CN112080126B - Polyphenylene ether-containing resin composition - Google Patents
Polyphenylene ether-containing resin composition Download PDFInfo
- Publication number
- CN112080126B CN112080126B CN202010534008.1A CN202010534008A CN112080126B CN 112080126 B CN112080126 B CN 112080126B CN 202010534008 A CN202010534008 A CN 202010534008A CN 112080126 B CN112080126 B CN 112080126B
- Authority
- CN
- China
- Prior art keywords
- resin composition
- mass
- polyphenylene ether
- methyl
- independently
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001955 polyphenylene ether Polymers 0.000 title claims abstract description 115
- 239000011342 resin composition Substances 0.000 title claims abstract description 86
- -1 vinyl aromatic compound Chemical class 0.000 claims abstract description 262
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 51
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 25
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 21
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 18
- 229920001400 block copolymer Polymers 0.000 claims abstract description 13
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920001519 homopolymer Polymers 0.000 claims abstract description 5
- 239000004744 fabric Substances 0.000 claims description 22
- 229920005989 resin Polymers 0.000 claims description 22
- 239000011347 resin Substances 0.000 claims description 22
- 239000003063 flame retardant Substances 0.000 claims description 19
- 125000001424 substituent group Chemical group 0.000 claims description 18
- 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 17
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 17
- 239000011521 glass Substances 0.000 claims description 17
- 239000011888 foil Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 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
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 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
- 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
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 239000002131 composite material Substances 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
- 239000005062 Polybutadiene Substances 0.000 claims description 5
- 229920002857 polybutadiene Polymers 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims 1
- 229910052727 yttrium Inorganic materials 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- 239000000047 product Substances 0.000 description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 24
- 150000002430 hydrocarbons Chemical group 0.000 description 20
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- 239000002966 varnish Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 238000005259 measurement Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 13
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 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
- 125000000524 functional group Chemical group 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 9
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 9
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 101100353036 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pme-1 gene Proteins 0.000 description 8
- 101150047750 PPE1 gene Proteins 0.000 description 8
- 239000004793 Polystyrene Substances 0.000 description 8
- 239000000945 filler Substances 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 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 8
- 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 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 229920002223 polystyrene Polymers 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 239000000203 mixture Substances 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
- 238000003756 stirring Methods 0.000 description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 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 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 6
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 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
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000002431 hydrogen Chemical group 0.000 description 5
- 238000004519 manufacturing process Methods 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
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 4
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical compound C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-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
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- MNLAVFKVRUQAKW-UHFFFAOYSA-N VR nerve agent Chemical group CCN(CC)CCSP(C)(=O)OCC(C)C MNLAVFKVRUQAKW-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 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 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
- 230000009257 reactivity Effects 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
- 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 3
- 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 3
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000001035 drying 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
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 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
- 230000003287 optical effect Effects 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 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
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 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
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 2
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-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
- 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
- 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
- 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 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000005336 allyloxy 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
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 238000006664 bond formation reaction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method 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
- 230000008034 disappearance Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 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
- 229910000679 solder Inorganic materials 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 238000003856 thermoforming Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 230000002087 whitening effect Effects 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
- KIDCBURHSOLNFD-UHFFFAOYSA-N (2-benzoyl-3-methylbenzoyl) 2-benzoyl-3-methylbenzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)C=1C(C)=CC=CC=1C(=O)OOC(=O)C1=CC=CC(C)=C1C(=O)C1=CC=CC=C1 KIDCBURHSOLNFD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-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
- 125000005837 1,2-cyclopentylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([*:2])C1([H])[H] 0.000 description 1
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 1
- XYXJKPCGSGVSBO-UHFFFAOYSA-N 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C)=C1CN1C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C1=O XYXJKPCGSGVSBO-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 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 1
- 125000006023 1-pentenyl group Chemical group 0.000 description 1
- GOAHRBQLKIZLKG-UHFFFAOYSA-N 1-tert-butylperoxybutane Chemical compound CCCCOOC(C)(C)C GOAHRBQLKIZLKG-UHFFFAOYSA-N 0.000 description 1
- SZVMZLJAAGWNPG-UHFFFAOYSA-N 1-tert-butylperoxyoctane Chemical compound CCCCCCCCOOC(C)(C)C SZVMZLJAAGWNPG-UHFFFAOYSA-N 0.000 description 1
- 125000003660 2,3-dimethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003764 2,4-dimethylpentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- JGBAASVQPMTVHO-UHFFFAOYSA-N 2,5-dihydroperoxy-2,5-dimethylhexane Chemical compound OOC(C)(C)CCC(C)(C)OO JGBAASVQPMTVHO-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- LKALLEFLBKHPTQ-UHFFFAOYSA-N 2,6-bis[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound OC=1C(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=CC(C)=CC=1CC1=CC(C)=CC(C(C)(C)C)=C1O LKALLEFLBKHPTQ-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- KUNNUNBSGQSGDY-UHFFFAOYSA-N 2-butyl-6-methylphenol Chemical compound CCCCC1=CC=CC(C)=C1O KUNNUNBSGQSGDY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- BRQMAAFGEXNUOL-UHFFFAOYSA-N 2-ethylhexyl (2-methylpropan-2-yl)oxy carbonate Chemical compound CCCCC(CC)COC(=O)OOC(C)(C)C BRQMAAFGEXNUOL-UHFFFAOYSA-N 0.000 description 1
- YAQDPWONDFRAHF-UHFFFAOYSA-N 2-methyl-2-(2-methylpentan-2-ylperoxy)pentane Chemical compound CCCC(C)(C)OOC(C)(C)CCC YAQDPWONDFRAHF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- WXDJDZIIPSOZAH-UHFFFAOYSA-N 2-methylpentan-2-yl benzenecarboperoxoate Chemical compound CCCC(C)(C)OOC(=O)C1=CC=CC=C1 WXDJDZIIPSOZAH-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- 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 1
- GRXOKDOOUFYKLX-UHFFFAOYSA-N 3,5-dichloro-7-oxabicyclo[2.2.1]hepta-1(6),2,4-triene Chemical compound ClC1=C(O2)C(Cl)=CC2=C1 GRXOKDOOUFYKLX-UHFFFAOYSA-N 0.000 description 1
- GVLZQVREHWQBJN-UHFFFAOYSA-N 3,5-dimethyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound CC1=C(O2)C(C)=CC2=C1 GVLZQVREHWQBJN-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- XYFRHHAYSXIKGH-UHFFFAOYSA-N 3-(5-methoxy-2-methoxycarbonyl-1h-indol-3-yl)prop-2-enoic acid Chemical compound C1=C(OC)C=C2C(C=CC(O)=O)=C(C(=O)OC)NC2=C1 XYFRHHAYSXIKGH-UHFFFAOYSA-N 0.000 description 1
- KXRLIZRDCCQKDZ-UHFFFAOYSA-N 3-ethyl-5-methyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound CC1=C(O2)C(CC)=CC2=C1 KXRLIZRDCCQKDZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- DYIZJUDNMOIZQO-UHFFFAOYSA-N 4,5,6,7-tetrabromo-2-[2-(4,5,6,7-tetrabromo-1,3-dioxoisoindol-2-yl)ethyl]isoindole-1,3-dione Chemical compound O=C1C(C(=C(Br)C(Br)=C2Br)Br)=C2C(=O)N1CCN1C(=O)C2=C(Br)C(Br)=C(Br)C(Br)=C2C1=O DYIZJUDNMOIZQO-UHFFFAOYSA-N 0.000 description 1
- BRPSWMCDEYMRPE-UHFFFAOYSA-N 4-[1,1-bis(4-hydroxyphenyl)ethyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=C(O)C=C1 BRPSWMCDEYMRPE-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical group CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- FKIOYBLZUCCLTL-UHFFFAOYSA-N 4-butyl-2-tert-butyl-5-methylphenol Chemical compound CCCCC1=CC(C(C)(C)C)=C(O)C=C1C FKIOYBLZUCCLTL-UHFFFAOYSA-N 0.000 description 1
- NGNBLQAYJAKWKR-UHFFFAOYSA-N 5-methyl-3-phenyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound O1C=2C(C)=CC1=CC=2C1=CC=CC=C1 NGNBLQAYJAKWKR-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- JHRZBZIXHOHYHF-UHFFFAOYSA-N C=CCC.C=CC=C.C=CC1=CC=CC=C1 Chemical compound C=CCC.C=CC=C.C=CC1=CC=CC=C1 JHRZBZIXHOHYHF-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000006959 Williamson synthesis reaction Methods 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- TYMZLIDQEUWXEL-UHFFFAOYSA-N bis(2,3-dimethylphenyl) hydrogen phosphate Chemical compound CC1=CC=CC(OP(O)(=O)OC=2C(=C(C)C=CC=2)C)=C1C TYMZLIDQEUWXEL-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical group C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000011874 heated mixture Substances 0.000 description 1
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical class OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229920002577 polybenzoxazole Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005995 polystyrene-polyisobutylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 238000009774 resonance method Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000011191 terminal modification Methods 0.000 description 1
- JIYXDFNAPHIAFH-UHFFFAOYSA-N tert-butyl 3-tert-butylperoxycarbonylbenzoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC(C(=O)OC(C)(C)C)=C1 JIYXDFNAPHIAFH-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- JZFHXRUVMKEOFG-UHFFFAOYSA-N tert-butyl dodecaneperoxoate Chemical compound CCCCCCCCCCCC(=O)OOC(C)(C)C JZFHXRUVMKEOFG-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- XPEMYYBBHOILIJ-UHFFFAOYSA-N trimethyl(trimethylsilylperoxy)silane Chemical compound C[Si](C)(C)OO[Si](C)(C)C XPEMYYBBHOILIJ-UHFFFAOYSA-N 0.000 description 1
- KBAOLOSFEJJQPL-UHFFFAOYSA-N trimethyl(triphenylsilylperoxy)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(OO[Si](C)(C)C)C1=CC=CC=C1 KBAOLOSFEJJQPL-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/126—Polyphenylene oxides modified by chemical after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2371/00—Polyethers, e.g. PEEK, i.e. polyether-etherketone; PEK, i.e. polyetherketone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2371/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Polyethers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
A polyphenylene ether-containing resin composition. The resin composition containing polyphenylene ether (PPE) is required to have good compatibility with PPE, good coatability to a base material or the like, and excellent substrate properties when assembled to an electronic circuit substrate, and therefore, an object of the present invention is to satisfy these requirements. Provided is a resin composition comprising: (a) A polyphenylene ether component { wherein X, a, R, in the formula }, having a structure represented by the following formula (1) and a number average molecular weight of 500 to 8,000 5 K, Y, n, A and L are as defined in the specification; (b) a cross-linking agent; (c) an organic peroxide; and (d) a thermoplastic resin having a weight average molecular weight of 150,000 ～ 800,000 selected from at least 1 kind of a block copolymer of a vinyl aromatic compound and an alkenyl olefin compound, a hydrogenated product thereof, and a homopolymer of the vinyl aromatic compound, wherein the thermoplastic resin is contained in an amount of 2 to 20 parts by mass based on 100 parts by mass of the total mass of the polyphenylene ether component A and the crosslinking agent. (1)
Description
Technical Field
The present invention relates to a polyphenylene ether-containing resin composition and the like.
Background
In recent years, with remarkable progress in information network technology and expansion of services using an information network, electronic devices are demanded to increase the capacity of information and to increase the processing speed. In order to meet these demands, materials for substrates such as printed wiring boards are required to have low dielectric constant and low dielectric loss tangent in addition to properties such as flame retardancy, heat resistance and peel strength with copper foil, which have been conventionally demanded. Accordingly, further improvements of resin compositions used for materials for substrates such as printed circuit boards have been studied.
Among materials for substrates, polyphenylene ether (PPE) has a low dielectric constant and a low dielectric loss tangent, and is therefore suitable as a material for printed wiring boards that can cope with the above-mentioned requirements. For example, the polyphenylene ether-containing resin composition described in patent document 1 is intended to improve moldability, heat resistance, adhesion and electrical characteristics by controlling the average phenolic hydroxyl number per 1 molecule of polyphenylene ether to a specific range or specifying the contents of a plurality of polyphenylene ethers having different molecular weights.
Prior art literature
Patent literature
Patent document 1: international publication No. 2012/081705
Disclosure of Invention
Problems to be solved by the invention
Resin compositions containing polyphenylene ether (PPE) are required to have good compatibility with PPE, good coatability to a base material or the like, and excellent substrate properties when assembled to an electronic circuit substrate. The polyphenylene ether-containing resin composition described in patent document 1 has room for investigation from the viewpoint of satisfying all of these requirements.
Accordingly, an object of the present invention is to provide a polyphenylene ether-containing resin composition excellent in compatibility, coatability and substrate properties, and an electronic circuit substrate material, a resin film, a prepreg and a laminate using the same.
Solution for solving the problem
The present inventors have conducted intensive studies to solve the above problems, and as a result, found that: the present invention has been completed by defining the structure and molecular weight of polyphenylene ether, and the structure and molecular weight and content of thermoplastic resin in a resin composition comprising polyphenylene ether, a crosslinking agent, an organic peroxide and a thermoplastic resin, so that compatibility, coatability and substrate properties are excellent. The following examples of embodiments of the present invention are given.
[1] A resin composition comprising:
(a) A polyphenylene ether component A having a structure represented by the following formula (1) and having a number average molecular weight of 500 to 8,000;
(b) A cross-linking agent;
(c) An organic peroxide; and
(d) At least 1 selected from the group consisting of block copolymers of vinyl aromatic compounds and olefin compounds, hydrogenated products thereof, and homopolymers of the vinyl aromatic compounds, and a thermoplastic resin having a weight average molecular weight of 150,000 ～ 800,000,
the content of the thermoplastic resin is 2 to 20 parts by mass based on 100 parts by mass of the total mass of the polyphenylene ether component a and the crosslinking agent.
(1)
In the case of the {, the following,
x is an arbitrary linking group having a valence of a, a is a number of 2.5 or more,
R 5 Each independently is an optional substituent, k is each independently an integer of 1 to 4, and k R are present 5 At least 1 of which comprises a partial structure represented by the following formula (2),
y is each independently a divalent linking group having a structure represented by the following formula (3), n represents the number of repetitions of Y, each independently an integer of 1 to 200,
l is any divalent linking group or single bond, and
a each independently represents a substituent containing a carbon-carbon double bond and/or an epoxy bond,
(2)
(wherein R is 11 Each independently is C 1-8 Alkyl of R 12 Each independently is C 1-8 Alkylene groups of (a), b are each independently 0 or 1, R 13 Represents a hydrogen atom, C 1-8 Any of the alkyl groups or phenyl groups of (C), and the foregoing alkyl groups, alkylene groups and phenyl groups are those satisfying C 1-8 Optionally having substituents within the scope of the conditions of (2)
(3)
(wherein R is 21 Each independently is C 1-6 Saturated or unsaturated hydrocarbon radicals, R 22 Each independently is a hydrogen atom or C 1-6 Saturated or unsaturated hydrocarbon groups of (2), and the saturated or unsaturated hydrocarbon groups are as defined above for C 1-6 Optionally having substituents within the scope of the conditions of (c).
[2] The resin composition according to item 1, wherein the content of the unit derived from the vinyl aromatic compound in the block copolymer or hydrogenated product thereof is 20% by mass or more and 70% by mass or less.
[3] The resin composition according to item 1 or 2, wherein the crosslinking agent has an average of 2 or more carbon-carbon unsaturated double bonds in 1 molecule, the crosslinking agent has a number average molecular weight of 4,000 or less, and the polyphenylene ether component A is contained in a weight ratio of 25:75 to 95:5.
[4] The resin composition according to any one of items 1 to 3, wherein the crosslinking agent contains at least one compound selected from the group consisting of triallyl cyanurate, triallyl isocyanurate and polybutadiene.
[5] The resin composition according to any one of items 1 to 4, wherein the half-life temperature of the organic peroxide in 1 minute is 155℃to 185 ℃.
[6] The resin composition according to any one of items 1 to 5, wherein the content of the organic peroxide is 0.05 to 5 parts by mass based on 100 parts by mass of the total mass of the polyphenylene ether component A and the crosslinking agent.
[7] The resin composition according to any one of items 1 to 6, wherein the resin composition further comprises a flame retardant, and the flame retardant is not compatible with other components contained in the resin composition after the resin composition is cured.
[8] An electronic circuit substrate material comprising the resin composition according to any one of items 1 to 7.
[9] A resin film comprising the resin composition according to any one of items 1 to 7.
[10] A prepreg which is a composite of a substrate and the resin composition according to any one of items 1 to 7.
[11] The prepreg according to item 10, wherein the substrate is glass cloth.
[12] A laminate comprising a metal foil and the resin film according to item 9 or the cured product of the prepreg according to item 10 or 11.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, the polyphenylene ether-containing resin composition is excellent in compatibility and coatability, and an electronic circuit board material, a resin film, a prepreg, and a laminate excellent in board characteristics can be provided using the same.
Drawings
FIG. 1 is a block diagram showing a modified polyphenylene ether 1 (modified PPE 1) obtained in production example 1 1 H-NMR measurement results.
Detailed Description
Hereinafter, a specific embodiment of the present invention (hereinafter simply referred to as "this embodiment") will be described in detail. The present invention is not limited to the following embodiments, and may be implemented by various modifications within the scope of the gist thereof.
Resin composition
The PPE-containing resin composition of the present embodiment (hereinafter also simply referred to as "resin composition") contains polyphenylene ether (PPE), a crosslinking agent, an organic peroxide, and a thermoplastic resin, and may further contain a flame retardant, other additives, a silica filler, a solvent, and the like, as desired. The constituent elements of the resin composition according to the present embodiment are described below.
Polyphenylene Ether (PPE)
In general, polyphenylene ether (PPE) has a repeating structure composed of a substituted or unsubstituted phenylene ether unit. In the present specification, the term "polyphenylene ether" includes dimers, trimers, oligomers and polymers. The PPE may contain copolymerized constituent units other than the phenylene ether units, and the amount of such copolymerized constituent units is typically 0% or more, or more than 0% and 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, or 5% or less, relative to the number of the entire unit structure.
Typical PPE 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), copolymers of 2, 6-dimethylphenol with other phenols (e.g., 2,3, 6-trimethylphenol, 2-methyl-6-butylphenol, etc.), and PPE copolymers obtained by coupling 2, 6-dimethylphenol with diphenols or bisphenols.
Polyphenylene ether component A (PPE-A)
The resin composition of the present embodiment contains, as the polyphenylene ether component, a polyphenylene ether component a having a structure represented by the following formula (1) and having a number average molecular weight of 500 to 8,000.
(1)
In the formula (1), X is an arbitrary linking group with a valence; 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 hydrocarbon groups; a hydrocarbon group containing one or more elements selected from nitrogen, phosphorus, silicon, or oxygen; or an element containing nitrogen, phosphorus, silicon or the like or a group of these elements.
In addition, R 5 Is an optional substituent; k is an integer of 1 to 4, and when k is 2 or more, 2R are optionally selected 5 Are linked to form a ring, k R's are present 5 At least 1 of (a) comprises a partial structure represented by the following formula (2).
(2)
In the formula (2), R 11 Each independently is C 1-8 Alkyl, R 12 Each independently is C 1-8 Alkylene, b is independently 0 or 1, R 13 Represents a hydrogen atom, C 1-8 Any of alkyl or phenyl, where the alkyl, alkylene and phenyl are C 1-8 Optionally having substituents within the scope of the conditions of (2).
The partial structure represented by the formula (2) preferably has a secondary carbon and/or a tertiary carbon, and may have, for example, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-amyl group, a 2, 2-dimethylpropyl group, a structure containing a phenyl group at the terminal thereof, or the like. The partial structure represented by formula (2) is preferably the same as R in formula (1) 5 The bonded benzene rings are directly bonded. In addition, the partial structure represented by formula (2) is preferably bonded to R in formula (1) 5 The 2-and/or 6-positions (ortho with respect to-O-position) of the bonded benzene ring.
Regarding the following portions among the structures shown in formula (1):
preferably any of the following structures:
specific examples thereof include a structure in which all of the hydrogens of the terminal phenolic hydroxyl group are removed from the following compounds:
4, 6-di-tert-butylphenyl-1, 2, 3-triol, 2, 6-bis (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenol, 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 2,4, 6-tris (3 ',5' -di-tert-butyl-4 ' -hydroxybenzyl) mesitylene, 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.
Y in formula (1) is each independently a divalent linking group (phenol unit having a substituent) having a structure represented by formula (3) below, and n in formula (1) represents the number of repetitions of Y and is each independently an integer of 0 to 200.
(3)
In formula (3), R 21 Independently C 1-6 The saturated or unsaturated hydrocarbon group of (a) is preferably a methyl group, an ethyl group, an n-propyl group, a vinyl group, an allyl group, an ethynyl group, a propargyl group, or the like, more preferably a methyl group, an ethyl group, and still more preferably a methyl group. R is R 22 Independently a hydrogen atom or C 1-6 The saturated or unsaturated hydrocarbon group of (2) is preferably a hydrogen atom, a methyl group, an ethyl group, or an n-propyl group, more preferably a hydrogen atom or a methyl group, and still more preferably a hydrogen atom. Here, the saturated or unsaturated hydrocarbon radical is such that C 1-6 May have a substituent in the range of the condition(s).
A in the formula (1) is a substituent containing a carbon-carbon double bond and/or an epoxy bond, and specific examples of A are represented by the following formulas (4) to (8):
in the formulae (4) to (8), R 31 Each independently is hydrogen, hydroxy or C 1-30 Is selected from the group consisting of hydrocarbyl, aryl, alkoxy, allyloxy, amino, and hydroxyalkyl. R is R 32 Each independently is C 1-30 Is a hydrocarbon group of (a). R is R 33 Each independently is hydrogen, hydroxy or C 1-30 Is selected from the group consisting of hydrocarbyl, aryl, alkoxy, allyloxy, amino, hydroxyalkyl, vinyl, and isopropenyl, R 33 At least one of which is vinyl or isopropenyl. s and t are integers from 0 to 5.
As R 31 Specific examples of the hydrocarbon group of (a) include: methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, pentyl, cyclopentyl, 2-dimethylpropyl, 1-dimethylpropyl, n-hexyl, cyclohexyl, 1-ethylbutyl, 2-ethylbutyl 3-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentylene, 4-methylpentylene, 1-dimethylbutylene, 2-dimethylbutylene, 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-dimethylpentyl, 2-dimethylpentyl, 3-dimethylpentyl, 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, 1,2, 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 A radical, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, 1-dimethylhexyl, 2-dimethylhexyl, 3-dimethylhexyl 4, 4-dimethylhexyl, 5-dimethylhexyl, 1, 2-dimethylhexyl, 1, 3-dimethylhexyl, 1, 4-dimethylhexyl, 1, 5-dimethylhexyl, 2, 3-dimethylhexyl, 2, 4-dimethylhexyl, 2, 5-dimethylhexyl, 1-ethylmethylpentyl, 2, 2-ethylmethylpentyl, 3-ethylmethylpentyl, 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-methylpentyl, 1- (2-methylpropyl) butyl, 1- (2-methylpropyl) -2-methylbutyl, 1,1- (2-methylpropyl) ethyl, 1- (2-methylpropyl) ethylpropyl, 1-diethylpropyl, 2-diethylpropyl, 1-ethylmethyl-2, 2-dimethylpropyl 2, 2-ethylmethyl-1, 1-dimethylpropyl, 2-ethyl-1, 1-dimethylbutyl, 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-cyclohexyl-2-ethylene, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, benzyl, 2-phenylethyl and the like.
R 31 The hydrocarbon radical of (C) is preferably methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, pentyl, 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-methylheptyl, 2-ethylhexyl, 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, tert-butyl, n-pentyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, pentyl, 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, dodecyl, benzyl and the like, still more preferably methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 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, dodecyl, benzyl and the like.
As R 32 Specific examples of the hydrocarbon group of (a) include: methylene, ethylene, trimethylene, 1, 2-propylene, tetramethylene, 2-methyl-1, 3-trimethylene, 1-dimethylethylene, pentamethylene, 1-ethyl-1, 3-propylene, 1-methyl-1, 4-butylene, 2-methyl-1, 4-butylene, 3-methyl-1, 4-butylene, 2-dimethyl-1, 3-propylene, 1, 2-cyclopentylene, 1, 3-cyclopentylene 2, 2-dimethyl-1, 3-propylene, 1-dimethyl-1, 3-propylene, 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-methyl-Cyclopentylene, 1-dimethyl-1, 4-butylene, 2-dimethyl-1, 4-butylene, 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-dimethyl-1, 5-pentylene, 3-dimethyl-1, 5-pentylene, 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, 1,2, 3-trimethyl-1, 4-butylene, and the like.
In addition, as R 32 Specific examples of the hydrocarbon group of (a) include: 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-cyclopentylene, 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-dimethyl-1, 6-hexylene, 2-dimethyl-1, 6-hexylene, 3-dimethyl-1, 6-hexylene, 4-dimethyl-1, 6-hexylene, 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-ethylmethyl-1, 5-pentylene, 2-ethylmethyl-1, 5-pentylene, 3-ethylmethyl And 1, 5-pentylene, 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-4-methyl-1, 5-pentylene, 4-ethyl-3-methyl-1, 5-pentylene.
Further, R is 32 Specific examples of the hydrocarbon group of (a) include: 1- (2-methylpropyl) -1, 4-butylene, 1- (2-methylpropyl) -2-methyl-1, 4-butylene, 1- (2-methylpropyl) ethylene, 1- (2-methylpropyl) ethyl-1, 3-propylene, 1-diethyl-1, 3-propylene, 2-diethyl-1, 3-propylene 1, 1-ethylmethyl-2, 2-dimethyl-1, 3-propylene, 2-ethylmethyl-1, 1-dimethyl-1, 3-propylene, 2-ethyl-1, 1-dimethyl-1, 4-butylene, 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-methylene, 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-cyclohexyl-2-ethylene, nonylmethylene, 1-methyl-1, 8-octylene, decyl methylene, 1-methyl-1, 8-nonylene, undecylenimethylene, dodecyl methylene, 1, 4-phenylene, 1, 3-phenylene, 1, 2-phenylene, methylene-1, 4-phenylene-methylene, ethylene-1, 4-phenylene-ethylene, and the like.
R 32 The hydrocarbon group of (C) is preferably methylene, ethylene, trimethylene, 1, 2-propylene, tetramethylene, 2-methyl-1, 2-propylene, 1-dimethylethylene, pentamethylene, 1-ethyl-1, 3-propylene, 1-methyl-1, 4-butylene, 2-methyl-1, 4-butylene, 3-methyl-1, 4-butylene, 2-dimethyl-1, 3-propylene, 1, 3-cyclopentyl, 1, 6-hexamethylene, 1, 4-cyclohexyl, 1-ethyl-1, 4-butylene, 2-ethyl-1, 4-butylene, 3-ethylethylene1, 4-butylene, 1-methyl-1, 5-pentylene, 2-methyl-1, 5-pentylene, 3-methyl-1, 5-pentylene, 4-methyl-1, 5-cyclohexylene, 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-hexylene, 1-methyl-1, 6-decylene, 2-methyl-1, 6-decylene, 1-methyl-1, 6-decylene, 1-methyl-1, 6-decylene, 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-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, dodecylene and the like, further preferred are methylene, ethylene, trimethylene, 1, 2-propylene, tetramethylene, 2-methyl-1, 2-propylene, 1-dimethylethylene, pentamethylene, 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 Dodecyl methylene, and the like.
Specific examples of the substituent containing a carbon-carbon double bond include a in formula (1): vinyl, allyl, isopropenyl, 1-butenyl, 1-pentenyl, p-vinylphenyl, p-isopropenylphenyl, m-vinylphenyl, m-isopropenylphenyl, o-vinylphenyl, o-isopropenylphenyl, p-vinylbenzyl, p-isopropenylbenzyl, m-vinylbenzyl, m-isopropenylbenzyl, o-vinylbenzyl, p-vinylphenylvinyl, p-vinylphenylpropenyl, p-vinylphenylbutenyl, m-vinylphenylvinyl, m-vinylphenylpropenyl, m-vinylphenylbutenyl, o-vinylphenylvinyl, o-vinylphenylbutenyl, methacryloyl, acryl, 2-ethylpropoyl, 2-hydroxymethylpropoyl, and the like.
L in formula (1) is any divalent linking group or a single bond (direct bond). When L is a single bond, the structure represented by formula (1) is represented by the following formula.
Further, when L is an arbitrary divalent linking group, specific examples of L have a structure represented by the following formula:
{ in which a, R 5 K, X, Y and n are as defined in the description of formula (1)
The structure represented by formula (1) can have various branched structures according to the value of the valence a of X. For example, when a=3 in the formula (1), a branched structure represented by the following formula and the like are exemplified.
In the expression, n represents the repetition number of Y and is an integer of 0 to 200 }
The structure represented by the formula (1) is specifically described below.
In the above formula, Z is an arbitrary linking group corresponding to X in formula (1). R is R 1 Is a substituent represented by formula (2), and b is an integer of 1 to 4. R is as follows 1 The position of R is not limited, R 1 Any position may be taken. When b is 2 or more, a plurality of R' s 1 The same structure may be adopted, or different structures may be adopted. As R 1 Examples include: isopropyl, isobutyl, sec-butyl, tert-amyl, 2-dimethylpropyl, or a structure having a phenyl group at the end thereof, and the like. A is a substituent containing a carbon-carbon double bond and/or an epoxy bond. R is R 2 Hydrogen or a hydrocarbon group having a chain or cyclic structure having 1 to 8 carbon atoms. Where there are a plurality of R 2 In the above-mentioned examples, the substituents may be the same or different. As R 2 Specific examples of (a) include: methyl, ethyl, n-propyl, n-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, phenyl, benzyl, 2-ethylhexyl and the like are preferred from the viewpoint of reactivity during synthesis and the likeA group, a cyclopentyl group, a n-hexyl group, a cyclohexyl group, a n-heptyl group, and a n-octyl group. However, R can be appropriately set 2 In the case where the reactivity at the time of synthesis is controlled by the position of (2) or the reaction condition at the time of synthesis, R 2 Is not limited in structure, in satisfying C 1-8 Any structure is possible within the scope of the conditions of (a). Z is a hydrocarbon group; a hydrocarbon group containing one or more elements selected from nitrogen, phosphorus, silicon, and oxygen; or nitrogen, phosphorus, silicon, etc., or groups containing them.
Specific examples of the hydrocarbon group as Z are, for example, structures represented by the following formulas.
In the above formula, R 4 ～R 10 Which may be the same or different and represents hydrogen or C 1-8 Is a hydrocarbon group of (a). In addition, R 31 ～R 33 Which may be the same or different and represents hydrogen or C 1-6 Is a hydrocarbon group of (a). j. k, l and m may be the same or different and are integers of 0 to 4. As R 4 ～R 10 Specific examples of (a) include: hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, 2-pentyl, 3-pentyl, cyclopentyl, n-hexyl, 2-hexyl, 3-hexyl, cyclohexyl, n-heptyl, 2-heptyl, 3-heptyl, n-octyl, 2-ethylhexyl, and the like. As R 31 ～R 33 Specific examples of (a) include: hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, 2-pentyl, 3-pentyl, cyclopentyl, n-hexyl, 2-hexyl, 3-hexyl, cyclohexyl.
Further, as Z, a specific example of the hydrocarbon group containing one or more elements selected from the group consisting of nitrogen, phosphorus, silicon, and oxygen is shown by the following formula.
In the above formula, R 4 ～R 10 Which may be the same or different and represents hydrogen or C 1-8 Is a hydrocarbon group of (a). j. k, l and m may be the same or different and are integers of 0 to 4. As R 4 ～R 10 Specific examples of (a) include: hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, 2-pentyl, 3-pentyl, cyclopentyl, n-hexyl, 2-hexyl, 3-hexyl, cyclohexyl, n-heptyl, 2-heptyl, 3-heptyl, n-octyl, 2-ethylhexyl, and the like.
Specific examples of the group containing nitrogen, phosphorus, oxygen, and the like as Z are shown below.
In the specific example, when the structure of a is embodied as the first example, the structure is represented by the following formula. In the case of 4 to 6 branches, R in the following formula is also the same as above 31 、R 32 S and t are as defined in the embodiment of A.
Among polystyrene-equivalent molecular weights using GPC, the number average molecular weight (Mn) of the polyphenylene ether component A is 500 to 8,000, preferably 700 to 6,000, more preferably 900 to 4,500, from the viewpoints of flowability, compatibility with other components, and the like. 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.
The modified polyphenylene ether having the structure of formula (1) of the present embodiment can be produced, for example, by preparing a polyphenylene ether by a redistribution reaction using a phenylene ether polymer having a higher molecular weight and introducing a group A at the terminal thereof. In the case of producing polyphenylene ether by the redistribution reaction, the production can be performed under the conditions specified by the known reaction conditions. In this case, since the molecular weight of the obtained polymer is reduced as compared with the phenylene ether polymer as the raw material, the ratio of the raw material polyphenylene ether to the polyfunctional phenol compound can be adjusted according to the target molecular weight.
The method of introducing the substituent a in the formula (1), for example, the functional groups represented by the formulae (4) to (7), into the terminal of the obtained polyphenylene ether polymer is not limited, and various known methods may be employed depending on the kind of the functional group. For example, the functional group having the structure of formula (4), (6) or (7) may be introduced generally by an ether bond formed by the Williamson synthesis method. The functional group having the structure of formula (5) is introduced by an ester bond formation reaction between a hydroxyl group at the terminal of the polyphenylene ether polymer and a carboxylic acid having a carbon-carbon double bond (hereinafter referred to as a carboxylic acid), and a known ester bond formation method can be used.
The polyphenylene ether component a (PPE-a) has high curing reactivity, low dielectric properties, good flowability, good moldability, and excellent heat resistance, and therefore can be suitably used as a material for various electric and electronic devices, and particularly can be suitably used for producing prepregs for electric and electronic parts (printed circuit board substrates, etc.). The PPE-A may be used in the form of a resin alone, or may be used in combination with polyphenylene ether having other structures, or may be used in combination with various known additives. The content of PPE-A in the resin composition may be, for example, 0.5 to 95% by mass.
Polyphenylene ether component B (PPE-B)
The resin composition of the present embodiment may further contain a polyphenylene ether component B having an average phenolic hydroxyl number of 1.2 or more and a number average molecular weight of 8,000 or more and 50,000 or less per 1 molecule, in addition to the polyphenylene ether component A having a number average molecular weight of 500 to 8,000 described above. Since the polyphenylene ether component B is stable in its production process and is excellent in dielectric properties and heat resistance, there is a tendency to improve the electrical characteristics of a cured product of the resin composition without interfering with the polyphenylene ether component a.
The polyphenylene ether component B (PPE-B) may be any polyphenylene ether (PPE) as long as it is distinguishable from the polyphenylene ether component A (PPE-A) and satisfies an average of 1.2 or more phenolic hydroxyl groups per 1 molecule and a number average molecular weight of 8,000 to 50,000. From the viewpoint of use in combination with PPE-A, the number average molecular weight of PPE-B is preferably more than 8,000 and 50,000 or less. In the case of using PPE-A and PPE-B in combination in the resin composition, the content of PPE-A is preferably 1 to 99.9% by mass and the content of PPE-B is preferably 0.1 to 99% by mass, more preferably 20 to 98% by mass and the content of PPE-B is 2 to 80% by mass, still more preferably 40 to 95% by mass and the content of PPE-B is 5 to 60% by mass, based on 100% by mass of the total mass of PPE-A and PPE-B, in view of the stability and heat resistance of the resin composition.
Crosslinking agent
In this embodiment, any crosslinking agent having the ability to initiate or promote a crosslinking reaction may be used. The crosslinking agent preferably has a number average molecular weight of 4,000 or less. If the number average molecular weight of the crosslinking agent is 4,000 or less, an increase in viscosity of the resin composition can be suppressed, and good resin flowability at the time of thermoforming can be obtained. The number average molecular weight may be a value measured by a conventional molecular weight measurement method, and specifically, a value measured by GPC may be mentioned.
From the viewpoint of the crosslinking reaction, the crosslinking agent preferably has an average of 2 or more carbon-carbon unsaturated double bonds in 1 molecule. The crosslinking agent may be composed of 1 kind of compound or 2 or more kinds of compounds. The term "carbon-carbon unsaturated double bond" as used herein refers to a double bond located at a terminal branching from the main chain when the crosslinking agent is a polymer or oligomer. Examples of the carbon-carbon unsaturated double bond include a 1, 2-vinyl bond in polybutadiene.
In the case where the number average molecular weight of the crosslinking agent is less than 600, the number (average value) of carbon-carbon unsaturated double bonds per 1 molecule of the crosslinking agent is preferably 2 to 4. In the case where the number average molecular weight of the crosslinking agent is 600 to 1500, the number (average value) of carbon-carbon unsaturated double bonds per 1 molecule of the crosslinking agent is preferably 4 to 26. In the case where the number average molecular weight of the crosslinking agent is 1,500 to 4,000, the number (average value) of the carbon-carbon unsaturated double bonds per 1 molecule of the crosslinking agent is preferably 26 to 60. When the number average molecular weight of the crosslinking agent is within the above range, the reactivity of the crosslinking agent in the resin composition of the present embodiment is further improved by setting the number of carbon-carbon unsaturated double bonds to a predetermined value or more, and as a result, the crosslinking 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 crosslinking agent is within the above range, by setting the number of carbon-carbon unsaturated double bonds to a predetermined value or less, more excellent resin flowability can be imparted during thermoforming.
Examples of the crosslinking agent include: trialkenyl isocyanurate compounds such as triallyl isocyanurate (TAIC), trialkenyl cyanurate compounds such as triallyl cyanurate (TAC), polyfunctional methacrylate compounds having 2 or more methacryloyl groups in the molecule, polyfunctional acrylate compounds having 2 or more acryloyl groups in the molecule, polyfunctional vinyl compounds having 2 or more vinyl groups in the molecule such as polybutadiene, vinylbenzyl compounds such as divinylbenzene having vinylbenzyl groups in the molecule, polyfunctional maleimide compounds having 2 or more maleimide groups in the molecule such as 4,4' -bismaleimide diphenylmethane, and the like. These crosslinking agents may be used singly or in combination of 2 or more. Of these, the crosslinking agent preferably contains at least 1 compound selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, and polybutadiene. The crosslinking agent contains at least 1 or more of the above-described compounds, and thus the compatibility and coatability of the resin composition with PPE tend to be more excellent, and the substrate properties tend to be more excellent when the resin composition is mounted on an electronic circuit substrate.
The weight ratio of the PPE to the crosslinking agent is preferably 25:75 to 95:5, more preferably 32:68 to 85:15, from the viewpoints of compatibility of the crosslinking agent with the PPE, coatability of the resin composition, and more excellent characteristics of the electronic circuit board. From the same viewpoint, the weight ratio of PPE-A to the crosslinking agent is preferably 25:75 to 95:5, more preferably 32:68 to 85:15.
Organic peroxides
In this embodiment, any organic peroxide having an ability to promote polymerization of a resin composition containing polyphenylene ether and a crosslinking agent may be used. Examples of the organic peroxide include: benzoyl peroxide, cumene hydroperoxide, 2, 5-dimethylhexane-2, 5-dihydroperoxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexyne-3, di-t-butylperoxide, t-butylcumylperoxide, di (2-t-butylperoxyisopropyl) benzene, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, dicumylperoxide, di-t-butyl peroxyisophthalate, t-butyl peroxybenzoate, 2-bis (t-butylperoxy) butane, 2-bis (t-butylperoxy) octane, 2, 5-dimethyl-2, 5-di (benzoyl peroxy) hexane, di (trimethylsilyl) peroxide, trimethylsilyl triphenylsilyl peroxide and the like. The radical generator such as 2, 3-dimethyl-2, 3-diphenylbutane may be used as a reaction initiator for the resin composition. Among them, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexyne-3, di (2-t-butylperoxyisopropyl) benzene and 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane are preferable from the viewpoint of being capable of providing a cured product excellent in heat resistance and mechanical properties and further having a low dielectric constant and dielectric loss tangent.
The 1-minute half-life temperature of the organic peroxide is preferably 155℃or more and 185℃or less, more preferably 160℃to 180℃or 165℃to 175 ℃. In the present specification, the 1-minute half-life temperature is a temperature at which decomposition of the organic peroxide occurs and the time for which the amount of active oxygen reaches half is 1 minute. The 1-minute half-life temperature is a value confirmed by a method of dissolving an organic peroxide in a solvent inactive to a radical, for example, benzene or the like to a concentration of 0.05mol/L to 0.1mol/L and thermally decomposing the organic peroxide solution under a nitrogen atmosphere.
By setting the 1-minute half-life temperature of the organic peroxide to a range of 155 to 185 ℃, compatibility of the organic peroxide with PPE, coatability of the resin composition, and characteristics of the electronic circuit board tend to be more excellent.
Examples of the organic peroxide having a 1-minute half-life temperature in the range of 155 to 185℃include: tert-hexyl peroxyisopropyl monocarbonate (155.0 ℃), tert-butyl peroxy-3, 5-trimethylhexanoate (166.0 ℃), tert-butyl peroxylaurate (159.4 ℃), tert-butyl peroxyisopropyl monocarbonate (158.8 ℃), tert-butyl peroxy2-ethylhexyl monocarbonate (161.4 ℃), tert-hexyl peroxybenzoate (160.3 ℃), 2, 5-dimethyl-2, 5-bis (benzoyl-peroxy) hexane (158.2 ℃), tert-butyl peroxyacetate (159.9 ℃), 2-bis- (tert-butyl-peroxy) butane (159.9 ℃), tert-butyl peroxybenzoate (166.8 ℃), n-butyl 4, 4-bis- (tert-butyl-peroxy) valerate (172.5 ℃), bis (2-tert-butyl-peroxyisopropyl) benzene (175.4 ℃), dicumyl peroxide (175.2 ℃), di-tert-hexyl peroxide (176.7 ℃), 2, 5-dimethyl-2, 5-bis (tert-butyl-peroxy) hexane (179.8 ℃), etc.
The content of the organic peroxide is preferably 0.05 parts by mass or more, more preferably 0.5 parts by mass or more or 1 part by mass or more, still more preferably 1.5 parts by mass or more, based on 100 parts by mass of the total of the PPE and the crosslinking agent, from the viewpoint of more excellent compatibility between the organic peroxide and the PPE and coating property of the resin composition, and is preferably 5 parts by mass or less, more preferably 4.5 parts by mass or less, from the viewpoint of excellent substrate properties when the resin composition is mounted on an electronic circuit board. The content of the organic peroxide is preferably 0.05 parts by mass or more and 5 parts by mass or less, more preferably 0.5 parts by mass or more and 4.5 parts by mass or less, still 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, based on 100 parts by mass of the total of the PPE-a and the crosslinking agent, from the same viewpoint.
Thermoplastic resin
The thermoplastic resin of the present embodiment is at least 1 selected from the group consisting of a block copolymer of a vinyl aromatic compound and an alkenyl olefin compound, a hydrogenated block copolymer obtained by hydrogenating a block copolymer of a vinyl aromatic compound and an alkenyl olefin compound, and a homopolymer of a vinyl aromatic compound, and has a weight average molecular weight of 150,000 ～ 800,000. When the resin composition contains PPE, a crosslinking agent and an organic peroxide and also contains a thermoplastic resin having the above-described type and weight average molecular weight, compatibility between PPE and other components and coating properties on a base material or the like tend to be good, and further, substrate characteristics when assembled to an electronic circuit substrate may be excellent. The weight average molecular weight was determined by the method described in examples below.
The lower limit of the content of the unit derived from the vinyl aromatic compound in the block copolymer or hydrogenated product thereof is preferably 20 mass% or more, more preferably 22 mass% or more, 24 mass% or more, 26 mass% or more, 28 mass% or more, 30 mass% or more, or 32 mass% or more, and the upper limit is preferably 70 mass% or less, more preferably 69 mass% or less, 68 mass% or less, or 67 mass% or less. When the content of the unit derived from the vinyl aromatic compound in the block copolymer or hydrogenated product thereof is 20 to 70% by mass, the compatibility with polyphenylene ether tends to be further improved and/or the adhesion strength with a metal foil tends to be further improved.
The vinyl aromatic compound may have an aromatic ring and a vinyl group in the molecule, and examples thereof include styrene. The alkenylene compound may be an olefin having a linear or branched structure in the molecule, and examples thereof include: ethylene, propylene, butene, isobutylene, butadiene and isoprene. Among these, from the viewpoint of more excellent compatibility with polyphenylene ether, the thermoplastic resin is preferably at least 1 selected from the group consisting of a styrene-butadiene block copolymer, a styrene-ethylene-butene block copolymer, a styrene-butadiene-butene block copolymer, a styrene-isoprene block copolymer, a styrene-ethylene-propylene block copolymer, a styrene-isobutylene block copolymer, a hydrogenated product of a styrene-butadiene block copolymer, a hydrogenated product of a styrene-ethylene-butadiene-butene block copolymer, a hydrogenated product of a styrene-isoprene block copolymer, and a homopolymer of styrene (polystyrene), more preferably 1 or more selected from the group consisting of a styrene-butadiene block copolymer, a hydrogenated product of a styrene-butadiene block copolymer, and polystyrene.
The hydrogenation rate in the hydrogenated product is not particularly limited, and a part of carbon-carbon unsaturated double bonds derived from the olefin compound may be optionally remained.
From the viewpoint of further excellent compatibility with PPE, resin flowability, coatability of the resin composition, heat resistance at the time of curing, and the like, the weight average molecular weight of the thermoplastic resin is preferably more than 150,000 and 780,000 or less, more preferably 155,000 ～ 750,000, further preferably 160,000 ～ 700,000.
The content of the thermoplastic resin having the above-described kind and weight average molecular weight is 2 to 20 parts by mass, preferably 3 to 19 parts by mass, more preferably 4 to 18 parts by mass or 5 to 17 parts by mass based on 100 parts by mass of the total of the PPE and the crosslinking agent. When the content is within the above-mentioned numerical range, compatibility and coatability of the resin composition of the present embodiment with PPE are more excellent, and substrate characteristics are more excellent when the resin composition is mounted on an electronic circuit substrate. The content of the thermoplastic resin is 2 to 20 parts by mass, preferably 3 to 19 parts by mass, more preferably 4 to 18 parts by mass, or 5 to 17 parts by mass, based on 100 parts by mass of the total of the PPE-a and the crosslinking agent, from the same viewpoint.
The resin composition of the present embodiment may contain a thermoplastic resin other than the thermoplastic resin having the type and weight average molecular weight described above.
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 contained in the resin composition after curing of the resin composition, in view of improving heat resistance. Preferably, the flame retardant is incompatible with the PPE and/or the crosslinking 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, zinc borate, and the like; aromatic bromine compounds such as hexabromobenzene, decabromodiphenylethane, 4-dibromobiphenyl, ethylene bis (tetrabromophthalimide); phosphorus flame retardants such as resorcinol bis (diphenyl phosphate) and resorcinol bis (di (xylyl) phosphate). These flame retardants may be used singly or in combination of 2 or more. Among these, decabromodiphenylethane is preferable as the flame retardant from the viewpoints of compatibility of the flame retardant with PPE, coatability of the resin composition, and more excellent characteristics of the electronic circuit board.
The content of the flame retardant is not particularly limited, but is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 15 parts by mass or more, based on 100 parts by mass of the total of the polyphenylene ether (PPE) resin and the crosslinking agent, in terms of maintaining the flame retardancy of the UL standard 94V-0 level. In view of keeping the dielectric constant and dielectric loss tangent of the cured product obtained low, the content of the flame retardant is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and still more preferably 40 parts by mass or less.
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 may be 10 parts by mass to 100 parts by mass relative to 100 parts by mass of the total of the polyphenylene ether (PPE) resin and the crosslinking agent. Further, the surface of the silica filler may be surface-treated with a silane coupling agent or the like.
The resin composition of the present embodiment may contain additives such as heat stabilizer, antioxidant, UV absorber, surfactant, lubricant, and the like, solvents, and the like in addition to the flame retardant and the silica filler. When the resin composition of the present embodiment contains a solvent, the resin composition may be in the form of a varnish in which a solid component in the resin composition is dissolved or dispersed in the solvent. Further, a resin film may be formed from the resin composition of the present embodiment.
Solvent(s)
The solvent is preferably selected from aromatic compounds such as toluene and xylene, methyl Ethyl Ketone (MEK), cyclopentanone, cyclohexanone and chloroform from the viewpoint of solubility. These solvents may be used singly or in combination of 2 or more.
Prepreg material
The prepreg of the present embodiment includes a base material and the resin composition of the present embodiment impregnated into or applied to the base material. The prepreg can be obtained, for example, by impregnating a base material such as glass cloth with the varnish, and drying and removing the solvent component with a hot air dryer or the like.
The substrate may be: various glass cloths such as roving cloth, chopped strand mat, surface mat and the like; asbestos cloth, metal fiber cloth and other synthetic or natural inorganic fiber cloth; woven or nonwoven fabrics obtained from liquid crystal fibers such as wholly aromatic polyamide fibers, wholly aromatic polyester fibers, and polybenzoxazole fibers; natural fiber cloths such as cotton cloth, linen, felt, etc.; natural cellulose base materials such as carbon fiber cloth, kraft paper, cotton paper, and cloth obtained from paper-glass mixed yarn; porous polytetrafluoroethylene films, and the like. These substrates may be used alone or in combination of 2 or more.
The ratio 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 ratio is 30 mass% or more, the insulation reliability tends to be more excellent when the prepreg is used for an electronic substrate or the like. When the ratio is 80 mass% or less, mechanical properties such as flexural modulus tend to be more excellent in applications such as electronic substrates.
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 with a metal foil. The metal-clad laminate is preferably in a form in which a cured product of a prepreg (also referred to as a "cured product composite") is laminated and adhered to a metal foil, and can be suitably 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 of low resistance. The cured product composite to be combined with the metal foil may be 1 sheet or a plurality of sheets, and the metal foil may be laminated on one side or both sides of the composite according to the application, and processed into a laminated sheet. As a method for producing the laminated board, for example, the following methods are mentioned: a composite (for example, the prepreg described above) comprising a thermosetting resin composition and a base material is formed, and after being laminated with a metal foil, the thermosetting resin composition is cured, whereby a laminate sheet in which a cured laminate and a metal foil are laminated is obtained. One of the particularly preferred uses of the aforementioned laminate is printed circuit board. The printed circuit board preferably removes at least a portion of the metal foil from the metal clad laminate.
Printed circuit board with improved heat dissipation
The printed circuit board of the present embodiment removes a portion of the metal foil from the metal-clad laminate. The printed wiring board of the present embodiment can be typically formed by a press-heating molding method using the prepreg of the present invention. The substrate may be the same as that 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), and further can suppress the change of electrical characteristics with environmental changes, and also has excellent insulation reliability and mechanical characteristics by including the resin composition of the present embodiment.
Examples
The present embodiment will be described in detail with reference to examples, but the present embodiment is not limited to the examples.
Synthesis reaction of polyphenylene ether
The following reaction was carried out under an atmosphere of an inert gas. The solvent used in the reaction is a commercially available reagent. The raw materials and reagent types used are as follows.
1. Solvent(s)
Toluene: the reagent special grade product manufactured by the optical purity chemical company is directly used.
Methyl ethyl ketone: the reagent special grade product manufactured by the optical purity chemical company is directly used.
Methanol: the reagent special grade product manufactured by the optical purity chemical company is directly used.
2. And (3) an initiator:
nyber BMT: the product of japan oil and fat corporation is directly used.
3. Raw material polyphenylene ether S202A (number average molecular weight in terms of polystyrene: 16,000): a product manufactured by Asahi chemical Co., ltd.
S202A has the following structure.
4. Raw phenol (multifunctional/difunctional phenol)
4-1 phenols having a partial structure of formula (2) and a valence of a (a=3 to 6)
1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane: the product of ADEKA company (ADEKASTAB AO-30) was used as it is.
4-2 phenols having a valence of 3 and containing no partial structure of the formula (2)
Tris (4-hydroxyphenyl) ethane: a product of Asahi organic materials Co was used as it is.
5. Modified group raw material
Methacrylic anhydride: aldrich reagent was used directly.
Dimethylaminopyridine: aldrich reagent was used directly.
Identification/analysis of polyphenylene ether
1. Number average molecular weight determination
The number average molecular weight was measured by GPC in chloroform solvent. The number average molecular weight was determined by a polystyrene substitution algorithm based on a standard curve using standard polystyrene.
NMR measurement
The sample was dissolved in deuterated chloroform to a concentration of 5 mass%, and NMR measurement was performed. The progress of the reaction was confirmed by the decrease in the hydroxyl group peak from the ratio of the aromatic peak to the proton peak of the hydroxyl group of the polyfunctional phenol unit.
3. Melt viscosity
200ml of a 20% by mass methyl ethyl ketone solution of the sample was poured into a beaker, and the viscosity was measured at a rotational speed of 30rpm at 25℃using a type B rotary viscometer.
4. Average terminal functional group number
The average number of terminal functional groups per molecule of PPE was determined by the following method. That is, according to the method described in "Polymer paper (Japanese: polymer paper), vol.51, no.7 (1994), page 480", the change in absorbance at a wavelength of 318nm of a sample obtained by adding a tetramethylammonium hydroxide solution to a methylene chloride solution of PPE was measured by an ultraviolet-visible absorbance photometer. From this measurement value, the phenolic hydroxyl number of PPE before and after terminal modification was determined. The number of PPE molecules (number average molecular weight) was determined using the number average molecular weight of PPE and the mass of PPE determined by the method of 1 above.
From these values, the average phenolic hydroxyl number per 1 molecule of PPE before and after the modification was determined according to the following formula (1).
Average phenolic hydroxyl number per 1 molecule
=phenolic hydroxyl number/number average molecular number … (1)
The modified average terminal functional group number was obtained according to the following formula (2).
Average number of terminal functional groups per 1 molecule
Average phenolic hydroxyl number before modification-average phenolic hydroxyl number after modification … (2)
Production example 1
Synthesis of polyphenylene ether 1 (PPE 1)
A three-way cock was mounted on a 500ml 3-neck flask, and a serpentine condenser and an isobaric dropping funnel were further provided. After the flask was replaced with nitrogen, 100g of polyphenylene ether S202A, 200g of toluene, and 12.8g of 1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane as a polyfunctional phenol were added as raw materials. A thermometer was placed in the flask, and the flask was heated to 90℃in an oil bath while stirring with a magnetic stirrer, so that the raw polyphenylene ether was dissolved. As an initiator, a compound which is a compound having a radical initiator,37.5g of a 40% m-xylene solution (manufactured by Nippon oil Co., ltd.: NYPER BMT) of a mixture of benzoyl peroxide, benzoyl-m-methylbenzoyl peroxide and m-toluoyl peroxide was diluted with 87.5g of toluene, and poured into an isobaric dropping funnel. After the temperature in the flask was lowered to 80 ℃, the initiator solution was started to be added dropwise to the flask, and the reaction was started. The initiator was added dropwise over 2 hours, after which the temperature was raised again to 90℃and stirring was continued for 4 hours. After the reaction, the polymer solution was added dropwise to methanol, reprecipitated, and the solution was filtered off to recover the polymer. Then, it was dried under vacuum at 100℃for 3 hours. By passing through 1 H-NMR confirmed that the low molecular phenol was incorporated into the polymer, and that the peak of the hydroxyl group had disappeared. According to the following 1 As a result of H-NMR measurement, it was confirmed that the obtained polymer was a polyphenylene ether having a structure represented by the following formula (hereinafter referred to as PPE 1).
In the formula, l, m and n are arbitrarily selected numbers satisfying the following number average molecular weight }
As a result of GPC measurement, the molecular weight mn=1,500 of the obtained PPE1 in terms of polystyrene. In addition, the solution viscosity of PPE1 in 20% methyl ethyl ketone solvent was 125cPoise.
Synthesis of modified polyphenylene ether 1 (Low molecular weight modified PPE 1)
80g of toluene and 26g of the above synthesized PPE1 were mixed and heated to about 85 ℃. To the heated mixture was added 0.55g of dimethylaminopyridine. At the time point when the solid was considered to have completely dissolved, 4.9g of methacrylic anhydride was slowly added to the dissolved matter. The resulting solution was maintained at 85℃for 3 hours while continuously mixing. Then, the solution was cooled to room temperature to obtain a toluene solution of the methacrylate-modified polyphenylene ether.
Taking a part of the solution, drying and then implementing 1 H-NMR measurement. The reaction was judged to have progressed based on the disappearance of the peak derived from the hydroxyl group of the polyphenylene ether, and the operation was shifted to the purification operation. Toluene solution 120 of the above methacrylate-modified polyphenylene ether was prepared by dissolving the above methacrylate-modified polyphenylene ether in toluene for 30 minutes g was added dropwise to 360g of methanol vigorously stirred in a 1L beaker with a magnetic stirrer. The obtained precipitate was filtered under reduced pressure with a membrane filter and dried to obtain 38g of a polymer. To dry the polymer 1 The results of the H-NMR measurement are shown in FIG. 1. It was confirmed that the peak of the hydroxyl group derived from polyphenylene ether was disappeared in the vicinity of 4.5ppm and the peak of the alkene derived from methacryloyl group was appeared in the vicinity of 5.75 ppm. Further, the peak derived from the methacryloyl group in NMR was judged to be the peak of the methacryloyl group bonded to the terminal of the polyphenylene ether, based on the substantial disappearance of the peak derived from dimethylaminopyridine, methacrylic anhydride, and methacrylic acid by GC measurement. From this result, it was confirmed that the obtained polymer was a modified polyphenylene ether having a structure represented by the following formula (hereinafter referred to as low molecular weight modified PPE 1).
In the formula, l, m and n are arbitrarily selected numbers satisfying the following number average molecular weight }
Further, as a result of GPC measurement, the molecular weight mn=1,600 of the obtained low molecular weight modified PPE1 in terms of polystyrene. The average terminal functional group number of the low molecular weight modified PPE1 was calculated to be 2.5 or more according to the above formula (2). Further, the solution viscosity of the modified PPE1 in a 20% methyl ethyl ketone solvent was 131cPoise.
Material for forming resin composition and cured product thereof
PPE
The low molecular weight modified polyphenylene ether 1 (low molecular weight modified PPE 1) obtained above
Crosslinking agent
TAIC (molecular weight: 249.7, number of unsaturated double bonds: 3, manufactured by Japanese chemical Co., ltd.)
Organic peroxides
Bis (1-tert-butylperoxy-1-methylethyl) benzene
Product name: PERBUTYL P (manufactured by Nipple Co., ltd.)
Thermoplastic resin
SEBS N525: product name "TUFTEC N525", manufactured by asahi chemical company, mw:20 ten thousand styrene unit content: 67 mass%
SEBS N504: product name "TUFTEC N504", manufactured by asahi chemical company, mw:20 ten thousand styrene unit content: 32 mass%
SEBS N516: product name "TUFTEC N516", manufactured by asahi chemical company, mw:16 ten thousand styrene unit content: 40 mass%
SEBS N517: product name "TUFTEC N517", manufactured by asahi chemical company, mw:40 ten thousand styrene unit content: 40 mass%
SEBS H1041: product names "TUFTEC H1041", manufactured by asahi chemical company, mw:5.7 ten thousand styrene unit content: 31 mass%
SEBS H1221: product names "TUFTEC H1221", manufactured by asahi chemical industry, mw:12 ten thousand styrene unit content: 12 mass%
Flame retardant
Decabromodiphenylethane "product name SAYTEX8010" (manufactured by ALBEMARRE Co., ltd.)
Filler (B)
Spherical silica (Dragon company system)
Substrate material
L glass cloth
(Asahi-Schwebel Co., ltd., model: 2116)
Evaluation method
Number average molecular weight of PPE, weight average molecular weight of thermoplastic resin
The number average molecular weight of PPE and the weight average molecular weight of the thermoplastic resin were determined by GPC analysis 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 0.2w/vol% (solvent: chloroform), the measurement apparatus was set up in a chromatographic column using HLC-8220GPC (manufactured by Tosoh Corp.). Shodex GPCKF-405LHQ×3 (manufactured by Showa Denko Co., ltd.), eluent: chloroform, injection amount: 20 μl, flow rate: 0.3 mL/min, column temperature: 40 ℃, detector: RI.
2. Varnish viscosity
200ml of the resin varnish (solid content: 53% by mass) prepared from each resin composition and toluene was poured into a beaker, and the viscosity was measured at 25℃with a type B rotary viscometer at 30rpm for 30 seconds. The measured viscosities were evaluated on 5 scales.
5: more than 50 mPas and not more than 150 mPas
4: more than 150 mPas and not more than 200 mPas
3: more than 200 mPas and 300 mPas or less
2: more than 300 mPas and 500 mPas or less
1: more than 500 mPas and 1000 mPas or less
3. Impregnating ability
A resin varnish (solid content: 53% by mass) prepared from each resin composition and toluene was poured into a pot, and an L glass cloth (Asahi-Schwebel co., ltd., model: 2116) cut into 50mm square was placed from above the pot, and the state of impregnation of the resin varnish into the glass cloth was visually observed. The resin varnish was evaluated for the impregnation of glass cloth on a 5-grade scale.
5: the resin varnish is impregnated into the whole glass cloth within 1 minute
4: the resin varnish is impregnated into the whole glass cloth within 2 minutes
3: the resin varnish is impregnated into the whole glass cloth within 3 minutes
2: in the case that the whole glass cloth is impregnated with the resin varnish within 5 minutes
1: after 5 minutes, infiltration was not completed
4. Dispersibility of
The mixture containing the components shown in table 1 was mixed with the solvent, stirred, and visually observed for the state of the mixture after the stirring was stopped, and evaluated according to the following criteria.
And (2) the following steps: after the stirring is stopped, the insoluble substances are uniformly dispersed without sedimentation for more than 2 hr.
X: the insoluble matter was settled within 1hr after the poor stirring was stopped.
5. Dielectric constant and dielectric loss tangent (electrical characteristics) of the laminated board
The dielectric constant and dielectric loss tangent of the laminate at 10GHz were measured by the cavity resonance method. As the measurement device, measurement was performed using a network analyzer (manufactured by N5230A, agilent Technologies, inc.) and a cavity resonator (Cavity Resornator CP series) manufactured by kanto electronics application development company. The laminated sheet having a thickness of about 0.5mm, which was produced by the method described later, was cut into a size of about 2mm in width and 50mm in length with warp yarns of glass cloth as long sides. Then, the mixture was dried in an oven at 105.+ -. 2 ℃ for 2 hours, and then allowed to stand at 23 ℃ in an environment of 50.+ -. 5% relative humidity for 96.+ -. 5 hours. Then, the dielectric constant and the dielectric loss tangent were measured by using the above measuring apparatus under an environment of 23℃and a relative humidity of 50.+ -. 5%, and evaluated on 5 scale.
5: a dielectric constant of 3.0 to 3.3, and a dielectric loss tangent exceeding 0.0020 and 0.0024 or less
4: a dielectric constant of 3.0 to 3.3, and a dielectric loss tangent exceeding 0.0024 and 0.0026 or less
3: a dielectric constant of 3.0 to 3.3, and a dielectric loss tangent exceeding 0.0026 and 0.0030 or less
2: a dielectric constant of 3.0 to 3.3, and a dielectric loss tangent exceeding 0.0030 to 0.0035
1: dielectric constant of more than 3.3 and dielectric loss tangent of more than 0.0035
6. Glass transition temperature (Tg) of the laminate
The dynamic viscoelasticity of the laminate was measured, and the temperature at which tan δ reached the maximum was obtained as the glass transition temperature (Tg). The measuring device used was a dynamic viscoelasticity device (RHEVIBRON model DDV-01FP, ORIENTEC Co., ltd.). A laminate sheet having a thickness of about 0.3mm, which was produced by the method described below, was cut into test pieces having a length of about 35mm and a width of about 5mm, with warp yarns of glass cloth as the long sides, and the test pieces were produced in a stretching mode and at a frequency of: the measurement was performed at 10 rad/s.
The evaluation was performed on 5 grades according to the Tg value.
5: exceeding 200 DEG C
4: above 190 ℃ and below 200 DEG C
3: above 180deg.C and below 190 deg.C
2: above 170 ℃ and below 180 DEG C
1: above 160deg.C and below 170deg.C
7. Heat resistance of laminated board
The prepregs obtained in examples and comparative examples were stacked 8 and the laminate produced by the method described below was cut into 50mm square pieces, and then the cut samples were placed in an oven at 105.+ -. 2 ℃ and dried for 2 hours, and then a pressure cooker test was performed under conditions of 2 atmospheres and 4 hours. Heat resistance test the laminate after the water absorption acceleration test was visually evaluated according to the following criteria.
And (2) the following steps: when the laminate after the accelerated test of water absorption was immersed in a solder bath at 288℃for 20 seconds, no swelling, peeling and whitening were observed.
X: when the laminate sheet after the water absorption acceleration test was immersed in a solder bath at 288 ℃ for 20 seconds, any of swelling, peeling and whitening was observed.
8. Copper foil peel strength (peel strength N/mm) of laminate
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 Gu electric industries Co., ltd.) manufactured by the method described later was cut into a size of 15mm in width by 150mm in length, and the average value of the load when the copper foil was peeled off at a speed of 50 mm/min at an angle of 90℃to the removal surface was measured by using an Autograph (AG-5000D manufactured by Shimadzu corporation), and the average value of 5 measurements was obtained and evaluated on 5 grades.
5: exceeding 1.0N/mm
4: more than 0.80N/mm and 1.0N/mm or less
3: more than 0.70N/mm and less than 0.80N/mm
2: more than 0.5N/mm and less than 0.70N/mm
1: is less than 0.5N/mm
Example 1
According to the composition shown in Table 1, phasesTo 287 parts by mass of toluene, a thermoplastic resin was added and dissolved by stirring, and then a flame retardant, spherical silica and low molecular weight modified PPE1 were added, respectively, and stirring was continued until the low molecular weight modified PPE1 was dissolved (solid content concentration 53% by mass). Then, a crosslinking agent and an organic peroxide were added to the dissolved substances, respectively, and the mixture was sufficiently stirred to obtain a varnish. After impregnating the L glass cloth with the varnish, excess varnish was scraped off by passing the varnish through a predetermined slit, and the resultant was dried in a drying oven at 105 ℃ for a predetermined period of time to remove toluene, thereby obtaining a prepreg. The prepreg was cut into a predetermined size, and the weight of the prepreg was compared with the weight of the glass cloth of the same size to calculate the solid content of the resin composition in the prepreg, and as a result, the solid content was 58 mass%. The prepregs were laminated to a predetermined number of sheets, and copper foils (35 μm thick GTS-MP foils manufactured by gulch electric industries, inc.) were further laminated on both sides of the laminated prepregs, and vacuum pressing was performed in this state, to thereby obtain a copper-clad laminate. In the vacuum pressing step, first, a pressure of 10kg/cm was used while heating at a temperature rising rate of 3℃per minute from room temperature 2 After reaching 130 ℃, the temperature was raised at a rate of 3℃per minute, and a pressure of 40kg/cm was applied 2 Is a condition of (2). After the temperature reached 200 ℃, the pressure was 40kg/cm while maintaining the temperature at 200 ℃ 2 And conditions for 60 minutes. Next, the copper foil is removed from the copper-clad laminate by etching, thereby obtaining a laminate.
Examples 2 to 6 and comparative examples 1 to 4
Resin compositions, varnishes, prepregs, copper-clad laminates and laminated sheets were obtained and evaluated in examples 2 to 6 and comparative examples 1 to 4, respectively, in the same manner as in example 1 except that the compositions were changed as shown in table 1.
TABLE 1
Claims (10)
1. A resin composition comprising:
(a) A polyphenylene ether component A having a structure represented by the following formula (1) and having a number average molecular weight of 500 to 8,000;
(b) A cross-linking agent;
(c) An organic peroxide; and
(d) At least 1 selected from the group consisting of block copolymers of vinyl aromatic compounds and alkenyl olefin compounds and hydrogenated products thereof, and homopolymers of the vinyl aromatic compounds, and a thermoplastic resin having a weight average molecular weight of 150,000 ～ 800,000,
and the thermoplastic resin is contained in an amount of 2 to 20 parts by mass based on 100 parts by mass of the total mass of the polyphenylene ether component A and the crosslinking agent,
(1)
In the formula (1), the components are as follows,
x is an arbitrary linking group having a valence of a, a is a number of 2.5 or more,
R 5 each independently is an optional substituent, k is each independently an integer of 1 to 4, and k R are present 5 At least 1 of which comprises a partial structure represented by the following formula (2),
y is each independently a divalent linking group having a structure represented by the following formula (3), n represents the number of repetitions of Y, each independently an integer of 1 to 200,
l is any divalent linking group or single bond, and
a each independently represents a substituent containing a carbon-carbon double bond and/or an epoxy bond,
(2)
In the formula (2), R 11 Each independently is C 1-8 Alkyl of R 12 Each independently is C 1-8 Alkylene groups of (a), b are each independently 0 or 1, R 13 Represents a hydrogen atom, C 1-8 Any of alkyl or phenyl, and the alkyl, alkylene and phenyl are at a level C 1-8 Optionally having substituents within the scope of the conditions of (2),
(3)
In the formula (3), R 21 Each independently is C 1-6 Saturated or unsaturated hydrocarbon radicals, R 22 Each independently is a hydrogen atom or C 1-6 Saturated or unsaturated hydrocarbon groups of (2), and the saturated or unsaturated hydrocarbon groups are in a condition of satisfying C 1-6 Optionally having substituents within the scope of the conditions of (2);
wherein the crosslinking agent has more than 2 carbon-carbon unsaturated double bonds in 1 molecule on average, the number average molecular weight of the crosslinking agent is less than 4,000, and the weight ratio of the polyphenyl ether component A to the crosslinking agent is 25:75-95:5;
The content of the organic peroxide is 0.05 to 5 parts by mass based on 100 parts by mass of the total mass of the polyphenylene ether component A and the crosslinking agent.
2. The resin composition according to claim 1, wherein the content of the unit derived from the vinyl aromatic compound in the block copolymer or hydrogenated product thereof is 20 mass% or more and 70 mass% or less.
3. The resin composition according to claim 1 or 2, wherein the crosslinking agent comprises at least one compound selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, and polybutadiene.
4. The resin composition according to claim 1 or 2, wherein the 1 minute half-life temperature of the organic peroxide is 155 ℃ to 185 ℃.
5. The resin composition according to claim 1 or 2, wherein the resin composition further comprises a flame retardant, and the flame retardant is not compatible with other containing ingredients in the resin composition after the resin composition is cured.
6. An electronic circuit substrate material comprising the resin composition according to any one of claims 1 to 5.
7. A resin film comprising the resin composition according to any one of claims 1 to 5.
8. A prepreg which is a composite of a substrate and the resin composition according to any one of claims 1 to 5.
9. The prepreg of claim 8, wherein the substrate is a glass cloth.
10. A laminate of a metal foil and the resin film according to claim 7 or the cured product of the prepreg according to claim 8 or 9.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019110419A JP7308082B2 (en) | 2019-06-13 | 2019-06-13 | Polyphenylene ether-containing resin composition |
| JP2019-110419 | 2019-06-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112080126A CN112080126A (en) | 2020-12-15 |
| CN112080126B true CN112080126B (en) | 2023-06-27 |
Family
ID=73735041
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010534008.1A Active CN112080126B (en) | 2019-06-13 | 2020-06-12 | Polyphenylene ether-containing resin composition |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP7308082B2 (en) |
| CN (1) | CN112080126B (en) |
| TW (1) | TWI760763B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114127183B (en) * | 2019-07-17 | 2024-07-26 | 松下知识产权经营株式会社 | Resin composition, prepreg, resin-coated film, resin-coated metal foil, metal foil-clad laminate, and wiring board |
| WO2022239631A1 (en) * | 2021-05-11 | 2022-11-17 | 旭化成株式会社 | Novel terminal-modified polyphenylene ether and terminal-modified polyphenylene ether composition |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103228703A (en) * | 2010-12-16 | 2013-07-31 | 旭化成电子材料株式会社 | Curable resin composition |
| CN105518055A (en) * | 2013-06-03 | 2016-04-20 | 普立万公司 | Low molecular weight polyphenylene ether prepared without solvents |
| CN105694425A (en) * | 2014-12-16 | 2016-06-22 | 松下知识产权经营株式会社 | Poly(phenylene ether) resin composition, prepreg, metal-clad laminate, and printed-wiring board |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7413791B2 (en) * | 2003-01-28 | 2008-08-19 | Matsushita Electric Works, Ltd. | Poly (phenylene ether) resin composition, prepreg, and laminated sheet |
| US9455067B2 (en) * | 2013-03-18 | 2016-09-27 | Iteq Corporation | Low dielectric materials |
| US10358585B2 (en) * | 2015-12-22 | 2019-07-23 | Industrial Technology Research Institute | Polyphenylene ether oligomer and high-frequency copper clad laminate |
| 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 |
| JP2019023263A (en) * | 2017-07-25 | 2019-02-14 | パナソニックＩｐマネジメント株式会社 | Resin composition, prepreg, film with resin, metal foil with resin, metal-clad laminate, and wiring board |
-
2019
- 2019-06-13 JP JP2019110419A patent/JP7308082B2/en active Active
-
2020
- 2020-06-10 TW TW109119412A patent/TWI760763B/en active
- 2020-06-12 CN CN202010534008.1A patent/CN112080126B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103228703A (en) * | 2010-12-16 | 2013-07-31 | 旭化成电子材料株式会社 | Curable resin composition |
| CN105518055A (en) * | 2013-06-03 | 2016-04-20 | 普立万公司 | Low molecular weight polyphenylene ether prepared without solvents |
| CN105694425A (en) * | 2014-12-16 | 2016-06-22 | 松下知识产权经营株式会社 | Poly(phenylene ether) resin composition, prepreg, metal-clad laminate, and printed-wiring board |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI760763B (en) | 2022-04-11 |
| JP7308082B2 (en) | 2023-07-13 |
| TW202102604A (en) | 2021-01-16 |
| CN112080126A (en) | 2020-12-15 |
| JP2020200432A (en) | 2020-12-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7508244B2 (en) | Polyphenylene ether resin composition | |
| JP6906171B2 (en) | Polyphenylene ether resin composition, prepreg, metal-clad laminate and printed wiring board | |
| CN111886267B (en) | Resin composition, and prepreg, resin-equipped film, resin-equipped metal foil, metal-clad laminate and wiring board using the same | |
| KR102601823B1 (en) | Resin composition, prepreg, resin-attached film, resin-attached metal foil, metal-clad laminate, and wiring board | |
| KR930005399B1 (en) | Curable polyphenyleneether resin composition | |
| CN107709370B (en) | Curable composition, prepreg, metal foil with composition, metal-clad laminate, and wiring board | |
| JPWO2018074278A1 (en) | Resin composition, method for producing resin composition, prepreg, film with resin, metal foil with resin, metal-clad laminate, and wiring board | |
| CN112080126B (en) | Polyphenylene ether-containing resin composition | |
| CN111886263A (en) | Resin composition, prepreg using same, resin-containing film, resin-containing metal foil, metal-clad laminate, and wiring board | |
| CN111592751B (en) | Polyphenylene ether-containing resin composition | |
| KR20220024148A (en) | Resin composition, prepreg, resin-added film, resin-added metal foil, metal clad laminate, and wiring board | |
| WO2021166649A1 (en) | Curable resin composition, prepreg, metal-clad laminate, and printed wiring board | |
| JP7462399B2 (en) | Polyphenylene ether-containing printed wiring board | |
| JP2020200427A (en) | Polyphenylene ether-containing resin composition | |
| JP7339025B2 (en) | Polyphenylene ether-containing resin composition | |
| CN111886264B (en) | Resin composition, and prepreg, resin-equipped film, resin-equipped metal foil, metal-clad laminate and wiring board using the same | |
| TWI724783B (en) | Resin composition containing polyphenylene ether | |
| JP7328801B2 (en) | Polyphenylene ether-containing resin composition | |
| JP2020200434A (en) | Polyphenylene ether-containing resin composition | |
| JP2020132758A (en) | Polyphenylene ether-containing resin composition | |
| JP2021167372A (en) | Resin composition containing polyphenylene ether | |
| WO2024214530A1 (en) | Resin composition, prepreg, resin film, metal-clad laminate, printed wiring board, semiconductor package, and acenaphthylene homopolymer | |
| JP2023143358A (en) | Crosslinked heat-resistant prepolymer and curable resin composition | |
| JP2021167371A (en) | Resin cured material, metal-clad laminate board, and printed circuit board |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |