JP2019192343A - Resin film for interlayer insulating layer, laminate, printed wiring board, semiconductor device, and method of manufacturing laminate - Google Patents
Resin film for interlayer insulating layer, laminate, printed wiring board, semiconductor device, and method of manufacturing laminateInfo
- Publication number
- JP2019192343A JP2019192343A JP2018080066A JP2018080066A JP2019192343A JP 2019192343 A JP2019192343 A JP 2019192343A JP 2018080066 A JP2018080066 A JP 2018080066A JP 2018080066 A JP2018080066 A JP 2018080066A JP 2019192343 A JP2019192343 A JP 2019192343A
- Authority
- JP
- Japan
- Prior art keywords
- resin film
- resin
- resin composition
- group
- groups
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 167
- 239000011347 resin Substances 0.000 title claims abstract description 167
- 239000010410 layer Substances 0.000 title claims abstract description 91
- 239000011229 interlayer Substances 0.000 title claims abstract description 60
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 239000004065 semiconductor Substances 0.000 title claims abstract description 14
- -1 maleimide compound Chemical class 0.000 claims abstract description 122
- 239000011342 resin composition Substances 0.000 claims abstract description 98
- 239000003822 epoxy resin Substances 0.000 claims abstract description 43
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 43
- 229920001971 elastomer Polymers 0.000 claims abstract description 29
- 239000000806 elastomer Substances 0.000 claims abstract description 29
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 27
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 26
- 239000007787 solid Substances 0.000 claims abstract description 19
- 238000009413 insulation Methods 0.000 claims description 25
- 239000011256 inorganic filler Substances 0.000 claims description 23
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 23
- 125000003277 amino group Chemical group 0.000 claims description 16
- 238000010030 laminating Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229920000800 acrylic rubber Polymers 0.000 claims description 8
- 229920000058 polyacrylate Polymers 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000005641 methacryl group Chemical group 0.000 claims description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
- 239000012792 core layer Substances 0.000 abstract description 26
- 125000004432 carbon atom Chemical group C* 0.000 description 34
- 238000000034 method Methods 0.000 description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 22
- 230000001681 protective effect Effects 0.000 description 20
- 229920001721 polyimide Polymers 0.000 description 17
- 239000004642 Polyimide Substances 0.000 description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 239000011521 glass Substances 0.000 description 14
- 239000011889 copper foil Substances 0.000 description 12
- 239000002966 varnish Substances 0.000 description 12
- 125000002947 alkylene group Chemical group 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 11
- 239000006087 Silane Coupling Agent Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 125000001118 alkylidene group Chemical group 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229920003986 novolac Polymers 0.000 description 7
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 125000005843 halogen group Chemical group 0.000 description 6
- 238000003475 lamination Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 229930003836 cresol Natural products 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000011800 void material Substances 0.000 description 5
- XAZPKEBWNIUCKF-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]propan-2-yl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=CC=1C(C)(C)C(C=C1)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O XAZPKEBWNIUCKF-UHFFFAOYSA-N 0.000 description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-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 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000004450 alkenylene group Chemical group 0.000 description 3
- 125000004419 alkynylene group Chemical group 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 3
- 125000000732 arylene group Chemical group 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000005350 fused silica glass Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 239000012756 surface treatment agent Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- 239000013585 weight reducing agent Substances 0.000 description 3
- GUIACFHOZIQGKX-UHFFFAOYSA-N 1-[4-[4-(2,5-dioxopyrrol-1-yl)phenyl]sulfonylphenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=C(S(=O)(=O)C=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=C1 GUIACFHOZIQGKX-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- HUWXDEQWWKGHRV-UHFFFAOYSA-N 3,3'-Dichlorobenzidine Chemical group C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HUWXDEQWWKGHRV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003849 aromatic solvent Substances 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
- 239000011324 bead Substances 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000006081 fluorescent whitening agent Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 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 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920000728 polyester 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
- 230000008569 process Effects 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 2
- 229920006132 styrene block copolymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 1
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- XOJRVZIYCCJCRD-UHFFFAOYSA-N 1-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1OC1=CC=C(N2C(C=CC2=O)=O)C=C1 XOJRVZIYCCJCRD-UHFFFAOYSA-N 0.000 description 1
- VDNSZPNSUQRUMS-UHFFFAOYSA-N 1-cyclohexyl-4-ethenylbenzene Chemical compound C1=CC(C=C)=CC=C1C1CCCCC1 VDNSZPNSUQRUMS-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- VVTGQMLRTKFKAM-UHFFFAOYSA-N 1-ethenyl-4-propylbenzene Chemical compound CCCC1=CC=C(C=C)C=C1 VVTGQMLRTKFKAM-UHFFFAOYSA-N 0.000 description 1
- UXOXUHMFQZEAFR-UHFFFAOYSA-N 2,2',5,5'-Tetrachlorobenzidine Chemical group C1=C(Cl)C(N)=CC(Cl)=C1C1=CC(Cl)=C(N)C=C1Cl UXOXUHMFQZEAFR-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
- OJSPYCPPVCMEBS-UHFFFAOYSA-N 2,8-dimethyl-5,5-dioxodibenzothiophene-3,7-diamine Chemical compound C12=CC(C)=C(N)C=C2S(=O)(=O)C2=C1C=C(C)C(N)=C2 OJSPYCPPVCMEBS-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical group C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- VZQSBJKDSWXLKX-UHFFFAOYSA-N 3-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C=C(O)C=CC=2)=C1 VZQSBJKDSWXLKX-UHFFFAOYSA-N 0.000 description 1
- MOSSLXZUUKTULI-UHFFFAOYSA-N 3-[3-(2,5-dioxopyrrol-3-yl)-4-methylphenyl]pyrrole-2,5-dione Chemical compound CC1=CC=C(C=2C(NC(=O)C=2)=O)C=C1C1=CC(=O)NC1=O MOSSLXZUUKTULI-UHFFFAOYSA-N 0.000 description 1
- WCXGOVYROJJXHA-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 WCXGOVYROJJXHA-UHFFFAOYSA-N 0.000 description 1
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-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
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical group CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 1
- KHYXYOGWAIYVBD-UHFFFAOYSA-N 4-(4-propylphenoxy)aniline Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N)C=C1 KHYXYOGWAIYVBD-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- SSDBTLHMCVFQMS-UHFFFAOYSA-N 4-[4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C(F)(F)F)C(F)(F)F)C=C1 SSDBTLHMCVFQMS-UHFFFAOYSA-N 0.000 description 1
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 1
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- PHICKPBIPXXFIP-UHFFFAOYSA-N 5-amino-2-(4-amino-5-methyl-2-sulfophenyl)-4-methylbenzenesulfonic acid Chemical compound C1=C(N)C(C)=CC(C=2C(=CC(N)=C(C)C=2)S(O)(=O)=O)=C1S(O)(=O)=O PHICKPBIPXXFIP-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- SXEHKFHPFVVDIR-UHFFFAOYSA-N [4-(4-hydrazinylphenyl)phenyl]hydrazine Chemical compound C1=CC(NN)=CC=C1C1=CC=C(NN)C=C1 SXEHKFHPFVVDIR-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- NOHQTLHHNIKWBA-UHFFFAOYSA-N [SiH4].NC(=O)N Chemical compound [SiH4].NC(=O)N NOHQTLHHNIKWBA-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 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
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229940118662 aluminum carbonate Drugs 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- LNEUSAPFBRDCPM-UHFFFAOYSA-N carbamimidoylazanium;sulfamate Chemical compound NC(N)=N.NS(O)(=O)=O LNEUSAPFBRDCPM-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- JAWGVVJVYSANRY-UHFFFAOYSA-N cobalt(3+) Chemical compound [Co+3] JAWGVVJVYSANRY-UHFFFAOYSA-N 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012772 electrical insulation material Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000005567 fluorenylene group Chemical group 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 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
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 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
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- LTURHSAEWJPFAA-UHFFFAOYSA-N sulfuric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OS(O)(=O)=O.NC1=NC(N)=NC(N)=N1 LTURHSAEWJPFAA-UHFFFAOYSA-N 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- QLAGHGSFXJZWKY-UHFFFAOYSA-N triphenylborane;triphenylphosphane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QLAGHGSFXJZWKY-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
- Organic Insulating Materials (AREA)
- Insulating Bodies (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本発明は、層間絶縁層用樹脂フィルム、積層体、プリント配線板、半導体装置及び積層体の製造方法に関する。 The present invention relates to a resin film for an interlayer insulating layer, a laminate, a printed wiring board, a semiconductor device, and a method for manufacturing the laminate.
近年、地球環境保護の観点から、はんだの鉛フリー化が進行しており、プリント配線板への部品実装時及び半導体パッケージ組み立て時におけるリフロー工程の温度が非常に高くなっている。これに伴って、プリント配線板用の積層板には、耐熱性の向上等による信頼性向上の要求が強まっている。 In recent years, lead-free solder has been developed from the viewpoint of protecting the global environment, and the temperature of the reflow process when mounting components on a printed wiring board and assembling a semiconductor package has become extremely high. In connection with this, the request | requirement of the reliability improvement by the heat resistant improvement etc. is increasing to the laminated board for printed wiring boards.
プリント配線板用の積層板としては、エポキシ樹脂を主剤とした樹脂組成物とガラスクロスとを含むプリプレグを硬化及び一体成形化したものが一般的である。
エポキシ樹脂は、絶縁性、耐熱性、成形性、コスト等のバランスに優れるが、近年のプリント配線板の高密度実装及び高多層化構成に伴う耐熱性向上への要請に対応するには、さらなる改良が必要となっており、耐熱性に優れる材料として、ポリビスマレイミド樹脂がプリント配線板用の積層板材料に広く使用されている。
As a laminated board for printed wiring boards, a prepreg containing a resin composition mainly composed of an epoxy resin and glass cloth is cured and integrally formed.
Epoxy resin has an excellent balance of insulation, heat resistance, moldability, cost, etc., but in order to respond to the demand for improved heat resistance due to the recent high-density mounting of printed wiring boards and multi-layered configuration, Improvement is required, and polybismaleimide resin is widely used as a laminated board material for printed wiring boards as a material having excellent heat resistance.
また、近年の電子機器の小型化及び高性能化の流れに伴い、プリント配線板では配線密度の高度化及び高集積化が進展している。そのため、電子部品の実装密度を向上するために、多層プリント配線板の微細配線化の開発が進められている。これらの要求に合致する多層プリント配線板としては、ガラスクロスと樹脂とを含有する積層板又は配線板からなる層（以下、「コア層」ともいう）に、ガラスクロスを含まない層間絶縁層用樹脂フィルムを、プリプレグの代わりに絶縁層（以下、「ビルドアップ層」ともいう）として用いるビルドアップ構造の多層プリント配線板が、軽量化、小型化及び微細化に適したプリント配線板として主流になりつつある。 In addition, with the trend of recent miniaturization and higher performance of electronic devices, advancement in wiring density and higher integration are progressing in printed wiring boards. For this reason, in order to improve the mounting density of electronic components, development of fine wiring of multilayer printed wiring boards is being promoted. Multilayer printed wiring boards that meet these requirements are for interlayer insulation layers that do not contain glass cloth in layers (hereinafter also referred to as “core layers”) made of laminated boards or wiring boards containing glass cloth and resin. A multilayer printed wiring board with a build-up structure that uses a resin film as an insulating layer (hereinafter also referred to as “build-up layer”) instead of a prepreg has become the mainstream as a printed wiring board suitable for weight reduction, miniaturization, and miniaturization. It is becoming.
しかしながら、パッケージ基板は反りが発生し易く、実装工程等で問題が発生しやすいため、ビルドアップ層には高弾性率、低熱膨張係数といった反りを低減する特性が求められている。そのため、多量の無機充填材を含有する樹脂組成物が検討されている。（例えば、特許文献１参照） However, since the package substrate is likely to be warped and problems are likely to occur in the mounting process and the like, the buildup layer is required to have a characteristic of reducing warpage such as a high elastic modulus and a low thermal expansion coefficient. Therefore, a resin composition containing a large amount of inorganic filler has been studied. (For example, see Patent Document 1)
一方、多量の無機充填材を含有する樹脂組成物は、層間絶縁層用樹脂フィルムを取り扱う際に端部から樹脂欠けが発生する、折れ目が発生するなど、樹脂フィルムの取り扱い性が悪化するという新たな問題が発生した。樹脂フィルムの取り扱い性を向上させることを目的として、液状エポキシ樹脂を配合する方法が検討されているが、液状エポキシ樹脂は耐デスミア性が低い傾向にある。したがって、低熱膨張係数を実現しつつ、取り扱い性と耐デスミア性とを両立させることが望まれている。
さらには、多量の無機充填材を含有する樹脂組成物を使用するビルドアップ層は、コア層との間にボイドが発生し易くなる問題が確認されており、改善が望まれている。
On the other hand, the resin composition containing a large amount of inorganic filler is said to deteriorate the handleability of the resin film, such as when the resin film for an interlayer insulating layer is handled, the resin chipping occurs from the end, or the crease occurs. A new problem has occurred. For the purpose of improving the handleability of the resin film, a method of blending a liquid epoxy resin has been studied, but the liquid epoxy resin tends to have low desmear resistance. Therefore, it is desired to achieve both handleability and desmear resistance while realizing a low thermal expansion coefficient.
Furthermore, the build-up layer using a resin composition containing a large amount of an inorganic filler has been confirmed to have a problem that voids are easily generated between the build-up layer and the core layer, and improvement is desired.
本発明は、上記事情に鑑みてなされたものであり、取り扱い性及び耐デスミア性に優れ、コア層に積層した場合に、コア層との界面におけるボイドの発生を抑制することができる層間絶縁層用樹脂フィルム、該層間絶縁層用樹脂フィルムを用いた積層体、プリント配線板、半導体装置及び積層体の製造方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and is an interlayer insulating layer that is excellent in handleability and desmear resistance, and can suppress generation of voids at the interface with the core layer when laminated on the core layer. An object of the present invention is to provide a resin film, a laminate using the resin film for an interlayer insulating layer, a printed wiring board, a semiconductor device, and a method for producing the laminate.
本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、特定の組成を有する樹脂組成物を含有する層間絶縁層用樹脂フィルムが上記目的に沿うものであることを見出し、本発明に到達した。
すなわち、本発明は、下記［１］〜［１７］に関する。
［１］（Ａ）固形エポキシ樹脂と、
（Ｂ）１分子中に２個以上のＮ−置換マレイミド基を有するマレイミド化合物と、
（Ｃ）１分子中に２個以上の１級アミノ基を有するアミン化合物と、
（Ｄ）エラストマーと、
を含有する熱硬化性樹脂組成物を含有する、層間絶縁層用樹脂フィルム。
［２］（Ｄ）エラストマーが、エポキシ基、アミノ基、水酸基、メタクリル基、メルカプト基、カルボキシ基及びアルコキシ基からなる群から選択される１種以上の反応性官能基を有する、上記［１］に記載の層間絶縁層用樹脂フィルム。
［３］（Ｄ）エラストマーが、アクリル系エラストマーである、上記［１］又は［２］に記載の層間絶縁層用樹脂フィルム。
［４］前記熱硬化性樹脂組成物中における（Ｄ）エラストマーの含有量が、前記熱硬化性樹脂組成物中の樹脂成分の総和１００質量部に対して、５〜６０質量部である、上記［１］〜［３］のいずれかに記載の層間絶縁層用樹脂フィルム。
［５］前記熱硬化性樹脂組成物が、さらに、（Ｅ）無機充填材を含有する、上記［１］〜［４］のいずれかに記載の層間絶縁層用樹脂フィルム。
［６］前記熱硬化性樹脂組成物中における（Ｅ）無機充填材の含有量が、前記熱硬化性樹脂組成物中の樹脂成分の総和１００質量部に対して、２０〜３００質量部である、上記［５］に記載の層間絶縁層用樹脂フィルム。
［７］前記熱硬化性樹脂組成物が、さらに、（Ｆ）硬化促進剤を含有する、上記［１］〜［６］のいずれかに記載の層間絶縁層用樹脂フィルム。
［８］（Ｃ）１分子中に２個以上の１級アミノ基を有するアミン化合物が、シロキサン骨格を含有する化合物である、上記［１］〜［７］のいずれかに記載の層間絶縁層用樹脂フィルム。
［９］プリプレグ又はプリプレグを硬化してなる絶縁層に積層して用いられる、上記［１］〜［８］のいずれかに記載の層間絶縁層用樹脂フィルム。
［１０］前記プリプレグが、
（ａ）エポキシ樹脂と、
（ｂ）１分子中に２個以上のＮ−置換マレイミド基を有するマレイミド化合物と、
（ｃ）１分子中に２個以上の１級アミノ基を有するアミン化合物と、
を含有する熱硬化性樹脂組成物を含有するものである、上記［９］に記載の層間絶縁層用樹脂フィルム。
［１１］（ｃ）１分子中に２個以上の１級アミノ基を有するアミン化合物が、シロキサン骨格を含有する化合物である、上記［１０］に記載の層間絶縁層用樹脂フィルム。
［１２］上記［１］〜［１１］のいずれかに記載の層間絶縁層用樹脂フィルムと、プリプレグ又はプリプレグを硬化してなる絶縁層と、を積層してなる、積層体。
［１３］前記プリプレグが、
（ａ）エポキシ樹脂と、
（ｂ）１分子中に２個以上のＮ−置換マレイミド基を有するマレイミド化合物と、
（ｃ）１分子中に２個以上の１級アミノ基を有するアミン化合物と、
を含有する熱硬化性樹脂組成物を含有するものである、上記［１２］に記載の積層体。
［１４］（ｃ）１分子中に２個以上の１級アミノ基を有するアミン化合物が、シロキサン骨格を含有する化合物である、上記［１３］に記載の積層体。
［１５］上記［１］〜［１１］のいずれかに記載の層間絶縁層用樹脂フィルムを用いて形成される層間絶縁層、又は上記［１２］〜［１４］のいずれかに記載の積層体を用いて形成される層間絶縁層を含有する、プリント配線板。
［１６］上記［１５］に記載のプリント配線板を含有する、半導体装置。
［１７］上記［１２］〜［１４］のいずれかに記載の積層体を製造する方法であって、前記プリプレグを硬化してなる絶縁層の片面又は両面に、上記［１］〜［１１］のいずれかに記載の層間絶縁層用樹脂フィルムをラミネートする、積層体の製造方法。
As a result of intensive studies to achieve the above object, the present inventors have found that a resin film for an interlayer insulating layer containing a resin composition having a specific composition meets the above object. The invention has been reached.
That is, the present invention relates to the following [1] to [17].
[1] (A) a solid epoxy resin;
(B) a maleimide compound having two or more N-substituted maleimide groups in one molecule;
(C) an amine compound having two or more primary amino groups in one molecule;
(D) an elastomer;
A resin film for an interlayer insulating layer, comprising a thermosetting resin composition containing
[2] The above [1], wherein the elastomer (D) has one or more reactive functional groups selected from the group consisting of epoxy groups, amino groups, hydroxyl groups, methacryl groups, mercapto groups, carboxy groups, and alkoxy groups. The resin film for interlayer insulation layers as described in 2.
[3] The resin film for an interlayer insulating layer according to the above [1] or [2], wherein the (D) elastomer is an acrylic elastomer.
[4] The content of (D) elastomer in the thermosetting resin composition is 5 to 60 parts by mass with respect to 100 parts by mass of the total resin components in the thermosetting resin composition. The resin film for interlayer insulation layers according to any one of [1] to [3].
[5] The resin film for an interlayer insulating layer according to any one of [1] to [4], wherein the thermosetting resin composition further contains (E) an inorganic filler.
[6] The content of the (E) inorganic filler in the thermosetting resin composition is 20 to 300 parts by mass with respect to 100 parts by mass of the total resin components in the thermosetting resin composition. The resin film for interlayer insulation layers according to [5] above.
[7] The resin film for an interlayer insulating layer according to any one of [1] to [6], wherein the thermosetting resin composition further contains (F) a curing accelerator.
[8] (C) The interlayer insulating layer according to any one of [1] to [7], wherein the amine compound having two or more primary amino groups in one molecule is a compound containing a siloxane skeleton. Resin film.
[9] The resin film for an interlayer insulating layer according to any one of the above [1] to [8], which is used by being laminated on an insulating layer formed by curing a prepreg or a prepreg.
[10] The prepreg is
(A) an epoxy resin;
(B) a maleimide compound having two or more N-substituted maleimide groups in one molecule;
(C) an amine compound having two or more primary amino groups in one molecule;
The resin film for an interlayer insulation layer according to the above [9], which contains a thermosetting resin composition containing
[11] The resin film for an interlayer insulating layer according to [10], wherein the amine compound having two or more primary amino groups in one molecule is a compound containing a siloxane skeleton.
[12] A laminate obtained by laminating the resin film for an interlayer insulating layer according to any one of [1] to [11] above and a prepreg or an insulating layer obtained by curing the prepreg.
[13] The prepreg
(A) an epoxy resin;
(B) a maleimide compound having two or more N-substituted maleimide groups in one molecule;
(C) an amine compound having two or more primary amino groups in one molecule;
The laminate according to [12] above, which contains a thermosetting resin composition containing
[14] (c) The laminate according to the above [13], wherein the amine compound having two or more primary amino groups in one molecule is a compound containing a siloxane skeleton.
[15] An interlayer insulating layer formed using the resin film for an interlayer insulating layer according to any one of [1] to [11], or a laminate according to any one of [12] to [14] The printed wiring board containing the interlayer insulation layer formed using.
[16] A semiconductor device comprising the printed wiring board according to [15].
[17] A method for producing the laminate according to any one of [12] to [14] above, wherein the above [1] to [11] are provided on one or both sides of an insulating layer obtained by curing the prepreg. A method for producing a laminate, comprising laminating the resin film for an interlayer insulating layer according to any one of the above.
本発明によると、取り扱い性及び耐デスミア性に優れ、コア層に積層した場合に、コア層との界面におけるボイドの発生を抑制することができる層間絶縁層用樹脂フィルム、該層間絶縁層用樹脂フィルムを用いた積層体、プリント配線板、半導体装置及び積層体の製造方法を提供することができる。 According to the present invention, the resin film for an interlayer insulating layer, which is excellent in handleability and desmear resistance and can suppress the generation of voids at the interface with the core layer when laminated on the core layer, the resin for the interlayer insulating layer A laminate using a film, a printed wiring board, a semiconductor device, and a method for manufacturing the laminate can be provided.
以下、本発明の一実施形態について詳述するが、本発明は以下の実施形態に限定されるものではない。 Hereinafter, one embodiment of the present invention will be described in detail, but the present invention is not limited to the following embodiment.
［層間絶縁層用樹脂フィルム］
本実施形態の層間絶縁層用樹脂フィルム（以下、単に「樹脂フィルム」ともいう）は、（Ａ）固形エポキシ樹脂と、（Ｂ）１分子中に２個以上のＮ−置換マレイミド基を有するマレイミド化合物と、（Ｃ）１分子中に２個以上の１級アミノ基を有するアミン化合物と、（Ｄ）エラストマーと、を含有する熱硬化性樹脂組成物を含有するものである。
なお、本実施形態の樹脂フィルムは、該樹脂フィルムの一方の表面に支持体が付いている「支持体付き樹脂フィルム」の状態であることが好ましく、更に樹脂フィルムの他方の面に保護フィルムが付いている「支持体及び保護フィルム付き樹脂フィルム」の状態であってもよい。
以下、本実施形態の樹脂フィルムに含有される熱硬化性樹脂組成物を「樹脂組成物（I）」とも称する。
[Resin film for interlayer insulation layer]
The resin film for interlayer insulation layers of the present embodiment (hereinafter also simply referred to as “resin film”) includes (A) a solid epoxy resin and (B) a maleimide having two or more N-substituted maleimide groups in one molecule. A thermosetting resin composition containing a compound, (C) an amine compound having two or more primary amino groups in one molecule, and (D) an elastomer is contained.
The resin film of the present embodiment is preferably in a state of “resin film with support” in which a support is attached to one surface of the resin film, and a protective film is provided on the other surface of the resin film. It may be in the state of “resin film with support and protective film” attached.
Hereinafter, the thermosetting resin composition contained in the resin film of the present embodiment is also referred to as “resin composition (I)”.
＜（Ａ）固形エポキシ樹脂＞
本実施形態の樹脂フィルムは、（Ａ）固形エポキシ樹脂（以下、「（Ａ）成分」ともいう）を含有することにより耐デスミア性に優れたものとなる。
なお、本実施形態における「固形」とは常温（２５℃）において流動性を示さない固体状態を呈することを意味し、「液状」とは常温（２５℃）において流動性を示す液体状態を呈することを意味する。
<(A) Solid epoxy resin>
The resin film of this embodiment becomes excellent in desmear resistance by containing (A) a solid epoxy resin (hereinafter also referred to as “component (A)”).
In this embodiment, “solid” means a solid state that does not exhibit fluidity at normal temperature (25 ° C.), and “liquid” indicates a liquid state that exhibits fluidity at normal temperature (25 ° C.). Means that.
（Ａ）固形エポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、α−ナフトール／クレゾールノボラック型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、ビスフェノールＦノボラック型エポキシ樹脂、スチルベン型エポキシ樹脂、トリアジン骨格含有エポキシ樹脂、フルオレン骨格含有エポキシ樹脂、トリフェノールメタン型エポキシ樹脂、ビフェニル型エポキシ樹脂、キシリレン型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂、ナフタレン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、脂環式エポキシ樹脂、多官能フェノール類及びアントラセン等の多環芳香族類のジグリシジルエーテル化合物、これらにリン化合物を導入したリン含有エポキシ樹脂などが挙げられる。これらの中でも、耐デスミア性、耐熱性及び難燃性の観点から、ナフタレン骨格含有型エポキシ樹脂が好ましく、α−ナフトール／クレゾールノボラック型エポキシ樹脂がより好ましい。
（Ａ）固形エポキシ樹脂は、１種を単独で使用してもよいし、２種以上を併用してもよい。
(A) As the solid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin, α-naphthol / cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, stilbene type epoxy resin, triazine skeleton containing epoxy resin, fluorene skeleton containing epoxy resin, triphenolmethane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type Epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, alicyclic epoxy resin, polyfunctional phenols and anthracene Diglycidyl ether compounds of polycyclic aromatics, such as those in the phosphorus-containing epoxy resin obtained by introducing a phosphorus compound. Among these, from the viewpoint of desmear resistance, heat resistance, and flame retardancy, a naphthalene skeleton-containing epoxy resin is preferable, and an α-naphthol / cresol novolac epoxy resin is more preferable.
(A) A solid epoxy resin may be used individually by 1 type, and may use 2 or more types together.
（Ａ）固形エポキシ樹脂のエポキシ当量は、１５０〜５００ｇ／ｅｑが好ましく、１５０〜４００ｇ／ｅｑがより好ましく、２００〜３００ｇ／ｅｑがさらに好ましい。
ここで、エポキシ当量は、エポキシ基あたりの樹脂の質量（ｇ／ｅｑ）であり、ＪＩＳ Ｋ ７２３６：２００９に準拠して測定することができる。
(A) The epoxy equivalent of the solid epoxy resin is preferably 150 to 500 g / eq, more preferably 150 to 400 g / eq, and further preferably 200 to 300 g / eq.
Here, the epoxy equivalent is the mass of the resin per epoxy group (g / eq), and can be measured according to JIS K 7236: 2009.
（Ａ）固形エポキシ樹脂の含有量に特に制限はないが、耐デスミア性、成形性、電気絶縁性及び金属回路との接着強度の観点から、樹脂組成物（I）中の樹脂成分の総和１００質量部に対して、１〜４０質量部が好ましく、３〜３５質量部がより好ましく、５〜２０質量部がさらに好ましい。
なお、本実施形態において、樹脂成分とは、（Ａ）〜（Ｄ）成分、後述する（Ｘ）成分及び任意で用いられる樹脂を意味し、後述する硬化促進剤は樹脂成分には含まないものとする。
(A) Although there is no restriction | limiting in particular in content of a solid epoxy resin, From the viewpoint of desmear resistance, a moldability, an electrical insulation, and the adhesive strength with a metal circuit, the sum total 100 of the resin component in resin composition (I) 1-40 mass parts is preferable with respect to mass parts, 3-35 mass parts is more preferable, and 5-20 mass parts is further more preferable.
In addition, in this embodiment, a resin component means (A)-(D) component, the (X) component mentioned later, and resin used arbitrarily, and the hardening accelerator mentioned later is not contained in a resin component. And
＜（Ｂ）１分子中に２個以上のＮ−置換マレイミド基を有するマレイミド化合物＞
本実施形態の樹脂フィルムは、（Ｂ）１分子中に２個以上のＮ−置換マレイミド基を有するマレイミド化合物（以下、単に「（Ｂ）マレイミド化合物」又は「（Ｂ）成分」ともいう）を含有することにより、コア層との界面におけるボイドの発生を抑制することができる。
（Ｂ）マレイミド化合物は、１分子中に２個のＮ−置換マレイミド基を有するマレイミド化合物であることが好ましい。
（Ｂ）マレイミド化合物は、１種を単独で使用してもよいし、２種以上を併用してもよい。
<(B) Maleimide compound having two or more N-substituted maleimide groups in one molecule>
The resin film of the present embodiment includes (B) a maleimide compound having two or more N-substituted maleimide groups in one molecule (hereinafter, also simply referred to as “(B) maleimide compound” or “(B) component”). By containing, generation | occurrence | production of the void in an interface with a core layer can be suppressed.
(B) The maleimide compound is preferably a maleimide compound having two N-substituted maleimide groups in one molecule.
(B) A maleimide compound may be used individually by 1 type, and may use 2 or more types together.
（Ｂ）マレイミド化合物としては、複数のマレイミド基のうちの任意の２個のマレイミド基の間に芳香族炭化水素基を有さずに脂肪族炭化水素基を有するマレイミド化合物、複数のマレイミド基のうちの任意の２個のマレイミド基の間に芳香族炭化水素基を含有するマレイミド化合物（以下、「芳香族マレイミド化合物」ともいう）等が挙げられる。
これらの中でも、耐熱性、誘電特性、ガラス転移温度、熱膨張係数、成形性及びコア層との界面におけるボイドの発生を抑制する観点から、芳香族マレイミド化合物が好ましく、１分子中に２個のＮ−置換マレイミド基を有する芳香族マレイミド化合物がより好ましい。芳香族マレイミド化合物は、任意に選択した２つのマレイミド基の組み合わせのいずれかの間に芳香族炭化水素基を含有していればよい。
(B) As a maleimide compound, a maleimide compound having an aliphatic hydrocarbon group without an aromatic hydrocarbon group between any two maleimide groups of a plurality of maleimide groups, Examples thereof include a maleimide compound containing an aromatic hydrocarbon group between any two maleimide groups (hereinafter also referred to as “aromatic maleimide compound”).
Among these, aromatic maleimide compounds are preferable from the viewpoint of heat resistance, dielectric properties, glass transition temperature, thermal expansion coefficient, moldability, and suppression of void formation at the interface with the core layer. An aromatic maleimide compound having an N-substituted maleimide group is more preferred. The aromatic maleimide compound only needs to contain an aromatic hydrocarbon group between any combination of two maleimide groups selected arbitrarily.
１分子中に２個のＮ−置換マレイミド基を有する芳香族マレイミド化合物としては、下記一般式（Ｂ−１）で表される化合物が好ましい。 The aromatic maleimide compound having two N-substituted maleimide groups in one molecule is preferably a compound represented by the following general formula (B-1).
（式中、ＲＢ１及びＲＢ２は、各々独立に、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子を示す。ＸＢ１は、炭素数１〜５のアルキレン基、炭素数２〜５のアルキリデン基、−Ｏ−、−Ｃ（＝Ｏ）−、−Ｓ−、−Ｓ−Ｓ−、スルホニル基、カルボニルオキシ基、単結合又は下記一般式（Ｂ１−１−１）で表される基を示す。ｍ及びｎは、各々独立に、０〜４の整数である。）
(In the formula, R B1 and R B2 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. X B1 represents an alkylene group having 1 to 5 carbon atoms and 2 to 5 carbon atoms. An alkylidene group, -O-, -C (= O)-, -S-, -S-S-, a sulfonyl group, a carbonyloxy group, a single bond, or the following general formula (B1-1-1) And m and n are each independently an integer of 0 to 4.)
（式中、ＲＢ３及びＲＢ４は、各々独立に、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子を示す。ＸＢ２は、炭素数１〜５のアルキレン基、炭素数２〜５のアルキリデン基、−Ｏ−、−Ｃ（＝Ｏ）−、−Ｓ−、−Ｓ−Ｓ−、スルホニル基、カルボニルオキシ基又は単結合を示す。ｍ１及びｎ１は、各々独立に、０〜４の整数である。）
(In the formula, R B3 and R B4 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. X B2 represents an alkylene group having 1 to 5 carbon atoms and 2 to 5 carbon atoms. An alkylidene group, —O—, —C (═O) —, —S—, —S—S—, a sulfonyl group, a carbonyloxy group or a single bond, m1 and n1 each independently represents 0 to 4; Is an integer.)
上記一般式（Ｂ−１）中、ＲＢ１及びＲＢ２が示す炭素数１〜５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、イソブチル基、ｔ−ブチル基、ｎ−ペンチル基等が挙げられる。
ＲＢ１及びＲＢ２が示すハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。
ＸＢ１が示す炭素数１〜５のアルキレン基としては、メチレン基、１，２−ジメチレン基、１，３−トリメチレン基、１，４−テトラメチレン基、１，５−ペンタメチレン基等が挙げられる。これらの中でも、メチレン基が好ましい。
ＸＢ１が示す炭素数２〜５のアルキリデン基としては、エチリデン基、プロピリデン基、イソプロピリデン基、ブチリデン基、イソブチリデン基、ペンチリデン基、イソペンチリデン基等が挙げられる。
ｍ及びｎは、各々独立に、０〜４の整数であり、０〜２の整数が好ましく、０又は１の整数がより好ましく、０がさらに好ましい。
In the general formula (B-1), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R B1 and R B2 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, An isobutyl group, t-butyl group, n-pentyl group, etc. are mentioned.
Examples of the halogen atom represented by R B1 and R B2 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
As the alkylene group having 1 to 5 carbon atoms which X B1 shows, methylene group, 1,2-dimethylene group, a 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group and the like It is done. Among these, a methylene group is preferable.
The alkylidene group having 2 to 5 carbon atoms which X B1 shows, ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group, and the like.
m and n are each independently an integer of 0 to 4, an integer of 0 to 2 is preferable, an integer of 0 or 1 is more preferable, and 0 is more preferable.
上記一般式（Ｂ１−１−１）中、ＲＢ３及びＲＢ４が示す炭素数１〜５の脂肪族炭化水素基、ハロゲン原子としては、上記ＲＢ１及びＲＢ２の場合と同じものが挙げられ、好ましいものも同じである。
ＸＢ２が示す炭素数１〜５のアルキレン基、炭素数２〜５のアルキリデン基としては、上記ＸＢ１が示す炭素数１〜５のアルキレン基、炭素数２〜５のアルキリデン基と同じものが挙げられ、好ましいものも同じである。
ＸＢ２としては、上記選択肢の中でも、炭素数２〜５のアルキリデン基が好ましく、イソプロピリデン基がより好ましい。
ｍ１及びｎ１は０〜４の整数であり、入手容易性の観点から、いずれも、好ましくは０〜２の整数、より好ましくは０又は１、さらに好ましくは０である。
また、前記一般式（Ｂ１−１−１）は、下記一般式（Ｂ１−１−１’）で表されることが好ましい。
In the general formula (B1-1-1), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R B3 and R B4 include the same as those in the case of R B1 and R B2. The preferred ones are the same.
Examples of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X B2 include the same as the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X B1. The preferred ones are also the same.
X B2 is preferably an alkylidene group having 2 to 5 carbon atoms and more preferably an isopropylidene group among the above options.
m1 and n1 are integers of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, more preferably 0 or 1, and even more preferably 0.
Moreover, it is preferable that the said general formula (B1-1-1) is represented by the following general formula (B1-1-1 ').
（式中、ＸＢ２、ＲＢ３、ＲＢ４、ｍ１及びｎ１は、一般式（Ｂ１−１−１）中のものと同じであり、好ましいものも同じである。）
(Wherein, X B2, R B3, R B4, m1 and n1 are the same as those of the general formula (b1-1-1), and preferred ones are also the same.)
（Ｂ）マレイミド化合物としては、ビス（４−マレイミドフェニル）メタン、ポリフェニルメタンマレイミド、ビス（４−マレイミドフェニル）エーテル、ビス（４−マレイミドフェニル）スルホン、３，３’−ジメチル−５，５’−ジエチル−４，４’−ジフェニルメタンビスマレイミド、４−メチル−１，３−フェニレンビスマレイミド、ｍ−フェニレンビスマレイミド、２，２−ビス［４−（４−マレイミドフェノキシ）フェニル］プロパン等が挙げられる。これらの中でも、反応率が高く、より高耐熱性化できるという観点及びコア層との界面におけるボイドの発生を抑制する観点から、ビス（４−マレイミドフェニル）メタン、ビス（４−マレイミドフェニル）スルホン、３，３’−ジメチル−５，５’−ジエチル−４，４’−ジフェニルメタンビスマレイミド、２，２−ビス［４−（４−マレイミドフェノキシ）フェニル］プロパンが好ましく、ビス（４−マレイミドフェニル）メタン、２，２−ビス［４−（４−マレイミドフェノキシ）フェニル］プロパンがより好ましい。 (B) As a maleimide compound, bis (4-maleimidophenyl) methane, polyphenylmethanemaleimide, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, 3,3′-dimethyl-5,5 '-Diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, m-phenylene bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, etc. Can be mentioned. Among these, bis (4-maleimidophenyl) methane and bis (4-maleimidophenyl) sulfone are preferred from the viewpoints of high reaction rate and higher heat resistance, and suppression of void formation at the interface with the core layer. 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane are preferred, and bis (4-maleimidophenyl) ) Methane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane is more preferred.
（Ｂ）マレイミド化合物の含有量に特に制限はないが、耐熱性、誘電特性、ガラス転移温度、熱膨張係数、成形性及びコア層との界面におけるボイドの発生を抑制する観点から、樹脂組成物（I）中の樹脂成分の総和１００質量部に対して、３０〜９５質量部が好ましく、３５〜９０質量部がより好ましく、４０〜８５質量部がさらに好ましく、４５〜８０質量部が特に好ましい。 (B) Although there is no restriction | limiting in particular in content of a maleimide compound, From a viewpoint which suppresses generation | occurrence | production of the void in an interface with heat resistance, a dielectric characteristic, a glass transition temperature, a thermal expansion coefficient, a moldability, and a core layer, a resin composition. 30-95 mass parts is preferable with respect to 100 mass parts of sum total of the resin component in (I), 35-90 mass parts is more preferable, 40-85 mass parts is more preferable, 45-80 mass parts is especially preferable. .
＜（Ｃ）１分子中に２個以上の１級アミノ基を有するアミン化合物＞
本実施形態の樹脂フィルムは、（Ｃ）１分子中に２個以上の１級アミノ基を有するアミン化合物（以下、単に「（Ｃ）アミン化合物」又は「（Ｃ）成分」ともいう）を含有することにより、コア層との界面におけるボイドの発生を抑制することができる。
（Ｃ）アミン化合物は、１分子中に２個の１級アミノ基を有するアミン化合物であることが好ましい。
（Ｃ）アミン化合物は、１種を単独で使用してもよいし、２種以上を併用してもよい。
<(C) Amine compound having two or more primary amino groups in one molecule>
The resin film of this embodiment contains (C) an amine compound having two or more primary amino groups in one molecule (hereinafter, also simply referred to as “(C) amine compound” or “(C) component”). By doing so, the generation of voids at the interface with the core layer can be suppressed.
(C) The amine compound is preferably an amine compound having two primary amino groups in one molecule.
(C) An amine compound may be used individually by 1 type, and may use 2 or more types together.
（Ｃ）アミン化合物としては、脂肪族アミン化合物、芳香族アミン化合物等が挙げられる。芳香族アミン化合物としては、下記一般式（Ｃ−１）で表される芳香族ジアミン化合物が好ましい。 (C) As an amine compound, an aliphatic amine compound, an aromatic amine compound, etc. are mentioned. As an aromatic amine compound, the aromatic diamine compound represented by the following general formula (C-1) is preferable.
（式中、ＲＣ１及びＲＣ２は、各々独立に、炭素数１〜５のアルキル基、炭素数１〜５のアルコキシ基、ハロゲン原子、水酸基、カルボキシ基又はスルホン酸基を示す。ＸＣ１は、炭素数１〜５のアルキレン基、炭素数２〜５のアルキリデン基、−Ｏ−、スルホニル基、−Ｃ（＝Ｏ）−、フルオレニレン基、フェニレンジオキシ基又は単結合を示す。ｖ及びｗは、各々独立に、０〜４の整数である。）
(Wherein R C1 and R C2 each independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group, a carboxy group, or a sulfonic acid group. X C1 represents , An alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, -O-, a sulfonyl group, -C (= O)-, a fluorenylene group, a phenylenedioxy group, or a single bond. Are each independently an integer of 0 to 4.)
ＲＣ１及びＲＣ２が示す炭素数１〜５のアルキル基、ハロゲン原子としては、上記一般式（Ｂ−１）中のＲＢ１及びＲＢ２と同じものが挙げられ、炭素数１〜５のアルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基等が挙げられる。
ＸＣ１が示す炭素数１〜５のアルキレン基及び炭素数２〜５のアルキリデン基としては、上記一般式（Ｂ−１）中のＸＢ１と同じものが挙げられる。
Examples of the alkyl group having 1 to 5 carbon atoms and the halogen atom represented by R C1 and R C2 include the same as R B1 and R B2 in the general formula (B-1), and an alkoxy having 1 to 5 carbon atoms. Examples of the group include a methoxy group, an ethoxy group, and a propoxy group.
Examples of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X C1 include the same as X B1 in the general formula (B-1).
（Ｃ）アミン化合物は、シロキサン骨格を含有する化合物であることが好ましく、１分子中に２個の１級アミノ基を有するシロキサン化合物がより好ましく、両末端に１級アミノ基を有するシロキサン化合物がさらに好ましい。
両末端に１級アミノ基を有するシロキサン化合物としては、下記一般式（Ｃ−２）で表される化合物が好ましい。
(C) The amine compound is preferably a compound containing a siloxane skeleton, more preferably a siloxane compound having two primary amino groups in one molecule, and a siloxane compound having primary amino groups at both ends. Further preferred.
As the siloxane compound having a primary amino group at both ends, a compound represented by the following general formula (C-2) is preferable.
（式中、ＲＣ３、ＲＣ４、ＲＣ５及びＲＣ６は、各々独立に、アルキル基、フェニル基又は置換フェニル基を示し、ＸＣ２及びＸＣ３は、各々独立に、２価の有機基を示す。ｓは１〜１００の整数を示す。）
(Wherein R C3 , R C4 , R C5 and R C6 each independently represents an alkyl group, a phenyl group or a substituted phenyl group, and X C2 and X C3 each independently represent a divalent organic group. S represents an integer of 1 to 100.)
上記一般式（Ｃ−２）中、ＲＣ３、ＲＣ４、ＲＣ５及びＲＣ６が示すアルキル基としては、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、イソブチル基、ｔ−ブチル基、ｎ−ペンチル基等が挙げられる。該アルキル基としては、炭素数１〜５のアルキル基が好ましく、炭素数１〜３のアルキル基がより好ましく、メチル基がさらに好ましい。
置換フェニル基におけるフェニル基が有する置換基としては、炭素数１〜５のアルキル基、炭素数２〜５のアルケニル基、炭素数２〜５のアルキニル基等が挙げられる。炭素数１〜５のアルキル基としては、上記したものと同じものが挙げられる。炭素数２〜５のアルケニル基としては、ビニル基、アリル基等が挙げられる。炭素数２〜５のアルキニル基としては、エチニル基、プロパルギル基等が挙げられる。
ＲＣ３、ＲＣ４、ＲＣ５及びＲＣ６としては、いずれも炭素数１〜５のアルキル基が好ましく、メチル基がより好ましい。
ｓは、低熱膨張性の観点から、１〜１００の整数であり、相溶性及び高弾性化の観点から、５〜５０の整数が好ましく、１０〜４０の整数がより好ましい。
上記一般式（Ｃ−２）中、ＸＣ２及びＸＣ３が示す２価の有機基としては、アルキレン基、アルケニレン基、アルキニレン基、アリーレン基、−Ｏ−又はこれらが組み合わされた２価の連結基等が挙げられる。アルキレン基としては、メチレン基、１，２−ジメチレン基、１，３−トリメチレン基、１，４−テトラメチレン基、１，５−ペンタメチレン基等の炭素数１〜１０のアルキレン基が挙げられる。アルケニレン基としては、炭素数２〜１０のアルケニレン基が挙げられる。アルキニレン基としては、炭素数２〜１０のアルキニレン基が挙げられる。アリーレン基としては、フェニレン基、ナフチレン基等の炭素数６〜２０のアリーレン基が挙げられる。これらの中でも、アルキレン基が好ましく、１，３−トリメチレン基がより好ましい。
In the general formula (C-2), examples of the alkyl group represented by R C3 , R C4 , R C5 and R C6 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, Examples include t-butyl group and n-pentyl group. As this alkyl group, a C1-C5 alkyl group is preferable, a C1-C3 alkyl group is more preferable, and a methyl group is further more preferable.
Examples of the substituent of the phenyl group in the substituted phenyl group include an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and an alkynyl group having 2 to 5 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms include the same ones as described above. Examples of the alkenyl group having 2 to 5 carbon atoms include a vinyl group and an allyl group. Examples of the alkynyl group having 2 to 5 carbon atoms include an ethynyl group and a propargyl group.
As R C3 , R C4 , R C5 and R C6 , all are preferably alkyl groups having 1 to 5 carbon atoms, and more preferably methyl groups.
s is an integer of 1 to 100 from the viewpoint of low thermal expansion, and an integer of 5 to 50 is preferable and an integer of 10 to 40 is more preferable from the viewpoint of compatibility and high elasticity.
In the general formula (C-2), as the divalent organic group represented by X C2 and X C3 , an alkylene group, an alkenylene group, an alkynylene group, an arylene group, —O— or a divalent linkage in which these are combined. Groups and the like. Examples of the alkylene group include alkylene groups having 1 to 10 carbon atoms such as a methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, and 1,5-pentamethylene group. . Examples of the alkenylene group include alkenylene groups having 2 to 10 carbon atoms. Examples of the alkynylene group include alkynylene groups having 2 to 10 carbon atoms. Examples of the arylene group include arylene groups having 6 to 20 carbon atoms such as a phenylene group and a naphthylene group. Among these, an alkylene group is preferable and a 1,3-trimethylene group is more preferable.
両末端に１級アミノ基を有するシロキサン化合物のアミノ基当量は、１００〜６，０００ｇ／ｅｑが好ましく、４００〜２，０００ｇ／ｅｑがより好ましく、６００〜１，５００ｇ／ｅｑがさらに好ましい。 The amino group equivalent of the siloxane compound having a primary amino group at both ends is preferably 100 to 6,000 g / eq, more preferably 400 to 2,000 g / eq, and still more preferably 600 to 1,500 g / eq.
（Ｃ）アミン化合物は、市販品を用いることができる。（Ｃ）アミン化合物の市販品としては、例えば、両末端に１級アミノ基を有するシロキサン化合物である「ＰＡＭ−Ｅ」（アミノ基当量１３０）、「ＫＦ−８０１０」（アミノ基当量４３０）、「Ｘ−２２−１６１Ａ」（アミノ基当量８００）、「Ｘ−２２−１６１Ｂ」（アミノ基当量１，５００）、「ＫＦ−８０１２」（アミノ基当量２，２００）、「ＫＦ−８００８」（アミノ基当量５，７００）〔以上、信越化学工業株式会社製〕、「ＢＹ１６−８７１」（アミノ基当量１３０）、「ＢＹ１６−８５３Ｕ」（アミノ基当量４６０）〔以上、東レダウコーニング株式会社製〕等が挙げられる。なお、アミノ基当量の単位はｇ／ｅｑである。 (C) A commercial item can be used for an amine compound. (C) As a commercial item of an amine compound, for example, “PAM-E” (amino group equivalent 130), “KF-8010” (amino group equivalent 430) which is a siloxane compound having primary amino groups at both ends, “X-22-161A” (amino group equivalent 800), “X-22-161B” (amino group equivalent 1,500), “KF-8012” (amino group equivalent 2,200), “KF-8008” ( Amino group equivalent 5,700) [manufactured by Shin-Etsu Chemical Co., Ltd.], “BY16-871” (amino group equivalent 130), “BY16-853U” (amino group equivalent 460) [manufactured by Toray Dow Corning Co., Ltd. ] Etc. are mentioned. The unit of amino group equivalent is g / eq.
（Ｃ）アミン化合物の具体例としては、ジアミノベンジジン、ジアミノジフェニルメタン、ジアミノジフェニルエーテル、ジアミノジフェニルスルホン、３，３’−ジクロロ−４，４’−ジアミノビフェニル、３，３’−ジメトキシ−４，４’−ジアミノビフェニル、３，３’−ジメチル−４，４’−ジアミノビフェニル、３，３’−ジクロロ−４，４’−ジアミノビフェニル、３，３’−ジメチル−４，４’−ジアミノビフェニル−６，６’−ジスルホン酸、２，２’，５，５’−テトラクロロ−４，４’−ジアミノビフェニル、４，４’−メチレン−ビス（２−クロロアニリン）、１，３’−ビス（４−アミノフェノキシ）ベンゼン、２，２’−ビス［４−（４−アミノフェノキシ）フェニル］プロパン、ビス［４−（４−アミノフェノキシ）フェニル］スルホン、ビス［４−（３−アミノフェノキシ）フェニル］スルホン、４，４’−ビス（４−アミノフェノキシ）ビフェニル、２，２’−ビス［４−（４−アミノフェノキシ）フェニル］ヘキサフルオロプロパン、１，４’−ビス（４−アミノフェノキシ）ベンゼン、４，４’−ジアミノジフェニルスルフィド、２，２’−ジメチル−４，４’−ジアミノビフェニル、４，４’−ジアミノ−３，３’−ビフェニルジオール、９，９’−ビス（４−アミノフェニル）フルオレン、ｏ−トリジンスルホン、上記した１分子中に少なくとも２個の１級アミノ基を有するシロキサン化合物等が挙げられる。 (C) Specific examples of the amine compound include diaminobenzidine, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenylsulfone, 3,3′-dichloro-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4 ′. -Diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl-6 , 6′-disulfonic acid, 2,2 ′, 5,5′-tetrachloro-4,4′-diaminobiphenyl, 4,4′-methylene-bis (2-chloroaniline), 1,3′-bis ( 4-aminophenoxy) benzene, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (4-aminopheno) Cis) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2′-bis [4- (4-aminophenoxy) phenyl ] Hexafluoropropane, 1,4'-bis (4-aminophenoxy) benzene, 4,4'-diaminodiphenyl sulfide, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino- Examples include 3,3′-biphenyldiol, 9,9′-bis (4-aminophenyl) fluorene, o-tolidine sulfone, and a siloxane compound having at least two primary amino groups in one molecule.
（Ｃ）アミン化合物の含有量に特に制限はないが、低反り性、寸法安定性、低熱膨張性、低弾性、耐熱性、金属回路との接着性及びコア層との界面におけるボイドの発生を抑制する観点から、樹脂組成物（I）中の樹脂成分の総和１００質量部に対して、１〜４０質量部が好ましく、２〜３０質量部がより好ましく、３〜２５質量部がさらに好ましい。 (C) The content of the amine compound is not particularly limited, but low warpage, dimensional stability, low thermal expansion, low elasticity, heat resistance, adhesion to the metal circuit, and generation of voids at the interface with the core layer. From the viewpoint of suppression, the amount is preferably 1 to 40 parts by weight, more preferably 2 to 30 parts by weight, and still more preferably 3 to 25 parts by weight with respect to 100 parts by weight of the total resin components in the resin composition (I).
＜（Ｘ）変性ポリイミド＞
本実施形態に用いられる樹脂組成物（I）は、（Ｂ）マレイミド化合物及び（Ｃ）アミン化合物を反応させてなる（Ｘ）変性ポリイミド（以下、「（Ｘ）成分」ともいう）を含有していてもよい。
本実施形態においては、（Ｘ）変性ポリイミドを含有することは、すなわち（Ｂ）マレイミド化合物及び（Ｃ）アミン化合物を含有することと同義である。したがって、樹脂組成物（I）が（Ｘ）変性ポリイミドを含有するとき、樹脂組成物（I）は、（Ｂ）マレイミド化合物及び／又は（Ｃ）アミン化合物を含有していなくてもよいし、（Ｂ）マレイミド化合物及び（Ｃ）アミン化合物からなる群から選択される１つ以上を含有していてもよい。
（Ｘ）変性ポリイミドは、１種を単独で使用してもよいし、２種以上を併用してもよい。
<(X) Modified polyimide>
The resin composition (I) used in this embodiment contains (B) a maleimide compound and (C) an amine compound (X) modified polyimide (hereinafter also referred to as “component (X)”). It may be.
In this embodiment, containing (X) a modified polyimide is synonymous with containing (B) a maleimide compound and (C) an amine compound. Therefore, when the resin composition (I) contains (X) modified polyimide, the resin composition (I) may not contain (B) a maleimide compound and / or (C) an amine compound, One or more selected from the group consisting of (B) a maleimide compound and (C) an amine compound may be contained.
(X) A modified polyimide may be used individually by 1 type, and may use 2 or more types together.
（Ｘ）変性ポリイミドは、（Ｂ）成分と（Ｃ）成分とを反応させて得られるものであり、（Ｂ）成分由来の構造単位（Ｂ’）と、（Ｃ）成分由来の構造単位（Ｃ’）と、を含有するものである。
（Ｂ）成分と（Ｃ）成分との反応方法に特に制限はなく、反応温度は、生産性及び十分に反応を進行させる観点から、例えば、７０〜２００℃であり、反応時間は、例えば、０．５〜１０時間である。
The (X) modified polyimide is obtained by reacting the component (B) and the component (C). The structural unit (B ′) derived from the component (B) and the structural unit derived from the component (C) ( C ′).
There is no restriction | limiting in particular in the reaction method of (B) component and (C) component, Reaction temperature is 70-200 degreeC from a viewpoint of making productivity and fully advance reaction, for example, reaction time is, for example, 0.5 to 10 hours.
（Ｂ）成分と（Ｃ）成分との反応は、有機溶媒中で行うことが好ましい。有機溶媒としては、エタノール、プロパノール、ブタノール、メチルセロソルブ、ブチルセロソルブ、プロピレングリコールモノメチルエーテル等のアルコール系溶媒；ケトン系溶媒；エステル系溶媒；エーテル系溶媒；芳香族系溶媒；窒素原子含有溶媒；硫黄原子含有溶媒などが挙げられる。これらの中でも、溶解性、低毒性及び揮発性が高く残溶媒として残り難いという観点から、プロピレングリコールモノメチルエーテルが好ましい。 The reaction between the component (B) and the component (C) is preferably performed in an organic solvent. Organic solvents include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents; ester solvents; ether solvents; aromatic solvents; nitrogen atom-containing solvents; Examples thereof include solvents. Among these, propylene glycol monomethyl ether is preferable from the viewpoint of high solubility, low toxicity, and high volatility that hardly remains as a residual solvent.
（Ｘ）変性ポリイミドの含有量は、構造単位（Ｂ’）及び構造単位（Ｃ’）の含有量を、各々の原料である（Ｂ）マレイミド化合物及び（Ｃ）アミン化合物の含有量に換算して決定すればよい。
例えば、樹脂組成物（I）が、（Ｂ）成分及び（Ｃ）成分を含有せずに、（Ｘ）変性ポリイミドを含有する場合、樹脂組成物（I）中の構造単位（Ｂ’）の量から換算される原料（Ｂ）成分の含有量、並びに、樹脂組成物（I）中の構造単位（Ｃ’）の量から換算される原料（Ｃ）成分の含有量が、上記した（Ｂ）成分及び（Ｃ）成分の好適な含有量の範囲となることが好ましい。
また、例えば、樹脂組成物（I）が、（Ｂ）成分及び（Ｃ）成分と、（Ｘ）変性ポリイミドと、を含有する場合、樹脂組成物（I）中の構造単位（Ｂ’）の量から換算される原料（Ｂ）成分の含有量と、別に配合した（Ｂ）成分との合計含有量が、上記した（Ｂ）成分の好適な含有量の範囲となることが好ましく、樹脂組成物（I）中の構造単位（Ｃ’）の量から換算される原料（Ｃ）成分の含有量と、別に配合した（Ｃ）成分との合計含有量が、上記した（Ｃ）成分の好適な含有量の範囲となることが好ましい。
(X) The content of the modified polyimide is calculated by converting the contents of the structural unit (B ′) and the structural unit (C ′) into the contents of the respective raw materials (B) maleimide compound and (C) amine compound. To decide.
For example, when the resin composition (I) does not contain the component (B) and the component (C) but contains the (X) modified polyimide, the structural unit (B ′) in the resin composition (I) The content of the raw material (B) component converted from the amount and the content of the raw material (C) component converted from the amount of the structural unit (C ′) in the resin composition (I) are as described above (B ) Component and (C) component are preferably in the range of suitable contents.
Moreover, for example, when the resin composition (I) contains the component (B) and the component (C) and (X) the modified polyimide, the structural unit (B ′) in the resin composition (I) The total content of the raw material (B) component converted from the amount and the separately blended (B) component is preferably within the preferred content range of the above-described (B) component, and the resin composition The content of the raw material (C) component converted from the amount of the structural unit (C ′) in the product (I) and the total content of the component (C) separately blended are suitable for the component (C) described above. It is preferable that the content is within a range.
樹脂組成物（I）が（Ｘ）変性ポリイミドを含有する場合、その含有量は、耐熱性、誘電特性、ガラス転移温度、熱膨張係数、成形性及びコア層との界面におけるボイドの発生を抑制する観点から、樹脂組成物（I）中の樹脂成分の総和１００質量部に対して、３０〜８０質量部が好ましく、４０〜７０質量部がより好ましく、５０〜６０質量部がさらに好ましい。 When the resin composition (I) contains (X) modified polyimide, its content suppresses heat resistance, dielectric properties, glass transition temperature, thermal expansion coefficient, moldability, and generation of voids at the interface with the core layer. From the viewpoint to do, 30-80 mass parts is preferable with respect to 100 mass parts of sum total of the resin component in resin composition (I), 40-70 mass parts is more preferable, and 50-60 mass parts is further more preferable.
＜（Ｄ）エラストマー＞
本実施形態の樹脂フィルムは、（Ｄ）エラストマー（以下、「（Ｄ）成分」ともいう）を含有することにより、取り扱い性に優れたものとなる。
（Ｄ）エラストマーは、１種を単独で使用してもよいし、２種以上を併用してもよい。
<(D) Elastomer>
The resin film of this embodiment is excellent in handleability by containing (D) an elastomer (hereinafter also referred to as “component (D)”).
(D) An elastomer may be used individually by 1 type and may use 2 or more types together.
（Ｄ）エラストマーとしては、ポリエステル系エラストマー、ポリアミド系エラストマー、ポリウレタン系エラストマー、スチレン系エラストマー、アクリル系エラストマー、これらの誘導体等が挙げられる。これらの中でも、耐熱性及び絶縁信頼性の観点から、スチレン系エラストマーが好ましく、銅箔との接着性を良好に保ちながら樹脂組成物の弾性率を低減する観点からは、アクリル系エラストマーがより好ましい。 Examples of (D) elastomers include polyester elastomers, polyamide elastomers, polyurethane elastomers, styrene elastomers, acrylic elastomers, and derivatives thereof. Among these, from the viewpoint of heat resistance and insulation reliability, a styrene elastomer is preferable, and from the viewpoint of reducing the elastic modulus of the resin composition while maintaining good adhesion with the copper foil, an acrylic elastomer is more preferable. .
（Ｄ）エラストマーは、分子末端及び分子鎖中のうち少なくとも一方に反応性官能基を有することが好ましい。反応性官能基を有することにより、他の樹脂成分との相溶性が向上し、樹脂フィルムの取り扱い性を向上させる効果がより顕著に発現すると共に、樹脂組成物の硬化時に発生する内部応力を効果的に低減することができ、結果として、基板の反りを低減することも可能となる。
反応性官能基としては、エポキシ基、アミノ基、水酸基、アクリル基、メタクリル基、メルカプト基、カルボキシ基、アルコキシ基、アミド基、イソシアナト基、ビニル基等が挙げられる。これらの中でも、低熱膨張性、金属回路との接着強度及び樹脂フィルムの取り扱い性を向上させる観点から、エポキシ基、アミノ基、水酸基、メタクリル基、メルカプト基、カルボキシ基及びアルコキシ基からなる群から選ばれる１種以上が好ましく、エポキシ基がより好ましい。
（Ｄ）エラストマーが、反応性官能基を有する場合、その官能基の含有量は、０．０５〜０．４０ｅｑ／ｋｇが好ましく、０．１０〜０．３０ｅｑ／ｋｇがより好ましく、０．１５〜０．２５ｅｑ／ｋｇがさらに好ましい。
(D) It is preferable that the elastomer has a reactive functional group at least one of the molecular terminal and the molecular chain. By having a reactive functional group, compatibility with other resin components is improved, and the effect of improving the handleability of the resin film is more pronounced, and the internal stress generated when the resin composition is cured is effective As a result, it is possible to reduce the warpage of the substrate.
Examples of the reactive functional group include an epoxy group, amino group, hydroxyl group, acrylic group, methacryl group, mercapto group, carboxy group, alkoxy group, amide group, isocyanato group, vinyl group and the like. Among these, from the viewpoint of improving low thermal expansion, adhesion strength with metal circuits, and handling properties of resin films, selected from the group consisting of epoxy groups, amino groups, hydroxyl groups, methacryl groups, mercapto groups, carboxy groups and alkoxy groups 1 or more types are preferable, and an epoxy group is more preferable.
(D) When the elastomer has a reactive functional group, the content of the functional group is preferably 0.05 to 0.40 eq / kg, more preferably 0.10 to 0.30 eq / kg, and 0.15 More preferably, ˜0.25 eq / kg.
（スチレン系エラストマー）
スチレン系エラストマーとしては、スチレン−ブタジエン−スチレンブロックコポリマー等のスチレン−ブタジエン共重合体；スチレン−イソプレン−スチレンブロックコポリマー等のスチレン−イソプレン共重合体；スチレン−エチレン−ブチレン−スチレンブロックコポリマー、スチレン−エチレン−プロピレン−スチレンブロックコポリマーなどが挙げられる。スチレン系エラストマーの原料モノマーとしては、スチレンの他に、α−メチルスチレン、３−メチルスチレン、４−プロピルスチレン、４−シクロヘキシルスチレン等のスチレン誘導体を用いることができる。これらの中でも、スチレン−ブタジエン共重合体、スチレン−イソプレン共重合体が好ましく、これらの共重合体の二重結合部分を水素添加した水添スチレン−ブタジエン共重合樹脂、水添スチレン−イソプレン共重合樹脂等がより好ましく、水添スチレン−ブタジエン共重合樹脂がさらに好ましい。
(Styrene elastomer)
Styrene elastomers include styrene-butadiene copolymers such as styrene-butadiene-styrene block copolymers; styrene-isoprene copolymers such as styrene-isoprene-styrene block copolymers; styrene-ethylene-butylene-styrene block copolymers, styrene- Examples include ethylene-propylene-styrene block copolymers. As a raw material monomer for the styrene-based elastomer, styrene derivatives such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene and the like can be used in addition to styrene. Among these, styrene-butadiene copolymer and styrene-isoprene copolymer are preferable, and hydrogenated styrene-butadiene copolymer resin and hydrogenated styrene-isoprene copolymer obtained by hydrogenating the double bond portion of these copolymers. A resin or the like is more preferable, and a hydrogenated styrene-butadiene copolymer resin is more preferable.
（アクリル系エラストマー）
アクリル系エラストマーとしては、少なくともアクリル酸エステルに由来する構造単位を含む分子で形成される重合体である。アクリル系エラストマーは、分子中に異なる複数種のアクリル酸エステルに由来する構造単位を含んでいてもよく、さらに、アクリル酸エステル以外の単量体に由来する構造単位を含んでもよい。また、アクリル系エラストマーは、複数種のアクリル酸エステルに由来する構造単位からなるものであってもよい。
アクリル酸エステルとしては、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸イソプロピル、アクリル酸ブチル、アクリル酸イソブチル、アクリル酸ｔ−ブチル、アクリル酸ペンチル、アクリル酸ヘキシル、アクリル酸シクロヘキシル、アクリル酸オクチル、アクリル酸デシル、アクリル酸ラウリル、アクリル酸ベンジル等が挙げられる。
上記アクリル酸エステル以外の単量体としては、アクリロニトリル、アクリルアミド、アクリル酸、メタクリル酸、メタクリル酸エステル、スチレン、エチレン、プロピレン、ブタジエン等のビニル系単量体が挙げられる。アクリル酸エステル以外の単量体は、１種を単独で使用してもよいし、２種以上を併用してもよい。
(Acrylic elastomer)
The acrylic elastomer is a polymer formed of molecules including at least a structural unit derived from an acrylate ester. The acrylic elastomer may contain structural units derived from a plurality of different acrylate esters in the molecule, and may further contain structural units derived from monomers other than the acrylate ester. The acrylic elastomer may be composed of structural units derived from a plurality of types of acrylic esters.
Acrylic acid esters include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, t-butyl acrylate, pentyl acrylate, hexyl acrylate, cyclohexyl acrylate, acrylic acid Examples include octyl, decyl acrylate, lauryl acrylate, and benzyl acrylate.
Examples of the monomer other than the acrylic acid ester include vinyl monomers such as acrylonitrile, acrylamide, acrylic acid, methacrylic acid, methacrylic acid ester, styrene, ethylene, propylene, and butadiene. Monomers other than acrylic acid esters may be used alone or in combination of two or more.
アクリル系エラストマーの重量平均分子量（Ｍｗ）に特に制限はないが、１０，０００〜２，０００，０００が好ましく、５０，０００〜１，２００，０００がより好ましく、１００，０００〜９００，０００がさらに好ましく、５００，０００〜９００，０００が特に好ましい。重量平均分子量（Ｍｗ）が１０，０００以上であれば、低弾性率を維持し易い傾向にあり、２，０００，０００以下であれば、相溶性及び流動性が良好となる傾向にある。
なお、本明細書中、重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）（東ソー株式会社製）により、標準ポリスチレンの検量線を用いて測定したものである。
Although there is no restriction | limiting in particular in the weight average molecular weight (Mw) of an acryl-type elastomer, 10,000-2,000,000 are preferable, 50,000-1,200,000 are more preferable, 100,000-900,000 are More preferred is 500,000 to 900,000. If the weight average molecular weight (Mw) is 10,000 or more, it tends to maintain a low elastic modulus, and if it is 2,000,000 or less, compatibility and fluidity tend to be good.
In the present specification, the weight average molecular weight is measured by gel permeation chromatography (GPC) (manufactured by Tosoh Corporation) using a standard polystyrene calibration curve.
（Ｄ）エラストマーの含有量に特に制限はないが、耐デスミア性及び樹脂フィルムの取り扱い性を向上させる観点から、樹脂組成物（I）中の樹脂成分の総和１００質量部に対して、５〜６０質量部が好ましく、７〜５０質量部がより好ましく、８〜３０質量部がさらに好ましく、１０〜２０質量部が特に好ましい。 (D) Although there is no restriction | limiting in particular in content of an elastomer, from a viewpoint of improving the desmear resistance and the handleability of a resin film, it is 5-5 with respect to 100 mass parts of sum total of the resin component in resin composition (I). 60 mass parts is preferable, 7-50 mass parts is more preferable, 8-30 mass parts is further more preferable, and 10-20 mass parts is especially preferable.
＜（Ｅ）無機充填材＞
樹脂組成物（I）は、さらに、（Ｅ）無機充填材（以下、「（Ｅ）成分」ともいう）を含有することが好ましい。
（Ｅ）無機充填材としては、シリカ、アルミナ、硫酸バリウム、タルク、マイカ、カオリン、ベーマイト、ベリリア、チタン酸バリウム、チタン酸カリウム、チタン酸ストロンチウム、チタン酸カルシウム、炭酸アルミニウム、水酸化マグネシウム、水酸化アルミニウム、ホウ酸アルミニウム、ケイ酸アルミニウム、炭酸カルシウム、ケイ酸カルシウム、ケイ酸マグネシウム、ホウ酸亜鉛、スズ酸亜鉛、酸化亜鉛、酸化チタン、炭化ケイ素、窒化ケイ素、窒化ホウ素、焼成クレー等のクレー、ガラス短繊維、ガラス粉、中空ガラスビーズなどが挙げられる。ガラスとしては、Ｅガラス、Ｔガラス、Ｄガラス等が挙げられる。
（Ｅ）無機充填材は、１種を単独で使用してもよいし、２種以上を併用してもよい。
<(E) Inorganic filler>
The resin composition (I) preferably further contains (E) an inorganic filler (hereinafter also referred to as “component (E)”).
(E) As an inorganic filler, silica, alumina, barium sulfate, talc, mica, kaolin, boehmite, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, water Clays such as aluminum oxide, aluminum borate, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, zinc borate, zinc stannate, zinc oxide, titanium oxide, silicon carbide, silicon nitride, boron nitride, calcined clay, etc. , Short glass fibers, glass powder, hollow glass beads and the like. Examples of the glass include E glass, T glass, and D glass.
(E) An inorganic filler may be used individually by 1 type, and may use 2 or more types together.
（Ｅ）無機充填材としては、誘電特性、耐熱性及び低熱膨張性の観点から、シリカが好ましい。シリカとしては、例えば、湿式法で製造され含水率の高い沈降シリカ、乾式法で製造され結合水等をほとんど含まない乾式法シリカ等が挙げられる。乾式法シリカとしては、さらに、製造法の違いにより破砕シリカ、フュームドシリカ、溶融シリカ（溶融球状シリカ）等が挙げられる。（Ｅ）無機充填材に用いられるシリカは、低熱膨張性及び樹脂に充填した際の高流動性の観点から、溶融シリカが好ましい。 (E) As the inorganic filler, silica is preferable from the viewpoints of dielectric properties, heat resistance and low thermal expansion. Examples of the silica include precipitated silica produced by a wet method and having a high water content, and dry method silica produced by a dry method and containing almost no bound water. Examples of the dry process silica include crushed silica, fumed silica, fused silica (fused spherical silica) and the like depending on the production method. (E) The silica used for the inorganic filler is preferably fused silica from the viewpoint of low thermal expansibility and high fluidity when filled in a resin.
（Ｅ）無機充填材の平均粒子径は、０．１〜１０μｍが好ましく、０．２〜５μｍがより好ましく、０．３〜１μｍがさらに好ましい。平均粒子径が０．１μｍ以上であると、樹脂に高充填した際の流動性を良好に保つことができ、１０μｍ以下であると、粗大粒子の混入確率を低減し、粗大粒子起因の不良の発生を抑えることができる。
なお、本明細書中、平均粒子径とは、粒子の全体積を１００％として粒子径による累積度数分布曲線を求めたとき、体積５０％に相当する点の粒子径のことであり、レーザー回折散乱法を用いた粒度分布測定装置等で測定することができる。
(E) 0.1-10 micrometers is preferable, as for the average particle diameter of an inorganic filler, 0.2-5 micrometers is more preferable, and 0.3-1 micrometer is further more preferable. When the average particle size is 0.1 μm or more, the fluidity when the resin is highly filled can be kept good, and when the average particle size is 10 μm or less, the mixing probability of coarse particles is reduced, and defects due to coarse particles are reduced. Occurrence can be suppressed.
In the present specification, the average particle diameter is the particle diameter at a point corresponding to a volume of 50% when the cumulative frequency distribution curve based on the particle diameter is obtained with the total volume of the particles as 100%. It can be measured by a particle size distribution measuring apparatus using a scattering method.
（Ｅ）無機充填材は、シランカップリング剤、シリコーンオリゴマー等の表面処理剤で表面処理されたものであってもよい。表面処理された（Ｅ）無機充填材を用いると、（Ｅ）無機充填材と樹脂成分との接着力が向上し、（Ｅ）無機充填材の脱落が抑制され、表面粗さが低下する傾向にある。
シランカップリング剤としては、アミノシラン系カップリング剤、エポキシシラン系カップリング剤、フェニルシラン系カップリング剤、アルキルシラン系カップリング剤、アルケニルシラン系カップリング剤、シロキサン系カップリング剤等が挙げられる。
シランカップリング剤等の表面処理剤を用いる場合、その添加方式は、樹脂組成物（I）中に（Ｅ）無機充填材を配合した後、表面処理剤を添加する、いわゆるインテグラルブレンド処理方式であってもよい。
(E) The inorganic filler may be surface-treated with a surface treatment agent such as a silane coupling agent or a silicone oligomer. When the surface-treated (E) inorganic filler is used, the adhesive force between the (E) inorganic filler and the resin component is improved, and (E) the inorganic filler is prevented from falling off, and the surface roughness tends to decrease. It is in.
Examples of the silane coupling agent include amino silane coupling agents, epoxy silane coupling agents, phenyl silane coupling agents, alkyl silane coupling agents, alkenyl silane coupling agents, and siloxane coupling agents. .
When using a surface treatment agent such as a silane coupling agent, the addition method is a so-called integral blend treatment method in which the surface treatment agent is added after the (E) inorganic filler is blended in the resin composition (I). It may be.
樹脂組成物（I）が（Ｅ）無機充填材を含有する場合、その含有量に特に制限はないが、低熱膨張性及び樹脂フィルムの取り扱い性の観点から、樹脂組成物（I）中の樹脂成分の総和１００質量部に対して、２０〜３００質量部が好ましく、５０〜２５０質量部がより好ましく、８０〜２００質量部がさらに好ましく、１００〜１７０質量部が特に好ましい。 When the resin composition (I) contains (E) an inorganic filler, the content is not particularly limited, but the resin in the resin composition (I) is from the viewpoint of low thermal expansion and handleability of the resin film. 20-300 mass parts is preferable with respect to 100 mass parts of total of a component, 50-250 mass parts is more preferable, 80-200 mass parts is more preferable, 100-170 mass parts is especially preferable.
＜（Ｆ）硬化促進剤＞
樹脂組成物（I）は、さらに、（Ｆ）硬化促進剤（以下、「（Ｆ）成分」ともいう）を含有することが好ましい。
（Ｆ）硬化促進剤としては、ナフテン酸亜鉛、ナフテン酸コバルト、オクチル酸スズ、オクチル酸コバルト、ビスアセチルアセトナートコバルト（ＩＩ）、トリスアセチルアセトナートコバルト（ＩＩＩ）等の有機金属塩；有機リン系化合物；イミダゾール化合物及びその誘導体；第２級アミン化合物、第３級アミン化合物、第４級アンモニウム塩などが挙げられる。これらの中でも、低熱膨張性の観点から、有機リン系化合物が好ましい。
（Ｆ）硬化促進剤は、１種を単独で使用してもよいし、２種以上を併用してもよい。
<(F) Curing accelerator>
The resin composition (I) preferably further contains (F) a curing accelerator (hereinafter also referred to as “component (F)”).
(F) Curing accelerators include organic metal salts such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), trisacetylacetonate cobalt (III); System compounds; imidazole compounds and derivatives thereof; secondary amine compounds, tertiary amine compounds, quaternary ammonium salts, and the like. Among these, an organic phosphorus compound is preferable from the viewpoint of low thermal expansion.
(F) A hardening accelerator may be used individually by 1 type, and may use 2 or more types together.
樹脂組成物（I）が（Ｆ）硬化促進剤を含有する場合、その含有量に特に制限はないが、樹脂組成物（I）中の樹脂成分の総和１００質量部に対して、耐熱性、難燃性、経日安定性及び硬化性の観点から、０．１〜１０質量部が好ましく、０．３〜５質量部がより好ましく、０．５〜３質量部がさらに好ましい。 When the resin composition (I) contains (F) a curing accelerator, the content thereof is not particularly limited, but the heat resistance, with respect to 100 parts by mass of the total resin components in the resin composition (I), From the viewpoint of flame retardancy, aging stability and curability, 0.1 to 10 parts by mass is preferable, 0.3 to 5 parts by mass is more preferable, and 0.5 to 3 parts by mass is more preferable.
＜その他の成分＞
樹脂組成物（I）は、本発明の目的を阻害しない範囲で、上記各成分以外の熱硬化性樹脂（以下、「その他の熱硬化性樹脂」ともいう）、難燃剤、紫外線吸収剤、酸化防止剤、光重合開始剤、蛍光増白剤、接着性向上剤等を含有していてもよい。
その他の熱硬化性樹脂としては、上記各成分以外の、フェノール樹脂、不飽和イミド樹脂、シアネート樹脂、イソシアネート樹脂、ベンゾオキサジン樹脂、オキセタン樹脂、アミノ樹脂、不飽和ポリエステル樹脂、アリル樹脂、ジシクロペンタジエン樹脂、シリコーン樹脂、トリアジン樹脂、メラミン樹脂等が挙げられる。
難燃剤としては、臭素及び／又は塩素を含有するハロゲン系難燃剤；トリフェニルホスフェート、トリクレジルホスフェート、トリスジクロロプロピルホスフェート、リン酸エステル系化合物、赤リン等のリン系難燃剤；スルファミン酸グアニジン、硫酸メラミン、ポリリン酸メラミン、メラミンシアヌレート等の窒素系難燃剤；シクロホスファゼン、ポリホスファゼン等のホスファゼン系難燃剤などが挙げられる。
紫外線吸収剤としては、ベンゾトリアゾール系紫外線吸収剤等が挙げられる。
酸化防止剤としては、ヒンダードフェノール系酸化防止剤、ヒンダードアミン系酸化防止剤等が挙げられる。
光重合開始剤としては、ベンゾフェノン類、ベンジルケタール類、チオキサントン系の光重合開始剤等が挙げられる。
蛍光増白剤としては、スチルベン誘導体の蛍光増白剤等が挙げられる。
接着性向上剤としては、尿素シラン等の尿素化合物；シラン系カップリング剤、チタネート系カップリング剤、アルミネート系カップリング剤等のカップリング剤などが挙げられる。
<Other ingredients>
The resin composition (I) is a thermosetting resin other than the above components (hereinafter, also referred to as “other thermosetting resin”), a flame retardant, an ultraviolet absorber, an oxidation, and the like within a range not impairing the object of the present invention. An inhibitor, a photopolymerization initiator, a fluorescent brightening agent, an adhesion improver and the like may be contained.
Other thermosetting resins include phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, dicyclopentadiene other than the above components. Resins, silicone resins, triazine resins, melamine resins and the like can be mentioned.
Examples of flame retardants include halogen flame retardants containing bromine and / or chlorine; phosphorus flame retardants such as triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphate ester compounds, red phosphorus; guanidine sulfamate And nitrogen-based flame retardants such as melamine sulfate, melamine polyphosphate and melamine cyanurate; phosphazene-based flame retardants such as cyclophosphazene and polyphosphazene.
Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers.
Examples of the antioxidant include hindered phenol-based antioxidants and hindered amine-based antioxidants.
Examples of the photopolymerization initiator include benzophenones, benzyl ketals, and thioxanthone photopolymerization initiators.
Examples of the fluorescent whitening agent include a fluorescent whitening agent of a stilbene derivative.
Examples of the adhesion improver include urea compounds such as urea silane; coupling agents such as silane coupling agents, titanate coupling agents, and aluminate coupling agents.
樹脂組成物（I）は、樹脂フィルムの製造を容易にするため、各成分が有機溶媒中に溶解及び／又は分散されたワニスの状態としてもよい。
有機溶媒としては、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶媒；メチルセロソルブ等のアルコール系溶媒；テトラヒドロフラン等のエーテル系溶媒；トルエン、キシレン、メシチレン等の芳香族系溶媒などが挙げられる。有機溶媒は、１種を単独で使用してもよいし、２種以上を併用してもよい。
ワニスの固形分濃度は、４０〜９０質量％が好ましく、５０〜８０質量％がより好ましい。ワニスの固形分濃度が上記範囲内であると、塗工性を良好に保ち、樹脂フィルムの厚さ等を適切な範囲に調整し易くなる。
In order to facilitate the production of the resin film, the resin composition (I) may be in the form of a varnish in which each component is dissolved and / or dispersed in an organic solvent.
Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohol solvents such as methyl cellosolve; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene, and mesitylene. . An organic solvent may be used individually by 1 type, and may use 2 or more types together.
The solid content concentration of the varnish is preferably 40 to 90% by mass, and more preferably 50 to 80% by mass. When the solid content concentration of the varnish is within the above range, it is easy to adjust the thickness and the like of the resin film to an appropriate range while maintaining good coating properties.
樹脂組成物（I）は、上記各成分を混合することにより製造することができる。混合方法としては、公知の方法を適用することができ、ニーダー、ボールミル、ビーズミル、３本ロール、ナノマイザー等の公知の混練及び分散方法を適用することができる。 The resin composition (I) can be produced by mixing the above components. As a mixing method, a known method can be applied, and a known kneading and dispersing method such as a kneader, a ball mill, a bead mill, a three roll, a nanomizer can be applied.
＜支持体＞
本実施形態の樹脂フィルムは、そのいずれか一方の面に支持体が設けられたものであってもよい。
支持体としては、ポリエチレン、ポリプロピレン、ポリ塩化ビニル等のポリオレフィンのフィルム；ポリエチレンテレフタレート（以下、「ＰＥＴ」ともいう）、ポリエチレンナフタレート等のポリエステルのフィルム；ポリカーボネートフィルム、ポリイミドフィルム等の各種プラスチックフィルムなどが挙げられる。また、銅箔、アルミニウム箔等の金属箔、離型紙などを使用してもよい。支持体及び後述する保護フィルムには、マット処理、コロナ処理等の表面処理が施してあってもよい。また、支持体及び後述する保護フィルムにはシリコーン樹脂系離型剤、アルキッド樹脂系離型剤、フッ素樹脂系離型剤等による離型処理が施してあってもよい。
支持体の厚さは、例えば、１０〜１５０μｍであり、２５〜５０μｍであってもよい。
<Support>
The resin film of this embodiment may be one in which a support is provided on any one surface thereof.
Examples of the support include polyolefin films such as polyethylene, polypropylene, and polyvinyl chloride; polyester films such as polyethylene terephthalate (hereinafter also referred to as “PET”) and polyethylene naphthalate; various plastic films such as polycarbonate films and polyimide films. Is mentioned. Moreover, you may use metal foil, release paper, etc., such as copper foil and aluminum foil. The support and the protective film described later may be subjected to surface treatment such as mat treatment or corona treatment. Further, the support and the protective film described later may be subjected to a release treatment with a silicone resin release agent, an alkyd resin release agent, a fluororesin release agent, or the like.
The thickness of the support is, for example, 10 to 150 μm, and may be 25 to 50 μm.
＜保護フィルム＞
支持体上に形成された樹脂フィルムの、支持体とは反対側の面には、保護フィルムを設けてもよい。保護フィルムの厚さは、例えば、１〜４０μｍである。保護フィルムを積層することにより、樹脂フィルムの表面へのゴミ等の付着及び傷付きを防止することができる。保護フィルムの材質は、支持体と同様のものが挙げられる。
<Protective film>
A protective film may be provided on the surface of the resin film formed on the support opposite to the support. The thickness of the protective film is, for example, 1 to 40 μm. By laminating the protective film, it is possible to prevent adhesion of the dust and the like to the surface of the resin film and damage. The material of the protective film is the same as that of the support.
＜樹脂フィルムの製造方法＞
本実施形態の樹脂フィルムの製造方法に特に制限はなく、公知の方法を利用できる。
例えば、まず、樹脂フィルムに含有させる各成分を有機溶媒の存在下で混合することで、ワニス状の樹脂組成物（I）として、該ワニスを支持体へ塗布した後、有機溶媒を除去し、樹脂組成物（I）を半硬化（Ｂ−ステージ化）することによって、支持体付き樹脂フィルムを形成することができる。
<Method for producing resin film>
There is no restriction | limiting in particular in the manufacturing method of the resin film of this embodiment, A well-known method can be utilized.
For example, first, by mixing each component to be contained in the resin film in the presence of an organic solvent, as a varnish-like resin composition (I), after applying the varnish to a support, the organic solvent is removed, A resin film with a support can be formed by semi-curing (B-staging) the resin composition (I).
ワニスを塗布する方法としては、コンマコーター、バーコーター、キスコーター、ロールコーター、グラビアコーター、ダイコーター等の公知の塗工装置を用いることができる。これらの塗工装置は、膜厚によって、適宜選択することが好ましい。
塗布後の乾燥条件は、樹脂フィルム中の揮発成分（主に有機溶媒）の含有量が、例えば、１０質量％以下となる条件であり、６質量％以下となる条件が好ましい。
乾燥温度及び乾燥時間は、有機溶媒の使用量、有機溶媒の沸点等によって異なるが、例えば、３０〜６０質量％の有機溶媒を含むワニスの場合、５０〜１５０℃で３〜１０分間乾燥させることにより、樹脂フィルムを好適に形成することができる。
得られる樹脂フィルムの最低溶融粘度は、８００〜５，０００ＭＰａ・ｓとなるように乾燥することが好ましい。
As a method for applying the varnish, known coating apparatuses such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, and a die coater can be used. These coating apparatuses are preferably selected as appropriate depending on the film thickness.
The drying conditions after the application are such that the content of volatile components (mainly organic solvents) in the resin film is, for example, 10% by mass or less, and preferably 6% by mass or less.
The drying temperature and drying time vary depending on the amount of organic solvent used, the boiling point of the organic solvent, etc. For example, in the case of a varnish containing 30 to 60% by mass of the organic solvent, it is dried at 50 to 150 ° C. for 3 to 10 minutes. Thus, the resin film can be suitably formed.
It is preferable to dry the resin film obtained so that the minimum melt viscosity is 800 to 5,000 MPa · s.
本実施形態の樹脂フィルムの厚さは、求める性能に応じて適宜決定すればよいが、導体層上に配置して用いる場合、回路基板の導体層を埋め込む観点から、回路基板の導体層の厚さ以上であってもよい。具体的には、樹脂フィルムの厚さは、１〜１００μｍが好ましく、３〜５０μｍがより好ましく、４〜４０μｍがさらに好ましい。 The thickness of the resin film of the present embodiment may be appropriately determined according to the required performance, but when used on the conductor layer, the thickness of the conductor layer of the circuit board is used from the viewpoint of embedding the conductor layer of the circuit board. It may be more than that. Specifically, the thickness of the resin film is preferably 1 to 100 μm, more preferably 3 to 50 μm, and still more preferably 4 to 40 μm.
本実施形態の樹脂フィルムは、回路基板、ソルダーレジスト、アンダーフィル材、ダイボンディング材、半導体封止材、穴埋め樹脂、部品埋め込み樹脂等の層間絶縁層を形成するために用いられる樹脂フィルムとして好適である。これらの中でも、プリント配線板の製造において層間絶縁層を形成するために用いられることが好ましく、後述する本実施形態の積層体の製造において層間絶縁層を形成するため用いられることがより好ましい。 The resin film of this embodiment is suitable as a resin film used for forming an interlayer insulating layer such as a circuit board, a solder resist, an underfill material, a die bonding material, a semiconductor sealing material, a hole filling resin, and a component embedding resin. is there. Among these, it is preferably used for forming an interlayer insulating layer in the production of a printed wiring board, and more preferably used for forming an interlayer insulating layer in the production of a laminate according to this embodiment described later.
［積層体］
本実施形態の積層体は、本実施形態の層間絶縁層用樹脂フィルムと、プリプレグ又はプリプレグを硬化してなる絶縁層と、を積層してなる積層体である。
[Laminate]
The laminate of this embodiment is a laminate obtained by laminating the interlayer insulating layer resin film of this embodiment and an insulating layer formed by curing a prepreg or a prepreg.
＜プリプレグ＞
本実施形態の積層体に用いられるプリプレグは、（ａ）エポキシ樹脂（以下、「（ａ）成分」ともいう）、（ｂ）１分子中に２個以上のＮ−置換マレイミド基を有するマレイミド化合物（以下、「（ｂ）成分」ともいう）と、（ｃ）１分子中に２個以上の１級アミノ基を有するアミン化合物（以下、「（ｃ）成分」ともいう）と、を含有する熱硬化性樹脂組成物（以下、「樹脂組成物（II）」ともいう）を含有するプリプレグであることが好ましい。なお、本実施形態に用いられる樹脂組成物（II）は、樹脂組成物（I）と同様、（ｂ）成分及び（ｃ）成分を、（ｂ）成分及び（ｃ）成分を反応させてなる（ｘ）変性ポリイミドとして含有する態様も好ましい。
また、樹脂組成物（II）は、上記各成分に加え、（ｄ）エラストマー（以下、「（ｄ）成分」ともいう）、（ｅ）無機充填材（以下、「（ｅ）成分」ともいう）及び（ｆ）硬化促進剤（以下、「（ｆ）成分」ともいう）からなる群から選択される少なくとも１種を含有していてもよい。
なお、（ａ）成分は上記（Ａ）成分、（ｂ）成分は上記（Ｂ）成分、（ｃ）成分は上記（Ｃ）成分、（ｄ）成分は上記（Ｄ）成分、（ｅ）成分は上記（Ｅ）成分、（ｆ）成分は上記（Ｆ）成分、（ｘ）成分は上記（Ｘ）成分と、各々同じものが挙げられ、好ましい種類も同じである。また、これらは、各々について、１種を単独で使用してもよく、２種以上を併用してもよい。
<Prepreg>
The prepreg used in the laminate of this embodiment includes (a) an epoxy resin (hereinafter also referred to as “component (a)”), and (b) a maleimide compound having two or more N-substituted maleimide groups in one molecule. (Hereinafter also referred to as “component (b)”) and (c) an amine compound having two or more primary amino groups in one molecule (hereinafter also referred to as “component (c)”). A prepreg containing a thermosetting resin composition (hereinafter also referred to as “resin composition (II)”) is preferable. In addition, resin composition (II) used for this embodiment makes (b) component and (c) component react with (b) component and (c) component similarly to resin composition (I). (X) The aspect contained as a modified polyimide is also preferable.
In addition to the above components, the resin composition (II) is also referred to as (d) an elastomer (hereinafter also referred to as “(d) component”), (e) an inorganic filler (hereinafter referred to as “(e) component”). ) And (f) a curing accelerator (hereinafter also referred to as “component (f)”) may be contained.
The component (a) is the component (A), the component (b) is the component (B), the component (c) is the component (C), the component (d) is the component (D), and the component (e). Are the same as (E), (f) is the same as (F), and (x) is the same as (X). The preferred types are also the same. Moreover, these may be used individually by 1 type, respectively, and may use 2 or more types together, respectively.
本実施形態の積層体は、コア層及びビルドアップ層の両方に、１分子中に２個以上のＮ−置換マレイミド基を有するマレイミド化合物と１分子中に２個以上の１級アミノ基を有するアミン化合物又は変性ポリイミドを使用することで、コア層とビルドアップ層との界面におけるボイドの発生を顕著に抑制することができる。その機構は定かではないが、コア層及びビルドアップ層の両方に同一又は類似する樹脂を使用することで、コア層とビルドアップ層との親和性が向上することで濡れ性が向上し、これによってボイドの発生が抑制されたものと考えられる。
したがって、コア層とビルドアップ層との界面におけるボイドの発生を抑制する観点から、本実施形態の積層体に使用する樹脂フィルム及びプリプレグは、各々を構成する樹脂組成物の組成が近いことが好ましい。具体的には、樹脂組成物（II）が、（ａ）〜（ｆ）成分及び（ｘ）成分からなる群から選択される１種以上を含有する場合、当該成分の構造は、樹脂組成物（Ｉ）が含有する（Ａ）〜（Ｆ）成分及び（Ｘ）成分のうち、対応する成分の構造と同一であるか、類似していることが好ましい。
The laminate of this embodiment has a maleimide compound having two or more N-substituted maleimide groups in one molecule and two or more primary amino groups in one molecule in both the core layer and the buildup layer. By using an amine compound or a modified polyimide, it is possible to remarkably suppress the generation of voids at the interface between the core layer and the buildup layer. The mechanism is not clear, but by using the same or similar resin for both the core layer and the buildup layer, the wettability is improved by improving the affinity between the core layer and the buildup layer. It is considered that the generation of voids was suppressed.
Therefore, from the viewpoint of suppressing the generation of voids at the interface between the core layer and the buildup layer, it is preferable that the resin film and the prepreg used in the laminate of the present embodiment have close resin compositions. . Specifically, when the resin composition (II) contains one or more selected from the group consisting of the components (a) to (f) and the component (x), the structure of the component is the resin composition. Among the components (A) to (F) and the component (X) contained in (I), it is preferable that the structure is the same as or similar to the structure of the corresponding component.
樹脂組成物（II）が（ａ）成分を含有する場合、樹脂組成物（II）中における（ａ）成分の含有量は、耐デスミア性、成形性、電気絶縁性及び金属回路との接着強度の観点から、樹脂組成物（II）中の樹脂成分の総和１００質量部に対して、１〜８５質量部が好ましく、５〜７０質量部がより好ましく、１０〜５０質量部がさらに好ましく、１５〜３０質量部が特に好ましい。 When the resin composition (II) contains the component (a), the content of the component (a) in the resin composition (II) is desmear resistance, moldability, electrical insulation, and adhesive strength with a metal circuit. From the viewpoint of 1 to 85 parts by mass, preferably 5 to 70 parts by mass, more preferably 10 to 50 parts by mass, with respect to 100 parts by mass of the total of the resin components in the resin composition (II), 15 -30 mass parts is especially preferable.
樹脂組成物（II）が（ｂ）成分を含有する場合、樹脂組成物（II）中における（ｂ）成分の含有量は、耐熱性、誘電特性、ガラス転移温度、熱膨張係数、成形性及びビルドアップ層との界面におけるボイドの発生を抑制する観点から、樹脂組成物（II）中の樹脂成分の総和１００質量部に対して、５〜８０質量部が好ましく、１０〜７０質量部がより好ましく、１５〜６０質量部がさらに好ましく、２０〜５０質量部がよりさらに好ましく、２５〜４０質量部が特に好ましい。 When the resin composition (II) contains the component (b), the content of the component (b) in the resin composition (II) includes heat resistance, dielectric properties, glass transition temperature, thermal expansion coefficient, moldability and From the viewpoint of suppressing the generation of voids at the interface with the buildup layer, 5 to 80 parts by mass is preferable and 10 to 70 parts by mass is more preferable with respect to 100 parts by mass of the total resin components in the resin composition (II). Preferably, 15-60 mass parts is more preferable, 20-50 mass parts is still more preferable, 25-40 mass parts is especially preferable.
樹脂組成物（II）が（ｃ）成分を含有する場合、樹脂組成物（II）中における（ｃ）成分の含有量は、低反り性、寸法安定性、低熱膨張性、低弾性、耐熱性、金属回路との接着性及びコア層との界面におけるボイドの発生を抑制する観点から、樹脂組成物（II）中の樹脂成分の総和１００質量部に対して、１〜４０質量部が好ましく、２〜２５質量部がより好ましく、５〜１５質量部がさらに好ましい。 When the resin composition (II) contains the component (c), the content of the component (c) in the resin composition (II) is low warpage, dimensional stability, low thermal expansion, low elasticity, heat resistance. From the viewpoint of suppressing the occurrence of voids at the interface with the metal circuit and the core layer, 1 to 40 parts by mass is preferable with respect to 100 parts by mass of the total resin components in the resin composition (II). 2-25 mass parts is more preferable, and 5-15 mass parts is still more preferable.
樹脂組成物（II）が（ｘ）成分を含有する場合、樹脂組成物（II）中における（ｘ）成分の含有量は、耐熱性、誘電特性、ガラス転移温度、熱膨張係数、成形性及びコア層との界面におけるボイドの発生を抑制する観点から、樹脂組成物（II）中の樹脂成分の総和１００質量部に対して、１０〜８０質量部が好ましく、２０〜６０質量部がより好ましく、３０〜５０質量部がさらに好ましい。 When the resin composition (II) contains the component (x), the content of the component (x) in the resin composition (II) includes heat resistance, dielectric properties, glass transition temperature, thermal expansion coefficient, moldability and From the viewpoint of suppressing the generation of voids at the interface with the core layer, 10 to 80 parts by mass is preferable and 20 to 60 parts by mass is more preferable with respect to 100 parts by mass of the total resin components in the resin composition (II). 30 to 50 parts by mass is more preferable.
樹脂組成物（II）が（ｄ）成分を含有する場合、樹脂組成物（II）中における（ｄ）成分の含有量は、耐デスミア性及び樹脂フィルムの取り扱い性を向上させる観点から、樹脂組成物（II）中の樹脂成分の総和１００質量部に対して、５〜５５質量部が好ましく、１０〜５０質量部がより好ましく、２０〜４５質量部がさらに好ましく、３０〜４０質量部が特に好ましい。 When the resin composition (II) contains the component (d), the content of the component (d) in the resin composition (II) is a resin composition from the viewpoint of improving desmear resistance and handleability of the resin film. 5-55 mass parts is preferable with respect to 100 mass parts of sum total of the resin component in thing (II), 10-50 mass parts is more preferable, 20-45 mass parts is further more preferable, and 30-40 mass parts is especially. preferable.
樹脂組成物（II）が（ｅ）成分を含有する場合、樹脂組成物（II）中における（ｅ）成分の含有量は、耐熱性、難燃性、経日安定性及び硬化性の観点から、樹脂組成物（II）中の樹脂成分の総和１００質量部に対して、２０〜３００質量部が好ましく、５０〜２５０質量部がより好ましく、８０〜２００質量部がさらに好ましく、１００〜１７０質量部が特に好ましい。 When the resin composition (II) contains the component (e), the content of the component (e) in the resin composition (II) is from the viewpoints of heat resistance, flame retardancy, aging stability and curability. The resin component (II) is preferably 20 to 300 parts by weight, more preferably 50 to 250 parts by weight, still more preferably 80 to 200 parts by weight, and more preferably 100 to 170 parts by weight with respect to 100 parts by weight of the total resin components. Part is particularly preferred.
樹脂組成物（II）が（ｆ）成分を含有する場合、樹脂組成物（II）中における（ｆ）成分の含有量は、低熱膨張性、回路埋め込み性及び樹脂フィルムの取り扱い性の観点から、樹脂組成物（II）中の樹脂成分の総和１００質量部に対して、０．１〜１０質量部が好ましく、０．３〜５質量部がより好ましく、０．５〜３質量部がさらに好ましい。 When the resin composition (II) contains the component (f), the content of the component (f) in the resin composition (II) is from the viewpoint of low thermal expansion, circuit embedding property, and resin film handling properties. 0.1-10 mass parts is preferable with respect to 100 mass parts of the sum total of the resin component in resin composition (II), 0.3-5 mass parts is more preferable, 0.5-3 mass parts is further more preferable. .
樹脂組成物（II）は、本発明の目的を阻害しない範囲で、上記各成分以外のその他の成分を含有していてもよい。その他の成分としては、樹脂組成物（I）が含有していてもよいその他の成分と同じものが挙げられる。 The resin composition (II) may contain other components other than the above-mentioned components as long as the object of the present invention is not impaired. Examples of the other components include the same components as the other components that may be contained in the resin composition (I).
樹脂組成物（II）は、上記各成分を混合することにより製造することができる。混合方法は、樹脂組成物（I）と同じ方法を適用することができる。 The resin composition (II) can be produced by mixing the above components. The same method as the resin composition (I) can be applied as the mixing method.
（プリプレグの製造方法）
プリプレグは、例えば、樹脂組成物（II）を、基材に含浸する方法により製造することができる。具体的には、本実施形態の樹脂組成物（II）を、基材に含浸した後、例えば、加熱等により半硬化することにより、基材と半硬化した樹脂組成物（II）とを含有するプリプレグを製造することができる。
樹脂組成物（II）を基材に含浸する方法は、例えば、基材を上記ワニスに浸漬する方法、各種コーターにより塗布する方法、スプレーによる吹き付ける方法等が挙げられる。これらの中でも、含浸性の観点から、基材をワニスに浸漬する方法が好ましい。
樹脂組成物（II）を基材に含浸した後、例えば、１００〜２００℃で１〜３０分間、加熱乾燥し、樹脂組成物（II）を半硬化させて、プリプレグを製造することができる。
(Manufacturing method of prepreg)
The prepreg can be produced, for example, by a method of impregnating the base material with the resin composition (II). Specifically, after impregnating the substrate with the resin composition (II) of the present embodiment, the substrate and the semi-cured resin composition (II) are contained by, for example, semi-curing by heating or the like. The prepreg to be manufactured can be manufactured.
Examples of the method of impregnating the base material with the resin composition (II) include a method of immersing the base material in the varnish, a method of applying with various coaters, and a spraying method. Among these, the method of immersing the base material in the varnish is preferable from the viewpoint of impregnation.
After impregnating the resin composition (II) on the substrate, for example, the resin composition (II) can be semi-cured by heating and drying at 100 to 200 ° C. for 1 to 30 minutes to produce a prepreg.
プリプレグに用いられる基材としては、例えば、各種の電気絶縁材料用積層板に用いられている周知のものが使用できる。その材質としては、例えば、Ｅガラス、Ｄガラス、Ｓガラス、Ｑガラス等の無機物繊維；ポリイミド、ポリエステル、テトラフルオロエチレン等の有機繊維；炭素繊維及びこれらの混合物などが挙げられる。
これらの基材は、例えば、織布、不織布、ロービンク、チョップドストランドマット、サーフェシングマット等の形状を有する。基材の材質及び形状は、目的とする成形物の用途及び性能により選択すればよく、必要により、単独又は２種類以上の材質及び形状を組み合わせることができる。
基材は、シランカップリング剤等で表面処理したもの又は機械的に開繊処理を施したものが、耐熱性、耐湿性及び加工性の面から好適である。
基材の厚さは、例えば、約０．０３〜０．５ｍｍである。
プリプレグ中における樹脂組成物（II）の含有量は、２０〜９０質量％が好ましい。
As a base material used for a prepreg, the well-known thing used for the laminated board for various electrical insulation materials can be used, for example. Examples of the material include inorganic fibers such as E glass, D glass, S glass, and Q glass; organic fibers such as polyimide, polyester, and tetrafluoroethylene; carbon fibers and a mixture thereof.
These base materials have shapes, such as a woven fabric, a nonwoven fabric, a robink, a chopped strand mat, a surfacing mat, for example. What is necessary is just to select the material and shape of a base material with the use and performance of the target molded object, and if necessary, it can combine individually or two or more types of materials and shapes.
A substrate that is surface-treated with a silane coupling agent or the like or that has been mechanically subjected to a fiber opening treatment is suitable from the viewpoint of heat resistance, moisture resistance, and workability.
The thickness of the substrate is, for example, about 0.03 to 0.5 mm.
The content of the resin composition (II) in the prepreg is preferably 20 to 90% by mass.
（積層体の製造方法）
本実施形態の積層体は、上記プリプレグ又は上記プリプレグを硬化してなる絶縁層に、本実施形態の樹脂フィルムをラミネートして製造することができる。
以下、プリプレグを硬化してなる絶縁層に本実施形態の樹脂フィルムをラミネートする積層体の製造方法について説明する。
プリプレグを硬化してなる絶縁層は、例えば、上記プリプレグを単独又は２〜２０枚重ねて、その片面又は両面に、銅、アルミニウム等の金属箔を配置した構成で積層成形して製造することができる。積層成形の条件としては、例えば、加熱温度が１００〜２５０℃、加熱時間が０．１〜５時間、圧着圧力が０．２〜１０ＭＰａである。
続いて、得られた成形物を銅エッチング液に浸漬することにより両面の金属箔をエッチングして、上記プリプレグを硬化してなる絶縁層が得られる。
(Manufacturing method of laminated body)
The laminate of this embodiment can be manufactured by laminating the resin film of this embodiment on the prepreg or an insulating layer formed by curing the prepreg.
Hereinafter, the manufacturing method of the laminated body which laminates the resin film of this embodiment on the insulating layer formed by hardening | curing a prepreg is demonstrated.
The insulating layer formed by curing the prepreg can be manufactured, for example, by laminating and forming the above prepreg alone or by stacking 2 to 20 sheets, and arranging a metal foil such as copper or aluminum on one or both sides thereof. it can. As conditions for the lamination molding, for example, the heating temperature is 100 to 250 ° C., the heating time is 0.1 to 5 hours, and the pressure bonding pressure is 0.2 to 10 MPa.
Subsequently, the obtained molded product is immersed in a copper etching solution to etch the metal foils on both sides, thereby obtaining an insulating layer obtained by curing the prepreg.
次に、上記で得られた絶縁層の片面又は両面に本実施形態の樹脂フィルムをラミネートする。上記ラミネートにおいて、樹脂フィルムが保護フィルムを有している場合には該保護フィルムを除去した後、樹脂フィルムを加圧及び加熱しながら絶縁層に圧着する。
本実施形態の樹脂フィルムにおいては、真空ラミネート法により減圧下で回路基板にラミネートする方法が好ましい。ラミネートにおける圧着温度（ラミネート温度）は、例えば、７０〜１４０℃であり、圧着圧力は、例えば、０．１〜１．１ＭＰａであり、空気圧２０ｍｍＨｇ（２６．７ｈＰａ）以下の減圧下でラミネートすることが好ましい。また、ラミネートの方法は、バッチ式であってもロールでの連続式であってもよい。
Next, the resin film of this embodiment is laminated on one side or both sides of the insulating layer obtained above. In the above laminate, when the resin film has a protective film, after removing the protective film, the resin film is pressure-bonded to the insulating layer while being pressurized and heated.
In the resin film of this embodiment, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is preferable. The pressure bonding temperature (laminating temperature) in the lamination is, for example, 70 to 140 ° C., the pressure bonding pressure is, for example, 0.1 to 1.1 MPa, and the lamination is performed under a reduced pressure of an air pressure of 20 mmHg (26.7 hPa) or less. Is preferred. The laminating method may be a batch method or a continuous method using a roll.
［プリント配線板］
本実施形態のプリント配線板は、本実施形態の樹脂フィルムを用いて形成される層間絶縁層、又は本実施形態の積層体を用いて形成される層間絶縁層を含有するものである。
換言すると、本実施形態のプリント配線板は、層間絶縁層を有し、該層間絶縁層のうち少なくとも一層が本実施形態の樹脂フィルムの硬化物を含むものである。
本実施形態のプリント配線板を製造するに当たっては、例えば、まず、コア層の導体層を公知のエッチング法によって配線加工を行い、コア層の片面又は両面に本実施形態の樹脂フィルムをラミネートする。次に、樹脂フィルムを熱硬化してビルドアップ層を形成し、ドリル加工、レーザー加工等によるスルーホール又はブラインドビアホールの形成と、メッキ又は導電性ペーストによる層間配線の形成を経て、プリント配線板を製造することができる。
[Printed wiring board]
The printed wiring board of this embodiment contains the interlayer insulation layer formed using the resin film of this embodiment, or the interlayer insulation layer formed using the laminated body of this embodiment.
In other words, the printed wiring board of the present embodiment has an interlayer insulating layer, and at least one of the interlayer insulating layers includes a cured product of the resin film of the present embodiment.
In manufacturing the printed wiring board of the present embodiment, for example, first, the conductor layer of the core layer is processed by a known etching method, and the resin film of the present embodiment is laminated on one side or both sides of the core layer. Next, the resin film is thermally cured to form a build-up layer, and through the formation of through holes or blind via holes by drilling, laser processing, etc., and formation of interlayer wiring by plating or conductive paste, the printed wiring board is formed. Can be manufactured.
［半導体装置］
本実施形態の半導体装置は、本実施形態のプリント配線板を含有するものである。
本実施形態の半導体装置は、本実施形態のプリント配線板の所定の位置に、公知の方法により、半導体チップ、メモリ等を搭載して製造することができる。
[Semiconductor device]
The semiconductor device of this embodiment contains the printed wiring board of this embodiment.
The semiconductor device of this embodiment can be manufactured by mounting a semiconductor chip, a memory, or the like on a predetermined position of the printed wiring board of this embodiment by a known method.
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。各例で得られた樹脂フィルムは以下の方法で評価した。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The resin film obtained in each example was evaluated by the following method.
［樹脂フィルムの取り扱い性］
樹脂フィルムの取り扱い性は、以下に示す方法で評価した。
（１）カッターでの切断による評価
各例で得られた支持体及び保護フィルムを有する樹脂フィルムをカッターで切断した際の粉落ちの有無を目視で確認し、粉落ちが無いものを取り扱い性良好とした。
（２）折り曲げによる評価
各例で得られた支持体及び保護フィルムを有する樹脂フィルムの保護フィルムを剥離し、支持体から樹脂塗工面に向かって１８０°折り曲げ、フィルムの割れの有無を目視で確認し、割れが発生しないものを取り扱い性良好とした。
上記（１）及び（２）の評価において、どちらも良好となったものを「Ａ」、少なくともいずれかが良好でないものを「Ｂ」とした。
[Handling of resin film]
The handleability of the resin film was evaluated by the following method.
(1) Evaluation by cutting with a cutter The resin film having a support and a protective film obtained in each example was visually checked for the presence or absence of powder falling, and those with no powder falling had good handleability. It was.
(2) Evaluation by bending The protective film of the resin film having the support and protective film obtained in each example was peeled off, bent 180 ° from the support toward the resin coating surface, and the presence or absence of cracking of the film was confirmed visually. And the thing which does not generate | occur | produce a crack was made favorable in handling property.
In the evaluations (1) and (2) above, “A” was given when both were good, and “B” was given when at least one was not good.
［デスミア重量減少量（耐デスミア性の評価）］
ラミネーター内において、各例で得られた支持体及び保護フィルムを有する樹脂フィルムの保護フィルムを剥離し、銅箔（電解銅箔、厚さ１２μｍ）の光沢面上に樹脂フィルムをラミネートした。ラミネートは、３０秒間減圧して圧力を０．５ＭＰａとした後、１４０℃で３０秒間、圧着圧力０．５ＭＰａの条件で行った。ラミネート後、支持体を剥離して、片面銅箔付き樹脂フィルムを得た。同様の操作により、別の片面銅箔付き樹脂フィルムを作製し、２つの片面銅箔付き樹脂フィルムの樹脂面同士を合わせ、真空プレスを用いて、１７５℃で６０分間、圧着圧力１．０ＭＰａの条件でプレス成型を行い、両面銅箔付き樹脂板を得た。得られた両面銅箔付き樹脂板を、１９０℃で２時間防爆乾燥機を用いて硬化させた。続いて、塩化第二鉄で両面の銅箔をエッチングすることで、厚さ約０．２ｍｍの樹脂板を得た。この樹脂板を４ｃｍ角に切断して、耐デスミア性の試験片とした。次いで、該試験片に表１に示す処理を順次施してデスミア処理を行った。なお、薬液はアトテック社製のものを用いた。デスミア重量減少量は、デスミア処理前乾燥重量と、デスミア処理後重量との差（処理前重量−処理後重量）を算出し、これを耐デスミア性の指標とした。
[Desmear weight reduction (desmear resistance evaluation)]
In the laminator, the protective film of the resin film having the support and protective film obtained in each example was peeled, and the resin film was laminated on the glossy surface of the copper foil (electrolytic copper foil, thickness 12 μm). Lamination was performed under the conditions of a pressure of 0.5 MPa for 30 seconds at 140 ° C. after reducing pressure for 30 seconds. After lamination, the support was peeled off to obtain a resin film with a single-sided copper foil. According to the same operation, another resin film with a single-sided copper foil was prepared, the resin surfaces of two resin films with a single-sided copper foil were combined, and using a vacuum press at 175 ° C. for 60 minutes at a pressure of 1.0 MPa. Press molding was performed under conditions to obtain a resin plate with double-sided copper foil. The obtained resin plate with double-sided copper foil was cured at 190 ° C. for 2 hours using an explosion-proof dryer. Subsequently, the copper foil on both sides was etched with ferric chloride to obtain a resin plate having a thickness of about 0.2 mm. This resin plate was cut into 4 cm square to obtain a desmear-resistant test piece. Subsequently, the test piece was sequentially subjected to the treatment shown in Table 1 to perform a desmear treatment. A chemical solution manufactured by Atotech was used. The desmear weight reduction amount was calculated as the difference between the dry weight before desmear treatment and the weight after desmear treatment (pre-treatment weight-post-treatment weight), and this was used as an index of desmear resistance.
［ボイド数の測定］
各製造例で作製したプリプレグ（２５ｃｍ角）を４枚重ね、最外層（両面）に厚さ１２μｍの電解銅箔を配置し、圧着圧力３．０ＭＰａ、温度２４０℃で６０分間プレスを行った。その後、銅エッチング液に浸漬することにより両面の銅箔を除去して、銅無し積層板を得た。続いて、ラミネーター内において、各例で作製した支持体及び保護フィルムを有する樹脂フィルムの保護フィルムを剥離し、銅無し積層板の両面に樹脂フィルムをラミネートした。ラミネートは、３０秒間減圧して圧力を０．５ＭＰａとした後、１４０℃で３０秒間、圧着圧力０．５ＭＰａの条件で行った。その後、防爆乾燥機を用いて、１９０℃で２時間加熱して樹脂フィルムを硬化させ、観察基板を得た。得られた観察基板の両面を目視で観察し、ボイド数を計測した。
[Measurement of the number of voids]
Four prepregs (25 cm square) produced in each production example were stacked, and an electrolytic copper foil having a thickness of 12 μm was disposed on the outermost layer (both sides), and pressing was performed at a pressure of 3.0 MPa and a temperature of 240 ° C. for 60 minutes. Thereafter, the copper foil on both sides was removed by immersing in a copper etching solution to obtain a copper-free laminate. Then, the protective film of the resin film which has the support body and protective film which were produced in each example in the laminator was peeled, and the resin film was laminated on both surfaces of the copperless laminated board. Lamination was performed under the conditions of a pressure of 0.5 MPa for 30 seconds at 140 ° C. after reducing pressure for 30 seconds. Then, using an explosion-proof dryer, the resin film was cured by heating at 190 ° C. for 2 hours to obtain an observation substrate. Both surfaces of the obtained observation substrate were visually observed, and the number of voids was measured.
［（Ｘ）変性ポリイミドの製造］
製造例１
（変性ポリイミド（Ｘ−１））
温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積２リットルの反応容器に、Ｘ−２２−１６１Ａ（両末端ジアミン変性シロキサン、信越化学工業株式会社製、アミノ基当量８００ｇ／ｅｑ）７２ｇと、ビス（４−マレイミドフェニル）メタン２５２ｇと、プロピレングリコールモノメチルエーテル２７０．０ｇを入れ、１１０℃で３時間反応させて、変性ポリイミド（Ｘ−１）含有溶液を得た。
[Production of (X) Modified Polyimide]
Production Example 1
(Modified polyimide (X-1))
In a reaction vessel with a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture quantifier with a reflux condenser, X-22-161A (both ends diamine-modified siloxane, manufactured by Shin-Etsu Chemical Co., Ltd., amino group) Equivalent 800 g / eq) 72 g, bis (4-maleimidophenyl) methane 252 g and propylene glycol monomethyl ether 270.0 g were added and reacted at 110 ° C. for 3 hours to obtain a modified polyimide (X-1) -containing solution. .
［層間絶縁層用樹脂フィルム及びプリプレグの製造］
実施例１〜２、比較例１〜３
（樹脂フィルムＡ〜Ｅ）
表２に示す配合組成（単位：質量部。但し、溶液又は分散液の場合は固形分換算量を示す。）で各成分を混合し、希釈溶媒にメチルエチルケトンを用いて、固形分濃度６５質量％のワニスＡ〜Ｅを得た。
次に、該ワニスＡ〜Ｅを、２７０ｍｍ幅のＰＥＴフィルム（帝人デュポンフィルム株式会社製、商品名：Ｇ−２）に、塗布幅２５０ｍｍ、乾燥後の樹脂フィルム（樹脂組成物層）の厚さが１５μｍになるように塗布した後、１００℃で３分間乾燥した。次いで、樹脂フィルムの支持体が設けられていない面に、保護フィルムとしてポリプロピレンフィルムを貼り合わせながらロール状に巻き取り、支持体及び保護フィルムを有する樹脂フィルムＡ〜Ｅを得た。
[Production of resin film and prepreg for interlayer insulating layer]
Examples 1-2 and Comparative Examples 1-3
(Resin films A to E)
Each component is mixed in the composition shown in Table 2 (unit: part by mass, but in the case of a solution or dispersion, the solid content is converted), and methyl ethyl ketone is used as a diluting solvent, and the solid content concentration is 65% by mass. Varnishes A to E were obtained.
Next, the varnishes A to E are applied to a 270 mm wide PET film (trade name: G-2, manufactured by Teijin DuPont Films, Ltd.) with a coating width of 250 mm, and the thickness of the resin film (resin composition layer) after drying. Was applied to a thickness of 15 μm and dried at 100 ° C. for 3 minutes. Subsequently, it rolled up in roll shape, bonding a polypropylene film as a protective film on the surface in which the support body of a resin film is not provided, and obtained resin film AE which has a support body and a protective film.
製造例２〜４
（プリプレグI〜III）
表３に示す配合組成（単位：質量部。但し、溶液又は分散液の場合は固形分換算量を示す。）で各成分を混合し、溶媒にメチルエチルケトンを用いて固形分濃度６５質量％のワニスI〜IIIを得た。
上記で得られたワニスI〜IIIを、ガラスクロス（種類：１０３７クロス、厚さ：２５μｍ）に塗工機を用いて塗布した後、１３０℃で３分間乾燥して、溶媒を除去させると共に、熱硬化性樹脂組成物を半硬化させて、プリプレグI〜IIIを得た。なお、塗布重量の調整はスクイズロール法で行い、得られたプリプレグ中における熱硬化性樹脂組成物の含有量は、７２質量％であった。
Production Examples 2 to 4
(Prepreg I ~ III)
Each component is mixed with the composition shown in Table 3 (unit: parts by mass; however, in the case of a solution or dispersion, the amount is expressed in terms of solid content), and varnish having a solid content concentration of 65% by mass using methyl ethyl ketone as the solvent. I to III were obtained.
The varnishes I to III obtained above were applied to a glass cloth (type: 1037 cloth, thickness: 25 μm) using a coating machine, and then dried at 130 ° C. for 3 minutes to remove the solvent, The thermosetting resin composition was semi-cured to obtain prepregs I to III. In addition, adjustment of application | coating weight was performed by the squeeze roll method, and content of the thermosetting resin composition in the obtained prepreg was 72 mass%.
なお、表２及び表３に示す各成分の詳細は以下の通りである。
［（Ａ）固形エポキシ樹脂、（ａ）エポキシ樹脂］
・ＮＣ−７０００−Ｌ：α−ナフトール／クレゾールノボラック型エポキシ樹脂（ナフタレン骨格含有型エポキシ樹脂）（日本化薬株式会社製、エポキシ当量：２３４ｇ／ｅｑ）
・ＮＣ−３０００−Ｈ：ビフェニルアラルキル型エポキシ樹脂（日本化薬株式会社製、エポキシ当量：２８８ｇ／ｅｑ）
［液状エポキシ樹脂］
・ｊＥＲ８２８ＵＳ：液状ビスフェノールＡ型エポキシ樹脂（三菱ケミカル株式会社製、エポキシ当量：１８４〜１９４ｇ／ｅｑ）
［エポキシ硬化剤］
・ＬＡ３０１８−５０Ｐ：トリアジン骨格含有クレゾールノボラック型硬化剤（ＤＩＣ株式会社製）
［（Ｂ）マレイミド化合物、（ｂ）マレイミド化合物］
・ＢＭＩ−４０００：２，２−ビス［４−（４−マレイミドフェノキシ）フェニル］プロパン（大和化成工業株式会社製）
［（Ｃ）アミン化合物、（ｃ）アミン化合物］
・Ｘ−２２−１６１Ａ：両末端ジアミン変性シロキサン（両末端に１級アミノ基を有するシロキサン化合物）（信越化学工業株式会社製、アミノ基当量：８００ｇ／ｅｑ）
［（Ｄ）エラストマー、（ｄ）エラストマー］
・ＳＧ−Ｐ３：エポキシ基含有アクリル系熱可撓性エラストマー（ナガセケムテックス株式会社製、重量平均分子量：８５０，０００、エポキシ価：０．２１ｅｑ／ｋｇ）
［（Ｅ）無機充填材、（ｅ）無機充填材］
・ＳＣ−２０５０ＫＣ：溶融シリカ（株式会社アドマテックス製、平均粒子径：０．５μｍ）
・ＳＯ−Ｃ２：球状シリカ（株式会社アドマテックス製、平均粒子径：０．５μｍ）
［（Ｆ）硬化促進剤、（ｆ）硬化促進剤］
・ＴＰＰ−Ｓ：トリフェニルホスフィントリフェニルボラン（北興化学株式会社製）
・ＤＭＡＰ：４−ジメチルアミノピリジン
In addition, the detail of each component shown in Table 2 and Table 3 is as follows.
[(A) Solid epoxy resin, (a) Epoxy resin]
NC-7000-L: α-naphthol / cresol novolac type epoxy resin (naphthalene skeleton-containing type epoxy resin) (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 234 g / eq)
NC-3000-H: biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 288 g / eq)
[Liquid epoxy resin]
JER828US: Liquid bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 184 to 194 g / eq)
[Epoxy curing agent]
LA3018-50P: Triazine skeleton-containing cresol novolac type curing agent (manufactured by DIC Corporation)
[(B) Maleimide compound, (b) Maleimide compound]
BMI-4000: 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (manufactured by Daiwa Kasei Kogyo Co., Ltd.)
[(C) amine compound, (c) amine compound]
X-22-161A: Both-end diamine-modified siloxane (siloxane compound having a primary amino group at both ends) (manufactured by Shin-Etsu Chemical Co., Ltd., amino group equivalent: 800 g / eq)
[(D) Elastomer, (d) Elastomer]
SG-P3: Epoxy group-containing acrylic heat-flexible elastomer (manufactured by Nagase ChemteX Corporation, weight average molecular weight: 850,000, epoxy value: 0.21 eq / kg)
[(E) inorganic filler, (e) inorganic filler]
SC-2050KC: fused silica (manufactured by Admatechs Co., Ltd., average particle size: 0.5 μm)
SO-C2: spherical silica (manufactured by Admatechs Co., Ltd., average particle size: 0.5 μm)
[(F) Curing accelerator, (f) Curing accelerator]
TPP-S: Triphenylphosphine triphenylborane (made by Hokuko Chemical Co., Ltd.)
DMAP: 4-dimethylaminopyridine
表２から、本実施形態の実施例１及び２の樹脂フィルムは、取り扱い性に優れ、耐デスミア性に優れることが分かる。一方、（Ａ）〜（Ｄ）成分の少なくとも１成分を使用しなかった比較例１〜３の樹脂フィルムは、取り扱い性又は耐デスミア性に劣っていた。 From Table 2, it can be seen that the resin films of Examples 1 and 2 of this embodiment are excellent in handleability and excellent in desmear resistance. On the other hand, the resin films of Comparative Examples 1 to 3 that did not use at least one of the components (A) to (D) were inferior in handleability or desmear resistance.
実施例３〜６、比較例４〜６
次に、上記で製造した樹脂フィルムＡ、Ｂ及びＥ並びにプリプレグI〜IIIを使用して、上記［ボイド数の測定］に記載の方法に従って積層体を製造し、ボイド数の評価を行った。評価結果を表４に示す。
Examples 3-6, Comparative Examples 4-6
Next, using the resin films A, B, and E produced above and prepregs I to III, a laminate was produced according to the method described in [Measurement of the number of voids], and the number of voids was evaluated. The evaluation results are shown in Table 4.
表４から、本実施形態の層間絶縁層用樹脂フィルムを使用した実施例３〜６の積層体は、ボイド数が少なく、コア層との濡れ性に優れていることが分かる。一方、本実施形態の層間絶縁層用樹脂フィルムとは異なる層間絶縁層用樹脂フィルムを使用した比較例４〜６の積層体は、ボイド数が多く、コア層との濡れ性に劣っていることが分かる。 From Table 4, it turns out that the laminated body of Examples 3-6 using the resin film for interlayer insulation layers of this embodiment has few void numbers, and is excellent in wettability with a core layer. On the other hand, the laminates of Comparative Examples 4 to 6 using the interlayer insulating layer resin film different from the interlayer insulating layer resin film of the present embodiment have a large number of voids and are inferior in wettability with the core layer. I understand.
Claims (17)
（Ｂ）１分子中に２個以上のＮ−置換マレイミド基を有するマレイミド化合物と、
（Ｃ）１分子中に２個以上の１級アミノ基を有するアミン化合物と、
（Ｄ）エラストマーと、
を含有する熱硬化性樹脂組成物を含有する、層間絶縁層用樹脂フィルム。 (A) a solid epoxy resin;
(B) a maleimide compound having two or more N-substituted maleimide groups in one molecule;
(C) an amine compound having two or more primary amino groups in one molecule;
(D) an elastomer;
A resin film for an interlayer insulating layer, comprising a thermosetting resin composition containing
（ａ）エポキシ樹脂と、
（ｂ）１分子中に２個以上のＮ−置換マレイミド基を有するマレイミド化合物と、
（ｃ）１分子中に２個以上の１級アミノ基を有するアミン化合物と、
を含有する熱硬化性樹脂組成物を含有するものである、請求項９に記載の層間絶縁層用樹脂フィルム。 The prepreg is
(A) an epoxy resin;
(B) a maleimide compound having two or more N-substituted maleimide groups in one molecule;
(C) an amine compound having two or more primary amino groups in one molecule;
The resin film for interlayer insulation layers of Claim 9 which contains the thermosetting resin composition containing this.
（ａ）エポキシ樹脂と、
（ｂ）１分子中に２個以上のＮ−置換マレイミド基を有するマレイミド化合物と、
（ｃ）１分子中に２個以上の１級アミノ基を有するアミン化合物と、
を含有する熱硬化性樹脂組成物を含有するものである、請求項１２に記載の積層体。 The prepreg is
(A) an epoxy resin;
(B) a maleimide compound having two or more N-substituted maleimide groups in one molecule;
(C) an amine compound having two or more primary amino groups in one molecule;
The laminated body of Claim 12 which contains the thermosetting resin composition containing this.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018080066A JP7124410B2 (en) | 2018-04-18 | 2018-04-18 | Resin film for interlayer insulating layer, laminate, printed wiring board, semiconductor device, and method for producing laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018080066A JP7124410B2 (en) | 2018-04-18 | 2018-04-18 | Resin film for interlayer insulating layer, laminate, printed wiring board, semiconductor device, and method for producing laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2019192343A true JP2019192343A (en) | 2019-10-31 |
| JP7124410B2 JP7124410B2 (en) | 2022-08-24 |
Family
ID=68390627
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2018080066A Active JP7124410B2 (en) | 2018-04-18 | 2018-04-18 | Resin film for interlayer insulating layer, laminate, printed wiring board, semiconductor device, and method for producing laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP7124410B2 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014084310A1 (en) * | 2012-11-28 | 2014-06-05 | 日立化成株式会社 | Amino-modified siloxane compound, modified imide resin, thermosetting resin composition, prepreg, resin-equipped film, laminated plate, multilayer printed circuit board, and semiconductor package |
-
2018
- 2018-04-18 JP JP2018080066A patent/JP7124410B2/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014084310A1 (en) * | 2012-11-28 | 2014-06-05 | 日立化成株式会社 | Amino-modified siloxane compound, modified imide resin, thermosetting resin composition, prepreg, resin-equipped film, laminated plate, multilayer printed circuit board, and semiconductor package |
Also Published As
| Publication number | Publication date |
|---|---|
| JP7124410B2 (en) | 2022-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101733646B1 (en) | Thermosetting resin composition, and prepreg, insulating film with support, laminate plate, and printed wiring board, each obtained using same | |
| JP5692201B2 (en) | Thermosetting resin composition, and prepreg, laminate and multilayer printed wiring board using the same | |
| JP6658721B2 (en) | Prepreg, laminate using the same, and printed wiring board | |
| JP7151834B2 (en) | Thermosetting resin compositions, prepregs, laminates, printed wiring boards, and high-speed communication modules | |
| JP2017132858A (en) | Thermosetting resin composition, prepreg, film with resin, laminate and multilayer printed board | |
| US10681807B2 (en) | Coreless substrate prepreg, coreless substrate, coreless substrate manufacturing method and semiconductor package | |
| JP5914988B2 (en) | Prepreg, laminate and printed wiring board using thermosetting resin composition | |
| JP6816551B2 (en) | Thermosetting resin composition for coreless substrates, prepregs for coreless substrates, coreless substrates, coreless substrate manufacturing methods and semiconductor packages | |
| JP7130922B2 (en) | Printed wiring boards, prepregs, laminates and semiconductor packages | |
| JP6844298B2 (en) | Manufacturing method of prepreg, laminated board, printed wiring board, coreless board, semiconductor package and coreless board | |
| JP6152246B2 (en) | Pre-preg for printed wiring board, laminated board and printed wiring board | |
| WO2018151287A1 (en) | Prepreg, laminate, printed wiring board, coreless substrate, semiconductor package and method for producing coreless substrate | |
| JP6040605B2 (en) | Thermosetting resin composition, prepreg, laminate and printed wiring board using the same | |
| JP7484422B2 (en) | Prepreg, laminate, metal-clad laminate and semiconductor package, and method for manufacturing laminate and metal-clad laminate | |
| JP6819062B2 (en) | Thermosetting resin composition, prepreg using it, film with resin, laminated board, printed wiring board and semiconductor package, and imide resin and its manufacturing method. | |
| JP7243077B2 (en) | Prepregs, cured prepregs, laminates, printed wiring boards and semiconductor packages | |
| JP2018182004A (en) | Method for manufacturing laminate board, method for manufacturing printed wiring board, and method for manufacturing semiconductor package | |
| JP7124410B2 (en) | Resin film for interlayer insulating layer, laminate, printed wiring board, semiconductor device, and method for producing laminate | |
| JP7176186B2 (en) | Thermosetting resin compositions, prepregs, laminates, printed wiring boards, and high-speed communication modules | |
| JP6164318B2 (en) | Pre-preg for printed wiring board, laminated board and printed wiring board | |
| JP2021011070A (en) | Metal foil with resin, coreless substrate, and semiconductor package |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20200907 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20210305 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20220125 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20220208 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20220411 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20220712 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20220725 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 7124410 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |