JP2022077847A - Thermosetting maleimide resin composition, and uncured resin film and cured resin film comprising the resin composition - Google Patents
Thermosetting maleimide resin composition, and uncured resin film and cured resin film comprising the resin composition Download PDFInfo
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- JP2022077847A JP2022077847A JP2020188889A JP2020188889A JP2022077847A JP 2022077847 A JP2022077847 A JP 2022077847A JP 2020188889 A JP2020188889 A JP 2020188889A JP 2020188889 A JP2020188889 A JP 2020188889A JP 2022077847 A JP2022077847 A JP 2022077847A
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- bisphenol
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- thermosetting
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- 229920005989 resin Polymers 0.000 title claims abstract description 63
- 239000011347 resin Substances 0.000 title claims abstract description 63
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000011342 resin composition Substances 0.000 title claims abstract description 46
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 42
- 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 abstract description 43
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 30
- -1 aromatic maleimide compound Chemical class 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 8
- 125000000962 organic group Chemical group 0.000 claims description 41
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 125000001931 aliphatic group Chemical group 0.000 claims description 12
- 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
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 8
- 150000001875 compounds Chemical class 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
- 230000009477 glass transition Effects 0.000 abstract description 8
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 59
- 239000000203 mixture Substances 0.000 description 25
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 229920001721 polyimide Polymers 0.000 description 14
- 239000002966 varnish Substances 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 11
- 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
- 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
- 239000002904 solvent 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
- 239000000758 substrate Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 125000002723 alicyclic group Chemical group 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
- 238000000465 moulding Methods 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229920005992 thermoplastic resin Polymers 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
- 239000012787 coverlay film Substances 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 125000005843 halogen group Chemical group 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
- 150000002500 ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing 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
- 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
- 239000011247 coating layer Substances 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
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 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
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 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
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 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
- 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
- 239000005977 Ethylene Substances 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
- 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
- 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
- 229910052799 carbon 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
- 238000010438 heat treatment Methods 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
- 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
- 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
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) 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
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000004065 semiconductor Substances 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
- 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
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- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
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 an uncured and cured resin film 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, the next-generation mobile communication system of 5G has become popular, and is trying to realize high-speed, large-capacity, and low-delay communication. In order to realize these, materials for high frequency bands are required, and reduction of transmission loss is indispensable as a noise countermeasure. Therefore, development of an insulating material having excellent dielectric properties is required.
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 them, there is a demand for an insulating material having such excellent dielectric properties for substrate applications. Generally, a substrate called a flexible printed wiring board (FPC) is used in various electronic devices such as smartphones and liquid crystal televisions. Polyimide has been widely used as a base material for this FPC, but in recent years, a product called a liquid crystal polymer (LCP) or a modified polyimide (MPI) having improved properties has been used 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 improvement of LCP performance and FPC base film and coverlay film using LCP (for example, Patent Documents 1 and 2), but LCP meets the demand. The use is limited due to the difficulty of mass production, molding at a high temperature of 300 ° C or higher, which is a problem peculiar to thermoplastic resins, is essential, and low dielectric is used to bond copper-clad laminates. There are many points that need to be improved, such as the need for an adhesive with properties.
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 studied depending on the frequency band, and many inventions have been disclosed regarding MPI (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 are caused by the hygroscopicity peculiar to polyimides. Therefore, it is known that the dielectric property becomes very poor. An MPI having a diamine diamine skeleton is also disclosed in order to solve these problems (Patent Document 7), but the glass transition temperature (Tg) is significantly lower than that of the conventional MPI, and the dimensional stability is also lacking. Further, when producing MPI, it is essential to use a large amount of an aprotic polar solvent, for example, N-methylpyrrolidone (NMP), and the use of an aprotic polar solvent is not preferable from the viewpoint of environmental protection. ..
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 a substantially dimerdiamine skeleton as a material for FPC and a cured product thereof have been disclosed (Patent Document 8), although they are very excellent in dielectric properties but low. It has Tg and a high coefficient of thermal expansion (CTE), and is still lacking in 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, and the characteristics and curing of the composition and its cured product are uneven. 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。 In addition, epoxy resin and modified polyphenylene ether resin (PPE), which are generally used for rigid wiring boards, are very difficult to apply to FPC from the viewpoint of handling as a film.
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 has a high glass transition temperature (Tg) and absorbs moisture without using an insulating material having excellent dielectric properties, particularly an aprotonic solvent such as NMP, which is suitable for flexible printed wiring board (FPC) applications. It is an object of the present invention to provide a thermosetting maleimide resin composition, and an uncured resin film and a cured resin film made from the thermosetting maleimide resin composition, which also give a cured product having 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 studies to solve the above problems, the present inventors have found that the following thermosetting maleimide resin composition can achieve the above object, and have 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>
Thermosetting containing (A) an allyl group-containing carbonate resin having a bisphenol structure and an aromatic maleimide (B) bisphenol structure having a number average molecular weight of 3,000 to 50,000 and (C) 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 and
A 1 and A 2 are independent of each other, and the following equation (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 of the formula (1) and X 1 of 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 made of 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 is excellent in dielectric properties. In addition, it is excellent in handleability as a film or sheet before and after curing. Further, 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 has excellent dielectric properties even after absorbing moisture.
Therefore, the thermosetting maleimide resin composition of the present invention can be suitably used for FPC, and specifically, as a core substrate or a coverlay film, and further, because it is thermosetting, itself is an adhesive. Can also be used as.
以下、本発明につき更に詳しく説明する。 Hereinafter, the present invention will be described in more detail.
＜（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>
The component (A) is an aromatic maleimide having a bisphenol structure and a number average molecular weight of 3,000 to 50,000. The component (A) has two or more, preferably 2 to 5 maleimide groups in one molecule, and is preferably aromatic bismaleimide.
（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 of the component (A) is 3,000 to 50,000, preferably 5,000 to 40,000. If the number average molecular weight is less than 3,000, the processability / moldability into a film is deteriorated, and if the number average molecular weight exceeds 50,000, the solubility in a solvent becomes unstable, which is not preferable. The number average molecular weight referred to in the present invention refers to the number average molecular weight using polystyrene as a standard substance measured by gel permeation chromatography (GPC) under the following conditions.
[Measurement condition]
Developing solvent: Tetrahydrofuran (THF)
Flow rate: 0.35 mL / min
Detector: Differential Refractometer Detector (RI)
Column: TSK Guardcolum SuperH-L
TSKgel SuperHZ4000 (4.6mm ID x 15cm x 1)
TSKgel SuperHZ3000 (4.6mm ID x 15cm x 1)
TSKgel SuperHZ2000 (4.6mmID x 15cm x 2)
(Both manufactured by Tosoh)
Column temperature: 40 ° C
Sample injection volume: 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。）
As the aromatic maleimide of the component (A), the aromatic bismaleimide compound represented by the following formula (1) is preferable. When the following formula (1) is used, the mechanical properties of the obtained film are good both before and after curing, and it becomes 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 and
A 1 and A 2 are independent of each other, and the following equation (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。
As X 1 , from the viewpoint of easy availability of raw materials, −CH 2 − and −C (CH 3 ) 2 − are preferable. m is a number of 1 to 30, preferably a number of 2 to 20, and more preferably 2 to 8. When m is in this range, the balance between the solubility and film-forming ability of the aromatic bismaleimide compound in a solution when uncured and the toughness and heat resistance of the obtained cured product are good. n is a number of 1 to 5, preferably 1 to 4, more preferably 1 to 3, and even more preferably 1.
As X 2 , from the viewpoint of easy availability of raw materials, −CH 2 − and −C (CH 3 ) 2 − are preferable. Further, 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 the unsubstituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group and a cyclohexyl group. Examples thereof include a group in which a part or all of the hydrogen atom of these groups is substituted with a halogen atom such as F, Cl, Br, etc., for example, a trifluoromethyl group. 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 formula (1), when A 1 is the formula (2), A 2 is the formula (3), or when A 1 is the formula (3), A 2 is the formula (2). In some cases.
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 of the formula (1) and X 1 of the formula (3) are the same divalent group. This means that it has two or more of the same bisphenol skeleton, and that the aromatic bismaleimide compound of the present invention is produced using a divalent acid anhydride and a diamine having 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 of the component (A) may be used alone or in combination of two or more. The content of the component (A) in the total of the component (A), the component (B) and other thermosetting resin components of the present invention is preferably 60 to 95% by mass, 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 the component (A). Since the component (B), which is a curing agent, has a bisphenol structure, the component (A) has excellent compatibility with the aromatic maleimide, and the occurrence of uneven curing can be reduced.
（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。
The "divalent organic group having an allyl group-containing bisphenol structure" is a divalent organic group obtained by removing two phenolic hydroxy groups from bisphenol, having one or more allyl groups as a substituent, and the like. A divalent organic group which may have a substituent of.
Examples of bisphenol structures that are the main skeleton other than substituents are 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. However, bisphenol A type, bisphenol AP type, bisphenol E type, and bisphenol F type are preferable because of their compatibility with the component (A) and the availability of 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。
The "divalent organic group having an allyl group-containing biphenol structure" is a divalent organic group obtained by removing two phenolic hydroxy groups from biphenol, having one or more allyl groups as a substituent, and the like. A divalent organic group which may have a substituent of.
The biphenol structure, which is the main skeleton other than the substituent, is a structure in which carbon atoms on the aromatic ring other than the carbon atom to which the phenolic hydroxy group is 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。 Further, as the substituent of the bisphenol structure and the biphenol structure, an allyl group is essential, and in addition to the allyl group, a halogen atom, an alkyl group and the like can be mentioned as other substituents. The number of substituents may be 1 or 2 or more in one molecule for allyl groups, and 0 or more in one molecule for other substituents.
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 one or more divalent groups selected from a divalent organic group having a bisphenol structure independently, a divalent organic group having a biphenol structure, and a divalent organic group having an alicyclic dimethanol structure. Indicates an organic group of. As for the divalent organic group having a bisphenol structure and the divalent organic group having a biphenol structure, the same ones as described 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。
The "divalent organic group having an alicyclic dimethanol structure" is a compound having an alicyclic ring and two methanol groups (-CH 2 OH) bonded to the alicyclic ring, and two OH groups. A divalent organic group excluding a divalent organic group which may have a substituent. The aliphatic ring may be a monocyclic ring or a polycyclic ring. This alicyclic dimethanol structure strongly contributes to lowering the dielectric constant of the cured product.
The aliphatic ring is preferably a saturated hydrocarbon aliphatic ring in order to reduce the influence of oxidation during heat. The number of carbon atoms in the aliphatic ring is preferably 6 to 20, more preferably 8 to 15.
Specific examples of the aliphatic ring include a cyclohexane ring, a tricyclo [5.2.1.0 2,6 ] decane ring, a bicyclo [4.4.0] decane ring, a bicyclo [2.2.1] heptane ring, and the like. 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, and more preferably a number of 0 to 40. Further, the repeating unit enclosed in b may be one kind of homopolymer or two or more kinds of copolymers, and in the case of a copolymer, one or more (b or less) repeating units are alicyclics. It preferably has a formula dimethanol structure.
（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。
The component (B) has a divalent organic group having one or more bisphenol structures in one molecule. Further, the allyl group does not necessarily have to be contained in all the units of X 3 and X 4 , but the presence of the allyl group allows it to be preferably used as a curing agent for maleimide.
The number of allyl groups in the component (B) is preferably 2 or more, and more preferably 3 to 20 in one molecule.
（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。
The component (B) preferably has a softening point of 70 to 130 ° C, more preferably 90 to 120 ° C. The softening point referred to 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 in this range, the tackiness when the uncured resin film is formed, and the balance between the fluidity at the time of molding and the embedding property (moldability) are good. When the component (B) is at such a softening point, the ICI viscosity at 150 ° C. is in the range of 1 to 10 Pa · s, preferably in the range of 2 to 8 Pa · s.
The blending amount of the allyl group-containing carbonate resin having the bisphenol structure of the component (B) is 5 to 40% by mass in the total of the component (A), the component (B) and other thermosetting resin components of the present invention. Is preferable, and 10 to 35% by mass is more preferable.
＜（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 of the component (C) used in the present invention promotes the single cross-linking reaction of the maleimide group of the component (A) and the allyl group of the component (B) and the cross-linking reaction between the component (A) and the component (B). It is added for the purpose.
The component (C) is not particularly limited as long as it promotes the cross-linking reaction, and is, for example, imidazoles, tertiary amines, quaternary ammonium salts, boron trifluoride amine complex, and organophosphines. , Ion catalysts such as organophosphonium salts; radical polymerization initiators such as organic peroxides, hydroperoxides, azoisobutyronitrile and the like. Among these, organic peroxides are particularly preferable from the viewpoint of promoting cross-linking between the component (A) and the component (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 of the component (C) 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 blending amount of the reaction initiator of the component (C) is preferably 0.05 to 10 parts by mass, preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total of the components (A) and (B). Is more preferable. If it is out of the above range, the balance between the heat resistance and the moisture resistance of the cured product may become poor, and the curing speed at the time of molding may become very slow or fast.
Further, as is a known fact, the curing rate at the time of molding differs depending on the type, and for example, when using an organic peroxide, the half-life temperature of the organic peroxide is confirmed. There is a strong correlation between the half-life temperature and the reaction start 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 the thermosetting maleimide resin composition of the present invention, in addition to the components (A) to (C), it is preferable to add (D) an organic solvent for the purpose of varnishing the resin composition. 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>
Various additives can be further added to the thermosetting maleimide resin composition of the present invention, if necessary. As the additive, a thermoplastic resin such as an acrylic resin, an epoxy resin, a maleimide resin having an aliphatic ring other than the component (A), and an organopolysiloxane in order to improve the resin characteristics without impairing the effect of the present invention. , Silicone oil, thermoplastic resin, thermoplastic elastomer, organic synthetic rubber, light stabilizer, polymerization inhibitor, flame retardant, pigment, dye, adhesive aid, etc. may be blended to improve electrical properties. An ion trapping agent or the like may be blended. Further, a fluorine-containing material or the like may be blended to improve the dielectric property, or 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 the component (A), the component (B) and the component (C), and other additives added as needed.
This thermosetting maleimide resin composition can be processed into a film or a sheet, and the handleability of the film is good both uncured and after curing. For example, even if the film is bent at 180 °, the film becomes two. It never cuts. The following is an example of a film manufacturing method and usage examples, but the present 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, the components (A) to (C) and other additives added as needed are added to an organic solvent (D) such as anisole to prepare a varnish containing a thermosetting maleimide resin composition. Is applied to the support sheet and then heated at a temperature of usually 80 ° C. or higher, preferably 100 ° C. or higher for 0.5 to 5 hours to remove the organic solvent and prepare an uncured film-shaped 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 maleimide-cured resin film having a flat surface and a strong surface can be formed. In order to efficiently remove the solvent in the resin composition to the outside of the system and effectively promote the reaction of the resin, it is preferable to raise the curing temperature stepwise in some cases.
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 of applying the varnish to the support sheet is not particularly limited, and examples thereof include a gap coater, a curtain coater, a roll coater, and a laminator. The thickness of the coating layer is also 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. Further, a cover film may be used on the coating layer. Further, the components (A) to (C) and other components may be premixed without being varnished and kneaded with an extruder or the like to obtain a sheet-like composition as 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。 Further, as the support sheet used when coated and used in the form of a film, generally used ones may be used, for example, polyethylene (PE) resin, polypropylene (PP) resin, polystyrene (PS) resin and the like. Examples thereof include a polyolefin resin, a polyethylene terephthalate (PET) resin, a polybutylene terephthalate (PBT) resin, a polyester resin such as a polycarbonate (PC) resin, and the like, and the surface thereof may be demolded.
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 is excellent in heat resistance, mechanical properties, electrical properties, adhesiveness to a substrate and solvent resistance, and has a low dielectric constant. , Various base materials by various methods, for example, a passive film on the surface of a semiconductor device, a protective film, a junction protective film at a junction such as a diode or a transistor, an α-ray shielding film of VLSI, an interlayer insulating film, and an ion. In addition to injection masks, etc., 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 in which an inorganic filler is mixed with a resin composition, It can be used in a wide range such as a paste composition such as a conductive paste composition containing a conductive filler.
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 them, application to FPC applications is particularly preferable. The cured resin film is suitable as an FPC core substrate or a coverlay film, and can also be used as a copper-clad laminate by attaching a copper foil. Further, since it is a thermosetting resin, the uncured resin film can be used as it is as an adhesive or a die bond 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。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
（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 the component (A) is shown below. In the following, the number average molecular weight (Mn) is measured under the following measurement conditions with polystyrene as a reference.
Developing solvent: Tetrahydrofuran (THF)
Flow rate: 0.35 mL / min
Detector: Differential Refractometer Detector (RI)
Column: TSK Guardcolum SuperH-L
TSKgel SuperHZ4000 (4.6mm ID x 15cm x 1)
TSKgel SuperHZ3000 (4.6mm ID x 15cm x 1)
TSKgel SuperHZ2000 (4.6mmID x 15cm x 2)
(Both manufactured by Tosoh)
Column temperature: 40 ° C
Sample injection volume: 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 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 the mixture was stirred at 80 ° C. for 3 hours to synthesize an amic acid. Then, the temperature was raised to 150 ° C. as it was, and the mixture was stirred for 2 hours while distilling off the by-produced 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 a flask containing a block copolymer solution cooled to room temperature, and the mixture is stirred at 80 ° C. for 3 hours. As a result, Amic acid was synthesized. Then, the temperature was raised to 150 ° C. as it was, and the mixture was stirred for 2 hours while distilling off the by-produced water to synthesize a diamine compound at both ends.
The obtained flask containing the biterminal diamine solution 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 an amic acid. Then, the temperature was raised to 150 ° C. as it was, 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). The 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 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 the mixture was stirred at 80 ° C. for 3 hours to synthesize an amic acid. .. Then, the temperature was raised to 150 ° C. as it was, and the mixture was stirred for 2 hours while distilling off the by-produced 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 a flask containing a block copolymer solution cooled to room temperature, and the mixture is stirred at 80 ° C. for 3 hours. As a result, Amic acid was synthesized. Then, the temperature was raised to 150 ° C. as it was, and the mixture was stirred for 2 hours while distilling off the generated water to synthesize a diamine compound at both ends.
The flask containing the obtained biterminal diamine solution 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 an amic acid. Then, the temperature was raised to 150 ° C. as it was, 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 (6). The 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]
Prepare 100 g of anisole varnish having a non-volatile content of 40% by mass containing the aromatic maleimide compound of the formula (5) synthesized in Synthesis Example 1 and prepare an allylbisphenol F / tricyclodecanedimethanol cocondensate carbonate resin (Gunei Chemical Industry Co., Ltd.). 12 g of the product (softening point 103 ° C.) was added, and the mixture was stirred at 110 ° C. to dissolve all of the mixture and allowed to cool to room temperature. 0.4 g of dicumylperoxide was added to the varnish and all of them were 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]
40 g of anisole varnish containing 40% by mass of the aromatic maleimide compound of the formula (5) synthesized in Synthesis Example 1 is replaced with 100 g of the anisole varnish containing the aromatic maleimide compound of the formula (6) synthesized in Synthesis Example 2. 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 having a non-volatile content of 40% by mass containing the aromatic maleimide compound of the formula (5) synthesized in Synthesis Example 1, add 0.4 g of dicumylperoxide to the varnish, dissolve all of them, and heat. 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]
Anisole varnish having a non-volatile content of 40% by mass containing the aromatic maleimide compound of the formula (5) synthesized in Synthesis Example 1 was prepared, and an alkenyl group-containing phenol resin (manufactured by Gunei Chemical Industry Co., Ltd., product name: 1PP- (2, Solid at 25 ° C.) was added, and the mixture was stirred at 110 ° C. to dissolve all of the mixture and allowed to cool to room temperature. 0.4 g of dicumylperoxide was added to the varnish and all of them were 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]
40 g of phenylmethane maleimide (manufactured by Daiwa Kasei Kogyo Co., Ltd., product name: BMI-2300) instead of 100 g of anisole varnish containing a non-volatile content of 40% by mass containing the aromatic maleimide compound of the formula (5) synthesized in Synthesis Example 1. A thermosetting maleimide resin composition was prepared in the same manner as in Example 1 except that the above was used.
［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 (manufactured by Designer Molecules Inc., product name: BMI-3000J) having the following structure and 0.4 g of dicumylperoxide, and add these to 60 g of toluene to dissolve all of them. To prepare a thermosetting maleimide resin composition.
［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 Toray DuPont, 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 an 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。
<Making a film>
[Examples 1 and 2, Comparative Examples 1 to 4]
The varnish-like thermosetting maleimide resin composition prepared in Examples 1 and 2 and Comparative Examples 1 to 4 is applied onto a PET film having a thickness of 38 μm with a roller coater so that the thickness after drying becomes 50 μm. Then, it was dried at 100 ° C. for 20 minutes to obtain an uncured resin film. Further, the uncured resin film is placed on a 100 μm-thick tetrafluoroethylene-ethylene copolymer resin film (manufactured by AGC Co., Ltd., product name: Aflex), and the resin layer of the uncured resin film is tetrafluoroethylene-ethylene. A cured resin film was obtained by placing it in contact with the copolymer resin film and curing it at 180 ° C. for 1 hour.
In the following evaluation tests, the uncured resin film from which the PET film was peeled off, the PET film, and the cured resin film from which the tetrafluoroethylene-ethylene copolymer resin film was peeled off 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>
The uncured resin film and the cured resin film were bent 5 times at 180 °, and those without defects such as cracks in the film were marked with ◯, and those with defects such as cracks were marked with x.
In Comparative Example 5 and Comparative Example 6, the above-mentioned polyimide film and the modified polyimide film were used to improve the film handling property as in the uncured resin films and the cured resin films of Examples 1 and 2 and Comparative Examples 1 to 4, respectively. 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 Co., Ltd.) and a strip line (manufactured by Keycom Co., Ltd.) were connected, and the relative permittivity 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 relative permittivity and the dielectric loss tangent were measured using the above-mentioned polyimide film and modified polyimide film, respectively, in the same manner as in the cured resin films of Examples 1 and 2, and Comparative Examples 1 to 4. ..
＜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 by 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 in 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。
<Effects of relative permittivity and dielectric loss tangent due to moisture absorption>
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 each predetermined time. A network analyzer (E5063-2D5 manufactured by Keysight Co., Ltd.) and a strip line (manufactured by Keycom Co., Ltd.) were connected using the resin film after moisture absorption, and the relative permittivity 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 moisture absorption, and is an uncured resin composed of the composition. Since the film and the cured resin film are excellent in handleability, it was confirmed that they are useful for FPC applications.
Claims (8)
（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。 Thermosetting containing (A) an allyl group-containing carbonate resin having a bisphenol structure and an aromatic maleimide (B) bisphenol structure having a number average molecular weight of 3,000 to 50,000 and (C) a reaction initiator. Maleimide resin composition.
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。） The thermosetting maleimide resin composition according to claim 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 and
A 1 and A 2 are independent of each other, and the following equation (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. )
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| JP2020188889A 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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|---|---|---|---|---|
| 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 |
| 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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2020
- 2020-11-12 JP JP2020188889A patent/JP7387235B2/en active Active
Patent Citations (6)
| 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 |
| 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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