JP7387235B2 - Thermosetting maleimide resin composition, uncured resin film and cured resin film comprising the resin composition - Google Patents
Thermosetting maleimide resin composition, uncured resin film and cured resin film comprising the resin composition Download PDFInfo
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- JP7387235B2 JP7387235B2 JP2020188889A JP2020188889A JP7387235B2 JP 7387235 B2 JP7387235 B2 JP 7387235B2 JP 2020188889 A JP2020188889 A JP 2020188889A JP 2020188889 A JP2020188889 A JP 2020188889A JP 7387235 B2 JP7387235 B2 JP 7387235B2
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- bisphenol
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- 229920005989 resin Polymers 0.000 title claims description 61
- 239000011347 resin Substances 0.000 title claims description 61
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 title claims description 45
- 239000011342 resin composition Substances 0.000 title claims description 42
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 39
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 42
- 125000000962 organic group Chemical group 0.000 claims description 41
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 29
- -1 aromatic bismaleimide compound Chemical class 0.000 claims description 24
- 125000001931 aliphatic group Chemical group 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 claims description 4
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 239000010408 film Substances 0.000 description 60
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 20
- 239000000203 mixture Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 239000002966 varnish Substances 0.000 description 15
- 229920001721 polyimide Polymers 0.000 description 14
- 125000001424 substituent group Chemical group 0.000 description 12
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 10
- 229920000106 Liquid crystal polymer Polymers 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 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 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 150000001451 organic peroxides Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000012787 coverlay film Substances 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 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 2
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical group OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 2
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 2
- NJWZAJNQKJUEKC-UHFFFAOYSA-N 4-[4-[2-[4-[(1,3-dioxo-2-benzofuran-4-yl)oxy]phenyl]propan-2-yl]phenoxy]-2-benzofuran-1,3-dione Chemical compound C=1C=C(OC=2C=3C(=O)OC(=O)C=3C=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=CC2=C1C(=O)OC2=O NJWZAJNQKJUEKC-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000004427 diamine group Chemical group 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 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 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- OWEYKIWAZBBXJK-UHFFFAOYSA-N 1,1-Dichloro-2,2-bis(4-hydroxyphenyl)ethylene Chemical compound C1=CC(O)=CC=C1C(=C(Cl)Cl)C1=CC=C(O)C=C1 OWEYKIWAZBBXJK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- WFGHUOGOUOTVBO-UHFFFAOYSA-N 2,6-dipropylaniline Chemical compound CCCC1=CC=CC(CCC)=C1N WFGHUOGOUOTVBO-UHFFFAOYSA-N 0.000 description 1
- RFSCGDQQLKVJEJ-UHFFFAOYSA-N 2-methylbutan-2-yl benzenecarboperoxoate Chemical compound CCC(C)(C)OOC(=O)C1=CC=CC=C1 RFSCGDQQLKVJEJ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- NWIVYGKSHSJHEF-UHFFFAOYSA-N 4-[(4-amino-3,5-diethylphenyl)methyl]-2,6-diethylaniline Chemical compound CCC1=C(N)C(CC)=CC(CC=2C=C(CC)C(N)=C(CC)C=2)=C1 NWIVYGKSHSJHEF-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013039 cover film Substances 0.000 description 1
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical group C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical group CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical group C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- XDOBJOBITOLMFI-UHFFFAOYSA-N pyrrole-2,5-dione;toluene Chemical compound CC1=CC=CC=C1.O=C1NC(=O)C=C1 XDOBJOBITOLMFI-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber 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
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
本発明は、熱硬化性マレイミド樹脂組成物、並びにその樹脂組成物からなる未硬化及び硬化樹脂フィルムに関する。 The present invention relates to a thermosetting maleimide resin composition, and uncured and cured resin films comprising the resin composition.
近年、５Ｇという次世代の移動通信システムが流行しており、高速、大容量、低遅延通信を実現しようとしている。これらを実現するためには、高周波帯用の材料が必要であり、ノイズ対策として伝送損失の低減が必須となるために、誘電特性の優れた絶縁材料の開発が求められている。 In recent years, a next-generation mobile communication system called 5G has become popular, and is attempting to realize high-speed, large-capacity, and low-latency communication. In order to realize these, materials for high frequency bands are required, and reduction of transmission loss is essential as a noise countermeasure, so there is a need for the development of insulating materials with excellent dielectric properties.
その中でも基板用途で、このような誘電特性の優れた絶縁材料が求められている。一般にフレキシブルプリント配線板（ＦＰＣ）と呼ばれる基板はスマートフォンや液晶テレビを始めとして様々な電子機器に使用されている。このＦＰＣのベース材料としてはポリイミドが多く使用されてきたが、近年高周波用途として、液晶ポリマー（ＬＣＰ）や特性を改良した変性ポリイミド（ＭＰＩ）と呼ばれる製品が使用されるようになってきている。 Among these, insulating materials with excellent dielectric properties are in demand for substrate applications. Substrates generally called flexible printed circuit boards (FPC) are used in various electronic devices including smartphones and liquid crystal televisions. Polyimide has often been used as the base material for FPCs, but in recent years, products called liquid crystal polymer (LCP) and modified polyimide (MPI) with improved properties have come into use for high frequency applications.
すでにＬＣＰに関しては、ＬＣＰのさらなる高性能化や、ＬＣＰを使用したＦＰＣのベースフィルムやカバーレイフィルムなど、多くの発明が開示されている（例えば特許文献１及び２）が、ＬＣＰは需要に見合った量産が困難であるために使用は限定的であったり、熱可塑性樹脂特有の問題点である３００℃以上の高温での成形が必須であったり、銅張積層板を接着させるために低誘電特性を有する接着剤を必要とするなど改善すべき点が多く残されている。 Regarding LCP, many inventions have already been disclosed, such as further improving the performance of LCP and FPC base films and coverlay films using LCP (for example, Patent Documents 1 and 2), but LCP does not meet the demand. Its use is limited because it is difficult to mass produce, it must be molded at high temperatures of 300°C or higher, which is a problem unique to thermoplastic resins, and it has low dielectric properties to bond copper-clad laminates. There are many points that need to be improved, such as the need for adhesives with special characteristics.
そこで、周波数帯によってはＭＰＩの使用が検討されており、ＭＰＩに関しても多くの発明が開示されている（例えば特許文献３～６）。これらのＭＰＩは現行のポリイミドと比べて誘電特性が改善されているものの、ＬＣＰと同様に熱可塑性樹脂であるため、ＬＣＰと同じような課題を抱えている上に、ポリイミド固有の吸湿性に起因して、誘電特性が非常に悪くなることがわかっている。これらを解消するためにダイマージアミン骨格を有するＭＰＩも開示されている（特許文献７）が、従来のＭＰＩと比べてガラス転移温度（Ｔｇ）が著しく低く、寸法安定性にも欠ける。また、ＭＰＩを製造する際には、非プロトン性極性溶媒、例えば、Ｎ－メチルピロリドン（ＮＭＰ）の大量使用が必須であり、非プロトン性極性溶媒の使用は、環境保全の観点からも好ましくない。 Therefore, the use of MPI is being considered depending on the frequency band, and many inventions regarding MPI have been disclosed (for example, Patent Documents 3 to 6). Although these MPIs have improved dielectric properties compared to current polyimides, they are thermoplastic resins like LCPs, so they have the same problems as LCPs, and they also have problems due to the inherent hygroscopicity of polyimides. It is known that the dielectric properties become very poor. In order to solve these problems, MPI having a dimer diamine skeleton has also been disclosed (Patent Document 7), but it has a significantly lower glass transition temperature (Tg) and lacks dimensional stability compared to conventional MPI. Furthermore, when producing MPI, it is essential to use a large amount of aprotic polar solvents, such as N-methylpyrrolidone (NMP), and the use of aprotic polar solvents is not preferable from the perspective of environmental conservation. .
これに対して、実質的にダイマージアミン骨格を有するマレイミド化合物をＦＰＣ用材料として使用した組成物及びその硬化物が開示されている（特許文献８）が、非常に誘電特性には優れるものの、低Ｔｇ、高熱膨張係数（ＣＴＥ）であり、依然として寸法安定性に欠けている。加えて、長鎖アルキル基を有するビスマレイミド樹脂と、硬質の低分子の芳香族系マレイミド樹脂との混合物であるため相溶性が悪く、該組成物及びその硬化物の特性や硬化にムラが発生しやすい。 On the other hand, a composition using a maleimide compound having substantially a dimer diamine skeleton as an FPC material and a cured product thereof have been disclosed (Patent Document 8), but although it has very excellent dielectric properties, it has low Tg, high coefficient of thermal expansion (CTE), and still lacks dimensional stability. In addition, since it is a mixture of a bismaleimide resin having a long-chain alkyl group and a hard, low-molecular-weight aromatic maleimide resin, the compatibility is poor, resulting in unevenness in the properties and curing of the composition and its cured product. It's easy to do.
また、一般的にリジッド配線板に使用されるエポキシ樹脂や変性ポリフェニレンエーテル樹脂（ＰＰＥ）はフィルムとしての取り扱いの観点からＦＰＣへの適用は非常に難しい。 Furthermore, it is very difficult to apply epoxy resins and modified polyphenylene ether resins (PPE), which are generally used in rigid wiring boards, to FPCs from the viewpoint of handling them as films.
従って、本発明は、誘電特性に優れた絶縁材料、特にフレキシブルプリント配線板（ＦＰＣ）用途に好適な、ＮＭＰ等の非プロトン性溶媒を使用せずに、ガラス転移温度（Ｔｇ）が高く、吸湿後も誘電特性に優れる硬化物を与える、熱硬化性マレイミド樹脂組成物並びにそれからなる未硬化樹脂フィルム及び硬化樹脂フィルムを提供することを目的とする。 Therefore, the present invention provides an insulating material with excellent dielectric properties, which is particularly suitable for use in flexible printed circuit boards (FPC), has a high glass transition temperature (Tg), and has a high moisture absorption without using an aprotic solvent such as NMP. It is an object of the present invention to provide a thermosetting maleimide resin composition, as well as an uncured resin film and a cured resin film made from the same, which give a cured product with excellent dielectric properties.
本発明者らは、上記課題を解決するため鋭意研究を重ねた結果、下記熱硬化性マレイミド樹脂組成物が、上記目的を達成できることを見出し、本発明を完成した。 As a result of intensive research to solve the above-mentioned problems, the present inventors discovered that the following thermosetting maleimide resin composition can achieve the above-mentioned objects, and completed the present invention.
＜１＞
（Ａ）ビスフェノール構造を有し、かつ数平均分子量が３，０００～５０，０００である芳香族マレイミド
（Ｂ）ビスフェノール構造を有するアリル基含有カーボネート樹脂
及び
（Ｃ）反応開始剤
を含む熱硬化性マレイミド樹脂組成物。
＜２＞
前記（Ａ）成分が下記一般式（１）で示される芳香族ビスマレイミド化合物である＜１＞に記載の熱硬化性マレイミド樹脂組成物。
Ｘ1は独立して、下記式
ｍは１～３０の数であり、
ｎは１～５の数であり、
Ａ1及びＡ2はそれぞれ独立して、下記式（２）
Ｘ2は独立して、下記式
Ｒ1は独立して、水素原子、塩素原子、又は炭素数１～６の脂肪族炭化水素基である）
又は下記式（３）
で示される２価の芳香族基である。）
＜３＞
前記式（１）のＸ1と前記式（３）のＸ1とが同じ２価の基である＜２＞に記載の熱硬化性マレイミド樹脂組成物。
＜４＞
（Ｂ）成分が下記式（４）で表される化合物を含むものである＜１＞から＜３＞のいずれか１つに記載の熱硬化性マレイミド樹脂組成物。
＜５＞
前記式（４）中のビスフェノール構造がビスフェノールＡ型、ビスフェノールＡＰ型、ビスフェノールＥ型及びビスフェノールＦ型からなる群から選択される１種以上のビスフェノール構造である＜４＞に記載の熱硬化性マレイミド樹脂組成物。
＜６＞
前記式（４）中のＸ4の１個以上が脂環式ジメタノール構造を有する２価の有機基である＜４＞又は＜５＞に記載の熱硬化性マレイミド樹脂組成物。
＜７＞
＜１＞に記載の熱硬化性マレイミド樹脂組成物からなる未硬化樹脂フィルム。
＜８＞
＜１＞に記載の熱硬化性マレイミド樹脂組成物の硬化物からなる硬化樹脂フィルム。
<1>
(A) an aromatic maleimide having a bisphenol structure and a number average molecular weight of 3,000 to 50,000; (B) an allyl group-containing carbonate resin having a bisphenol structure; and (C) a thermosetting product containing a reaction initiator. Maleimide resin composition.
<2>
The thermosetting maleimide resin composition according to <1>, wherein the component (A) is an aromatic bismaleimide compound represented by the following general formula (1).
X 1 is independently the following formula
m is a number from 1 to 30,
n is a number from 1 to 5,
A 1 and A 2 are each independently expressed by the following formula (2)
X 2 is independently the following formula
R 1 is independently a hydrogen atom, a chlorine atom, or an aliphatic hydrocarbon group having 1 to 6 carbon atoms)
Or the following formula (3)
It is a divalent aromatic group represented by )
<3>
The thermosetting maleimide resin composition according to <2>, wherein X 1 in the formula (1) and X 1 in the formula (3) are the same divalent group.
<4>
The thermosetting maleimide resin composition according to any one of <1> to <3>, wherein the component (B) contains a compound represented by the following formula (4).
<5>
The thermosetting maleimide according to <4>, wherein the bisphenol structure in the formula (4) is one or more bisphenol structures selected from the group consisting of bisphenol A type, bisphenol AP type, bisphenol E type, and bisphenol F type. Resin composition.
<6>
The thermosetting maleimide resin composition according to <4> or <5>, wherein one or more of X 4 in the formula (4) is a divalent organic group having an alicyclic dimethanol structure.
<7>
An uncured resin film comprising the thermosetting maleimide resin composition according to <1>.
<8>
A cured resin film comprising a cured product of the thermosetting maleimide resin composition according to <1>.
本発明の熱硬化性マレイミド樹脂組成物は、硬化物のガラス転移温度が高く、誘電特性に優れる。また、硬化前後でのフィルム又はシートとしてのハンドリング性に優れる。さらに、本発明の熱硬化性マレイミド樹脂組成物は、ＮＭＰ等の非プロトン性極性溶媒を用いずに製造可能であり、その硬化物は吸湿後も誘電特性に優れるものである。
従って、本発明の熱硬化性マレイミド樹脂組成物は、ＦＰＣ用に好適に用いることができ、具体的にはコア基板やカバーレイフィルムとして、さらには熱硬化性であるためにこれ自体を接着剤としても使用することができる。
The thermosetting maleimide resin composition of the present invention has a high glass transition temperature of the cured product and excellent dielectric properties. Moreover, it has excellent handling properties as a film or sheet before and after curing. Furthermore, the thermosetting maleimide resin composition of the present invention can be produced without using an aprotic polar solvent such as NMP, and the cured product thereof has excellent dielectric properties even after moisture absorption.
Therefore, the thermosetting maleimide resin composition of the present invention can be suitably used for FPC, and specifically as a core substrate or coverlay film, and since it is thermosetting, it can also be used as an adhesive. It can also be used as
以下、本発明につき更に詳しく説明する。 The present invention will be explained in more detail below.
＜（Ａ）ビスフェノール構造を有し、かつ数平均分子量が３，０００～５０，０００である芳香族マレイミド＞
（Ａ）成分はビスフェノール構造を有し、かつ数平均分子量が３，０００～５０，０００である芳香族マレイミドである。（Ａ）成分は１分子中に２個以上、好ましくは２～５個のマレイミド基を有し、中でも芳香族ビスマレイミドであることが好ましい。
<(A) Aromatic maleimide having a bisphenol structure and a number average molecular weight of 3,000 to 50,000>
Component (A) is an aromatic maleimide having a bisphenol structure and a number average molecular weight of 3,000 to 50,000. Component (A) has two or more maleimide groups, preferably 2 to 5 maleimide groups in one molecule, and aromatic bismaleimide is especially preferred.
（Ａ）成分の芳香族マレイミドの数平均分子量は３，０００～５０，０００であり、好ましくは５，０００～４０，０００である。数平均分子量が３，０００未満であると、フィルムへの加工性／成形性が悪くなり、数平均分子量が５０，０００を超えると、溶剤に対する溶解性が不安定になるため好ましくない。なお、本発明中で言及する数平均分子量とは、下記条件で測定したゲルパーミエーションクロマトグラフィ（ＧＰＣ）によるポリスチレンを標準物質とした数平均分子量を指すこととする。
［測定条件］
展開溶媒：テトラヒドロフラン（ＴＨＦ）
流量：０．３５ｍＬ／ｍｉｎ
検出器：示差屈折率検出器（ＲＩ）
カラム： ＴＳＫ Ｇｕａｒｄｃｏｌｕｍｎ ＳｕｐｅｒＨ－Ｌ
ＴＳＫｇｅｌ ＳｕｐｅｒＨＺ４０００（４．６ｍｍＩ．Ｄ．×１５ｃｍ×１）
ＴＳＫｇｅｌ ＳｕｐｅｒＨＺ３０００（４．６ｍｍＩ．Ｄ．×１５ｃｍ×１）
ＴＳＫｇｅｌ ＳｕｐｅｒＨＺ２０００（４．６ｍｍＩ．Ｄ．×１５ｃｍ×２）
（いずれも東ソー社製）
カラム温度：４０℃
試料注入量：５μＬ（濃度０．２質量％のＴＨＦ溶液）
The number average molecular weight of the aromatic maleimide as component (A) is from 3,000 to 50,000, preferably from 5,000 to 40,000. If the number average molecular weight is less than 3,000, processability/formability into a film will be poor, and if the number average molecular weight exceeds 50,000, the solubility in solvents will become unstable, which is not preferable. Note that the number average molecular weight referred to in the present invention refers to the number average molecular weight measured by gel permeation chromatography (GPC) under the following conditions using polystyrene as a standard substance.
[Measurement condition]
Developing solvent: Tetrahydrofuran (THF)
Flow rate: 0.35mL/min
Detector: Differential refractive index detector (RI)
Column: TSK Guardcolumn SuperHL
TSKgel SuperHZ4000 (4.6mm I.D. x 15cm x 1)
TSKgel SuperHZ3000 (4.6mm I.D. x 15cm x 1)
TSKgel SuperHZ2000 (4.6mm I.D. x 15cm x 2)
(Both manufactured by Tosoh Corporation)
Column temperature: 40℃
Sample injection amount: 5 μL (THF solution with a concentration of 0.2% by mass)
（Ａ）成分の芳香族マレイミドとしては、下記式（１）で示す芳香族ビスマレイミド化合物が好ましいものとして挙げられる。この下記式（１）のものを使用すると、硬化前後共に、得られるフィルムの機械的特性が良く、ハンドリングしやすくなる。
Ｘ1は独立して、下記式
ｍは１～３０の数であり、
ｎは１～５の数であり、
Ａ1及びＡ2はそれぞれ独立して、下記式（２）
Ｘ2は独立して、下記式
Ｒ1は独立して、水素原子、塩素原子、または炭素数１～６の脂肪族炭化水素基である）
又は下記式（３）
で示される２価の芳香族基である。）
Preferred examples of the aromatic maleimide as component (A) include aromatic bismaleimide compounds represented by the following formula (1). When a film expressed by the following formula (1) is used, the resulting film has good mechanical properties both before and after curing, and is easy to handle.
X 1 is independently the following formula
m is a number from 1 to 30,
n is a number from 1 to 5,
A 1 and A 2 are each independently expressed by the following formula (2)
X 2 is independently the following formula
R 1 is independently a hydrogen atom, a chlorine atom, or an aliphatic hydrocarbon group having 1 to 6 carbon atoms)
Or the following formula (3)
It is a divalent aromatic group represented by )
Ｘ1としては、原料の入手のしやすさの観点から－ＣＨ2－、－Ｃ（ＣＨ3）2－が好ましい。ｍは１～３０の数であり、好ましくは２～２０の数であり、より好ましくは２～８である。ｍがこの範囲にある場合、上記芳香族ビスマレイミド化合物の未硬化時の溶液への溶解性やフィルム化能と、得られる硬化物の強靭性や耐熱性とのバランスが良いものとなる。ｎは１～５の数であり、好ましくは１～４であり、より好ましくは１～３であり、更に好ましくは１である。
Ｘ2としては、原料の入手のしやすさの観点から－ＣＨ2－、－Ｃ（ＣＨ3）2－が好ましい。また、Ｒ1は独立して、水素原子、塩素原子、又は非置換もしくは置換の炭素数１～６の脂肪族炭化水素基である。非置換もしくは置換の炭素数１～６の脂肪族炭化水素基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｔ－ブチル基、シクロヘキシル基等が挙げられ、これらの基の水素原子の一部又は全部が、Ｆ、Ｃｌ、Ｂｒ等のハロゲン原子等で置換された基、例えば、トリフルオロメチル基等を挙げることができる。Ｒ1としては、原料の入手のしやすさの観点から、水素原子又は非置換もしくは置換の炭素数１～３の脂肪族炭化水素基であることが好ましく、Ａ1とＡ2は異なることがより好ましい。前記式（１）において、Ａ1が前記式（２）のとき、Ａ2が前記式（３）の場合か、またはＡ1が前記式（３）のとき、Ａ2が前記式（２）の場合がある。
From the viewpoint of easy availability of raw materials, -CH 2 - and -C(CH 3 ) 2 - are preferable as X 1 . m is a number from 1 to 30, preferably from 2 to 20, more preferably from 2 to 8. When m is within this range, there will be a good balance between the solubility of the aromatic bismaleimide compound in a solution and film-forming ability when uncured, and the toughness and heat resistance of the resulting cured product. n is a number from 1 to 5, preferably from 1 to 4, more preferably from 1 to 3, and even more preferably from 1.
As X 2 , -CH 2 - and -C(CH 3 ) 2 - are preferable from the viewpoint of easy availability of raw materials. Furthermore, R 1 is independently a hydrogen atom, a chlorine atom, or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms. Examples of unsubstituted or substituted aliphatic hydrocarbon groups having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, cyclohexyl group, etc. Examples include groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as F, Cl, Br, etc., such as trifluoromethyl groups. From the viewpoint of availability of raw materials, R 1 is preferably a hydrogen atom or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 3 carbon atoms, and A 1 and A 2 may be different. More preferred. In the above formula (1), when A 1 is the above formula (2), A 2 is the above formula (3), or when A 1 is the above formula (3), A 2 is the above formula (2). There are cases where
また、前記式（１）のＸ1と前記式（３）のＸ1とが同じ２価の基であることが好ましい。これは２つ以上の同じビスフェノール骨格を有することを意味し、本発明の芳香族ビスマレイミド化合物は、同じビスフェノール骨格を有する２価の酸無水物とジアミンを用いて製造されることを意味する。 Further, it is preferable that X 1 in the formula (1) and X 1 in the formula (3) are the same divalent group. This means that it has two or more of the same bisphenol skeletons, and means that the aromatic bismaleimide compound of the present invention is produced using a divalent acid anhydride and diamine that have the same bisphenol skeleton.
（Ａ）成分の芳香族ビスマレイミド化合物は、１種単独で用いてもよいし、２種以上を併用してもよい。本発明の(Ａ)成分、（Ｂ）成分及びその他の熱硬化樹脂成分の総和中、（Ａ）成分の含有量は６０～９５質量％であることが好ましく、６５～９０質量％であることがより好ましい。 The aromatic bismaleimide compound as the component (A) may be used alone or in combination of two or more. In the total of component (A), component (B), and other thermosetting resin components of the present invention, the content of component (A) is preferably 60 to 95% by mass, and preferably 65 to 90% by mass. is more preferable.
［（Ｂ）ビスフェノール構造を有するアリル基含有カーボネート樹脂］
本発明では（Ａ）成分の硬化剤として（Ｂ）ビスフェノール構造を有するアリル基含有カーボネート樹脂を使用する。硬化剤である（Ｂ）成分がビスフェノール構造を有することから（Ａ）成分の芳香族マレイミドとの相溶性に優れ、硬化ムラ等の発生も減少させることができる。
[(B) Allyl group-containing carbonate resin having a bisphenol structure]
In the present invention, (B) an allyl group-containing carbonate resin having a bisphenol structure is used as the curing agent for component (A). Since component (B), which is a curing agent, has a bisphenol structure, it has excellent compatibility with the aromatic maleimide of component (A), and can also reduce the occurrence of curing unevenness.
（Ｂ）成分のビスフェノール構造を有するアリル基含有カーボネート樹脂としては、下記式（４）で表される化合物が好ましいものとして挙げられる。
Ｘ3は、独立してアリル基含有ビスフェノール構造を有する２価の有機基及び／又はアリル基含有ビフェノール構造を有する２価の有機基を示す。 X 3 independently represents a divalent organic group having an allyl group-containing bisphenol structure and/or a divalent organic group having an allyl group-containing biphenol structure.
「アリル基含有ビスフェノール構造を有する２価の有機基」とは、ビスフェノールから２つのフェノール性ヒドロキシ基を除いた２価の有機基であって、置換基としてアリル基を１つ以上有し、他の置換基を有していてもよい２価の有機基をいう。
置換基以外の主骨格であるビスフェノール構造の例としては、ビスフェノールＡ型、ビスフェノールＦ型、ビスフェノールＢ型、ビスフェノールＡＰ型、ビスフェノールＣ型、ビスフェノールＥ型、ビスフェノールＳ型、ビスフェノールＺ型、ビスフェノールＡＦ型など挙げられるが、（Ａ）成分との相溶性や原料の入手のしやすさからビスフェノールＡ型、ビスフェノールＡＰ型、ビスフェノールＥ型、ビスフェノールＦ型が好ましい。
"Divalent organic group having an allyl group-containing bisphenol structure" is a divalent organic group obtained by removing two phenolic hydroxy groups from bisphenol, which has one or more allyl groups as a substituent, and other Refers to a divalent organic group which may have a substituent.
Examples of bisphenol structures that are main skeletons other than substituents include bisphenol A type, bisphenol F type, bisphenol B type, bisphenol AP type, bisphenol C type, bisphenol E type, bisphenol S type, bisphenol Z type, and bisphenol AF type. Among them, bisphenol A type, bisphenol AP type, bisphenol E type, and bisphenol F type are preferred from the viewpoint of compatibility with component (A) and ease of obtaining raw materials.
「アリル基含有ビフェノール構造を有する２価の有機基」とは、ビフェノールから２つのフェノール性ヒドロキシ基を除いた２価の有機基であって、置換基としてアリル基を１つ以上有し、他の置換基を有していてもよい２価の有機基をいう。
置換基以外の主骨格であるビフェノール構造とは、２つのフェノールの、フェノール性ヒドロキシ基が結合する炭素原子以外の芳香族環上の炭素原子同士が直接結合した構造である。
"Divalent organic group having an allyl group-containing biphenol structure" is a divalent organic group obtained by removing two phenolic hydroxy groups from biphenol, which has one or more allyl groups as a substituent, and other Refers to a divalent organic group which may have a substituent.
The biphenol structure, which is the main skeleton other than substituents, is a structure in which the carbon atoms on the aromatic rings of two phenols other than the carbon atoms to which the phenolic hydroxyl groups are bonded are directly bonded to each other.
また、ビスフェノール構造及びビフェノール構造の置換基としては、アリル基を必須とし、アリル基以外にその他の置換基としてハロゲン原子、アルキル基等が挙げられる。置換基の数は、アリル基は１分子中に１つでもよく２つ以上でもよく、その他の置換基は１分子中に０以上である。 Furthermore, as a substituent for the bisphenol structure and the biphenol structure, an allyl group is essential, and other substituents other than the allyl group include a halogen atom, an alkyl group, and the like. Regarding the number of substituents, the allyl group may be one or two or more in one molecule, and the number of other substituents is zero or more in one molecule.
Ｘ4は、独立してビスフェノール構造を有する２価の有機基、ビフェノール構造を有する２価の有機基、及び脂環式ジメタノール構造を有する２価の有機基から選ばれる１種以上の２価の有機基を示す。ビスフェノール構造を有する２価の有機基とビフェノール構造を有する２価の有機基に関しては、それぞれ上述のものと同様のものが例示できる。 X 4 is independently one or more divalent organic groups selected from a divalent organic group having a bisphenol structure, a divalent organic group having a biphenol structure, and a divalent organic group having an alicyclic dimethanol structure. represents an organic group. As for the divalent organic group having a bisphenol structure and the divalent organic group having a biphenol structure, the same ones as those mentioned above can be exemplified.
「脂環式ジメタノール構造を有する２価の有機基」とは、脂肪族環と、脂肪族環に結合した２つのメタノール基（－ＣＨ2ＯＨ）とを有する化合物から２個のＯＨ基を除いた２価の有機基であって、置換基を有していてもよい２価の有機基をいう。脂肪族環は、単環でもよく多環でもよい。この脂環式ジメタノール構造が硬化物の低誘電化に強く寄与する。
脂肪族環は、熱時の酸化による影響を減らすために飽和炭化水素脂肪族環であることが好ましい。脂肪族環の炭素数は、６～２０が好ましく、８～１５がより好ましい。
脂肪族環の具体例としては、シクロヘキサン環、トリシクロ［５．２．１．０2,6］デカン環、ビシクロ［４．４．０］デカン環、ビシクロ［２．２．１］ヘプタン環等が挙げられる。
また、置換基としては、アリル基、アルキル基、ハロゲン原子等が挙げられる。
"Divalent organic group having an alicyclic dimethanol structure" refers to a compound that has an aliphatic ring and two methanol groups (-CH 2 OH) bonded to the aliphatic ring. Refers to a divalent organic group which is removed and which may have a substituent. The aliphatic ring may be monocyclic or polycyclic. This alicyclic dimethanol structure strongly contributes to low dielectricity of the cured product.
The aliphatic ring is preferably a saturated hydrocarbon aliphatic ring in order to reduce the effects of oxidation during heating. The number of carbon atoms in the aliphatic ring is preferably 6 to 20, more preferably 8 to 15.
Specific examples of aliphatic rings include cyclohexane ring, tricyclo[5.2.1.0 2,6 ]decane ring, bicyclo[4.4.0]decane ring, bicyclo[2.2.1]heptane ring, etc. can be mentioned.
Further, examples of the substituent include an allyl group, an alkyl group, a halogen atom, and the like.
ｂは０以上の数であり、０～５０の数が好ましく、０～４０の数がより好ましい。また、ｂで括られた繰り返し単位が１種のホモポリマーでもよいし、２種以上のコポリマーであってもよく、コポリマーである場合は、繰り返し単位の１個以上（ｂ個以下）が脂環式ジメタノール構造を有することが好ましい。 b is a number of 0 or more, preferably a number of 0 to 50, more preferably a number of 0 to 40. Furthermore, the repeating units bounded by b may be one type of homopolymer or two or more types of copolymers, and in the case of a copolymer, one or more of the repeating units (not more than b) may be an alicyclic Preferably, it has a structure of the formula dimethanol.
（Ｂ）成分は１分子中に１個以上のビスフェノール構造を有する２価の有機基を有する。また、アリル基は必ずしもＸ3及びＸ4のすべての単位に含有している必要はないが、アリル基があることでマレイミドの硬化剤として好ましく使用することができる。
（Ｂ）成分中のアリル基の数は、１分子中に２個以上であることが好ましく、３～２０個であることがより好ましい。
Component (B) has one or more divalent organic groups having a bisphenol structure in one molecule. Further, although the allyl group does not necessarily need to be contained in all units of X 3 and X 4 , the presence of the allyl group allows it to be preferably used as a curing agent for maleimide.
The number of allyl groups in component (B) is preferably 2 or more in one molecule, more preferably 3 to 20.
（Ｂ）成分は軟化点が、７０～１３０℃のものが好ましく、９０～１２０℃のものがより好ましい。なお、本発明でいう軟化点とは、ＪＩＳ Ｋ ７２３４：１９８６記載の環球法により測定した値を指す。軟化点がこの範囲であると、未硬化樹脂フィルムにした際のタック性、かつ成形時の流動性や埋め込み性（成形性）のバランスの良いものとなる。（Ｂ）成分がこのような軟化点にあると、１５０℃におけるＩＣＩ粘度が１～１０Ｐａ・ｓの範囲となり、好ましくは２～８Ｐａ・ｓの範囲となる。
（Ｂ）成分のビスフェノール構造を有するアリル基含有カーボネート樹脂の配合量は、本発明の(Ａ)成分、（Ｂ）成分及びその他の熱硬化樹脂成分の総和中、５～４０質量％であることが好ましく、１０～３５質量％でより好ましい。
Component (B) preferably has a softening point of 70 to 130°C, more preferably 90 to 120°C. In addition, the softening point as used in the present invention refers to a value measured by the ring and ball method described in JIS K 7234:1986. When the softening point is within this range, the uncured resin film has a good balance of tackiness, fluidity and embeddability (moldability) during molding. When component (B) has such a softening point, the ICI viscosity at 150° C. will be in the range of 1 to 10 Pa·s, preferably in the range of 2 to 8 Pa·s.
The amount of the allyl group-containing carbonate resin having a bisphenol structure as component (B) shall be 5 to 40% by mass based on the total of component (A), component (B), and other thermosetting resin components of the present invention. It is preferably 10 to 35% by mass, and more preferably 10 to 35% by mass.
＜（Ｃ）反応開始剤＞
本発明で用いられる（Ｃ）成分の反応開始剤は、（Ａ）成分のマレイミド基及び（Ｂ）成分のアリル基の単独架橋反応や（Ａ）成分と（Ｂ）成分の架橋反応を促進するために添加するものである。
（Ｃ）成分としては架橋反応を促進するものであれば特に制限されるものではなく、例えば、イミダゾール類、第３級アミン類、第４級アンモニウム塩類、三フッ化ホウ素アミン錯体、オルガノホスフィン類、オルガノホスホニウム塩等のイオン触媒；有機過酸化物、ヒドロペルオキシド、アゾイソブチロニトリル等のラジカル重合開始剤などが挙げられる。これらの中でも、特に（Ａ）成分と（Ｂ）成分の架橋を促進する観点から有機過酸化物が好ましい。有機過酸化物としては、ジクミルパーオキシド、ｔ－ブチルパーオキシベンゾエート、ｔ－アミルパーオキシベンゾエート、ジベンゾイルパーオキシド、ジウラロイルパーオキシド等が挙げられる。
（Ｃ）成分の反応開始剤は、１種単独で用いてもよいし、２種以上を併用してもよい。
<(C) Reaction initiator>
The reaction initiator as component (C) used in the present invention promotes the independent crosslinking reaction of the maleimide group of component (A) and the allyl group of component (B), and the crosslinking reaction of component (A) and component (B). It is added for this purpose.
Component (C) is not particularly limited as long as it promotes the crosslinking reaction, and examples include imidazoles, tertiary amines, quaternary ammonium salts, boron trifluoride amine complexes, and organophosphines. , ionic catalysts such as organophosphonium salts; radical polymerization initiators such as organic peroxides, hydroperoxides, azoisobutyronitrile, and the like. Among these, organic peroxides are particularly preferred from the viewpoint of promoting crosslinking between components (A) and (B). Examples of the organic peroxide include dicumyl peroxide, t-butyl peroxybenzoate, t-amyl peroxybenzoate, dibenzoyl peroxide, diuraloyl peroxide, and the like.
The reaction initiator (C) component may be used alone or in combination of two or more.
（Ｃ）成分の反応開始剤の配合量は、（Ａ）成分と（Ｂ）成分の総和１００質量部に対して０．０５～１０質量部とすることが好ましく、０．１～５質量部とすることがより好ましい。上記範囲を外れると硬化物の耐熱性と耐湿性とのバランスが悪くなったり、成形時の硬化速度が非常に遅くなったり、速くなったりするおそれがある。
また、公知の事実であるが、種類によって成形時の硬化速度は異なり、例えば有機過酸化物を使用する際は有機過酸化物の半減期温度を確認する。半減期温度と反応開始温度には相関が強い。
The amount of the reaction initiator (C) is preferably 0.05 to 10 parts by weight, and preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total of components (A) and (B). It is more preferable that If it is out of the above range, the balance between heat resistance and moisture resistance of the cured product may become poor, and the curing speed during molding may become extremely slow or fast.
Furthermore, it is a well-known fact that the curing speed during molding differs depending on the type; for example, when using an organic peroxide, the half-life temperature of the organic peroxide is checked. There is a strong correlation between the half-life temperature and the reaction initiation temperature.
＜（Ｄ）有機溶剤＞
本発明の熱硬化性マレイミド樹脂組成物は、前記（Ａ）～（Ｃ）成分の他に、前記樹脂組成物をワニス化する目的で（Ｄ）有機溶剤を添加することが好ましい。前記有機溶剤の例としては、アニソール、テトラリン、キシレン、トルエン、テトラヒドロフラン（ＴＨＦ）、ジメチルホルムアミド（ＤＭＦ）、ジメチルスルホキシド（ＤＭＳＯ）、アセトニトリル等が挙げられる。これらは、１種単独で用いてもよいし、２種以上を併用してもよい。
<(D) Organic solvent>
In addition to the components (A) to (C), the thermosetting maleimide resin composition of the present invention preferably contains (D) an organic solvent for the purpose of converting the resin composition into a varnish. Examples of the organic solvent include anisole, tetralin, xylene, toluene, tetrahydrofuran (THF), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetonitrile, and the like. These may be used alone or in combination of two or more.
＜その他の添加剤＞
本発明の熱硬化性マレイミド樹脂組成物には、更に必要に応じて各種の添加剤を配合することができる。該添加剤として本発明の効果を損なわない範囲で、樹脂特性を改善するためにアクリル樹脂、エポキシ樹脂、（Ａ）成分以外の脂肪族環を有するマレイミド樹脂などの熱硬化性樹脂、オルガノポリシロキサン、シリコーンオイル、熱可塑性樹脂、熱可塑性エラストマー、有機合成ゴム、光安定剤、重合禁止剤、難燃剤、顔料、染料、接着助剤等を配合してもよいし、電気特性を改善するためにイオントラップ剤等を配合してもよい。さらには誘電特性を改善するために含フッ素材料等を配合してもよいし、熱膨張率（ＣＴＥ）の調整のためにシリカなどの無機充填材を加えてもよい。
<Other additives>
The thermosetting maleimide resin composition of the present invention may further contain various additives as necessary. As the additive, thermosetting resins such as acrylic resins, epoxy resins, maleimide resins having aliphatic rings other than component (A), and organopolysiloxanes are used to improve resin properties, within a range that does not impair the effects of the present invention. , silicone oil, thermoplastic resin, thermoplastic elastomer, organic synthetic rubber, light stabilizer, polymerization inhibitor, flame retardant, pigment, dye, adhesion aid, etc. may be added to improve the electrical properties. An ion trapping agent or the like may be added. Furthermore, a fluorine-containing material or the like may be added to improve the dielectric properties, and an inorganic filler such as silica may be added to adjust the coefficient of thermal expansion (CTE).
本発明の熱硬化性マレイミド樹脂組成物は、（Ａ）成分、（Ｂ）成分及び（Ｃ）成分並びに必要に応じて添加されるその他の添加剤を混合することにより製造することができる。
この熱硬化性マレイミド樹脂組成物は、フィルム状やシート状に加工することができ、未硬化でも硬化後でもそのフィルムのハンドリング性は良く、例えば１８０°にフィルムを折り曲げてもフィルムが二つに切れることがない。以下にフィルムの作製方法や使用例を例示するが、これに限定されるものではない。
The thermosetting maleimide resin composition of the present invention can be produced by mixing component (A), component (B), component (C), and other additives added as necessary.
This thermosetting maleimide resin composition can be processed into a film or sheet, and the film has good handling properties whether uncured or after curing. It never breaks. A method for producing a film and an example of its use are illustrated below, but the invention is not limited thereto.
例えば、アニソールなどの（Ｄ）有機溶剤に、（Ａ）～（Ｃ）成分及び必要に応じて添加されるその他の添加剤を入れ、熱硬化性マレイミド樹脂組成物を含むワニスを作製し、それを支持シートに塗工した後、通常８０℃以上、好ましくは１００℃以上の温度で０．５～５時間加熱することにより、有機溶剤が除去され、未硬化のフィルム状樹脂組成物を作製することができる。さらに１５０℃以上、好ましくは１７５℃以上の温度で０．５～１０時間加熱することで、表面が平坦で強固なマレイミド硬化樹脂フィルムを形成することができる。樹脂組成物中の溶剤を効率的に系外へ除去するとともに樹脂の反応を効果的に進めるため、場合によっては段階的に硬化温度を上げていくのが好ましい。 For example, a varnish containing a thermosetting maleimide resin composition is prepared by adding components (A) to (C) and other additives added as necessary to an organic solvent (D) such as anisole. After coating the support sheet, the organic solvent is removed by heating at a temperature of usually 80°C or higher, preferably 100°C or higher for 0.5 to 5 hours, producing an uncured film-like resin composition. be able to. Further, by heating at a temperature of 150° C. or higher, preferably 175° C. or higher for 0.5 to 10 hours, a strong maleimide cured resin film with a flat surface can be formed. In order to efficiently remove the solvent in the resin composition from the system and to effectively advance the reaction of the resin, it is preferable to raise the curing temperature in stages depending on the case.
ワニスの支持シートへの塗工方法も特に限定されず、ギャップコーター、カーテンコーター、ロールコーター及びラミネータ等が挙げられる。また、塗工層の厚みも特に限定されないが、有機溶剤留去後の厚みが１～１００μｍ、好ましくは３～８０μｍの範囲である。さらに塗工層の上にカバーフィルムを使用しても構わない。また、ワニス化せずに（Ａ）～（Ｃ）成分やその他の成分をプレ混合し、押し出し機等で混練し、シート状の混練物としてシート状組成物を得てもよい。 The method for applying the varnish to the support sheet is not particularly limited, and examples thereof include a gap coater, curtain coater, roll coater, and laminator. Further, the thickness of the coating layer is not particularly limited, but the thickness after distilling off the organic solvent is in the range of 1 to 100 μm, preferably 3 to 80 μm. Furthermore, a cover film may be used on the coating layer. Alternatively, components (A) to (C) and other components may be pre-mixed without being made into a varnish, and then kneaded using an extruder or the like to obtain a sheet-like kneaded product.
また塗工してフィルム状に使用する際に使用する、支持シートとしては、一般的に用いられるのを用いてよく、例えばポリエチレン（ＰＥ）樹脂、ポリプロピレン（ＰＰ）樹脂、ポリスチレン（ＰＳ）樹脂などのポリオレフィン樹脂、ポリエチレンテレフタレート（ＰＥＴ）樹脂、ポリブチレンテレフタレート（ＰＢＴ）樹脂、ポリカーボネート（ＰＣ）樹脂などのポリエステル樹脂、などが挙げられ、この表面を離形処理したものでも構わない。 In addition, as the support sheet used when coating and using it in the form of a film, commonly used materials may be used, such as polyethylene (PE) resin, polypropylene (PP) resin, polystyrene (PS) resin, etc. Examples include polyester resins such as polyolefin resins, polyethylene terephthalate (PET) resins, polybutylene terephthalate (PBT) resins, and polycarbonate (PC) resins, and those whose surfaces have been subjected to mold release treatment may also be used.
本発明の組成物の硬化により得られる硬化樹脂フィルムは、耐熱性、機械的特性、電気的特性、基材に対する接着性及び耐溶剤性に優れている上、低誘電率を有しているため、各種方法により各種基材、例えば半導体装置、具体的には半導体素子表面のパッシベーション膜、保護膜、ダイオード、トランジスタ等の接合部のジャンクション保護膜、ＶＬＳＩのα線遮蔽膜、層間絶縁膜、イオン注入マスク等のほか、プリントサーキットボードのコンフォーマルコート、液晶表面素子の配向膜、ガラスファイバーの保護膜、太陽電池の表面保護膜、更に樹脂組成物に無機フィラーを配合した印刷用ペースト組成物、導電性充填材を配合した導電性ペースト組成物といったペースト組成物など幅広い範囲にわたり利用することができる。 The cured resin film obtained by curing the composition of the present invention has excellent heat resistance, mechanical properties, electrical properties, adhesion to substrates, and solvent resistance, and has a low dielectric constant. By various methods, various substrates, such as semiconductor devices, specifically passivation films on the surface of semiconductor elements, protective films, diodes, junction protective films at junctions of transistors, etc., α-ray shielding films for VLSI, interlayer insulating films, ions In addition to injection masks, we also produce conformal coats for printed circuit boards, alignment films for liquid crystal surface elements, protective films for glass fibers, surface protective films for solar cells, and printing paste compositions containing inorganic fillers in resin compositions. It can be used in a wide range of paste compositions, such as conductive paste compositions containing conductive fillers.
その中でも、特にＦＰＣ用途への適用が好ましい。硬化樹脂フィルムに関しては、ＦＰＣのコア基板やカバーレイフィルムとして好適であり、銅箔を貼りつけることで銅張積層板としても使用することができる。また、熱硬化樹脂であるため、未硬化樹脂フィルムをそのまま接着剤やダイボンドフィルムとして使用することもできる。 Among these, application to FPC applications is particularly preferable. The cured resin film is suitable as a core substrate of FPC or a coverlay film, and can also be used as a copper-clad laminate by pasting copper foil. Moreover, since it is a thermosetting resin, the uncured resin film can also be used as it is as an adhesive or a die-bonding film.
以下、実施例及び比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。 EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples, but the present invention is not limited to the Examples below.
（Ａ）成分の製造方法を以下に示す。尚、以下において数平均分子量（Ｍｎ）はポリスチレンを基準として、下記測定条件により測定されたものである。
展開溶媒：テトラヒドロフラン（ＴＨＦ）
流量：０．３５ｍＬ／ｍｉｎ
検出器：示差屈折率検出器（ＲＩ）
カラム： ＴＳＫ Ｇｕａｒｄｃｏｌｕｍｎ ＳｕｐｅｒＨ－Ｌ
ＴＳＫｇｅｌ ＳｕｐｅｒＨＺ４０００（４．６ｍｍＩ．Ｄ．×１５ｃｍ×１）
ＴＳＫｇｅｌ ＳｕｐｅｒＨＺ３０００（４．６ｍｍＩ．Ｄ．×１５ｃｍ×１）
ＴＳＫｇｅｌ ＳｕｐｅｒＨＺ２０００（４．６ｍｍＩ．Ｄ．×１５ｃｍ×２）
（いずれも東ソー社製）
カラム温度：４０℃
試料注入量：５μＬ（濃度０．２質量％のＴＨＦ溶液）
The method for producing component (A) is shown below. In the following, the number average molecular weight (Mn) is measured under the following measurement conditions using polystyrene as a reference.
Developing solvent: Tetrahydrofuran (THF)
Flow rate: 0.35mL/min
Detector: Differential refractive index detector (RI)
Column: TSK Guardcolumn SuperHL
TSKgel SuperHZ4000 (4.6mm I.D. x 15cm x 1)
TSKgel SuperHZ3000 (4.6mm I.D. x 15cm x 1)
TSKgel SuperHZ2000 (4.6mm I.D. x 15cm x 2)
(Both manufactured by Tosoh Corporation)
Column temperature: 40℃
Sample injection amount: 5 μL (THF solution with a concentration of 0.2% by mass)
［合成例１］
攪拌機、ディーンスターク管、冷却コンデンサー及び温度計を備えた１Ｌのガラス製４つ口フラスコに、２，２－ビス［４－（２，３－ジカルボキシフェノキシ）フェニル］プロパン二無水物６５．０６ｇ（０．１２５モル）、４，４－メチレンビス（２，６－ジエチルアニリン）３５．２６ｇ（０．１１５モル）及びアニソール２５０ｇを加え、８０℃で３時間撹拌することでアミック酸を合成した。その後、そのまま１５０℃に昇温し、副生した水分を留去しながら２時間撹拌し、ブロックコポリマーを合成した。
その後、室温まで冷却したブロックコポリマー溶液入りのフラスコに、２，２－ビス［４－（４－アミノフェノキシ）フェニル］プロパン７．０５ｇ（０．０１５モル）を加え、８０℃で３時間撹拌することでアミック酸を合成した。その後、そのまま１５０℃に昇温し、副生した水分を留去しながら２時間撹拌し、両末端ジアミン体を合成した。
得られた両末端ジアミン体溶液入りのフラスコを室温まで冷却してから無水マレイン酸を１．４５ｇ（０．０１５モル）加え、８０℃で３時間撹拌することでアミック酸を合成した。その後、そのまま１５０℃に昇温し、副生した水分を留去しながら２時間撹拌し、下記式（５）で示される芳香族マレイミド化合物のワニスを得た。芳香族マレイミド化合物のＭｎは１１，５００であった。
65.06 g of 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride was placed in a 1 L glass four-necked flask equipped with a stirrer, Dean-Stark tube, cooling condenser, and thermometer. (0.125 mol), 35.26 g (0.115 mol) of 4,4-methylenebis(2,6-diethylaniline), and 250 g of anisole were added and stirred at 80° C. for 3 hours to synthesize amic acid. Thereafter, the temperature was raised to 150° C., and the mixture was stirred for 2 hours while distilling off by-product water to synthesize a block copolymer.
Then, 7.05 g (0.015 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane is added to the flask containing the block copolymer solution cooled to room temperature, and the mixture is stirred at 80°C for 3 hours. In this way, amic acid was synthesized. Thereafter, the temperature was raised to 150° C., and the mixture was stirred for 2 hours while distilling off the by-produced water to synthesize a diamine compound at both ends.
The flask containing the obtained solution of the diamine at both terminals was cooled to room temperature, 1.45 g (0.015 mol) of maleic anhydride was added, and the mixture was stirred at 80° C. for 3 hours to synthesize amic acid. Thereafter, the temperature was raised to 150° C., and the mixture was stirred for 2 hours while distilling off the by-produced water, to obtain a varnish of an aromatic maleimide compound represented by the following formula (5). Mn of the aromatic maleimide compound was 11,500.
［合成例２］
攪拌機、ディーンスターク管、冷却コンデンサー及び温度計を備えた１Ｌのガラス製４つ口フラスコに、２，２－ビス［４－（２，３－ジカルボキシフェノキシ）フェニル］プロパン二無水物６５．０６ｇ（０．１２５モル）、４，４－メチレンビス（２，６－ジプロピルアニリン）４０．７８ｇ（０．１１５モル）及びアニソール２５０ｇを加え、８０℃で３時間撹拌することでアミック酸を合成した。その後、そのまま１５０℃に昇温し、副生した水分を留去しながら２時間撹拌し、ブロックコポリマーを合成した。
その後、室温まで冷却したブロックコポリマー溶液入りのフラスコに、２，２－ビス［４－（４－アミノフェノキシ）フェニル］プロパン７．０５ｇ（０．０１５モル）を加え、８０℃で３時間撹拌することでアミック酸を合成した。その後、そのまま１５０℃に昇温し、発生した水分を留去しながら２時間撹拌し、両末端ジアミン体を合成した。
得られた両末端ジアミン体溶液の入ったフラスコを室温まで冷却させてから無水マレイン酸を１．４５ｇ（０．０１５モル）加え、８０℃で３時間撹拌することでアミック酸を合成した。その後、そのまま１５０℃に昇温し、副生した水分を留去しながら２時間撹拌し、下記式（６）で示される芳香族マレイミド化合物のワニスを得た。芳香族マレイミド化合物のＭｎは１２，５００であった。
65.06 g of 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride was placed in a 1 L glass four-necked flask equipped with a stirrer, Dean-Stark tube, cooling condenser, and thermometer. (0.125 mol), 40.78 g (0.115 mol) of 4,4-methylenebis(2,6-dipropylaniline) and 250 g of anisole were added and stirred at 80°C for 3 hours to synthesize amic acid. . Thereafter, the temperature was raised to 150° C., and the mixture was stirred for 2 hours while distilling off by-product water to synthesize a block copolymer.
Then, 7.05 g (0.015 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane is added to the flask containing the block copolymer solution cooled to room temperature, and the mixture is stirred at 80°C for 3 hours. In this way, amic acid was synthesized. Thereafter, the temperature was raised to 150° C., and the mixture was stirred for 2 hours while distilling off the water generated, thereby synthesizing a diamine compound at both ends.
The flask containing the obtained solution of the diamine at both ends was cooled to room temperature, 1.45 g (0.015 mol) of maleic anhydride was added, and the mixture was stirred at 80° C. for 3 hours to synthesize amic acid. Thereafter, the temperature was directly raised to 150° C., and the mixture was stirred for 2 hours while distilling off by-produced water to obtain a varnish of an aromatic maleimide compound represented by the following formula (6). Mn of the aromatic maleimide compound was 12,500.
［実施例１］
合成例１で合成した式（５）の芳香族マレイミド化合物を含む不揮発分４０質量％のアニソールワニス１００ｇ準備し、アリルビスフェノールＦ・トリシクロデカンジメタノール共縮合カーボネート樹脂（群栄化学工業（株）製、軟化点１０３℃）を１２ｇ添加し、１１０℃で撹拌し、すべて溶解させて室温まで放冷した。そのワニスに０．４ｇのジクミルパーオキシドを添加し、すべて溶解させて熱硬化性マレイミド樹脂組成物を調製した。
[Example 1]
100 g of anisole varnish with a nonvolatile content of 40% by mass containing the aromatic maleimide compound of formula (5) synthesized in Synthesis Example 1 was prepared, and allylbisphenol F/tricyclodecane dimethanol cocondensed carbonate resin (Gun-ei Chemical Industry Co., Ltd.) was prepared. Added thereto was 12 g of 100% polyamide, with a softening point of 103°C), and the mixture was stirred at 110°C to dissolve everything and allowed to cool to room temperature. 0.4 g of dicumyl peroxide was added to the varnish and completely dissolved to prepare a thermosetting maleimide resin composition.
［実施例２］
合成例１で合成した式（５）の芳香族マレイミド化合物を含む不揮発分４０質量％のアニソールワニス１００ｇに替えて、合成例２で合成した式（６）の芳香族マレイミド化合物を含む不揮発分４０％のアニソールワニス１００ｇを用いた他は実施例１と同様の方法で熱硬化性マレイミド樹脂組成物を調製した。
[Example 2]
In place of 100 g of anisole varnish with a non-volatile content of 40% by mass containing the aromatic maleimide compound of formula (5) synthesized in Synthesis Example 1, 40 g of non-volatile content containing the aromatic maleimide compound of formula (6) synthesized in Synthesis Example 2 was used. A thermosetting maleimide resin composition was prepared in the same manner as in Example 1, except that 100 g of % anisole varnish was used.
［比較例１］
合成例１で合成した式（５）の芳香族マレイミド化合物を含む不揮発分４０質量％のアニソールワニス１００ｇを準備し、そのワニスに０．４ｇのジクミルパーオキシドを添加し、すべて溶解させて熱硬化性マレイミド樹脂組成物を調製した。
[Comparative example 1]
Prepare 100 g of anisole varnish containing the aromatic maleimide compound of formula (5) synthesized in Synthesis Example 1 and having a nonvolatile content of 40% by mass, add 0.4 g of dicumyl peroxide to the varnish, dissolve it all, and heat it. A curable maleimide resin composition was prepared.
［比較例２］
合成例１で合成した式（５）の芳香族マレイミド化合物を含む不揮発分４０質量％のアニソールワニス１００ｇを準備し、アルケニル基含有フェノール樹脂（群栄化学工業（株）製、製品名：１ＰＰ－２、２５℃で固体）を１２ｇ添加し、１１０℃で撹拌し、すべて溶解させて室温まで放冷した。そのワニスに０．４ｇのジクミルパーオキシドを添加し、すべて溶解させて熱硬化性マレイミド樹脂組成物を調製した。
[Comparative example 2]
100 g of anisole varnish containing the aromatic maleimide compound of formula (5) synthesized in Synthesis Example 1 and having a nonvolatile content of 40% by mass was prepared, and an alkenyl group-containing phenol resin (manufactured by Gun-ei Chemical Industry Co., Ltd., product name: 1PP-) was prepared. 2. Solid at 25° C.) was added thereto, and the mixture was stirred at 110° C. to dissolve everything and allowed to cool to room temperature. 0.4 g of dicumyl peroxide was added to the varnish and completely dissolved to prepare a thermosetting maleimide resin composition.
［比較例３］
合成例１で合成した式（５）の芳香族マレイミド化合物を含む不揮発分４０質量％のアニソールワニス１００ｇに替えて、フェニルメタンマレイミド（大和化成工業（株）製、製品名：ＢＭＩ－２３００）４０ｇを用いた他は実施例１と同様の方法で熱硬化性マレイミド樹脂組成物を調製した。
[Comparative example 3]
In place of 100 g of anisole varnish containing the aromatic maleimide compound of formula (5) synthesized in Synthesis Example 1 and having a non-volatile content of 40% by mass, 40 g of phenylmethane maleimide (manufactured by Daiwa Kasei Kogyo Co., Ltd., product name: BMI-2300) was used. A thermosetting maleimide resin composition was prepared in the same manner as in Example 1 except that .
［比較例４］
下記構造を有する長鎖アルキル基含有マレイミド化合物（Ｄｅｓｉｇｎｅｒ Ｍｏｌｅｃｕｌｅｓ Ｉｎｃ．製、製品名：ＢＭＩ－３０００Ｊ）４０ｇ、ジクミルパーオキシドを０．４ｇ準備し、これらを６０ｇのトルエンに添加し、すべて溶解させて熱硬化性マレイミド樹脂組成物を調製した。
Prepare 40 g of a long-chain alkyl group-containing maleimide compound having the following structure (manufactured by Designer Molecules Inc., product name: BMI-3000J) and 0.4 g of dicumyl peroxide, add these to 60 g of toluene, and dissolve them all. A thermosetting maleimide resin composition was prepared.
［比較例５］
比較用のポリイミドとして、ポリイミド製フィルム（東レ・デュポン社製、製品名：カプトン、厚さ５０μｍ）を用いた。
[Comparative example 5]
As a polyimide for comparison, a polyimide film (manufactured by DuPont-Toray, product name: Kapton, thickness 50 μm) was used.
［比較例６］
比較用のＭＰＩ（変性ポリイミド）として、変性ポリイミド製フィルム（カネカ製、製品名：アピカルＮＰＩ、厚さ５０μｍ）を用いた。
[Comparative example 6]
As MPI (modified polyimide) for comparison, a modified polyimide film (manufactured by Kaneka, product name: Apical NPI, thickness 50 μm) was used.
＜フィルムの作製＞
［実施例１、２、比較例１～４］
実施例１、２、比較例１～４で調製したワニス状の熱硬化性マレイミド樹脂組成物を、厚さ３８μｍのＰＥＴフィルム上に、乾燥後の厚さが５０μｍになるようにローラーコーターで塗布し、１００℃で２０分間乾燥させて未硬化樹脂フィルムを得た。さらに、前記未硬化樹脂フィルムを、厚さ１００μｍのテトラフルオロエチレン－エチレン共重合樹脂フィルム（ＡＧＣ株式会社製、製品名：アフレックス）上に、未硬化樹脂フィルムの樹脂層がテトラフルオロエチレン－エチレン共重合樹脂フィルムに接するように載せ、１８０℃で１時間の条件で硬化させることで硬化樹脂フィルムを得た。
なお、下記評価試験では、ＰＥＴフィルムを剥がした未硬化樹脂フィルム、ＰＥＴフィルム及びテトラフルオロエチレン－エチレン共重合樹脂フィルムを剥がした硬化樹脂フィルムを各評価試験に供した。その結果を表１及び表２に示す。
<Production of film>
[Examples 1 and 2, Comparative Examples 1 to 4]
The varnish-like thermosetting maleimide resin compositions prepared in Examples 1 and 2 and Comparative Examples 1 to 4 were applied onto a PET film with a thickness of 38 μm using a roller coater so that the thickness after drying was 50 μm. Then, it was dried at 100° C. for 20 minutes to obtain an uncured resin film. Furthermore, the uncured resin film was placed on a 100 μm thick tetrafluoroethylene-ethylene copolymer resin film (manufactured by AGC Corporation, product name: Afflex), and the resin layer of the uncured resin film was coated with tetrafluoroethylene-ethylene copolymer resin film. A cured resin film was obtained by placing it in contact with a copolymer resin film and curing it at 180° C. for 1 hour.
In the evaluation tests described below, an uncured resin film from which the PET film was removed, and a cured resin film from which the PET film and the tetrafluoroethylene-ethylene copolymer resin film were removed were subjected to each evaluation test. The results are shown in Tables 1 and 2.
＜フィルムハンドリング性＞
前記未硬化樹脂フィルム及び硬化樹脂フィルムを１８０°に５回折り曲げ、フィルムに割れなどの欠陥がでないものを○、フィルムに割れなどの欠陥が出たものを×とした。
比較例５及び比較例６では、それぞれ上記ポリイミド製フィルム及び変性ポリイミド製フィルムを用いて、実施例１、２、比較例１～４の未硬化樹脂フィルム及び硬化樹脂フィルムと同様にフィルムハンドリング性を試験し、評価した。
<Film handling properties>
The uncured resin film and the cured resin film were bent 5 times at 180°, and a film with no defects such as cracks was rated ◯, and a film with defects such as cracks was rated ×.
In Comparative Examples 5 and 6, using the polyimide film and modified polyimide film, respectively, film handling properties were evaluated in the same way as the uncured resin films and cured resin films of Examples 1 and 2 and Comparative Examples 1 to 4. Tested and evaluated.
＜比誘電率、誘電正接＞
前記硬化樹脂フィルムを用いて、ネットワークアナライザ（キーサイト社製 Ｅ５０６３－２Ｄ５）とストリップライン（キーコム株式会社製）を接続し、上記硬化樹脂フィルムの周波数１０ＧＨｚにおける比誘電率と誘電正接を測定した。
比較例５及び比較例６では、それぞれ上記ポリイミド製フィルム及び変性ポリイミド製フィルムを用いて、実施例１、２、比較例１～４の硬化樹脂フィルムと同様に比誘電率と誘電正接を測定した。
<Relative permittivity, dielectric loss tangent>
Using the cured resin film, a network analyzer (E5063-2D5 manufactured by Keysight Corporation) and a strip line (manufactured by Keycom Corporation) were connected, and the dielectric constant and dielectric loss tangent of the cured resin film at a frequency of 10 GHz were measured.
In Comparative Example 5 and Comparative Example 6, the dielectric constant and dielectric loss tangent were measured in the same manner as the cured resin films of Examples 1, 2, and Comparative Examples 1 to 4 using the above polyimide film and modified polyimide film, respectively. .
＜ガラス転移温度＞
前記硬化樹脂フィルムのガラス転移温度（Ｔｇ）をＴＡインスツルメント製ＤＭＡ－８００により測定した。
比較例５及び比較例６では、それぞれ上記ポリイミド製フィルム及び変性ポリイミド製フィルムを用いて、実施例１、２、比較例１～４の硬化樹脂フィルムと同様にガラス転移温度を測定した。
<Glass transition temperature>
The glass transition temperature (Tg) of the cured resin film was measured using DMA-800 manufactured by TA Instruments.
In Comparative Example 5 and Comparative Example 6, the glass transition temperature was measured in the same manner as the cured resin films of Examples 1 and 2 and Comparative Examples 1 to 4 using the above-mentioned polyimide film and modified polyimide film, respectively.
＜吸湿による比誘電率、誘電正接への影響＞
実施例１の前記硬化樹脂フィルムと比較例５、６の樹脂フィルムを、８５℃、８５％ＲＨの恒温恒湿器に入れ、各樹脂フィルムを各所定の時間吸湿させた。吸湿後の樹脂フィルムを用いてネットワークアナライザ（キーサイト社製 Ｅ５０６３－２Ｄ５）とストリップライン（キーコム株式会社製）を接続し、上記樹脂フィルムの周波数１０ＧＨｚにおける比誘電率と誘電正接を測定した。
<Influence of moisture absorption on relative permittivity and dielectric loss tangent>
The cured resin film of Example 1 and the resin films of Comparative Examples 5 and 6 were placed in a constant temperature and humidity chamber at 85° C. and 85% RH, and each resin film was allowed to absorb moisture for a predetermined period of time. A network analyzer (E5063-2D5 manufactured by Keysight Corporation) and a strip line (manufactured by Keycom Corporation) were connected using the resin film after absorbing moisture, and the dielectric constant and dielectric loss tangent of the resin film at a frequency of 10 GHz were measured.
以上から本発明の熱硬化性マレイミド樹脂組成物は、ＮＭＰを用いずに製造することができ、硬化物のガラス転移温度が高く、吸湿前後において誘電特性に優れ、該組成物からなる未硬化樹脂フィルム及び硬化樹脂フィルムはハンドリング性に優れることから、ＦＰＣ用途への有用性が確認できた。 From the above, the thermosetting maleimide resin composition of the present invention can be produced without using NMP, has a high glass transition temperature of the cured product, has excellent dielectric properties before and after absorbing moisture, and has an uncured resin composition made of the composition. Since the film and the cured resin film had excellent handling properties, their usefulness for FPC applications was confirmed.
Claims (7)
Ｘ 1 は独立して、下記式
ｍは１～３０の数であり、
ｎは１～５の数であり、
Ａ 1 及びＡ 2 はそれぞれ独立して、下記式（２）
Ｘ 2 は独立して、下記式
Ｒ 1 は独立して、水素原子、塩素原子、又は炭素数１～６の脂肪族炭化水素基である）
又は下記式（３）
で示される２価の芳香族基である。）
（Ｂ）ビスフェノール構造を有するアリル基含有カーボネート樹脂
及び
（Ｃ）反応開始剤
を含む熱硬化性マレイミド樹脂組成物。 (A) An aromatic bismaleimide compound represented by the following general formula (1), which has a bisphenol structure and a number average molecular weight of 3,000 to 50,000.
X 1 is independently the following formula
m is a number from 1 to 30,
n is a number from 1 to 5,
A 1 and A 2 are each independently expressed by the following formula (2)
X 2 is independently the following formula
R 1 is independently a hydrogen atom, a chlorine atom, or an aliphatic hydrocarbon group having 1 to 6 carbon atoms)
Or the following formula (3)
It is a divalent aromatic group represented by )
A thermosetting maleimide resin composition comprising (B) an allyl group-containing carbonate resin having a bisphenol structure and (C) a reaction initiator.
A cured resin film comprising a cured product of the thermosetting maleimide resin composition according to claim 1.
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| JP2020188889A Active JP7387235B2 (en) | 2020-11-12 | 2020-11-12 | Thermosetting maleimide resin composition, uncured resin film and cured resin film comprising the resin composition |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013001872A (en) | 2011-06-20 | 2013-01-07 | Hitachi Cable Ltd | Polyamideimide resin insulating coating material, insulated wire, and coil |
| US20140058057A1 (en) | 2012-08-24 | 2014-02-27 | Sajal Das | Polyimide oligomers |
| JP2019089967A (en) | 2017-11-16 | 2019-06-13 | 群栄化学工業株式会社 | Allyl group-containing carbonate resin, method for producing the same, resin varnish, and method for producing laminated plate |
| JP2020136311A (en) | 2019-02-13 | 2020-08-31 | 住友ベークライト株式会社 | Resin composition, resin film with carrier using the same, pre-preg, laminate sheet, printed wiring board and semiconductor device |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0388810A (en) * | 1989-09-01 | 1991-04-15 | Hitachi Ltd | Thermosetting resin composition |
| JPH05255564A (en) * | 1991-10-22 | 1993-10-05 | Toray Ind Inc | Maleimide resin composition, prepreg and fiber-reinforced plastic |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013001872A (en) | 2011-06-20 | 2013-01-07 | Hitachi Cable Ltd | Polyamideimide resin insulating coating material, insulated wire, and coil |
| US20140058057A1 (en) | 2012-08-24 | 2014-02-27 | Sajal Das | Polyimide oligomers |
| JP2019089967A (en) | 2017-11-16 | 2019-06-13 | 群栄化学工業株式会社 | Allyl group-containing carbonate resin, method for producing the same, resin varnish, and method for producing laminated plate |
| JP2020136311A (en) | 2019-02-13 | 2020-08-31 | 住友ベークライト株式会社 | Resin composition, resin film with carrier using the same, pre-preg, laminate sheet, printed wiring board and semiconductor device |
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| JP2022077847A (en) | 2022-05-24 |
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