JPH02185517A - Thermosetting resin composition and prepreg and laminate prepared therefrom - Google Patents
Thermosetting resin composition and prepreg and laminate prepared therefromInfo
- Publication number
- JPH02185517A JPH02185517A JP398289A JP398289A JPH02185517A JP H02185517 A JPH02185517 A JP H02185517A JP 398289 A JP398289 A JP 398289A JP 398289 A JP398289 A JP 398289A JP H02185517 A JPH02185517 A JP H02185517A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- epoxy
- formula
- group
- orthotolylguanidine
- 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.)
- Pending
Links
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 34
- 239000011342 resin composition Substances 0.000 title claims description 50
- -1 poly(p-hydroxystyrene) Polymers 0.000 claims abstract description 95
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 59
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 59
- 229920005989 resin Polymers 0.000 claims abstract description 46
- 239000011347 resin Substances 0.000 claims abstract description 46
- OPNUROKCUBTKLF-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N\C(N)=N\C1=CC=CC=C1C OPNUROKCUBTKLF-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000004593 Epoxy Substances 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 26
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 13
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- 238000010030 laminating Methods 0.000 claims abstract description 3
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical class OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 claims description 23
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 125000005843 halogen group Chemical group 0.000 claims description 16
- 125000003700 epoxy group Chemical group 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 229920000647 polyepoxide Polymers 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 abstract description 16
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 abstract description 12
- 150000001412 amines Chemical class 0.000 abstract description 5
- 238000013329 compounding Methods 0.000 abstract description 5
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 abstract description 4
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 abstract description 3
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 239000002966 varnish Substances 0.000 description 38
- 239000010410 layer Substances 0.000 description 26
- 238000001723 curing Methods 0.000 description 24
- 239000011521 glass Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- 238000002156 mixing Methods 0.000 description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 14
- 239000003063 flame retardant Substances 0.000 description 14
- 239000002648 laminated material Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000002585 base Substances 0.000 description 12
- 229920001721 polyimide Polymers 0.000 description 12
- 238000005452 bending Methods 0.000 description 10
- 239000003822 epoxy resin Substances 0.000 description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 9
- 229910052794 bromium Inorganic materials 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 229920003986 novolac Polymers 0.000 description 9
- 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 description 8
- 239000004020 conductor Substances 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000000835 fiber Substances 0.000 description 7
- 229920003192 poly(bis maleimide) Polymers 0.000 description 7
- 239000007870 radical polymerization initiator Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000009719 polyimide resin Substances 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000001294 propane Substances 0.000 description 6
- 230000035939 shock Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 5
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 5
- 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 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000004760 aramid Substances 0.000 description 4
- 150000004982 aromatic amines Chemical class 0.000 description 4
- 150000004984 aromatic diamines Chemical class 0.000 description 4
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 230000008054 signal transmission Effects 0.000 description 4
- 238000005476 soldering Methods 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 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
- 239000004305 biphenyl Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- ZSVFYHKZQNDJEV-UHFFFAOYSA-N (2,3,4-tribromophenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=C(Br)C(Br)=C1Br ZSVFYHKZQNDJEV-UHFFFAOYSA-N 0.000 description 2
- BUPRYTFTHBNSBD-UHFFFAOYSA-N (2,3,4-tribromophenyl) prop-2-enoate Chemical compound BrC1=CC=C(OC(=O)C=C)C(Br)=C1Br BUPRYTFTHBNSBD-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 2
- QDEQBRUNBFJJPW-UHFFFAOYSA-N 1-(3-chlorophenyl)pyrrole-2,5-dione Chemical compound ClC1=CC=CC(N2C(C=CC2=O)=O)=C1 QDEQBRUNBFJJPW-UHFFFAOYSA-N 0.000 description 2
- UNCUTNPWBZKJHD-UHFFFAOYSA-N 1-(3-methoxyphenyl)pyrrole-2,5-dione Chemical compound COC1=CC=CC(N2C(C=CC2=O)=O)=C1 UNCUTNPWBZKJHD-UHFFFAOYSA-N 0.000 description 2
- XAHCEMQKWSQGLQ-UHFFFAOYSA-N 1-(4-methoxyphenyl)pyrrole-2,5-dione Chemical compound C1=CC(OC)=CC=C1N1C(=O)C=CC1=O XAHCEMQKWSQGLQ-UHFFFAOYSA-N 0.000 description 2
- DSHSEHBLBSCNAV-UHFFFAOYSA-N 1-[4-[2-[4-(2,5-dioxopyrrol-1-yl)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(N2C(C=CC2=O)=O)C=CC=1C(C(F)(F)F)(C(F)(F)F)C(C=C1)=CC=C1N1C(=O)C=CC1=O DSHSEHBLBSCNAV-UHFFFAOYSA-N 0.000 description 2
- MUSBHZSCJOVTRF-UHFFFAOYSA-N 1-acetyl-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(C(=O)C)C(=O)C=C1C1=CC=CC=C1 MUSBHZSCJOVTRF-UHFFFAOYSA-N 0.000 description 2
- HHVCCCZZVQMAMT-UHFFFAOYSA-N 1-hydroxy-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(O)C(=O)C=C1C1=CC=CC=C1 HHVCCCZZVQMAMT-UHFFFAOYSA-N 0.000 description 2
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 2
- NNXKHUXDXSVBTB-UHFFFAOYSA-N 1-pyridin-2-ylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=N1 NNXKHUXDXSVBTB-UHFFFAOYSA-N 0.000 description 2
- NOSXUFXBUISMPR-UHFFFAOYSA-N 1-tert-butylperoxyhexane Chemical compound CCCCCCOOC(C)(C)C NOSXUFXBUISMPR-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
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 2
- OWMNWOXJAXJCJI-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxymethyl)oxirane;phenol Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1.C1OC1COCC1CO1 OWMNWOXJAXJCJI-UHFFFAOYSA-N 0.000 description 2
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 2
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical class OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 2
- 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 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-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
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229940125810 compound 20 Drugs 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000002241 glass-ceramic Substances 0.000 description 2
- JAXFJECJQZDFJS-XHEPKHHKSA-N gtpl8555 Chemical compound OC(=O)C[C@H](N)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](C(C)C)C(=O)N1CCC[C@@H]1C(=O)N[C@H](B1O[C@@]2(C)[C@H]3C[C@H](C3(C)C)C[C@H]2O1)CCC1=CC=C(F)C=C1 JAXFJECJQZDFJS-XHEPKHHKSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000012784 inorganic fiber Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 238000001259 photo etching Methods 0.000 description 2
- XOKSLPVRUOBDEW-UHFFFAOYSA-N pinane Chemical compound CC1CCC2C(C)(C)C1C2 XOKSLPVRUOBDEW-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- ROEHNQZQCCPZCH-UHFFFAOYSA-N tert-butyl 2-tert-butylperoxycarbonylbenzoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)OC(C)(C)C ROEHNQZQCCPZCH-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 2
- 235000019801 trisodium phosphate Nutrition 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- RXHAESOIONKORJ-UHFFFAOYSA-N (2,5-dioxo-3-phenylpyrrol-1-yl) acetate Chemical compound O=C1N(OC(=O)C)C(=O)C=C1C1=CC=CC=C1 RXHAESOIONKORJ-UHFFFAOYSA-N 0.000 description 1
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- LJDGDRYFCIHDPX-UHFFFAOYSA-N 1-(2-methoxyphenyl)pyrrole-2,5-dione Chemical compound COC1=CC=CC=C1N1C(=O)C=CC1=O LJDGDRYFCIHDPX-UHFFFAOYSA-N 0.000 description 1
- PRZFFHNZHXGTRC-UHFFFAOYSA-N 1-(3-methylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC=CC(N2C(C=CC2=O)=O)=C1 PRZFFHNZHXGTRC-UHFFFAOYSA-N 0.000 description 1
- KCFXNGDHQPMIAQ-UHFFFAOYSA-N 1-(4-methylphenyl)pyrrole-2,5-dione Chemical compound C1=CC(C)=CC=C1N1C(=O)C=CC1=O KCFXNGDHQPMIAQ-UHFFFAOYSA-N 0.000 description 1
- WZZBNLYBHUDSHF-DHLKQENFSA-N 1-[(3s,4s)-4-[8-(2-chloro-4-pyrimidin-2-yloxyphenyl)-7-fluoro-2-methylimidazo[4,5-c]quinolin-1-yl]-3-fluoropiperidin-1-yl]-2-hydroxyethanone Chemical compound CC1=NC2=CN=C3C=C(F)C(C=4C(=CC(OC=5N=CC=CN=5)=CC=4)Cl)=CC3=C2N1[C@H]1CCN(C(=O)CO)C[C@@H]1F WZZBNLYBHUDSHF-DHLKQENFSA-N 0.000 description 1
- FTFULVSESZARHS-UHFFFAOYSA-N 1-[2-chloro-4-[[3-chloro-4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(N2C(C=CC2=O)=O)C(Cl)=CC=1CC(C=C1Cl)=CC=C1N1C(=O)C=CC1=O FTFULVSESZARHS-UHFFFAOYSA-N 0.000 description 1
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- MBNMVPPPCZKPIJ-UHFFFAOYSA-N 1-[3-[3-[3-(2,5-dioxopyrrol-1-yl)phenoxy]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(OC=2C=C(OC=3C=C(C=CC=3)N3C(C=CC3=O)=O)C=CC=2)=C1 MBNMVPPPCZKPIJ-UHFFFAOYSA-N 0.000 description 1
- GABSEQUVYVNDHQ-UHFFFAOYSA-N 1-[4-[4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C1=CC(C(C(F)(F)F)C(F)(F)F)=CC=C1OC1=CC=C(N2C(C=CC2=O)=O)C=C1 GABSEQUVYVNDHQ-UHFFFAOYSA-N 0.000 description 1
- SLHJINOEGOLHQE-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]-3-methylphenyl]propan-2-yl]-2-methylphenoxy]phenyl]pyrrole-2,5-dione Chemical compound CC1=CC(C(C)(C)C=2C=C(C)C(OC=3C=CC(=CC=3)N3C(C=CC3=O)=O)=CC=2)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O SLHJINOEGOLHQE-UHFFFAOYSA-N 0.000 description 1
- PYTZZNUKESXWLN-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=CC=1C(C(F)(F)F)(C(F)(F)F)C(C=C1)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O PYTZZNUKESXWLN-UHFFFAOYSA-N 0.000 description 1
- XAZPKEBWNIUCKF-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]propan-2-yl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=CC=1C(C)(C)C(C=C1)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O XAZPKEBWNIUCKF-UHFFFAOYSA-N 0.000 description 1
- MKRBAPNEJMFMHU-UHFFFAOYSA-N 1-benzylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CC1=CC=CC=C1 MKRBAPNEJMFMHU-UHFFFAOYSA-N 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical compound CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- XKBHBVFIWWDGQX-UHFFFAOYSA-N 2-bromo-3,3,4,4,5,5,5-heptafluoropent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Br)=C XKBHBVFIWWDGQX-UHFFFAOYSA-N 0.000 description 1
- MYGMGGHRPDDQCN-UHFFFAOYSA-N 2-methyl-1-(2-methylprop-1-enoxy)prop-1-ene Chemical compound CC(C)=COC=C(C)C MYGMGGHRPDDQCN-UHFFFAOYSA-N 0.000 description 1
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 1
- ZUWDLQJPRYEONL-UHFFFAOYSA-N 3-acetyl-4-phenylpyrrole-2,5-dione Chemical compound C(C)(=O)C1=C(C(=O)NC1=O)C1=CC=CC=C1 ZUWDLQJPRYEONL-UHFFFAOYSA-N 0.000 description 1
- GTYRFVGHYNRSKT-UHFFFAOYSA-N 3-benzylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(CC=2C=CC=CC=2)=C1 GTYRFVGHYNRSKT-UHFFFAOYSA-N 0.000 description 1
- YQIMPOZJASMUNN-UHFFFAOYSA-N 4-(4,4-diaminocyclohexa-1,5-dien-1-yl)sulfonylcyclohexa-2,4-diene-1,1-diamine Chemical compound C1=CC(N)(N)CC=C1S(=O)(=O)C1=CCC(N)(N)C=C1 YQIMPOZJASMUNN-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- RPJFWRZEEKJTGN-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=CC(O)=CC=2)=C1 RPJFWRZEEKJTGN-UHFFFAOYSA-N 0.000 description 1
- GPUXFSMLTRCLFL-UHFFFAOYSA-N 4-ethenylphenol Chemical class OC1=CC=C(C=C)C=C1.OC1=CC=C(C=C)C=C1 GPUXFSMLTRCLFL-UHFFFAOYSA-N 0.000 description 1
- LTSCBXDGJFSJMR-UHFFFAOYSA-N 4-methylcyclohexa-2,4-diene-1,1-diamine Chemical compound CC1=CCC(N)(N)C=C1 LTSCBXDGJFSJMR-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 229940125904 compound 1 Drugs 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
- NECNAXWJIQPTKG-UHFFFAOYSA-N disodium;zinc;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Na+].[Zn+2] NECNAXWJIQPTKG-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- WHOPEPSOPUIRQQ-UHFFFAOYSA-N oxoaluminum Chemical compound O1[Al]O[Al]1 WHOPEPSOPUIRQQ-UHFFFAOYSA-N 0.000 description 1
- 229930006728 pinane Natural products 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 229960002218 sodium chlorite Drugs 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は熱硬化性樹脂組成物、それを用いたプリプレグ
および積層板に係り、特に難燃性、耐熱性および電機特
性に優れ、硬化時の収縮率の小さい多層プリント回路板
に好適な積層材料に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a thermosetting resin composition, prepregs and laminates using the same, and has particularly excellent flame retardancy, heat resistance, and electrical properties, and has excellent properties when cured. The present invention relates to a laminated material suitable for multilayer printed circuit boards that has a small shrinkage rate.
従来、多層プリント回路板用積層材料として、難燃性を
付与する為にブロム化変性樹脂や添加型難燃性を用いた
フェノール樹脂、エポキシ樹脂およびポリイミド樹脂等
が主に使用されている。特に大型計算機には高密度化が
望まれ、耐熱性、寸法安定性に優れたポリイミド系樹脂
が用いられている。しかし、近年、大型計算機の高速演
算処理化な伴い、信号伝送速度の向上のため、低誘電率
のプリント回路板が要求されている。このような低誘電
率積層材料として四フッ化エチレン（ＰＴＦＥ）樹脂、
ポリブタジェン樹脂から成る積層板が開発されている。Conventionally, phenol resins, epoxy resins, polyimide resins, etc. using brominated modified resins or additive flame retardants have been mainly used as laminated materials for multilayer printed circuit boards to impart flame retardancy. In particular, high density is desired for large computers, and polyimide resins with excellent heat resistance and dimensional stability are used. However, in recent years, with the increase in high-speed calculation processing of large computers, printed circuit boards with a low dielectric constant are required to improve signal transmission speed. Tetrafluoroethylene (PTFE) resin is used as such a low dielectric constant laminated material.
Laminates made of polybutadiene resin have been developed.
この種の積層板に関するものとして、例えばプロシージ
インーグ・エヌ・イー・ビー・シー・オー・エヌ（１９
８１年）第１６０頁から第１６９頁（Ｐｒｏｃ、ＮＥＰ
ＣＯＮ（１９８１） Ｐ １６Ｏ−１６９）および特開
昭５５−１２６４５１号公報等が挙げられる。Regarding this type of laminate, for example, Procedures N.B.C.O.N.
1981) pages 160 to 169 (Proc, NEP
CON (1981) P 16O-169) and JP-A-55-126451.
また、難燃性樹脂組成物で低誘電率のものとしては、ポ
リ （ｐ−ヒドロキシスチレン）誘電体とエポキシ化ポ
リブタジェンとから成るものが特開昭６２−１９２４０
６号公報にある。In addition, as a flame retardant resin composition with a low dielectric constant, one consisting of a poly(p-hydroxystyrene) dielectric and an epoxidized polybutadiene is disclosed in Japanese Patent Application Laid-Open No. 62-19240.
It is in Publication No. 6.
しかしＰＴＦＥ積層板は、樹脂が熱可塑性であり、ガラ
ス転移温度が低いため、高温における熱膨脹率が大きく
寸法安定性が十分でないなどの問題があり、特に多層化
接着した際のスルーホール信頼性等が不安がある。また
、ＰＴＦＥには適当な溶媒がないので、一般に加熱溶融
圧着による接着法がとられているが、溶融温度が非常に
高いという欠点がある。また、ポリブタジェン樹脂は分
子構造上、易燃性であるという欠点があり、難燃性を付
与する為にデカブロモジフェニルエーテル、トリフェニ
ルホスフェート等の添加型難燃剤やトリブロモフェニル
メタクリレート、トリブロモフェニルアクリレート等の
反応型難燃剤を添加する必要があり、これらを添加する
ことによりポリブタジェン樹脂本来の電気特性、耐熱性
、寸法安定性を損うという問題がある。However, since the resin of PTFE laminates is thermoplastic and the glass transition temperature is low, there are problems such as a large coefficient of thermal expansion at high temperatures and insufficient dimensional stability, especially through-hole reliability when bonded in multiple layers. I feel anxious. Furthermore, since there is no suitable solvent for PTFE, bonding by heating and melting and pressure bonding is generally used, but this method has the disadvantage of a very high melting temperature. In addition, polybutadiene resin has the disadvantage of being easily flammable due to its molecular structure, so additive flame retardants such as decabromodiphenyl ether and triphenyl phosphate, tribromophenyl methacrylate, and tribromophenyl acrylate are used to impart flame retardancy. It is necessary to add reactive flame retardants such as, and there is a problem that the addition of these impairs the electrical properties, heat resistance, and dimensional stability inherent to polybutadiene resin.
本発明の目的は、従来、大型計算機に使用されているポ
リイミド系多層プリント配線板に代わる材料として、ポ
リイミド積層材料と同程度の高密度配線が可能で難燃性
を有する低誘電率積層材料に関するものである。The purpose of the present invention is to relate to a low dielectric constant laminate material that is flame retardant and capable of high-density wiring comparable to that of polyimide laminate materials, as a material that can replace the polyimide multilayer printed wiring boards conventionally used in large-scale computers. It is something.
第一の発明は難燃性の熱硬化性樹脂組成物に関し、その
特徴は、下記一般式（Ｉ）
（式中は、Ａハロゲン基であり、Ｒ３は炭素数２〜４の
アルケニルまたはアルケノイルであり、ｍは１〜４、ｎ
は１〜１００の数を示す）で表わさレルボ’Ｊ（ｐ−ヒ
ドロキシスチレン）誘導体から成るプレポリマーに下記
一般式（ＩＩ）（式中、Ｂはグリシジルエーテル系エポ
キシのコポリマであり、ｎは４〜１． ＯＯの数を示す
）で表わされるエポキシ変性ポリブタジェンと下記一般
式（ＩＩＩ）
含む芳香族基、ｎは１〜４）表わされる芳香族マレイミ
ド化合物と１，３−ジ−オルトトリルグアニジン（ＴＶ
）を配合して成ることにある。The first invention relates to a flame-retardant thermosetting resin composition, which is characterized by the following general formula (I) (wherein A halogen group, R3 is alkenyl or alkenoyl having 2 to 4 carbon atoms Yes, m is 1 to 4, n
represents a number from 1 to 100), and the following general formula (II) (where B is a glycidyl ether-based epoxy copolymer and n is 4) 1. Epoxy-modified polybutadiene represented by the following general formula (III) (indicating the number of OO), an aromatic maleimide compound represented by the following general formula (III) (where n is 1 to 4), and 1,3-di-orthotolylguanidine ( TV
).
第二の発明は前記樹脂組成物を用いたプリプレグに関し
、繊維基材に一般式（Ｉ）
（式中は、Ａはハロゲン基であり、Ｒ１はアルカリ基、
ブテニル基、ビニル基、アクリノイル基、メタクリノイ
ル基、エポキシメタクリノイル基であり、ｍは１〜４、
ｎは１〜１００の数を示す）で表わされるポリ （ｐ−
ヒドロキシスチレン）誘導体から成るプレポリマーと下
記一般式（旧（式中、Ｂはグリシジルエーテル系エポキ
シのコポリマであり、ｎは４〜１００の数を示す）で表
わされるエポキシ変性ポリブタジェンと下記一般式（Ｉ
［ｌ）
含む芳香族基、ｎは１〜４）で表わされる芳香族系マレ
イミド化合物と１．３−ジ−オルトトリルグアニジン（
ＩＶ）を溶媒に溶かしたワニス状とし含浸したものであ
る。 第三の発明は上記樹脂組成物を用いた積層板に関
し、その特徴は、繊維基材に一般式（Ｔ）
（式中は、Ａハロゲン基であり、Ｒ＋ はアルカリ基、
ブテニル基、ビニル基、アクリノイル基、メタクリノイ
ル基、エポキシメタクリノイル基であり、ｍは１〜４、
ｎは１〜１００の数を示す）で表わされるポリ （ｐ−
ヒドロキシスチレン）誘導体から成るプレポリマーと下
記一般式（ｎ）（式中、Ｂはグリシジルエーテル系エポ
キシのコポリマであり、ｎは４〜１００の数を示す）で
表わされるエポキシ変性ポリブタジェンと下記一般式（
Ｉ［［）
（式中、Ｒ２は少なくともベンゼン環を１ヶ以上含む芳
香族基、ｎは１〜４）で表わされる芳香族系マレイミド
化合物と１．３−ジ−オルトトリルグアニジンとから成
る組成物を含浸したプリプレグを積層接着した積層板に
ある。A second invention relates to a prepreg using the resin composition, and a fiber base material having a general formula (I) (wherein A is a halogen group, R1 is an alkali group,
butenyl group, vinyl group, acrinoyl group, methacrynoyl group, epoxymethacrynoyl group, m is 1 to 4,
(n is a number from 1 to 100)
A prepolymer consisting of a hydroxystyrene) derivative, an epoxy-modified polybutadiene represented by the following general formula (former formula (in which B is a glycidyl ether-based epoxy copolymer, and n represents a number from 4 to 100)), and an epoxy-modified polybutadiene represented by the following general formula ( I
[l) An aromatic maleimide compound represented by an aromatic group containing (n is 1 to 4) and 1,3-di-orthotolylguanidine (
IV) is dissolved in a solvent and impregnated in the form of a varnish. The third invention relates to a laminate using the above resin composition, and its characteristics are that the fiber base material has a general formula (T) (wherein A is a halogen group, R+ is an alkali group,
butenyl group, vinyl group, acrinoyl group, methacrynoyl group, epoxymethacrynoyl group, m is 1 to 4,
(n is a number from 1 to 100)
A prepolymer consisting of a hydroxystyrene) derivative, an epoxy-modified polybutadiene represented by the following general formula (n) (wherein B is a glycidyl ether-based epoxy copolymer, and n represents a number from 4 to 100), and the following general formula (
I It is a laminated board made by laminating and bonding prepregs impregnated with substances.
本発明の熱硬化性樹脂組成物は、前記のように一般式（
Ｉ）、（Ｉ［）、（Ｉ［［）及び１．３−ジオルトトリ
ルグアニジン（ｒＶ）から成る組成物である。その具体
例をあげれば、前記一般式（１）で示される化合物とし
ては、ポリ （ｐ−ヒドロキシスチレン）のビニルエー
テル、イソブテニルエーテル、アリルエーテルと、アク
リル酸エステル、メタクリル酸エステル、エポキシメタ
クリル酸エステル等の臭化物がある。これらは所望に応
じ１種または２種以上使用される。The thermosetting resin composition of the present invention has the general formula (
I), (I[), (I[[) and 1,3-diorthotolylguanidine (rV). To give specific examples, the compounds represented by the general formula (1) include poly(p-hydroxystyrene) vinyl ether, isobutenyl ether, allyl ether, acrylic ester, methacrylic ester, and epoxy methacrylic acid. There are bromides such as esters. One or more of these may be used as desired.
前記一般式（ＩＩ）で表わされる本発明の熱硬化性樹脂
の１つであるエポキシ変性ポリブタジェンにおいて、変
性に用いられるグリシジルエーテル系のエポキシ樹脂の
具体例をあげれば、ジグリシジルエーテルビスフェノー
ルＡ１ジグリシジルエーテル２．２゛−ジブロモビスフ
ェノールＡ、ジグリシジルエーテル２．２’ 、４．４
’ −テトラブロモビスフェノールＡ１ジグリシジルエ
ーテル２．２”−ジメチルビスフェノールＡ、ジグリシ
ジルエーテル２．２”、４−トリメチルビスフェノール
Ａ、フェノールノボラック型エポキシ樹脂、オルソクレ
ゾールノボラック型エポキシ樹脂である。これらは所望
に応じ、１種または２種以上使用される。In the epoxy-modified polybutadiene, which is one of the thermosetting resins of the present invention represented by the general formula (II), specific examples of glycidyl ether-based epoxy resins used for modification include diglycidyl ether bisphenol A1 diglycidyl. Ether 2.2'-dibromobisphenol A, diglycidyl ether 2.2', 4.4
'-Tetrabromobisphenol A1 diglycidyl ether 2.2''-dimethylbisphenol A, diglycidyl ether 2.2'', 4-trimethylbisphenol A, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin. One or more of these may be used as desired.
又、前記一般式（Ｉ［［）で表わされる本発明の熱硬化
性樹脂の１つである芳香族系マレイミド化合物の具体例
をあげれば、Ｎ、Ｎ’ −ｍ−フェニレンビスマレイミ
ド、Ｎ、Ｎ” −ｐ−フェニレンビスマレイミド、Ｎ、
Ｎ’−４，４° −ジフェニルメタンビスマレイミド、
Ｎ、Ｎ’−４，４’ −ジフェニルエーテルビスマレ
イミド、Ｎ、Ｎ’ −メチレンビス（３−クロロ−ｐ−
フェニレン）ビスマレイミド、Ｎ、Ｎ”−４，４° −
ジフェニルサルフォンビスマレイミド、Ｎ、Ｎ’ −
ｍ−キシレンビスマレイミド、Ｎ、Ｎ’−４，４” −
ジフェニルシクロヘキサンビスマレイミド、Ｎ、Ｎ”４
．４゛ −ジフェニルプロパン−ビス−マレイミド、２
．２″ −ビス（４−（４−マレイミドフェノキシ）フ
ェニル〕プロパン、２．２−ビス〔３メチル−４−（４
−マレイミドフェノキシ）フェニル〕プロパン、２．２
゛−ビス（４−（４マレイミドフエノキシ）フェニルヘ
キサフロロプロパン、２，２−ビス（４−マレイミドフ
ェニル）へキサフロロプロパン、１．３−ビス（３マレ
イミドフエノキシ）ベンゼン、３，３° −ビスマレイ
ミドベンゾフェノキシ等のビスマレイミド及びＮ−フェ
ニルマレイミド、Ｎ−３−クロロフェニルマレイミド、
Ｎ−ｏ−）リルマレイミド、Ｎ−ｍ−トリルマレイミド
、Ｎ−ｐ−）リルマレイミド、Ｎ−ｏ−メトキシフェニ
ルマレイミド、Ｎ−ｍ−メトキシフェニルマレイミド、
Ｎ−ｐ−メトキシフェニルマレイミド、Ｎ−ベンジルマ
レイミド、Ｎ−ピリジルマレイミド、Ｎ−ヒドロキシフ
ェニルマレイミド、Ｎ−アセチルフェニルマレイミド、
Ｎ−ジクロロフェニルマレイミド、Ｎ−ベンゾフェノン
マレイミド、Ｎ−ジフェニルエーテルマレイミド、Ｎ−
アセチルフェニルマレイミド、等のモノマレイミドがあ
る。これらは所望に応じ、１種または２種以上使用され
る。Further, specific examples of aromatic maleimide compounds which are one of the thermosetting resins of the present invention represented by the general formula (I[[) include N,N'-m-phenylenebismaleimide, N, N”-p-phenylene bismaleimide, N,
N'-4,4°-diphenylmethane bismaleimide,
N,N'-4,4'-diphenyl ether bismaleimide, N,N'-methylenebis(3-chloro-p-
phenylene) bismaleimide, N, N”-4,4° −
Diphenylsulfone bismaleimide, N, N'-
m-xylene bismaleimide, N,N'-4,4"-
Diphenylcyclohexane bismaleimide, N, N”4
．． 4゛-diphenylpropane-bis-maleimide, 2
．． 2″-bis(4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis[3methyl-4-(4
-maleimidophenoxy)phenyl]propane, 2.2
゛-bis(4-(4maleimidophenoxy)phenylhexafluoropropane, 2,2-bis(4-maleimidophenyl)hexafluoropropane, 1,3-bis(3maleimidophenoxy)benzene, 3, Bismaleimides such as 3°-bismaleimidebenzophenoxy and N-phenylmaleimide, N-3-chlorophenylmaleimide,
N-o-) lylmaleimide, N-m-tolylmaleimide, N-p-) lylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide,
N-p-methoxyphenylmaleimide, N-benzylmaleimide, N-pyridylmaleimide, N-hydroxyphenylmaleimide, N-acetylphenylmaleimide,
N-dichlorophenyl maleimide, N-benzophenone maleimide, N-diphenyl ether maleimide, N-
There are monomaleimides such as acetylphenylmaleimide. One or more of these may be used as desired.
本発明で、芳香族系マレイミド化合物は、脂肪族系に比
べて耐熱性が優れている。In the present invention, aromatic maleimide compounds have better heat resistance than aliphatic maleimide compounds.
本発明において用いられる１、３−ジ−オルトトリルグ
アニジン（ＩＶ）は、一般式（Ｉｌ）のエポキシ変性ポ
リブタジェン中のエポキシ基と反応し、架橋密度を向上
させる働きをする。同様の働きをするエポキシ硬化剤と
して各種芳香族ジアミンやベンゾグアナミン、ジシアン
ジアミド等が知られているが、芳香族ジアミンは毒性お
よびボットライフの問題があり、ベンゾグアナミンやジ
シアンジアミドはワニスへの溶解性あるいは樹脂の不均
一性の問題ある。本発明で使用する１、３−ジオルトト
リルグアニジンには前記問題点がなく、特にワニスへの
溶解性、樹脂の均一性の点で優れている。The 1,3-di-orthotolylguanidine (IV) used in the present invention reacts with the epoxy group in the epoxy-modified polybutadiene of general formula (Il) and functions to improve the crosslink density. Various aromatic diamines, benzoguanamine, dicyandiamide, etc. are known as epoxy curing agents that have similar functions, but aromatic diamines have problems with toxicity and bot life, and benzoguanamine and dicyandiamide have problems with solubility in varnish or resin. There is a problem of heterogeneity. The 1,3-diorthotolylguanidine used in the present invention does not have the above-mentioned problems and is particularly excellent in solubility in varnish and uniformity of the resin.
又、前記、一般式（１）、（ＩＩ）、（Ｉ［ｌ）、（Ｔ
Ｖ）を配合した熱硬化性樹脂組成物には、ラジカル重合
開始剤を添加することにより硬化反応を早めることがで
きる。Moreover, the general formula (1), (II), (I[l), (T
The curing reaction can be accelerated by adding a radical polymerization initiator to the thermosetting resin composition containing V).
ラジカル重合剤としての典型的例としては、ベンゾイル
パーオキシド、ジクミルパーオキシド、メチルエチルケ
トンパーオキシド、ｔ−プチルパーオキシラウエート、
ジ−ｔ−ブチルパーオキシフタレート、ジヘンジルオキ
シド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパー
オキシ）ヘキサン、ｔ−ブチルクミルパーオキシド、ｔ
−ブチルハイドロパーオキシド、ジ−ｔ−ブチルパーオ
キシド、２．５−ジメチル−２，５−ジ（ｔ−フチルバ
ーオキシ）ヘキサン（３）、ジイソプロピルヘンゼンハ
イドロバーオキシド、ｐ−メンタンハイドロパーオキシ
ド、ビナンハイドロオキシド、２．５−ジメチルヘキサ
ン−２，２−シバイドロバ−オキシド、クメンハイドロ
パーオキシドなどがある。これらは樹脂組成物１００重
量部に対して好ましくは０．１〜１０重量部添加する。Typical examples of radical polymerization agents include benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, t-butyl peroxylauate,
Di-t-butyl peroxyphthalate, dihenzyl oxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, t
-Butyl hydroperoxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-phthyl baroxy)hexane (3), diisopropylhensen hydroperoxide, p-menthane hydroperoxide , vinylane hydroxide, 2,5-dimethylhexane-2,2-cybidroba-oxide, and cumene hydroperoxide. These are preferably added in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the resin composition.
前記熱硬化性樹脂組成物の配合割合は、必要に応じて種
々変えることができる。一般に、一般式（ｒ）のポリ
（ｐ−ヒドロキシスチレン）誘導体の配合割合が多くな
ると難燃性、機械的強度が向上がする可撓性が低下し、
硬化時の収縮率が大きくなる傾向がある。一般式（ＩＴ
）のエポキシ変性ポリブタジェンの配合割合が多くなる
と、可撓性、銅箔との接着性が向上するが、耐熱性が低
下する傾向があり、一般式（ＩＩＩ）芳香族系マレイミ
ドの配合割合が多くなると、難燃性、耐熱性が向上し、
硬化時の収縮率が小さくなり、寸法安定が向上する傾向
がある。１，３−ジーオルトトリルグアニジンの配合割
合は、一般式（ｎ）のエポキシ変性ポリブタジェンのエ
ポキシ当量に依存し、適当な配合量の範囲がある。１．
３−ジ−オルトトリルグアニジン量が少量の場合、ある
いは多量の場合、硬化樹脂板の熱膨張係数が大きく、曲
げ強度が低い値であり、たいねつ耐熱性も低い値となる
。The blending ratio of the thermosetting resin composition can be varied as necessary. Generally, poly of general formula (r)
When the proportion of the (p-hydroxystyrene) derivative increases, flame retardancy and mechanical strength improve, but flexibility decreases.
The shrinkage rate during curing tends to increase. General formula (IT
) When the blending ratio of epoxy-modified polybutadiene increases, flexibility and adhesion with copper foil improve, but heat resistance tends to decrease, and the blending ratio of aromatic maleimide of general formula (III) increases. As a result, flame retardancy and heat resistance improve,
There is a tendency for the shrinkage rate during curing to be reduced and dimensional stability to be improved. The blending ratio of 1,3-di-orthotolylguanidine depends on the epoxy equivalent of the epoxy-modified polybutadiene of general formula (n), and there is an appropriate range of blending amount. 1.
When the amount of 3-di-orthotolyl guanidine is small or large, the cured resin plate has a large coefficient of thermal expansion, a low bending strength, and a low thermal resistance.
上記組成物として好ましく範囲は、式（Ｉ）１０〜６０
重量％、重量に２０〜４０重量％：式（ｎ）１０〜５０
重量％、とくに１０〜３０重量％：式（ｍ）２０〜７０
重量％、重量に３０〜６０重量％で、これら３種を上記
範囲内で調整する。The preferred range for the above composition is formula (I) 10-60
% by weight, 20-40% by weight: Formula (n) 10-50
% by weight, especially 10-30% by weight: formula (m) 20-70
These three types are adjusted within the above range at 30 to 60% by weight.
１．３−ジ−オルトトリルグアニジン（ＴＶ）の配合量
の好ましい範囲は、１．３−ジ−オルトトリルグアニジ
ンのアミン当量／エポキシ当量の当量比が０．３〜１．
５であり、とくに好ましい範囲は０９５〜１．２の範囲
である。The preferred range of the amount of 1.3-di-orthotolylguanidine (TV) is such that the ratio of amine equivalent to epoxy equivalent of 1.3-di-orthotolyl guanidine is 0.3 to 1.
5, and a particularly preferable range is 095 to 1.2.
本発明の組成物には、第５成分として、芳香族アミンを
必要に応じて配合することができる。An aromatic amine can be added to the composition of the present invention as a fifth component, if necessary.
芳香族アミンとしては、例えば、４，４−ジアミノフェ
ニルメタン、４．４−ジアミノフェニルスルホン、４．
４〜ジアミノジフエニルスルホン、２．２−ビス〔４−
アミノフェノキシ）フェニル〕プロパン、２．２−ビス
〔４−アミノフェノキシ）フェニル〕へキサフロロプロ
パン、４．４ビス（３−アミノフェノキシ）ビフェニル
、１３−ビス（３−アミノフェノキシ）ベンゼンなどが
ある。Examples of aromatic amines include 4,4-diaminophenylmethane, 4,4-diaminophenylsulfone, and 4.
4-diaminodiphenyl sulfone, 2,2-bis[4-
Examples include aminophenoxy)phenyl]propane, 2.2-bis[4-aminophenoxy)phenyl]hexafluoropropane, 4.4bis(3-aminophenoxy)biphenyl, and 13-bis(3-aminophenoxy)benzene. .
次に本発明における積層板の一般的な製造方法について
説明する。Next, a general method for manufacturing a laminate according to the present invention will be explained.
まず、ポリ （ｐ−ヒドロキシスチレン）誘導体、エポ
キシ変性ポリブタジェンおよび芳香族系マレイミドを有
機溶媒に溶解させてワニスを調製する。First, a varnish is prepared by dissolving a poly(p-hydroxystyrene) derivative, an epoxy-modified polybutadiene, and an aromatic maleimide in an organic solvent.
有機溶媒としては例えば、メチルイソブチルケトン、Ｎ
、Ｎ−ジメチルホルムアミド、シクロヘキサン、アルキ
レングリコールモノアルキルエーテル類、アルキレング
リコールジアルキルエーテル類、Ｎ−メチルヒロリドン
、ジメチルスルホキシド、トリクロロエチレン、トリク
ロロエタン、塩化メチレン、ジオキサン、酢酸エチル等
が使用できる。Examples of organic solvents include methyl isobutyl ketone, N
, N-dimethylformamide, cyclohexane, alkylene glycol monoalkyl ethers, alkylene glycol dialkyl ethers, N-methylhyloridone, dimethyl sulfoxide, trichloroethylene, trichloroethane, methylene chloride, dioxane, ethyl acetate, etc. can be used.
なお、積層板を作製する際の樹脂の流動性、ゲル化時間
等の必要に応じてワニスを加熱して予備反応しておいて
もよい。又、基材との密着性を向上させるためカンプレ
ング剤を添加しても良い。Note that the varnish may be pre-reacted by heating depending on the fluidity of the resin, gelling time, etc. when producing the laminate, as required. Additionally, a camping agent may be added to improve adhesion to the base material.
調整したワニスに１．３−ジ−オルトトリルグアニジン
および必要に応じてラジカル重合開始剤を添加して含浸
用ワニスとする。次に得られた含浸用ワニスをシート状
基材に含浸塗工し、室温〜１７０℃で乾燥し、粘着性の
ないプリプレグを得る。1,3-di-orthotolylguanidine and, if necessary, a radical polymerization initiator are added to the prepared varnish to prepare a varnish for impregnation. Next, the obtained impregnating varnish is impregnated and coated on a sheet-like base material and dried at room temperature to 170°C to obtain a non-tacky prepreg.
この時の乾燥温度の設定は用いた溶媒および開始剤等ら
よって決まる。最後に得られたプリプレグを必要枚数重
ね、１００〜２５０℃で１〜１００ｋ ｇ ｆ ／ ｃ
％の圧力下で加熱硬化反応を行い積層板を得る。The setting of the drying temperature at this time is determined by the solvent, initiator, etc. used. Finally, stack the required number of prepregs and heat at 100-250℃ to 1-100kg f/c.
% of the pressure to obtain a laminate.
シート状基材としては、一般に積層材料に使用されてい
るものはほとんどすべて使用できる。無機繊維としては
、Ｓ ｉｏｚ 、Ａｄｚ ０３等を成分とするＥガラス
、Ｃガラス、Ａガラス、Ｓガラス、Ｄガラス、ＴＭ−３
１−Ａガラスおよび石英を使用したＣガラス等の各種ガ
ラス繊維およびセラミック繊維がある。また有機繊維と
しては、芳香族ポリアミド骨格を有する高分子化合物を
成分とするアラミド繊維等がある。As the sheet-like base material, almost all those commonly used for laminated materials can be used. Examples of inorganic fibers include E glass, C glass, A glass, S glass, D glass, and TM-3 containing Sioz, Adz 03, etc.
There are various glass fibers and ceramic fibers such as 1-A glass and C glass using quartz. Examples of organic fibers include aramid fibers containing a polymer compound having an aromatic polyamide skeleton.
（作用）
本発明の樹脂組成物の硬化時の収縮率が小さくなる理由
は判らない。マレイミド系化合物の配合によって生ずる
ものと考える。(Function) It is not known why the shrinkage rate of the resin composition of the present invention decreases during curing. This is thought to be caused by the combination of maleimide compounds.
硬化収縮率が小さいために、硬化時の積層板など硬化物
へのストレスの蓄積も小さく、従ってクランク等の発生
も少ない。Since the curing shrinkage rate is low, the accumulation of stress on the cured product such as the laminate during curing is also small, and therefore the occurrence of cranks and the like is small.
更に、１．３−ジ−オルトトリルグアニジンの配合量を
適切に選ぶことにより、硬化樹脂板の曲げ強度が向上し
、破壊時の伸びの値も大きくなる。Furthermore, by appropriately selecting the blending amount of 1,3-di-orthotolylguanidine, the bending strength of the cured resin plate can be improved, and the elongation at break can also be increased.
これによりクランク等の発生も少なくなる。This reduces the occurrence of cranks, etc.
（実施例）
実施例１
臭化化ポリ （ｐ−ヒドロキシスチレン）のメタクリル
酸エステル（分子量７０００〜１２０００、臭素含有率
４２％）５０重量部、タレゾールノボラックエポキシで
変性したポリブタジェン（エボキシ当量５７５ｇ／ｅｑ
）３０重量部、２，２゜ビス（４−４（マレイミドフェ
ノキシ）フェニル〕プロパン２０重量部を、メチルイソ
ブチルケトン１００重量部とジメチルホルムアミド１５
０重量部の混合溶媒に溶解させ、１００〜１２０℃で１
時間加熱攪拌した。更に、ワニスを室温にまで冷却後、
１．３−ジ−オルトトリルグアニジン（アミン当量８０
）４．２重量部（エポキシ変性ポリブタジェン１当量に
対し、１．３−ジ−オルトトリルグアニジン１．０当量
）、ラジカル重合開始剤として２，５−ジメチル−２，
５−ジ（ｔ−ブチルパーオキシ）−ヘキサン（３）０．
５重量部を加えて攪拌し完全に溶解させてワニスを得た
。このワニスを一週間室温で放置しても、均一なワニス
のままであった。(Example) Example 1 50 parts by weight of brominated poly (p-hydroxystyrene) methacrylic ester (molecular weight 7000-12000, bromine content 42%), polybutadiene modified with Talezol novolac epoxy (epoxy equivalent weight 575 g/ eq
), 20 parts by weight of 2,2゜bis(4-4(maleimidophenoxy)phenyl)propane, 100 parts by weight of methyl isobutyl ketone and 15 parts by weight of dimethylformamide.
Dissolved in 0 parts by weight of mixed solvent and heated at 100 to 120°C.
The mixture was heated and stirred for hours. Furthermore, after cooling the varnish to room temperature,
1.3-di-orthotolylguanidine (amine equivalent 80
) 4.2 parts by weight (1.0 equivalent of 1.3-di-orthotolylguanidine per equivalent of epoxy-modified polybutadiene), 2,5-dimethyl-2, as a radical polymerization initiator
5-di(t-butylperoxy)-hexane (3) 0.
5 parts by weight was added and stirred to completely dissolve it to obtain a varnish. Even after this varnish was left at room temperature for a week, it remained a uniform varnish.
上記ワニスをエバポレータで４０〜５０℃に加熱しなが
ら減圧脱気し溶媒を除去し固形の樹脂組成物を得た。更
に、該樹脂組成物を離型処理した金型に入れ１３０℃〜
１５．０℃に加熱し液状にして減圧脱気し泡を除いて１
７０℃で１２０分、２００℃で１２０分、２２０℃で１
２０分の条件で加熱硬化し樹脂板を得た。The above varnish was heated to 40 to 50°C using an evaporator and degassed under reduced pressure to remove the solvent, thereby obtaining a solid resin composition. Furthermore, the resin composition is placed in a mold that has been subjected to mold release treatment and heated at 130°C to
Heat to 15.0℃, liquefy, degas under reduced pressure and remove bubbles.
120 minutes at 70℃, 120 minutes at 200℃, 1 at 220℃
The resin plate was cured by heating for 20 minutes.
実施例２〜１３および比較例１〜２
表１に示した配合組成で実施例１とほぼ同様にして樹脂
板を得た。Examples 2 to 13 and Comparative Examples 1 to 2 Resin plates were obtained in substantially the same manner as in Example 1 using the blending compositions shown in Table 1.
なお、実施例１１に於て、臭化ポリ （ｐ−ヒドロキシ
スチレン）のアクリル酸エステルは分子量７０００〜１
２０００、臭素含有率４５％、実施例１２に於て、臭化
ポリ （ｐ−ヒドロキシスチレン）のアクリルは分子量
７０００〜１２０００゜臭素含有率４３％、実施例１３
に於て、臭化ポリ（ｐ−ヒドロキシスチレン）のエポキ
シメタクリル酸エステルは分子量７０００〜１２０００
．臭素含有率３５％のものをそれぞれ用いた。In Example 11, the acrylic ester of bromide poly(p-hydroxystyrene) had a molecular weight of 7,000 to 1.
2000, bromine content 45%, Example 12, brominated poly(p-hydroxystyrene) acrylic has a molecular weight of 7000-12000°, bromine content 43%, Example 13
In this case, the epoxy methacrylate ester of bromide poly(p-hydroxystyrene) has a molecular weight of 7,000 to 12,000.
．． Those with a bromine content of 35% were used.
前記、実施例および比較例による樹脂板の主な特性を表
２に示す。Table 2 shows the main characteristics of the resin plates according to the above examples and comparative examples.
なお、比較例１のワニス（ベンゾグアナミン使用）は室
温で一週間放置するとワニスの底部に析出物の沈澱がみ
られた。Note that when the varnish of Comparative Example 1 (using benzoguanamine) was left at room temperature for one week, precipitates were observed at the bottom of the varnish.
実施例１４
臭化化ポリ （ｐ−ヒドロキシスチレン）のメタクリル
酸エステル（分子Ｍ７０００〜１２０００、臭素含有率
４２％）５０重量部、タレゾールノボラソクエボキシで
変性したポリブタン１フ３０重量部、２．２゛−ビス（
４−（４−マレイミドフッキシ）フェニル〕プロパンの
２０重量部をメチルイソブチルケトン１００重量部とジ
チメルホルムアミド１５０重量部の混合溶媒に溶解させ
、１００〜１２０°Ｃで１時間加熱攪拌した。Example 14 50 parts by weight of brominated poly(p-hydroxystyrene) methacrylic ester (molecule M7000-12000, bromine content 42%), 30 parts by weight of polybutane 1 modified with Talezol noborasoquevoxy, 2 .2゛-bis (
20 parts by weight of 4-(4-maleimidofuxy)phenyl]propane was dissolved in a mixed solvent of 100 parts by weight of methyl isobutyl ketone and 150 parts by weight of dithymerformamide, and the mixture was heated and stirred at 100 to 120°C for 1 hour.
更に、ワニスを室温にまで冷却後、１，３−ジ−オルト
トリルグアニジン４．２重量部、ラジカル重合開始剤と
して、２．５−ジメチル−２，５ジ（ｔ−ブチルパーオ
キシ）ヘキサン（３）０．５重量部を加えて攪拌して完
全に溶解させてワニスを得た。Furthermore, after cooling the varnish to room temperature, 4.2 parts by weight of 1,3-di-orthotolylguanidine and 2,5-dimethyl-2,5 di(t-butylperoxy)hexane ( 3) 0.5 part by weight was added and stirred to completely dissolve it to obtain a varnish.
このワニスをガラスクロス（Ｅガラス、厚さ０゜１ｍｍ
）に含浸塗工し、室温で風乾燥、１５０℃で１０〜２０
分間乾燥してタックフリーのプリプレグを得た。次に、
該プリプレグを１０枚重ねて上下に厚さ３５μｍの電解
銅箔を重ねて圧力４０Ｋｇｆ／ｃｒｒｒ、温度１３０℃
で３０分間加熱し、更に１７０℃で１時間、２２０℃で
２時間プレスを行い積層板を得た。Apply this varnish to glass cloth (E glass, thickness 0°1mm)
), air-dried at room temperature, 10-20% at 150℃
After drying for a minute, a tack-free prepreg was obtained. next,
10 sheets of the prepreg were stacked, electrolytic copper foil with a thickness of 35 μm was stacked on top and bottom, and the pressure was 40 Kgf/crrr and the temperature was 130°C.
The mixture was heated for 30 minutes, and then pressed at 170°C for 1 hour and at 220°C for 2 hours to obtain a laminate.
実施例１５〜２０および比較例３〜６
表３に示した配合組成で実施例１４と同様にして積層板
を得た。Examples 15 to 20 and Comparative Examples 3 to 6 Laminated plates were obtained in the same manner as in Example 14 using the compounding compositions shown in Table 3.
エポキシ樹脂積層板、ポリイミド樹脂積層板を比較例５
．６とする。Comparative example 5 of epoxy resin laminate and polyimide resin laminate
．． Set it to 6.
比較例７
１２−ポリブタジエンプレボリマ５０重量部、タレゾー
ルノボラック型エポキシ変性ポリブタジェン５０重量部
をキシレンに溶解させ、固形分量２０〜３０重量％のワ
ニスを得る。更に、ラジカル重量開始剤としてジクミル
パーオキシド２重量部、エポキシ硬化剤として２−エチ
ル−４メチＪＬｚイミダゾ一ル１重量部を添加し、実施
例１４と同様にして積層板を得た。Comparative Example 7 50 parts by weight of 12-polybutadiene prevolima and 50 parts by weight of Talesol novolac type epoxy-modified polybutadiene are dissolved in xylene to obtain a varnish having a solid content of 20 to 30% by weight. Further, 2 parts by weight of dicumyl peroxide as a radical weight initiator and 1 part by weight of 2-ethyl-4-methyl-JLz imidazol as an epoxy curing agent were added, and a laminate was obtained in the same manner as in Example 14.
前記、実施例および比較例による積層板の主な特性を表
４に示す。Table 4 shows the main properties of the laminates according to the Examples and Comparative Examples.
実施例２１
表５に示した樹脂組成で、実施例１４で示した方法で得
られたプリプレグを用い、該プリプレグ側を表面粗化し
た銅箔（３５μｍ厚）を両面に積層して、圧力３０ Ｋ
ｇｆ／ ｃ ｒｄ、温度１３０℃テ３０分間加熱し、さ
らに、１７０℃で１時間、２００℃で２時間プレスを行
い銅張り積層板を得た。この絶縁層の厚さは約１００μ
ｍである。得られた銅張り積層板をフォトエツチング法
によって信号層、電源層、整合層等の内層回路パターン
を形成させ、次の方法によって回路パターンの銅表面を
処理し、両面配線単位回路シートを形成した。Example 21 Using a prepreg obtained by the method shown in Example 14 with the resin composition shown in Table 5, copper foil (35 μm thick) with a roughened surface was laminated on both sides of the prepreg side, and a pressure of 30 μm was applied. K
gf/crd, heated at 130°C for 30 minutes, and further pressed at 170°C for 1 hour and at 200°C for 2 hours to obtain a copper-clad laminate. The thickness of this insulating layer is approximately 100μ
It is m. Inner layer circuit patterns such as a signal layer, a power supply layer, and a matching layer were formed on the obtained copper-clad laminate by a photoetching method, and the copper surface of the circuit pattern was treated by the following method to form a double-sided wiring unit circuit sheet. .
（１）濃塩酸３００ｇ、塩化第２銅５０ｇ、蒸會水６５
０ｇ （銅表面の粗化）。(1) Concentrated hydrochloric acid 300g, cupric chloride 50g, steamed water 65g
0g (roughening of copper surface).
（２）水酸化ナトリウム５ｇ、リン酸三ナトリウムＬｏ
ｇ、亜鉛素酸ナトリウム３０ｇ、蒸留水９５５ｇ（銅表
面の安定化）。(2) Sodium hydroxide 5g, trisodium phosphate Lo
g, sodium zinc oxide 30 g, distilled water 955 g (stabilization of copper surface).
上記の処理を終了後、第１図に示すような構成で、前記
のプリプレグ樹脂シートを用いて、回路導体層２として
３０層形成し、１７０℃で、圧力４０ ｋ ｇ ／ ｃ
ｒｄ、１７０℃９０分、２２０℃で９０分の条件で接
着形成を行い、多層プリント回路板を作成した。After completing the above treatment, 30 layers were formed as the circuit conductor layer 2 using the prepreg resin sheet with the configuration shown in FIG. 1 at 170° C. and a pressure of 40 kg/c.
rd, 170°C for 90 minutes, and 220°C for 90 minutes to create a multilayer printed circuit board.
多層化接着はシートの四方に設けた穴にガイドビンを挿
入する方法で位置ずれを防止して行った。Multilayer adhesion was performed by inserting guide bins into holes provided on all sides of the sheet to prevent positional shift.
多層化接着後穴径Ｑ、３ｍｍ又は０．６ｍｍの穴をマイ
クロドリルによってあけ、全面に化学銅めっきを行って
スルーホール導体４を形成させた。次に、最外層回路を
エツチングにより形成させて多層プリント板を形成した
。After multilayer adhesion, a hole with a hole diameter Q of 3 mm or 0.6 mm was drilled using a microdrill, and the entire surface was chemically plated with copper to form a through-hole conductor 4. Next, the outermost layer circuit was formed by etching to form a multilayer printed board.
本実施例では厚さが３．５ｍｍＸ ５７０ｍｍＸ ４２
０ｍｍの大きさでライン幅７０μｍおよび１００μｍの
種（チャルネル／グリッド）が２〜３本の／１．３ｍｍ
、層間ずれが約１００μｍ以下のものを得ることができ
た。ガラスクロスは絶縁層の約３０体積であった。In this example, the thickness is 3.5 mm x 570 mm x 42
2-3 seeds (channels/grids) with line widths of 70 μm and 100 μm at 0 mm size/1.3 mm
, it was possible to obtain a layer with an interlayer misalignment of about 100 μm or less. The glass cloth was approximately 30 volumes of the insulating layer.
第１図において１．３は絶縁層、２は回路導体層、４は
スルーホールであり、■は前述の銅張り積層板および３
はプリプレグ樹脂シートである。In Fig. 1, 1.3 is an insulating layer, 2 is a circuit conductor layer, 4 is a through hole, and ■ is the aforementioned copper-clad laminate and 3.
is a prepreg resin sheet.
実施例２２〜２７、比較例８
それぞれ表５に示した樹脂組成で、実施例２１と同様に
して多層プリント回路板を製造した。Examples 22 to 27, Comparative Example 8 Multilayer printed circuit boards were manufactured in the same manner as in Example 21 using the resin compositions shown in Table 5, respectively.
表６に多層プリント回路板の一部分を切り出し、半田耐
熱性および熱衝撃性を測定した結果を示した。Table 6 shows the results of cutting out a portion of the multilayer printed circuit board and measuring its solder heat resistance and thermal shock resistance.
以下空白
なお、熱分解温度は樹脂硬化物を粉砕した試料１０ｍｇ
について、空気雰囲気中、昇温速度５℃／ｍｉｎで測定
し、５％減量したときの温度を熱分解速度とした。The following is blank.The thermal decomposition temperature is a sample of 10mg of crushed resin cured product.
The temperature was measured in an air atmosphere at a heating rate of 5° C./min, and the temperature at which the weight was reduced by 5% was defined as the thermal decomposition rate.
線膨張係数は厚さ芳香の熱膨張率を昇温速度２’Ｃ／
ｍ ｉ ｎで測定し、５０°Ｃから２００℃までの変化
量から求めた。The coefficient of linear expansion is the coefficient of thermal expansion of the thickness aroma at the heating rate 2'C/
It was measured at min, and was determined from the amount of change from 50°C to 200°C.
硬化時の体積収縮率は、硬化時の固形の比重と硬化後の
比重差から求めた。曲げ強度は積層板を２５Ｘ５０ｍｍ
に切断し支点間距離３０ｍｍ、曲げ強度１ｍｍ／ｍｉｎ
の条件で室温、１８０°Ｃで測定した。The volume shrinkage rate during curing was determined from the difference between the specific gravity of the solid at the time of curing and the specific gravity after curing. The bending strength of the laminated board is 25 x 50 mm.
Cut to 30mm distance between fulcrums, bending strength 1mm/min
Measurements were made at room temperature and 180°C under the following conditions.
比誘電率の測定はＪＩＳ Ｃ６４８１に準じて行い周波
数ＩＭＨｚの静電容量を測定して比誘電率を求めた。The relative permittivity was measured in accordance with JIS C6481, and the capacitance at a frequency of IMHz was measured to determine the relative permittivity.
その他、半田耐熱性、曲げ特性ＪＩＳ Ｃ６４８１に準
じて行い、半田耐熱性は２６０℃、３００秒で外観の異
常の有無を調べた。In addition, soldering heat resistance and bending properties were conducted according to JIS C6481, and the soldering heat resistance was checked for abnormalities in appearance at 260° C. for 300 seconds.
難燃性はＵＬ−９４垂直法に準して測定を行った。熱衝
撃試験は一６０℃から＋１２５°Ｃを１すイクル（〜）
として、クラックの入るまでのサイクルを測定した。Flame retardancy was measured according to the UL-94 vertical method. Thermal shock test is from -60°C to +125°C for 1 cycle (~)
The cycles until cracks appeared were measured.
本発明における樹脂組成物は硬化時の体積収縮率が従来
の低誘電率の樹脂組成物（比較例２）に比べて小さく成
型性が良好である。The resin composition of the present invention has a smaller volume shrinkage rate during curing than a conventional low dielectric constant resin composition (Comparative Example 2) and has good moldability.
又本発明における樹脂組成物を用いた積層材料は低誘電
率材料として一般的に知られているポリブタジェン系材
料と同様、低誘電率特性を有し、現在、大型計算機の多
層プリント板に適用されているエポキシ系材料やポリイ
ミド系材料に比べ比誘電率４．７から３．５付近にでき
ることから信号伝送遅延時間を１５％低減できる。Furthermore, the laminated material using the resin composition of the present invention has a low dielectric constant characteristic similar to the polybutadiene material which is generally known as a low dielectric constant material, and is currently being applied to multilayer printed boards for large computers. Compared to epoxy-based materials and polyimide-based materials, the dielectric constant can be reduced from 4.7 to around 3.5, reducing signal transmission delay time by 15%.
更に、多層プリント回路板を本発明の樹脂組成物を用い
て製造することによって、熱衝撃特性の優れた基板を得
ることができる。Furthermore, by manufacturing a multilayer printed circuit board using the resin composition of the present invention, a board with excellent thermal shock properties can be obtained.
（発明の効果）
本発明によれば均質な樹脂組成物が得られ、しかもその
成形物の収縮率を小さくでき、耐クラツク性が良好で、
耐熱性、難燃性の低誘電率積層板を提供することが可能
となった。(Effects of the Invention) According to the present invention, a homogeneous resin composition can be obtained, and the shrinkage rate of the molded product can be reduced, and the crack resistance is good.
It has become possible to provide a heat-resistant, flame-retardant, low dielectric constant laminate.
第１図は本発明の一実施例である多層プリント回路板の
断面斜視図である。FIG. 1 is a cross-sectional perspective view of a multilayer printed circuit board according to an embodiment of the present invention.
符号の説明
１ 基板 ２ 回路導体
３ プリプレグシート ４ スルーボール手続
（甫 正
書（自発）
明 細 書
平成１年９月８日
平成 １年 特許願 第３Ｉｔ８２号
２、発明の名称
熱硬化性樹脂組成物並びにそれを用いたプリプレグおよ
び積層板
３、補正をする者
事件との関係 特許出願人
住所 東京都新宿区西新宿二丁目１番１号名称（
４４５） 日立化成工業株式会社代表者 横 山 亮
次 （他１名）
４、代理人
■１６３
居所 東京都新宿区西新宿二丁目１番１号日立化
成工業株式会社内
電話 東京 ３４６−３１１１ （大代表）６、補正の
内容
７′−≧＼
］、 発明の名称
熱硬化性樹脂組成物並びにそれを用いたプリプレグおよ
び積層板
２、特許請求の範囲
１、（ａ）一般式
（式中Ａは、ハロゲン基、Ｒ１は炭素数２〜４のアルケ
ニル基、アルケノイル基であり、ｍは１〜４）で示され
る繰返し単位からなるポリ（ｐ−ヒドロキシスチレン）
誘導体のプレポリマと、（ｂ）エポキシ変性ポリブタジ
ェンと、（ｃ）芳香族マレイミド化合物と、
（ｄ）１３−ジ−オルトトリルグアニジンを必須成分と
して含存することを特徴とする熱硬化性樹脂組成物。Explanation of symbols 1 Substrate 2 Circuit conductor 3 Prepreg sheet 4 Through-ball procedure (spontaneous) Specification September 8, 1999 1999 Patent Application No. 3It82 2, Name of invention Thermosetting resin composition Products, prepregs and laminates using the same 3, and their relationship to the case of the person making the amendment Patent applicant address: 2-1-1 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (
445) Hitachi Chemical Co., Ltd. Representative Ryoji Yokoyama (1 other person) 4. Agent 163 Address 2-1-1 Nishi-Shinjuku, Shinjuku-ku, Tokyo Hitachi Chemical Co., Ltd. Phone: Tokyo 346-3111 Representative) 6, Contents of amendment 7'-≧\], Name of the invention Thermosetting resin composition, prepreg and laminate using the same 2, Claim 1, (a) General formula (wherein A is , a halogen group, R1 is an alkenyl group or an alkenoyl group having 2 to 4 carbon atoms, and m is 1 to 4) Poly(p-hydroxystyrene) consisting of a repeating unit represented by
A thermosetting resin composition comprising a derivative prepolymer, (b) an epoxy-modified polybutadiene, (c) an aromatic maleimide compound, and (d) 13-di-orthotolylguanidine as essential components.
２、 前記（ａ）（ｐ−ヒドロキシスチレン）誘導体
のプレポリマが１０〜６０重量％
（ｂ）エポキシ変性ポリブタジェンが１０〜６０重量％
（ｃ）芳香族マレイミド化合物が２０〜７０重量％
（ｄ）１．３−ジ−オルトトリルグアニジンがエポキシ
基１当量に対し、０．３〜１．５当量である請求項１に
記載の熱硬化性樹脂組成物。2. (a) Prepolymer of (p-hydroxystyrene) derivative is 10 to 60% by weight (b) Epoxy-modified polybutadiene is 10 to 60% by weight (c) Aromatic maleimide compound is 20 to 70% by weight (d) 1 2. The thermosetting resin composition according to claim 1, wherein the amount of 3-di-orthotolylguanidine is 0.3 to 1.5 equivalents per equivalent of epoxy group.
３、 前記（ａ）（ｐ−ヒドロキシスチレン）誘導体
のプレポリマが２０〜４０重量％
（ｂ）エポキシ変性ポリブタジェンが１０〜３０重量％
（ｃ）芳香族マレイミド化合物が３０〜６０重量％
（ｄ）１．３−ジ−オルトトリルグアニジンがエポキシ
基１当量に対し、０．５〜１．２当量である請求項１に
記載の熱硬化性樹脂組成物。3. (a) Prepolymer of (p-hydroxystyrene) derivative is 20 to 40% by weight (b) Epoxy-modified polybutadiene is 10 to 30% by weight (c) Aromatic maleimide compound is 30 to 60% by weight (d) 1 2. The thermosetting resin composition according to claim 1, wherein the amount of 3-di-orthotolylguanidine is 0.5 to 1.2 equivalents per equivalent of epoxy group.
（ａ）一般式
（式中Ａは、ハロゲン基、Ｒ１は炭素数２〜４のアルケ
ニル基、アルケノイル基であり、ｍは１〜４）で示され
る繰返し単位からなるポリ（ｐ−ヒドロキシスチレン）
誘導体のプレポリマと、（ｂ）一般式
（式中Ｂはグリシジルエーテル系エポキシのコポリマ、
ｎは整数）で示されるエポキシ変性ポリブタジェンと、
（ｃ）一般式
（式中Ｒ２は少なくともベンゼン環を１個以上含む芳香
族基、ｎは１〜４）で示される芳香族マレイミド化合物
（ｄ）１．３−ジ−オルトトリルグアニジンを含むこと
を特徴とする熱硬化性樹脂組成物。(a) Poly(p-hydroxystyrene) consisting of repeating units represented by the general formula (wherein A is a halogen group, R1 is an alkenyl group or alkenoyl group having 2 to 4 carbon atoms, and m is 1 to 4)
a derivative prepolymer, (b) general formula (where B is a glycidyl ether epoxy copolymer,
(c) an aromatic maleimide compound represented by the general formula (wherein R2 is an aromatic group containing at least one benzene ring, and n is 1 to 4) (d) 1. A thermosetting resin composition comprising 3-di-orthotolylguanidine.
５、 前記（ａ）（ｐ−ヒドロキシスチレン）誘導体の
プレポリマが１０〜６０重量％
（ｂ）エポキシ変性ポリブタジェンが１０〜６０重量％
（ｃ）芳香族マレイミド化合物が２０〜７０重量％
（ｄ）１．３−ジ−オルトトリルグアニジンがエポキシ
基合物１当量に対し、０．３〜１．５当量である請求項
４に記載の熱硬化性樹脂組成物。5. (a) Prepolymer of (p-hydroxystyrene) derivative 10 to 60% by weight (b) Epoxy-modified polybutadiene 10 to 60% by weight (c) Aromatic maleimide compound 20 to 70% by weight (d) 1 5. The thermosetting resin composition according to claim 4, wherein the amount of 3-di-orthotolylguanidine is 0.3 to 1.5 equivalents per equivalent of the epoxy group compound.
６、 前記（ａ） （ｐ ｈドロキシスチレン）
誘導体のプレポリマが２０〜４０重量％
（重量エポキシ変性ポリブタジェンが１０〜３０重量％
（ｃ）芳香族マレイミド化合物が３０〜６０重量％
（ｄ）１．３−ジ−オルトトリルグアニジンがエポキシ
基１当量に対し、０．５〜１．２当量である請求項４に
記載の熱硬化性樹脂組成物。6. (a) (ph droxystyrene)
20-40% by weight of the derivative prepolymer (10-30% by weight of epoxy-modified polybutadiene (c) 30-60% by weight of aromatic maleimide compound (d) 1,3-di-orthotolylguanidine with 1 equivalent of epoxy group) 5. The thermosetting resin composition according to claim 4, wherein the amount is 0.5 to 1.2 equivalents.
７、繊維質基材に、（ａ）一般式
（式中Ａは、ハロゲン基、Ｒ３は炭素数２〜４のアルケ
ニル基、アルケノイル基であり、ｍは１〜４）で示され
る繰返し単位からなるポリ（ｐ−ヒドロキシスチレン）
誘導体のプレポリマと、（ｂ）エポキシ変性ポリブタジ
ェンと、（ｃ）芳香族マレイミド化合物と、
（ｄ）１．３−ジ−オルトトリルグアニジンとからなる
熱硬化性樹脂を含有してなるプリプレグ。7. In the fibrous base material, (a) from a repeating unit represented by the general formula (wherein A is a halogen group, R3 is an alkenyl group or alkenoyl group having 2 to 4 carbon atoms, and m is 1 to 4) poly(p-hydroxystyrene)
A prepreg comprising a thermosetting resin consisting of a derivative prepolymer, (b) epoxy-modified polybutadiene, (c) an aromatic maleimide compound, and (d) 1,3-di-orthotolylguanidine.
８、 前記（ａ）（ｐ−ヒドロキシスチレン）誘導体
のプレポリマが１０〜６０重量％
（ｂ）エポキシ変性ポリブタジェンが１０〜６０重量％
（ｃ）芳香族マレイミド化合物が２０〜７０重量％
（ｄ）１．３−ジ−オルトトリルグアニジンがエポキシ
基１当量に対し、０．３〜１．５当量である請求項７に
記載のプリプレグ。8. (a) Prepolymer of (p-hydroxystyrene) derivative is 10 to 60% by weight (b) Epoxy-modified polybutadiene is 10 to 60% by weight (c) Aromatic maleimide compound is 20 to 70% by weight (d) 1 8. The prepreg according to claim 7, wherein the amount of 3-di-orthotolylguanidine is 0.3 to 1.5 equivalents per equivalent of epoxy group.
９、 前記（ａ）（ｐ−ヒドロキシスチレン）誘導体
のプレポリマが２０〜４０重量％
（重量エポキシ変性ポリブタジェンが１０〜３０重量％
（ｃ）芳香族マレイミド化合物が３０〜６０重量％
（ｄ）１．３−ジ−オルトトリルグアニジンがエポキシ
基１当量に対し、０．５〜１．０当量である請求項７に
記載のプリプレグ。9. (a) Prepolymer of (p-hydroxystyrene) derivative 20 to 40% by weight (weight epoxy-modified polybutadiene 10 to 30% by weight (c) aromatic maleimide compound 30 to 60% by weight (d) 1. 8. The prepreg according to claim 7, wherein the amount of 3-di-orthotolylguanidine is 0.5 to 1.0 equivalent per equivalent of epoxy group.
１０、繊維質基材、（ａ）一般式
（式中Ａは、ハロゲン基、Ｒ，は炭素数２〜４のアルケ
ニル基、アルケノイル基であり、ｍは１〜４）で示され
る繰返し単位からなるポリ（ｐ−ヒドロキシスチレン）
誘導体のプレポリマと、（ｂ）一般式
（式中Ｂはグリシジルエーテル系エポキシのコポリマ、
ｎは整数）で示されるエポキシ変性ポリブタジェンと、
（ｃ）一般式
（式中Ｒ２は少なくともヘンゼン環を１個以上含む芳香
族基、ｎは１〜４）で示される芳香族マレイミド化合物
と、
（ｄ）１．３−ジ−オルトトリルグアニジンとからなる
熱硬化性樹脂を含有してなるプリプレグ。10. Fibrous base material, (a) from a repeating unit represented by the general formula (wherein A is a halogen group, R is an alkenyl group or alkenoyl group having 2 to 4 carbon atoms, and m is 1 to 4) poly(p-hydroxystyrene)
a derivative prepolymer, (b) general formula (where B is a glycidyl ether epoxy copolymer,
(n is an integer); (c) an aromatic maleimide compound represented by the general formula (wherein R2 is an aromatic group containing at least one Hensen ring; n is 1 to 4); d) A prepreg containing a thermosetting resin consisting of 1,3-di-orthotolylguanidine.
１１、前記（ａ ） （ｐ−ヒドロキシスチレン）誘
導体のプレポリマが１０〜６０重量％
（重量エポキシ変性ポリブタジェンが１０〜６０重量％
（ｃ）芳香族マレイミド化合物が２０〜７０重量％
（ｄ）１．３−ジ−オルトトリルグアニジンがエポキシ
基１当量に対し、０．３〜１．５当量である請求項］０
に記載のプリプレグ。11. (a) Prepolymer of (p-hydroxystyrene) derivative 10 to 60% by weight (weight epoxy-modified polybutadiene 10 to 60% by weight (c) aromatic maleimide compound 20 to 70% by weight (d) 1. Claim in which 3-di-orthotolylguanidine is used in an amount of 0.3 to 1.5 equivalents per equivalent of epoxy group]0
The prepreg described in .
１２、 前記（ａ ） （ｐ−ヒドロキシスチレン）
誘導体のプレポリマが２０〜４０重量％
（ｂ）エポキシ変性ポリブタジェンが１０〜３０重量％
（ｃ）芳香族マレイミド化合物が３０〜６０重量％
（ｄ）１．３−ジ−オルトトリルグアニジンがエポキシ
化合物１当量に対し、０．５〜１．２当量である請求項
１０記載のプリプレグ。12. (a) (p-hydroxystyrene)
20-40% by weight of derivative prepolymer (b) 10-30% by weight of epoxy-modified polybutadiene (c) 30-60% by weight of aromatic maleimide compound (d) 1,3-di-orthotolylguanidine as epoxy compound 1 The prepreg according to claim 10, wherein the amount is 0.5 to 1.2 equivalents.
１３、繊維質基材に、（ａ）一般式
（式中Ａは、ハロゲン基、Ｒ，は炭素数２〜４のアルケ
ニル基、アルケノイル基であり、ｍは１〜４）で示され
る繰返し単位からなるポリ（ｐ−ヒドロキシスチレン）
誘導体のプレポリマと、（ｂ）エポキシ変性ポリブタジ
ェンと、（ｃ）芳香族マレイミド化合物と、
（ｄ）１．３−ジ−オルトトリルグアニジンとからなる
熱硬化性樹脂を含有してなるプリプレグが積層成形され
た積層板。13. In the fibrous base material, (a) a repeating unit represented by the general formula (wherein A is a halogen group, R is an alkenyl group or alkenoyl group having 2 to 4 carbon atoms, and m is 1 to 4); poly(p-hydroxystyrene) consisting of
A prepreg containing a thermosetting resin consisting of a derivative prepolymer, (b) epoxy-modified polybutadiene, (c) an aromatic maleimide compound, and (d) 1,3-di-orthotolylguanidine is laminated and molded. laminate board.
３、発明の詳細な説明
〔産業上の利用分野〕
本発明は熱硬化性樹ｙＪＦｉ組成物、それを用いたプリ
プレグおよび積層板に係り、特に難燃性、耐熱性および
電気特性に優れ、硬化時の収縮率の小さい多層プリント
回路板に好適な積層材料に関する。3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a thermosetting resin yJFi composition, prepregs and laminates using the same, and particularly has excellent flame retardancy, heat resistance, and electrical properties, and has excellent hardening properties. The present invention relates to a laminated material suitable for multilayer printed circuit boards that has a small shrinkage rate.
従来、多層プリント回路板用積層材料として、難燃性を
付与する為にブロム化変性樹脂や添加型難燃性を用いた
フェノール樹脂、エポキシ樹脂およびポリイミド樹脂等
が主に使用されている。特に大型計算機には高密度化が
望まれ、耐熱性、寸法安定性に優れたポリイミド系樹脂
が用いられている。しかし、近年、大型計算機の高速演
算処理化に伴い、信号伝送速度の向上のため、低誘電率
のプリント回路板が要求されている。このような低誘電
率積層材料として四フッ化エチレン（ＰＴＦＥ）樹脂、
ポリブタジェン樹脂から成る積層板が開発されている。Conventionally, phenol resins, epoxy resins, polyimide resins, etc. using brominated modified resins or additive flame retardants have been mainly used as laminated materials for multilayer printed circuit boards to impart flame retardancy. In particular, high density is desired for large computers, and polyimide resins with excellent heat resistance and dimensional stability are used. However, in recent years, with the increase in high-speed calculation processing of large computers, printed circuit boards with a low dielectric constant are required to improve signal transmission speed. Tetrafluoroethylene (PTFE) resin is used as such a low dielectric constant laminated material.
Laminates made of polybutadiene resin have been developed.
この種の積層板に関するものとして、例えばプロシージ
ング・エヌ・イー・ピー・シー・オー・エヌ（１９８１
年）第１６０頁から第１６９頁（Ｐｒｏｃ、ＮＥＰＣＯ
Ｎ（１９８１） Ｐ １６０１６９）および特開昭５５
−１２６４５１号公報等が挙げられる。Regarding this type of laminate, for example, Proceedings N.E.P.C.O.N. (1981
) pages 160 to 169 (Proc, NEPCO
N (1981) P 160169) and JP-A-1989
-126451 publication etc. are mentioned.
また、離燃性樹脂組成物で低誘電率のものとしては、ポ
リ（ｐ−ヒドロキシスチレン）誘電体とエポキシ化ポリ
ブタジェンとから成るものが特開昭６２−１９２４０６
号公報にある。In addition, as a flame retardant resin composition with a low dielectric constant, one consisting of a poly(p-hydroxystyrene) dielectric and an epoxidized polybutadiene is disclosed in Japanese Patent Application Laid-open No. 62-192406.
It is in the bulletin.
しかしＰＴＦＥ積層板は、樹脂が熱可塑性であり、ガラ
ス転移温度が低いため、高温における熱膨張率が大きく
寸法安定性が十分でないなどの問題があり、特に多層化
接着した際のスルーホール信転性等に不安がある。また
、ＰＴＦＥには適当な溶媒がないので、一般に加熱溶融
圧着による接着法がとられているが、溶融温度が非常に
高いという欠点がある。また、ポリブタジェン樹脂は分
子構造上、易燃性であるという欠点があり、難燃性を付
与する為にデカブロモジフェニルエーテル、トリフェニ
ルホスフェート等の添加型難燃剤やトリブロモフェニル
メタクリレート、トリブロモフェニルアクリレート等の
反応型難燃剤を添加する必要があり、これらを添加する
ことによりポリブタジェン樹脂本来の電気特性、耐熱性
、寸法安定性を損うという問題がある。However, since the resin of PTFE laminates is thermoplastic and the glass transition temperature is low, there are problems such as a large coefficient of thermal expansion at high temperatures and insufficient dimensional stability, especially when through-holes are bonded in multiple layers. I have concerns about sexuality, etc. Furthermore, since there is no suitable solvent for PTFE, bonding by heating and melting and pressure bonding is generally used, but this method has the disadvantage of a very high melting temperature. In addition, polybutadiene resin has the disadvantage of being easily flammable due to its molecular structure, so additive flame retardants such as decabromodiphenyl ether and triphenyl phosphate, tribromophenyl methacrylate, and tribromophenyl acrylate are used to impart flame retardancy. It is necessary to add reactive flame retardants such as, and there is a problem that the addition of these impairs the electrical properties, heat resistance, and dimensional stability inherent to polybutadiene resin.
本発明の目的は、従来、大型計算機に使用されているポ
リイミド系多層プリント配線板に代わる材料として、ポ
リイミド積層材料と同程度の高密度配線が可能で難燃性
を有する低誘電率積層材料に関するものである。The purpose of the present invention is to relate to a low dielectric constant laminate material that is flame retardant and capable of high-density wiring comparable to that of polyimide laminate materials, as a material that can replace the polyimide multilayer printed wiring boards conventionally used in large-scale computers. It is something.
第一の発明は難燃性の熱硬化性樹脂組成物に関し、その
特徴は、下記一般式（１）
（式中、Ａはハロゲン基であり、Ｒ３は炭素数２〜４の
アルケニルまたはアルケノイルであり、ｍは１〜４、ｎ
は１〜１００の数を示す）で表わされるポリ（ｐ−ヒド
ロキシスチレン）誘導体から成るプレポリマーに下記一
般式（ｎ）
（式中、Ｂはグリシジルエーテル系エポキシのコポリマ
であり、ｎは４〜１００の数を示す）で表わされるエポ
キシ変性ポリブタジェンと下記一般式（ＩＩＩ）
（式中、Ｒ２は少なくともベンゼン環を１ヶ以上含む芳
香族基、ｎは１〜４）表わされる芳香族マ１ル
イミド化合物と１．３−ジ−オルトトリルグアニジン（
ＩＶ）を配合して成ることにある。The first invention relates to a flame-retardant thermosetting resin composition, which is characterized by the following general formula (1) (wherein A is a halogen group, and R3 is an alkenyl or alkenoyl having 2 to 4 carbon atoms. Yes, m is 1 to 4, n
is a number from 1 to 100) is a prepolymer composed of a poly(p-hydroxystyrene) derivative represented by the following general formula (n) (where B is a glycidyl ether-based epoxy copolymer, and n is 4 to 100). 100) and an aromatic malimide represented by the following general formula (III) (wherein R2 is an aromatic group containing at least one benzene ring, and n is 1 to 4). compound and 1,3-di-orthotolylguanidine (
IV).
第二の発明は前記樹脂組成物を用いたプリプレグに関し
、繊維基材に一般式（１）
（式中、Ａははハロゲン基であり、Ｒ，はアリル基、ブ
テニル基、ビニル基、アクリノイル基、メタクリノイル
基、エポキシメタクリノイル基であり、ｍは１〜４、ｎ
は１〜１００の数を示す）で表わされるポリ（ｐ−ヒド
ロキシスチレン）誘導体から成るプレポリマーと下記一
般式（ｎ）（式中、Ｂはグリシジルエーテル系エポキシ
のコポリマであり、ｎは４〜１００の数を示す）で表わ
されるエポキシ変性ポリブタジェンと下記一般式（Ｉｔ
）
（式中、Ｒ２は少なくともベンゼン環を１ヶ以上含む芳
香族基、ｎは１〜４）で表わされる芳香族系マレイミド
化合物と１．３−ジ−オルトトリルグアニジン（ＩＶ）
を溶媒に溶かしたワニス状とし含浸したものである。
第三の発明は上記樹脂組成物を用いた積層板に関し、そ
の特徴は、繊維基材に一般式（１）
（式中、Ｂはグリシジルエーテル系エポキシのコポリマ
であり、ｎは４〜１００の数を示す）で表わされるエポ
キシ変性ポリブタジェンと下記一般式（ＩＩＩ）
（式中、Ａはハロゲン基であり、Ｒ３はアリル基、ブテ
ニル基、ビニル基、アクリノイル基、メタクリノイル基
、エポキシメタクリノイル基であり、ｍは１〜４、ｎは
１〜１００の数を示す）で表わされるポリ（ｐ−ヒドロ
キシスチレン）誘導体から成るプレポリマーと下記一般
式（Ｉｔ）含む芳香族基、ｎは１〜４）で表わされる芳
香族系マレイミド化合物と１．３−ジ−オルトトリルグ
アニジンとから成る組成物を含浸したプリプレグを積層
接着した積層板にある。The second invention relates to a prepreg using the resin composition, and a fiber base material having the general formula (1) (wherein A is a halogen group, and R is an allyl group, a butenyl group, a vinyl group, or an acrinoyl group). , methacrynoyl group, epoxymethacrynoyl group, m is 1 to 4, n
represents a number from 1 to 100) and a prepolymer consisting of a poly(p-hydroxystyrene) derivative represented by the following general formula (n) (where B is a glycidyl ether-based epoxy copolymer, and n is 4 to 100). epoxy-modified polybutadiene represented by the number 100) and the following general formula (It
) (wherein R2 is an aromatic group containing at least one benzene ring, n is 1 to 4) and 1,3-di-orthotolylguanidine (IV)
is dissolved in a solvent to form a varnish and then impregnated.
The third invention relates to a laminate using the above-described resin composition. epoxy-modified polybutadiene represented by the following general formula (III) (where A is a halogen group, and R3 is an allyl group, a butenyl group, a vinyl group, an acrinoyl group, a methacrynoyl group, an epoxymethacrynoyl group) , m is a number from 1 to 4, n is a number from 1 to 100), and an aromatic group containing the following general formula (It), where n is 1 to 1. The present invention is a laminate in which prepregs impregnated with a composition consisting of an aromatic maleimide compound represented by 4) and 1,3-di-orthotolylguanidine are laminated and bonded together.
本発明の熱硬化性樹脂組成物は、前記のように一般式（
１）、（ＩＴ）、（ＩＩＩ）及び１．３−ジルオルトト
リルグアニジン（ＩＶ）から成る組成物である。その具
体例をあげれば、前記一般式（Ｉ）で示される化合物と
しては、ポリ （Ｐ−ヒドロキシスチレン）のビニルエ
ーテル、イソブテニルエ一チル、アリルエーテルと、ア
クリル酸エステル、メタクリル酸エステル、エポキシメ
タクリル酸エステル等の臭化物がある。これらは所望に
応じ１種または２種以上使用される。The thermosetting resin composition of the present invention has the general formula (
1), (IT), (III) and 1,3-dylorthotolylguanidine (IV). To give specific examples, the compounds represented by the general formula (I) include poly(P-hydroxystyrene) vinyl ether, isobutenyl ethyl, allyl ether, acrylic ester, methacrylic ester, and epoxy methacrylic ester. There are bromides such as One or more of these may be used as desired.
前記一般式（ＩＩ）で表わされる本発明の熱硬化性樹脂
の１つであるエポキシ変性ポリブタジェンにおいて、変
性に用いられるグリシジルエーテル系のエポキシ樹脂の
具体例をあげれば、ジグリシジルエーテルビスフェノー
ルＡ１ジグリシジルエテル２．２“−ジブロモビスフェ
ノールＡ、ジグリシジルエーテル２．２’、４．４”−
テトラブロモビスフェノールＡ１ジグリシジルエーテル
２．２−ジメチルビスフェノールＡ、ジグリシジルエー
テル２．２’ 、４−）ジメチルビスフェノールＡ、フ
ェノールノボラック型エポキシ樹脂、オルソクレゾール
ノボラック型エポキシ樹脂である。これらは所望に応じ
、１種または２種以上使用される。In the epoxy-modified polybutadiene, which is one of the thermosetting resins of the present invention represented by the general formula (II), specific examples of glycidyl ether-based epoxy resins used for modification include diglycidyl ether bisphenol A1 diglycidyl. Ether 2.2"-dibromobisphenol A, diglycidyl ether 2.2', 4.4"-
Tetrabromobisphenol A1 diglycidyl ether 2.2-dimethylbisphenol A, diglycidyl ether 2.2', 4-)dimethylbisphenol A, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin. One or more of these may be used as desired.
又、前記一般式（Ｉ［ｉ）で表わされる本発明の熱硬化
性樹脂の１つである芳香族系マレイミド化合物の具体例
をあげれば、Ｎ、Ｎ”−ｍ−フェニレンビスマレイミド
、Ｎ、Ｎ−ｐ−フェニレンビスマレイミド、ＮＮ”−４
４゛−ジフェニルメタンビスマレイミド、Ｎ、Ｎ’−４
４”−ジフェニルエーテルビスマレイミド、ＮＮ’ −
メチレンビス（３−クロロ−ｐ−フェニレン）ビスマレ
イミド、Ｎ、Ｎ’−４４“−ジフェニルサルフォンビス
マレイミド、ＮＮ−ｍ−キシレンビスマレイミド、Ｎ
Ｎ −４４“−ジフェニルシクロヘキサンビスマレ
イミド、Ｎ、Ｎ４．４′−ジフェニルプロパン−ビス−
マレイミド、２，２−ビス（４−（４−マレイミドフェ
ノキシ）フェニル）プロパン、２．２−ビス〔３メチル
−４−（４−マレイミドフェノキシ）フェニル〕プロパ
ン、２，２−ビス（４−（４−マレイミドフェノキシ）
フェニル〕へキサフロロプロパン、２．２−ビス（４−
マレイミドフェニル）へキサフロロプロパン、１，３−
ビス（３−マレイミドフェノキシ）ヘンゼン、３．３′
−ビスマレイミドヘンシフエノキシ等のビスマレイミド
及びＮ−フェニルマレイミド、Ｎ−３−クロロフェニル
マレイミド、Ｎ−ｏ−）リルマレイミド、Ｎｍ−トリル
マレイミド、Ｎ−ｐ−トリルマレイミド、Ｎ−０−メト
キシフェニルマレイミド、Ｎ−ｍ−メトキシフェニルマ
レイミド、Ｎ−ｐ−メトキシフェニルマレイミド、Ｎ−
ベンジルマレイミド、Ｎ−ピリジルマレイミド、Ｎ−ヒ
ドロキシフェニルマレイミド、Ｎ−アセトキシフェニル
マレイミド、Ｎ−ジクロロフェニルマレイミド、Ｎベン
ゾフェノンマレイミド、Ｎ−ジフェニルエーテルマレイ
ミド、Ｎ−アセチルフェニルマレイミド、等のモノマレ
イミドがある。これらは所望に応じ、１種または２種以
上使用される。Further, specific examples of the aromatic maleimide compound, which is one of the thermosetting resins of the present invention represented by the general formula (I[i), include N,N''-m-phenylenebismaleimide, N, N-p-phenylene bismaleimide, NN''-4
4゛-diphenylmethane bismaleimide, N, N'-4
4”-diphenyl ether bismaleimide, NN′ −
Methylenebis(3-chloro-p-phenylene)bismaleimide, N,N'-44"-diphenylsulfonebismaleimide, NN-m-xylenebismaleimide, N
N-44"-diphenylcyclohexane bismaleimide, N,N4.4'-diphenylpropane-bis-
Maleimide, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis[3methyl-4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis(4-( 4-maleimidophenoxy)
phenyl]hexafluoropropane, 2,2-bis(4-
maleimidophenyl) hexafluoropropane, 1,3-
Bis(3-maleimidophenoxy)henzen, 3.3'
-Bismaleimide and N-phenylmaleimide such as bismaleimidehensiphenoxy, N-3-chlorophenylmaleimide, N-o-)lylmaleimide, Nm-tolylmaleimide, N-p-tolylmaleimide, N-0-methoxyphenyl Maleimide, N-m-methoxyphenylmaleimide, N-p-methoxyphenylmaleimide, N-
Examples of monomaleimides include benzylmaleimide, N-pyridylmaleimide, N-hydroxyphenylmaleimide, N-acetoxyphenylmaleimide, N-dichlorophenylmaleimide, N-benzophenonemaleimide, N-diphenyl ethermaleimide, and N-acetylphenylmaleimide. One or more of these may be used as desired.
本発明で、芳香族系マレイミド化合物は、脂肪族系に比
べて耐熱性が優れている。In the present invention, aromatic maleimide compounds have better heat resistance than aliphatic maleimide compounds.
本発明において用いられる１、３−ジ−オルトトリルグ
アニジン（ＩＶ）は、一般式（ＩＩ）のエポキシ変性ポ
リブタジェン中のエポキシ基と反応し、架橋密度を向上
させる働きをする。同様の働きをするエポキシ硬化剤と
して各種芳香族ジアミンやベンゾグアナミン、ジシアン
ジアミド等が知られているが、芳香族ジアミンは毒性お
よびポットライフの問題があり、ベンゾグアナミンやジ
シアンジアミドはワニスへの溶解性あるいは樹脂の不均
一性の問題ある。本発明で使用する１、３−ジオルトト
リルグアニジンには前記問題点がなく、特にワニスへの
溶解性、樹脂の均一性の点で優れている。The 1,3-di-orthotolylguanidine (IV) used in the present invention reacts with the epoxy group in the epoxy-modified polybutadiene of general formula (II) and functions to improve the crosslink density. Various aromatic diamines, benzoguanamine, dicyandiamide, etc. are known as epoxy curing agents that have similar functions, but aromatic diamines have problems with toxicity and pot life, and benzoguanamine and dicyandiamide have problems with solubility in varnish or resin. There is a problem of heterogeneity. The 1,3-diorthotolylguanidine used in the present invention does not have the above-mentioned problems and is particularly excellent in solubility in varnish and uniformity of the resin.
又、前記、一般式（Ｉ）、（Ｉ［）、（Ｉ［）、（ＩＶ
）を配合した熱硬化性樹脂組成物には、ラジカル重合開
始剤を添加することにより硬化反応を早めることができ
る。Moreover, the general formula (I), (I[), (I[), (IV
) The curing reaction can be accelerated by adding a radical polymerization initiator to the thermosetting resin composition containing the above.
ラジカル重合剤としての典型的例としては、ベンゾイル
パーオキシド、ジクミルパーオキシド、メチルエチルケ
トンパーオキシド、ｔ−ブチルパーオキシラウレート、
ジ−ｔ−ブチルパーオキシフタレート、ジヘンジルオキ
シド、２．５−ジメチル−２，５−ジ（ｔ−ブチルパー
オキシ）ヘキサン、ｔ−ブチルクミルパーオキシド、む
−ブチルハイドロパーオキシド、ジーＬ−ブチルパー第
キシド、２．５−ジメチル−２，５−ジ（ｔ−ブチルパ
ーオキシ）ヘキシン（３）、ジイソプロビルヘンゼンハ
イドロパーオキシド、ｐ−メンタンハイドロパーオキシ
ド、ピナンハイドロオキシド、２．５−ジメチルヘキサ
ン−２，２−シバイドロバ−オキシド、クメンハイドロ
パーオキシドなどがある。これらは樹脂組成物１００重
量部に対して好ましくは０．１〜１０重量部添加する。Typical examples of radical polymerization agents include benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, t-butyl peroxylaurate,
Di-t-butyl peroxyphthalate, dihenzyl oxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, butyl hydroperoxide, Di-L -Butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne (3), diisoprobylhenzene hydroperoxide, p-menthane hydroperoxide, pinane hydroxide, 2. Examples include 5-dimethylhexane-2,2-cybidroba-oxide and cumene hydroperoxide. These are preferably added in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the resin composition.
前記熱硬化性樹脂組成物の配合割合は、必要に応じて種
々変えることができる。一般に、一般式（Ｉ）のポリ（
ｐ−ヒドロキシスチレン）誘導体の配合割合が多くなる
と難燃性、機械的強度が向上がする可撓性が低下し、硬
化時の収縮率が大きくなる傾向がある。一般式（ＩＩ）
のエポキシ変性ポリブタジェンの配合割合が多くなると
、可撓性、銅箔との接着性が向上するが、耐熱性が低下
する傾向があり、一般式（ＩＩＩ）芳香族系マレイミド
の配合割合が多くなると、難燃性、耐熱性が向上し、硬
化時の収縮率が小さくなり、寸法安定性が向上する（頃
向がある。１．３−ジ−オルトトリルグアニシンの配合
割合は、一般式（Ｉ［）のエポキシ変性ポリブタジェン
のエポキシ当量に依存し、適当な配合量の範囲がある。The blending ratio of the thermosetting resin composition can be varied as necessary. In general, poly(
When the blending ratio of p-hydroxystyrene (p-hydroxystyrene) derivative increases, flame retardancy and mechanical strength improve, but flexibility tends to decrease and shrinkage rate during curing tends to increase. General formula (II)
When the blending ratio of epoxy-modified polybutadiene increases, flexibility and adhesion with copper foil improve, but heat resistance tends to decrease, and when the blending ratio of aromatic maleimide of general formula (III) increases. , flame retardancy and heat resistance are improved, the shrinkage rate during curing is reduced, and dimensional stability is improved. There is a suitable range of blending amount depending on the epoxy equivalent of the epoxy-modified polybutadiene I[).
１．３−ジ−オルトトリルグアニジン量が少量の場合、
あるいは多量の場合、硬化樹脂板の熱膨脹係数が大きく
、曲げ強度が低い値であり、たいねつ耐熱性も低い値と
なる。1. When the amount of 3-di-orthotolylguanidine is small,
Alternatively, if the amount is large, the cured resin plate will have a large coefficient of thermal expansion, a low bending strength, and a low thermal resistance.
上記組成物として好ましく範囲は、式（Ｉ）１０〜６０
重量％、とくに２０〜４０重量％：式（ＩＩ）１０〜５
０重量％、とくに１０〜３０重量％二式（ＩＩＩ）２０
〜７０重量％、とくに３０〜６０重量％で、これら３種
を上記範囲内で調整する。The preferred range for the above composition is formula (I) 10-60
% by weight, especially 20-40% by weight: formula (II) 10-5
0% by weight, especially 10-30% by weight of formula II (III) 20
-70% by weight, especially 30-60% by weight, and adjust these three types within the above range.
１、３−ジ−オルトトリルグアニジン（ＩＶ）の配合量
の好ましい範囲は、１．３−ジ−オルトトリルグアニジ
ンのアミン当量／エポキシ当量の当量比が０．３〜１．
５であり、とくに好ましい範囲は０。The preferable range of the blending amount of 1,3-di-orthotolylguanidine (IV) is such that the equivalent ratio of amine equivalent/epoxy equivalent of 1,3-di-orthotolylguanidine is 0.3 to 1.
5, and a particularly preferable range is 0.
５〜１．２の範囲である。It is in the range of 5 to 1.2.
本発明の組成物には、第５成分として、芳香族アミンを
必要に応して配合することができる。An aromatic amine can be added to the composition of the present invention as a fifth component, if necessary.
芳香族アミンとしては、例えば、４，４”−ジアミノジ
フェニルメタン、４，４′−ジアミノフェニルエーテル
、４，４′−ジアミノジフェニルスルホン、２．２−ビ
ス（１（４−アミノフェノキシ）フェニル〕プロパン、
２，２−ビス〔４（４−アミノフェノキシ）フェニル〕
へキサフロロプロパン、４４゛−ビス（３−アミノフェ
ノキシ）ビフェニル、１，３−ビス（３−アミノフェノ
キシ）ベンゼンなどがある。Examples of aromatic amines include 4,4''-diaminodiphenylmethane, 4,4'-diaminophenyl ether, 4,4'-diaminodiphenylsulfone, and 2,2-bis(1(4-aminophenoxy)phenyl)propane. ,
2,2-bis[4(4-aminophenoxy)phenyl]
Examples include hexafluoropropane, 44'-bis(3-aminophenoxy)biphenyl, and 1,3-bis(3-aminophenoxy)benzene.
次に本発明における積層板の一般的な製造方法について
説明する。Next, a general method for manufacturing a laminate according to the present invention will be explained.
まず、ポリ（ｐ−ヒドロキシスチレン）誘導体、エポキ
シ変性ポリブタジェンおよび芳香族系マレイミドを有機
溶媒に溶解させてワニスを調製する。First, a varnish is prepared by dissolving a poly(p-hydroxystyrene) derivative, an epoxy-modified polybutadiene, and an aromatic maleimide in an organic solvent.
有ｍｌ媒としては例えば、メチルイソブチルケトン、Ｎ
、Ｎ−ジメチルホルムアミド、シクロヘキサン、アルキ
レングリコールモノアルキルエーテル類、アルキレング
リコールジアルキルエーテル類、Ｎ−メチルピロリドン
、ジメチルスルホキシド、トリクロロエチレン、トリク
ロロエタン、塩化メチレン、ジオキサン、酢酸エチル等
が使用できる。As the ml medium, for example, methyl isobutyl ketone, N
, N-dimethylformamide, cyclohexane, alkylene glycol monoalkyl ethers, alkylene glycol dialkyl ethers, N-methylpyrrolidone, dimethyl sulfoxide, trichloroethylene, trichloroethane, methylene chloride, dioxane, ethyl acetate, etc. can be used.
なお、積層板を作製する際の樹脂の流動性、ゲル化時間
等の調整に、必要に応じてワニスを加熱して予備反応し
ておいてもよい。又、基材との密着性を向上させるため
カンプリング剤を添加しても良い。調整したワニスに１
，３−ジ−オルト］・リルグアニジンおよび必要に応じ
てラジカル重合開始剤を添加して含浸用ワニスとする。In addition, in order to adjust the fluidity of the resin, gelling time, etc. when producing a laminate, the varnish may be heated and pre-reacted as necessary. Further, a compres- ing agent may be added to improve adhesion to the base material. 1 on the adjusted varnish
, 3-di-ortho]-lylguanidine and, if necessary, a radical polymerization initiator to prepare a varnish for impregnation.
次に得られた含浸用ワニスをシート状基材に含浸塗工し
、室温〜１７０°Ｃで乾燥し、粘着性のないプリプレグ
を得る。この時の乾燥温度の設定は用いた溶媒および開
始剤等らよって決まる。最後に得られたプリプレグを必
要枚数重ね、１００〜２５０°Ｃで１〜１００ｋｇｆ／
ｃｎ（の圧力下で加熱硬化反応を行い積層板を得る。Next, the obtained impregnating varnish is impregnated and coated on a sheet-like base material and dried at room temperature to 170°C to obtain a non-tacky prepreg. The setting of the drying temperature at this time is determined by the solvent, initiator, etc. used. Layer the required number of prepregs finally obtained and heat at 100 to 250°C at 1 to 100 kgf/
A heat curing reaction is performed under the pressure of cn() to obtain a laminate.
シート状基材としては、一般に積層材料に使用されてい
るものはほとんどすべて使用できる。無機繊維としては
、５ｉＯｚ、Ａｌ２Ｏ２等を成分とするＥガラス、Ｃガ
ラス、Ａガラス、Ｓガラス、Ｄガラス、ＴＭ−３１Ａガ
ラスおよび石英を使用したＣガラス等の各種ガラス繊維
およびセラミツク繊維がある。また有機繊維としては、
芳香族ポリアミド骨格を有する高分子化合物を成分とす
るアラミド繊維等がある。As the sheet-like base material, almost all those commonly used for laminated materials can be used. Examples of inorganic fibers include various glass fibers and ceramic fibers such as E glass, C glass, A glass, S glass, D glass, TM-31A glass, and C glass using quartz, which contain 5iOz, Al2O2, etc. as components. Also, as an organic fiber,
There are aramid fibers and the like whose component is a polymer compound having an aromatic polyamide skeleton.
（作用）
本発明の樹脂組成物の硬化時の収縮率が小さくなる理由
は判らない。マレイミド系化合物の配合によって生ずる
ものと考える。(Function) It is not known why the shrinkage rate of the resin composition of the present invention decreases during curing. This is thought to be caused by the combination of maleimide compounds.
硬化収縮率が小さいために、硬化時の積層板など硬化物
へのストレスの蓄積も小さく、従ってクラック等の発生
も少ない。Since the curing shrinkage rate is low, the accumulation of stress on cured products such as laminates during curing is also small, and therefore cracks and the like are less likely to occur.
更に、１．３−ジ−オルトトリルグアニジンの配合量を
適切に選ぶことにより、硬化樹脂板の曲げ強度が向上し
、破壊時の伸びの値も大きくなる。Furthermore, by appropriately selecting the blending amount of 1,3-di-orthotolylguanidine, the bending strength of the cured resin plate can be improved, and the elongation at break can also be increased.
これによりクラック等の発生も少なくなる。This also reduces the occurrence of cracks and the like.
（実施例）
実施例１
臭素化ポリ（Ｐ−ヒドロキシスチレン）のメタクリル酸
エステル（分子量７０００〜１２０００、臭素含有率４
２％）５０重量部、タレゾールノボラックエポキシで変
性したポリブタジェン（エポキシ当量５７５ｇ／ｅｑ）
３０重量部、２，２ビス（１−（４−マレイミドフェノ
キシ）フェニル〕プロパン２０重量部を、メチルイソブ
チルケトン１００重量部とジメチルホルムアミド１５０
重量部の混合溶媒に溶解させ、１００〜１２０°Ｃで１
時間加熱撹拌した。更に、ワニスを室温にまで冷却後、
１．３−ジ−オルトトリルグアニジン（アミン当量８０
）４．２重量部（エポキシ変性ポリブタジェン１当量に
対し、■、３−ジーオルトトリルグアニジン１．０当量
）、ラジカル重合開始剤として２．５−ジメチル−２，
５−ジ（ｔ−ブチルパーオキシ）−ヘキシン（３）０．
５重量部を加えて撹拌し完全に溶解させてワニスを得た
。このワニスを一週間室温で放置しても、均一なワニス
のままであった。(Example) Example 1 Methacrylic acid ester of brominated poly(P-hydroxystyrene) (molecular weight 7000-12000, bromine content 4
2%) 50 parts by weight of polybutadiene modified with Talesol novolak epoxy (epoxy equivalent weight 575 g/eq)
30 parts by weight, 20 parts by weight of 2,2bis(1-(4-maleimidophenoxy)phenyl)propane, 100 parts by weight of methyl isobutyl ketone and 150 parts by weight of dimethylformamide.
Dissolve in 1 part by weight of mixed solvent and heat at 100 to 120°C.
The mixture was heated and stirred for hours. Furthermore, after cooling the varnish to room temperature,
1.3-di-orthotolylguanidine (amine equivalent 80
) 4.2 parts by weight (1.0 equivalent of ■,3-di-orthotolylguanidine per equivalent of epoxy-modified polybutadiene), 2,5-dimethyl-2, as a radical polymerization initiator
5-di(t-butylperoxy)-hexyne (3) 0.
A varnish was obtained by adding 5 parts by weight and stirring to completely dissolve the mixture. Even after this varnish was left at room temperature for a week, it remained a uniform varnish.
上記ワニスをエバポレータで４０〜５０°Ｃに加熱しな
がら減圧脱気し溶媒を除去し固形の樹脂組成物を得た。The varnish was heated to 40 to 50°C using an evaporator and degassed under reduced pressure to remove the solvent, thereby obtaining a solid resin composition.
更に、該樹脂組成物を離型処理した金型に入れ１３０°
Ｃ〜１５０°Ｃに加熱し液状にして減圧脱気し泡を除い
て１７０°Ｃで１２０分、２００°Ｃで１２０分、２２
０°Ｃで１２０分の条件で加熱硬化し樹脂板を得た。Furthermore, the resin composition was placed in a mold that had been subjected to mold release treatment and heated at 130°.
Heat to 150°C to liquefy, degas under reduced pressure, remove bubbles, heat to 170°C for 120 minutes, 200°C for 120 minutes, 22
The resin plate was cured by heating at 0°C for 120 minutes.
実施例２〜１３および比較例１〜２
表１に示した配合組成で実施例１とほぼ同様にして樹脂
板を得た。Examples 2 to 13 and Comparative Examples 1 to 2 Resin plates were obtained in substantially the same manner as in Example 1 using the blending compositions shown in Table 1.
なお、実施例１１に於て、臭化ポリ（ｐ−ヒドロキシス
チレン）のアクリル酸エステルは分子量７０００〜１２
０００、臭素含有率４５％、実施例１２に於て、臭化ポ
リ（ｐ−ヒドロキシスチレン）のアリルは分子量７００
０〜１２０００、臭素含有率４３％、実施例１３に於て
、臭化ポリ（ｐ−ヒドロキシスチレン）のエポキシメタ
クリル酸エステルは分子量７０００〜１２０００、臭素
含有率３５％のものをそれぞれ用いた。In addition, in Example 11, the acrylic ester of bromide poly(p-hydroxystyrene) had a molecular weight of 7,000 to 12
000, bromine content 45%, in Example 12, the allyl bromide poly(p-hydroxystyrene) had a molecular weight of 700.
In Example 13, the epoxy methacrylate ester of bromide poly(p-hydroxystyrene) had a molecular weight of 7,000 to 12,000 and a bromine content of 35%.
前記、実施例および比較例による樹脂板の主な特性を表
２に示す。Table 2 shows the main characteristics of the resin plates according to the above examples and comparative examples.
なお、比較例１のワニス（ヘンゾグアナミン使用）は室
温で一週間放置するとワニスの底部に析出物の沈澱がみ
られた。In addition, when the varnish of Comparative Example 1 (using Henzoguanamine) was left at room temperature for one week, precipitates were observed at the bottom of the varnish.
実施例１４
臭素化ポリ（ｐ−ヒドロキシスチレン）のメタクリル酸
エステル（分子量７０００〜１２０００、臭素含有率４
２％）５０重量部、タレゾールノボラックエポキシで変
性したポリブタジェン３０重量部、２，２−ビス（４−
（４−マレイミドフッキシ）フェニル〕プロパンの２０
重量部をメチルイソブチルケトン１００重量部とジチメ
ルホルムアミド１５０重量部の混合溶媒に溶解させ、１
００〜１２０°Ｃで１時間加熱撹拌した。Example 14 Methacrylic acid ester of brominated poly(p-hydroxystyrene) (molecular weight 7000-12000, bromine content 4
2%) 50 parts by weight, 30 parts by weight of polybutadiene modified with Talesol novolak epoxy, 2,2-bis(4-
(4-maleimidofuxy)phenyl]propane 20
Part by weight was dissolved in a mixed solvent of 100 parts by weight of methyl isobutyl ketone and 150 parts by weight of dithymelformamide, and 1 part by weight was dissolved.
The mixture was heated and stirred at 00 to 120°C for 1 hour.
更に、ワニスを室温にまで冷却後、１．３−ジオルトト
リルグアニジン４．２重量部、ラジカル重合開始剤とし
て、２．５−ジメチル−２，５ジ（ｔ−ブチルパーオキ
シ）ヘキシン（３）０．５重量部を加えて撹拌して完全
に溶解させてワニスを得た。Furthermore, after cooling the varnish to room temperature, 4.2 parts by weight of 1,3-diorthotolylguanidine and 2,5-dimethyl-2,5 di(t-butylperoxy)hexyne (3 parts by weight) were added as a radical polymerization initiator. ) 0.5 part by weight was added and stirred to completely dissolve it to obtain a varnish.
このワニスをガラスクロス（Ｅガラス、厚さ０゜１ｍｍ
）に含浸塗工し、室温で風乾燥後、１５０°Ｃで１０〜
２０分間乾燥してタックフリーのプリプレグを得た。次
に、該プリプレグを１０枚重ねて上下に厚さ３５μｍの
電解銅箔を重ねて圧力４０Ｋｇｆ／ｃｎ（、温度１３０
°Ｃで３０分間加熱し、更に１７０ ’Ｃで１時間、２
２０℃で２時間プレスを行い積層板を得た。Apply this varnish to glass cloth (E glass, thickness 0°1mm)
), and after air drying at room temperature, 10 to 150°C.
A tack-free prepreg was obtained by drying for 20 minutes. Next, 10 sheets of the prepreg were stacked, and electrolytic copper foils with a thickness of 35 μm were stacked on top and bottom, and the pressure was 40 Kgf/cn (and the temperature was 130 Kgf/cn).
Heat for 30 minutes at 170'C, then 1 hour at 170'C for 2 hours.
Pressing was performed at 20° C. for 2 hours to obtain a laminate.
実施例１５〜２０および比較例３〜６
表３に示した配合組成で実施例１４と同様にして積層板
を得た。Examples 15 to 20 and Comparative Examples 3 to 6 Laminated plates were obtained in the same manner as in Example 14 using the compounding compositions shown in Table 3.
エポキシ樹脂積層板、ポリイミド樹脂積層板を比較例５
．６とする。Comparative example 5 of epoxy resin laminate and polyimide resin laminate
．． Set it to 6.
比較例７
１．２−ポリブタジエンプレボリマ５０重量部、タレゾ
ールノボラック型エポキシ変性ポリブタジェン５０重量
部をキシレンに溶解させ、固形分量２０〜３０重量％の
ワニスを得る。更に、ラジカル重量開始剤としてジクミ
ルパーオキシド２重量部、エポキシ硬化剤として２−エ
チル−４メチルイミダゾ一ル１重量部を添加し、実施例
１４と同様にして積層板を得た。Comparative Example 7 50 parts by weight of 1.2-polybutadiene prevolima and 50 parts by weight of Talesol novolac type epoxy-modified polybutadiene are dissolved in xylene to obtain a varnish having a solid content of 20 to 30% by weight. Further, 2 parts by weight of dicumyl peroxide as a radical weight initiator and 1 part by weight of 2-ethyl-4 methyl imidazole as an epoxy curing agent were added, and a laminate was obtained in the same manner as in Example 14.
前記、実施例および比較例による積層板の主な特性を表
４に示す。Table 4 shows the main properties of the laminates according to the above examples and comparative examples.
実施例２１
表５に示した樹脂組成で、実施例１４で示した方法で得
られたプリプレグを用い、該プリプレグ側を表面粗化し
た銅箔（３５μｍ厚）を両面に積層して、圧力３０Ｋｇ
ｆ／ｃｎｆ、温度１３０°Ｃで３０分間加熱し、さらに
、１７０°Ｃで１時間、２００°Ｃで２時間プレスを行
い銅張り積層板を得た。この絶縁層の厚さは約１００μ
ｍである。得られた銅張り積層板をフォトエツチング法
によって信号層、電源層、整合層等の内層回路パターン
を形成させ、次の方法によって回路パターンの銅表面を
処理し、両面配線単位回路シートを形成した。Example 21 Using a prepreg obtained by the method shown in Example 14 with the resin composition shown in Table 5, copper foil (35 μm thick) with the surface roughened on the prepreg side was laminated on both sides, and a pressure of 30 kg was applied.
f/cnf for 30 minutes at a temperature of 130°C, and further pressed at 170°C for 1 hour and 200°C for 2 hours to obtain a copper-clad laminate. The thickness of this insulating layer is approximately 100μ
It is m. Inner layer circuit patterns such as a signal layer, a power supply layer, and a matching layer were formed on the obtained copper-clad laminate by a photoetching method, and the copper surface of the circuit pattern was treated by the following method to form a double-sided wiring unit circuit sheet. .
溶液組成：
（１）濃塩酸３００ｇ、塩化第２銅５０ｇ、蒸留水６５
０ｇ （銅表面の粗化）。Solution composition: (1) 300 g of concentrated hydrochloric acid, 50 g of cupric chloride, 65 g of distilled water
0g (roughening of copper surface).
（２）水酸化ナトリウム５ｇ、リン酸三ナトリウム１０
ｇ、亜塩素酸ナトリウム３０ｇ、蒸留水９５５ｇ（銅表
面の安定化）。(2) 5g of sodium hydroxide, 10g of trisodium phosphate
g, 30 g of sodium chlorite, 955 g of distilled water (stabilization of copper surface).
上記の処理を終了後、第１図に示すような構成で、前記
のプリプレグ樹脂シートを用いて、回路導体層２として
３０層形成し、１７０°Ｃで、圧力４０ｋｇ／ｃｒｒｆ
、１７０°Ｃ９０分、２２０°Ｃで９０分の条件で接着
形成を行い、多層プリント回路板を作成した。After completing the above process, 30 layers were formed as the circuit conductor layer 2 using the prepreg resin sheet with the configuration shown in FIG.
, 170°C for 90 minutes and 220°C for 90 minutes to produce a multilayer printed circuit board.
多層化接着はシートの四方に設けた穴にガイドピンを挿
入する方法で位置ずれを防止して行った。Multilayer adhesion was performed by inserting guide pins into holes provided on all sides of the sheet to prevent positional shift.
多層化接着後穴径０．３ ｍ ｍ又は０．６ｍｍの穴を
マイクロドリルによってあけ、全面に化学銅めっきを行
ってスルーホール導体４を形成させた。次に、最外層回
路をエツチングにより形成させて多層プリント板を形成
した。After multilayer adhesion, a hole with a diameter of 0.3 mm or 0.6 mm was drilled using a microdrill, and the entire surface was chemically plated with copper to form a through-hole conductor 4. Next, the outermost layer circuit was formed by etching to form a multilayer printed board.
本実施例では厚さが３．５ｍｍＸ５７０ｍｍＸ４２０ｍ
ｍの大きさでライン幅７０μｍおよび１００μｍの２種
、（チャルネル／グリッド）が２〜３本／１．３ｍｍ、
層間ずれが約１００１！ｍ以下のものを得ることができ
た。ガラスクロスは絶縁層の約３０体積％であった。In this example, the thickness is 3.5 mm x 570 mm x 420 m.
2 types of line widths of 70 μm and 100 μm, (channel/grid) 2 to 3 lines/1.3 mm,
The gap between layers is about 1001! I was able to obtain one below m. The glass cloth was about 30% by volume of the insulating layer.
第１図において１．３は絶縁層、２は回路導体層、４は
スルーホールであり、１は前述の銅張り積層板および３
はプリプレグ樹脂シートである。In FIG. 1, 1.3 is an insulating layer, 2 is a circuit conductor layer, 4 is a through hole, 1 is the aforementioned copper-clad laminate, and 3 is an insulating layer.
is a prepreg resin sheet.
実施例２２〜２７、比較例８
それぞれ表５に示した樹脂組成で、実施例２１と同様に
して多層プリント回路板を製造した。Examples 22 to 27, Comparative Example 8 Multilayer printed circuit boards were manufactured in the same manner as in Example 21 using the resin compositions shown in Table 5, respectively.
表６に多層プリント回路板の一部分を切り出し、半田耐
熱性および熱衝撃性を測定した結果を示した。Table 6 shows the results of cutting out a portion of the multilayer printed circuit board and measuring its solder heat resistance and thermal shock resistance.
以下空白
なお、熱分解温度は樹脂硬化物を粉砕した試料ＬＯｍｇ
について、空気雰囲気中、昇温速度５°Ｃ／ｍｉｎで測
定し、５％′ｔＩｉ量したときの温度を熱分解温度とし
た。The following is blank.The thermal decomposition temperature is LOmg of the sample obtained by crushing the cured resin.
The temperature was measured in an air atmosphere at a heating rate of 5°C/min, and the temperature at which the amount of tIi was 5% was taken as the thermal decomposition temperature.
線膨脹係数は厚さ方向の熱膨脹率を昇温速度２’Ｃ／ｍ
ｊｎで測定し、５０ ’Ｃから２００ ’Ｃまでの変化
量から求めた。The coefficient of linear expansion is the coefficient of thermal expansion in the thickness direction at a heating rate of 2'C/m.
jn, and was determined from the amount of change from 50'C to 200'C.
硬化時の体積収縮率は、硬化時の固形の比重と硬化後の
比重差から求めた。曲げ強度は積層板を２５Ｘ５０ｍｍ
に切断し支点間距離３０ｍｍ、曲げ強度１ｍｍ／ｍｉｎ
の条件で室温、１８０°Ｃで測定した。The volume shrinkage rate during curing was determined from the difference between the specific gravity of the solid at the time of curing and the specific gravity after curing. The bending strength of the laminated board is 25 x 50 mm.
Cut to 30mm distance between fulcrums, bending strength 1mm/min
Measurements were made at room temperature and 180°C under the following conditions.
比誘電率の測定はＪＩＳ Ｃ６４８１に準じて行い周波
数ＩＭＨｚの静電容量を測定して比誘電率を求めた。The relative permittivity was measured in accordance with JIS C6481, and the capacitance at a frequency of IMHz was measured to determine the relative permittivity.
その他、半田耐熱性、曲げ特性ＪＩＳ Ｃ６４８１に準
じて行い、半田耐熱性は２６０°Ｃ１３００秒で外観の
異常の有無を調べた。In addition, soldering heat resistance and bending properties were conducted according to JIS C6481, and the soldering heat resistance was checked for abnormalities in appearance at 260° C. for 1300 seconds.
離燃性はＵ Ｌ −９４垂直法に準じて測定を行った。The flammability was measured according to the UL-94 vertical method.
熱衝撃試験は一６０°Ｃから＋１２５“Ｃを１サイクル
（−ｆ−）として、クランクの入るまでのサイクルを測
定した。In the thermal shock test, one cycle (-f-) was from -60°C to +125"C, and the cycles until cranking were measured.
本発明における樹脂組成物は硬化時の体積収縮率が従来
の低誘電率の樹脂組成物（比較例２）に比べて小さく成
型性が良好である。The resin composition of the present invention has a smaller volume shrinkage rate during curing than a conventional low dielectric constant resin composition (Comparative Example 2) and has good moldability.
又本発明における樹脂組成物を用いた積層材料は低誘電
率材料として一般的に知られているポリブタジェン系材
料と同様、低誘電率特性を有し、現在、大型計算機の多
層プリント板に適用されているエポキシ系材料やポリイ
ミド系材料に比べ比誘電率４．７から３，５付近にでき
ることから信号伝送遅延時間を１５％低減できる。Furthermore, the laminated material using the resin composition of the present invention has a low dielectric constant characteristic similar to the polybutadiene material which is generally known as a low dielectric constant material, and is currently being applied to multilayer printed boards for large computers. Compared to epoxy-based materials and polyimide-based materials, the dielectric constant can be reduced from 4.7 to around 3.5, reducing signal transmission delay time by 15%.
更に、多層プリント回路板を本発明の樹脂組成物を用い
て製造することによって、熱衝撃特性の優れた基板を得
ることができる。Furthermore, by manufacturing a multilayer printed circuit board using the resin composition of the present invention, a board with excellent thermal shock properties can be obtained.
（発明の効果）
本発明によれば均質な樹脂組成物が得られ、しかもその
成形物の収縮率を小さくでき、耐クラツク性が良好で、
耐熱性、難燃性の低誘電率積層板を提供することが可能
となった。(Effects of the Invention) According to the present invention, a homogeneous resin composition can be obtained, and the shrinkage rate of the molded product can be reduced, and the crack resistance is good.
It has become possible to provide a heat-resistant, flame-retardant, low dielectric constant laminate.
第１図は本発明の一実施例である多層プリント回路板の
断面斜視図である。FIG. 1 is a cross-sectional perspective view of a multilayer printed circuit board according to an embodiment of the present invention.
符号の説明 １ 基板 ２ 回路導体 ３ プリプレグシート ４ スルーホール第１図Explanation of symbols 1. Board 2. Circuit conductor 3 Prepreg sheet 4 Through hole Diagram 1
Claims (1)
ケニル基、アルケノイル基であり、ｍは１〜４）で示さ
れる繰返し単位からなるポリ（ｐ−ヒドロキシスチレン
）誘導体のプレポリマと、（ｂ）エポキシ変性ポリブタ
ジエンと、 （ｃ）芳香族マレイミド化合物と、 （ｄ）１，３−ジ−オルトトリルグアニジンを必須成分
として含有することを特徴とする熱硬化性樹脂組成物。 ２、前記（ａ）（ｐ−ヒドロキシスチレン）誘導体のプ
レポリマが１０〜６０重量％ （ｂ）エポキシ変性ポリブタジエンが１０〜６０重量％ （ｃ）芳香族マレイミド化合物が２０〜７０重量％ （ｄ）１，３−ジ−オルトトリルグアニジンがエポキシ
基１当量に対し、０．３〜１．５当量である請求項１に
記載の熱硬化性樹脂組成 物。 ３、前記（ａ）（ｐ−ヒドロキシスチレン）誘導体のプ
レポリマが２０〜４０重量％ （ｂ）エポキシ変性ポリブタジエンが１０〜３０重量％ （ｃ）芳香族マレイミド化合物が３０〜６０重量％ （ｄ）１，３−ジ−オルトトリルグアニジンがエポキシ
基１当量に対し、０．５〜１．２当量である請求項１に
記載の熱硬化性樹脂組成 物。 ４、（ａ）一般式 ▲数式、化学式、表等があります▼（１） （式中Ａは、ハロゲン基、Ｒ＿１は炭素数２〜４のアル
ケニル基、アルケノイル基であり、ｍは１〜４）で示さ
れる繰返し単位からなるポリ（ｐ−ヒドロキシスチレン
）誘導体のプレポリマと、（ｂ）一般式 ▲数式、化学式、表等があります▼（２） （式中Ｂはグリシジルエーテル系エポキシのコポリマ、
ｎは整数）で示されるエポキシ変性ポリブタジエンと、 （ｃ）一般式 ▲数式、化学式、表等があります▼（３） （式中Ｒ＿２は少なくともベンゼン環を１個以上含む芳
香族基、ｎは１〜４）で示される芳香族マレイミド化合
物 （ｄ）１，３−ジ−オルトトリルグアニジンを含むこと
を特徴とする熱硬化性樹脂組成物。 ５、前記（ａ）（ｐ−ヒドロキシスチレン）誘導体のプ
レポリマが１０〜６０重量％ （ｂ）エポキシ変性ポリブタジエンが１０〜６０重量％ （ｃ）芳香族マレイミド化合物が２０〜７０重量％ （ｄ）１，３−ジ−オルトトリルグアニジンがエポキシ
基合物１当量に対し、０．３〜１．５当量である請求項
４に記載の熱硬化性樹脂 組成物。 ６、前記（ａ）（ｐ−ヒドロキシスチレン）誘導体のプ
レポリマが２０〜４０重量％ （ｂ）エポキシ変性ポリブタジエンが１０〜３０重量％ （ｃ）芳香族マレイミド化合物が３０〜６０重量％ （ｄ）１，３−ジ−オルトトリルグアニジンがエポキシ
基１当量に対し、０．５〜１．２当量である請求項４に
記載の熱硬化性樹脂組成 物。 ７、繊維質基材に、（ａ）一般式 ▲数式、化学式、表等があります▼（１） （式中Ａは、ハロゲン基、Ｒ＿１は炭素数２〜４のアル
ケニル基、アルケノイル基であり、ｍは１〜４）で示さ
れる繰返し単位からなるポリ（ｐ−ヒドロキシスチレン
）誘導体のプレポリマと、（ｂ）エポキシ変性ポリブタ
ジエンと、 （ｃ）芳香族マレイミド化合物と、 （ｄ）１，３−ジ−オルトトリルグアニジンとからなる
熱硬化性樹脂を含有してなるプリプレグ。 ８、前記（ａ）（ｐ−ヒドロキシスチレン）誘導体のプ
レポリマが１０〜６０重量％ （ｂ）エポキシ変性ポリブタジエンが１０〜６０重量％ （ｃ）芳香族マレイミド化合物が２０〜７０重量％ （ｄ）１，３−ジ−オルトトリルグアニジンがエポキシ
基１当量に対し、０．３〜１．５当量である請求項７に
記載のプリプレグ。 ９、前記（ａ）（ｐ−ヒドロキシスチレン）誘導体のプ
レポリマが２０〜４０重量％ （ｂ）エポキシ変性ポリブタジエンが１０〜３０重量％ （ｃ）芳香族マレイミド化合物が３０〜６０重量％ （ｄ）１，３−ジ−オルトトリルグアニジンがエポキシ
基１当量に対し、０．５〜１．０当量である請求項７に
記載のプリプレグ。 １０、繊維質基材、（ａ）一般式 ▲数式、化学式、表等があります▼（１） （式中Ａは、ハロゲン基、Ｒ＿１は炭素数２〜４のアル
ケニル基、アルケノイル基であり、ｍは１〜４）で示さ
れる繰返し単位からなるポリ（ｐ−ヒドロキシスチレン
）誘導体のプレポリマと、（ｂ）一般式 ▲数式、化学式、表等があります▼（２） （式中Ｂはグリシジルエーテル系エポキシのコポリマ、
ｎは整数）で示されるエポキシ変性ポリブタジエンと、 （ｃ）一般式 ▲数式、化学式、表等があります▼（３） （式中Ｒ＿２は少なくともベンゼン環を１個以上含む芳
香族基、ｎは１〜４）で示される芳香族マレイミド化合
物と、 （ｄ）１，３−ジ−オルトトリルグアニジンとからなる
熱硬化性樹脂を含有してなるプリプレグ。 １１、前記（ａ）（ｐ−ヒドロキシスチレン）誘導体の
プレポリマが１０〜６０重量％ （ｂ）エポキシ変性ポリブタジエンが１０〜６０重量％ （ｃ）芳香族マレイミド化合物が２０〜７０重量％ （ｄ）１，３−ジ−オルトトリルグアニジンがエポキシ
基１当量に対し、０．３〜１．５当量である請求項１０
に記載のプリプレグ。 １２、前記（ａ）（ｐ−ヒドロキシスチレン）誘導体の
プレポリマが２０〜４０重量％ （ｂ）エポキシ変性ポリブタジエンが１０〜３０重量％ （ｃ）芳香族マレイミド化合物が３０〜６０重量％ （ｄ）１，３−ジ−オルトトリルグアニジンがエポキシ
化合物１当量に対し、０．５〜１．２当量である請求項
１０記載のプリプレグ。 １３、繊維質基材に、（ａ）一般式 ▲数式、化学式、表等があります▼（１） （式中Ａは、ハロゲン基、Ｒ＿１は炭素数２〜４のアル
ケニル基、アルケノイル基であり、ｍは１〜４）で示さ
れる繰返し単位からなるポリ（ｐ−ヒドロキシスチレン
）誘導体のプレポリマと、（ｂ）エポキシ変性ポリブタ
ジエンと、 （ｃ）芳香族マレイミド化合物と、 （ｄ）１，３−ジ−オルトトリルグアニジンとからなる
熱硬化性樹脂を含有してなるプリプレグが積層成形され
た積層板。[Claims] 1. (a) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (1) (In the formula, A is a halogen group, and R_1 is an alkenyl group or an alkenoyl group having 2 to 4 carbon atoms. , m is 1 to 4)); (b) epoxy-modified polybutadiene; (c) aromatic maleimide compound; (d) 1,3- A thermosetting resin composition containing di-orthotolylguanidine as an essential component. 2. (a) Prepolymer of (p-hydroxystyrene) derivative is 10 to 60% by weight (b) Epoxy-modified polybutadiene is 10 to 60% by weight (c) Aromatic maleimide compound is 20 to 70% by weight (d) 1 , 3-di-orthotolylguanidine in an amount of 0.3 to 1.5 equivalents per equivalent of the epoxy group. 3. (a) Prepolymer of (p-hydroxystyrene) derivative is 20 to 40% by weight (b) Epoxy-modified polybutadiene is 10 to 30% by weight (c) Aromatic maleimide compound is 30 to 60% by weight (d) 1 , 3-di-orthotolylguanidine in an amount of 0.5 to 1.2 equivalents per equivalent of the epoxy group. 4. (a) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (1) (In the formula, A is a halogen group, R_1 is an alkenyl group or alkenoyl group having 2 to 4 carbon atoms, and m is 1 to 4 ) A prepolymer of a poly(p-hydroxystyrene) derivative consisting of repeating units represented by
(c) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (3) (In the formula, R_2 is an aromatic group containing at least one benzene ring, n is 1 -4) A thermosetting resin composition comprising an aromatic maleimide compound (d) 1,3-di-orthotolylguanidine. 5. (a) Prepolymer of (p-hydroxystyrene) derivative is 10 to 60% by weight (b) Epoxy-modified polybutadiene is 10 to 60% by weight (c) Aromatic maleimide compound is 20 to 70% by weight (d) 1 5. The thermosetting resin composition according to claim 4, wherein the amount of 3-di-orthotolylguanidine is 0.3 to 1.5 equivalents per equivalent of the epoxy group compound. 6. (a) Prepolymer of (p-hydroxystyrene) derivative is 20-40% by weight (b) Epoxy-modified polybutadiene is 10-30% by weight (c) Aromatic maleimide compound is 30-60% by weight (d) 1 5. The thermosetting resin composition according to claim 4, wherein the amount of 3-di-orthotolylguanidine is 0.5 to 1.2 equivalents per equivalent of epoxy group. 7. For the fibrous base material, (a) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (1) (In the formula, A is a halogen group, R_1 is an alkenyl group or an alkenoyl group having 2 to 4 carbon atoms. , m is 1 to 4)); (b) epoxy-modified polybutadiene; (c) aromatic maleimide compound; (d) 1,3- A prepreg containing a thermosetting resin consisting of di-orthotolylguanidine. 8. (a) Prepolymer of (p-hydroxystyrene) derivative is 10 to 60% by weight (b) Epoxy-modified polybutadiene is 10 to 60% by weight (c) Aromatic maleimide compound is 20 to 70% by weight (d) 1 8. The prepreg according to claim 7, wherein the amount of 3-di-orthotolylguanidine is 0.3 to 1.5 equivalents per equivalent of the epoxy group. 9. (a) Prepolymer of (p-hydroxystyrene) derivative is 20 to 40% by weight (b) Epoxy-modified polybutadiene is 10 to 30% by weight (c) Aromatic maleimide compound is 30 to 60% by weight (d) 1 8. The prepreg according to claim 7, wherein the amount of 3-di-orthotolylguanidine is 0.5 to 1.0 equivalent per equivalent of epoxy group. 10. Fibrous base material, (a) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (1) (In the formula, A is a halogen group, R_1 is an alkenyl group or alkenoyl group having 2 to 4 carbon atoms, m is a prepolymer of poly(p-hydroxystyrene) derivative consisting of repeating units represented by 1 to 4), and (b) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (2) (In the formula, B is glycidyl ether copolymers of epoxies,
(c) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (3) (In the formula, R_2 is an aromatic group containing at least one benzene ring, n is 1 A prepreg containing a thermosetting resin consisting of an aromatic maleimide compound represented by ~4) and (d) 1,3-di-orthotolylguanidine. 11. (a) Prepolymer of (p-hydroxystyrene) derivative is 10 to 60% by weight (b) Epoxy-modified polybutadiene is 10 to 60% by weight (c) Aromatic maleimide compound is 20 to 70% by weight (d) 1 , 3-di-orthotolylguanidine in an amount of 0.3 to 1.5 equivalents per equivalent of the epoxy group.
The prepreg described in . 12. (a) Prepolymer of (p-hydroxystyrene) derivative is 20 to 40% by weight (b) Epoxy-modified polybutadiene is 10 to 30% by weight (c) Aromatic maleimide compound is 30 to 60% by weight (d) 1 11. The prepreg according to claim 10, wherein the amount of ,3-di-orthotolylguanidine is 0.5 to 1.2 equivalents per equivalent of the epoxy compound. 13. In the fibrous base material, (a) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (1) (In the formula, A is a halogen group, R_1 is an alkenyl group or an alkenoyl group having 2 to 4 carbon atoms. , m is 1 to 4)); (b) epoxy-modified polybutadiene; (c) aromatic maleimide compound; (d) 1,3- A laminate plate formed by laminating and molding prepregs containing a thermosetting resin consisting of di-orthotolylguanidine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP398289A JPH02185517A (en) | 1989-01-11 | 1989-01-11 | Thermosetting resin composition and prepreg and laminate prepared therefrom |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP398289A JPH02185517A (en) | 1989-01-11 | 1989-01-11 | Thermosetting resin composition and prepreg and laminate prepared therefrom |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02185517A true JPH02185517A (en) | 1990-07-19 |
Family
ID=11572243
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP398289A Pending JPH02185517A (en) | 1989-01-11 | 1989-01-11 | Thermosetting resin composition and prepreg and laminate prepared therefrom |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02185517A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006225484A (en) * | 2005-02-16 | 2006-08-31 | Murata Mfg Co Ltd | Composite dielectric material and electronic component |
| WO2008041453A1 (en) * | 2006-09-29 | 2008-04-10 | Hitachi Chemical Company, Ltd. | Thermosetting resin composition and prepreg and laminate obtained with the same |
| JP2010248495A (en) * | 2009-03-27 | 2010-11-04 | Hitachi Chem Co Ltd | Thermosetting insulating resin composition, and insulating film with support, prepreg, laminate plate and multilayer printed wiring board using the same |
-
1989
- 1989-01-11 JP JP398289A patent/JPH02185517A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006225484A (en) * | 2005-02-16 | 2006-08-31 | Murata Mfg Co Ltd | Composite dielectric material and electronic component |
| WO2008041453A1 (en) * | 2006-09-29 | 2008-04-10 | Hitachi Chemical Company, Ltd. | Thermosetting resin composition and prepreg and laminate obtained with the same |
| US9603244B2 (en) | 2006-09-29 | 2017-03-21 | Hitachi Chemical Company, Ltd | Thermosetting resin composition and prepreg and laminate obtained with the same |
| JP2010248495A (en) * | 2009-03-27 | 2010-11-04 | Hitachi Chem Co Ltd | Thermosetting insulating resin composition, and insulating film with support, prepreg, laminate plate and multilayer printed wiring board using the same |
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