JP2022059975A - Resin composition, prepreg, laminate, multilayer printed wiring board, and semiconductor package - Google Patents
Resin composition, prepreg, laminate, multilayer printed wiring board, and semiconductor package Download PDFInfo
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- JP2022059975A JP2022059975A JP2020167916A JP2020167916A JP2022059975A JP 2022059975 A JP2022059975 A JP 2022059975A JP 2020167916 A JP2020167916 A JP 2020167916A JP 2020167916 A JP2020167916 A JP 2020167916A JP 2022059975 A JP2022059975 A JP 2022059975A
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- 239000011342 resin composition Substances 0.000 title claims abstract description 81
- 239000004065 semiconductor Substances 0.000 title claims abstract description 24
- -1 maleimide compound Chemical class 0.000 claims abstract description 142
- 150000001875 compounds Chemical class 0.000 claims abstract description 49
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 24
- 239000004642 Polyimide Substances 0.000 claims abstract description 21
- 229920001721 polyimide Polymers 0.000 claims abstract description 21
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 21
- 239000007870 radical polymerization initiator Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 21
- 239000000835 fiber Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 15
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 10
- 239000011888 foil Substances 0.000 claims description 7
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 238000006845 Michael addition reaction Methods 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 76
- 238000006243 chemical reaction Methods 0.000 description 28
- 125000001931 aliphatic group Chemical group 0.000 description 21
- 238000000034 method Methods 0.000 description 21
- 229920005989 resin Polymers 0.000 description 21
- 239000011347 resin Substances 0.000 description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 20
- 125000002947 alkylene group Chemical group 0.000 description 20
- 125000001118 alkylidene group Chemical group 0.000 description 16
- 239000003960 organic solvent Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 14
- 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 11
- 125000000217 alkyl group Chemical group 0.000 description 11
- 239000011256 inorganic filler Substances 0.000 description 11
- 229910003475 inorganic filler Inorganic materials 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000004020 conductor Substances 0.000 description 10
- 239000003063 flame retardant Substances 0.000 description 10
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 125000005843 halogen group Chemical group 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 229920002725 thermoplastic elastomer Polymers 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229930185605 Bisphenol Natural products 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 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
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 235000021317 phosphate Nutrition 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 5
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 125000001033 ether group Chemical group 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 5
- 125000000468 ketone group Chemical group 0.000 description 5
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 125000000962 organic group Chemical group 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 5
- 125000000101 thioether group Chemical group 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000000732 arylene group Chemical group 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 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 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- MFFNRVNPBJQZFO-UHFFFAOYSA-N (2,6-dimethylphenyl) dihydrogen phosphate Chemical compound CC1=CC=CC(C)=C1OP(O)(O)=O MFFNRVNPBJQZFO-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- KWOIWTRRPFHBSI-UHFFFAOYSA-N 4-[2-[3-[2-(4-aminophenyl)propan-2-yl]phenyl]propan-2-yl]aniline Chemical compound C=1C=CC(C(C)(C)C=2C=CC(N)=CC=2)=CC=1C(C)(C)C1=CC=C(N)C=C1 KWOIWTRRPFHBSI-UHFFFAOYSA-N 0.000 description 3
- HESXPOICBNWMPI-UHFFFAOYSA-N 4-[2-[4-[2-(4-aminophenyl)propan-2-yl]phenyl]propan-2-yl]aniline Chemical compound C=1C=C(C(C)(C)C=2C=CC(N)=CC=2)C=CC=1C(C)(C)C1=CC=C(N)C=C1 HESXPOICBNWMPI-UHFFFAOYSA-N 0.000 description 3
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000004450 alkenylene group Chemical group 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000004419 alkynylene group Chemical group 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000004414 alkyl thio group Chemical group 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
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 125000005110 aryl thio group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 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
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- IMYCVFRTNVMHAD-UHFFFAOYSA-N 1,1-bis(2-methylbutan-2-ylperoxy)cyclohexane Chemical compound CCC(C)(C)OOC1(OOC(C)(C)CC)CCCCC1 IMYCVFRTNVMHAD-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 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
- 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 1
- 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 1
- SEULWJSKCVACTH-UHFFFAOYSA-N 1-phenylimidazole Chemical compound C1=NC=CN1C1=CC=CC=C1 SEULWJSKCVACTH-UHFFFAOYSA-N 0.000 description 1
- WVGXBYVKFQJQGN-UHFFFAOYSA-N 1-tert-butylperoxy-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1OOC(C)(C)C WVGXBYVKFQJQGN-UHFFFAOYSA-N 0.000 description 1
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- UHIDYCYNRPVZCK-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C=C(O)C(N)=CC=1C(C)(C)C1=CC=C(O)C(N)=C1 UHIDYCYNRPVZCK-UHFFFAOYSA-N 0.000 description 1
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)phenol Chemical compound C1=C(O)C(N)=CC=C1C1=CC=C(N)C(O)=C1 ZGDMDBHLKNQPSD-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- YAQDPWONDFRAHF-UHFFFAOYSA-N 2-methyl-2-(2-methylpentan-2-ylperoxy)pentane Chemical compound CCCC(C)(C)OOC(C)(C)CCC YAQDPWONDFRAHF-UHFFFAOYSA-N 0.000 description 1
- HDCMRFUDMYGBFU-UHFFFAOYSA-N 2-methylbutan-2-yl 7-methyloctaneperoxoate Chemical compound CCC(C)(C)OOC(=O)CCCCCC(C)C HDCMRFUDMYGBFU-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Reinforced Plastic Materials (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
本発明は、樹脂組成物、プリプレグ、積層板、多層プリント配線板及び半導体パッケージに関する。 The present invention relates to resin compositions, prepregs, laminated boards, multilayer printed wiring boards and semiconductor packages.
近年、電子機器の小型化及び高性能化により、プリント配線板の配線密度の高度化及び高集積化が進展し、これに伴って、プリント配線板に対する信頼性向上の要求が強まっている。特に、半導体パッケージでは、小型化及び薄型化に伴い、部品実装時及びパッケージ組み立て時における反りの発生が大きな課題となっている。 In recent years, with the miniaturization and higher performance of electronic devices, the wiring density of printed wiring boards has become more sophisticated and highly integrated, and along with this, the demand for improving the reliability of printed wiring boards has increased. In particular, in a semiconductor package, the occurrence of warpage at the time of component mounting and package assembly has become a major problem with the miniaturization and thinning.
半導体パッケージが反る要因の1つとして、半導体素子と該半導体素子を搭載するプリント配線板との熱膨張率の差が挙げられる。一般的にプリント配線板の熱膨張率は、半導体素子の熱膨張率よりも大きいため、半導体素子を実装する際の加熱等の熱履歴を受けたパッケージには、上記熱膨張率差に起因する反り応力が発生する。そのため、半導体パッケージの反りを抑制する方法としては、プリント配線板の熱膨張率を小さくして半導体素子の熱膨張率との差を小さくすることが必要である。 One of the factors that cause the semiconductor package to warp is the difference in the coefficient of thermal expansion between the semiconductor element and the printed wiring board on which the semiconductor element is mounted. In general, the coefficient of thermal expansion of a printed wiring board is larger than the coefficient of thermal expansion of a semiconductor element. Warpage stress is generated. Therefore, as a method of suppressing the warp of the semiconductor package, it is necessary to reduce the coefficient of thermal expansion of the printed wiring board to reduce the difference from the coefficient of thermal expansion of the semiconductor element.
プリント配線板の熱膨張率を小さくする方法として、配線板用の樹脂組成物に、1分子構造中に少なくとも2個のアミノ基を有するシリコーン化合物を配合する方法が検討されている(例えば、特許文献1参照)。特許文献1の技術によると、耐熱性を損なうことなく熱膨張率を小さくすることができる。 As a method for reducing the coefficient of thermal expansion of a printed wiring board, a method of blending a silicone compound having at least two amino groups in a single molecular structure with a resin composition for a wiring board has been studied (for example, a patent). See Document 1). According to the technique of Patent Document 1, the coefficient of thermal expansion can be reduced without impairing the heat resistance.
ところで、携帯電話に代表される移動体通信機器、その基地局装置、サーバー、ルーター等のネットワークインフラ機器、大型コンピュータなどでは、使用する信号の高速化及び大容量化が年々進んでいる。これに伴い、これらの電子機器に搭載されるプリント配線板には高周波化対応が必要となり、伝送損失の低減を可能とする高周波数帯(例えば、10GHz以上)における誘電特性(低誘電率及び低誘電正接;以下、高周波特性と称することがある。)に優れる基板材料が求められている。
特許文献1に記載の樹脂組成物は、耐熱性及び低反りの両立という点に優れるものの、近年要求される高度な誘電特性という点においては改善の余地がある。
By the way, in mobile communication devices typified by mobile phones, their base station devices, servers, network infrastructure devices such as routers, large computers, etc., the speed and capacity of signals used are increasing year by year. Along with this, the printed wiring boards mounted on these electronic devices need to support high frequency, and the dielectric characteristics (low dielectric constant and low) in the high frequency band (for example, 10 GHz or more) that enables reduction of transmission loss. There is a demand for a substrate material having excellent dielectric loss tangent; hereinafter sometimes referred to as high frequency characteristics).
Although the resin composition described in Patent Document 1 is excellent in both heat resistance and low warpage, there is room for improvement in the high dielectric property required in recent years.
本発明は、このような現状に鑑み、10GHz帯以上の高周波数帯において優れた誘電特性を発現する樹脂組成物、該樹脂組成物を用いたプリプレグ、積層板、多層プリント配線板及び半導体パッケージを提供することを課題とする。 In view of this situation, the present invention provides a resin composition exhibiting excellent dielectric properties in a high frequency band of 10 GHz or higher, a prepreg using the resin composition, a laminated board, a multilayer printed wiring board, and a semiconductor package. The challenge is to provide.
本発明者らは、上記の課題を解決すべく鋭意研究した結果、下記の本発明によって、上記課題を解決できることを見出し、本発明を完成するに至った。
すなわち、本発明は、下記[1]~[11]に関するものである。
[1]N-置換マレイミド基を少なくとも2個有するマレイミド化合物(a1)由来の構造単位と第1級アミノ基を有するアミン化合物(a2)由来の構造単位とを含有するポリイミド化合物(A)と、
ラジカル重合性基を有するシリコーン化合物(B)と、
ラジカル重合開始剤(C)と、
を含有する、樹脂組成物。
[2]前記(B)成分が、前記ラジカル重合性基として、ビニル基、(メタ)アクリロイル基又はエポキシ基を、片末端又は両末端に有するシリコーン化合物である、上記[1]に記載の樹脂組成物。
[3]前記(B)成分が、前記ラジカル重合性基として、ビニル基又は(メタ)アクリロイル基を両末端に有するシリコーン化合物である、上記[1]又は[2]に記載の樹脂組成物。
[4]前記(B)成分の官能基当量が、300~3,000g/molである、上記[1]~[3]のいずれかに記載の樹脂組成物。
[5]前記第1級アミノ基を有するアミン化合物(a2)が、第1級アミノ基を少なくとも2個有するアミン化合物である、上記[1]~[4]のいずれかに記載の樹脂組成物。
[6]前記(A)成分が、前記N-置換マレイミド基を少なくとも2個有するマレイミド化合物(a1)と、前記第1級アミノ基を有するアミン化合物(a2)と、をマイケル付加反応させてなるものである、上記[1]~[5]のいずれかに記載の樹脂組成物。
[7]さらに、N-置換マレイミド基を少なくとも2個有するマレイミド化合物(A’)を含有する、上記[1]~[6]のいずれかに記載の樹脂組成物。
[8]上記[1]~[7]のいずれかに記載の樹脂組成物とシート状繊維補強基材とを含有してなるプリプレグ。
[9]上記[8]に記載のプリプレグと金属箔とを含有してなる積層板。
[10]上記[8]に記載のプリプレグ又は上記[9]に記載の積層板を含有してなる多層プリント配線板。
[11]上記[10]に記載の多層プリント配線板に半導体素子を搭載してなる半導体パッケージ。
As a result of diligent research to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by the following inventions, and have completed the present invention.
That is, the present invention relates to the following [1] to [11].
[1] A polyimide compound (A) containing a structural unit derived from a maleimide compound (a1) having at least two N-substituted maleimide groups and a structural unit derived from an amine compound (a2) having a primary amino group.
Silicone compound (B) having a radically polymerizable group and
Radical polymerization initiator (C) and
A resin composition containing.
[2] The resin according to the above [1], wherein the component (B) is a silicone compound having a vinyl group, a (meth) acryloyl group or an epoxy group as the radically polymerizable group at one end or both ends. Composition.
[3] The resin composition according to the above [1] or [2], wherein the component (B) is a silicone compound having a vinyl group or a (meth) acryloyl group at both ends as the radically polymerizable group.
[4] The resin composition according to any one of the above [1] to [3], wherein the functional group equivalent of the component (B) is 300 to 3,000 g / mol.
[5] The resin composition according to any one of the above [1] to [4], wherein the amine compound (a2) having a primary amino group is an amine compound having at least two primary amino groups. ..
[6] The component (A) comprises a Michael addition reaction between the maleimide compound (a1) having at least two N-substituted maleimide groups and the amine compound (a2) having the primary amino group. The resin composition according to any one of the above [1] to [5].
[7] The resin composition according to any one of the above [1] to [6], further containing a maleimide compound (A') having at least two N-substituted maleimide groups.
[8] A prepreg containing the resin composition according to any one of the above [1] to [7] and a sheet-shaped fiber reinforced base material.
[9] A laminated board containing the prepreg according to the above [8] and a metal foil.
[10] A multilayer printed wiring board comprising the prepreg according to the above [8] or the laminate according to the above [9].
[11] A semiconductor package in which a semiconductor element is mounted on the multilayer printed wiring board according to the above [10].
本発明によると、10GHz帯以上の高周波数帯において優れた誘電特性を発現する樹脂組成物、該樹脂組成物を用いたプリプレグ、積層板、多層プリント配線板及び半導体パッケージを提供することができる。 According to the present invention, it is possible to provide a resin composition that exhibits excellent dielectric properties in a high frequency band of 10 GHz or higher, a prepreg, a laminated board, a multilayer printed wiring board, and a semiconductor package using the resin composition.
本明細書において、「~」を用いて示された数値範囲は、「~」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。
本明細書中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。また、数値範囲の下限値及び上限値は、それぞれ他の数値範囲の下限値又は上限値と任意に組み合わせられる。
また、本明細書に例示する各成分及び材料は、特に断らない限り、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。本明細書において、組成物中の各成分の含有量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。
本明細書における記載事項を任意に組み合わせた態様も本発明に含まれる。
In the present specification, the numerical range indicated by using "-" indicates a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively.
In the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. Further, the lower limit value and the upper limit value of the numerical range are arbitrarily combined with the lower limit value or the upper limit value of another numerical range.
Further, as for each component and material exemplified in this specification, one kind may be used alone or two or more kinds may be used in combination unless otherwise specified. In the present specification, the content of each component in the composition is the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified. Means.
The present invention also includes aspects in which the items described in the present specification are arbitrarily combined.
[樹脂組成物]
本実施形態の樹脂組成物は、
N-置換マレイミド基を少なくとも2個有するマレイミド化合物(a1)由来の構造単位と第1級アミノ基を有するアミン化合物(a2)由来の構造単位とを含有するポリイミド化合物(A)[以下、「ポリイミド化合物(A)」又は「(A)成分」と略称することがある。]と、
ラジカル重合性基を有するシリコーン化合物(B)[以下、「シリコーン化合物(B)」又は「(B)成分」と略称することがある。]と、
ラジカル重合開始剤(C)[以下、「(C)成分」と略称することがある。]と、
を含有する、樹脂組成物である。
以下、本実施形態の樹脂組成物が含有する各成分について詳述する。
[Resin composition]
The resin composition of this embodiment is
A polyimide compound (A) containing a structural unit derived from a maleimide compound (a1) having at least two N-substituted maleimide groups and a structural unit derived from an amine compound (a2) having a primary amino group [hereinafter, "polyimide". It may be abbreviated as "compound (A)" or "component (A)". ]When,
Silicone compound (B) having a radically polymerizable group [hereinafter, may be abbreviated as "silicone compound (B)" or "component (B)". ]When,
Radical polymerization initiator (C) [hereinafter, may be abbreviated as "component (C)". ]When,
It is a resin composition containing.
Hereinafter, each component contained in the resin composition of the present embodiment will be described in detail.
<ポリイミド化合物(A)>
ポリイミド化合物(A)は、N-置換マレイミド基を少なくとも2個有するマレイミド化合物(a1)[以下、「マレイミド化合物(a1)」又は「(a1)成分」と略称することがある。]由来の構造単位と第1級アミノ基を有するアミン化合物(a2)[以下、「アミン化合物(a2)」又は「(a2)成分」と略称することがある。]由来の構造単位と、を有するポリイミド化合物(A)である。
本実施形態の樹脂組成物は、マレイミド化合物(A)を含有することで耐熱性に優れたものとなる。
ポリイミド化合物(A)は、N-置換マレイミド基を少なくとも2個有するマレイミド化合物(a1)と、第1級アミノ基を有するアミン化合物(a2)と、をマイケル付加反応させてなるものであることが好ましい。
ポリイミド化合物(A)は、1種類を単独で用いてもよいし、2種類以上を併用してもよい。
<Polyimide compound (A)>
The polyimide compound (A) may be abbreviated as a maleimide compound (a1) having at least two N-substituted maleimide groups [hereinafter, "maleimide compound (a1)" or "component (a1)". ] Derived structural unit and an amine compound (a2) having a primary amino group [hereinafter, may be abbreviated as "amine compound (a2)" or "(a2) component". ] Derived structural unit, is a polyimide compound (A) having.
The resin composition of the present embodiment has excellent heat resistance by containing the maleimide compound (A).
The polyimide compound (A) may be obtained by carrying out a Michael addition reaction between a maleimide compound (a1) having at least two N-substituted maleimide groups and an amine compound (a2) having a primary amino group. preferable.
As the polyimide compound (A), one type may be used alone, or two or more types may be used in combination.
(マレイミド化合物(a1))
マレイミド化合物(a1)としては、N-置換マレイミド基を2個以上有するマレイミド化合物であれば特に限定されないが、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]プロパン等の芳香族マレイミド化合物;1,6-ビスマレイミド-(2,2,4-トリメチル)ヘキサン、ピロリン酸バインダ型長鎖アルキルビスマレイミド等の脂肪族マレイミド化合物などが挙げられる。これらの中でも、導体との接着性及び機械特性の観点から、芳香族マレイミド化合物が好ましく、芳香族ビスマレイミド化合物がより好ましく、2,2-ビス[4-(4-マレイミドフェノキシ)フェニル]プロパンがさらに好ましい。
(Maleimide compound (a1))
The maleimide compound (a1) is not particularly limited as long as it is a maleimide compound having two or more N-substituted maleimide groups, but bis (4-maleimidephenyl) methane, polyphenylmethane maleimide, and bis (4-maleimidephenyl) ether. , Bis (4-maleimidephenyl) sulfone, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide , 2,2-Bis [4- (4-maleimidephenoxy) phenyl] Aromatic maleimide compounds such as propane; 1,6-bismaleimide- (2,2,4-trimethyl) hexane, Binder-type long-chain alkyl pyrophosphate Examples thereof include aliphatic maleimide compounds such as bismaleimide. Among these, aromatic maleimide compounds are preferable, aromatic bismaleimide compounds are more preferable, and 2,2-bis [4- (4-maleimidephenoxy) phenyl] propane is preferable from the viewpoint of adhesiveness to conductors and mechanical properties. More preferred.
マレイミド化合物(a1)としては、下記一般式(A1-1)で表される化合物が好ましい。 As the maleimide compound (a1), a compound represented by the following general formula (A1-1) is preferable.
(式中、Xa1は2価の有機基を示す。)
(In the formula, Xa1 represents a divalent organic group.)
上記一般式(A1-1)中のXa1が示す2価の有機基としては、下記一般式(A1-2)、(A1-3)、(A1-4)、(A1-5)又は(A1-6)で表される基が挙げられる。 Examples of the divalent organic group represented by Xa1 in the general formula (A1-1) include the following general formulas (A1-2), (A1-3), (A1-4), (A1-5) or ( Examples thereof include groups represented by A1-6).
(式中、Ra1は、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。na1は、0~4の整数を示す。*は結合部位を表す。)
(In the formula, R a1 represents an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms. n a1 represents an integer of 0 to 4. * Represents a bond site.)
Ra1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。該脂肪族炭化水素基としては、炭素数1~3の脂肪族炭化水素基が好ましく、メチル基がより好ましい。
na1は0~4の整数を示し、入手容易性の観点から、0~2の整数が好ましく、0であることがより好ましい。na1が2以上の整数である場合、複数のRa1同士は同一であっても異なっていてもよい。
Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms indicated by Ra1 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group and the like. Can be mentioned. As the aliphatic hydrocarbon group, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.
n a1 represents an integer of 0 to 4, and from the viewpoint of availability, an integer of 0 to 2 is preferable, and 0 is more preferable. When n a1 is an integer of 2 or more, a plurality of Ra1s may be the same or different from each other.
(式中、Ra2及びRa3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。Xa2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、エーテル基、スルフィド基、スルホニル基、カルボニルオキシ基、ケト基、単結合、又は下記一般式(A1-3-1)で表される2価の基を示す。na2及びna3は、各々独立に、0~4の整数を示す。*は結合部位を表す。)
(In the formula, R a2 and R a3 independently represent an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms. X a2 is an alkylene group having 1 to 5 carbon atoms and 2 to 5 carbon atoms. An alkylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a single bond, or a divalent group represented by the following general formula ( A1-3-1 ) is shown . , Each independently indicates an integer from 0 to 4. * Represents the binding site.)
Ra2及びRa3が示す炭素数1~5の脂肪族炭化水素基についての説明は、上記一般式(A1-2)中のRa1が示す炭素数1~5の脂肪族炭化水素基についての説明と同じである。
Xa2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。該アルキレン基としては、炭素数1~3のアルキレン基が好ましく、メチレン基がより好ましい。
Xa2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。該アルキリデン基としては、イソプロピリデン基が好ましい。
na2及びna3は、0~4の整数を示し、入手容易性の観点から、0~2の整数が好ましく、0又は2がより好ましい。na2又はna3が2以上の整数である場合、複数のRa2同士又は複数のRa3同士は、それぞれ同一であっても異なっていてもよい。
Xa2が示す一般式(A1-3-1)で表される2価の基は以下の通りである。
The description of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R a2 and Ra 3 describes the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R a1 in the above general formula (A1-2). Same as the description.
Examples of the alkylene group having 1 to 5 carbon atoms indicated by Xa2 include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group and the like. Be done. As the alkylene group, an alkylene group having 1 to 3 carbon atoms is preferable, and a methylene group is more preferable.
Examples of the alkylidene group having 2 to 5 carbon atoms indicated by Xa2 include an ethylidene group, a propyridene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group and an isopentylidene group. As the alkylidene group, an isopropylidene group is preferable.
n a2 and n a3 indicate an integer of 0 to 4, and from the viewpoint of availability, an integer of 0 to 2 is preferable, and 0 or 2 is more preferable. When n a2 or na 3 is an integer of 2 or more, the plurality of R a2s or the plurality of R a3s may be the same or different from each other.
The divalent group represented by the general formula (A1-3-1) represented by X a2 is as follows.
(式中、Ra4及びRa5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。Xa3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、エーテル基、スルフィド基、スルホニル基、カルボニルオキシ基、ケト基又は単結合を示す。na4及びna5は、各々独立に、0~4の整数を示す。*は結合部位を表す。)
(In the formula, R a4 and R a5 each independently represent an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms. X a3 is an alkylene group having 1 to 5 carbon atoms and 2 to 5 carbon atoms. It represents an alkylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond. N a4 and n a5 each independently represent an integer of 0 to 4. * Represents a bond site. )
Ra4及びRa5が示す炭素数1~5の脂肪族炭化水素基についての説明は、上記一般式(A1-2)中のRa1が示す炭素数1~5の脂肪族炭化水素基についての説明と同じである。
Xa3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、上記一般式(A1-3)中のXa2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る。
Xa3が示す基の中でも、高周波特性、導体との接着性、耐熱性、ガラス転移温度、熱膨張係数及び難燃性の観点から、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。
na4及びna5は0~4の整数を示し、入手容易性の観点から、0~2の整数が好ましく、0であることがより好ましい。na4又はna5が2以上の整数である場合、複数のRa4同士又は複数のRa5同士は、それぞれ同一であっても異なっていてもよい。
The description of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R a4 and R a5 describes the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R a1 in the above general formula (A1-2). Same as the description.
As the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X a3 , the alkylene group having 1 to 5 carbon atoms and 2 carbon atoms represented by X a2 in the above general formula (A1-3). The same as the alkylidene group of ~ 5 can be mentioned.
Among the groups indicated by Xa3 , an alkylidene group having 2 to 5 carbon atoms is preferable, and an isopropylidene group is preferable from the viewpoints of high frequency characteristics, adhesiveness to a conductor, heat resistance, glass transition temperature, coefficient of thermal expansion and flame retardancy. More preferred.
n a4 and n a5 indicate an integer of 0 to 4, and from the viewpoint of availability, an integer of 0 to 2 is preferable, and 0 is more preferable. When n a4 or n a5 is an integer of 2 or more, the plurality of R a4s or the plurality of R a5s may be the same or different from each other.
(式中、na6は、1~10の整数を示す。*は結合部位を表す。)
(In the formula, n a6 indicates an integer from 1 to 10. * Represents a binding site.)
na6は、入手容易性の観点から、1~5の整数が好ましく、1~3の整数がより好ましい。 From the viewpoint of availability, n a6 is preferably an integer of 1 to 5, and more preferably an integer of 1 to 3.
(式中、Ra6及びRa7は、各々独立に、水素原子又は炭素数1~5の脂肪族炭化水素基を示す。na7は、1~8の整数を示す。*は結合部位を表す。)
(In the formula, R a6 and R a7 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. n a7 represents an integer of 1 to 8; * represents a binding site. .)
Ra6及びRa7が示す炭素数1~5の脂肪族炭化水素基についての説明は、上記一般式(A1-2)中のRa1が示す炭素数1~5の脂肪族炭化水素基についての説明と同じである。
na7は1~8の整数を示し、1~3の整数が好ましく、1であることがより好ましい。
na7が2以上の整数である場合、複数のRa6同士又は複数のRa7同士は、それぞれ同一であっても異なっていてもよい。
The description of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R a6 and R a7 is about the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R a1 in the above general formula (A1-2). Same as the description.
n a7 indicates an integer of 1 to 8, preferably an integer of 1 to 3, and more preferably 1.
When n a7 is an integer of 2 or more, the plurality of R a6s or the plurality of R a7s may be the same or different from each other.
(式中、Ra8及びRa9は、各々独立に、炭素数1~10のアルキル基、炭素数1~10のアルキルオキシ基もしくは炭素数1~10のアルキルチオ基、炭素数6~10のアリール基、炭素数6~10のアリールオキシ基もしくは炭素数6~10のアリールチオ基、炭素数3~10のシクロアルキル基、ハロゲン原子、ニトロ基、水酸基又はメルカプト基を示す。na8及びna9は、各々独立に、0~4の整数を示す。na8又はna9が2~4の整数の場合、複数のRa8同士又は複数のRa9同士は、それぞれ同一であっても異なっていてもよい。Ra10及びRa11は、各々独立に、炭素数1~10のアルキル基、炭素数1~10のアルキルオキシ基もしくは炭素数1~10のアルキルチオ基、炭素数6~10のアリール基、炭素数6~10のアリールオキシ基もしくは炭素数6~10のアリールチオ基、炭素数3~10のシクロアルキル基、ハロゲン原子、水酸基又はメルカプト基を示す。na10及びna11は、各々独立に、0~3の整数を示す。na10又はna11が2又は3の場合、複数のRa10同士又は複数のRa11同士は、それぞれ同一であっても異なっていてもよい。na12は、0.95~10.0の数値を示す。*は結合部位を表す。)
(In the formula, R a8 and R a9 are independently an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms or an alkylthio group having 1 to 10 carbon atoms, and an aryl having 6 to 10 carbon atoms. A group, an aryloxy group having 6 to 10 carbon atoms or an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group or a mercapto group. , Each independently indicates an integer of 0 to 4. When n a8 or n a9 is an integer of 2 to 4, a plurality of R a8s or a plurality of R a9s may be the same or different from each other. R a10 and R a11 are independently an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms or an alkylthio group having 1 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms. It represents an aryloxy group having 6 to 10 carbon atoms or an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group. Indicates an integer from 0 to 3. When n a10 or na11 is 2 or 3, the plurality of R a10s or the plurality of R a11s may be the same or different, respectively. N a12 is 0. A numerical value from .95 to 10.0 is shown. * Indicates a binding site.)
上記一般式(A1-1)中のXa1としては、高周波特性の観点から、上記一般式(A1-3)、上記一般式(A1-5)又は上記一般式(A1-6)のいずれかで表される2価の基であることが好ましく、下記式(Xa1-1)~(Xa1-3)のいずれかで表される2価の基であることがより好ましく、下記式(Xa1-3)で表される2価の基であることがさらに好ましい。 The Xa1 in the general formula (A1-1) is any one of the general formula (A1-3), the general formula (A1-5), or the general formula (A1-6) from the viewpoint of high frequency characteristics. It is preferably a divalent group represented by, more preferably a divalent group represented by any of the following formulas (X a1-1) to (X a1 -3), and more preferably the following formula (X a1 -1). It is more preferably a divalent group represented by X a1 -3).
(*は結合部位を表す。)
(* Represents the binding site.)
(a1)成分由来の構造単位としては、例えば、下記一般式(A1-7)で表される基及び下記一般式(A1-8)で表される基からなる群から選択される1種以上が挙げられる。 As the structural unit derived from the component (a1), for example, one or more selected from the group consisting of a group represented by the following general formula (A1-7) and a group represented by the following general formula (A1-8). Can be mentioned.
(式中、Xa1は上記一般式(A1-1)中のXa1と同じであり、*は他の構造への結合位置を示す。)
(In the formula, X a1 is the same as X a1 in the above general formula (A1-1), and * indicates the bonding position to another structure.)
ポリイミド化合物(A)中における(a1)成分由来の構造単位の含有量は、特に限定されないが、60~99質量%が好ましく、70~95質量%がより好ましく、80~90質量%がさらに好ましい。(a1)成分由来の構造単位の含有量が上記範囲内であると、高周波特性がより良好となり、且つ、良好なフィルムハンドリング性が得られる傾向にある。 The content of the structural unit derived from the component (a1) in the polyimide compound (A) is not particularly limited, but is preferably 60 to 99% by mass, more preferably 70 to 95% by mass, still more preferably 80 to 90% by mass. .. (A1) When the content of the structural unit derived from the component is within the above range, the high frequency characteristics tend to be better and good film handling properties tend to be obtained.
(アミン化合物(a2))
アミン化合物(a2)は、第1級アミノ基を有するアミン化合物であり、第1級アミノ基を少なくとも2個有するアミン化合物が好ましく、第1級アミノ基を2個有するジアミン化合物がより好ましい。
アミン化合物(a2)としては、4,4’-ジアミノジフェニルメタン、4,4’-ジアミノ-3,3’-ジメチルジフェニルメタン、4,4’-ジアミノ-3,3’-ジエチルジフェニルメタン、4,4’-ジアミノジフェニルエーテル、4,4’-ジアミノジフェニルスルホン、3,3’-ジアミノジフェニルスルホン、4,4’-ジアミノジフェニルケトン、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、2,2’-ジメチル-4,4’-ジアミノビフェニル、3,3’-ジヒドロキシベンジジン、2,2-ビス(3-アミノ-4-ヒドロキシフェニル)プロパン、3,3’-ジメチル-5,5’-ジエチル-4,4’-ジアミノジフェニルメタン、2,2-ビス(4-アミノフェニル)プロパン、2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパン、1,3-ビス(3-アミノフェノキシ)ベンゼン、1,3-ビス(4-アミノフェノキシ)ベンゼン、1,4-ビス(4-アミノフェノキシ)ベンゼン、4,4’-ビス(4-アミノフェノキシ)ビフェニル、1,3-ビス〔1-[4-(4-アミノフェノキシ)フェニル]-1-メチルエチル〕ベンゼン、1,4-ビス〔1-[4-(4-アミノフェノキシ)フェニル]-1-メチルエチル〕ベンゼン、4,4’-[1,3-フェニレンビス(1-メチルエチリデン)]ビスアニリン、4,4’-[1,4-フェニレンビス(1-メチルエチリデン)]ビスアニリン、3,3’-[1,3-フェニレンビス(1-メチルエチリデン)]ビスアニリン、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、9,9-ビス(4-アミノフェニル)フルオレン等の芳香族ジアミン化合物;第1級アミノ基を有するアミン変性シロキサン化合物などが挙げられる。
(Amine compound (a2))
The amine compound (a2) is an amine compound having a primary amino group, preferably an amine compound having at least two primary amino groups, and more preferably a diamine compound having two primary amino groups.
Examples of the amine compound (a2) include 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'. -Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenylketone, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4' -Diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 3,3'-dimethyl -5,5'-diethyl-4,4'-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3 -Bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 1,3-bis [1- [4- (4-aminophenoxy) phenyl] -1-methylethyl] benzene, 1,4-bis [1- [4- (4-aminophenoxy) phenyl] -1-methyl] Ethyl] benzene, 4,4'-[1,3-phenylenebis (1-methylethylidene)] bisaniline, 4,4'-[1,4-phenylenebis (1-methylethylidene)] bisaniline, 3,3' -[1,3-Phenylenebis (1-methylethylidene)] bisaniline, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 9,9-bis Aromatic diamine compounds such as (4-aminophenyl) fluorene; amine-modified siloxane compounds having a primary amino group and the like can be mentioned.
これらの中でも、(a2)成分としては、有機溶媒への溶解性、(a1)成分との反応性、及び耐熱性に優れるという観点から、4,4’-ジアミノジフェニルメタン、4,4’-ジアミノ-3,3’-ジメチルジフェニルメタン、3,3’-ジエチル-4,4’-ジアミノジフェニルメタン、2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパン、4,4’-[1,3-フェニレンビス(1-メチルエチリデン)]ビスアニリン、及び4,4’-[1,4-フェニレンビス(1-メチルエチリデン)]ビスアニリンが好ましい。また、高周波特性及び低吸水性に優れるという観点からは、3,3’-ジエチル-4,4’-ジアミノジフェニルメタンが好ましい。また、導体との高接着性、伸び、破断強度等の機械特性に優れるという観点からは、2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパンが好ましい。さらに、有機溶媒への溶解性、合成時の反応性、耐熱性、導体との高接着性に優れることに加えて、高周波特性及び低吸湿性に優れるという観点からは、4,4’-[1,3-フェニレンビス(1-メチルエチリデン)]ビスアニリン、4,4’-[1,4-フェニレンビス(1-メチルエチリデン)]ビスアニリンが好ましい。また、低熱膨張性の観点からは、アミン変性シロキサン化合物が好ましい。 Among these, the component (a2) includes 4,4'-diaminodiphenylmethane and 4,4'-diamino from the viewpoint of excellent solubility in an organic solvent, reactivity with the component (a1), and heat resistance. -3,3'-dimethyldiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4'-[1, 3-Phenylenebis (1-methylethylidene)] bisaniline and 4,4'-[1,4-phenylenebis (1-methylethylidene)] bisaniline are preferred. Further, from the viewpoint of excellent high frequency characteristics and low water absorption, 3,3'-diethyl-4,4'-diaminodiphenylmethane is preferable. Further, from the viewpoint of excellent mechanical properties such as high adhesiveness to a conductor, elongation and breaking strength, 2,2-bis [4- (4-aminophenoxy) phenyl] propane is preferable. Furthermore, from the viewpoint of excellent high-frequency characteristics and low hygroscopicity, in addition to excellent solubility in organic solvents, reactivity during synthesis, heat resistance, and high adhesion to conductors, 4,4'-[ 1,3-phenylenebis (1-methylethylidene)] bisaniline and 4,4'-[1,4-phenylenebis (1-methylethylidene)] bisaniline are preferred. Further, from the viewpoint of low thermal expansion, an amine-modified siloxane compound is preferable.
アミン化合物(a2)としては、下記一般式(A2-1)で表される化合物が好ましい。 As the amine compound (a2), a compound represented by the following general formula (A2-1) is preferable.
(式中、Xa4は2価の有機基を示す。)
(In the formula, Xa4 represents a divalent organic group.)
(a2)成分は、上記一般式(A2-1)中のXa4が、下記一般式(A2-2)で表される2価の基である芳香族ジアミン化合物を含有することが好ましい。 The component (a2) preferably contains an aromatic diamine compound in which X a4 in the general formula (A2-1) is a divalent group represented by the following general formula (A2-2).
(式中、Ra12及びRa13は、各々独立に、炭素数1~5の脂肪族炭化水素基、炭素数1~5のアルコキシ基、水酸基又はハロゲン原子を示す。Xa5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、エーテル基、スルフィド基、スルホニル基、カルボニルオキシ基、ケト基、フルオレニレン基、単結合、又は下記一般式(A2-2-1)若しくは(A2-2-2)で表される2価の基を示す。na13及びna14は、各々独立に、0~4の整数を示す。*は結合部位を表す。)
(In the formula, R a12 and R a13 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group or a halogen atom. X a5 has 1 carbon atom. An alkylene group of ~ 5, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a fluorenylene group, a single bond, or the following general formula (A2-2-1) or ( A2-2-2) indicates a divalent group. N a13 and n a14 each independently indicate an integer of 0 to 4. * Represents a binding site.)
上記一般式(A2-2)中のRa12及びRa13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。
Xa5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。
Xa5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。
na13及びna14は、0~4の整数を示し、入手容易性の観点から、0又は1が好ましい。na13又はna14が2以上の整数である場合、複数のRa12同士又は複数のRa13同士は、それぞれ同一であっても異なっていてもよい。
上記一般式(A2-2)中のXa5が示す一般式(A2-2-1)で表される2価の基は以下の通りである。
Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by Ra 12 and Ra 13 in the above general formula (A2-2) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl group. Examples thereof include an isobutyl group, a t-butyl group and an n-pentyl group.
Examples of the alkylene group having 1 to 5 carbon atoms indicated by Xa5 include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group and the like. Be done.
Examples of the alkylidene group having 2 to 5 carbon atoms indicated by Xa5 include an ethylidene group, a propyridene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, and an isopentylidene group.
n a13 and na 14 represent an integer of 0 to 4, and 0 or 1 is preferable from the viewpoint of availability. When n a13 or na 14 is an integer of 2 or more, the plurality of Ra 12s or the plurality of Ra 13s may be the same or different from each other.
The divalent group represented by the general formula (A2-2-1) represented by Xa5 in the general formula (A2-2) is as follows.
(式中、Ra14及びRa15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。Xa6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、m-フェニレンジイソプロピリデン基、p-フェニレンジイソプロピリデン基、エーテル基、スルフィド基、スルホニル基、カルボニルオキシ基、ケト基又は単結合を示す。na15及びna16は、各々独立に、0~4の整数を示す。*は結合部位を表す。)
(In the formula, R a14 and R a15 each independently represent an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms. X a6 is an alkylene group having 1 to 5 carbon atoms and 2 to 5 carbon atoms. It represents an alkylidene group, an m- phenylenediisopropylidene group, a p-phenylenediisopropyridene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond. , Indicates an integer from 0 to 4. * Represents the binding site.)
上記一般式(A2-2-1)中のRa14及びRa15が示す炭素数1~5の脂肪族炭化水素基についての説明は、上記一般式(A2-2)中のRa12及びRa13が示す炭素数1~5の脂肪族炭化水素基についての説明と同じである。
Xa6が示す炭素数1~5のアルキレン基、炭素数2~5のアルキリデン基についての説明は、上記一般式(A2-2)中のXa5が示す炭素数1~5のアルキレン基、炭素数2~5のアルキリデン基についての説明と同じである。
na15及びna16は0~4の整数を示し、入手容易性の観点から、0~2の整数が好ましく、0であることがより好ましい。na15又はna16が2以上の整数である場合、複数のRa14同士又は複数のRa15同士は、それぞれ同一であっても異なっていてもよい。
上記一般式(A2-2)中のXa5が示す一般式(A2-2-2)で表される2価の基は以下の通りである。
The description of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by Ra 14 and Ra 15 in the general formula ( A2-2-1 ) is described in R a12 and R a13 in the general formula (A2-2). Is the same as the description of the aliphatic hydrocarbon group having 1 to 5 carbon atoms shown in.
The description of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X a6 describes the alkylene group having 1 to 5 carbon atoms represented by X a5 in the above general formula (A2-2) and carbon. It is the same as the description about the alkylidene group of the number 2-5.
n a15 and na 16 represent an integer of 0 to 4, and from the viewpoint of availability, an integer of 0 to 2 is preferable, and 0 is more preferable. When n a15 or na 16 is an integer of 2 or more, the plurality of R a14s or the plurality of R a15s may be the same or different from each other.
The divalent group represented by the general formula (A2-2-2) represented by Xa5 in the general formula (A2-2) is as follows.
(式中、Ra16は、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。Xa7及びXa8は、各々独立に、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、エーテル基、スルフィド基、スルホニル基、カルボニルオキシ基、ケト基又は単結合を示す。na17は、0~4の整数を示す。*は結合部位を表す。)
(In the formula, R a16 represents an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms. X a7 and X a8 are independently alkylene groups having 1 to 5 carbon atoms and 2 to 5 carbon atoms, respectively. Indicates an alkylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond. N a17 indicates an integer of 0 to 4. * Indicates a bond site.)
上記一般式(A2-2-2)中のRa16が示す炭素数1~5の脂肪族炭化水素基についての説明は、上記一般式(A2-2)中のRa12及びRa13が示す炭素数1~5の脂肪族炭化水素基についての説明と同じである。
Xa7及びXa8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、上記一般式(A2-2)中のXa5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例示される。これらの中でも、Xa7及びXa8としては、炭素数2~5のアルキリデン基であることが好ましく、イソプロピリデン基であることがより好ましい。
na17は0~4の整数を示し、入手容易性の観点から、0~2の整数が好ましく、0であることがより好ましい。na17が2以上の整数である場合、複数のRa16同士は同一であっても異なっていてもよい。
The description of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R a16 in the general formula ( A2-2-2 ) is the carbon represented by R a12 and R a13 in the general formula (A2-2). It is the same as the description about the aliphatic hydrocarbon group of the number 1-5.
Examples of the alkylene group having 1 to 5 carbon atoms represented by X a7 and X a8 and the alkylidene group having 2 to 5 carbon atoms include the alkylene group having 1 to 5 carbon atoms represented by X a5 in the above general formula (A2-2). The same as the alkylidene group having 2 to 5 carbon atoms is exemplified. Among these, X a7 and X a8 are preferably an alkylidene group having 2 to 5 carbon atoms, and more preferably an isopropylidene group.
n a17 represents an integer of 0 to 4, and from the viewpoint of availability, an integer of 0 to 2 is preferable, and 0 is more preferable. When n a17 is an integer of 2 or more, the plurality of Ra 16s may be the same or different from each other.
(a2)成分由来の構造単位としては、例えば、下記一般式(A2-3)で表される基及び下記一般式(A2-4)で表される基からなる群から選択される1種以上が挙げられる。 As the structural unit derived from the component (a2), for example, one or more selected from the group consisting of a group represented by the following general formula (A2-3) and a group represented by the following general formula (A2-4). Can be mentioned.
(式中、Xa4は上記一般式(A2-1)中のXa4と同じであり、*は他の構造への結合位置を示す。)
(In the formula, X a4 is the same as X a4 in the above general formula (A2-1), and * indicates the bonding position to another structure.)
ポリイミド化合物(A)中における(a2)成分由来の構造単位の含有量は、特に限定されないが、1~40質量%が好ましく、5~30質量%がより好ましく、10~20質量%がさらに好ましい。(a2)成分由来の構造単位の含有量が上記範囲内であると、高周波特性に優れ、且つより良好な耐熱性、難燃性及びガラス転移温度が得られる傾向にある。 The content of the structural unit derived from the component (a2) in the polyimide compound (A) is not particularly limited, but is preferably 1 to 40% by mass, more preferably 5 to 30% by mass, still more preferably 10 to 20% by mass. .. (A2) When the content of the structural unit derived from the component is within the above range, there is a tendency that excellent high frequency characteristics and better heat resistance, flame retardancy and glass transition temperature can be obtained.
ポリイミド化合物(A)中における(a1)成分由来の構造単位と、(a2)成分由来の構造単位の合計含有量は、特に限定されないが、80質量%以上が好ましく、90質量%以上がより好ましく、95質量%以上がさらに好ましく、100質量%(すなわち、(a1)成分由来の構造単位及び(a2)成分由来の構造単位のみからなるもの)であることが特に好ましい。 The total content of the structural unit derived from the component (a1) and the structural unit derived from the component (a2) in the polyimide compound (A) is not particularly limited, but is preferably 80% by mass or more, more preferably 90% by mass or more. , 95% by mass or more, more preferably 100% by mass (that is, one consisting only of the structural unit derived from the component (a1) and the structural unit derived from the component (a2)).
ポリイミド化合物(A)中における(a1)成分由来の構造単位と、(a2)成分由来の構造単位との含有比率は、特に限定されないが、(a2)成分の-NH2基由来の基(-NH2も含む)の合計モル当量(Ta2)に対する、(a1)成分に由来するマレイミド基由来の基(マレイミド基も含む)の合計モル当量(Ta1)のモル当量比(Ta1/Ta2)が、好ましくは0.05~20、より好ましくは1~10、さらに好ましくは2~8となる含有比率である。モル当量比(Ta1/Ta2)が上記範囲内であると、高周波特性に優れ、且つより良好な耐熱性、難燃性及びガラス転移温度が得られる傾向にある。 The content ratio of the structural unit derived from the component (a1) and the structural unit derived from the component (a2) in the polyimide compound (A) is not particularly limited, but the group derived from the -NH 2 group of the component (a2) (-). The molar equivalent ratio (Ta1 / Ta2) of the total molar equivalent (Ta1) of the maleimide group-derived group (including the maleimide group) derived from the component (a1) to the total molar equivalent (Ta2) of (including NH 2 ) is The content ratio is preferably 0.05 to 20, more preferably 1 to 10, and even more preferably 2 to 8. When the molar equivalent ratio (Ta1 / Ta2) is within the above range, there is a tendency that excellent high frequency characteristics and better heat resistance, flame retardancy and glass transition temperature can be obtained.
ポリイミド化合物(A)は、高周波特性、有機溶媒への溶解性、導体との高接着性、成形性等の観点から、(a1)成分が有するマレイミド基と(a2)成分が有する第1級アミノ基とが付加反応してなる、下記式(A-1)で表される構造を含む化合物であることが好ましい。 The polyimide compound (A) has a maleimide group contained in the component (a1) and a primary amino contained in the component (a2) from the viewpoints of high frequency characteristics, solubility in an organic solvent, high adhesion to a conductor, moldability, and the like. It is preferable that the compound contains a structure represented by the following formula (A-1), which is formed by an addition reaction with a group.
(*は他の構造への結合位置を示す。)
(* Indicates the position of connection to other structures.)
ポリイミド化合物(A)は、高周波特性、有機溶媒への溶解性、導体との高接着性、成形性等の観点から、下記一般式(A-2)で表される化合物を含有することが好ましい。 The polyimide compound (A) preferably contains a compound represented by the following general formula (A-2) from the viewpoints of high frequency characteristics, solubility in an organic solvent, high adhesiveness to a conductor, moldability, and the like. ..
(式中、Xa1及びXa4は、上記一般式(A1-1)及び(A2-1)における説明の通りである。)
(In the formula, X a1 and X a4 are as described in the above general formulas (A1-1) and (A2-1).)
(ポリイミド化合物(A)の製造方法)
(A)成分は、例えば、(a1)成分と(a2)成分とを有機溶媒中で反応させることで製造することができる。
具体的には、(a1)成分、(a2)成分、必要によりその他の成分を合成釜に所定量仕込み、(a1)成分と(a2)成分とをマイケル付加反応[以下、「プレ反応」と略称することがある。]を行うことにより、ポリイミド化合物(A)が得られる。
反応に供する(a1)成分と(a2)成分の使用量比としては、(a2)成分の-NH2基の合計モル当量(Ta2)に対する、(a1)成分に由来するマレイミド基の合計モル当量(Ta1)のモル当量比(Ta1/Ta2)が、好ましくは0.05~20、より好ましくは1~10、さらに好ましくは2~8となる含有比率である。当量比(Ta1/Ta2)が上記範囲内であると、高周波特性に優れ、且つより良好な耐熱性、難燃性及びガラス転移温度が得られる傾向にある。
プレ反応における反応条件は特に限定されないが、ゲル化を抑制しつつ、良好な反応性及び作業性が得られるという観点からは、反応温度は50~160℃、反応時間は1~10時間が好ましい。
(Manufacturing method of polyimide compound (A))
The component (A) can be produced, for example, by reacting the component (a1) and the component (a2) in an organic solvent.
Specifically, (a1) component, (a2) component, and if necessary, other components are charged in a predetermined amount, and the (a1) component and the (a2) component are subjected to a Michael addition reaction [hereinafter referred to as "pre-reaction". May be abbreviated. ], The polyimide compound (A) can be obtained.
The ratio of the amount of the component (a1) to the component (a2) used in the reaction is the total molar equivalent of the maleimide group derived from the component (a1) to the total molar equivalent of -NH 2 of the component (a2) (Ta2). The molar equivalent ratio (Ta1 / Ta2) of (Ta1) is preferably 0.05 to 20, more preferably 1 to 10, and even more preferably 2 to 8. When the equivalent ratio (Ta1 / Ta2) is within the above range, there is a tendency that excellent high frequency characteristics and better heat resistance, flame retardancy and glass transition temperature can be obtained.
The reaction conditions in the pre-reaction are not particularly limited, but the reaction temperature is preferably 50 to 160 ° C. and the reaction time is preferably 1 to 10 hours from the viewpoint of obtaining good reactivity and workability while suppressing gelation. ..
プレ反応では、必要に応じて触媒を使用してもよい。触媒としては、p-トルエンスルホン酸等の酸性触媒;トリエチルアミン、ピリジン、トリブチルアミン等のアミン類;メチルイミダゾール、フェニルイミダゾール等のイミダゾール類;トリフェニルホスフィン等のリン系触媒などが挙げられる。これらは1種類を単独で用いてもよいし、2種類以上を併用してもよい。また、触媒の配合量に特に制限はないが、(a1)成分及び(a2)成分の合計量100質量部に対して、例えば、0.01~5質量部である。 In the pre-reaction, a catalyst may be used if necessary. Examples of the catalyst include acidic catalysts such as p-toluenesulfonic acid; amines such as triethylamine, pyridine and tributylamine; imidazoles such as methylimidazole and phenylimidazole; and phosphorus-based catalysts such as triphenylphosphine. One of these may be used alone, or two or more thereof may be used in combination. The amount of the catalyst blended is not particularly limited, but is, for example, 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of the component (a1) and the component (a2).
また、プレ反応では、必要に応じて有機溶媒を追加又は濃縮して反応原料の固形分濃度及び溶液粘度を調整してもよい。反応原料の固形分濃度は、特に限定されないが、10~90質量%が好ましく、20~80質量%がより好ましい。反応原料の固形分濃度が上記下限値以上であると、十分な反応速度が得られ、製造コストの面で有利となる傾向にあり、上記上限値以下であると、より良好な溶解性が得られ、撹拌効率が良くなり、ゲル化し難くなる傾向にある。 Further, in the pre-reaction, an organic solvent may be added or concentrated as necessary to adjust the solid content concentration and the solution viscosity of the reaction raw material. The solid content concentration of the reaction raw material is not particularly limited, but is preferably 10 to 90% by mass, more preferably 20 to 80% by mass. When the solid content concentration of the reaction raw material is at least the above lower limit value, a sufficient reaction rate can be obtained, which tends to be advantageous in terms of production cost, and when it is at least the above upper limit value, better solubility can be obtained. Therefore, the stirring efficiency is improved and gelation tends to be difficult.
プレ反応では、(a1)成分の一部が未反応のまま残存していてもよい。その場合、プレ反応によって、(A)成分と未反応(a1)成分との混合物が得られることになり、本実施形態の樹脂組成物は、この(A)成分と未反応(a1)成分との混合物を含有することが好ましい。 In the pre-reaction, a part of the component (a1) may remain unreacted. In that case, a mixture of the component (A) and the unreacted component (a1) is obtained by the pre-reaction, and the resin composition of the present embodiment contains the component (A) and the unreacted component (a1). It is preferable to contain a mixture of.
プレ反応の反応率は、10~80%が好ましく、20~50%がより好ましく、25~38%がさらに好ましい。なお、プレ反応の反応率は、実施例に記載の方法によって求めることができる。なお、プレ反応の反応率とは、仕込み原料成分の全量のうち、反応した原料成分の量の割合を意味し、実施例に記載の方法によって求めることができる。 The reaction rate of the pre-reaction is preferably 10 to 80%, more preferably 20 to 50%, still more preferably 25 to 38%. The reaction rate of the pre-reaction can be determined by the method described in Examples. The reaction rate of the pre-reaction means the ratio of the amount of the reacted raw material component to the total amount of the charged raw material component, and can be obtained by the method described in Examples.
ポリイミド化合物(A)の重量平均分子量(Mw)は、特に限定されないが、400~10,000が好ましく、1,000~5,000がより好ましく、1,500~4,000がさらに好ましく、2,000~3,000が特に好ましい。
なお、本明細書において、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)により、標準ポリスチレンを用いた検量線から換算した値である。具体的には、検量線は、標準ポリスチレン:TSKstandard POLYSTYRENE(Type;A-2500、A-5000、F-1、F-2、F-4、F-10、F-20、F-40)[東ソー株式会社製、商品名]を用いて3次式で近似し、GPCは実施例に記載の方法により測定することができる。
The weight average molecular weight (Mw) of the polyimide compound (A) is not particularly limited, but is preferably 400 to 10,000, more preferably 1,000 to 5,000, still more preferably 1,500 to 4,000, and 2 3,000 to 3,000 are particularly preferable.
In the present specification, the weight average molecular weight is a value converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). Specifically, the calibration curve is standard polystyrene: TSK standard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [ Approximate with a cubic equation using Tosoh Corporation, trade name], and GPC can be measured by the method described in the examples.
本実施形態の樹脂組成物は、(A)成分の他に、N-置換マレイミド基を少なくとも2個有するマレイミド化合物(A’)[以下、「マレイミド化合物(A’)」と称する場合がある。]を含有していてもよい。マレイミド化合物(A’)は、上記したプレ反応において未反応のまま残存したマレイミド化合物(a1)であってもよいし、別に配合したものであってもよい。なお、本実施形態の樹脂組成物中の(A)成分に含まれる(a1)成分に由来する構造単位とマレイミド化合物(A’)の総量を「マレイミド化合物及びマレイミド化合物に由来する構造単位の総量」と称する場合がある。以下の説明において、「マレイミド化合物及びマレイミド化合物に由来する構造単位の総量」は、マレイミド化合物(A’)を含有しない場合においては「マレイミド化合物に由来する構造単位の総量」を意味する。 The resin composition of the present embodiment may be referred to as a maleimide compound (A') having at least two N-substituted maleimide groups in addition to the component (A) [hereinafter, referred to as "maleimide compound (A')". ] May be contained. The maleimide compound (A') may be the maleimide compound (a1) that remains unreacted in the above-mentioned prereaction, or may be separately compounded. In addition, the total amount of the structural unit derived from the component (a1) and the maleimide compound (A') contained in the component (A) in the resin composition of the present embodiment is referred to as "the total amount of the structural units derived from the maleimide compound and the maleimide compound". May be called. In the following description, "the total amount of the maleimide compound and the structural unit derived from the maleimide compound" means "the total amount of the structural unit derived from the maleimide compound" when the maleimide compound (A') is not contained.
本実施形態の樹脂組成物中における(A)成分の含有量は、特に限定されないが、高周波特性、耐熱性及び成形性の観点から、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、30~65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、樹脂組成物を構成する固形分のうち、無機充填材等の無機化合物、難燃剤及び難燃助剤を除く、すべての成分と定義する。
また、本実施形態における固形分とは、水分、後述する溶媒等の揮発する物質以外の樹脂組成物中の成分のことをいう。すなわち、固形分は、25℃付近の室温で液状、水飴状又はワックス状のものも含み、必ずしも固体であることを意味するものではない。
The content of the component (A) in the resin composition of the present embodiment is not particularly limited, but from the viewpoint of high frequency characteristics, heat resistance and moldability, 5 to 80 mass by mass with respect to 100 parts by mass of the total resin component. Parts are preferable, 10 to 70 parts by mass are more preferable, and 30 to 65 parts by mass are further preferable.
In the present embodiment, the "resin component" is defined as all components other than inorganic compounds such as inorganic fillers, flame retardants and flame retardant aids among the solid contents constituting the resin composition.
Further, the solid content in the present embodiment means a component in the resin composition other than a volatile substance such as water and a solvent described later. That is, the solid content includes liquid, starch syrup-like or wax-like substances at room temperature around 25 ° C., and does not necessarily mean that the solid content is solid.
本実施形態の樹脂組成物中におけるマレイミド化合物及びマレイミド化合物に由来する構造単位の総量は、特に限定されないが、高周波特性、耐熱性及び成形性の観点から、樹脂成分の総和100質量部に対して、20~95質量部が好ましく、50~92質量部がより好ましく、80~90質量部がさらに好ましい。 The total amount of the maleimide compound and the structural unit derived from the maleimide compound in the resin composition of the present embodiment is not particularly limited, but from the viewpoint of high frequency characteristics, heat resistance and moldability, the total amount of the resin components is 100 parts by mass. , 20 to 95 parts by mass, more preferably 50 to 92 parts by mass, and even more preferably 80 to 90 parts by mass.
<ラジカル重合性基を有するシリコーン化合物(B)>
シリコーン化合物(B)は、低熱膨張性に寄与するシリコーン骨格を有しながらも、極性が低いラジカル重合性基を有するものであるため、(B)成分を含有する本実施形態の樹脂組成物は、低熱膨張性と優れた誘電特性とを両立するものになる。
<Silicone compound (B) having a radically polymerizable group>
Since the silicone compound (B) has a radically polymerizable group having a low polarity while having a silicone skeleton that contributes to low thermal expansion, the resin composition of the present embodiment containing the component (B) is , Both low thermal expansion and excellent dielectric properties are achieved.
シリコーン化合物(B)が有するラジカル重合性基としては、ビニル基、アリル基、プロパルギル基、ブテニル基、エチニル基、フェニルエチニル基、マレイミド基、ナジイミド基、(メタ)アクリロイル基等の、エチレン性不飽和結合含有基;エポキシ基などが挙げられる。なお、「エチレン性不飽和結合」とは、付加反応が可能な炭素-炭素二重結合を意味し、芳香環の二重結合は含まないものとする。これらの中でも、誘電特性の観点から、ビニル基、(メタ)アクリロイル基、エポキシ基が好ましく、ビニル基、(メタ)アクリロイル基がより好ましい。なお、(メタ)アクリロイル基は、(メタ)アクリロイルオキシ基に含まれるものであってもよく、その場合は、シリコーン化合物(B)は、ラジカル重合性基として、(メタ)アクリロイルオキシ基を有するものであるとも言える。
また、本明細書において、(メタ)アクリロイル基とは、アクリロイル基及びメタクリロイル基の双方を意味し、(メタ)アクリロイルオキシ基とは、アクリロイルオキシ基及びメタクリロイルオキシ基の双方を意味するものである。
Examples of the radically polymerizable group of the silicone compound (B) include a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadiimide group, and a (meth) acryloyl group. Saturated bond-containing group; epoxy group and the like can be mentioned. The "ethylenically unsaturated bond" means a carbon-carbon double bond capable of an addition reaction, and does not include a double bond of an aromatic ring. Among these, a vinyl group, a (meth) acryloyl group, and an epoxy group are preferable, and a vinyl group and a (meth) acryloyl group are more preferable, from the viewpoint of dielectric properties. The (meth) acryloyl group may be contained in the (meth) acryloyloxy group, in which case the silicone compound (B) has a (meth) acryloyloxy group as a radically polymerizable group. It can be said that it is a thing.
Further, in the present specification, the (meth) acryloyl group means both an acryloyl group and a methacryloyl group, and the (meth) acryloyloxy group means both an acryloyloxy group and a methacryloyloxy group. ..
シリコーン化合物(B)が1分子中に有するラジカル重合性基の数としては、誘電特性及び熱膨張係数の観点から、1以上が好ましく、2~4がより好ましく、2~3がさらに好ましい。
シリコーン化合物(B)は、ラジカル重合性基を末端に有していてもよく、側鎖に有していてもよいが、誘電特性及び反応性の観点から、末端に有することが好ましく、両末端に有することがより好ましく、両末端のみに有することがさらに好ましい。
同様の観点から、シリコーン化合物(B)としては、ラジカル重合性基として、ビニル基、(メタ)アクリロイル基又はエポキシ基を、片末端又は両末端に有するシリコーン化合物が好ましく、ラジカル重合性基として、ビニル基又は(メタ)アクリロイル基を両末端に有するシリコーン化合物がより好ましい。
The number of radically polymerizable groups contained in one molecule of the silicone compound (B) is preferably 1 or more, more preferably 2 to 4, and even more preferably 2 to 3 from the viewpoint of dielectric properties and the coefficient of thermal expansion.
The silicone compound (B) may have a radically polymerizable group at the end or a side chain, but it is preferable to have it at the end from the viewpoint of dielectric properties and reactivity, and both ends are preferable. It is more preferable to have it at both ends, and it is further preferable to have it only at both ends.
From the same viewpoint, the silicone compound (B) is preferably a silicone compound having a vinyl group, a (meth) acryloyl group or an epoxy group at one end or both ends as the radically polymerizable group, and the radically polymerizable group is preferably used. Silicone compounds having vinyl or (meth) acryloyl groups at both ends are more preferred.
シリコーン化合物(B)は、下記一般式(B-1)で表される構造単位を含有するものが好ましく、下記一般式(B-2)で表されるものがより好ましい。 The silicone compound (B) preferably contains a structural unit represented by the following general formula (B-1), and more preferably one represented by the following general formula (B-2).
(式中、Rb1及びRb2は、各々独立に、炭素数1~5のアルキル基、フェニル基又は置換フェニル基を表す。)
(In the formula, R b1 and R b2 each independently represent an alkyl group, a phenyl group, or a substituted phenyl group having 1 to 5 carbon atoms.)
(式中、Rb1及びRb2は、上記一般式(B-1)中のものと同じであり、Rb3及びRb4は、各々独立に、炭素数1~5のアルキル基、フェニル基又は置換フェニル基を示す。Xb1及びXb2は、各々独立に、2価の有機基を示し、nb1は、2~100の整数を示す。Yb1及びYb2は、各々独立に、ラジカル重合性基を示す。)
(In the formula, R b1 and R b2 are the same as those in the above general formula (B-1), and R b3 and R b4 are each independently an alkyl group having 1 to 5 carbon atoms, a phenyl group or a group. X b1 and X b2 each independently represent a divalent organic group, n b1 represents an integer of 2 to 100; Y b1 and Y b2 each independently radically polymerize. Indicates a sex group.)
上記一般式(B-1)及び(B-2)中のRb1~Rb4が示す炭素数1~5のアルキル基としては、メチル基、エチル基、n-プロピル基、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1~3のアルキル基が好ましく、メチル基がより好ましい。
Rb1~Rb4が示す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。該炭素数1~5のアルキル基としては、メチル基、エチル基、n-プロピル基、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。該炭素数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。
Xb1及びXb2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。該アルキレン基としては、メチレン基、エチレン基、プロピレン基等の炭素数1~10のアルキレン基が挙げられる。該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。該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。該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、Xb1及びXb2としては、アルキレン基、アリーレン基が好ましく、アルキレン基がより好ましい。
nb1は2~100の整数を示し、2~50の整数が好ましく、3~40の整数がより好ましく、5~30の整数がさらに好ましい。nb1が2以上の整数である場合、複数のRb1同士又は複数のRb2同士は、それぞれ同一であっても異なっていてもよい。
Yb1及びYb2が示すラジカル重合性基としては、上記で説明した通りである。
Examples of the alkyl group having 1 to 5 carbon atoms represented by R b1 to R b4 in the general formulas (B-1) and (B-2) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-. Examples thereof include a butyl group, an isobutyl group, a t-butyl group, an n-pentyl group and the like. As the alkyl group, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.
Examples of the substituent having the phenyl group in the substituted phenyl group represented by R b1 to R b4 include an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms and the like. .. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group and an n-pentyl group. 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.
Examples of the divalent organic group indicated by X b1 and X b2 include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, —O— or a divalent linking group in which these are combined. Examples of the alkylene group include an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group and a propylene group. Examples of the alkenylene group include an alkenylene group having 2 to 10 carbon atoms. Examples of the alkynylene group include an alkynylene group having 2 to 10 carbon atoms. Examples of the arylene group include an arylene group having 6 to 20 carbon atoms such as a phenylene group and a naphthylene group.
Among these, as X b1 and X b2 , an alkylene group and an arylene group are preferable, and an alkylene group is more preferable.
n b1 indicates an integer of 2 to 100, preferably an integer of 2 to 50, more preferably an integer of 3 to 40, and even more preferably an integer of 5 to 30. When n b1 is an integer of 2 or more, the plurality of R b1s or the plurality of R b2s may be the same or different from each other.
The radically polymerizable groups indicated by Y b1 and Y b2 are as described above.
シリコーン化合物(B)の官能基当量は、特に限定されないが、誘電特性及び熱膨張係数の観点から、300~3,000g/molが好ましく、400~2,000g/molがより好ましく、600~1,000g/molがさらに好ましい。 The functional group equivalent of the silicone compound (B) is not particularly limited, but is preferably 300 to 3,000 g / mol, more preferably 400 to 2,000 g / mol, and 600 to 1 from the viewpoint of dielectric properties and a coefficient of thermal expansion. 000 g / mol is more preferable.
(シリコーン化合物(B)の含有量)
本実施形態の樹脂組成物中におけるシリコーン化合物(B)の含有量は、特に限定されないが、誘電特性及び熱膨張係数の観点から、マレイミド化合物及びマレイミド化合物に由来する構造単位の総量100質量部に対して、1~20質量部が好ましく、3~15質量部がより好ましく、4~10質量部がさらに好ましい。
(Content of Silicone Compound (B))
The content of the silicone compound (B) in the resin composition of the present embodiment is not particularly limited, but from the viewpoint of the dielectric property and the coefficient of thermal expansion, the total amount of the maleimide compound and the structural unit derived from the maleimide compound is 100 parts by mass. On the other hand, 1 to 20 parts by mass is preferable, 3 to 15 parts by mass is more preferable, and 4 to 10 parts by mass is further preferable.
<ラジカル重合開始剤(C)>
ラジカル重合開始剤(C)は、ラジカル重合の重合開始剤として作用するものであり、光、熱等のエネルギーに暴露されたときに、不対電子を有するものに分解するものである。
(C)成分は、1種類を単独で用いてもよく、2種類以上を併用してもよい。
<Radical polymerization initiator (C)>
The radical polymerization initiator (C) acts as a polymerization initiator for radical polymerization, and decomposes into an unpaired electron when exposed to energy such as light or heat.
As the component (C), one type may be used alone, or two or more types may be used in combination.
ラジカル重合開始剤(C)としては、1,1-ジ(t-ブチルパーオキシ)シクロヘキサン、2,2-ジ(t-ブチルパーオキシ)ブタン、2,2-ジ(4,4-ジ-t-ブチルパーオキシシクロヘキシル)プロパン、1,1-ジ(t-アミルパーオキシ)シクロヘキサン等のパーオキシケタール類;クメンハイドロパーオキサイド、t-ブチルハイドロパーオキサイド等のハイドロパーオキサイド類;t-ブチルパーオキシアセテート、t-アミルパーオキシイソノナノエート等のアルキルパーオキサイド類;t-ブチルクミルパーオキサイド、ジ-t-ブチルパーオキサイド、ジクミルパーオキサイド、ジ-t-ヘキシルパーオキサイド、1,3-ビス(2-t-ブチルパーオキシイソプロピル)ベンゼン、2,5-ジメチル-2,5-ビス(t-ブチルパーオキシ)ヘキシン-3等のジアルキルパーオキサイド類;t-ブチルパーオキシアセテート、t-ブチルパーオキシベンゾエート、t-ブチルパーオキシイソプロピルモノカーボネート等のパーオキシエステル類;t-ブチルパーオキシイソプロピルカーボネート、ポリエーテルテトラキス(t-ブチルパーオキシカーボネート)等のパーオキシカーボネート類;ジベンゾイルパーオキサイド等のジアシルパーオキサイド類などの有機過酸化物;2,2’-アゾビスイソブチロニトリル、2,2’-アゾビス(2,4-ジメチルバレロニトリル)、2,2’-アゾビス(4-メトキシ-2’-ジメチルバレロニトリル)等のアゾ化合物などが挙げられる。 Examples of the radical polymerization initiator (C) include 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (t-butylperoxy) butane, and 2,2-di (4,4-di-). Peroxyketals such as t-butylperoxycyclohexyl) propane, 1,1-di (t-amylperoxy) cyclohexane; hydroperoxides such as cumenehydroperoxide, t-butylhydroperoxide; t-butyl Alkyl peroxides such as peroxyacetate and t-amylperoxyisononanoate; t-butylcumyl peroxide, di-t-butyl peroxide, dicumyl peroxide, di-t-hexyl peroxide, 1,3 -Dialkyl peroxides such as bis (2-t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexin-3; t-butylperoxyacetate, t -Peroxyesters such as butylperoxybenzoate and t-butylperoxyisopropyl monocarbonate; peroxycarbonates such as t-butylperoxyisopropylcarbonate and polyethertetrakis (t-butylperoxycarbonate); dibenzoylper Organic peroxides such as diacyl peroxides such as oxides; 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4) An azo compound such as -methoxy-2'-dimethylvaleronitrile) can be mentioned.
((C)成分の含有量)
本実施形態の樹脂組成物中におけるラジカル重合開始剤(C)の含有量は、特に限定されないが、誘電特性、耐熱性及び熱膨張係数の観点から、マレイミド化合物及びマレイミド化合物に由来する構造単位の総量100質量部に対して、0.1~5質量部が好ましく、0.2~3質量部がより好ましく、0.3~1質量部がさらに好ましい。
(Contents of component (C))
The content of the radical polymerization initiator (C) in the resin composition of the present embodiment is not particularly limited, but is a structural unit derived from the maleimide compound and the maleimide compound from the viewpoint of dielectric properties, heat resistance and thermal expansion coefficient. With respect to 100 parts by mass of the total amount, 0.1 to 5 parts by mass is preferable, 0.2 to 3 parts by mass is more preferable, and 0.3 to 1 part by mass is further preferable.
本実施形態の樹脂組成物は、上記各成分以外にも、他の成分を含有していてもよい。
以下、本実施形態の樹脂組成物が含有し得る他の成分について説明する。
The resin composition of the present embodiment may contain other components in addition to the above-mentioned components.
Hereinafter, other components that may be contained in the resin composition of the present embodiment will be described.
<スチレン系熱可塑性エラストマー(D)>
本実施形態の樹脂組成物は、スチレン系熱可塑性エラストマー(D)を含有してもよい。スチレン系熱可塑性エラストマー(D)を含有することにより、高周波特性、成形性、導体との接着性、はんだ耐熱性、ガラス転移温度、熱膨張係数及び難燃性のバランスが良くなる傾向にある。
スチレン系熱可塑性エラストマー(D)は、1種類を単独で用いてもよいし、2種類以上を併用してもよい。
<Styrene-based thermoplastic elastomer (D)>
The resin composition of the present embodiment may contain a styrene-based thermoplastic elastomer (D). By containing the styrene-based thermoplastic elastomer (D), the balance between high frequency characteristics, moldability, adhesion to conductors, solder heat resistance, glass transition temperature, coefficient of thermal expansion and flame retardancy tends to be improved.
As the styrene-based thermoplastic elastomer (D), one type may be used alone, or two or more types may be used in combination.
スチレン系熱可塑性エラストマー(D)は、スチレン系化合物由来の構造単位に加えて、スチレン系化合物由来の構造単位以外の構造単位を有していてもよく、例えば、ブタジエン由来の構造単位、イソプレン由来の構造単位、マレイン酸由来の構造単位、無水マレイン酸由来の構造単位等が挙げられる。
上記ブタジエン由来の構造単位及び上記イソプレン由来の構造単位は、水素添加されていることが好ましい。水素添加されている場合、ブタジエン由来の構造単位はエチレン単位とブチレン単位とが混合した構造単位となり、イソプレン由来の構造単位はエチレン単位とプロピレン単位とが混合した構造単位となる。
The styrene-based thermoplastic elastomer (D) may have a structural unit other than the structural unit derived from the styrene-based compound in addition to the structural unit derived from the styrene-based compound. The structural unit of the above, the structural unit derived from maleic acid, the structural unit derived from maleic anhydride and the like can be mentioned.
The structural unit derived from butadiene and the structural unit derived from isoprene are preferably hydrogenated. When hydrogenated, the structural unit derived from butadiene is a structural unit in which ethylene units and butylene units are mixed, and the structural unit derived from isoprene is a structural unit in which ethylene units and propylene units are mixed.
スチレン系熱可塑性エラストマー(D)としては、スチレン-ブタジエン-スチレンブロック共重合体(SBS)の水素添加物、スチレン-イソプレン-スチレンブロック共重合体(SIS)の水素添加物等が挙げられる。これらの中でも、高周波特性、導体との接着性、耐熱性、ガラス転移温度及び熱膨張係数の観点から、スチレン-ブタジエン-スチレンブロック共重合体(SBS)の水素添加物が好ましい。 Examples of the styrene-based thermoplastic elastomer (D) include a hydrogenated additive of a styrene-butadiene-styrene block copolymer (SBS), a hydrogenated additive of a styrene-isoprene-styrene block copolymer (SIS), and the like. Among these, styrene-butadiene-styrene block copolymer (SBS) hydrogenated additives are preferable from the viewpoints of high frequency characteristics, adhesion to conductors, heat resistance, glass transition temperature and coefficient of thermal expansion.
スチレン-ブタジエン-スチレンブロック共重合体(SBS)の水素添加物としては、ブタジエンブロック中の炭素-炭素二重結合を完全水添してなるスチレン-エチレン-ブチレン-スチレン共重合体(SEBS)と、ブタジエンブロック中の1,2-結合部位の炭素-炭素二重結合を部分水添してなるスチレン-ブタジエン-ブチレン-スチレン(SBBS)が挙げられる。なお、SEBSにおける完全水添とは、通常、全体の炭素-炭素二重結合に対して90%以上であり、95%以上であってもよく、99%以上であってもよく、実質的に100%であってもよい。また、SBBSにおける部分水添率は、例えば、全体の炭素-炭素二重結合に対して60~85%である。
SEBSにおいて、スチレン由来の構造単位の含有率は、特に限定されないが、高周波特性、導体との接着性、耐熱性、ガラス転移温度及び熱膨張係数の観点から、5~80質量%が好ましく、10~70質量%がより好ましく、15~60質量%がさらに好ましい。
The hydrogenated styrene-butadiene-styrene block copolymer (SBS) is a styrene-ethylene-butylene-styrene copolymer (SEBS) completely hydrogenated with carbon-carbon double bonds in the butadiene block. , Styrene-butadiene-butylene-styrene (SBBS) formed by partially hydrogenating the carbon-carbon double bond at the 1,2-bonding site in the butadiene block. The complete hydrogenation in SEBS is usually 90% or more, 95% or more, 99% or more, and substantially the total carbon-carbon double bond. It may be 100%. The partial hydrogenation rate in SBBS is, for example, 60 to 85% with respect to the total carbon-carbon double bond.
In SEBS, the content of the structural unit derived from styrene is not particularly limited, but is preferably 5 to 80% by mass from the viewpoint of high frequency characteristics, adhesion to conductors, heat resistance, glass transition temperature and coefficient of thermal expansion. It is more preferably from 70% by mass, still more preferably from 15 to 60% by mass.
本実施形態の樹脂組成物がスチレン系熱可塑性エラストマー(D)を含有する場合、その含有量は、特に限定されないが、高周波特性及び耐熱性の観点から、樹脂成分の総和100質量部に対して、2~60質量部が好ましく、6~40質量部がより好ましく、8~30質量部がさらに好ましい。 When the resin composition of the present embodiment contains the styrene-based thermoplastic elastomer (D), the content thereof is not particularly limited, but from the viewpoint of high frequency characteristics and heat resistance, the total amount of the resin components is 100 parts by mass. 2 to 60 parts by mass is preferable, 6 to 40 parts by mass is more preferable, and 8 to 30 parts by mass is further preferable.
<無機充填材(E)>
本実施形態の樹脂組成物は、無機充填材(E)を含有することにより、より優れた低熱膨張性、高弾性率性、耐熱性及び難燃性が得られる傾向にある。
無機充填材(E)は、1種類を単独で用いてもよいし、2種類以上を併用してもよい。
<Inorganic filler (E)>
By containing the inorganic filler (E), the resin composition of the present embodiment tends to obtain more excellent low thermal expansion property, high elastic modulus, heat resistance and flame retardancy.
As the inorganic filler (E), one type may be used alone, or two or more types may be used in combination.
無機充填材(E)としては、シリカ、アルミナ、酸化チタン、マイカ、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、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、窒化ケイ素、窒化ホウ素、クレー(焼成クレー等)、タルク、ホウ酸アルミニウム、炭化ケイ素等が挙げられる。これらの中でも、熱膨張係数、弾性率、耐熱性及び難燃性の観点から、シリカ、アルミナ、マイカ、タルクが好ましく、シリカ、アルミナがより好ましく、シリカがさらに好ましい。
なお、無機充填材(E)を用いる場合、無機充填材(E)の分散性及び無機充填材(E)と樹脂組成物中の有機成分との密着性を向上させる目的で、必要に応じて、カップリング剤を併用してもよい。
Examples of the inorganic filler (E) include silica, alumina, titanium oxide, mica, verilia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, and aluminum silicate. , Calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay (baked clay, etc.), talc, aluminum borate, silicon carbide and the like. Among these, silica, alumina, mica, and talc are preferable, silica and alumina are more preferable, and silica is further preferable, from the viewpoint of thermal expansion coefficient, elastic modulus, heat resistance, and flame retardancy.
When the inorganic filler (E) is used, it is necessary to improve the dispersibility of the inorganic filler (E) and the adhesion between the inorganic filler (E) and the organic component in the resin composition. , Coupling agent may be used in combination.
無機充填材(E)の平均粒子径は、特に限定されないが、0.01~20μmが好ましく、0.1~10μmがより好ましく、0.2~1μmがさらに好ましい。
ここで、本実施形態における平均粒子径とは、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る。平均粒子径は、レーザ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。
The average particle size of the inorganic filler (E) is not particularly limited, but is preferably 0.01 to 20 μm, more preferably 0.1 to 10 μm, and even more preferably 0.2 to 1 μm.
Here, the average particle size in the present embodiment is a particle size at a point corresponding to a volume of 50% when the cumulative frequency distribution curve based on the particle size is obtained with the total volume of particles as 100%. The average particle size can be measured by a particle size distribution measuring device or the like using a laser diffraction / scattering method.
本実施形態の樹脂組成物が無機充填材(E)を含有する場合、その含有量は、特に限定されないが、熱膨張係数、弾性率、耐熱性及び難燃性の観点から、樹脂成分の総和100質量部に対して、10~250質量部が好ましく、50~200質量部がより好ましく、80~180質量部がさらに好ましい。 When the resin composition of the present embodiment contains the inorganic filler (E), the content thereof is not particularly limited, but is the sum of the resin components from the viewpoint of the coefficient of thermal expansion, elastic modulus, heat resistance and flame retardancy. With respect to 100 parts by mass, 10 to 250 parts by mass is preferable, 50 to 200 parts by mass is more preferable, and 80 to 180 parts by mass is further preferable.
<難燃剤(F)>
本実施形態の製造方法において、難燃剤(F)を配合することにより、得られる樹脂組成物が、より優れた難燃性を有する傾向にある。
難燃剤(F)は、1種類を単独で用いてもよいし、2種類以上を併用してもよい。
<Flame retardant (F)>
In the production method of the present embodiment, the resin composition obtained by blending the flame retardant (F) tends to have more excellent flame retardancy.
One type of flame retardant (F) may be used alone, or two or more types may be used in combination.
難燃剤(F)としては、無機系のリン系難燃剤;有機系のリン系難燃剤;水酸化アルミニウムの水和物、水酸化マグネシウムの水和物等の金属水和物などが挙げられる。なお、金属水酸化物は無機充填材にも該当し得るが、難燃性を付与し得る材料の場合には難燃剤に分類する。
無機系のリン系難燃剤としては、赤リン;リン酸一アンモニウム、リン酸二アンモニウム、リン酸三アンモニウム、ポリリン酸アンモニウム等のリン酸アンモニウム;リン酸アミド等の無機系含窒素リン化合物;リン酸;ホスフィンオキシドなどが挙げられる。
有機系のリン系難燃剤としては、芳香族リン酸エステル、1置換ホスホン酸ジエステル及び2置換ホスフィン酸エステル;2置換ホスフィン酸の金属塩、有機系含窒素リン化合物、環状有機リン化合物等が挙げられる。これらの中でも、難燃性及び高周波特性の観点から、芳香族リン酸エステルが好ましい。
Examples of the flame retardant (F) include an inorganic phosphorus-based flame retardant; an organic phosphorus-based flame retardant; a hydrate of aluminum hydroxide, a metal hydrate such as a hydrate of magnesium hydroxide, and the like. The metal hydroxide may also correspond to an inorganic filler, but if it is a material that can impart flame retardancy, it is classified as a flame retardant.
Examples of the inorganic phosphorus-based flame retardant include red phosphorus; ammonium phosphate such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; and inorganic nitrogen-containing phosphorus compounds such as phosphoric acid amide; phosphorus. Acid; Phosphorus oxide and the like.
Examples of the organic phosphorus-based flame retardant include aromatic phosphoric acid esters, mono-substituted phosphonic acid diesters and di-substituted phosphinic acid esters; metal salts of di-substituted phosphinic acid, organic nitrogen-containing phosphorus compounds, cyclic organic phosphorus compounds and the like. Be done. Among these, aromatic phosphoric acid esters are preferable from the viewpoint of flame retardancy and high frequency characteristics.
芳香族リン酸エステルとしては、1,3-フェニレンビス(ジ-2,6-キシレニルホスフェート)、4,4’-ビフェノール-ジフェニルホスフェート、ビスフェノールA-ジフェニルホスフェート、4,4’-ビフェノール-ジクレジルホスフェート、ビスフェノールA-ジクレジルホスフェート、4,4’-ビフェノール-ジ(2,6-キシレニルホスフェート)、ビスフェノールA-ジ(2,6-キシレニルホスフェート)、4,4’-ビフェノール-ポリフェニルホスフェート、ビスフェノールA-ポリフェニルホスフェート、4,4’-ビフェノール-ポリクレジルホスフェート、ビスフェノールA-ポリクレジルホスフェート、4,4’-ビフェノール-ポリ(2,6-キシレニルホスフェート)、ビスフェノールA-ポリ(2,6-キシレニルホスフェート)等が挙げられる。これらの中でも、高周波特性、耐熱性、低熱膨張性、導体との接着性及び相分離状態の観点から、4,4’-ビフェノール-ジ(2,6-キシレニルホスフェート)が好ましい。 As aromatic phosphates, 1,3-phenylenebis (di-2,6-xylenyl phosphate), 4,4'-biphenol-diphenyl phosphate, bisphenol A-diphenyl phosphate, 4,4'-biphenol- Dicresyl phosphate, bisphenol A-dicresyl phosphate, 4,4'-biphenol-di (2,6-xylenyl phosphate), bisphenol A-di (2,6-xylenyl phosphate), 4,4'- Biphenol-polyphenyl phosphate, bisphenol A-polyphenyl phosphate, 4,4'-biphenol-polycresyl phosphate, bisphenol A-polycresyl phosphate, 4,4'-biphenol-poly (2,6-xylenyl phosphate) ), Bisphenol A-poly (2,6-xylenyl phosphate) and the like. Among these, 4,4'-biphenol-di (2,6-xylenyl phosphate) is preferable from the viewpoint of high frequency characteristics, heat resistance, low thermal expansion, adhesion to a conductor, and phase separation state.
2置換ホスフィン酸の金属塩としては、ジアルキルホスフィン酸の金属塩が好ましい。ここで、「金属塩」としては、リチウム塩、ナトリウム塩、カリウム塩、カルシウム塩、マグネシウム塩、アルミニウム塩、チタン塩、亜鉛塩等が挙げられる。また、ジアルキルホスフィン酸が有するアルキル基としては、炭素数1~10のアルキル基が挙げられる。 As the metal salt of disubstituted phosphinic acid, a metal salt of dialkylphosphinic acid is preferable. Here, examples of the "metal salt" include lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt, aluminum salt, titanium salt, zinc salt and the like. Examples of the alkyl group contained in the dialkylphosphinic acid include an alkyl group having 1 to 10 carbon atoms.
本実施形態の製造方法において難燃剤(F)を配合する場合、その配合量は、特に限定されないが、難燃性、高周波特性、成形性及び接着性の観点から、樹脂成分の総和100質量部に対して、3~50質量部が好ましく、5~45質量部がより好ましく、10~40質量部がさらに好ましい。 When the flame retardant (F) is blended in the production method of the present embodiment, the blending amount thereof is not particularly limited, but from the viewpoint of flame retardancy, high frequency characteristics, moldability and adhesiveness, the total of the resin components is 100 parts by mass. On the other hand, 3 to 50 parts by mass is preferable, 5 to 45 parts by mass is more preferable, and 10 to 40 parts by mass is further preferable.
<有機溶媒>
本実施形態の樹脂組成物は、取り扱いを容易にするという観点及び後述するプリプレグを製造し易くする観点から、有機溶媒を含有するワニス状の樹脂組成物であってもよい。
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;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;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;ジメチルホルムアミド、ジメチルアセトアミド、N-メチルピロリドン等の窒素原子含有溶媒;ジメチルスルホキシド等の硫黄原子含有溶媒;γ-ブチロラクトン等のエステル系溶媒などが挙げられる。これらの有機溶媒は、1種類を単独で用いてもよいし、2種類以上を併用してもよい。
<Organic solvent>
The resin composition of the present embodiment may be a varnish-like resin composition containing an organic solvent from the viewpoint of facilitating handling and the prepreg described later.
Examples of the organic solvent include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as tetrahydrofuran; toluene, Aromatic solvents such as xylene and mesitylen; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; sulfur atom-containing solvents such as dimethylsulfoxide; ester solvents such as γ-butyrolactone and the like can be mentioned. One type of these organic solvents may be used alone, or two or more types may be used in combination.
本実施形態の樹脂組成物が有機溶媒を含有する場合、その含有量は、特に限定されないが、本実施形態の樹脂組成物の固形分濃度が、30~90質量%となる量が好ましく、40~80質量%となる量がより好ましく、50~70質量%となる量がさらに好ましい。有機溶媒の含有量が上記範囲内であると、樹脂組成物の取り扱い性が容易となり、基材への含浸性及び製造されるプリプレグの外観が良好となる。さらに、後述するプリプレグ中の樹脂の固形分濃度の調整が容易となり、所望の厚みを有するプリプレグの製造がより容易となる傾向にある。 When the resin composition of the present embodiment contains an organic solvent, the content thereof is not particularly limited, but the solid content concentration of the resin composition of the present embodiment is preferably 30 to 90% by mass, preferably 40. An amount of about 80% by mass is more preferable, and an amount of 50 to 70% by mass is further preferable. When the content of the organic solvent is within the above range, the handleability of the resin composition becomes easy, the impregnation property into the base material and the appearance of the produced prepreg become good. Further, the solid content concentration of the resin in the prepreg, which will be described later, tends to be easily adjusted, and the production of the prepreg having a desired thickness tends to be easier.
<その他の任意成分>
本実施形態の樹脂組成物は、さらに、本発明の効果を損なわない範囲で、必要に応じて、上記各成分以外の樹脂材料、カップリング剤、酸化防止剤、熱安定剤、帯電防止剤、紫外線吸収剤、顔料、着色剤及び滑剤からなる群から選択される1種以上[以下、「その他の任意成分」と略称することがある。]を含有していてもよい。これらの成分は、各々について、1種類を単独で用いてもよいし、2種類以上を併用してもよい。また、本実施形態の樹脂組成物は、これらの成分を含有しないものであってもよい。
本実施形態の樹脂組成物が上記その他の任意成分を含有する場合、その各々の含有量は、特に限定されないが、樹脂成分の総和100質量部に対して、例えば、0.01質量部以上であってもよく、0.1質量部以上であってもよく、また、10質量部以下であってもよく、5質量部以下であってもよく、1質量部以下であってもよい。
<Other optional ingredients>
Further, the resin composition of the present embodiment further comprises, as necessary, a resin material other than the above-mentioned components, a coupling agent, an antioxidant, a heat stabilizer, an antistatic agent, and the like, as long as the effects of the present invention are not impaired. One or more selected from the group consisting of UV absorbers, pigments, colorants and lubricants [hereinafter, may be abbreviated as "other optional components". ] May be contained. For each of these components, one type may be used alone, or two or more types may be used in combination. Moreover, the resin composition of this embodiment may not contain these components.
When the resin composition of the present embodiment contains the above-mentioned other optional components, the content thereof is not particularly limited, but is, for example, 0.01 part by mass or more with respect to 100 parts by mass of the total of the resin components. It may be 0.1 parts by mass or more, 10 parts by mass or less, 5 parts by mass or less, or 1 part by mass or less.
本実施形態の樹脂組成物は、各成分を公知の方法で混合することで製造することができる。この際、各成分は、上記有機溶媒中で撹拌しながら溶解又は分散させてもよい。混合順序、温度、時間等の条件は、特に限定されず任意に設定することができる。 The resin composition of the present embodiment can be produced by mixing each component by a known method. At this time, each component may be dissolved or dispersed while stirring in the above organic solvent. Conditions such as mixing order, temperature, and time are not particularly limited and can be arbitrarily set.
[プリプレグ]
本実施形態のプリプレグは、本実施形態の樹脂組成物とシート状繊維補強基材とを含有してなるものである。
該プリプレグは、本実施形態の樹脂組成物とシート状繊維補強基材とを用いて形成することができ、例えば、本実施形態の樹脂組成物を、シート状繊維補強基材に含浸又は塗工し、乾燥炉中で、80~200℃の温度で1~30分間加熱乾燥し、樹脂組成物を半硬化(Bステージ化)させることにより製造することができる。
本実施形態のプリプレグ中における樹脂組成物由来の固形分含有量は、特に限定されないが、30~90質量%が好ましく、35~80質量%がより好ましく、40~70質量%がさらに好ましく、45~60質量%が特に好ましい。固形分濃度が上記範囲内であると、積層板とした際により良好な成形性が得られる傾向にある。
[Prepreg]
The prepreg of the present embodiment contains the resin composition of the present embodiment and a sheet-shaped fiber reinforced base material.
The prepreg can be formed by using the resin composition of the present embodiment and the sheet-shaped fiber reinforced base material. For example, the resin composition of the present embodiment is impregnated or coated on the sheet-shaped fiber reinforced base material. The resin composition can be produced by heating and drying the resin composition at a temperature of 80 to 200 ° C. for 1 to 30 minutes in a drying furnace to semi-cure the resin composition (B-stage).
The solid content derived from the resin composition in the prepreg of the present embodiment is not particularly limited, but is preferably 30 to 90% by mass, more preferably 35 to 80% by mass, still more preferably 40 to 70% by mass, and 45. ~ 60% by mass is particularly preferable. When the solid content concentration is within the above range, better formability tends to be obtained when the laminated board is formed.
プリプレグのシート状繊維補強基材としては、各種の電気絶縁材料用積層板に用いられている公知のものが用いられる。シート状繊維補強基材の材質としては、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;これらの混合物などが挙げられる。これらのシート状繊維補強基材は、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。また、シート状繊維補強基材の厚みは特に制限されず、例えば、0.02~0.5mmのものを用いることができる。また、樹脂組成物の含浸性、積層板とした際の耐熱性、耐吸湿性及び加工性の観点から、カップリング剤等で表面処理したもの、機械的に開繊処理を施したもの等を使用できる。 As the sheet-shaped fiber reinforced base material of the prepreg, known ones used for laminated boards for various electric insulating materials are used. Examples of the material of the sheet-shaped fiber reinforcing base material include inorganic fibers such as E glass, D glass, S glass and Q glass; organic fibers such as polyimide, polyester and tetrafluoroethylene; and a mixture thereof. These sheet-shaped fiber reinforced base materials have shapes such as woven fabrics, non-woven fabrics, robinks, chopped strand mats, and surfaced mats. Further, the thickness of the sheet-shaped fiber reinforced base material is not particularly limited, and for example, one having a thickness of 0.02 to 0.5 mm can be used. Further, from the viewpoints of impregnation property of the resin composition, heat resistance when made into a laminated board, hygroscopicity and processability, those surface-treated with a coupling agent or the like, those subjected to mechanically opening treatment, etc. are used. Can be used.
樹脂組成物をシート状繊維補強基材に含浸又は塗工させる方法としては、次のホットメルト法又はソルベント法を採用できる。
ホットメルト法は、樹脂組成物に有機溶媒を含有させず、(1)該樹脂組成物との剥離性の良い塗工紙に一旦コーティングし、それをシート状繊維補強基材にラミネートする方法、又は(2)ダイコーターによりシート状繊維補強基材に直接塗工する方法である。
一方、ソルベント法は、樹脂組成物に有機溶媒を含有させ、得られた樹脂組成物にシート状繊維補強基材を浸漬して、樹脂組成物をシート状繊維補強基材に含浸させ、その後、乾燥させる方法である。
The following hot melt method or solvent method can be adopted as a method for impregnating or coating the sheet-shaped fiber reinforced base material with the resin composition.
The hot melt method is a method in which the resin composition does not contain an organic solvent, and (1) is once coated on coated paper having good peelability from the resin composition and then laminated on a sheet-like fiber reinforced base material. Alternatively, (2) it is a method of directly coating the sheet-shaped fiber reinforced base material with a die coater.
On the other hand, in the solvent method, the resin composition contains an organic solvent, the sheet-shaped fiber reinforced base material is immersed in the obtained resin composition, the resin composition is impregnated into the sheet-shaped fiber reinforced base material, and then the sheet-shaped fiber reinforced base material is impregnated. It is a method of drying.
[積層板]
本実施形態の積層板は、本実施形態のプリプレグと金属箔とを含有してなる積層板である。
本実施形態の積層板は、本実施形態のプリプレグ1枚の片面若しくは両面に金属箔を配置するか、又は本実施形態のプリプレグを2枚以上重ねたものの片面若しくは両面に金属箔を配置し、次いで加熱加圧成形することによって積層板を得ることができる。金属箔を有する積層板は、金属張積層板と称されることもある。
金属箔の金属としては、電気絶縁材料用途で用いられるものであれば特に制限されないが、導電性の観点から、銅、金、銀、ニッケル、白金、モリブデン、ルテニウム、アルミニウム、タングステン、鉄、チタン、クロム、又はこれらの金属元素を1種以上含有する合金であってもよく、銅、アルミニウムが好ましく、銅がより好ましい。
加熱加圧成形の条件は特に制限されるものではなく、例えば、温度が100~300℃、圧力が0.2~10.0MPa、時間が0.1~5時間の範囲で実施することができる。また加熱加圧成形は真空プレス等を用いて真空状態を0.5~5時間保持する方法を採用できる。
[Laminate board]
The laminated board of this embodiment is a laminated board containing the prepreg of this embodiment and a metal foil.
In the laminated board of the present embodiment, the metal foil is arranged on one side or both sides of one prepreg of the present embodiment, or the metal foil is arranged on one side or both sides of a stack of two or more prepregs of the present embodiment. Next, a laminated plate can be obtained by heat-press molding. A laminated board having a metal foil is sometimes referred to as a metal-clad laminated board.
The metal of the metal foil is not particularly limited as long as it is used for electrical insulating materials, but from the viewpoint of conductivity, copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, and titanium. , Chromium, or an alloy containing one or more of these metal elements, preferably copper and aluminum, and more preferably copper.
The conditions for heat-press molding are not particularly limited, and for example, the temperature can be 100 to 300 ° C., the pressure can be 0.2 to 10.0 MPa, and the time can be 0.1 to 5 hours. .. Further, for heat pressure molding, a method of maintaining a vacuum state for 0.5 to 5 hours using a vacuum press or the like can be adopted.
[多層プリント配線板]
本実施形態の多層プリント配線板は、本実施形態のプリプレグ又は本実施形態の積層板を含有してなるものである。本実施形態の多層プリント配線板は、本実施形態のプリプレグ又は積層板を用いて、公知の方法によって、穴開け加工、金属めっき加工、金属箔のエッチング等による回路形成加工及び多層化接着加工を行うことによって製造することができる。
[Multilayer printed wiring board]
The multilayer printed wiring board of the present embodiment contains the prepreg of the present embodiment or the laminated board of the present embodiment. The multilayer printed wiring board of the present embodiment uses the prepreg or the laminated plate of the present embodiment, and is subjected to circuit forming processing and multi-layer bonding processing by drilling, metal plating, etching of metal leaf, etc. by a known method. It can be manufactured by doing.
[半導体パッケージ]
本実施形態の半導体パッケージは、本実施形態の多層プリント配線板に半導体素子を搭載してなるものである。
本実施形態の半導体パッケージは、例えば、本実施形態の多層プリント配線板の所定の位置に半導体チップ、メモリ等の半導体素子を公知の方法によって搭載し、封止樹脂等によって半導体素子を封止することによって製造できる。
[Semiconductor package]
The semiconductor package of the present embodiment is formed by mounting a semiconductor element on the multilayer printed wiring board of the present embodiment.
In the semiconductor package of the present embodiment, for example, a semiconductor element such as a semiconductor chip or a memory is mounted at a predetermined position on the multilayer printed wiring board of the present embodiment by a known method, and the semiconductor element is sealed with a sealing resin or the like. Can be manufactured by
以上、本発明の好適な実施形態を説明したが、これらは本発明の説明のための例示であり、本発明の範囲をこれらの実施形態にのみ限定する趣旨ではない。本発明は、その要旨を逸脱しない範囲で、上記実施形態とは異なる種々の態様で実施することができる。 Although the preferred embodiments of the present invention have been described above, these are examples for explaining the present invention, and the scope of the present invention is not limited to these embodiments. The present invention can be carried out in various embodiments different from the above embodiments without departing from the gist thereof.
以下、実施例を挙げて、本発明を具体的に説明する。ただし、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples.
[プレ反応の反応率の測定方法]
各例において、プレ反応の反応率は、反応後の溶液を測定試料としてゲルパーミエーションクロマトグラフィー(GPC)を測定した場合における、保持時間10分未満のピーク面積(反応生成物に相当)と原料成分に由来するピーク面積を用いて、(保持時間10分未満のピーク面積)×100/((保持時間10分未満のピーク面積)+(原料成分由来ピーク面積))として求めた。
GPCの測定条件を以下に示す。
装置:
HLP-8320GPC[東ソー株式会社製]
検出器:HLC-8320GPC内蔵RI検出器/UV-8320[東ソー株式会社製]
カラム:ガードカラム;TSKgel guardcolumn SuperMP(HZ)-N;TSKgel SuperMultiporeHZ-Mx2(すべて東ソー株式会社製、商品名)
カラムサイズ:4.6×20mm(ガードカラム)、7.8×300mm(カラム)
溶離液:テトラヒドロフラン
試料濃度:2mg/5mL
注入量:10μL
流量:0.35mL/分
測定温度:35℃
[Measurement method of reaction rate of pre-reaction]
In each example, the reaction rate of the pre-reaction is the peak area (corresponding to the reaction product) with a retention time of less than 10 minutes when gel permeation chromatography (GPC) is measured using the solution after the reaction as a measurement sample. Using the peak area derived from the component, it was determined as (peak area with a holding time of less than 10 minutes) × 100 / ((peak area with a holding time of less than 10 minutes) + (peak area derived from a raw material component)).
The measurement conditions of GPC are shown below.
Device:
HLP-8320GPC [manufactured by Tosoh Corporation]
Detector: HLC-8320GPC built-in RI detector / UV-8320 [manufactured by Tosoh Corporation]
Column: Guard column; TSKgel guardcollect SuperMP (HZ) -N; TSKgel SuperMultipore HZ-Mx2 (all manufactured by Tosoh Corporation, product name)
Column size: 4.6 x 20 mm (guard column), 7.8 x 300 mm (column)
Eluent: Tetrahydrofuran Sample concentration: 2 mg / 5 mL
Injection volume: 10 μL
Flow rate: 0.35 mL / min Measurement temperature: 35 ° C
[樹脂組成物の製造]
実施例1、比較例1~3
温度計、撹拌装置、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5リットルの反応容器に、表1に示す配合組成の(a1)成分、(a2)成分、プロピレングリコールモノメチルエーテル170質量部を仕込み、還流させながら1時間反応させた。次に反応容器に表1に示す(B)成分又は(B’)成分を加えた後、還流させながら1時間反応させた。これを還流温度にて1.5時間かけて濃縮し、ポリイミド化合物(A)を含有する固形分濃度が64質量%の溶液を製造した。上記方法によって測定したプレ反応の反応率を表1に示す。なお、ここで、未反応であった(a1)成分は、そのままマレイミド化合物(A’)として、樹脂組成物に含有されるものである。
上記の溶液に、表1に示す配合組成の(C)成分又は(C’)成分、及びジシアンジアミド0.9質量部を加え、65℃で1時間撹拌及び混合して、固形分濃度64質量%の樹脂組成物を調製した。
[Manufacturing of resin composition]
Example 1, Comparative Examples 1 to 3
In a reaction vessel having a volume of 5 liters capable of heating and cooling equipped with a thermometer, a stirrer, and a water meter with a reflux condenser, the components (a1), (a2), and propylene glycol monomethyl ether having the composition shown in Table 1 are shown. 170 parts by mass was charged and reacted for 1 hour while refluxing. Next, the component (B) or the component (B') shown in Table 1 was added to the reaction vessel, and then the mixture was reacted for 1 hour while refluxing. This was concentrated at a reflux temperature over 1.5 hours to produce a solution containing the polyimide compound (A) having a solid content concentration of 64% by mass. Table 1 shows the reaction rate of the pre-reaction measured by the above method. Here, the unreacted component (a1) is contained in the resin composition as a maleimide compound (A') as it is.
To the above solution, component (C) or component (C') of the composition shown in Table 1 and 0.9 parts by mass of dicyandiamide were added, and the mixture was stirred and mixed at 65 ° C. for 1 hour to have a solid content concentration of 64% by mass. Resin composition of.
[誘電特性の評価;誘電率及び誘電正接の測定]
次に、各例で得た樹脂組成物を、厚さ50μmのPETフィルム(帝人株式会社製、商品名:G2-50)に塗工した後、130℃で20分間加熱乾燥して、Bステージ状態の樹脂フィルムを作製した。この樹脂フィルムをPETフィルムから剥離した後、粉砕して樹脂粉末とし、厚さ1mm×長さ50mm×幅30mmのサイズに型抜きしたテフロン(登録商標)シートに該樹脂粉末を投入した。続いて、その上下に、厚さ18μmのロープロファイル銅箔(古河電気工業株式会社製、商品名:BF-ANP18)を、S面が投入した樹脂粉末に接するように配置し、温度230℃、圧力2.0MPa、時間90分間の条件で加熱加圧成形して、樹脂組成物を硬化させた。得られた銅箔付き樹脂板から銅箔をピールすることで厚さ1mmの樹脂板を作製した。
該樹脂板を評価試料として、空洞共振器摂動法に準拠して、10GHz帯で誘電率(Dk)及び誘電正接(Df)を測定した。結果を表1に示す。
[Evaluation of dielectric properties; measurement of permittivity and dielectric loss tangent]
Next, the resin composition obtained in each example was applied to a PET film having a thickness of 50 μm (manufactured by Teijin Limited, trade name: G2-50), and then heated and dried at 130 ° C. for 20 minutes to perform the B stage. A resin film in a state was produced. After peeling this resin film from the PET film, it was crushed into a resin powder, and the resin powder was put into a Teflon (registered trademark) sheet punched into a size of 1 mm in thickness × 50 mm in length × 30 mm in width. Subsequently, a low profile copper foil (manufactured by Furukawa Electric Co., Ltd., trade name: BF-ANP18) having a thickness of 18 μm was placed above and below it so that the S surface was in contact with the charged resin powder, and the temperature was 230 ° C. The resin composition was cured by heat and pressure molding under the conditions of a pressure of 2.0 MPa and a time of 90 minutes. A resin plate having a thickness of 1 mm was produced by peeling a copper foil from the obtained resin plate with a copper foil.
Using the resin plate as an evaluation sample, the permittivity (Dk) and the dielectric loss tangent (Df) were measured in the 10 GHz band according to the cavity resonator perturbation method. The results are shown in Table 1.
なお、表1における(B)成分及び(B’)成分の詳細は以下の通りである。
両末端にメタクリロイルオキシ基を有するポリジメチルシロキサン:信越化学工業株式会社製、商品名「X-22-164A」(メタクリロイルオキシ基の官能基当量860g/mol)
両末端に第1級アミノ基を有するポリジメチルシロキサンB’-1:モメンティブ社製、商品名「XF42-C5379」(第1級アミノ基当量730g/mol)
両末端に第1級アミノ基を有するポリジメチルシロキサンB’-2:モメンティブ社製、商品名「XF42-C6252」(第1級アミノ基当量1270g/mol)
The details of the component (B) and the component (B') in Table 1 are as follows.
Polydimethylsiloxane having a methacryloyloxy group at both ends: manufactured by Shin-Etsu Chemical Co., Ltd., trade name "X-22-164A" (functional group equivalent of methacryloyloxy group 860 g / mol)
Polydimethylsiloxane B'-1 having a primary amino group at both ends: manufactured by Momentive, trade name "XF42-C5379" (primary amino group equivalent 730 g / mol)
Polydimethylsiloxane B'-2 having a primary amino group at both ends: manufactured by Momentive, trade name "XF42-C6252" (primary amino group equivalent 1270 g / mol)
表1から、本実施形態の樹脂組成物を用いて作製した実施例1の樹脂板は、(B)成分及び/又は(C)成分を使用しなかった比較例1~3の樹脂板と比べると、低い誘電正接が得られている。このことから、本実施形態の樹脂組成物が、10GHz帯以上の高周波数帯において優れた誘電特性を発現するものであることが分かる。 From Table 1, the resin plate of Example 1 produced using the resin composition of the present embodiment is compared with the resin plates of Comparative Examples 1 to 3 in which the component (B) and / or the component (C) was not used. , A low dielectric loss tangent is obtained. From this, it can be seen that the resin composition of the present embodiment exhibits excellent dielectric properties in a high frequency band of 10 GHz band or higher.
本発明の樹脂組成物は、10GHz帯以上の高周波数帯において優れた誘電特性を発現するものであるため、該樹脂組成物を用いて得られるプリプレグ、積層板、多層プリント配線板、半導体パッケージ等は、高周波信号を扱う電子部品用途に好適である。 Since the resin composition of the present invention exhibits excellent dielectric properties in a high frequency band of 10 GHz or higher, prepregs, laminated boards, multilayer printed wiring boards, semiconductor packages, etc. obtained by using the resin composition can be used. Is suitable for electronic component applications that handle high frequency signals.
Claims (11)
ラジカル重合性基を有するシリコーン化合物(B)と、
ラジカル重合開始剤(C)と、
を含有する、樹脂組成物。 A polyimide compound (A) containing a structural unit derived from a maleimide compound (a1) having at least two N-substituted maleimide groups and a structural unit derived from an amine compound (a2) having a primary amino group.
Silicone compound (B) having a radically polymerizable group and
Radical polymerization initiator (C) and
A resin composition containing.
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