JP5030297B2 - Laminate resin composition, prepreg and laminate - Google Patents
Laminate resin composition, prepreg and laminate Download PDFInfo
- Publication number
- JP5030297B2 JP5030297B2 JP2008128246A JP2008128246A JP5030297B2 JP 5030297 B2 JP5030297 B2 JP 5030297B2 JP 2008128246 A JP2008128246 A JP 2008128246A JP 2008128246 A JP2008128246 A JP 2008128246A JP 5030297 B2 JP5030297 B2 JP 5030297B2
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- Japan
- Prior art keywords
- resin
- formula
- resin composition
- parts
- polymaleimide
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 32
- 229920005989 resin Polymers 0.000 claims abstract description 60
- 239000011347 resin Substances 0.000 claims abstract description 60
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 19
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 13
- 238000004132 cross linking Methods 0.000 claims abstract description 10
- -1 amine compound Chemical class 0.000 claims description 37
- 239000003822 epoxy resin Substances 0.000 claims description 36
- 229920000647 polyepoxide Polymers 0.000 claims description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 239000004643 cyanate ester Substances 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000000835 fiber Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 4
- 239000012783 reinforcing fiber Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 51
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 48
- 239000000243 solution Substances 0.000 description 39
- 238000002360 preparation method Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 18
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 15
- 150000002989 phenols Chemical class 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 14
- 230000000704 physical effect Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 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 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 11
- 238000001723 curing Methods 0.000 description 11
- 238000005227 gel permeation chromatography Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- AHZMUXQJTGRNHT-UHFFFAOYSA-N [4-[2-(4-cyanatophenyl)propan-2-yl]phenyl] cyanate Chemical compound C=1C=C(OC#N)C=CC=1C(C)(C)C1=CC=C(OC#N)C=C1 AHZMUXQJTGRNHT-UHFFFAOYSA-N 0.000 description 10
- 150000004982 aromatic amines Chemical class 0.000 description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 150000001299 aldehydes Chemical class 0.000 description 8
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 150000001448 anilines Chemical class 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- 150000002576 ketones Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920003192 poly(bis maleimide) Polymers 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 238000013329 compounding Methods 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
- 238000010438 heat treatment Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000010533 azeotropic distillation Methods 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 3
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000003799 water insoluble solvent Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical class O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 2
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical group C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 2
- IYSVFZBXZVPIFA-UHFFFAOYSA-N 1-ethenyl-4-(4-ethenylphenyl)benzene Chemical group C1=CC(C=C)=CC=C1C1=CC=C(C=C)C=C1 IYSVFZBXZVPIFA-UHFFFAOYSA-N 0.000 description 2
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical class C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- CZZZABOKJQXEBO-UHFFFAOYSA-N 2,4-dimethylaniline Chemical compound CC1=CC=C(N)C(C)=C1 CZZZABOKJQXEBO-UHFFFAOYSA-N 0.000 description 2
- VOWZNBNDMFLQGM-UHFFFAOYSA-N 2,5-dimethylaniline Chemical compound CC1=CC=C(C)C(N)=C1 VOWZNBNDMFLQGM-UHFFFAOYSA-N 0.000 description 2
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 2
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- MLPVBIWIRCKMJV-UHFFFAOYSA-N 2-ethylaniline Chemical compound CCC1=CC=CC=C1N MLPVBIWIRCKMJV-UHFFFAOYSA-N 0.000 description 2
- DOLQYFPDPKPQSS-UHFFFAOYSA-N 3,4-dimethylaniline Chemical compound CC1=CC=C(N)C=C1C DOLQYFPDPKPQSS-UHFFFAOYSA-N 0.000 description 2
- MKARNSWMMBGSHX-UHFFFAOYSA-N 3,5-dimethylaniline Chemical compound CC1=CC(C)=CC(N)=C1 MKARNSWMMBGSHX-UHFFFAOYSA-N 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- UFERIGCCDYCZLN-UHFFFAOYSA-N 3a,4,7,7a-tetrahydro-1h-indene Chemical compound C1C=CCC2CC=CC21 UFERIGCCDYCZLN-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- HRXZRAXKKNUKRF-UHFFFAOYSA-N 4-ethylaniline Chemical compound CCC1=CC=C(N)C=C1 HRXZRAXKKNUKRF-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical class OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical class O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical class OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 150000003935 benzaldehydes Chemical class 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- DMVOXQPQNTYEKQ-UHFFFAOYSA-N biphenyl-4-amine Chemical group C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Chemical class O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 2
- 229940117916 cinnamic aldehyde Drugs 0.000 description 2
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical class C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 2
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Chemical class CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 150000005205 dihydroxybenzenes Chemical class 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical class C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 description 2
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical class O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- QMTFKWDCWOTPGJ-KVVVOXFISA-N (z)-octadec-9-enoic acid;tin Chemical compound [Sn].CCCCCCCC\C=C/CCCCCCCC(O)=O QMTFKWDCWOTPGJ-KVVVOXFISA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
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- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004002 naphthaldehydes Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- LRTFPLFDLJYEKT-UHFFFAOYSA-N para-isopropylaniline Chemical compound CC(C)C1=CC=C(N)C=C1 LRTFPLFDLJYEKT-UHFFFAOYSA-N 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N phenyl propionaldehyde Natural products CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 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
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
本発明は、積層板用樹脂組成物、それを強化繊維に含浸させたプリプレグ、積層板用樹脂組成物の硬化物と強化繊維から構成される積層板（プリント配線板やビルドアップ積層板などの電気・電子部品用積層板）に関する。 The present invention relates to a resin composition for a laminate, a prepreg impregnated with a reinforcing fiber, a laminate comprising a cured product of the resin composition for a laminate and a reinforcing fiber (such as a printed wiring board or a build-up laminate). Laminates for electrical and electronic components).
近年、電気・電子部品を搭載する積層板はその利用分野の拡大により、要求特性が広範かつ高度化している。例えば従来、半導体チップは金属製のリードフレームに搭載することが主流であったが、ＣＰＵなどの高度な処理能力のある半導体チップは高分子材料で作られる積層板に搭載されることが多くなっている。ＣＰＵ等の素子の高速化が進みクロック周波数が高くなるにつれ、信号伝搬遅延や伝送損失が問題となり、配線板に低誘電率化、低誘電正接化が求められるようになっている。同時に素子の高速化に伴い、チップの発熱が大きくなっているため耐熱性を高める必要も生じている。また、近年携帯電話などのモバイル電子機器が普及してきており、精密電子機器が屋外環境や人体の極近傍で使用・携帯されるようになってきているため、外的環境（特に耐湿熱）に対する耐性が必要とされる。更に自動車分野においては急速に電子化が進み、エンジン近くに精密電子機器が配置されることもあり耐熱・耐湿性がより高いレベルで要求されるようになっている。一方自動車用途や携帯機器などに用いられる為、難燃性等の安全性もよりいっそう重要となっているが、近年の環境問題意識の向上によりハロゲン系の難燃剤を使用することが忌避されてきており、ハロゲンを使用しないで難燃性を付与する必要が増している。
従来、例えば特許文献１のようなビスフェノールＡ型シアネートエステル化合物とビスマレイミド化合物を併用した樹脂であるＢＴレジンを使用した配線板が耐熱性や耐薬品、電気特性などに優れており、高性能配線板として幅広く使用されてきたが、上記のように更なる高性能を要求される状況下において改善が必要となっている。
In recent years, the required characteristics of a laminated board on which electric / electronic components are mounted have been widened and advanced with the expansion of the field of use. For example, in the past, semiconductor chips were mainly mounted on metal lead frames, but semiconductor chips with high processing capability such as CPUs are often mounted on laminates made of polymer materials. ing. As the speed of elements such as CPUs increases and the clock frequency increases, signal propagation delay and transmission loss become a problem, and the wiring board is required to have a low dielectric constant and a low dielectric loss tangent. At the same time, as the device speed increases, the heat generated by the chip has increased, and it has become necessary to increase the heat resistance. In recent years, mobile electronic devices such as mobile phones have become widespread, and precision electronic devices have been used and carried in the outdoor environment and in the immediate vicinity of the human body, so that they can withstand external environments (especially moisture and heat resistance). Tolerance is required. Furthermore, in the automobile field, computerization is rapidly progressing, and precision electronic devices are arranged near the engine, so that a higher level of heat resistance and moisture resistance is required. On the other hand, since it is used for automobiles and portable devices, safety such as flame retardancy is even more important, but the use of halogenated flame retardants has been avoided due to the recent increase in awareness of environmental issues. Therefore, there is an increasing need to impart flame retardancy without using halogen.
Conventionally, for example, a wiring board using BT resin, which is a resin in which a bisphenol A-type cyanate ester compound and a bismaleimide compound are used together as described in Patent Document 1, is excellent in heat resistance, chemical resistance, electrical characteristics, and the like. Although it has been widely used as a plate, it needs to be improved in a situation where higher performance is required as described above.
本発明は耐熱性、低吸湿性、低誘電特性、難燃性に優れた硬化物及び積層板を得ることができる積層板用樹脂組成物を提供する。 The present invention provides a resin composition for laminates that can provide cured products and laminates excellent in heat resistance, low moisture absorption, low dielectric properties, and flame retardancy.
本発明者らは上記課題を解決するために鋭意研究した結果、本発明を完成させるに到った。 As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
すなわち本発明は
（１）下記式（１）
That is, the present invention provides (1) the following formula (1)
（式中、複数存在するＲはそれぞれ独立して存在し、水素原子、炭素数１〜５のアルキル基もしくはフェニル基を表す。ｎは平均値であり１＜ｎ≦５を表す。）で表されるポリマレイミド樹脂及びポリマレイミド樹脂と架橋反応可能な化合物を含有する積層板用樹脂組成物、
（２）ポリマレイミド樹脂と架橋反応可能な化合物が、（Ａ）アミン化合物及び／又は（Ｂ）シアネートエステル化合物である前項（１）記載の積層板用樹脂組成物、
（３）ポリマレイミド樹脂と架橋可能な化合物が下記式（２）
(In the formula, a plurality of Rs are present independently and each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group. N is an average value and 1 <n ≦ 5). A laminated male resin composition comprising a polymaleimide resin and a compound capable of crosslinking reaction with the polymaleimide resin,
(2) The resin composition for laminates according to (1) above, wherein the compound capable of undergoing a crosslinking reaction with the polymaleimide resin is (A) an amine compound and / or (B) a cyanate ester compound.
(3) A compound capable of crosslinking with polymaleimide resin is represented by the following formula (2)
（式中、複数存在するＲはそれぞれ独立して存在し、水素原子、炭素数１〜５のアルキル基もしくはフェニル基を表す。ｎは平均値であり１＜ｎ≦５を表す。）及び／又は下記式（３） (Wherein a plurality of R's are present independently and each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group. N is an average value and 1 <n ≦ 5) and / or Or the following formula (3)
（式中、複数存在するＲはそれぞれ独立して存在し、水素原子、炭素数１〜５のアルキル基もしくはフェニル基を表す。ｎは平均値であり１＜ｎ≦１０を表す。）である前項（２）記載の積層板用樹脂組成物、
（４）更に（Ｃ）エポキシ樹脂を含有する前項（１）記載の積層板用樹脂組成物、
（５）（Ｃ）エポキシ樹脂が下記式（４）
(Wherein a plurality of R's are present independently and each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group. N is an average value and 1 <n ≦ 10). The resin composition for laminates as described in (2) above,
(4) The resin composition for laminates according to (1) above, further comprising (C) an epoxy resin,
(5) (C) Epoxy resin is represented by the following formula (4)
（式中、複数存在するＲはそれぞれ独立して存在し、水素原子、炭素数１〜５のアルキル基もしくはフェニル基を表す。ｎは平均値であり１＜ｎ≦２０を表す。）である前項（４）記載の積層板用樹脂組成物、
（６）下記式（５）
(Wherein a plurality of R's are present independently and each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group. N is an average value and 1 <n ≦ 20). The resin composition for laminates as described in (4) above,
(6) Following formula (5)
（式中、複数存在するＲはそれぞれ独立して存在し、水素原子、炭素数１〜５のアルキル基もしくはフェニル基を表す。ｎは平均値であり１＜ｎ≦２０を表す。）で表されるエポキシ樹脂硬化剤を含有する前項（４）又は（５）記載の積層板用樹脂組成物、
（７）前項（１）〜（６）のいずれか１項に記載の積層板用樹脂組成物を繊維基材に含浸してなるプリプレグ、
（８）前項（１）〜（６）のいずれか１項に記載の積層板用樹脂組成物の硬化物と強化繊維を含む積層板、
を提供するものである。
(In the formula, a plurality of R's are present independently and each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group. N is an average value and 1 <n ≦ 20). The resin composition for laminates as described in (4) or (5) above, which contains an epoxy resin curing agent to be produced,
(7) A prepreg formed by impregnating a fiber base material with the resin composition for laminates according to any one of (1) to (6) above,
(8) A laminate comprising a cured product of the resin composition for laminates according to any one of (1) to (6) and reinforcing fibers,
Is to provide.
本発明の積層板用樹脂組成物はその硬化物において高耐熱性、低吸湿性、低誘電特性、難燃性に優れた特性を併せ持つため、プリント配線板やビルドアップ基板などの積層板を作成するのに極めて有用な材料である。 Since the resin composition for laminated boards of the present invention has excellent heat resistance, low moisture absorption, low dielectric properties, and excellent flame retardancy in the cured product, laminates such as printed wiring boards and build-up boards are created. It is a very useful material.
本発明の積層板用樹脂組成物は、式（１）のポリマレイミド樹脂を必須成分として含有する。 The resin composition for laminated boards of this invention contains the polymaleimide resin of Formula (1) as an essential component.
式（１）の化合物の製法は特に限定されず、マレイミド化合物合成法として公知のいかなる方法で製造しても良い。
式（１）の化合物の前駆体として式（２）の化合物が必要となるが、例えば特許文献２及び３にはアニリン類とジハロゲノメチル化合物やジアルコキシメチル化合物との反応が記載されているが、これらと同様の方法を採用してアニリン類とビスハロゲノメチルビフェニル類またはビスアルコキシメチルビフェニル類とを反応させることにより式（２）の化合物が得られる。式（２）の化合物の製造に使用されるアニリン類としては、アニリン、２−メチルアニリン、３−メチルアニリン、４−メチルアニリン、２−エチルアニリン、３−エチルアニリン、４−エチルアニリン、２，３−ジメチルアニリン、２，４−ジメチルアニリン、２，５−ジメチルアニリン、２，６−ジメチルアニリン、３，４−ジメチルアニリン、３，５−ジメチルアニリン、２−プロピルアニリン、３−プロピルアニリン、４−プロピルアニリン、２−イソプロピルアニリン、３−イソプロピルアニリン、４−イソプロピルアニリン、２−エチル−６−メチルアニリン、２−ｓｅｃ−ブチルアニリン、２−ｔｅｒｔ−ブチルアニリン、４−ブチルアニリン、４−ｓｅｃ−ブチルアニリン、４−ｔｅｒｔ−ブチルアニリン、２，６−ジエチルアニリン、２−イソプロピル−６−メチルアニリン、４−ペンチルアニリン等の炭素数１〜５のアルキル基を単数又は複数有するアルキル置換アニリン、２−アミノビフェニル、４−アミノビフェニル等のフェニル基を有するフェニルアニリンなどが挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。
使用されるビスハロゲノメチルビフェニル類またはビスアルコキシメチルビフェニル類としては、４，４´−ビス（クロロメチル）ビフェニル、４，４´−ビス（ブロモメチル）ビフェニル、４，４´−ビス（フルオロメチル）ビフェニル、４，４´−ビス（ヨードメチル）ビフェニル、４，４´−ジメトキシメチルビフェニル、４，４´−ジエトキシメチルビフェニル、４，４´−ジプロポキシメチルビフェニル、４，４´−ジイソプロポキシメチルビフェニル、４，４´−ジイソブトキシメチルビフェニル、４，４´−ジブトキシメチルビフェニル、４，４´−ジ−ｔｅｒｔ−ブトキシメチルビフェニルなどが挙げられる。これらは単独で用いてもよく、２種以上併用してもよい。ビスハロゲノメチルビフェニル類またはビスアルコキシメチルビフェニル類の使用量は、使用されるアニリン類１モルに対して０．０５〜０．８モル、好ましくは０．１〜０．６モルである。
The production method of the compound of the formula (1) is not particularly limited, and may be produced by any method known as a maleimide compound synthesis method.
Although the compound of Formula (2) is required as a precursor of the compound of Formula (1), for example, Patent Documents 2 and 3 describe reactions of anilines with dihalogenomethyl compounds and dialkoxymethyl compounds. However, a compound of the formula (2) can be obtained by reacting anilines with bishalogenomethylbiphenyls or bisalkoxymethylbiphenyls by employing the same method as these. Examples of anilines used for the production of the compound of formula (2) include aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, 2 , 3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 2-propylaniline, 3-propylaniline 4-propylaniline, 2-isopropylaniline, 3-isopropylaniline, 4-isopropylaniline, 2-ethyl-6-methylaniline, 2-sec-butylaniline, 2-tert-butylaniline, 4-butylaniline, 4 -Sec-butylaniline, 4-tert-butylaniline, 2,6-diethi An alkyl-substituted aniline having one or more alkyl groups having 1 to 5 carbon atoms such as aniline, 2-isopropyl-6-methylaniline, 4-pentylaniline, phenyl having a phenyl group such as 2-aminobiphenyl, 4-aminobiphenyl, etc. Examples include aniline. These may be used alone or in combination of two or more.
Examples of bishalogenomethylbiphenyls or bisalkoxymethylbiphenyls used include 4,4′-bis (chloromethyl) biphenyl, 4,4′-bis (bromomethyl) biphenyl, and 4,4′-bis (fluoromethyl). Biphenyl, 4,4'-bis (iodomethyl) biphenyl, 4,4'-dimethoxymethylbiphenyl, 4,4'-diethoxymethylbiphenyl, 4,4'-dipropoxymethylbiphenyl, 4,4'-diisopropoxy Examples include methyl biphenyl, 4,4′-diisobutoxymethyl biphenyl, 4,4′-dibutoxymethyl biphenyl, 4,4′-di-tert-butoxymethyl biphenyl, and the like. These may be used alone or in combination of two or more. The amount of bishalogenomethylbiphenyls or bisalkoxymethylbiphenyls to be used is 0.05 to 0.8 mol, preferably 0.1 to 0.6 mol, relative to 1 mol of the aniline used.
反応の際、必要により塩酸、燐酸、硫酸、蟻酸、塩化亜鉛、塩化第二鉄、塩化アルミニウム、ｐ−トルエンスルホン酸、メタンスルホン酸等の酸性触媒を使用しても良い。これらは単独でも二種以上併用しても良い。触媒の使用量は、使用されるアニリン類１モルに対して０．１〜０．８モル、好ましくは０．５〜０．７モルであり、多すぎると反応溶液の粘度が高すぎて攪拌が困難になり、少なすぎると反応の進行が遅くなる。
反応は必要によりトルエン、キシレンなどの有機溶剤を使用して行っても、無溶剤で行っても良い。例えば、アニリン類と溶剤の混合溶液に酸性触媒を添加した後、触媒が水を含む場合は共沸により水を系内から除く。しかる後に４０〜１００℃、好ましくは５０〜８０℃でビスハロゲノメチルビフェニル類またはビスアルコキシメチルビフェニル類を１〜５時間、好ましくは２〜４時間かけて添加し、その後溶剤を系内から除きながら昇温して１８０〜２４０℃、好ましくは１９０〜２２０℃で５〜３０時間、好ましくは１０〜２０時間反応を行う。反応終了後、アルカリ水溶液で酸性触媒を中和後、油層に非水溶性有機溶剤を加えて廃水が中性になるまで水洗を繰り返し、加熱減圧下で過剰のアニリン類や有機溶剤を留去することにより式（２）の化合物が得られる。
In the reaction, if necessary, an acidic catalyst such as hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, zinc chloride, ferric chloride, aluminum chloride, p-toluenesulfonic acid, methanesulfonic acid and the like may be used. These may be used alone or in combination of two or more. The amount of the catalyst used is 0.1 to 0.8 mol, preferably 0.5 to 0.7 mol, based on 1 mol of the anilines used. However, if the amount is too small, the reaction progresses slowly.
The reaction may be carried out using an organic solvent such as toluene or xylene, if necessary, or without solvent. For example, after adding an acidic catalyst to a mixed solution of anilines and a solvent, when the catalyst contains water, the water is removed from the system by azeotropic distillation. Thereafter, bishalogenomethylbiphenyls or bisalkoxymethylbiphenyls are added at 40 to 100 ° C., preferably 50 to 80 ° C. over 1 to 5 hours, preferably 2 to 4 hours, and then the solvent is removed from the system. The temperature is raised and the reaction is carried out at 180 to 240 ° C., preferably 190 to 220 ° C. for 5 to 30 hours, preferably 10 to 20 hours. After completion of the reaction, neutralize the acidic catalyst with an aqueous alkaline solution, add a water-insoluble organic solvent to the oil layer and repeat washing with water until the wastewater becomes neutral, and distill off excess anilines and organic solvent under heating and reduced pressure. This gives the compound of formula (2).
式（１）の化合物は式（２）の化合物に無水マレイン酸を溶剤、触媒の存在下に反応させて得られるが、例えば特許文献２や特許文献４に記載の方法等を採用すればよい。反応で使用する溶剤は反応中に生成する水を系内から除去する必要があるため、非水溶性の溶剤を使用する。例えばトルエン、キシレンなどの芳香族溶剤、シクロヘキサン、ｎ−ヘキサンなどの脂肪族溶剤、ジエチルエーテル、ジイソプロピルエーテルなどのエーテル類、酢酸エチル、酢酸ブチルなどのエステル系溶剤、メチルイソブチルケトン、シクロペンタノンなどのケトン系溶剤などが挙げられるがこれらに限定されるものではなく、２種以上を併用しても良い。また、前記非水溶性溶剤に加えて非プロトン性極性溶剤を併用することもできる。例えば、ジメチルスルホン、ジメチルスルホキシド、ジメチルホルムアミド、ジメチルアセトアミド、１，３−ジメチル−２−イミダゾリジノン、Ｎ−メチルピロリドンなどが挙げられ、２種以上を併用しても良い。非プロトン性極性溶剤を使用する場合は、併用する非水溶性溶剤よりも沸点の高いものを使用することが好ましい。触媒は酸性触媒で特に限定されないが、ｐ−トルエンスルホン酸、ヒドロキシ−ｐ−トルエンスルホン酸、メタンスルホン酸、硫酸、リン酸等が挙げられる。
例えばマレイン酸をトルエンに溶解し、撹拌下で式（２）の化合物のＮ−メチルピロリドン溶液を添加し、その後ｐ−トルエンスルホン酸を加えて、還流条件下で生成する水を系内から除去しながら反応を行う。
The compound of the formula (1) is obtained by reacting the compound of the formula (2) with maleic anhydride in the presence of a solvent and a catalyst. For example, the methods described in Patent Document 2 and Patent Document 4 may be employed. . As the solvent used in the reaction, it is necessary to remove water generated during the reaction from the system, and therefore a water-insoluble solvent is used. For example, aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane and n-hexane, ethers such as diethyl ether and diisopropyl ether, ester solvents such as ethyl acetate and butyl acetate, methyl isobutyl ketone, and cyclopentanone However, it is not limited to these, and two or more kinds may be used in combination. In addition to the water-insoluble solvent, an aprotic polar solvent may be used in combination. Examples thereof include dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone and the like, and two or more kinds may be used in combination. When using an aprotic polar solvent, it is preferable to use a solvent having a higher boiling point than the water-insoluble solvent used in combination. The catalyst is an acidic catalyst and is not particularly limited, and examples thereof include p-toluenesulfonic acid, hydroxy-p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, and phosphoric acid.
For example, maleic acid is dissolved in toluene, an N-methylpyrrolidone solution of the compound of formula (2) is added with stirring, and then p-toluenesulfonic acid is added to remove water generated under reflux conditions from the system. While doing the reaction.
式（１）における炭素数１〜５のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、ｉｓｏ−プロピル基、ｎ−ブチル基、ｉｓｏ−ブチル基、ｔｅｒｔ−ブチル基、ｓｅｃ−ブチル基、ｎ−ペンチル基等が挙げられる。また、式（１）のｎの値は、ポリマレイミド樹脂のゲルパーミエーションクロマトグラフィー（ＧＰＣ）の測定により求められた重量平均分子量の値から算出することが出来るが、近似的には原料である式（２）で表されるアミン化合物のＧＰＣの測定結果から算出したｎの値とほぼ同等と考えることが出来る。 Examples of the alkyl group having 1 to 5 carbon atoms in the formula (1) include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, sec-butyl. Group, n-pentyl group and the like. Further, the value of n in the formula (1) can be calculated from the value of the weight average molecular weight determined by gel permeation chromatography (GPC) of the polymaleimide resin, but is approximately a raw material. It can be considered that it is almost equivalent to the value of n calculated from the GPC measurement result of the amine compound represented by the formula (2).
本発明の積層板用樹脂組成物の必須成分であるポリマレイミド樹脂と架橋反応可能な化合物は、式（１）のポリマレイミド樹脂と架橋反応を起こし、ポリマレイミド樹脂の硬化剤として作用する。ポリマレイミド樹脂と架橋反応可能な化合物としては、アミノ基、シアネート基、フェノール性水酸基、アルコール性水酸基、アリル基、アクリル基、メタクリル基、ビニル基、共役ジエン基等ポリマレイミド樹脂と架橋反応し得る官能基（或いは構造）を有する化合物であれば特に限定されないが、耐熱性が必要なときは（Ａ）アミン化合物、誘電特性が必要なときは（Ｂ）シアネートエステル化合物を配合することが好ましい。前記（Ａ）〜（Ｂ）成分の配合量は特に限定されないが、好ましくは重量比でポリマレイミド樹脂の０．１〜１０倍、より好ましくは０．３〜２倍の範囲である。（Ａ）＋（Ｂ）の配合量がポリマレイミド樹脂の０．１倍以下になると耐熱性、誘電特性の向上が充分ではない可能性があり、１０倍以上になると耐熱性、誘電特性が低下してしまう可能性がある。 The compound capable of undergoing a crosslinking reaction with the polymaleimide resin, which is an essential component of the resin composition for laminates of the present invention, causes a crosslinking reaction with the polymaleimide resin of the formula (1) and acts as a curing agent for the polymaleimide resin. Compounds capable of crosslinking with polymaleimide resins include amino groups, cyanate groups, phenolic hydroxyl groups, alcoholic hydroxyl groups, allyl groups, acrylic groups, methacrylic groups, vinyl groups, conjugated diene groups, and other polymaleimide resins. Although it will not specifically limit if it is a compound which has a functional group (or structure), When heat resistance is required, it is preferable to mix | blend (A) amine compound and (B) cyanate ester compound when a dielectric characteristic is required. The blending amount of the components (A) to (B) is not particularly limited, but is preferably in the range of 0.1 to 10 times, more preferably 0.3 to 2 times that of the polymaleimide resin by weight ratio. If the blending amount of (A) + (B) is 0.1 times or less that of polymaleimide resin, the heat resistance and dielectric properties may not be sufficiently improved. There is a possibility that.
配合し得る（Ａ）アミン化合物としては従来公知のアミン化合物を使用することができる。（Ａ）アミン化合物の具体例としては、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ｍ−キシレンジアミン、トリメチルヘキサメチレンジアミン、２−メチルペンタメチレンジアミン、ジエチルアミノプロピルアミン、イソホロンジアミン、１，３−ビスアミノメチルシクロヘキサン、ビス（４−アミノシクロヘキシル）メタン、ビス（４−アミノ−３−メチルシクロヘキシル）メタン、ノルボルネンジアミン、１，２−ジアミノシクロヘキサン、ジアミノジフェニルメタン、メタフェニレンジアミン、ジアミノジフェニルスルホン、ジシアンジアミド、ポリオキシプロピレンジアミン、ポリオキシプロピレントリアミン、Ｎ−アミノエチルピペラジンなどが挙げられるがこれらに限定されるものではない。これらは単独で用いてもよく、２種以上を併用してもよい。 A conventionally known amine compound can be used as the amine compound (A) that can be blended. (A) Specific examples of the amine compound include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylaminopropylamine, isophoronediamine, 1,3- Bisaminomethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane, diaminodiphenylmethane, metaphenylenediamine, diaminodiphenylsulfone, dicyandiamide, Examples include, but are not limited to, polyoxypropylene diamine, polyoxypropylene triamine, and N-aminoethylpiperazine.These may be used alone or in combination of two or more.
また、式（２）で表される、本願のポリマレイミド樹脂の合成の際に中間体として合成されるアミン化合物は、低吸湿性、難燃性、誘電特性に優れているため（Ａ）アミン化合物として特に好ましい。式（２）における炭素数１〜５のアルキル基としては式（１）における炭素数１〜５のアルキル基の説明に記載したものと同じものが挙げられ、また式（２）中のｎの値はアミン化合物のゲルパーミエーションクロマトグラフィー（ＧＰＣ）の測定で求められた重量平均分子量の値から算出することが出来る。
（Ａ）アミン化合物の配合量は特に限定されないが、好ましくは重量比でポリマレイミド樹脂の０．１〜１０倍、より好ましくは０．３〜２倍の範囲である。
In addition, since the amine compound synthesized as an intermediate in the synthesis of the polymaleimide resin of the present invention represented by the formula (2) is excellent in low moisture absorption, flame retardancy, and dielectric properties, (A) amine Particularly preferred as a compound. Examples of the alkyl group having 1 to 5 carbon atoms in the formula (2) include the same as those described in the description of the alkyl group having 1 to 5 carbon atoms in the formula (1), and n in the formula (2) The value can be calculated from the value of the weight average molecular weight determined by gel permeation chromatography (GPC) measurement of the amine compound.
(A) Although the compounding quantity of an amine compound is not specifically limited, Preferably it is 0.1-10 times of polymaleimide resin by weight ratio, More preferably, it is the range of 0.3-2 times.
配合し得る（Ｂ）シアネートエステル化合物としては従来公知のシアネートエステル化合物を使用することができる。（Ｂ）シアネートエステル化合物の具体例としては、フェノール類と各種アルデヒドとの重縮合物、フェノール類と各種ジエン化合物との重合物、フェノール類とケトン類との重縮合物及びビスフェノール類と各種アルデヒドの重縮合物などをハロゲン化シアンと反応させることにより得られるシアネートエステル化合物が挙げられるがこれらに限定されるものではない。これらは単独で用いてもよく２種以上を用いてもよい。 A conventionally well-known cyanate ester compound can be used as (B) cyanate ester compound which can be mix | blended. (B) Specific examples of cyanate ester compounds include polycondensates of phenols and various aldehydes, polymers of phenols and various diene compounds, polycondensates of phenols and ketones, and bisphenols and various aldehydes. The cyanate ester compound obtained by reacting a polycondensate or the like with cyanogen halide is exemplified, but the invention is not limited thereto. These may be used alone or in combination of two or more.
上記フェノール類としては、フェノール、アルキル置換フェノール、芳香族置換フェノール、ナフトール、アルキル置換ナフトール、ジヒドロキシベンゼン、アルキル置換ジヒドロキシベンゼン、ジヒドロキシナフタレン等が挙げられる。 Examples of the phenols include phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, and dihydroxynaphthalene.
上記各種アルデヒドとしては、ホルムアルデヒド、アセトアルデヒド、アルキルアルデヒド、ベンズアルデヒド、アルキル置換ベンズアルデヒド、ヒドロキシベンズアルデヒド、ナフトアルデヒド、グルタルアルデヒド、フタルアルデヒド、クロトンアルデヒド、シンナムアルデヒド等が挙げられる。 Examples of the various aldehydes include formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, and cinnamaldehyde.
上記各種ジエン化合物としては、ジシクロペンタジエン、テルペン類、ビニルシクロヘキセン、ノルボルナジエン、ビニルノルボルネン、テトラヒドロインデン、ジビニルベンゼン、ジビニルビフェニル、ジイソプロペニルビフェニル、ブタジエン、イソプレン等が挙げられる。 Examples of the various diene compounds include dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, and isoprene.
上記ケトン類としてはアセトン、メチルエチルケトン、メチルイソブチルケトン、アセトフェノン、ベンゾフェノン等が挙げられる。 Examples of the ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone.
また、式（３）で表される、特開２００５−２６４１５４号公報（引用文献５）に合成方法が記載されているシアネートエステル化合物は、低吸湿性、難燃性、誘電特性に優れているため（Ｂ）シアネートエステル化合物として特に好ましい。式（３）における炭素数１〜５のアルキル基としては式（１）における炭素数１〜５のアルキル基の説明に記載したものと同じものが挙げられ、また式（３）中のｎの値はシアネートエステル化合物のゲルパーミエーションクロマトグラフィー（ＧＰＣ）の測定で求められた重量平均分子量の値から算出することが出来る。
（Ｂ）シアネートエステル化合物の配合量は特に限定されないが、好ましくは重量比でポリマレイミド樹脂の０．１〜１０倍、より好ましくは０．３〜２倍の範囲である。
Further, the cyanate ester compound represented by the formula (3) and described in Japanese Patent Application Laid-Open No. 2005-264154 (Cited document 5) is excellent in low hygroscopicity, flame retardancy, and dielectric properties. Therefore, it is particularly preferable as the (B) cyanate ester compound. Examples of the alkyl group having 1 to 5 carbon atoms in the formula (3) include the same as those described in the description of the alkyl group having 1 to 5 carbon atoms in the formula (1), and n in the formula (3) The value can be calculated from the value of the weight average molecular weight determined by gel permeation chromatography (GPC) measurement of the cyanate ester compound.
(B) Although the compounding quantity of a cyanate ester compound is not specifically limited, Preferably it is 0.1-10 times of polymaleimide resin by weight ratio, More preferably, it is the range of 0.3-2 times.
配合し得る（Ｃ）エポキシ樹脂としては、従来公知のエポキシ樹脂のいずれも使用することができる。（Ｃ）エポキシ樹脂の具体例としては、フェノール類と各種アルデヒドとの重縮合物、フェノール類と各種ジエン化合物との重合物、フェノール類とケトン類との重縮合物、ビスフェノール類と各種アルデヒドの重縮合物及びアルコール類等をグリシジル化したグリシジルエーテル系エポキシ樹脂、４−ビニル−１−シクロヘキセンジエポキシドや３，４−エポキシシクロヘキシルメチル−３，４´−エポキシシクロヘキサンカルボキシラートなどを代表とする脂環式エポキシ樹脂、テトラグリシジルジアミノジフェニルメタン（ＴＧＤＤＭ）やトリグリシジル−ｐ−アミノフェノールなどを代表とするグリシジルアミン系エポキシ樹脂、グリシジルエステル系エポキシ樹脂等が挙げられるがこれらに限定されるものではない。これらは単独で用いてもよく２種以上を用いてもよい。 Any conventionally known epoxy resin can be used as the epoxy resin (C) that can be blended. (C) Specific examples of epoxy resins include polycondensates of phenols and various aldehydes, polymers of phenols and various diene compounds, polycondensates of phenols and ketones, bisphenols and various aldehydes. Glycidyl ether epoxy resin obtained by glycidylation of polycondensates and alcohols, fats such as 4-vinyl-1-cyclohexene diepoxide and 3,4-epoxycyclohexylmethyl-3,4'-epoxycyclohexanecarboxylate Examples include, but are not limited to, cyclic epoxy resins, glycidyl amine epoxy resins such as tetraglycidyl diaminodiphenylmethane (TGDDM) and triglycidyl-p-aminophenol, and glycidyl ester epoxy resins. These may be used alone or in combination of two or more.
上記フェノール類、各種アルデヒド類、各種ジエン化合物及びケトン類としては、（Ｂ）シアネートエステル化合物の説明に記載したものと同じものが挙げられる。 As said phenols, various aldehydes, various diene compounds, and ketones, the same thing as what was described in description of (B) cyanate ester compound is mentioned.
また、式（４）で表される、フェノールと前記のビスハロゲノメチルビフェニル類またはビスアルコキシメチルビフェニル類とを縮合反応させることにより得られるフェノールアラルキル樹脂を原料とし、エピクロルヒドリンと脱塩酸反応させることにより得られるエポキシ樹脂は、低吸湿性、難燃性、誘電特性に優れているため（Ｃ）エポキシ樹脂として特に好ましい。式（４）における炭素数１〜５のアルキル基としては式（１）における炭素数１〜５のアルキル基の説明に記載したものと同じものが挙げられ、また、式（４）中のｎの値は、エポキシ樹脂のゲルパーミエーションクロマトグラフィー（ＧＰＣ）の測定で求められた重量平均分子量の値から算出することが出来る。
（Ｃ）エポキシ樹脂の配合量は特に限定されないが、好ましくは重量比でポリマレイミド樹脂の０．１〜１０倍、より好ましくは０．３〜２倍の範囲である。（Ｃ）エポキシ樹脂の配合量がポリマレイミド樹脂の０．１倍以下になると硬化物が脆くなる傾向があり、１０倍以上になると耐熱性、誘電特性が低下する。
Also, by using a phenol aralkyl resin represented by the formula (4) obtained by condensation reaction of phenol and the above bishalogenomethylbiphenyls or bisalkoxymethylbiphenyls as a raw material, by dehydrochlorination with epichlorohydrin The obtained epoxy resin is particularly preferable as the (C) epoxy resin because it is excellent in low moisture absorption, flame retardancy, and dielectric properties. Examples of the alkyl group having 1 to 5 carbon atoms in the formula (4) include the same as those described in the description of the alkyl group having 1 to 5 carbon atoms in the formula (1), and n in the formula (4) The value of can be calculated from the value of weight average molecular weight determined by gel permeation chromatography (GPC) measurement of epoxy resin.
(C) Although the compounding quantity of an epoxy resin is not specifically limited, Preferably it is 0.1-10 times of polymaleimide resin by weight ratio, More preferably, it is the range of 0.3-2 times. (C) When the compounding amount of the epoxy resin is 0.1 times or less of the polymaleimide resin, the cured product tends to be brittle, and when it is 10 times or more, the heat resistance and dielectric properties are deteriorated.
エポキシ樹脂を配合する場合、従来公知のエポキシ樹脂硬化剤を併用することができる。併用し得るエポキシ樹脂硬化剤の具体例としては、前記の(Ａ)アミン化合物や、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸などの酸無水物系化合物、ビスフェノール類、フェノール類（フェノール、アルキル置換フェノール、芳香族置換フェノール、ナフトール、アルキル置換ナフトール、ジヒドロキシベンゼン、アルキル置換ジヒドロキシベンゼン、ジヒドロキシナフタレン等）と各種アルデヒド（ホルムアルデヒド、アセトアルデヒド、アルキルアルデヒド、ベンズアルデヒド、アルキル置換ベンズアルデヒド、ヒドロキシベンズアルデヒド、ナフトアルデヒド、グルタルアルデヒド、フタルアルデヒド、クロトンアルデヒド、シンナムアルデヒド等）との重縮合物、フェノール類と各種ジエン化合物（ジシクロペンタジエン、テルペン類、ビニルシクロヘキセン、ノルボルナジエン、ビニルノルボルネン、テトラヒドロインデン、ジビニルベンゼン、ジビニルビフェニル、ジイソプロペニルビフェニル、ブタジエン、イソプレン等）との重合物、フェノール類とケトン類（アセトン、メチルエチルケトン、メチルイソブチルケトン、アセトフェノン、ベンゾフェノン等）との重縮合物、などが挙げられるがこれらに限定されるものではない。これらは単独で用いてもよく、２種以上併用してもよい。これらの配合量は、重量比でエポキシ樹脂の２倍以下、好ましくは１倍以下の範囲である。
また、式（４）のエポキシ樹脂の原料である式（５）で表される化合物は低吸湿、難燃性、誘電特性に優れるためエポキシ樹脂硬化剤として特に好ましい。
When blending an epoxy resin, a conventionally known epoxy resin curing agent can be used in combination. Specific examples of the epoxy resin curing agent that can be used in combination include the (A) amine compound, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, and methyltetrahydrophthalic anhydride. Acid anhydride compounds such as methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, bisphenols, phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene , Alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphtho) Polycondensates with aldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc., phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinyl Biphenyl, diisopropenyl biphenyl, butadiene, isoprene, etc.), and polycondensates of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), etc. Is not to be done. These may be used alone or in combination of two or more. These blending amounts are in the range of 2 times or less, preferably 1 time or less of the epoxy resin in weight ratio.
Further, the compound represented by the formula (5), which is a raw material for the epoxy resin of the formula (4), is particularly preferable as an epoxy resin curing agent because of its excellent low moisture absorption, flame retardancy, and dielectric properties.
本発明の積層板用樹脂組成物には、必要に応じて式（１）のポリマレイミド樹脂以外の公知のマレイミド系化合物を配合することができる。用いうるマレイミド化合物の具体例としては、４，４´−ジフェニルメタンビスマレイミド、ポリフェニルメタンマレイミド、ｍ−フェニレンビスマレイミド、２，２´−ビス〔４−（４−マレイミドフェノキシ）フェニル〕プロパン、３，３´−ジメチル−５，５´−ジエチル−４，４´−ジフェニルメタンビスマレイミド、４−メチル−１，３−フェニレンビスマレイミド、４，４´−ジフェニルエーテルビスマレイミド、４，４´−ジフェニルスルフォンビスマレイミド、１，３−ビス（３−マレイミドフェノキシ）ベンゼン、１，３−ビス（４−マレイミドフェノキシ）ベンゼンなどが挙げられるがこれらに限定されるものではない。これらは単独で用いてもよく、２種以上併用してもよい。マレイミド化合物の配合量は、重量比で式（１）のポリマレイミド樹脂の好ましくは５倍以下、より好ましくは２倍以下の範囲である。 A known maleimide compound other than the polymaleimide resin of the formula (1) can be blended with the resin composition for laminated boards of the present invention as necessary. Specific examples of maleimide compounds that can be used include 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylenebismaleimide, 2,2'-bis [4- (4-maleimidophenoxy) phenyl] propane, 3 , 3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone Examples thereof include, but are not limited to, bismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, and 1,3-bis (4-maleimidophenoxy) benzene. These may be used alone or in combination of two or more. The blending amount of the maleimide compound is preferably 5 times or less, more preferably 2 times or less of the polymaleimide resin of the formula (1) by weight ratio.
本発明の積層板用樹脂組成物には必要に応じて硬化用の触媒（硬化促進剤）を配合することができる。例えば２−メチルイミダゾール、２−エチルイミダゾール、２−フェニルイミダゾール、２−エチル−４−メチルイミダゾール、２−ウンデシルイミダゾール、１−シアノエチル−２−エチル−４−メチルイミダゾールなどのイミダゾール類、トリエチルアミン、トリエチレンジアミン、２−（ジメチルアミノメチル）フェノール、１，８−ジアザ−ビシクロ（５，４，０）ウンデセン−７、トリス（ジメチルアミノメチル）フェノール、ベンジルジメチルアミン等のアミン類、トリフェニルホスフィン、トリブチルホスフィン、トリオクチルホスフィンなどのホスフィン類、オクチル酸スズ、オクチル酸亜鉛、ジブチルスズジマレエート、ナフテン酸亜鉛、ナフテン酸コバルト、オレイン酸スズ等の有機金属塩、塩化亜鉛、塩化アルミニウム、塩化スズなどの金属塩化物、ジ−ｔｅｒｔ−ブチルパーオキサイド、ジクミルパーオキサイドなどの有機過酸化物、アゾビスイソブチロニトリル、アゾビスジメチルバレロニトリルなどのアゾ化合物、塩酸、硫酸、リン酸などの鉱酸、三フッ化ホウ素などのルイス酸、炭酸ナトリウムや塩化リチウム等の塩類などが挙げられる。硬化用の触媒の配合量は、式（１）のポリマレイミド樹脂（及び必要によりマレイミド系化合物）と（Ａ）〜（Ｃ）成分の合計１００重量部に対して好ましくは１０重量部以下、より好ましくは５重量部以下の範囲である。 A curing catalyst (curing accelerator) can be blended in the resin composition for laminates of the present invention as required. For example, imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, triethylamine, Amines such as triethylenediamine, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo (5,4,0) undecene-7, tris (dimethylaminomethyl) phenol, benzyldimethylamine, triphenylphosphine, Phosphines such as tributylphosphine and trioctylphosphine, tin octylate, zinc octylate, dibutyltin dimaleate, zinc naphthenate, cobalt naphthenate, tin oleate, zinc chloride, aluminum chloride Metal chlorides such as tin chloride, organic peroxides such as di-tert-butyl peroxide and dicumyl peroxide, azo compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile, hydrochloric acid, sulfuric acid, phosphorus Examples include mineral acids such as acids, Lewis acids such as boron trifluoride, and salts such as sodium carbonate and lithium chloride. The blending amount of the curing catalyst is preferably 10 parts by weight or less with respect to a total of 100 parts by weight of the polymaleimide resin of the formula (1) (and maleimide-based compound if necessary) and the components (A) to (C). The range is preferably 5 parts by weight or less.
本発明の積層板用樹脂組成物に有機溶剤を添加してワニス状の組成物（以下、単にワニスという）とすることができる。用いられる溶剤としては、例えばγ−ブチロラクトン類、Ｎ−メチルピロリドン、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルイミダゾリジノン等のアミド系溶剤、テトラメチレンスルフォン等のスルフォン類、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルモノアセテート、プロピレングリコールモノブチルエーテル等のエーテル系溶剤、メチルエチルケトン、メチルイソブチルケトン、シクロペンタノン、シクロヘキサノン等のケトン系溶剤、トルエン、キシレンなどの芳香族系溶剤が挙げられる。溶剤は、得られたワニス中の溶剤を除く固形分濃度が通常１０〜８０重量％、好ましくは２０〜７０重量％となる範囲で使用する。 An organic solvent can be added to the resin composition for laminates of the present invention to obtain a varnish-like composition (hereinafter simply referred to as varnish). Examples of the solvent used include amide solvents such as γ-butyrolactone, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone, and tetramethylene sulfone. Sulfones, ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, propylene glycol monobutyl ether, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone Aromatic solvents such as solvent, toluene, xylene and the like can be mentioned. The solvent is used in such a range that the solid content concentration excluding the solvent in the obtained varnish is usually 10 to 80% by weight, preferably 20 to 70% by weight.
更に本発明の積層板用樹脂組成物には、必要に応じて公知の添加剤を配合することが出来る。用いうる添加剤の具体例としては、エポキシ樹脂用硬化剤、ポリブタジエン及びこの変性物、アクリロニトリル共重合体の変性物、ポリフェニレンエーテル、ポリスチレン、ポリエチレン、ポリイミド、フッ素樹脂、マレイミド系化合物、シアネートエステル系化合物、シリコーンゲル、シリコーンオイル、並びにシリカ、アルミナ、炭酸カルシウム、石英粉、アルミニウム粉末、グラファイト、タルク、クレー、酸化鉄、酸化チタン、窒化アルミニウム、アスベスト、マイカ、ガラス粉末等の無機充填材、シランカップリング剤のような充填材の表面処理剤、離型剤、カーボンブラック、フタロシアニンブルー、フタロシアニングリーン等の着色剤が挙げられる。これら添加剤の配合量は、ポリマレイミド樹脂（及び必要によりマレイミド系化合物）と（Ａ）〜（Ｃ）成分の合計１００重量部に対して好ましくは１，０００重量部以下、より好ましくは７００重量部以下の範囲である。 Furthermore, a known additive can be blended in the resin composition for laminated boards of the present invention as required. Specific examples of additives that can be used include curing agents for epoxy resins, polybutadiene and modified products thereof, modified products of acrylonitrile copolymers, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, maleimide compounds, cyanate ester compounds , Silicone gel, silicone oil, inorganic fillers such as silica, alumina, calcium carbonate, quartz powder, aluminum powder, graphite, talc, clay, iron oxide, titanium oxide, aluminum nitride, asbestos, mica, glass powder, silane cup Coloring agents such as a surface treatment agent for a filler such as a ring agent, a release agent, carbon black, phthalocyanine blue, and phthalocyanine green can be used. The amount of these additives is preferably 1,000 parts by weight or less, more preferably 700 parts by weight, based on 100 parts by weight of the total of the polymaleimide resin (and maleimide compound if necessary) and the components (A) to (C). Part or less.
本発明の積層板用樹脂組成物の調製方法は特に限定されないが、各成分を均一に混合するだけでも、あるいはプレポリマー化してもよい。例えばポリマレイミド樹脂とシアネートエステル化合物を触媒の存在下または不存在下、溶剤の存在下または不存在下において加熱することによりプレポリマー化し、必要によりエポキシ樹脂、アミン化合物、マレイミド系化合物、シアネートエステル化合物及びその他添加剤を追加してもよい。各成分の混合またはプレポリマー化は溶剤の不存在下では例えば押出機、ニーダ、ロールなどを用い、溶剤の存在下では攪拌装置つきの反応釜などを使用する。 Although the preparation method of the resin composition for laminated boards of this invention is not specifically limited, Each component may be mixed only or it may prepolymerize. For example, polymaleimide resin and cyanate ester compound are prepolymerized by heating in the presence or absence of a catalyst and in the presence or absence of a solvent, and if necessary, epoxy resin, amine compound, maleimide compound, cyanate ester compound And other additives may be added. For mixing or prepolymerization of each component, for example, an extruder, a kneader, or a roll is used in the absence of a solvent, and a reaction kettle with a stirring device is used in the presence of a solvent.
本発明の積層板用樹脂組成物を加熱溶融し、低粘度化してガラス繊維、カ−ボン繊維、ポリエステル繊維、ポリアミド繊維、アルミナ繊維などの強化繊維に含浸させることにより本発明のプリプレグを得ることができる。
また、前記ワニスを、強化繊維に含浸させて加熱乾燥させることにより本発明のプリプレグを得ることもできる。
上記のプリプレグを所望の形に裁断、必要により銅箔などと積層後、積層物にプレス成形法やオートクレーブ成形法、シートワインディング成形法などで圧力をかけながら積層板用樹脂組成物を加熱硬化させることにより本発明の積層板を得ることができる。
更に、表面に銅箔を重ねてできた積層板に回路を形成し、その上にプリプレグや銅箔等を重ねて上記の操作を繰り返して多層の回路基板を得ることができる。
The prepreg of the present invention is obtained by heating and melting the resin composition for laminates of the present invention, reducing the viscosity, and impregnating the fibers with glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber or the like. Can do.
Moreover, the prepreg of this invention can also be obtained by impregnating the said varnish in a reinforced fiber and heat-drying.
After cutting the above prepreg into a desired shape and laminating with copper foil, etc., if necessary, heat curing the laminate resin composition while applying pressure to the laminate by press molding, autoclave molding, sheet winding molding, etc. Thus, the laminate of the present invention can be obtained.
Furthermore, a circuit can be formed on a laminated board made by superimposing copper foil on the surface, and a multilayer circuit board can be obtained by superimposing a prepreg or copper foil thereon and repeating the above operation.
以下、実施例、比較例により本発明を具体的に説明する。尚、本文中「部」及び「％」は、それぞれ「重量部」及び「重量％」を表す。実施例中、軟化点及び溶融粘度は下記の方法で測定した。
・ 軟化点 ：ＪＩＳ Ｋ−７２３４に準じた方法で測定
・ 溶融粘度：コーンプレート法での１５０℃における粘度
Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In the text, “parts” and “%” represent “parts by weight” and “% by weight”, respectively. In the examples, the softening point and melt viscosity were measured by the following methods.
-Softening point: measured by a method according to JIS K-7234-Melt viscosity: viscosity at 150 ° C by cone plate method
合成例１
温度計、冷却管、ディーンスターク共沸蒸留トラップ、撹拌機を取り付けたフラスコにアニリン５５９部とトルエン５００部を仕込み、室温で３５％塩酸１６７部を１時間で滴下した。滴下終了後加熱して共沸してくる水とトルエンを冷却・分液した後、有機層であるトルエンだけを系内に戻して脱水を行った。次いで４，４´−ビス（クロロメチル）ビフェニル２５１部を６０〜７０℃に保ちながら１時間かけて添加し、更に同温度で２時間反応を行った。反応終了後、昇温をしながらトルエンを留去して系内を１９０〜２００℃とし、この温度で１５時間反応をした。その後冷却しながら３０％水酸化ナトリウム水溶液５００部を系内が激しく還流しないようにゆっくりと滴下し、８０℃以下で留去したトルエンを系内に戻し、７０℃〜８０℃で静置した。分離した下層の水層を除去し、反応液の水洗を洗浄液が中性になるまで繰り返した。次いで油層から加熱減圧下において過剰のアニリンとトルエンを留去することにより式（２）においてＲが水素原子で表される芳香族アミン樹脂３３５部（Ａ１）を得た。芳香族アミン樹脂（Ａ１）の軟化点は５９℃、溶融粘度は０．０５Ｐａ・ｓであった。ゲルパーミエーションクロマトグラフィーの測定結果から算出した式（２）におけるｎの値は１．６であった。
Synthesis example 1
A flask equipped with a thermometer, a condenser, a Dean-Stark azeotropic distillation trap, and a stirrer was charged with 559 parts of aniline and 500 parts of toluene, and 167 parts of 35% hydrochloric acid was added dropwise at room temperature over 1 hour. After completion of the dropwise addition, the mixture was heated to cool and separate azeotropic water and toluene, and then only the organic layer of toluene was returned to the system for dehydration. Next, 251 parts of 4,4′-bis (chloromethyl) biphenyl was added over 1 hour while maintaining the temperature at 60 to 70 ° C., and the reaction was further carried out at the same temperature for 2 hours. After completion of the reaction, toluene was distilled off while raising the temperature to make the system at 190 to 200 ° C., and the reaction was carried out at this temperature for 15 hours. Thereafter, 500 parts of a 30% aqueous sodium hydroxide solution was slowly added dropwise while cooling so that the system did not vigorously reflux, and toluene distilled off at 80 ° C. or lower was returned to the system and allowed to stand at 70 ° C. to 80 ° C. The separated lower aqueous layer was removed, and the reaction solution was washed with water until the washing solution became neutral. Next, excess aniline and toluene were distilled off from the oil layer under reduced pressure by heating to obtain 335 parts (A1) of an aromatic amine resin in which R is a hydrogen atom in formula (2). The softening point of the aromatic amine resin (A1) was 59 ° C., and the melt viscosity was 0.05 Pa · s. The value of n in the formula (2) calculated from the measurement result of gel permeation chromatography was 1.6.
合成例２
合成例１においてアニリン５５９部を７４５部に、３５％塩酸１６７部を２９２部に、３０％水酸化ナトリウム水溶液５００部を６８０部に変えた以外は同様の操作を行った。その結果式（２）においてＲが水素原子で表される芳香族アミン樹脂３４３部（Ａ２）を得た。芳香族アミン樹脂（Ａ２）の軟化点は５４℃、溶融粘度は０．０４Ｐａ・ｓであった。ゲルパーミエーションクロマトグラフィーの測定結果から算出した式（２）におけるｎの値は１．４であった。
Synthesis example 2
The same operation as in Synthesis Example 1 was carried out except that 559 parts of aniline were changed to 745 parts, 167 parts of 35% hydrochloric acid were changed to 292 parts, and 500 parts of 30% aqueous sodium hydroxide solution were changed to 680 parts. As a result, 343 parts (A2) of an aromatic amine resin in which R in the formula (2) is a hydrogen atom was obtained. The softening point of the aromatic amine resin (A2) was 54 ° C., and the melt viscosity was 0.04 Pa · s. The value of n in the formula (2) calculated from the measurement result of gel permeation chromatography was 1.4.
合成例３
温度計、冷却管、ディーンスターク共沸蒸留トラップ、撹拌機を取り付けたフラスコに無水マレイン酸８８部とトルエン３００部を仕込み、加熱して共沸してくる水とトルエンを冷却・分液した後、有機層であるトルエンだけを系内に戻して脱水を行った。次に、芳香族アミン樹脂（Ａ１）１１６部をＮ−メチル−２−ピロリドン１１６部に溶解した樹脂溶液を、系内を８０〜８５℃に保ちながら１時間かけて滴下した。滴下終了後、同温度で２時間反応を行い、ｐ−トルエンスルホン酸２部を加えて、還流条件で共沸してくる縮合水とトルエンを冷却・分液した後、有機層であるトルエンだけを系内に戻して脱水を行いながら１０時間反応を行った。反応終了後、トルエンを１２０部追加し、水洗を繰り返してｐ−トルエンスルホン酸及び過剰の無水マレイン酸を除去し、加熱して共沸により水を系内から除いた。次いで反応溶液を濃縮して、式（１）においてＲが水素原子であるポリマレイミド樹脂（Ｍ１）を７０％含有する樹脂溶液を得た。
Synthesis example 3
A flask equipped with a thermometer, condenser, Dean-Stark azeotropic distillation trap, and stirrer was charged with 88 parts of maleic anhydride and 300 parts of toluene, and heated to cool and separate the azeotropic water and toluene. Then, only toluene which is an organic layer was returned to the system for dehydration. Next, a resin solution in which 116 parts of the aromatic amine resin (A1) was dissolved in 116 parts of N-methyl-2-pyrrolidone was added dropwise over 1 hour while maintaining the system at 80 to 85 ° C. After completion of the dropwise addition, the reaction is carried out at the same temperature for 2 hours, 2 parts of p-toluenesulfonic acid is added, condensed water and toluene azeotroped under reflux conditions are cooled and separated, and only toluene which is an organic layer Was returned to the system and reacted for 10 hours while dehydrating. 120 parts of toluene was added after completion | finish of reaction, water washing was repeated, p-toluenesulfonic acid and excess maleic anhydride were removed, and it heated and removed water from the system by azeotropy. Next, the reaction solution was concentrated to obtain a resin solution containing 70% of a polymaleimide resin (M1) in which R is a hydrogen atom in formula (1).
合成例４
合成例３において芳香族アミン樹脂（Ａ１）１１６部を芳香族アミン樹脂（Ａ２）１１６部に変えた以外は同様の操作を行った。その結果式（１）においてＲが水素原子であるポリマレイミド樹脂（Ｍ２）を７０％含有する樹脂溶液を得た。
Synthesis example 4
The same operation as in Synthesis Example 3 was performed except that 116 parts of the aromatic amine resin (A1) was changed to 116 parts of the aromatic amine resin (A2). As a result, a resin solution containing 70% of a polymaleimide resin (M2) in which R in formula (1) is a hydrogen atom was obtained.
実施例１
合成例３で得られたポリマレイミド樹脂（Ｍ１）溶液１２９部に、２，２−ビス（４−シアナートフェニル）プロパン１０部を混合し、更にメチルエチルケトンを加えて４０℃で１０分間攪拌して適当な粘度の調製液を得た。この調製液をガラスクロスに含浸させ、１４０℃で５分間乾燥させてプリプレグを得た。このプリプレグを４枚積み重ねて１７０℃で２時間、４０ｋg／ｃｍ2の圧力で成形し、２５０℃で２時間後硬化することにより厚さ０．６ｍｍの積層板を作成し、物性を測定した。
Example 1
To 129 parts of the polymaleimide resin (M1) solution obtained in Synthesis Example 3, 10 parts of 2,2-bis (4-cyanatophenyl) propane is added, and methyl ethyl ketone is further added and stirred at 40 ° C. for 10 minutes. A preparation having an appropriate viscosity was obtained. A glass cloth was impregnated with this preparation solution and dried at 140 ° C. for 5 minutes to obtain a prepreg. Four prepregs were stacked, molded at 170 ° C. for 2 hours at a pressure of 40 kg / cm 2 , and post-cured at 250 ° C. for 2 hours to produce a 0.6 mm thick laminate, and the physical properties were measured.
実施例２
合成例４で得られたポリマレイミド樹脂（Ｍ２）溶液８６部、２，２−ビス（４−シアナートフェニル）プロパン３０部、芳香族アミン樹脂（Ａ１）１０部を混合し、更にメチルエチルケトンを加えて４０℃で１０分間攪拌した後２−エチル−４−メチルイミダゾール１部を混合し、適当な粘度の調製液を得た。この調製液を用いて実施例１と同様に積層板を作成し、物性を測定した。
Example 2
86 parts of the polymaleimide resin (M2) solution obtained in Synthesis Example 4, 30 parts of 2,2-bis (4-cyanatophenyl) propane, and 10 parts of aromatic amine resin (A1) are mixed, and methyl ethyl ketone is further added. After stirring at 40 ° C. for 10 minutes, 1 part of 2-ethyl-4-methylimidazole was mixed to obtain a preparation having an appropriate viscosity. A laminate was prepared using this preparation solution in the same manner as in Example 1, and the physical properties were measured.
実施例３
２，２−ビス（４−シアナートフェニル）プロパン１００部のメチルエチルケトン溶液に芳香族アミン樹脂（Ａ１）１０部を加えて３０℃で３０分間攪拌混合した。この溶液に合成例４で得られたポリマレイミド樹脂（Ｍ２）溶液１４３部を１３０℃で１時間攪拌して予備反応させたものを加え、オクチル酸亜鉛０．１部、ベンジルジメチルアミン２部を加えて均一に混合した。このようにして得られた溶液を用いて実施例１と同様に積層板を作成し、物性を測定した。
Example 3
10 parts of the aromatic amine resin (A1) was added to a methyl ethyl ketone solution of 100 parts of 2,2-bis (4-cyanatophenyl) propane, and the mixture was stirred and mixed at 30 ° C. for 30 minutes. To this solution, 143 parts of the polymaleimide resin (M2) solution obtained in Synthesis Example 4 was pre-reacted by stirring at 130 ° C. for 1 hour, and 0.1 part of zinc octylate and 2 parts of benzyldimethylamine were added. In addition, it was mixed uniformly. A laminate was prepared in the same manner as in Example 1 using the solution thus obtained, and the physical properties were measured.
実施例４
２，２−ビス（４−シアナートフェニル）プロパン５０部を合成例４で得られたポリマレイミド樹脂（Ｍ２）溶液６４３部に溶解し、１３０℃で１０時間予備反応させてプレポリマーを得た。これに式（４）で表されるエポキシ樹脂（日本化薬製 ＮＣ−３０００ エポキシ当量２７６ｇ／ｅｑ． 軟化点５６℃）１５０部、オクチル酸亜鉛２部を加えて均一に混合した。このようにして得られた溶液を用いて実施例１と同様に積層板を作成し、物性を測定した。
Example 4
50 parts of 2,2-bis (4-cyanatophenyl) propane was dissolved in 643 parts of the polymaleimide resin (M2) solution obtained in Synthesis Example 4 and pre-reacted at 130 ° C. for 10 hours to obtain a prepolymer. . 150 parts of an epoxy resin represented by formula (4) (NC-3000, epoxy equivalent: 276 g / eq. Softening point: 56 ° C.) and 2 parts of zinc octylate represented by formula (4) were added and mixed uniformly. A laminate was prepared in the same manner as in Example 1 using the solution thus obtained, and the physical properties were measured.
実施例５
合成例４で得られたポリマレイミド樹脂（Ｍ２）溶液７１部に式（４）で表されるエポキシ樹脂（日本化薬製 ＮＣ−３０００ エポキシ当量２７６ｇ／ｅｑ． 軟化点５６℃）３０部と芳香族アミン樹脂（Ａ１）２０部を混合し、更にメチルエチルケトンを加えて４０℃で１０分間攪拌して適当な粘度の調製液を得た。この調製液を用いて実施例１と同様に積層板を作成し、物性を測定した。
Example 5
71 parts of the polymaleimide resin (M2) solution obtained in Synthesis Example 4 and 30 parts of an epoxy resin represented by the formula (4) (NC-3000 epoxy equivalent: 276 g / eq. Softening point: 56 ° C.) manufactured by Nippon Kayaku Co., Ltd. 20 parts of the amine amine resin (A1) was mixed, methyl ethyl ketone was further added, and the mixture was stirred at 40 ° C. for 10 minutes to obtain a preparation having an appropriate viscosity. A laminate was prepared using this preparation solution in the same manner as in Example 1, and the physical properties were measured.
実施例６
合成例４で得られたポリマレイミド樹脂（Ｍ２）溶液２３１部に式（４）で表されるエポキシ樹脂（日本化薬製 ＮＣ−３０００−Ｌ エポキシ当量２６９ｇ／ｅｑ． 軟化点５２℃）６０部と式（５）で表されるエポキシ樹脂硬化剤（日本化薬製 ＫＡＹＡＨＡＲＤ ＧＰＨ−６５ 水酸基当量１９９ｇ／ｅｑ． 軟化点６５℃）４４部を混合し、更にメチルエチルケトンを加えて４０℃で１０分間攪拌した後２−エチル−４−メチルイミダゾール１部を混合し、適当な粘度の調製液を得た。この調製液を用いて実施例１と同様に積層板を作成し、物性を測定した。
Example 6
60 parts of an epoxy resin (NC-3000-L epoxy equivalent 269 g / eq. Softening point 52 ° C., manufactured by Nippon Kayaku Co., Ltd.) represented by the formula (4) in 231 parts of the polymaleimide resin (M2) solution obtained in Synthesis Example 4 And 44 parts of an epoxy resin curing agent represented by formula (5) (KAYAHARD GPH-65, hydroxyl group equivalent: 199 g / eq. Softening point: 65 ° C., manufactured by Nippon Kayaku Co., Ltd.), methyl ethyl ketone was added, and the mixture was stirred at 40 ° C. for 10 minutes. After that, 1 part of 2-ethyl-4-methylimidazole was mixed to obtain a preparation having an appropriate viscosity. A laminate was prepared using this preparation solution in the same manner as in Example 1, and the physical properties were measured.
実施例７
合成例４で得られたポリマレイミド樹脂（Ｍ２）溶液１８０部に式（４）で表されるエポキシ樹脂（日本化薬製 ＮＣ−３０００−Ｌ エポキシ当量２６９ｇ／ｅｑ． 軟化点５２℃）５４部と芳香族アミン樹脂（Ａ２）６６部を混合し、更にメチルエチルケトンを加えて４０℃で１０分間攪拌した後２−エチル−４−メチルイミダゾール２部を混合し、適当な粘度の調製液を得た。この調製液を用いて実施例１と同様に積層板を作成し、物性を測定した。
Example 7
Epoxy resin represented by formula (4) in 180 parts of the polymaleimide resin (M2) solution obtained in Synthesis Example 4 (Nippon Kayaku NC-3000-L epoxy equivalent 269 g / eq. Softening point 52 ° C.) 54 parts And 66 parts of aromatic amine resin (A2) were mixed, methyl ethyl ketone was further added and stirred at 40 ° C. for 10 minutes, and then 2 parts of 2-ethyl-4-methylimidazole was mixed to obtain a preparation solution having an appropriate viscosity. . A laminate was prepared using this preparation solution in the same manner as in Example 1, and the physical properties were measured.
比較例１
４，４´−ジフェニルメタンビスマレイミド９０部のＮ−メチル−２−ピロリドン溶液に２，２−ビス（４−シアナートフェニル）プロパン１０部を混合し、更にメチルエチルケトンを加えて４０℃で１０分間攪拌して適当な粘度の調製液を得た。この調製液をガラスクロスに含浸させ、１４０℃で５分間乾燥させてプリプレグを得た。このプリプレグを４枚積み重ねて１７０℃で２時間、４０ｋg／ｃｍ2の圧力で成形し、２５０℃で２時間後硬化することにより厚さ０．６ｍｍの積層板を作成し、物性を測定した。
Comparative Example 1
To a N-methyl-2-pyrrolidone solution of 90 parts of 4,4'-diphenylmethane bismaleimide, 10 parts of 2,2-bis (4-cyanatophenyl) propane is added, and methyl ethyl ketone is added and stirred at 40 ° C for 10 minutes. Thus, a preparation liquid having an appropriate viscosity was obtained. A glass cloth was impregnated with this preparation solution and dried at 140 ° C. for 5 minutes to obtain a prepreg. Four prepregs were stacked, molded at 170 ° C. for 2 hours at a pressure of 40 kg / cm 2 , and post-cured at 250 ° C. for 2 hours to produce a 0.6 mm thick laminate, and the physical properties were measured.
比較例２
４，４´−ジフェニルメタンビスマレイミド６０部を含有するＮ−メチル−２−ピロリドン溶液に、２，２−ビス（４−シアナートフェニル）プロパン３０部、４，４´−ジアミノジフェニルメタン１０部を混合し、更にメチルエチルケトンを加えて４０℃で１０分間攪拌した後２−エチル−４−メチルイミダゾール１部を混合し、適当な粘度の調製液を得た。この調製液を用いて比較例１と同様に積層板を作成し、物性を測定した。
Comparative Example 2
Mix N-methyl-2-pyrrolidone solution containing 60 parts of 4,4'-diphenylmethane bismaleimide with 30 parts of 2,2-bis (4-cyanatophenyl) propane and 10 parts of 4,4'-diaminodiphenylmethane. Further, methyl ethyl ketone was added and stirred at 40 ° C. for 10 minutes, and then 1 part of 2-ethyl-4-methylimidazole was mixed to obtain a preparation having an appropriate viscosity. A laminate was prepared using this preparation solution in the same manner as in Comparative Example 1, and the physical properties were measured.
比較例３
２，２−ビス（４−シアナートフェニル）プロパン１００部のメチルエチルケトン溶液に４，４´−ジアミノジフェニルメタン１０部を加えて３０℃で３０分間攪拌混合した。この溶液に４，４´−ジフェニルメタンビスマレイミド１００部を１３０℃で１時間攪拌して予備反応させたものを加え、オクチル酸亜鉛０．１部、ジメチルベンジルアミン２部を加えて均一に混合した。このようにして得られた溶液を用いて比較例１と同様に積層板を作成し、物性を測定した。
Comparative Example 3
To a methyl ethyl ketone solution of 100 parts of 2,2-bis (4-cyanatophenyl) propane, 10 parts of 4,4′-diaminodiphenylmethane was added and stirred at 30 ° C. for 30 minutes. To this solution, 100 parts of 4,4′-diphenylmethane bismaleimide was stirred and pre-reacted at 130 ° C. for 1 hour, and 0.1 part of zinc octylate and 2 parts of dimethylbenzylamine were added and mixed uniformly. . A laminate was prepared using the solution thus obtained in the same manner as in Comparative Example 1, and the physical properties were measured.
比較例４
２，２−ビス（４−シアナートフェニル）プロパン５０部と４，４´−ジフェニルメタンビスマレイミド４５０部をＮ−メチル−２−ピロリドンに溶解して、１３０℃で１０時間予備反応させてプレポリマーを得た。これにフェノールノボラック型エポキシ樹脂（日本化薬製 ＥＰＰＮ−２０１ エポキシ当量１８６ｇ／ｅｑ． 軟化点７０℃）１５０部、オクチル酸亜鉛２部を加えて均一に混合した。このようにして得られた溶液を用いて比較例１と同様に積層板を作成し、物性を測定した。
Comparative Example 4
A prepolymer is prepared by dissolving 50 parts of 2,2-bis (4-cyanatophenyl) propane and 450 parts of 4,4′-diphenylmethane bismaleimide in N-methyl-2-pyrrolidone and prereacting at 130 ° C. for 10 hours. Got. To this, 150 parts of phenol novolac type epoxy resin (EPPN-201 manufactured by Nippon Kayaku Epoxy equivalent: 186 g / eq. Softening point: 70 ° C.) and 2 parts of zinc octylate were added and mixed uniformly. A laminate was prepared using the solution thus obtained in the same manner as in Comparative Example 1, and the physical properties were measured.
比較例５
４，４´−ジフェニルメタンビスマレイミド５０部のメチルエチルケトン溶液にフェノールノボラック型エポキシ樹脂（日本化薬製 ＥＰＰＮ−２０１ 比較例４と同じ）３０部と４，４´−ジアミノジフェニルメタン２０部を混合し、更にメチルエチルケトンを加えて４０℃で１０分間攪拌して適当な粘度の調製液を得た。この調製液を用いて比較例１と同様に積層板を作成し、物性を測定した。
Comparative Example 5
50 parts of 4,4'-diphenylmethane bismaleimide is mixed with 30 parts of a phenol novolac epoxy resin (same as EPPN-201 Comparative Example 4 manufactured by Nippon Kayaku) and 20 parts of 4,4'-diaminodiphenylmethane, Methyl ethyl ketone was added and stirred at 40 ° C. for 10 minutes to obtain a preparation having an appropriate viscosity. A laminate was prepared using this preparation solution in the same manner as in Comparative Example 1, and the physical properties were measured.
比較例６
４，４´−ジフェニルメタンビスマレイミド１６１部のメチルエチルケトン溶液に式（４）で表されるエポキシ樹脂（日本化薬製 ＮＣ−３０００−Ｌ エポキシ当量２６９ｇ／ｅｑ． 軟化点５２℃）６０部と式（５）で表されるエポキシ樹脂硬化剤（日本化薬製 ＫＡＹＡＨＡＲＤ ＧＰＨ−６５ 水酸基当量１９９ｇ／ｅｑ． 軟化点６５℃）４４部を混合し、更にメチルエチルケトンを加えて４０℃で１０分間攪拌した後２−エチル−４−メチルイミダゾール１部を混合し、適当な粘度の調製液を得た。この調製液を用いて比較例１と同様に積層板を作成し、物性を測定した。
Comparative Example 6
An epoxy resin (NC-3000-L, epoxy equivalent 269 g / eq. Softening point 52 ° C., manufactured by Nippon Kayaku Co., Ltd.) represented by the formula (4) in a methyl ethyl ketone solution of 161 parts of 4,4′-diphenylmethane bismaleimide and a formula ( 5 parts of epoxy resin curing agent represented by 5) (KAYAHARD GPH-65, hydroxyl group equivalent: 199 g / eq. Softening point: 65 ° C., manufactured by Nippon Kayaku Co., Ltd.), and methyl ethyl ketone was further added, followed by stirring at 40 ° C. for 10 minutes. -1 part of ethyl-4-methylimidazole was mixed, and the preparation liquid of suitable viscosity was obtained. A laminate was prepared using this preparation solution in the same manner as in Comparative Example 1, and the physical properties were measured.
比較例６
４，４´−ジフェニルメタンビスマレイミド６２部のメチルエチルケトン溶液に式（４）で表されるエポキシ樹脂（日本化薬製 ＮＣ−３０００−Ｌ エポキシ当量２６９ｇ／ｅｑ． 軟化点５２℃）５４部と芳香族アミン樹脂（Ａ２）５４部を混合し、更にメチルエチルケトンを加えて４０℃で１０分間攪拌した後２−エチル−４−メチルイミダゾール２部を混合し、適当な粘度の調製液を得た。この調製液を用いて比較例１と同様に積層板を作成し、物性を測定した。
Comparative Example 6
An epoxy resin represented by formula (4) in 54 parts of methyl ethyl ketone solution of 62 parts of 4,4′-diphenylmethane bismaleimide (NC-3000-L, epoxy equivalent: 269 g / eq. Softening point: 52 ° C.) and aromatic 54 parts of an amine resin (A2) was mixed, methyl ethyl ketone was further added and stirred at 40 ° C. for 10 minutes, and then 2 parts of 2-ethyl-4-methylimidazole was mixed to obtain a preparation having an appropriate viscosity. A laminate was prepared using this preparation solution in the same manner as in Comparative Example 1, and the physical properties were measured.
作成した積層板について以下の測定を行った。結果を表１に示す。
・ ガラス転移温度：動的粘弾性試験機により測定し、ｔａｎδが最大値のときの温度。
・ 吸湿率：１２１℃／１００％ＲＨで２４時間後の重量増加率。試験片は５０ｍｍ×５０ｍｍの正方形。
・ 誘電率：Ｋ６９９１に準拠して１ＧＨｚにおいて測定。
・ 難燃性：ＵＬ９４に準拠して行った。ただし、試験片は幅１２．５ｍｍ×長さ１５０ｍｍとした。
The following measurements were performed on the prepared laminate. The results are shown in Table 1.
Glass transition temperature: Temperature measured by a dynamic viscoelasticity tester and tan δ is the maximum value.
Moisture absorption: Weight increase rate after 24 hours at 121 ° C./100% RH. The test piece is a 50 mm × 50 mm square.
-Dielectric constant: measured at 1 GHz in accordance with K6991.
Flame retardance: Performed according to UL94. However, the test piece was 12.5 mm wide × 150 mm long.
表−１ 実施例及び比較例で得られた積層版の特性評価結果
表１から、式（１）のポリマレイミド樹脂を使用した実施例１〜７は、式（１）のポリマレイミド樹脂の代りにビスマレイミドを使用した比較例１〜７と比べて高耐熱性、低吸湿性、低誘電率特性及び難燃性に優れていることは明らかである。
具体的には、式（１）のポリマレイミド樹脂及び、式（４）のエポキシ樹脂及び／又は式（２）のアミノ化合物及び／又は２，２−ビス（４−シアナートフェニル）プロパンを組み合わせた実施例１〜７と、ビスマレイミド樹脂及び、フェノールノボラック型エポキシ樹脂及び／又は４，４´−ジアミノジフェニルメタン及び／又は２，２−ビス（４−シアナートフェニル）プロパンを組み合わせた比較例1〜７の比較において、実施例は比較例に比べてガラス転移温度が約１０〜３０℃高く、吸湿率が０．１〜０．３％程度低く、誘電率が０．２〜０．６程度低かった。また難燃性についても、比較例はいずれも難燃性を示さなかったのに対して、実施例はいずれもＶ−０からＶ−１の難燃性を有した。
From Table 1, Examples 1-7 using the polymaleimide resin of formula (1) have higher heat resistance than Comparative Examples 1-7 using bismaleimide instead of the polymaleimide resin of formula (1), It is clear that it is excellent in low hygroscopicity, low dielectric constant characteristics and flame retardancy.
Specifically, a combination of a polymaleimide resin of formula (1) and an epoxy resin of formula (4) and / or an amino compound of formula (2) and / or 2,2-bis (4-cyanatophenyl) propane Comparative Example 1 in which Examples 1 to 7 were combined with bismaleimide resin and phenol novolac type epoxy resin and / or 4,4′-diaminodiphenylmethane and / or 2,2-bis (4-cyanatophenyl) propane In the comparison of ˜7, the example has a glass transition temperature of about 10 to 30 ° C. higher than that of the comparative example, the moisture absorption is about 0.1 to 0.3% lower, and the dielectric constant is about 0.2 to 0.6. It was low. In addition, as for flame retardancy, none of the comparative examples showed flame retardancy, whereas all the examples had flame retardancy of V-0 to V-1.
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