JP2022179974A - Film comprising cured product of thermosetting maleimide resin composition, and flexible printed circuit board having the same - Google Patents
Film comprising cured product of thermosetting maleimide resin composition, and flexible printed circuit board having the same Download PDFInfo
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- JP2022179974A JP2022179974A JP2021086824A JP2021086824A JP2022179974A JP 2022179974 A JP2022179974 A JP 2022179974A JP 2021086824 A JP2021086824 A JP 2021086824A JP 2021086824 A JP2021086824 A JP 2021086824A JP 2022179974 A JP2022179974 A JP 2022179974A
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- Prior art keywords
- film
- maleimide resin
- component
- thermosetting
- cured product
- Prior art date
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- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 35
- 239000011342 resin composition Substances 0.000 title claims abstract description 26
- 229920005989 resin Polymers 0.000 claims abstract description 68
- 239000011347 resin Substances 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 125000003118 aryl group Chemical group 0.000 claims abstract description 15
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 11
- VYGUBTIWNBFFMQ-UHFFFAOYSA-N [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O Chemical group [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O VYGUBTIWNBFFMQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 6
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 9
- 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 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 239000007870 radical polymerization initiator Substances 0.000 claims description 3
- 230000009477 glass transition Effects 0.000 abstract description 7
- 239000010408 film Substances 0.000 description 57
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- 238000001723 curing Methods 0.000 description 11
- -1 maleimide compound Chemical class 0.000 description 11
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 10
- 239000002966 varnish Substances 0.000 description 10
- 229920000106 Liquid crystal polymer Polymers 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 239000011256 inorganic filler Substances 0.000 description 8
- 229910003475 inorganic filler Inorganic materials 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 6
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920001721 polyimide Polymers 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 238000013007 heat curing Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000000034 method Methods 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
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 3
- 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 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 239000009719 polyimide resin Substances 0.000 description 3
- 230000008569 process Effects 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
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012787 coverlay film Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000004427 diamine group Chemical group 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 108091063785 miR-3000 stem-loop Proteins 0.000 description 2
- 239000002798 polar solvent Substances 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
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction 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
- ROLAGNYPWIVYTG-UHFFFAOYSA-N 1,2-bis(4-methoxyphenyl)ethanamine;hydrochloride Chemical compound Cl.C1=CC(OC)=CC=C1CC(N)C1=CC=C(OC)C=C1 ROLAGNYPWIVYTG-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
- YIJYFLXQHDOQGW-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis(2-prop-2-enoyloxyethyl)-1,3,5-triazinan-1-yl]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCN1C(=O)N(CCOC(=O)C=C)C(=O)N(CCOC(=O)C=C)C1=O YIJYFLXQHDOQGW-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
- 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 1
- 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 1
- PJCCVNKHRXIAHZ-UHFFFAOYSA-N 4-[4-[[4-(4-aminophenoxy)phenyl]methyl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1CC(C=C1)=CC=C1OC1=CC=C(N)C=C1 PJCCVNKHRXIAHZ-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
- 229910052582 BN 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
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 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 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 239000013039 cover film Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 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 1
- 238000011161 development Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 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 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000000178 monomer Substances 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
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 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
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、熱硬化性マレイミド樹脂組成物の硬化物からなるフィルム、それを用いたフレキシブルプリント基板に関する。 TECHNICAL FIELD The present invention relates to a film made of a cured product of a thermosetting maleimide resin composition, and a flexible printed circuit board using the same.
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、特に誘電正接の低い、かつ吸湿しても誘電正接の値の変化の小さい絶縁材料の開発が求められている。 In recent years, 5G, a next-generation mobile communication system, has become popular, and attempts are being made to realize high-speed, large-capacity, low-delay communication. In order to achieve these, materials for high-frequency bands are necessary, and reduction of transmission loss is essential as a countermeasure against noise. There is a demand for the development of insulating materials with small changes in tangent value.
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。特にフレキシブルプリント基板(FPC)では、誘電特性の優れた絶縁材料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 use as a substrate. In flexible printed circuit boards (FPC) in particular, products called liquid crystal polymer (LCP) and modified polyimide (MPI) with improved properties have come to be used as insulating materials with excellent dielectric properties.
これらの材料は優れた特徴を有するが、多くの課題を有していることも事実である。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、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、熱処理方法にノウハウが必要であり、リフロー工程で形状維持が難しい。 Although these materials have excellent characteristics, it is also true that they have many problems. Regarding LCP, many inventions have been disclosed, such as further enhancement of LCP performance, FPC base films and coverlay films using LCP (for example, Patent Documents 1 and 2), but LCP has met the demand. The use is limited due to the difficulty of mass production, and molding at high temperatures of 300°C or higher, which is a problem unique to thermoplastic resins, is essential. Difficult to maintain shape.
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、4)。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5)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をワニス化して用いるには、非プロトン性極性溶媒、例えば、N-メチルピロリドン(NMP)の使用が必須であるが、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 regarding MPI have been disclosed (for example, Patent Documents 3 and 4). Although these MPIs have improved dielectric properties compared to current polyimides, they have the same problems as LCPs because they are thermoplastic resins like LCPs. As a result, the dielectric properties are known to be very poor. In order to solve these problems, MPI having a dimer diamine skeleton has also been disclosed (Patent Document 5), but it has a significantly lower glass transition temperature (Tg) than conventional MPI and lacks dimensional stability. In addition, in order to use MPI as a varnish, it is essential to use an aprotic polar solvent such as N-methylpyrrolidone (NMP), but the use of an aprotic polar solvent is preferable from the viewpoint of environmental conservation. do not have.
そこで近年、ポリイミドに近いものとしてマレイミド樹脂が注目されている。マレイミド樹脂の中でも、ビスマレイミド樹脂が一般的で、低分子のものが多く知られており、高Tgなど高温特性に優れるが、未硬化物ではフィルム性が乏しく、硬化物は硬く脆い、また誘電特性もLCPやMPIに比べると十分なものではなく、さらに溶剤選択性が乏しく安定的に使用するにはまだまだ改善の余地がある。 Therefore, in recent years, attention has been focused on maleimide resin as a material similar to polyimide. Among maleimide resins, bismaleimide resins are common, many of which are known to have low molecular weights and are excellent in high temperature properties such as high Tg. Its properties are not sufficient as compared with LCP and MPI, and its solvent selectivity is poor, so there is still room for improvement for stable use.
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6)が、誘電特性は非常に優れるものの、一般的なマレイミド樹脂の特徴とは逆で、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。
また、Tgなどの硬化特性だけでなく、溶剤選択性が広く、誘電特性にも優れる低分子のマレイミド樹脂(特許文献7)や、フィルム化剤を使用することなくフィルム化可能な高分子の芳香族ビスマレイミド化合物(特許文献8)が、開示されている。
On the other hand, a composition using a maleimide compound substantially having a dimer diamine skeleton as an FPC material and a cured product thereof are disclosed (Patent Document 6). It has a low Tg, a high coefficient of thermal expansion (CTE) and still lacks dimensional stability, contrary to the characteristics of conventional maleimide resins. 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 unevenness occurs in the properties and curing of the composition and its cured product. It's easy to do.
In addition to curing properties such as Tg, low-molecular-weight maleimide resins (Patent Document 7), which have wide solvent selectivity and excellent dielectric properties, and polymer fragrances that can be formed into films without the use of filming agents A group bismaleimide compound (US Pat. No. 5,300,002) is disclosed.
しかしながら、特許文献7の低分子のマレイミド樹脂は、強度に乏しくハンドリング性に難があり、リジッド基板用にしか適さず、FPC用には適さず、更に非常に吸湿しやすいため誘電特性が容易に悪化することがわかってきた。また、特許文献8の高分子の芳香族ビスマレイミド化合物は、各種有機溶媒への溶解性やフィルム化能に優れるものの、誘電特性が不十分であった。
従って、本発明は、ムラがなく均質であり、ハンドリング性に優れ、ガラス転移温度が高く、リフロー時の寸法安定性に優れ変形が少なく、誘電特性にも優れる、FPCに適したフィルムを提供することを目的とする。また、該フィルムを有するフレキシブルプリント基板を提供することも目的とする。
However, the low-molecular-weight maleimide resin of Patent Document 7 lacks strength and is difficult to handle, is suitable only for rigid substrates, is not suitable for FPCs, and is very susceptible to moisture absorption, so dielectric properties are easily reduced. I know it gets worse. Further, the polymeric aromatic bismaleimide compound of Patent Document 8 is excellent in solubility in various organic solvents and film-forming ability, but insufficient in dielectric properties.
Therefore, the present invention provides a film suitable for FPC, which is homogeneous without unevenness, has excellent handleability, has a high glass transition temperature, has excellent dimensional stability during reflow and little deformation, and has excellent dielectric properties. for the purpose. Another object of the present invention is to provide a flexible printed circuit board having the film.
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の硬化物からなるフィルムが、上記目的を達成できることを見出し、本発明を完成した。
なお、本発明の熱硬化性マレイミド樹脂組成物の硬化物からなるフィルムはフィルム状及びシート状の形態のもののいずれも含むものである。
The present inventors have made intensive studies to solve the above problems, and as a result, have found that a film made of a cured product of the thermosetting maleimide resin composition described below can achieve the above objects, and completed the present invention.
The film made of the cured product of the thermosetting maleimide resin composition of the present invention includes both film-like and sheet-like forms.
<1>
(A)数平均分子量3,000以上の芳香族マレイミド樹脂、
(B)1分子中に1個以上のアリル基及び1個以上のイソシアヌル環を有する有機化合物、
(C)数平均分子量3,000未満の下記式(1)で表されるマレイミド樹脂
及び
(D)反応開始剤
を含む熱硬化性マレイミド樹脂組成物の硬化物からなるフィルム。
<2>
(A)成分の芳香族マレイミド樹脂が下記式(2)で示されるビスマレイミドである<1>に記載のフィルム。
<3>
(B)成分のアリル基が1分子中に2つ以上有するものである<1>又は<2>に記載のフィルム。
<4>
(A)成分、(B)成分、(C)成分の質量の比が(A):(B):(C)=100:3~40:3~40である<1>~<3>のいずれか1つに記載のフィルム。
<5>
(D)成分の反応開始剤がラジカル重合開始剤である<1>~<4>のいずれか1つに記載のフィルム。
<6>
<1>~<5>のいずれか1つに記載のフィルムを有するフレキシブルプリント基板。
<1>
(A) an aromatic maleimide resin having a number average molecular weight of 3,000 or more,
(B) an organic compound having one or more allyl groups and one or more isocyanuric rings in one molecule;
A film comprising a cured product of a thermosetting maleimide resin composition containing (C) a maleimide resin represented by the following formula (1) having a number average molecular weight of less than 3,000 and (D) a reaction initiator.
<2>
The film according to <1>, wherein the aromatic maleimide resin of component (A) is a bismaleimide represented by the following formula (2).
<3>
The film according to <1> or <2>, wherein the component (B) has two or more allyl groups per molecule.
<4>
<1> to <3>, wherein the mass ratio of component (A), component (B), and component (C) is (A):(B):(C) = 100:3 to 40:3 to 40 A film according to any one of the preceding claims.
<5>
The film according to any one of <1> to <4>, wherein the reaction initiator of component (D) is a radical polymerization initiator.
<6>
A flexible printed circuit board comprising the film according to any one of <1> to <5>.
本発明の熱硬化性マレイミド樹脂組成物の硬化物からなるフィルムは、ムラがなく均質であり、ハンドリング性に優れ、ガラス転移温度が高く、リフロー時の寸法安定性に優れ変形が少なく、誘電特性に優れるため、特に、フレキシブルプリント基板用材料として有用である。 The film made of the cured product of the thermosetting maleimide resin composition of the present invention is homogeneous without unevenness, has excellent handleability, has a high glass transition temperature, has excellent dimensional stability during reflow, is less deformed, and has dielectric properties. is particularly useful as a material for flexible printed circuit boards.
以下、本発明につき更に詳しく説明する。
本発明のフィルムは下記(A)~(D)成分を含有する熱硬化性マレイミド樹脂組成物の硬化物である。まず、該組成物の各成分について説明する。
The present invention will be described in more detail below.
The film of the present invention is a cured product of a thermosetting maleimide resin composition containing the following components (A) to (D). First, each component of the composition will be described.
(A)数平均分子量3,000以上の芳香族マレイミド樹脂
本発明で用いられる(A)成分は、数平均分子量3,000以上の芳香族マレイミド樹脂である。一般に、マレイミド化合物は数平均分子量2,000以下の化合物が多い。これらの数平均分子量2,000以下のマレイミド化合物はTgが高いものが多いが、硬化前後のフィルムへの加工性・成形性に乏しく、特に基板用組成物の主成分として取り扱うのが困難である。このようなことからも、本発明では数平均分子量が3,000以上の高分子量の芳香族マレイミド樹脂を使用する。
(A) Aromatic maleimide resin having a number average molecular weight of 3,000 or more Component (A) used in the present invention is an aromatic maleimide resin having a number average molecular weight of 3,000 or more. In general, many maleimide compounds have a number average molecular weight of 2,000 or less. Many of these maleimide compounds having a number average molecular weight of 2,000 or less have a high Tg, but are poor in workability and formability into films before and after curing, and are particularly difficult to handle as the main component of substrate compositions. . For these reasons, the present invention uses a high molecular weight aromatic maleimide resin having a number average molecular weight of 3,000 or more.
(A)成分の芳香族マレイミド樹脂は室温で組成物のフィルム性を向上させるために使用され、数平均分子量(Mn)は、下記測定条件を用いたゲルパーミエーションクロマトグラフィー(GPC)測定によるポリスチレン標準で換算した数平均分子量が3,000以上であり、3,500~70,000であることがより好ましく、特に好ましくは4,000~50,000である。該分子量が3,000以上であれば、得られる組成物はフィルム化しやすく、ハンドリング性が良好である。 The aromatic maleimide resin of component (A) is used to improve the film properties of the composition at room temperature. The number average molecular weight converted to the standard is 3,000 or more, more preferably 3,500 to 70,000, and particularly preferably 4,000 to 50,000. When the molecular weight is 3,000 or more, the resulting composition is easily formed into a film and has good handleability.
[測定条件]
展開溶媒:テトラヒドロフラン(THF)
流速: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)
[Measurement condition]
Developing solvent: tetrahydrofuran (THF)
Flow rate: 0.35mL/min
Detector: Differential Refractive Index Detector (RI)
Column: TSK Guard column SuperH-L
TSKgel SuperHZ4000 (4.6mm ID x 15cm x 1)
TSKgel SuperHZ3000 (4.6mm ID x 15cm x 1)
TSKgel SuperHZ2000 (4.6mm I.D. x 15cm x 2)
(both manufactured by Tosoh Corporation)
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樹脂としては、下記式(2)で示されるビスマレイミドであることが好ましい。この下記式(2)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だけでなく、後述する(B)や(C)成分との相溶性が高く、特性が場所によってムラの無いフィルムを得ることができる。
式(2)中、mは平均値で3~40の数であり、好ましくは5~30の数である。mがこの範囲にある場合、上記芳香族マレイミド樹脂の未硬化時の溶媒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。 In formula (2), m is a number of 3 to 40 on average, preferably a number of 5 to 30. When m is within this range, the uncured solvent solubility and film forming ability of the aromatic maleimide resin and the toughness and heat resistance of the resulting cured product are well balanced.
次に、式(2)中のX1及びX2はそれぞれ独立であり、同じでも異なっていても構わないが、同じ2価の基を有することが好ましい。すなわち、芳香族マレイミド樹脂は、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が好ましい。原料の入手のしやすさの観点から、X1及びX2は-CH2-、-C(CH3)2-が好ましい。 Next, X 1 and X 2 in formula (2) are each independent and may be the same or different, but preferably have the same divalent group. That is, the aromatic maleimide resin is preferably produced using a divalent acid anhydride and a diamine having the same bisphenol skeleton. X 1 and X 2 are preferably -CH 2 - or -C(CH 3 ) 2 - from the viewpoint of availability of raw materials.
(A)成分の芳香族マレイミド樹脂は、1種単独で用いてもよいし、2種以上を併用してもよい。 The (A) component aromatic maleimide resin may be used alone or in combination of two or more.
(B)1分子中に1個以上のアリル基及び1個以上のイソシアヌル環を有する有機化合物
本発明で用いられる(B)成分は、1分子中に1個以上のアリル基及び1個以上のイソシアヌル環を有する有機化合物であり、架橋剤として用いられるものである。そのため、1分子中に1個以上、好ましくは2個以上のアリル基を有する。また、イソシアヌル環は高い耐熱性を有し、硬化前のワニスの粘度を下げたり、硬化後の機械物性や誘電特性の改善に作用する。
(B) an organic compound having one or more allyl groups and one or more isocyanuric rings in one molecule The component (B) used in the present invention contains one or more allyl groups and one or more It is an organic compound having an isocyanuric ring and is used as a cross-linking agent. Therefore, it has one or more, preferably two or more allyl groups in one molecule. In addition, the isocyanuric ring has high heat resistance, lowers the viscosity of the varnish before curing, and improves mechanical properties and dielectric properties after curing.
(B)成分としては、エポキシ基、アクリル基又はカルボキシル基を有するもの、シリコーン変性されたもの、エーテル変性されたものなどがあるが、その中でも、誘電特性の観点からトリアリルイソシアヌレート及びジアリルメチルイソシアヌレートなどのジアリルアルキルイソシアヌレートが好ましい。
(B)成分は、1種単独で用いても2種以上を併用してもよい。
Component (B) includes those having an epoxy group, acrylic group or carboxyl group, those modified with silicone, and those modified with ether. Diallylalkyl isocyanurates such as isocyanurates are preferred.
(B) component may be used individually by 1 type, or may use 2 or more types together.
(C)下記式(1)で表されるマレイミド樹脂
本発明で用いられる(C)成分は、下記式(1)で表されるマレイミド樹脂であり、その数平均分子量は3,000未満である。このマレイミド樹脂は本発明のフィルムのTgを高め、高温時の弾性率を上げることで高温時、特にリフロー工程でのフィルムの変形を抑え、かつ寸法安定性を高めることが出来る。
式(1)におけるR1はそれぞれ独立で同じでも異なっていてもよく、水素原子又は炭素数1~6のアルキル基である。炭素数1~6のアルキル基として、メチル基、エチル基、n-プロピル基、isо-プロピル基、n-ブチル基、isо-ブチル基、tert-ブチル基、n-ペンチル基、n-へキシル基、シクロへキシル基などが挙げられるが、原料の入手のしやすさから水素原子又はメチル基が好ましい。 Each R 1 in formula (1) may be independently the same or different and is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-pentyl group and n-hexyl. group, cyclohexyl group, and the like, but a hydrogen atom or a methyl group is preferable because of the availability of raw materials.
(C)成分のマレイミド樹脂は市販されたものを用いてもよい。具体例としては、日本化薬(株)製のMIR-3000などが挙げられる。なお、(C)成分のマレイミド樹脂は1種単独で用いても、2種以上混合して用いてもよい。 A commercially available maleimide resin may be used as the component (C). Specific examples include MIR-3000 manufactured by Nippon Kayaku Co., Ltd. and the like. In addition, the maleimide resin of the component (C) may be used alone or in combination of two or more.
(C)成分のマレイミド樹脂の数平均分子量は、3,000未満であり、好ましくは500~2,500であり、より好ましくは500~2,200である。
(C)成分の数平均分子量は、上述した(A)成分の数平均分子量と同じ測定方法及び測定条件で測定された値である。
式(1)中の繰り返し単位数の平均値lは1<l≦5であり、好ましくは1<l≦4であり、より好ましくは1<l≦3.5である。
The maleimide resin of component (C) has a number average molecular weight of less than 3,000, preferably 500 to 2,500, and more preferably 500 to 2,200.
The number average molecular weight of component (C) is a value measured by the same measurement method and under the same measurement conditions as the number average molecular weight of component (A) described above.
The average value l of the number of repeating units in formula (1) is 1<l≦5, preferably 1<l≦4, and more preferably 1<l≦3.5.
(A)成分、(B)成分及び(C)成分の質量比としては、(A):(B):(C)=100:3~40:3~40が好ましく、より好ましくは(A):(B):(C)=100:5~30:5~30である。
(B)成分の配合量が少なすぎると得られるフィルムの誘電特性の改善が見られず、多すぎると未硬化フィルムに強いタックが生じてしまったり、硬化後のTgが大きく低下するおそれがある。(C)成分の配合量が少なすぎると得られる硬化フィルムのTgや高温時の弾性率の改善が見られず、多すぎると得られる硬化フィルムが吸湿しやすく、その影響で誘電特性が悪化する場合がある。
The mass ratio of component (A), component (B) and component (C) is preferably (A):(B):(C) = 100:3 to 40:3 to 40, more preferably (A) :(B):(C)=100:5-30:5-30.
If the amount of component (B) is too small, the dielectric properties of the resulting film cannot be improved, and if it is too large, the uncured film may be strongly tacky or the Tg after curing may be greatly reduced. . If the amount of component (C) is too small, the resulting cured film cannot be improved in Tg or elastic modulus at high temperatures. Sometimes.
(D)反応開始剤
(D)成分の反応開始剤は、(A)成分や(C)成分のマレイミド基の単独架橋、(B)成分のアリル基の単独架橋反応又は(A)成分、(B)成分及び(C)成分の架橋反応を促進するために添加するものである。(D)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、(B)成分及び(C)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。
(D)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。
(D) Reaction initiator The reaction initiator of component (D) is a single cross-linking reaction of the maleimide group of component (A) or component (C), a single cross-linking reaction of the allyl group of component (B) or component (A), ( It is added to accelerate the cross-linking reaction of component B) and component (C). Component (D) is not particularly limited as long as it promotes the cross-linking reaction. 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 and azoisobutyronitrile. Among these, organic peroxides are particularly preferred from the viewpoint of promoting cross-linking of components (A), (B) and (C). Organic peroxides include dicumyl peroxide, t-butyl peroxybenzoate, t-amyl peroxybenzoate, dibenzoyl peroxide, diuraloyl peroxide and the like.
The (D) component reaction initiator may be used alone or in combination of two or more.
反応開始剤の配合量は、(A)成分、(B)成分及び(C)成分の総和100質量部に対して0.05~10質量部であり、0.1~5質量部とすることが好ましい。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、反応開始剤の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性が高い。
The amount of the reaction initiator compounded is 0.05 to 10 parts by mass, and 0.1 to 5 parts by mass, per 100 parts by mass of the total of components (A), (B) and (C). is preferred. If it is out of the above range, the balance between heat resistance and moisture resistance of the cured product may become poor, or the curing speed during molding may become very slow or fast.
In addition, although it is a well-known fact, the curing rate during molding differs depending on the type of reaction initiator. For example, when using an organic peroxide, the half-life temperature of the organic peroxide is checked. There is a high correlation between the half-life temperature and the reaction initiation temperature.
熱硬化性マレイミド樹脂組成物の全質量中、(A)、(B)、(C)及び(D)成分の配合量の合計は、20~100質量%であることが好ましく、30~100質量%であることがより好ましい。 The total amount of components (A), (B), (C) and (D) in the total weight of the thermosetting maleimide resin composition is preferably 20 to 100% by weight, preferably 30 to 100% by weight. % is more preferable.
<その他の添加剤>
熱硬化性マレイミド樹脂組成物には、本発明の効果を損なわない範囲で、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。その他の添加剤を以下に例示する。
<Other additives>
Various additives can be added to the thermosetting maleimide resin composition, if necessary, as long as the effects of the present invention are not impaired. Other additives are exemplified below.
マレイミド基と反応しうる反応性基を有する熱硬化性樹脂
前記(B)成分以外にも、マレイミド基と反応しうる反応性基を有する熱硬化性樹脂を熱硬化性マレイミド樹脂組成物に添加してもよい。
熱硬化性樹脂としてはその種類を限定するものではなく、例えば、エポキシ樹脂、フェノール樹脂、メラミン樹脂、シリコーン樹脂、環状イミド樹脂、ユリア樹脂、熱硬化性ポリイミド樹脂、変性ポリフェニレンエーテル樹脂、熱硬化性(メタ)アクリル樹脂、エポキシ・シリコーンハイブリッド樹脂など(A)~(C)成分以外の各種樹脂が挙げられる。また、マレイミド基と反応しうる反応性基としては、エポキシ基、マレイミド基、水酸基、酸無水物基、アリル基やビニル基のようなアルケニル基、(メタ)アクリル基、チオール基などが挙げられる。なお、その他の添加剤としてアリル基を有する化合物は、イソシアヌル環を有さないものであり(B)成分と区別される。
Thermosetting resin having a reactive group capable of reacting with a maleimide group In addition to the component (B), a thermosetting resin having a reactive group capable of reacting with a maleimide group is added to the thermosetting maleimide resin composition. may
The type of thermosetting resin is not limited, and examples thereof include epoxy resins, phenol resins, melamine resins, silicone resins, cyclic imide resins, urea resins, thermosetting polyimide resins, modified polyphenylene ether resins, and thermosetting resins. Various resins other than the components (A) to (C), such as (meth)acrylic resins and epoxy/silicone hybrid resins, can be mentioned. Examples of reactive groups capable of reacting with maleimide groups include epoxy groups, maleimide groups, hydroxyl groups, acid anhydride groups, alkenyl groups such as allyl groups and vinyl groups, (meth)acrylic groups, and thiol groups. . A compound having an allyl group as another additive does not have an isocyanuric ring and is distinguished from the component (B).
反応性の観点から、熱硬化性樹脂の反応性基は、エポキシ基、マレイミド基、水酸基、酸無水物基及びアルケニル基の中から選ばれるものであることが好ましく、さらに誘電特性の観点からはアルケニル基がより好ましい。
ただし、マレイミド基と反応しうる反応性基を有する熱硬化性樹脂の配合量は、(A)成分、(B)成分、(C)成分及びマレイミド基と反応しうる反応性基を有する熱硬化性樹脂の総和中、0~30質量%であることが好ましい。
From the viewpoint of reactivity, the reactive group of the thermosetting resin is preferably selected from epoxy group, maleimide group, hydroxyl group, acid anhydride group and alkenyl group. Alkenyl groups are more preferred.
However, the amount of the thermosetting resin having a reactive group capable of reacting with the maleimide group is the same as the components (A), (B), (C) and the thermosetting resin having a reactive group capable of reacting with the maleimide group. It is preferably 0 to 30% by mass based on the total amount of the organic resin.
無機充填材
無機充填材を熱硬化性マレイミド樹脂組成物に添加してもよい。本発明のフィルムの強度や剛性を高めたり、熱膨張係数や硬化物の寸法安定性を調整したりする目的で無機充填材を配合することができる。無機充填材としては、通常エポキシ樹脂組成物に配合されるものを使用することができる。例えば、球状シリカ、溶融シリカ及び結晶性シリカ等のシリカ類、アルミナ、窒化珪素、窒化アルミニウム、窒化ホウ素、硫酸バリウム、タルク、クレー、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、ガラス繊維及びガラス粒子等が挙げられる。さらに誘電特性改善のために含フッ素樹脂、コーティングフィラー、及び/又は中空粒子を用いてもよく、無機充填材は、1種単独で用いてもよいし、2種以上を併用してもよい。
Inorganic Fillers Inorganic fillers may be added to the thermosetting maleimide resin composition. Inorganic fillers can be blended for the purpose of increasing the strength and rigidity of the film of the present invention and adjusting the coefficient of thermal expansion and the dimensional stability of the cured product. As the inorganic filler, those usually blended in epoxy resin compositions can be used. For example, silicas such as spherical silica, fused silica and crystalline silica, alumina, silicon nitride, aluminum nitride, boron nitride, barium sulfate, talc, clay, aluminum hydroxide, magnesium hydroxide, calcium carbonate, glass fibers and glass particles etc. Furthermore, a fluorine-containing resin, a coating filler, and/or hollow particles may be used to improve dielectric properties, and the inorganic fillers may be used singly or in combination of two or more.
無機充填材の平均粒径及び形状は特に限定されないが、フィルムやフレキシブルプリント基板を成形する場合は特に平均粒径が0.3~5μmの球状シリカが好適に用いられる。なお、平均粒径は、レーザー光回折法による粒度分布測定における質量平均値D50(又はメジアン径)として求めた値である。 The average particle size and shape of the inorganic filler are not particularly limited, but spherical silica having an average particle size of 0.3 to 5 μm is preferably used when molding a film or a flexible printed circuit board. The average particle size is a value obtained as a mass average value D 50 (or median diameter) in particle size distribution measurement by a laser beam diffraction method.
さらに無機充填材は特性を向上させるために、マレイミド基と反応しうる有機基を有するシランカップリング剤で表面処理されていることが好ましい。このようなシランカップリング剤としては、エポキシ基含有アルコキシシラン、アミノ基含有アルコキシシラン、(メタ)アクリル基含有アルコキシシラン、及びアルケニル基含有アルコキシシラン等が挙げられる。シランカップリング剤は1種単独で用いてもよいし、2種以上を併用してもよい。 Further, the inorganic filler is preferably surface-treated with a silane coupling agent having an organic group capable of reacting with a maleimide group in order to improve the properties. Examples of such silane coupling agents include epoxy group-containing alkoxysilanes, amino group-containing alkoxysilanes, (meth)acrylic group-containing alkoxysilanes, and alkenyl group-containing alkoxysilanes. A silane coupling agent may be used individually by 1 type, and may use 2 or more types together.
その他
上記以外に、無官能シリコーンオイル、熱可塑性樹脂、熱可塑性エラストマー、有機合成ゴム、光増感剤、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。
また、無機充填材を使用していなくても、金属箔などと接着させるために使用する接着剤との接着力を向上させる目的でシランカップリング剤を配合してもよい。
Others In addition to the above, non-functional silicone oil, thermoplastic resin, thermoplastic elastomer, organic synthetic rubber, photosensitizer, light stabilizer, polymerization inhibitor, flame retardant, pigment, dye, adhesion aid, etc. Alternatively, an ion trapping agent or the like may be added to improve the electrical properties.
In addition, even if no inorganic filler is used, a silane coupling agent may be blended for the purpose of improving adhesive strength with an adhesive used for bonding to a metal foil or the like.
熱硬化性マレイミド樹脂組成物の製造方法としては、上述した(A)成分、(B)成分、(C)成分及び(D)成分並びに必要に応じて加えられるその他の添加剤を、例えば、プラネタリーミキサー(井上製作所(株)製)や、攪拌機THINKY CONDITIONING MIXER(シンキー(株)製)を使用して混合する方法が挙げられる。 As a method for producing a thermosetting maleimide resin composition, the above-described components (A), (B), (C) and (D) and other additives that are added as necessary are added to, for example, a planetary A method of mixing using a Lee mixer (manufactured by Inoue Seisakusho Co., Ltd.) or a stirrer THINKY CONDITIONING MIXER (manufactured by THINKY Co., Ltd.) can be used.
また、本発明の熱硬化性マレイミド樹脂組成物の硬化物からなるフィルムを製造するため、熱硬化性マレイミド樹脂組成物は、有機溶剤に溶解してワニスとして扱うことが好ましい。
有機溶剤は、(A)成分、(B)成分、(C)成分及びその他の添加剤としてのマレイミド基と反応しうる反応性基を有する熱硬化性樹脂が溶解するものであれば制限なく使用することができるが、例えば、アニソール、テトラリン、キシレン、トルエン、メシチレン、シクロヘキサノン、シクロペンタノン、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。
Moreover, in order to produce a film comprising a cured product of the thermosetting maleimide resin composition of the present invention, the thermosetting maleimide resin composition is preferably dissolved in an organic solvent and treated as a varnish.
The organic solvent can be used without limitation as long as it dissolves the thermosetting resin having a reactive group capable of reacting with the maleimide group as component (A), component (B), component (C) and other additives. Examples include anisole, tetralin, xylene, toluene, mesitylene, cyclohexanone, cyclopentanone, tetrahydrofuran (THF), dimethylformamide (DMF), dimethylsulfoxide (DMSO), and acetonitrile. These may be used individually by 1 type, and may use 2 or more types together.
本発明の熱硬化性マレイミド樹脂組成物の硬化物からなるフィルムの製造方法としては以下の製造方法を例示するが、これに限定されるものではない。
まず、有機溶剤に(A)~(D)成分及び必要に応じて配合されるその他の添加剤を溶解してワニスとする。
次に、このワニスを基材に塗工し、有機溶剤を揮発させることで未硬化樹脂シート又は未硬化樹脂フィルムを得る(乾燥工程)。
さらに、未硬化樹脂シート又は未硬化樹脂フィルムを硬化させることで熱硬化性マレイミド樹脂組成物の硬化物からなるシート又はフィルム(すなわち、硬化樹脂シート又は硬化樹脂フィルムを得る(加熱硬化工程)。
Examples of the method for producing a film composed of a cured product of the thermosetting maleimide resin composition of the present invention include, but are not limited to, the following production methods.
First, components (A) to (D) and other additives, if necessary, are dissolved in an organic solvent to prepare a varnish.
Next, this varnish is applied to a base material, and an uncured resin sheet or uncured resin film is obtained by volatilizing the organic solvent (drying step).
Further, the uncured resin sheet or uncured resin film is cured to obtain a sheet or film (that is, a cured resin sheet or cured resin film) composed of a cured product of the thermosetting maleimide resin composition (heat curing step).
例えば、有機溶剤に溶解した熱硬化性マレイミド樹脂組成物(ワニス)を基材に塗布した後、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って有機溶剤を除去し(乾燥工程)、さらに130℃以上、好ましくは150℃以上の温度で0.5~10時間加熱する(加熱硬化工程)ことで、表面が平坦で強固な熱硬化性マレイミド樹脂組成物の硬化物からなるフィルムを形成することができる。
有機溶剤を除去するための乾燥工程、及びその後の加熱硬化工程での温度は、それぞれ一定であってもよいが、段階的に温度を上げていくことが好ましい。これにより、有機溶剤を効率的に組成物外に除去するとともに、樹脂の硬化反応を効率よく進めることができる。
For example, after applying a thermosetting maleimide resin composition (varnish) dissolved in an organic solvent to a substrate, the organic solvent is heated at a temperature of usually 80° C. or higher, preferably 100° C. or higher for 0.5 to 5 hours. is removed (drying step), and further heated at a temperature of 130 ° C. or higher, preferably 150 ° C. or higher for 0.5 to 10 hours (heat curing step) to obtain a thermosetting maleimide resin composition with a flat and strong surface. It is possible to form a film consisting of a cured product of
The temperature in the drying process for removing the organic solvent and the subsequent heat-curing process may be constant, but it is preferable to raise the temperature stepwise. As a result, the organic solvent can be efficiently removed from the composition, and the curing reaction of the resin can be efficiently advanced.
ワニスの基材への塗布方法として、スピンコーター、スリットコーター、スプレー、ディップコーター、バーコーター等が挙げられるが特に制限はない。また、加熱硬化工程ではラジカル重合反応が進行する観点から酸素を含まない雰囲気が好ましく、具体的には窒素雰囲気での硬化が好ましい。 A spin coater, a slit coater, a spray, a dip coater, a bar coater and the like can be used as a method for applying the varnish to the base material, but there is no particular limitation. In addition, in the heat-curing step, an oxygen-free atmosphere is preferable from the viewpoint of progress of the radical polymerization reaction, and specifically, curing in a nitrogen atmosphere is preferable.
基材としては、一般的に用いられるものを用いることができ、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、さらにはポリイミド樹脂(PI)などが挙げられる。該基材の表面を離形処理していても構わない。また、塗工層の厚さも特に限定されないが、溶剤留去後の厚さが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。 As the base material, commonly used ones can be used, for example, polyethylene (PE) resin, polypropylene (PP) resin, polyolefin resin such as polystyrene (PS) resin, polyethylene terephthalate (PET) resin, polybutylene terephthalate. (PBT) resin, polyester resin such as polycarbonate (PC) resin, polyimide resin (PI), and the like. The surface of the substrate may be subjected to release treatment. Also, the thickness of the coating layer is not particularly limited, but the thickness after removal of the 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.
他にも、各成分をあらかじめプレ混合し、溶融混練機を用いてシート状又はフィルム状に押し出したものを上記のような加熱硬化工程に供して熱硬化性マレイミド樹脂組成物の硬化物からなるシート又はフィルムを得てもよい。 In addition, each component is premixed in advance and extruded into a sheet or film using a melt-kneader and subjected to the heat curing process as described above to obtain a cured product of the thermosetting maleimide resin composition. Sheets or films may be obtained.
本発明の熱硬化性マレイミド樹脂組成物の硬化物からなるフィルムは、耐熱性、機械的特性、電気的特性及び耐溶剤性に優れている上、低誘電率を有し誘電特性に優れる。そのため、例えばフレキシブルプリント基板のコア部材やカバーレイフィルムに好適に用いることができる。 A film made of a cured product of the thermosetting maleimide resin composition of the present invention is excellent in heat resistance, mechanical properties, electrical properties and solvent resistance, and has a low dielectric constant and excellent dielectric properties. Therefore, it can be suitably used for core members and cover lay films of flexible printed circuit boards, for example.
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 described by showing examples and comparative examples, but the present invention is not limited to the following examples.
実施例及び比較例で使用した各成分を以下に示す。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)
流速: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)
Components used in Examples and Comparative Examples are shown below. In the following, the number average molecular weight (Mn) is measured under the following measurement conditions using polystyrene as a standard.
Developing solvent: tetrahydrofuran (THF)
Flow rate: 0.35mL/min
Detector: Differential Refractive Index Detector (RI)
Column: TSK Guard column SuperH-L
TSKgel SuperHZ4000 (4.6mm ID x 15cm x 1)
TSKgel SuperHZ3000 (4.6mm ID x 15cm x 1)
TSKgel SuperHZ2000 (4.6mm I.D. x 15cm x 2)
(both manufactured by Tosoh Corporation)
Column temperature: 40°C
Sample injection volume: 5 μL (THF solution with a concentration of 0.2% by mass)
(A)数平均分子量3,000以上の芳香族マレイミド樹脂
[合成例1](マレイミド樹脂の製造、下記式A-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)、2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパン59.10g(0.144モル)及びメシチレン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(両末端ジアミン)を合成した。
得られた両末端ジアミン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2.9g(0.030モル)加え、80℃で3時間撹拌することでマレ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(A-1)で示されるマレイミド樹脂のワニスを得た。メシチレンを完全に除去せず、不揮発分40質量%に調製した。式(A-1)で示されるマレイミド樹脂のMnは22,500であった。
65.06 g of 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride was added to a 1 L glass 4-neck flask equipped with a stirrer, Dean-Stark tube, cooling condenser and thermometer. (0.125 mol), 59.10 g (0.144 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane and 250 g of mesitylene were added and stirred at 80°C for 3 hours to give an amic acid. was synthesized. Thereafter, the temperature was raised to 150° C. as it was, and the mixture was stirred for 2 hours while distilling off the by-produced moisture to synthesize a block copolymer (diamine at both ends).
The flask containing the resulting diamine solution at both ends was cooled to room temperature, 2.9 g (0.030 mol) of maleic anhydride was added, and the mixture was stirred at 80° C. for 3 hours to synthesize maleamic acid. Thereafter, the temperature was raised to 150° C. as it was, and the mixture was stirred for 2 hours while distilling off by-produced moisture to obtain a maleimide resin varnish represented by the following formula (A-1). The non-volatile content was adjusted to 40% by mass without completely removing the mesitylene. Mn of the maleimide resin represented by formula (A-1) was 22,500.
[合成例2](マレイミド樹脂の製造、下記式A-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、ビス[4-(2,3-ジカルボキシフェノキシ)フェニル]メタン二無水物61.55g(0.125モル)、ビス[4-(4-アミノフェノキシ)フェニル]メタン55.07g(0.144モル)及びメシチレン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(両末端ジアミン)を合成した。
得られた両末端ジアミン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2.9g(0.030モル)加え、80℃で3時間撹拌することでマレ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(A-1)で示されるマレイミド樹脂のワニスを得た。メシチレンを完全に除去せず、不揮発分40質量%に調製した。式(A-2)で示されるマレイミド樹脂のMnは21,500であった。
61.55 g (0.125 g) of bis[4-(2,3-dicarboxyphenoxy)phenyl]methane dianhydride was added to a 1 L glass four-necked flask equipped with a stirrer, Dean-Stark tube, cooling condenser and thermometer. mol), 55.07 g (0.144 mol) of bis[4-(4-aminophenoxy)phenyl]methane and 250 g of mesitylene were added and stirred at 80° C. for 3 hours to synthesize an amic acid. Thereafter, the temperature was raised to 150° C. as it was, and the mixture was stirred for 2 hours while distilling off by-produced moisture to synthesize a block copolymer (diamine at both ends).
The resulting flask containing the diamine solution at both ends was cooled to room temperature, 2.9 g (0.030 mol) of maleic anhydride was added, and the mixture was stirred at 80° C. for 3 hours to synthesize maleamic acid. Thereafter, the temperature was raised to 150° C. as it was, and the mixture was stirred for 2 hours while distilling off by-produced moisture to obtain a maleimide resin varnish represented by the following formula (A-1). The non-volatile content was adjusted to 40% by mass without completely removing the mesitylene. Mn of the maleimide resin represented by formula (A-2) was 21,500.
(A-3):下記式で示される直鎖アルキレン基含有ビスマレイミド樹脂(SLK-3000、信越化学工業(株)製、Mn:7,500、比較例用)
(B)1分子中に1個以上のアリル基及び1個以上のイソシアヌル環を有する有機化合物
(B-1):トリアリルイソシアヌレート(TAIC、三菱ケミカル(株)製)
(B-2):アルキルジアリルイソシアヌレート(L-DAIC、四国化成(株)製)
(B-3):ジアリルイソフタレート(ダイソーダップ100モノマー、(株)大阪ソーダ製、比較例用)
(B-4):イソシアヌル酸トリス(2-アクリロイルオキシエチル)(FA-731A、日立化成(株)製、比較例用)
(B) Organic compound having one or more allyl groups and one or more isocyanuric rings in one molecule (B-1): triallyl isocyanurate (TAIC, manufactured by Mitsubishi Chemical Corporation)
(B-2): Alkyl diallyl isocyanurate (L-DAIC, manufactured by Shikoku Kasei Co., Ltd.)
(B-3): diallyl isophthalate (Daiso Dap 100 monomer, manufactured by Osaka Soda Co., Ltd., for comparative examples)
(B-4): tris(2-acryloyloxyethyl) isocyanurate (FA-731A, manufactured by Hitachi Chemical Co., Ltd., for comparative examples)
(C)特定のマレイミド樹脂
(C-1):下記式(C-1)で表されるマレイミド樹脂(MIR-3000、日本化薬(株)製、Mn:580)
(C-2):4,4’-ジフェニルメタンビスマレイミド(BMI-1000:大和化成工業(株)製、Mn:358、比較例用)
(C-3):下記式で示される直鎖アルキレン基含有ビスマレイミド化合物(SLK-1500、信越化学工業(株)製、Mn:2,000、比較例用)
(C-2): 4,4′-diphenylmethanebismaleimide (BMI-1000: manufactured by Daiwa Kasei Kogyo Co., Ltd., Mn: 358, for comparative example)
(C-3): Linear alkylene group-containing bismaleimide compound represented by the following formula (SLK-1500, manufactured by Shin-Etsu Chemical Co., Ltd., Mn: 2,000, for comparative examples)
(D)反応開始剤
(D-1)ジクミルパーオキシド(パークミルD、日油(株)製)
(D) Reaction initiator (D-1) dicumyl peroxide (Percumyl D, manufactured by NOF Corporation)
<フィルム作製方法>
表1及び2に示す配合で、不揮発分45質量%のメシチレンワニスを調製し、このワニス状の熱硬化性マレイミド樹脂組成物を厚さ50μmの離型剤処理されたPETフィルム(TN010、東洋紡社製)上に、乾燥後の厚さが50μmとなるようにローラーコーターで塗布し、100℃で10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PETフィルム上に載せた状態で、180℃で2時間の条件で硬化させることで熱硬化性マレイミド樹脂組成物の硬化物からなるフィルムを得た。
フィルムを下記の各評価試験に供し、その結果を表1及び表2に示す。
<Film preparation method>
A mesitylene varnish having a non-volatile content of 45% by mass was prepared according to the formulations shown in Tables 1 and 2, and this varnish-like thermosetting maleimide resin composition was applied to a release agent-treated PET film (TN010, Toyobo Co., Ltd.) having a thickness of 50 μm. (manufactured) by a roller coater so that the thickness after drying was 50 μm, and dried at 100° C. for 10 minutes to obtain an uncured resin film. Further, the uncured resin film was placed on a PET film and cured at 180° C. for 2 hours to obtain a film of a cured thermosetting maleimide resin composition.
The films were subjected to the following evaluation tests, and the results are shown in Tables 1 and 2.
<フィルム外観>
前記フィルムの外観を目視で確認した。フィルムが透明であるものは〇、濁りがあるものを△、完全に分離が生じているものを×とした。
<Film Appearance>
The appearance of the film was visually confirmed. When the film was transparent, it was rated as ◯; when it was cloudy, it was rated as Δ;
<フィルムハンドリング性>
前記フィルムを180°に100回折り曲げ、フィルムに割れなどの欠陥が生じないものを○、フィルムに割れなどの欠陥が生じたものを×とした。
<Film handleability>
The film was bent 100 times at an angle of 180°, and ◯ was given when no defects such as cracks occurred in the film, and X was given when defects such as cracks occurred in the film.
前記フィルムを用いて、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。また、得られたフィルムを85℃、85%の恒温恒湿機に24時間静置し、吸湿させた後の周波数10GHzにおける比誘電率と誘電正接を同様の方法で測定した。 Using the above film, a network analyzer (E5063-2D5 manufactured by Keysight Co., Ltd.) and a stripline (manufactured by Keycom Co., Ltd.) were connected to measure the dielectric constant and dielectric loss tangent of the above film at a frequency of 10 GHz. In addition, the obtained film was allowed to stand in a thermo-hygrostat at 85° C. and 85% for 24 hours, and after moisture absorption, the dielectric constant and dielectric loss tangent at a frequency of 10 GHz were measured in the same manner.
<ガラス転移温度>
前記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。
<Glass transition temperature>
The glass transition temperature (Tg) of the film was measured with DMA-800 manufactured by TA Instruments.
<耐リフロー性>
前記フィルムをIRリフロー炉(最高温度260℃、炉内通貨温度10秒間)に3回通したサンプルについて、目視で変化が無いものを〇、カールが生じたものを△、カールし、フィルムの表面同士にくっつきが生じたものを×とした。
<Reflow resistance>
For samples in which the film was passed through an IR reflow furnace (maximum temperature 260 ° C., currency temperature in the furnace for 10 seconds) three times, ◯ for those with no visible change, △ for those with curls, curled, and the surface of the film When sticking occurred to each other, it was marked with x.
*2:Tg点が二つ以上確認された
以上より、本発明の熱硬化性マレイミド樹脂組成物の硬化物からなるフィルムは、ムラがなく均質であり、ハンドリング性に優れ、ガラス転移温度が高く、リフロー時の寸法安定性に優れ、変形も少なく、誘電特性にも優れることから、フレキシブルプリント基板用材料としての有用性が確認できた。 As described above, the film made of the cured product of the thermosetting maleimide resin composition of the present invention is homogeneous without unevenness, has excellent handleability, has a high glass transition temperature, has excellent dimensional stability during reflow, and is resistant to deformation. It is useful as a material for flexible printed circuit boards because it has excellent dielectric properties.
Claims (6)
(B)1分子中に1個以上のアリル基及び1個以上のイソシアヌル環を有する有機化合物、
(C)数平均分子量3,000未満の下記式(1)で表されるマレイミド樹脂
及び
(D)反応開始剤
を含む熱硬化性マレイミド樹脂組成物の硬化物からなるフィルム。
(B) an organic compound having one or more allyl groups and one or more isocyanuric rings in one molecule;
A film comprising a cured product of a thermosetting maleimide resin composition containing (C) a maleimide resin represented by the following formula (1) having a number average molecular weight of less than 3,000 and (D) a reaction initiator.
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