ましい。架橋剤が、上記で説明された少なくとも１種以上の化合物を含むことにより、硬化反応（架橋反応）時に架橋密度が一層高くなり、これにより、樹脂組成物の硬化物の耐熱性が一層向上する傾向にある。 Examples of the cross-linking agent include a trialkenyl isocyanurate compound such as triallyl isocyanurate (TAIC), a trialkenyl cyanurate compound such as triallyl cyanurate (TAC), and a polyfunctional methacrylate having two or more methacryl groups in the molecule. Compounds, polyfunctional acrylate compounds having two or more acrylic groups in the molecule, polyfunctional vinyl compounds having two or more vinyl groups in the molecule such as polybutadiene, vinylbenzyl compounds such as divinylbenzene having a vinylbenzyl group in the molecule , 4,4'-Bismaleimide diphenylmethane and the like, which include polyfunctional maleimide compounds having two or more maleimide groups in the molecule. These cross-linking agents may be used alone or in combination of two or more. Among these, the cross-linking agent preferably contains at least one compound selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, and polybutadiene. When the cross-linking agent contains at least one compound described above, the cross-linking density becomes higher during the curing reaction (cross-linking reaction), whereby the heat resistance of the cured product of the resin composition is further improved. There is a tendency.
ＰＰＥ：架橋剤の重量比は、硬化時の低誘電率及び低誘電正接と架橋構造物の架橋密度のバランスを取るという観点から、２５：７５〜９５：５であることが好ましく、より好ましくは、３２：６８〜８５：１５である。また、ＰＰＥ−Ａ：架橋剤の重量比は、同様の観点から、好ましくは２５：７５〜９５：５、より好ましくは、３２：６８〜８５：１５である。 The weight ratio of PPE: cross-linking agent is preferably 25:75 to 95: 5, and more preferably 25:75 to 95: 5, from the viewpoint of balancing the low dielectric constant and low dielectric loss tangent at the time of curing and the cross-linking density of the cross-linked structure. , 32:68 to 85:15. From the same viewpoint, the weight ratio of PPE-A: cross-linking agent is preferably 25:75 to 95: 5, and more preferably 32:68 to 85:15.
有機過酸化物
本実施形態では、ポリフェニレンエーテル及び架橋剤を含む樹脂組成物の重合反応を促進する能力を有する任意の有機過酸化物を使用することができる。有機過酸化物としては、例えば、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、ジ（２−ｔ−ブチルペルオキシイソプロピル）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、ジクミルパーオキサイド、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等の過酸化物が挙げられる。なお、２，３−ジメチル−２，３−ジフェニルブタン等のラジカル発生剤も樹脂組成物のための反応開始剤として使用することができる。中でも、得られる耐熱性及び機械特性に優れ、更に低い誘電率及び誘電正接を有する硬化物を提供することができるという観点から、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキシン−３、ジ（２−ｔ−ブチルペルオキシイソプロピル）ベンゼン、及び２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサンが好ましい。
Organic Peroxide In this embodiment, any organic peroxide having an ability to accelerate the polymerization reaction of the resin composition containing polyphenylene ether and a cross-linking agent can be used. Examples of the organic peroxide include benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, and 2,5-dimethyl-2,5-di (t-butylper). Oxy) Hexin-3, di-t-butyl peroxide, t-butyl cumyl peroxide, di (2-t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) ) Hexane, dicumyl peroxide, 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, trimethylsilyltriphenylsilyl peroxide and other peroxides. A radical generator such as 2,3-dimethyl-2,3-diphenylbutane can also be used as a reaction initiator for the resin composition. Above all, from the viewpoint that it is possible to provide a cured product having excellent heat resistance and mechanical properties obtained, and further having a low dielectric constant and dielectric loss tangent, 2,5-dimethyl-2,5-di (t-butylperoxy). ) Hexin-3, di (2-t-butylperoxyisopropyl) benzene, and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane are preferred.
有機過酸化物の１分間半減期温度は、好ましくは１５５℃以上１８５℃以下であり、より好ましくは１６０℃〜１８０℃又は１６５℃〜１７５℃である。本明細書では、１分間半減期温度は、有機過酸化物が分解して、その活性酸素量が半分になる時間が１分間となる温度である。１分間半減期温度は、ラジカルに対して不活性な溶剤、例えばベンゼン等に有機過酸化物を０．０５ｍｏｌ／Ｌ〜０．１ｍｏｌ／Ｌの濃度となるように溶解させ、有機過酸化物溶液を窒素雰囲気化で熱分解させる方法で確認される値である。 The 1-minute half-life temperature of the organic peroxide is preferably 155 ° C. or higher and 185 ° C. or lower, and more preferably 160 ° C. to 180 ° C. or 165 ° C. to 175 ° C. In the present specification, the 1-minute half-life temperature is a temperature at which the time during which the organic peroxide is decomposed and the amount of active oxygen is halved is 1 minute. For the 1-minute half-life temperature, an organic peroxide solution is dissolved in a radical-inactive solvent such as benzene so as to have a concentration of 0.05 mol / L to 0.1 mol / L. It is a value confirmed by the method of thermally decomposing the material in a nitrogen atmosphere.
有機過酸化物の１分間半減期温度が１５５℃以上であることにより、ＰＰＥ含有樹脂組成物を加熱加圧成型に供す際、ＰＰＥを十分に溶融させてから架橋剤との反応が開始されることになるので、成型性に優れる傾向にある。一方、有機過酸化物の１分間半減期温度が１８５℃以下であることにより、通常の加熱加圧成型条件（例えば最高到達温度２００℃）での有機過酸化物の分解速度が十分であるため、架橋剤との架橋反応を効率的かつ緩やかに進めることができるので、良好な電気特性（特に誘電正接）を有する硬化物を形成可能である。 When the 1-minute half-life temperature of the organic peroxide is 155 ° C. or higher, when the PPE-containing resin composition is subjected to heat and pressure molding, the reaction with the cross-linking agent is started after the PPE is sufficiently melted. Therefore, it tends to be excellent in moldability. On the other hand, since the one-minute half-life temperature of the organic peroxide is 185 ° C. or lower, the decomposition rate of the organic peroxide under normal heat and pressure molding conditions (for example, the maximum ultimate temperature of 200 ° C.) is sufficient. Since the cross-linking reaction with the cross-linking agent can proceed efficiently and slowly, it is possible to form a cured product having good electrical characteristics (particularly dielectric loss tangent).
１分間半減期温度が１５５℃〜１８５℃の範囲内にある有機過酸化物としては、例えば、ｔ−へキシルペルオキシイソプロピルモノカーボネート（１５５．０℃）、ｔ−ブチルペルオキシ−３，５，５−トリメチルヘキサノエート（１６６．０℃）、ｔ−ブチルペルオキシラウレート（１５９．４℃）、ｔ−ブチルペルオキシイソプロピルモノカーボネート（１５８．８℃）、ｔ−ブチルペルオキシ２−エチルへキシルモノカーボネート（１６１．４℃）、ｔ−へキシルパーオキシベンゾエート（１６０．３℃）、２，５−ジメチル−２，５−ジ（ベンゾイルパーオキシ）ヘキサン（１５８．２℃）、ｔ−ブチルペルオキシアセテート（１５９．９℃）、２，２−ジ−（ｔ−ブチルパーオキシ）ブタン（１５９．９℃）、ｔ−ブチルパーオキシベンゾエート（１６６．８℃）、ｎ−ブチル４，４−ジ−（ｔ−ブチルペルオキシ）バレラート（１７２．５℃）、ジ（２−ｔ−ブチルペルオキシイソプロピル）ベンゼン（１７５．４℃）、ジクミルパーオキサイド（１７５．２℃）、ジ−ｔ−へキシルパーオキサイド（１７６．７℃）、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン（１７９．８℃）、及びｔ−ブチルクミルパーオキサイド（１７３．３℃）などが挙げられる。 Examples of organic peroxides having a 1-minute half-life temperature in the range of 155 ° C to 185 ° C include t-hexylperoxyisopropyl monocarbonate (155.0 ° C) and t-butylperoxy-3,5,5. -Trimethylhexanoate (166.0 ° C), t-butylperoxylaurate (159.4 ° C), t-butylperoxyisopropylmonocarbonate (158.8 ° C), t-butylperoxy2-ethylhexylmonocarbonate (161.4 ° C), t-hexyl peroxybenzoate (160.3 ° C), 2,5-dimethyl-2,5-di (benzoylperoxy) hexane (158.2 ° C), t-butyl peroxyacetate (159.9 ° C), 2,2-di- (t-butylperoxy) butane (159.9 ° C), t-butylperoxybenzoate (166.8 ° C), n-butyl 4,4-di- (T-Butylperoxy) Valerate (172.5 ° C), Di (2-t-Butylperoxyisopropyl) benzene (175.4 ° C), Dicumyl peroxide (175.2 ° C), Di-t-hexylper Oxide (176.7 ° C), 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (179.8 ° C), t-butylcumyl peroxide (173.3 ° C) and the like. Be done.
有機過酸化物の含有量は、ＰＰＥと架橋剤の合計１００質量部を基準として、反応率を高くすることができるという観点から、好ましくは０．０５質量部以上、より好ましくは０．５質量部以上又は１質量部以上、更に好ましくは１．５質量部以上であり、得られる硬化物の誘電率及び誘電正接を低く抑えることができるという観点から、好ましくは５質量部以下、より好ましくは４．５質量部以下である。また、有機過酸化物の含有量は、同様の観点から、ＰＰＥ−Ａと架橋剤の合計１００質量部を基準として、好ましくは０．０５質量部以上かつ５質量部以下、より好ましくは、０．５質量部以上かつ４．５質量部以下、更に好ましくは、１質量部以上かつ４．５質量部以下、又は１．５質量部以上かつ４．５質量部以下である。 The content of the organic peroxide is preferably 0.05 parts by mass or more, more preferably 0.5 parts by mass, from the viewpoint that the reaction rate can be increased based on 100 parts by mass of the total of PPE and the cross-linking agent. It is preferably 5 parts by mass or more, more preferably 1.5 parts by mass or more, and more preferably 5 parts by mass or less, more preferably 1.5 parts by mass or more, and from the viewpoint that the dielectric constant and dielectric loss tangent of the obtained cured product can be suppressed low. It is 4.5 parts by mass or less. From the same viewpoint, the content of the organic peroxide is preferably 0.05 parts by mass or more and 5 parts by mass or less, more preferably 0, based on 100 parts by mass of the total of PPE-A and the cross-linking agent. It is 5.5 parts by mass or more and 4.5 parts by mass or less, more preferably 1 part by mass or more and 4.5 parts by mass or less, or 1.5 parts by mass or more and 4.5 parts by mass or less.
熱可塑性樹脂
樹脂組成物は、熱可塑性樹脂を含むことが好ましい。熱可塑性樹脂は、ビニル芳香族化合物とオレフィン系アルケン化合物とのブロック共重合体及びその水素添加物（ビニル芳香族化合物とオレフィン系アルケン化合物とのブロック共重合体を水素添加して得られる水添ブロック共重合体）、並びにビニル芳香族化合物の単独重合体から成る群より選択される少なくとも１種であることが好ましい。上記ブロック共重合体又はその水素添加物のビニル芳香族化合物由来の単位の含有率は、２０質量％以上であることが好ましく、２２質量％以上であることがより好ましく、９９質量％以下であることができる。上記ブロック共重合体又はその水素添加物のビニル芳香族化合物由来の単位の含有率が２０質量％以上であることにより、ポリフェニレンエーテルとの相溶性が一層向上し、金属箔との密着強度が一層向上する傾向にある。
Thermoplastic resin The resin composition preferably contains a thermoplastic resin. The thermoplastic resin is a block copolymer of a vinyl aromatic compound and an olefin-based alkene compound and a hydrogenated product thereof (hydrogenation obtained by hydrogenating a block copolymer of a vinyl aromatic compound and an olefin-based alkene compound). It is preferably at least one selected from the group consisting of block copolymers) and homopolymers of vinyl aromatic compounds. The content of the unit derived from the vinyl aromatic compound of the block copolymer or its hydrogenated product is preferably 20% by mass or more, more preferably 22% by mass or more, and 99% by mass or less. be able to. When the content of the unit derived from the vinyl aromatic compound of the block copolymer or its hydrogenated product is 20% by mass or more, the compatibility with polyphenylene ether is further improved, and the adhesion strength with the metal foil is further improved. It tends to improve.
ビニル芳香族化合物は、分子内に芳香環及びビニル基を有すればよく、例えば、スチレンが挙げられる。オレフィン系アルケン化合物は、分子内に、直鎖若しくは分岐構造を有するアルケンであればよく、例えば、エチレン、プロピレン、ブチレン、イソブチレン、ブタジエン、及びイソプレンが挙げられる。これらの中でも、熱可塑性樹脂は、ポリフェニレンエーテルとの相溶性に一層優れる観点から、スチレン−ブタジエンブロック共重合体、スチレン−エチレン−ブタジエンブロック共重合体、スチレン−エチレン−ブチレンブロック共重合体、スチレン−ブタジエン−ブチレンブロック共重合体、スチレン−イソプレンブロック共重合体、スチレン−エチレン−プロピレンブロック共重合体、スチレン−イソブチレンブロック共重合体、スチレン−ブタジエンブロック共重合体の水素添加物、スチレン−エチレン−ブタジエンブロック共重合体の水素添加物、スチレン−ブタジエン−ブチレンブロック共重合体の水素添加物、スチレン−イソプレンブロック共重合体の水素添加物、及びスチレンの単独重合体（ポリスチレン）から成る群より選択される少なくとも１種であることが好ましく、スチレン−ブタジエンブロック共重合体、スチレン−ブタジエンブロック共重合体の水素添加物、及びポリスチレンからなる群より選択される１種以上であることがより好ましい。 The vinyl aromatic compound may have an aromatic ring and a vinyl group in the molecule, and examples thereof include styrene. The olefin-based alkene compound may be an alkene having a linear or branched structure in the molecule, and examples thereof include ethylene, propylene, butylene, isobutylene, butadiene, and isoprene. Among these, the thermoplastic resin is a styrene-butadiene block copolymer, a styrene-ethylene-butadiene block copolymer, a styrene-ethylene-butylene block copolymer, and styrene from the viewpoint of being more excellent in compatibility with polyphenylene ether. -Butadiene-butylene block copolymer, styrene-isoprene block copolymer, styrene-ethylene-propylene block copolymer, styrene-isobutylene block copolymer, styrene-butadiene block copolymer hydrogenated product, styrene-ethylene From the group consisting of a hydrogenated product of a −butadiene block copolymer, a hydrogenated product of a styrene-butadiene-butylene block copolymer, a hydrogenated product of a styrene-isoprene block copolymer, and a homopolymer of styrene (polystyrene). It is preferably at least one selected, and more preferably one or more selected from the group consisting of a styrene-butadiene block copolymer, a hydrogenated additive of a styrene-butadiene block copolymer, and polystyrene. ..
上記水素添加物における水素添加率は、特に限定されず、オレフィン系アルケン化合物由来の炭素‐炭素不飽和二重結合が一部残存していてもよい。 The hydrogenation rate of the hydrogenated product is not particularly limited, and a carbon-carbon unsaturated double bond derived from an olefin-based alkene compound may partially remain.
熱可塑性樹脂の重量平均分子量は、好ましくは１０，０００〜３００，０００、より好ましくは２０，０００〜２９０，０００、さらに好ましくは３０，０００〜２８０，０００である。重量平均分子量が１０，０００以上であることにより、本実施形態の樹脂組成物は、硬化した際に耐熱性に一層優れる傾向にある。重量平均分子量が３００，０００以下であることにより、本実施形態の樹脂組成物は、加熱成形時に一層良好な樹脂流動性を有する傾向にある。重量平均分子量は、後述の実施例に記載の方法により求められる。 The weight average molecular weight of the thermoplastic resin is preferably 10,000 to 300,000, more preferably 20,000 to 290,000, and even more preferably 30,000 to 280,000. When the weight average molecular weight is 10,000 or more, the resin composition of the present embodiment tends to be more excellent in heat resistance when cured. Since the weight average molecular weight is 300,000 or less, the resin composition of the present embodiment tends to have better resin fluidity at the time of heat molding. The weight average molecular weight is determined by the method described in Examples described later.
熱可塑性樹脂の含有量は、ＰＰＥ及び架橋剤の合計１００質量部を基準として、２質量部〜２０質量部であることが好ましく、３質量部〜１９質量部であることがより好ましい。含有量が２質量部以上であることにより、本実施形態の樹脂組成物は、硬化した際に低誘電率性、低誘電正接性及び金属箔との密着性に一層優れる傾向にある。含有量が２０質量部以下であることにより、本実施形態の樹脂組成物は、加熱成形時に一層優れた樹脂流動性を有する傾向にある。また、熱可塑性樹脂の含有量は、同様の観点から、ＰＰＥ−Ａ及び架橋剤の合計１００質量部を基準として、好ましくは２質量部〜２０質量部、より好ましくは３質量部〜１９質量部である。 The content of the thermoplastic resin is preferably 2 parts by mass to 20 parts by mass, and more preferably 3 parts by mass to 19 parts by mass, based on a total of 100 parts by mass of PPE and the cross-linking agent. When the content is 2 parts by mass or more, the resin composition of the present embodiment tends to be more excellent in low dielectric constant, low dielectric loss tangent property and adhesion to the metal foil when cured. When the content is 20 parts by mass or less, the resin composition of the present embodiment tends to have more excellent resin fluidity at the time of heat molding. From the same viewpoint, the content of the thermoplastic resin is preferably 2 parts by mass to 20 parts by mass, more preferably 3 parts by mass to 19 parts by mass, based on a total of 100 parts by mass of PPE-A and the cross-linking agent. Is.
難燃剤
本実施形態の樹脂組成物は、難燃剤を含むことが好ましい。難燃剤としては、耐熱性を向上できる観点から、樹脂組成物の硬化後に樹脂組成物中の他の含有成分と相溶しないものであれば特に制限されない。好ましくは、難燃剤は、樹脂組成物の硬化後に樹脂組成物中のＰＰＥ及び／又は架橋剤と相溶しない。難燃剤としては、例えば、三酸化アンチモン、水酸化アルミニウム、水酸化マグネシウム、ホウ酸亜鉛等の無機難燃剤；ヘキサブロモベンゼン、デカブロモジフェニルエタン、４，４−ジブロモビフェニル、エチレンビステトラブロモフタルイミド等の芳香族臭素化合物；レゾルシノールビス−ジフェニルホスフェート、レゾルシノールビス−ジキシレニルホスフェート等のリン系難燃剤等が挙げられる。これらの難燃剤は、１種を単独で、又は２種以上を組み合わせて用いられる。これらの中でも、難燃剤は、樹脂組成物を硬化した際の低誘電率性及び低誘電正接性に一層優れる観点から、デカブロモジフェニルエタンであることが好ましい。
Flame Retardant The resin composition of the present embodiment preferably contains a flame retardant. The flame retardant is not particularly limited as long as it is incompatible with other components in the resin composition after curing from the viewpoint of improving heat resistance. Preferably, the flame retardant is incompatible with the PPE and / or the cross-linking agent in the resin composition after curing of the resin composition. Examples of the flame retardant include inorganic flame retardants such as antimony trioxide, aluminum hydroxide, magnesium hydroxide and zinc borate; hexabromobenzene, decabromodiphenylethane, 4,4-dibromobiphenyl, ethylenebistetrabromophthalimide and the like. Aromatic bromine compounds of the above; phosphorus-based flame retardants such as resorcinol bis-diphenyl phosphate and resorcinol bis-dixylenyl phosphate. These flame retardants may be used alone or in combination of two or more. Among these, the flame retardant is preferably decabromodiphenylethane from the viewpoint of further excellent low dielectric constant and low dielectric loss tangent when the resin composition is cured.
難燃剤の含有量は、特に限定されないが、ＵＬ規格９４Ｖ−０レベルの難燃性を維持するという観点から、ポリフェニレンエーテル（ＰＰＥ）樹脂と架橋剤との合計１００質量部に対して、好ましくは５質量部以上、より好ましくは１０質量部以上、更に好ましくは１５質量部以上である。また、得られる硬化物の誘電率及び誘電正接を低く維持できる観点から、難燃剤の含有量は、好ましくは５０質量部以下、より好ましくは４５質量部以下、更に好ましくは４０質量部以下である。 The content of the flame retardant is not particularly limited, but from the viewpoint of maintaining the flame retardancy of UL standard 94V-0 level, it is preferable with respect to a total of 100 parts by mass of the polyphenylene ether (PPE) resin and the cross-linking agent. It is 5 parts by mass or more, more preferably 10 parts by mass or more, and further preferably 15 parts by mass or more. Further, from the viewpoint that the dielectric constant and the dielectric loss tangent of the obtained cured product can be kept low, the content of the flame retardant is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and further preferably 40 parts by mass or less. ..
シリカフィラー
本実施形態の樹脂組成物は、シリカフィラーを含有してよい。シリカフィラーとしては、例えば、天然シリカ、溶融シリカ、合成シリカ、アモルファスシリカ、アエロジル、及び中空シリカが挙げられる。シリカフィラーの含有量は、ポリフェニレンエーテル（ＰＰＥ）樹脂及び架橋剤の合計１００質量部に対して、１０質量部〜１００質量部であることができる。また、シリカフィラーは、その表面にシランカップリング剤等を用いて表面処理をされたものであってもよい。
Silica filler The resin composition of the present embodiment may contain a silica filler. Examples of the silica filler include natural silica, fused silica, synthetic silica, amorphous silica, Aerosil, and hollow silica. The content of the silica filler can be 10 parts by mass to 100 parts by mass with respect to 100 parts by mass in total of the polyphenylene ether (PPE) resin and the cross-linking agent. Further, the silica filler may have its surface treated with a silane coupling agent or the like.
本実施形態の樹脂組成物は、難燃剤及びシリカフィラー以外に、熱安定剤、酸化防止剤、ＵＶ吸収剤、界面活性剤、滑剤などの添加剤、溶剤などを更に含んでもよい。本実施形態の樹脂組成物は、溶剤を含む場合には、樹脂組成物中の固形成分が溶剤に溶解又は分散したワニスの形態であることができる。また、本実施形態の樹脂組成物から樹脂フィルムを形成することができる。 In addition to the flame retardant and the silica filler, the resin composition of the present embodiment may further contain additives such as heat stabilizers, antioxidants, UV absorbers, surfactants, lubricants, solvents and the like. When the resin composition of the present embodiment contains a solvent, the resin composition can be in the form of a varnish in which the solid component in the resin composition is dissolved or dispersed in the solvent. Further, a resin film can be formed from the resin composition of the present embodiment.
溶剤
溶剤としては、溶解性の観点から、トルエン、キシレン等の芳香族系化合物、メチルエチルケトン（ＭＥＫ）、シクロペンタノン、シクロヘキサノン及びクロロホルムが好ましい。これらの溶剤は１種を単独で、又は２種以上を組み合わせて用いられる。
Solvent As the solvent, aromatic compounds such as toluene and xylene, methyl ethyl ketone (MEK), cyclopentanone, cyclohexanone and chloroform are preferable from the viewpoint of solubility. These solvents may be used alone or in combination of two or more.
プリプレグ
本実施形態のプリプレグは、基材と、この基材に含浸又は塗布された本実施形態の樹脂組成物とを含む。プリプレグは、例えば、ガラスクロス等の基材を上記ワニスに含浸させた後、熱風乾燥機等で溶剤分を乾燥除去することにより得られる。
Prepreg The prepreg of the present embodiment includes a base material and the resin composition of the present embodiment impregnated or coated on the base material. The prepreg can be obtained, for example, by impregnating the varnish with a base material such as glass cloth and then drying and removing the solvent component with a hot air dryer or the like.
基材としては、ロービングクロス、クロス、チョップドマット、サーフェシングマット等の各種ガラスクロス；アスベスト布、金属繊維布、及びその他の合成若しくは天然の無機繊維布；全芳香族ポリアミド繊維、全芳香族ポリエステル繊維、ポリベンゾオキサゾール繊維等の液晶繊維から得られる織布又は不織布；綿布、麻布、フェルト等の天然繊維布；カーボン繊維布、クラフト紙、コットン紙、紙−ガラス混繊糸から得られる布等の天然セルロース系基材；ポリテトラフルオロエチレン多孔質フィルム等が挙げられる。これらの基材は、１種を単独で、又は２種以上を組み合わせて用いられる。 As the base material, various glass cloths such as roving cloths, cloths, chopped mats, and surface mats; asbestos cloths, metal fiber cloths, and other synthetic or natural inorganic fiber cloths; all aromatic polyamide fibers, all aromatic polyesters. Woven or non-woven fabrics obtained from liquid crystal fibers such as fibers and polybenzoxazole fibers; natural fiber fabrics such as cotton cloth, linen cloth and felt; carbon fiber cloth, kraft paper, cotton paper, cloth obtained from paper-glass mixed fiber yarn, etc. Natural cellulose-based base material; polytetrafluoroethylene porous film and the like can be mentioned. These base materials may be used alone or in combination of two or more.
プリプレグ中の本実施形態の樹脂組成物固形分の割合は、３０〜８０質量％であることが好ましく、４０〜７０質量％であることがより好ましい。上記割合が３０質量％以上であることにより、プリプレグを電子基板用等に用いた場合に絶縁信頼性に一層優れる傾向にある。上記割合が８０質量％以下であることにより、電子基板などの用途において、曲げ弾性率等の機械特性に一層優れる傾向にある。 The proportion of the solid content of the resin composition of the present embodiment in the prepreg is preferably 30 to 80% by mass, more preferably 40 to 70% by mass. When the above ratio is 30% by mass or more, the insulation reliability tends to be further improved when the prepreg is used for an electronic substrate or the like. When the above ratio is 80% by mass or less, mechanical properties such as flexural modulus tend to be further excellent in applications such as electronic substrates.
金属張積層板
本実施形態の金属張積層板は、本実施形態の樹脂組成物若しくは樹脂フィルム又は本実施形態のプリプレグと、金属箔とを積層して硬化して得られる。金属張積層板は、プリプレグの硬化物（「硬化物複合体」ともいう）と金属箔とが積層して密着している形態を有することが好ましく、電子基板用材料として好適に用いられる。金属箔としては、例えば、アルミ箔及び銅箔が挙げられ、これらの中でも銅箔は電気抵抗が低いため好ましい。金属箔と組合せる硬化物複合体は、１枚でも複数枚でもよく、用途に応じて複合体の片面又は両面に金属箔を重ねて積層板に加工する。積層板の製造方法としては、例えば、熱硬化性樹脂組成物と基材とから構成される複合体（例えば、前述のプリプレグ）を形成し、これを金属箔と重ねた後、熱硬化性樹脂組成物を硬化させることにより、硬化物積層体と金属箔とが積層されている積層板を得る方法が挙げられる。前記積層板の特に好ましい用途の１つはプリント配線板である。プリント配線板は、金属張積層板から金属箔の少なくとも一部が除去されていることが好ましい。
Metal-clad laminate The metal-clad laminate of the present embodiment is obtained by laminating and curing the resin composition or resin film of the present embodiment or the prepreg of the present embodiment and a metal foil. The metal-clad laminate preferably has a form in which a cured product of a prepreg (also referred to as a “cured product composite”) and a metal foil are laminated and adhered to each other, and is preferably used as a material for an electronic substrate. Examples of the metal foil include aluminum foil and copper foil, and among these, copper foil is preferable because it has low electrical resistance. The cured product composite to be combined with the metal foil may be one or more, and the metal foil is laminated on one side or both sides of the composite depending on the application and processed into a laminated plate. As a method for producing a laminated board, for example, a composite composed of a thermosetting resin composition and a base material (for example, the above-mentioned prepreg) is formed, and after laminating this with a metal foil, the thermosetting resin is produced. Examples thereof include a method of obtaining a laminated plate in which a cured product laminate and a metal foil are laminated by curing the composition. One of the particularly preferable uses of the laminated board is a printed wiring board. The printed wiring board preferably has at least a part of the metal foil removed from the metal-clad laminate.
プリント配線板
本実施形態のプリント配線板は、金属張積層板から金属箔の一部が除去されている。本実施形態のプリント配線板は、典型的には、上述した本発明のプリプレグを用いて、加圧加熱成型する方法で形成できる。基材としてはプリプレグに関して前述したのと同様のものが挙げられる。本実施形態のプリント配線板は、本実施形態の樹脂組成物を含むことにより、優れた耐熱性及び電気特性（低誘電率及び低誘電正接）を有し、更には環境変動に伴う電気特性の変動を抑制可能であり、更には優れた絶縁信頼性及び機械特性を有する。
Printed wiring board In the printed wiring board of the present embodiment, a part of the metal foil is removed from the metal-clad laminate. The printed wiring board of the present embodiment can typically be formed by a method of pressure heating molding using the prepreg of the present invention described above. Examples of the base material include those similar to those described above for the prepreg. The printed wiring board of the present embodiment has excellent heat resistance and electrical characteristics (low dielectric constant and low dielectric loss tangent) by containing the resin composition of the present embodiment, and further has electrical characteristics due to environmental changes. Fluctuations can be suppressed, and it also has excellent insulation reliability and mechanical properties.
以下に実施例を挙げて、本実施形態を詳細に説明するが、本実施形態は実施例に限定されるものではない。 Hereinafter, the present embodiment will be described in detail with reference to examples, but the present embodiment is not limited to the examples.
ポリフェニレンエーテルの合成反応
次の反応を不活性ガスの雰囲気下で実施した。反応に使用する溶媒は、市販の試薬である。使用した原料及び試薬類は、以下のとおりである。
Synthesis reaction of polyphenylene ether The following reaction was carried out under the atmosphere of an inert gas. The solvent used in the reaction is a commercially available reagent. The raw materials and reagents used are as follows.
１．溶媒
トルエン：和光純薬製試薬特級品をそのまま使用した。
メチルエチルケトン：和光純薬製試薬特級品をそのまま使用した。
メタノール：和光純薬製試薬特級品をそのまま使用した。
２．開始剤：
ナイパーＢＭＴ：日本油脂製品をそのまま使用した。
３．原料ポリフェニレンエーテル
Ｓ２０２Ａ（ポリスチレン換算数平均分子量１６，０００）：旭化成株式会社製製品をそのまま使用した。
Ｓ２０２Ａは、下記の構造を有する。
Methyl ethyl ketone: A special grade reagent manufactured by Wako Pure Chemical Industries was used as it was.
Methanol: A special grade reagent manufactured by Wako Pure Chemical Industries was used as it was.
2. 2. Initiator:
NOF BMT: NOF products were used as they were.
3. 3. Raw material Polyphenylene ether S202A (polystyrene equivalent number average molecular weight 16,000): A product manufactured by Asahi Kasei Corporation was used as it was.
S202A has the following structure.
４．原料フェノール（多官能／二官能フェノール）
４−１．式（２）の部分構造を含む価数ａ（ａ＝３〜６）のフェノール類
１，１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔｅｒｔ−ブチルフェニル）ブタン：株式会社ＡＤＥＫＡ製品（アデカスタブＡＯ−３０）をそのまま使用した。
4. Raw material phenol (polyfunctional / bifunctional phenol)
4-1. Phenols 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane having a valence of a (a = 3 to 6) containing a partial structure of the formula (2): ADEKA CORPORATION The product (ADEKA STAB AO-30) was used as it was.
４−２．式（２）の部分構造を含まない価数３のフェノール類
トリス（４−ヒドロキシフェニル）エタン：旭有機材製品をそのまま使用した。
4-2. Phenols tris (4-hydroxyphenyl) ethane having a valence of 3 not including the partial structure of the formula (2): Asahi organic material products were used as they were.
５．変性基原料
無水メタクリル酸：アルドリッチ試薬品をそのまま使用した。
ジメチルアミノピリジン：アルドリッチ試薬品をそのまま使用した。
5. Denatured group raw material Methacrylic anhydride: The Aldrich reagent product was used as it was.
Dimethylaminopyridine: The Aldrich reagent product was used as it was.
ポリフェニレンエーテルの同定・分析
１．数平均分子量測定
クロロホルム溶媒下、ＧＰＣにより数平均分子量測定を行った。数平均分子量は、標準ポリスチレンを用いた検量線に基づいて、ポリスチレン換算法により求めた。
２．ＮＭＲ測定
重クロロホルムに、５質量％濃度となるように試料を溶解し、ＮＭＲ測定を実施した。反応の進行は、多官能フェノールユニットの芳香族のピークと、水酸基のプロトンピークの比率から、水酸基ピークの減少により確認した。
３．溶融粘度
試料の２０質量％メチルエチルケトン溶液２００ｍｌをビーカーに入れ、Ｂ型回転粘度計を用いて２５℃で回転数３０ｒｐｍで粘度を測定した。
Identification and analysis of polyphenylene ether 1. Number average molecular weight measurement The number average molecular weight was measured by GPC under chloroform solvent. The number average molecular weight was determined by the polystyrene conversion method based on the calibration curve using standard polystyrene.
2. 2. NMR measurement A sample was dissolved in deuterated chloroform to a concentration of 5% by mass, and NMR measurement was performed. The progress of the reaction was confirmed by the decrease of the hydroxyl group peak from the ratio of the aromatic peak of the polyfunctional phenol unit to the proton peak of the hydroxyl group.
3. 3. Melt Viscosity 200 ml of a 20 mass% methyl ethyl ketone solution of a sample was placed in a beaker, and the viscosity was measured at 25 ° C. and a rotation speed of 30 rpm using a B-type rotational viscometer.
４．平均末端官能基数
ＰＰＥ一分子当たりの平均末端官能基数を以下の方法により求めた。すなわち、「高分子論文集，ｖｏｌ．５１，Ｎｏ．７（１９９４），第４８０頁」記載の方法に準拠し、ＰＰＥの塩化メチレン溶液にテトラメチルアンモニウムハイドロオキシド溶液を加えることにより得られるサンプルの波長３１８ｎｍにおける吸光度変化を紫外可視吸光光度計で測定した。この測定値から、ＰＰＥの末端変性の前後のフェノール性水酸基の数を求めた。また、上記１の方法により求めたＰＰＥの数平均分子量と、ＰＰＥの質量とを用いてＰＰＥの分子数（数平均分子数）を求めた。
これらの値から、下記数式（１）に従って、変性前後のＰＰＥ１分子当たりの平均フェノール性水酸基数を求めた。：
１分子当たりの平均フェノール性水酸基数
＝フェノール性水酸基の数／数平均分子数・・・（１）
変性後の平均末端官能基数は、下記数式（２）に従って、変性後の平均末端官能基数を求めた。：
１分子当たりの平均末端官能基数
＝変性前の平均フェノール性水酸基数−変性後の平均フェノール性水酸基数・・・（２）
4. Average number of terminal functional groups The average number of terminal functional groups per molecule of PPE was determined by the following method. That is, a sample obtained by adding a tetramethylammonium hydroxide solution to a methylene chloride solution of PPE in accordance with the method described in "Polymer Papers, vol.51, No. 7 (1994), p. 480". The change in absorbance at a wavelength of 318 nm was measured with an ultraviolet-visible absorptiometer. From this measured value, the number of phenolic hydroxyl groups before and after terminal denaturation of PPE was determined. Further, the number of molecules of PPE (number average number of molecules) was determined by using the number average molecular weight of PPE obtained by the above method 1 and the mass of PPE.
From these values, the average number of phenolic hydroxyl groups per PPE molecule before and after denaturation was determined according to the following mathematical formula (1). :
Average number of phenolic hydroxyl groups per molecule = number of phenolic hydroxyl groups / number average number of molecules ... (1)
For the average number of terminal functional groups after modification, the average number of terminal functional groups after modification was determined according to the following mathematical formula (2). :
Average number of terminal functional groups per molecule = average number of phenolic hydroxyl groups before modification-average number of phenolic hydroxyl groups after modification ... (2)
製造例１
ポリフェニレンエーテル１（ＰＰＥ１）の合成
５００ｍｌの３つ口フラスコに、３方コックを付け、さらにジムロートと等圧滴下ロートを設置した。フラスコ内を窒素に置換した後、原料ポリフェニレンエーテルＳ２０２Ａ１００ｇ、トルエン２００ｇ、多官能フェノールとして１，１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔｅｒｔ−ブチルフェニル）ブタン１２．８ｇを加えた。フラスコに温度計を設置し、マグネチックスターラーにて撹拌しながら、オイルバスにてフラスコを９０℃に加熱し、原料ポリフェニレンエーテルを溶解させた。開始剤として、ベンゾイルペルオキシド、ベンゾイルｍ−メチルベンゾイルペルオキシド、ｍ−トルイルペルオキシドの混合物の４０％メタキシレン溶液（日油製：ナイパーＢＭＴ）の３７．５ｇをトルエン８７．５ｇに希釈し、等圧滴下ロートに仕込んだ。フラスコ内の温度を８０℃まで降温させた後、開始剤溶液を、フラスコ内へ滴下開始し、反応を開始した。開始剤を２時間かけて滴下し、滴下後、再び９０℃に昇温し，４時間撹拌を継続した。反応後、ポリマー溶液をメタノール中に滴下し、再沈させた後、溶液と濾別し、ポリマーを回収した。その後、これを真空下１００℃で３時間乾燥させた。１Ｈ−ＮＭＲにより、低分子フェノールがポリマー中に取り込まれ、水酸基のピークが消失していることを確認した。この１Ｈ−ＮＭＲ測定結果から、得られたポリマーは、下記式：
で表されるような構造を有するポリフェニレンエーテル（以下、ＰＰＥ１という）であると確認できた。ＧＰＣ測定の結果、得られたＰＰＥ１のポリスチレン換算での分子量はＭｎ＝１，５００であった。また、ＰＰＥ１の２０％メチルエチルケトン溶媒中での溶液粘度は１２５ｃＰｏｉｓｅであった。
Manufacturing example 1
Synthesis of polyphenylene ether 1 (PPE1) A 500 ml three-necked flask was provided with a three-way cock, and a Dimroth condenser and an isobaric dropping funnel were further installed. After replacing the inside of the flask with nitrogen, 100 g of the raw material polyphenylene ether S202A, 200 g of toluene, and 12.8 g of 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane as a polyfunctional phenol were added. It was. A thermometer was installed in the flask, and the flask was heated to 90 ° C. in an oil bath while stirring with a magnetic stirrer to dissolve the raw material polyphenylene ether. As an initiator, 37.5 g of a 40% metaxylene solution (Nippon Oil Co., Ltd .: Niper BMT) of a mixture of benzoyl peroxide, benzoyl m-methylbenzoyl peroxide, and m-toluyl peroxide was diluted to 87.5 g of toluene and added dropwise at isobaric pressure. I put it in the funnel. After lowering the temperature inside the flask to 80 ° C., the initiator solution was started dropping into the flask to start the reaction. The initiator was added dropwise over 2 hours, and after the addition, the temperature was raised to 90 ° C. again, and stirring was continued for 4 hours. After the reaction, the polymer solution was added dropwise to methanol, reprecipitated, and then filtered off from the solution to recover the polymer. Then, this was dried under vacuum at 100 ° C. for 3 hours. 1 It was confirmed by 1 H-NMR that low molecular weight phenol was incorporated into the polymer and the peak of the hydroxyl group disappeared. The polymer obtained from this 1 1 H-NMR measurement result has the following formula:
It was confirmed that it was a polyphenylene ether (hereinafter referred to as PPE1) having a structure represented by. As a result of GPC measurement, the molecular weight of the obtained PPE1 in terms of polystyrene was Mn = 1,500. The solution viscosity of PPE1 in a 20% methyl ethyl ketone solvent was 125 cPoise.
変性ポリフェニレンエーテル１（変性ＰＰＥ１）の合成
トルエン８０ｇ及び上記で合成したＰＰＥ１を２６ｇ混合して約８５℃に加熱した。加熱された混合物へジメチルアミノピリジン０．５５ｇを添加した。固体が全て溶解したと思われる時点で、溶解物へ無水メタクリル酸４．９ｇを徐々に添加した。得られた溶液を連続混合しながら８５℃に３時間維持した。次いで、溶液を室温に冷却して、メタクリレート変性ポリフェニレンエーテルのトルエン溶液を得た。
溶液の一部を採取し、乾燥後１Ｈ−ＮＭＲ測定を実施した。ポリフェニレンエーテルの水酸基由来のピークが消失していたことから、反応が進行しているものと判断し、精製操作に移った。上記メタクリレート変性ポリフェニレンエーテルのトルエン溶液１２０ｇを、１Ｌビーカー中マグネチックスターラーで激しく撹拌したメタノール３６０ｇ中に３０分掛けて滴下した。得られた沈殿物を、メンブランフィルターで減圧濾過した後に乾燥し、３８ｇのポリマーを得た。乾燥させたポリマーの１Ｈ−ＮＭＲ測定結果を図１に示す。４．５ｐｐｍ付近のポリフェニレンエーテルの水酸基由来のピークが消失したこと、及び、５．７５ｐｐｍ付近にメタクリル基のオレフィン由来のピークの発現を確認した。また、ＧＣ測定により、ジメチルアミノピリジン、無水メタクリル酸、メタクリル酸由来のピークがほぼ消失していることから、ＮＭＲのメタクリル基由来のピークは、ポリフェニレンエーテル末端に結合しているメタクリル基のものと判断した。この結果から、得られたポリマーは、下記式：
で表されるような構造を有する変性ポリフェニレンエーテル（以下、変性ＰＰＥ１という）であると確認できた。
また、ＧＰＣ測定の結果、得られた変性ＰＰＥ１のポリスチレン換算での分子量はＭｎ＝１，６００であった。また、変性ＰＰＥ１の平均末端官能基数は、上記数式（２）に従って、２．５以上であることが算出された。さらに、変性ＰＰＥ１の２０％メチルエチルケトン溶媒中での溶液粘度は１３１ｃＰｏｉｓｅであった。
Synthesis of Modified Polyphenylene Ether 1 (Modified PPE1) 80 g of toluene and 26 g of PPE1 synthesized above were mixed and heated to about 85 ° C. 0.55 g of dimethylaminopyridine was added to the heated mixture. When all the solids seemed to be dissolved, 4.9 g of methacrylic anhydride was gradually added to the lysate. The resulting solution was maintained at 85 ° C. for 3 hours with continuous mixing. The solution was then cooled to room temperature to give a toluene solution of methacrylate-modified polyphenylene ether.
A part of the solution was collected, dried, and then 1 H-NMR measurement was carried out. Since the peak derived from the hydroxyl group of the polyphenylene ether had disappeared, it was judged that the reaction was proceeding, and the purification operation was started. 120 g of the above-mentioned toluene solution of methacrylate-modified polyphenylene ether was added dropwise to 360 g of methanol vigorously stirred with a magnetic stirrer in a 1 L beaker over 30 minutes. The obtained precipitate was filtered under reduced pressure with a membrane filter and then dried to obtain 38 g of a polymer. The 1 H-NMR measurement result of the dried polymer is shown in FIG. It was confirmed that the peak derived from the hydroxyl group of the polyphenylene ether at around 4.5 ppm disappeared and the peak derived from the olefin of the methacrylic group was expressed at around 5.75 ppm. In addition, since the peaks derived from dimethylaminopyridine, methacrylic anhydride, and methacrylic acid have almost disappeared by GC measurement, the peaks derived from the methacrylic group of NMR are those of the methacrylic group bonded to the polyphenylene ether terminal. It was judged. From this result, the obtained polymer has the following formula:
It was confirmed that it was a modified polyphenylene ether (hereinafter referred to as modified PPE1) having a structure represented by.
Moreover, as a result of GPC measurement, the molecular weight of the obtained modified PPE1 in terms of polystyrene was Mn = 1,600. Further, the average number of terminal functional groups of the modified PPE1 was calculated to be 2.5 or more according to the above formula (2). Furthermore, the solution viscosity of the modified PPE1 in a 20% methyl ethyl ketone solvent was 131 cPoise.
樹脂組成物及びその硬化物の形成に使用される材料
ＰＰＥ
・上記で得られた変性ポリフェニレンエーテル１（変性ＰＰＥ１）
・末端メタクリル基変性ＰＰＥ「製品名ＳＡ９０００」
（Ｓａｂｉｃイノベーティブプラスチックス社製、Ｍｎ：２７５６、末端官能基数：２．０個）
・「ＰＰＥ Ｓ２０１Ａ」（旭化成株式会社製、高分子量ＰＰＥ、Ｍｎ２２，０００）
Material PPE used for forming resin compositions and cured products thereof
-Modified polyphenylene ether 1 (modified PPE1) obtained above.
-Terminal methacrylic acid modified PPE "Product name SA9000"
(Manufactured by Sabic Innovative Plastics, Mn: 2756, number of terminal functional groups: 2.0)
-"PPE S201A" (manufactured by Asahi Kasei Corporation, high molecular weight PPE, Mn22,000)
架橋剤
・ＴＡＩＣ（日本化成社製、分子量：２４９．７、不飽和二重結合数：３個）
・ポリブタジエン「製品名Ｂ−１０００」
（日本曹達社製、Ｍｎ：１２００、不飽和二重結合数：１８．４個）
Crosslinker ・ TAIC (manufactured by Nihon Kasei Co., Ltd., molecular weight: 249.7, number of unsaturated double bonds: 3)
-Polybutadiene "Product name B-1000"
(Made by Nippon Soda, Mn: 1200, number of unsaturated double bonds: 18.4)
有機過酸化物
・ビス（１−ｔｅｒｔ−ブチルペルオキシ−１−メチルエチル）ベンゼン
「製品名パーブチルＰ」（日油社製）
Organic peroxide ・ Bis (1-tert-butylperoxy-1-methylethyl) benzene "Product name Perbutyl P" (manufactured by NOF CORPORATION)
熱可塑性樹脂
・水添スチレン系熱可塑性樹脂（ＳＥＢＳ）「製品名タフテックＨ１５１７」
（旭化成株式会社製、２３０℃及び２．１６ｋｇｆの条件下でＩＳＯ１１３３に従うメルトフローレイトＭＦＲ：３．０、Ｍｗ：約５０，０００、スチレン単位含有率：４３質量％）
・水添スチレン系熱可塑性樹脂（ＳＥＢＳ）「製品名タフテックＮ５０４」
（旭化成株式会社製、２３０℃及び２．１６ｋｇｆの条件下でＩＳＯ１１３３に従うメルトフローレイトＭＦＲ：Ｎｏ Ｆｌｏｗ、Ｍｗ：約２００，０００、スチレン単位含有率：３２質量％）
Thermoplastic Resin-Hydrogenated Styrene-based Thermoplastic Resin (SEBS) "Product Name Tough Tech H1517"
(Made by Asahi Kasei Corporation, melt flow rate according to ISO 1133 under the conditions of 230 ° C. and 2.16 kgf: 3.0, Mw: about 50,000, styrene unit content: 43% by mass)
-Hydrogenated styrene-based thermoplastic resin (SEBS) "Product name Tough Tech N504"
(Made by Asahi Kasei Corporation, melt flow rate according to ISO1133 under the conditions of 230 ° C. and 2.16 kgf: No Flow, Mw: about 200,000, styrene unit content: 32% by mass)
難燃剤
・デカブロモジフェニルエタン「製品名ＳＡＹＴＥＸ８０１０」（アルベマール社製）
Flame Retardant ・ Decabromodiphenylethane "Product name SAYTEX8010" (manufactured by Albemarle)
充填剤
・球状シリカ（龍森社製）
Filler ・ Spherical silica (manufactured by Ryumori Co., Ltd.)
基材
・Ｌガラスクロス
（旭シュエーベル社製、スタイル：２１１６）
Base material ・ L glass cloth (manufactured by Asahi Schebel, style: 2116)
評価方法
１．ＰＰＥの数平均分子量、熱可塑性樹脂の重量平均分子量
ＧＰＣ分析を用い、分子量既知の標準ポリスチレンの溶出時間との比較によりＰＰＥの数平均分子量、熱可塑性樹脂の重量平均分子量を求めた。具体的には、試料濃度０．２ｗ／ｖｏｌ％（溶媒：クロロホルム）の測定試料を調製後、測定装置にはＨＬＣ−８２２０ＧＰＣ（東ソー株式会社製）を用い、カラム：Ｓｈｏｄｅｘ ＧＰＣ ＫＦ−４０５Ｌ ＨＱ×３（昭和電工株式会社製）、溶離液：クロロホルム、注入量：２０μＬ、流量：０．３ｍＬ／ｍｉｎ、カラム温度：４０℃、検出器：ＲＩ、の条件下にて測定した。
Evaluation method 1. Number average molecular weight of PPE, weight average molecular weight of thermoplastic resin Using GPC analysis, the number average molecular weight of PPE and the weight average molecular weight of the thermoplastic resin were determined by comparison with the elution time of standard polystyrene having a known molecular weight. Specifically, after preparing a measurement sample having a sample concentration of 0.2 w / vol% (solvent: chloroform), HLC-8220 GPC (manufactured by Tosoh Corporation) is used as a measuring device, and a column: Shodex GPC KF-405L HQ × Measured under the conditions of 3 (manufactured by Showa Denko Co., Ltd.), eluent: chloroform, injection amount: 20 μL, flow rate: 0.3 mL / min, column temperature: 40 ° C., detector: RI.
２．ワニス粘度
各樹脂組成物とトルエンで調製した樹脂ワニス（固形分５３質量％）２００ｍｌをビーカーに入れ、Ｂ型回転粘度計を用いて２５℃で回転数３０ｒｐｍ、３０秒の条件で粘度を測定した。測定された粘度を５段階で評価した。
５：５０ｍＰａ・ｓ〜１５０ｍＰａ・ｓ
４：１５０ｍＰａ・ｓ〜２００ｍＰａ・ｓ
３：２００ｍＰａ・ｓ〜３００ｍＰａ・ｓ
２：３００ｍＰａ・ｓ〜５００ｍＰａ・ｓ
１：５００ｍＰａ・ｓ〜１０００ｍＰａ・ｓ
2. 2. Varnish Viscosity 200 ml of resin varnish (solid content 53% by mass) prepared with each resin composition and toluene was placed in a beaker, and the viscosity was measured at 25 ° C. at 25 ° C. at 30 rpm and 30 seconds using a B-type rotational viscometer. .. The measured viscosity was evaluated on a 5-point scale.
5:50 mPa ・ s to 150 mPa ・ s
4: 150 mPa ・ s to 200 mPa ・ s
3: 200 mPa ・ s to 300 mPa ・ s
2: 300 mPa ・ s to 500 mPa ・ s
1: 500 mPa ・ s to 1000 mPa ・ s
３．含浸性
各樹脂組成物とトルエンで調製した樹脂ワニス（固形分５３質量％）をバットに入れ、その上から、５０ｍｍ角にカットしたＬガラスクロス(旭シュエーベル社製、スタイル：２１１６)を載せ、ガラスクロスに樹脂ワニスが含浸する様子を目視で観察した。ガラスクロスへの樹脂ワニスの含浸性に応じて、５段階で評価した。
５：１分以内にガラスクロス全体に樹脂ワニスが含浸した場合
４：２分以内にガラスクロス全体に樹脂ワニスが含浸した場合
３：３分以内にガラスクロス全体に樹脂ワニスが含浸した場合
２：５分以内にガラスクロス全体に樹脂ワニスが含浸した場合
１：５分経っても、含浸が完了しない場合
3. 3. Impregnation property A resin varnish (solid content 53% by mass) prepared with each resin composition and toluene is put in a bat, and an L glass cloth (manufactured by Asahi Schebel, style: 2116) cut into 50 mm squares is placed on it. The appearance of the resin varnish impregnating the glass cloth was visually observed. The evaluation was made on a 5-point scale according to the impregnation property of the resin varnish into the glass cloth.
5: 1 When the entire glass cloth is impregnated with resin varnish within 4: 2 minutes When the entire glass cloth is impregnated with resin varnish 3: When the entire glass cloth is impregnated with resin varnish within 3 minutes 2: When the entire glass cloth is impregnated with resin varnish within 5 minutes 1: When impregnation is not completed even after 5 minutes
４．積層板の誘電率及び誘電正接（電気特性）
積層板の１０ＧＨｚでの誘電率及び誘電正接を、空洞共振法にて測定した。測定装置としてネットワークアナライザー（Ｎ５２３０Ａ、ＡｇｉｌｅｎｔＴｅｃｈｎｏｌｏｇｉｅｓ社製）、及び関東電子応用開発社製の空洞共振器（Ｃａｖｉｔｙ Ｒｅｓｏｒｎａｔｏｒ ＣＰシリーズ）を用いて測定した。後述の方法で作製した厚さ約０．５ｍｍの積層板を、ガラスクロスの経糸が長辺となるように、幅約２ｍｍ、長さ５０ｍｍの大きさに切り出した。次に、１０５℃±２℃のオーブンに入れ２時間乾燥させた後、２３℃相対湿度５０±５％の環境下に９６±５時間静置した。その後、２３℃、相対湿度５０±５％の環境下で上記測定装置を用いることにより、誘電率及び誘電正接を測定し、５段階で評価した。
５：誘電率３．０以上３．３以下、且つ、誘電正接０．００２０超０．００２４以下
４：誘電率３．０以上３．３以下、且つ、誘電正接０．００２４超０．００２６以下
３：誘電率３．０以上３．３以下、且つ、誘電正接０．００２６超０．００３０以下
２：誘電率３．０以上３．３以下、且つ、誘電正接０．００３０超０．００３５以下
１：誘電率３．３超、且つ、誘電正接０．００３５超
4. Dielectric constant and dielectric loss tangent of laminated plate (electrical characteristics)
The permittivity and dielectric loss tangent of the laminated plate at 10 GHz were measured by the cavity resonance method. The measurement was performed using a network analyzer (N5230A, manufactured by Agilent Technologies) and a cavity resonator (Cavity Resonator CP series) manufactured by Kanto Electronics Applied Development Co., Ltd. as a measuring device. A laminated plate having a thickness of about 0.5 mm produced by the method described later was cut into a size having a width of about 2 mm and a length of 50 mm so that the warp threads of the glass cloth had long sides. Next, it was placed in an oven at 105 ° C. ± 2 ° C. and dried for 2 hours, and then allowed to stand in an environment at 23 ° C. and a relative humidity of 50 ± 5% for 96 ± 5 hours. Then, the dielectric constant and the dielectric loss tangent were measured by using the above measuring device in an environment of 23 ° C. and a relative humidity of 50 ± 5%, and evaluated in 5 steps.
5: Permittivity 3.0 or more and 3.3 or less and dielectric loss tangent 0.0020 or more and 0.0024 or less 4: Permittivity 3.0 or more and 3.3 or less and dielectric loss tangent 0.0024 or more and 0.0026 or less 3: Dielectric constant 3.0 or more and 3.3 or less and dielectric loss tangent 0.0026 or more and 0.0030 or less 2: Dielectric constant 3.0 or more and 3.3 or less and dielectric loss tangent 0.0030 or more and 0.0035 or less 1: Permittivity over 3.3 and dielectric loss tangent over 0.0035
５．積層板のガラス転移温度（耐熱性）
積層板の動的粘弾性を測定し、ｔａｎδが最大となる温度をガラス転移温度（Ｔｇ）として求めた。測定装置に動的粘弾性装置（ＲＨＥＯＶＩＢＲＯＮ モデルＤＤＶ−０１ＦＰ、ＯＲＩＥＮＴＥＣ社製）を用いた。後述の方法で作製した厚さ約０．３ｍｍの積層板を、ガラスクロスの経糸が長辺となるように、長さ約３５ｍｍ、幅約５ｍｍｍに切り出して、試験片とし、引張モード、周波数：１０ｒａｄ／ｓの条件で測定を行った。
Ｔｇの値により、５段階で評価した。
５：２００℃超
４：１９０℃超２００℃以下
３：１８０℃超１９０℃以下
２：１７０℃超１８０℃以下
１：１６０℃超１７０℃以下
5. Laminated glass transition temperature (heat resistance)
The dynamic viscoelasticity of the laminated board was measured, and the temperature at which tan δ was maximized was determined as the glass transition temperature (Tg). A dynamic viscoelastic device (RHEOVIBRON model DDV-01FP, manufactured by ORIENTEC) was used as the measuring device. A laminated plate having a thickness of about 0.3 mm produced by the method described later is cut into a length of about 35 mm and a width of about 5 mm so that the warp of the glass cloth has a long side, and used as a test piece. The measurement was performed under the condition of 10 rad / s.
It was evaluated on a 5-point scale according to the value of Tg.
5: Over 200 ° C 4: Over 190 ° C and below 200 ° C 3: Over 180 ° C and below 190 ° C 2: Over 170 ° C and below 180 ° C 1: Over 160 ° C and below 170 ° C
６．積層板の銅箔引き剥がし強さ（ピール強度 Ｎ／ｍｍ）
銅張積層板の銅箔を一定速度で引き剥がす際の応力を測定した。後述の方法で作製した、３５μｍ厚の銅箔（古川電気工業株式会社製、ＧＴＳ−ＭＰ箔）を用いた銅張積層板を、幅１５ｍｍ×長さ１５０ｍｍのサイズに切り出し、オートグラフ（ＡＧ−５０００Ｄ、株式会社島津製作所製）を用い、銅箔を除去面に対し９０℃の角度で５０ｍｍ／分の速度で引き剥がした際の荷重の平均値を測定し、５回の測定の平均値を求め、５段階で評価した。
５：１．Ｎ／ｍｍ超
４：０．８０Ｎ／ｍｍ超１．０Ｎ／ｍｍ以下
３：０．７０Ｎ／ｍｍ超０．８０Ｎ／ｍｍ以下
２：０．５Ｎ／ｍｍ超０．７０Ｎ／ｍｍ以下
１：０．５Ｎ／ｍｍ以下
6. Copper foil peeling strength of laminated board (peeling strength N / mm)
The stress when the copper foil of the copper-clad laminate was peeled off at a constant speed was measured. A copper-clad laminate using a 35 μm thick copper foil (GTS-MP foil manufactured by Furukawa Denki Kogyo Co., Ltd.) produced by the method described later was cut into a size of 15 mm in width × 150 mm in length, and an autograph (AG-) was cut out. Using 5000D, manufactured by Shimadzu Corporation), measure the average value of the load when the copper foil is peeled off at an angle of 90 ° C. at a speed of 50 mm / min, and calculate the average value of the five measurements. It was calculated and evaluated on a 5-point scale.
5: 1. Over N / mm 4: Over 0.80 N / mm Over 1.0 N / mm 3: Over 0.70 N / mm Over 0.80 N / mm 2: Over 0.5 N / mm Over 0.70 N / mm 1: 0. 5N / mm or less
実施例１
表１に示される組成及び溶剤に従って、トルエン２８７質量部に対し、熱可塑性樹脂を添加し、攪拌、溶解させ、次いで、難燃剤、球状シリカ、及び変性ＰＰＥ１をそれぞれ添加し、変性ＰＰＥ１が溶解するまで攪拌を継続した（固形分濃度５３質量％）。次いで、溶解物へ架橋剤及び有機過酸化物をそれぞれ添加し、十分に攪拌して、ワニスを得た。このワニスに、Ｌガラスクロスを含浸させた後、所定のスリットに通すことにより余分なワニスを掻き落とし、１０５℃の乾燥オーブンにて所定時間乾燥させ、トルエンを除去することにより、プリプレグを得た。このプリプレグを所定サイズに切り出し、その重量と同サイズのガラスクロスの重量を比較することで、プリプレグにおける樹脂組成物の固形分の含有量を算出したところ、５８質量％であった。このプリプレグを所定枚数重ね、更にその重ね合わせたプリプレグの両面に銅箔（古川電気工業株式会社製、厚み３５μｍ、ＧＴＳ−ＭＰ箔）を重ね合わせた状態で、真空プレスを行うことにより、銅張積層板を得た。この真空プレスの工程では、先ず、室温から昇温速度３℃／分で加熱しながら圧力１０ｋｇ／ｃｍ２の条件を採用し、次いで、１３０℃まで達した後に、昇温速度３℃／分で加熱しながら圧力４０ｋｇ／ｃｍ２の条件を採用した。温度が２００℃に達した後に、温度を２００℃に維持したまま圧力４０ｋｇ／ｃｍ２、及び時間６０分間の条件を採用した。次に、上記銅張積層板から、エッチングにより銅箔を除去することにより積層板を得た。
Example 1
According to the composition and solvent shown in Table 1, a thermoplastic resin is added to 287 parts by mass of toluene, stirred and dissolved, and then a flame retardant, spherical silica and modified PPE1 are added, respectively, to dissolve the modified PPE1. Stirring was continued until (solid content concentration 53% by mass). Next, a cross-linking agent and an organic peroxide were added to the lysate, and the mixture was sufficiently stirred to obtain a varnish. After impregnating this varnish with L glass cloth, excess varnish was scraped off by passing it through a predetermined slit, dried in a drying oven at 105 ° C. for a predetermined time, and toluene was removed to obtain a prepreg. .. The solid content of the resin composition in the prepreg was calculated by cutting out the prepreg to a predetermined size and comparing the weight of the glass cloth with the weight of the glass cloth, which was 58% by mass. A predetermined number of these prepregs are stacked, and copper foil (manufactured by Furukawa Denki Kogyo Co., Ltd., thickness 35 μm, GTS-MP foil) is superposed on both sides of the superposed prepreg, and then vacuum pressed to perform copper tensioning. A laminated board was obtained. In this vacuum pressing process, first, the condition of a pressure of 10 kg / cm 2 is adopted while heating from room temperature at a heating rate of 3 ° C./min, and then after reaching 130 ° C., the heating rate is 3 ° C./min. The condition of pressure 40 kg / cm 2 was adopted while heating. After the temperature reached 200 ° C., the conditions of a pressure of 40 kg / cm 2 and a time of 60 minutes were adopted while maintaining the temperature at 200 ° C. Next, a laminated plate was obtained by removing the copper foil from the copper-clad laminate by etching.
実施例２及び３と比較例１及び２
樹脂組成及び／又は基材を表１に示すとおりに変更したこと以外は実施例１と同じ方法に従って、実施例２と比較例１及び２において樹脂組成物、ワニス及びプリプレグをそれぞれ得て、評価した。
Examples 2 and 3 and Comparative Examples 1 and 2
The resin composition, varnish, and prepreg were obtained and evaluated in Example 2 and Comparative Examples 1 and 2, respectively, according to the same method as in Example 1 except that the resin composition and / or the base material was changed as shown in Table 1. did.
Claims (14)
Ｘは、ａ価の任意の連結基であり、ａは２．５以上の数であり、
Ｒ５は、各々独立に任意の置換基であり、ｋは各々独立に１〜４の整数であり、ｋ個あるＲ５のうちの少なくとも１つは、下記式（２）：
で表される部分構造を含み、
Ｙは、各々独立に下記式（３）：
で表される構造を有する２価の連結基であり、ｎはＹの繰り返し数を表し、各々独立に１〜２００の整数であり、
Ｌは、任意の２価の連結基、又は単結合であり、かつ
Ａは、各々独立に、炭素−炭素二重結合及び／又はエポキシ結合を含有する置換基を示す｝
で表される構造を有し、かつ数平均分子量が５００〜８，０００であるポリフェニレンエーテル成分Ａ；
（ｂ）架橋剤；及び
（ｃ）有機過酸化物；
を含む樹脂組成物。 (A) The following formula (1):
X is an arbitrary linking group of a value, and a is a number of 2.5 or more.
R 5 is any substituent independently, k are each independently 1 to 4 integer, at least one of the k is R 5 is represented by the following formula (2):
Including the partial structure represented by
Y is independently expressed by the following equation (3):
It is a divalent linking group having a structure represented by, n represents the number of repetitions of Y, and each is an integer of 1 to 200 independently.
L is an arbitrary divalent linking group or a single bond, and A is a substituent containing a carbon-carbon double bond and / or an epoxy bond, respectively}.
Polyphenylene ether component A having a structure represented by and having a number average molecular weight of 500 to 8,000;
(B) Crosslinker; and (c) Organic peroxide;
Resin composition containing.
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| JP2007308685A (en) * | 2006-03-15 | 2007-11-29 | Mitsubishi Gas Chem Co Inc | Polyvinyl benzyl ether compound, curable resin composition containing the same and curable film |
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| US7413791B2 (en) * | 2003-01-28 | 2008-08-19 | Matsushita Electric Works, Ltd. | Poly (phenylene ether) resin composition, prepreg, and laminated sheet |
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| KR101710854B1 (en) * | 2014-04-04 | 2017-02-27 | 히타치가세이가부시끼가이샤 | Polyphenylene ether derivative having n-substituted maleimide group, and heat curable resin composition, resin varnish, prepreg, metal-clad laminate, and multilayer printed wiring board using same |
| JP6506385B2 (en) * | 2015-02-19 | 2019-04-24 | 京セラ株式会社 | Resin composition, prepreg, metal-clad laminate and wiring board |
| CN106609031B (en) * | 2015-10-22 | 2018-11-27 | 广东生益科技股份有限公司 | A kind of polyphenyl ether resin composition and prepreg, laminate and printed circuit board containing it |
| TWI721236B (en) * | 2017-03-28 | 2021-03-11 | 日商京瓷股份有限公司 | Copper foil, copper foil laminated board and wiring board with adhesive |
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| WO2005073264A1 (en) * | 2004-01-30 | 2005-08-11 | Nippon Steel Chemical Co., Ltd. | Curable resin composition |
| JP2007308685A (en) * | 2006-03-15 | 2007-11-29 | Mitsubishi Gas Chem Co Inc | Polyvinyl benzyl ether compound, curable resin composition containing the same and curable film |
| US20080171817A1 (en) * | 2007-01-17 | 2008-07-17 | Edward Norman Peters | Poly(arylene ether) compositions and articles |
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| JP2018168347A (en) * | 2017-08-25 | 2018-11-01 | 新日鉄住金化学株式会社 | Curable resin composition, cured product of the same, curable composite material, metal foil with resin, and varnish for circuit board material |
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| CN111592751B (en) | 2023-09-29 |
| CN111592751A (en) | 2020-08-28 |
| JP7202920B2 (en) | 2023-01-12 |
| TW202035564A (en) | 2020-10-01 |
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