JP6822610B2 - Curable resin composition, cured product, acid-modified maleimide resin and curing agent - Google Patents
Curable resin composition, cured product, acid-modified maleimide resin and curing agent Download PDFInfo
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- JP6822610B2 JP6822610B2 JP2020520093A JP2020520093A JP6822610B2 JP 6822610 B2 JP6822610 B2 JP 6822610B2 JP 2020520093 A JP2020520093 A JP 2020520093A JP 2020520093 A JP2020520093 A JP 2020520093A JP 6822610 B2 JP6822610 B2 JP 6822610B2
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- curable resin
- acid
- resin composition
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- 229920005989 resin Polymers 0.000 title claims description 110
- 239000011347 resin Substances 0.000 title claims description 110
- 239000011342 resin composition Substances 0.000 title claims description 52
- 125000005439 maleimidyl group Chemical class C1(C=CC(N1*)=O)=O 0.000 title description 3
- -1 N-substituted maleimide group Chemical group 0.000 claims description 61
- 150000003923 2,5-pyrrolediones Chemical class 0.000 claims description 33
- 239000003822 epoxy resin Substances 0.000 claims description 24
- 229920000647 polyepoxide Polymers 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 239000003999 initiator Substances 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 17
- 125000001931 aliphatic group Chemical group 0.000 claims description 16
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 16
- 239000000194 fatty acid Substances 0.000 claims description 16
- 229930195729 fatty acid Natural products 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 150000004665 fatty acids Chemical class 0.000 claims description 14
- 229910000679 solder Inorganic materials 0.000 claims description 14
- 150000001993 dienes Chemical class 0.000 claims description 13
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 8
- 125000000962 organic group Chemical group 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 239000003085 diluting agent Substances 0.000 claims description 5
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000002521 alkyl halide group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000000958 aryl methylene group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229920001187 thermosetting polymer Polymers 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 description 44
- 239000010408 film Substances 0.000 description 42
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 36
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- 238000001723 curing Methods 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 11
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical class O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 8
- 239000004721 Polyphenylene oxide Substances 0.000 description 7
- 239000003513 alkali Substances 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- 239000007864 aqueous solution Substances 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
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 150000002576 ketones Chemical class 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000005698 Diels-Alder reaction Methods 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 5
- 239000013039 cover film Substances 0.000 description 5
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 239000011256 inorganic filler Substances 0.000 description 5
- 229910003475 inorganic filler Inorganic materials 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000004334 sorbic acid Substances 0.000 description 5
- 235000010199 sorbic acid Nutrition 0.000 description 5
- 229940075582 sorbic acid Drugs 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 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 4
- XAZPKEBWNIUCKF-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]propan-2-yl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=CC=1C(C)(C)C(C=C1)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O XAZPKEBWNIUCKF-UHFFFAOYSA-N 0.000 description 4
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 150000002334 glycols Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000003457 sulfones Chemical class 0.000 description 4
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-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
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001983 dialkylethers Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- AQGZJQNZNONGKY-UHFFFAOYSA-N 1-[4-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=C(N2C(C=CC2=O)=O)C=C1 AQGZJQNZNONGKY-UHFFFAOYSA-N 0.000 description 2
- FUWDFGKRNIDKAE-UHFFFAOYSA-N 1-butoxypropan-2-yl acetate Chemical compound CCCCOCC(C)OC(C)=O FUWDFGKRNIDKAE-UHFFFAOYSA-N 0.000 description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 2
- JECYUBVRTQDVAT-UHFFFAOYSA-N 2-acetylphenol Chemical compound CC(=O)C1=CC=CC=C1O JECYUBVRTQDVAT-UHFFFAOYSA-N 0.000 description 2
- HEQOJEGTZCTHCF-UHFFFAOYSA-N 2-amino-1-phenylethanone Chemical compound NCC(=O)C1=CC=CC=C1 HEQOJEGTZCTHCF-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- MOSSLXZUUKTULI-UHFFFAOYSA-N 3-[3-(2,5-dioxopyrrol-3-yl)-4-methylphenyl]pyrrole-2,5-dione Chemical compound CC1=CC=C(C=2C(NC(=O)C=2)=O)C=C1C1=CC(=O)NC1=O MOSSLXZUUKTULI-UHFFFAOYSA-N 0.000 description 2
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- KVXNKFYSHAUJIA-UHFFFAOYSA-N acetic acid;ethoxyethane Chemical compound CC(O)=O.CCOCC KVXNKFYSHAUJIA-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- PESYEWKSBIWTAK-UHFFFAOYSA-N cyclopenta-1,3-diene;titanium(2+) Chemical compound [Ti+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 PESYEWKSBIWTAK-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
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- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
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- XDOBJOBITOLMFI-UHFFFAOYSA-N pyrrole-2,5-dione;toluene Chemical compound CC1=CC=CC=C1.O=C1NC(=O)C=C1 XDOBJOBITOLMFI-UHFFFAOYSA-N 0.000 description 1
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- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
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- 229910052703 rhodium Inorganic materials 0.000 description 1
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
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- 239000008399 tap water Substances 0.000 description 1
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- 150000003512 tertiary amines Chemical class 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical class O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4042—Imines; Imides
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Materials For Photolithography (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Description
本発明は、酸変性マレイミド樹脂、硬化剤、当該硬化剤を含む硬化性樹脂組成物、特に、プリント配線板に用いられるソルダーレジストを形成するための硬化性樹脂組成物、並びにそれを用いたドライフィルムおよびプリント配線板に関する。 The present invention relates to an acid-modified maleimide resin, a curing agent, a curable resin composition containing the curing agent, particularly a curable resin composition for forming a solder resist used for a printed wiring board, and a dry using the same. Regarding film and printed wiring boards.
近年、電子機器(エレクトロニクス機器)の軽薄短小化に伴うプリント配線板の高密度化に対応して、ソルダーレジスト等の樹脂絶縁層用の硬化性樹脂組成物にも高性能化および作業性の向上が要求されている。特に、自動車、中でも駆動部の電気制御化が進んでおり、エンジンルームおよびその周辺等の、環境温度が高い場所にプリント配線板が搭載されることが多くなっている。車載用のプリント配線板は、搭載箇所によっては80℃から150℃の高温下に長期に亘って曝されることになるため、車載用プリント配線板に用いられる高性能ソルダーレジストには、優れた耐熱性が求められている。 In recent years, in response to the increase in density of printed wiring boards due to the miniaturization of electronic devices (electronic devices), the performance and workability of curable resin compositions for resin insulating layers such as solder resists have been improved. Is required. In particular, electric control of automobiles, especially drive units, is advancing, and printed wiring boards are often mounted in places where the environmental temperature is high, such as in the engine room and its surroundings. Since the printed wiring board for automobiles is exposed to a high temperature of 80 ° C. to 150 ° C. for a long period of time depending on the mounting location, it is excellent as a high-performance solder resist used for the printed wiring board for automobiles. Heat resistance is required.
このようなソルダーレジストに適した材料としてビスマレイミド化合物が挙げられる。ビスマレイミド化合物は耐熱性、難燃性、誘電特性などに優れる樹脂であるものの、エポキシ樹脂との硬化反応性を示さない公知のビスマレイミド化合物は、エポキシ硬化系の硬化性樹脂と併用した場合、耐熱性が不足する問題があった。そこで、アミノフェノール等のモノアミン化合物のアミノ基を、ビスマレイミド化合物の不飽和N−置換マレイミド基と反応させることによって得られたアミン変性ビスマレイミド化合物をエポキシ硬化系の硬化性樹脂と併用することが提案されている(例えば、特許文献1参照)。しかしながら、当該当該化合物はアルカリ現像性が十分でないため、ソルダーレジスト材料、特に、近年の微細化された回路を有するプリント配線板に求められるソルダーレジスト材料としては不十分であった。 Bismaleimide compounds can be mentioned as materials suitable for such solder resists. Although the bismaleimide compound is a resin having excellent heat resistance, flame retardancy, dielectric properties, etc., a known bismaleimide compound that does not show curing reactivity with an epoxy resin is used when used in combination with an epoxy curable resin. There was a problem of insufficient heat resistance. Therefore, an amine-modified bismaleimide compound obtained by reacting an amino group of a monoamine compound such as aminophenol with an unsaturated N-substituted maleimide group of a bismaleimide compound can be used in combination with an epoxy-curable curable resin. It has been proposed (see, for example, Patent Document 1). However, since the compound has insufficient alkali developability, it has been insufficient as a solder resist material, particularly as a solder resist material required for a printed wiring board having a miniaturized circuit in recent years.
また、アミノ安息香酸等のカルボキシ基を有するアミン化合物で変性したビスマレイミド化合物をエポキシ硬化系の硬化性樹脂と併用することも提案されている(例えば、特許文献2参照)。しかしながら、当該化合物は熱分解温度が低く、近年要求される鉛フリーはんだへの耐熱性に不足するものである。 It has also been proposed to use a bismaleimide compound modified with an amine compound having a carboxy group such as aminobenzoic acid in combination with an epoxy curable resin (see, for example, Patent Document 2). However, the compound has a low thermal decomposition temperature and lacks heat resistance to lead-free solder, which has been required in recent years.
そこで、本発明が解決しようとする課題は、アルカリ現像性および耐熱性に優れた硬化物を得ることが可能な酸変性マレイミド樹脂および当該樹脂を含む硬化性樹脂組成物、ソルダーレジスト形成用組成物、並びに上記硬化性樹脂組成物を用いたドライフィルムおよびプリント配線板を提供することにある。 Therefore, the problem to be solved by the present invention is an acid-modified maleimide resin capable of obtaining a cured product having excellent alkali developability and heat resistance, a curable resin composition containing the resin, and a solder resist forming composition. , And a dry film and a printed wiring board using the curable resin composition.
本願発明者らは種々の検討を行った結果、マレイミド樹脂中のN−置換マレイミド基に共役ジエンを有する脂肪酸をディールス・アルダー反応を利用して付加させてなる酸変性マレイミド樹脂を硬化剤として用いることで、耐熱性に優れるとともに、アルカリ現像性が良好な硬化物が得られることを見出し、上記課題を解決するに至った。 As a result of various studies, the inventors of the present application use an acid-modified maleimide resin as a curing agent, which is obtained by adding a fatty acid having a conjugated diene to an N-substituted maleimide group in the maleimide resin by using a Diels-Alder reaction. As a result, it has been found that a cured product having excellent heat resistance and good alkali developability can be obtained, and the above-mentioned problems have been solved.
すなわち本発明は、N−置換マレイミド基に共役ジエンを有する脂肪酸又はその誘導体(a1)を付加してなる構造(1)を含有する酸変性マレイミド樹脂(A)と、硬化性樹脂(B)を含むことを特徴とする硬化性樹脂組成物、その用途、硬化物、及び硬化剤として好適に用いることができる特定構造の酸変性マレイミド樹脂を提供するものである。 That is, the present invention comprises an acid-modified maleimide resin (A) containing a structure (1) in which a fatty acid having a conjugated diene or a derivative (a1) thereof is added to an N-substituted maleimide group, and a curable resin (B). It provides a curable resin composition characterized by containing, an application thereof, a cured product, and an acid-modified maleimide resin having a specific structure that can be suitably used as a curing agent.
本発明によれば、耐熱性およびアルカリ現像性に優れた硬化物を得ることが可能な酸変性マレイミド樹脂および当該化合物を含む硬化性樹脂組成物、ソルダーレジスト形成用組成物、並びに上記硬化性樹脂組成物を用いたドライフィルムおよびプリント配線板を提供することができる。 According to the present invention, an acid-modified maleimide resin capable of obtaining a cured product having excellent heat resistance and alkali developability, a curable resin composition containing the compound, a solder resist forming composition, and the curable resin. A dry film and a printed wiring board using the composition can be provided.
本発明の硬化性樹脂組成物は、N−置換マレイミド基に共役ジエンを有する脂肪酸又はその誘導体(a1)を付加してなる構造(1)を含有する酸変性マレイミド樹脂(A)と、硬化性樹脂(B)を含むことを特徴とする。 The curable resin composition of the present invention comprises an acid-modified maleimide resin (A) containing a structure (1) in which a fatty acid having a conjugated diene or a derivative (a1) thereof is added to an N-substituted maleimide group, and a curable resin composition. It is characterized by containing a resin (B).
前記N−置換マレイミド基は、いわゆるマレイミドの不飽和N−置換マレイミド基を示すものであり、すなわち、原料としてマレイミドを用いることが好ましい。 The N-substituted maleimide group represents a so-called unsaturated N-substituted maleimide group of maleimide, that is, it is preferable to use maleimide as a raw material.
前記マレイミドとしては、例えば、1分子中に2個のマレイミド基を有するビスマレイミド化合物や、1分子中に3個以上のマレイミド基を有するマレイミド樹脂が挙げられる。 Examples of the maleimide include a bismaleimide compound having two maleimide groups in one molecule and a maleimide resin having three or more maleimide groups in one molecule.
前記ビスマレイミド化合物としては、分子構造中に少なくとも2個の不飽和N−置換マレイミド基を有する化合物であれば任意のものを使用することができ、例えば、下記式(a1) As the bismaleimide compound, any compound having at least two unsaturated N-substituted maleimide groups in the molecular structure can be used, and for example, the following formula (a1) can be used.
で表されるビスマレイミド化合物を好ましいものとして例示することができる。当該R1は、得られる硬化物においてより耐熱性に優れる点から、芳香環を有する二価の有機基であることがより好ましい。
The bismaleimide compound represented by is exemplified as a preferable one. The R 1 is more preferably a divalent organic group having an aromatic ring from the viewpoint of being more excellent in heat resistance in the obtained cured product.
ここでR1の芳香環または脂肪族炭化水素を有する二価の有機基としては、アルキレン基、シクロアルキレン基、単環式または多環式のアリーレン基、またはそれらの基が2価の原子団(たとえばアルキレン基やシクロアルキレン基、酸素原子、硫黄原子、スルホン基、スルフィニル基、ジスルフィド基、カルボニル基など)によって結合された2価の基が好ましい構造として挙げられる。Here, as the divalent organic group having an aromatic ring or an aliphatic hydrocarbon of R 1 , an alkylene group, a cycloalkylene group, a monocyclic or polycyclic arylene group, or an atomic group in which those groups are divalent. A divalent group bonded by (for example, an alkylene group, a cycloalkylene group, an oxygen atom, a sulfur atom, a sulfone group, a sulfinyl group, a disulfide group, a carbonyl group, etc.) is mentioned as a preferable structure.
前記ビスマレイミド化合物として、具体的には、N,N’−エチレンビスマレイミド、N,N’−ヘキサメチレンビスマレイミド、N,N’−(1,3−フェニレン)ビスマレイミド、N,N’−〔1,3−(2−メチルフェニレン)〕ビスマレイミド、N,N’−〔1,3−(4−メチルフェニレン)〕ビスマレイミド、N,N’−(1,4−フェニレン)ビスマレイミド、ビス(4−マレイミドフェニル)メタン、ビス(3−メチル−4−マレイミドフェニル)メタン、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、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、ビス(4−マレイミドフェニル)スルフィド、ビス(4−マレイミドフェニル)ケトン、ビス(4−マレイミドシクロヘキシル)メタン、1,4−ビス(4−マレイミドフェニル)シクロヘキサン、1,4−ビス(マレイミドメチル)シクロヘキサン、1,4−ビス(マレイミドメチル)ベンゼン、1,3−ビス(4−マレイミドフェノキシ)ベンゼン、1,3-ビス(3−マレイミドフェノキシ)ベンゼン、ビス〔4−(3−マレイミドフェノキシ)フェニル〕メタン、ビス〔4−(4−マレイミドフェノキシ)フェニル〕メタン、1,1−ビス〔4−(3−マレイミドフェノキシ)フェニル〕エタン、1,1−ビス〔4−(4−マレイミドフェノキシ)フェニル〕エタン、1,2−ビス〔4−(3−マレイミドフェノキシ)フェニル〕エタン、1,2−ビス〔4−(4−マレイミドフェノキシ)フェニル〕エタン、2,2−ビス〔4−(3−マレイミドフェノキシ)フェニル〕プロパン、2,2−ビス〔4−(4−マレイミドフェノキシ)フェニル〕プロパン、2,2−ビス〔4−(3−マレイミドフェノキシ)フェニル〕ブタン、2,2−ビス〔4−(4−マレイミドフェノキシ)フェニル〕ブタン、2,2−ビス〔[4−(3−マレイミドフェノキシ)フェニル〕−1,1,1,3,3,3−ヘキサフルオロプロパン、2,2−ビス〔4−(4−マレイミドフェノキシ)フェニル〕−1,1,1,3,3,3−ヘキサフルオロプロパン、4,4−ビス(3−マレイミドフェノキシ)ビフェニル、4,4−ビス(4−マレイミドフェノキシ)ビフェニル、ビス〔4−(3−マレイミドフェノキシ)フェニル〕ケトン、ビス〔4−(4−マレイミドフェノキシ)フェニル〕ケトン、2,2’−ビス(4−マレイミドフェニル)ジスルフィド、ビス(4−マレイミドフェニル)ジスルフィド、ビス〔4−(3−マレイミドフェノキシ)フェニル〕スルフィド、ビス〔4−(4−マレイミドフェノキシ)フェニル〕スルフィド、ビス〔4−(3−マレイミドフェノキシ)フェニル〕スルホキシド、ビス〔4−(4−マレイミドフェノキシ)フェニル〕スルホキシド、ビス〔4−(3−マレイミドフェノキシ)フェニル〕スルホン、ビス〔4−(4−マレイミドフェノキシ)フェニル〕スルホン、ビス〔4−(3−マレイミドフェノキシ)フェニル〕エーテル、ビス〔4−(4−マレイミドフェノキシ)フェニル〕エーテル、1,4−ビス〔4−(4−マレイミドフェノキシ)−α,α−ジメチルベンジル〕ベンゼン、1,3−ビス〔4−(4−マレイミドフェノキシ)−α,α−ジメチルベンジル〕ベンゼン、1,4−ビス〔4−(3−マレイミドフェノキシ)−α,α−ジメチルベンジル〕ベンゼン、1,3−ビス〔4−(3−マレイミドフェノキシ)−α,α−ジメチルベンジル〕ベンゼン、1,4−ビス〔4−(4−マレイミドフェノキシ)−3,5−ジメチル−α,α−ジメチルベンジル〕ベンゼン、1,3−ビス〔4−(4−マレイミドフェノキシ)−3,5−ジメチル−α,α−ジメチルベンジル〕ベンゼン、1,4−ビス〔4−(3−マレイミドフェノキシ)−3,5−ジメチル−α,α−ジメチルベンジル〕ベンゼン、1,3−ビス〔4−(3−マレイミドフェノキシ)−3,5−ジメチル−α,α−ジメチルベンジル〕ベンゼン、4−メチル−1,3−フェニレンビスマレイミド、ポリフェニルメタンマレイミドなどが挙げられ、これらのマレイミド化合物は、単独で用いても2種類以上を混合して用いてもよい。 Specific examples of the bismaleimide compound include N, N'-ethylene bismaleimide, N, N'-hexamethylene bismaleimide, N, N'-(1,3-phenylene) bismaleimide, N, N'-. [1,3- (2-Methylphenylene)] bismaleimide, N, N'-[1,3- (4-methylphenylene)] bismaleimide, N, N'-(1,4-phenylene) bismaleimide, Bis (4-maleimidephenyl) methane, bis (3-methyl-4-maleimidephenyl) methane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, bis (4-maleimidephenyl) ether , Bis (4-maleimidephenyl) sulfone, Bis (4-maleimidephenyl) sulfide, Bis (4-maleimidephenyl) ketone, Bis (4-maleimidecyclohexyl) methane, 1,4-bis (4-maleimidephenyl) cyclohexane, 1,4-bis (maleimide methyl) cyclohexane, 1,4-bis (maleimide methyl) benzene, 1,3-bis (4-maleimide phenoxy) benzene, 1,3-bis (3-maleimide phenoxy) benzene, bis [ 4- (3-Maleimide phenoxy) phenyl] methane, bis [4- (4-maleimide phenoxy) phenyl] methane, 1,1-bis [4- (3-maleimide phenoxy) phenyl] ethane, 1,1-bis [ 4- (4-Maleimide phenoxy) phenyl] ethane, 1,2-bis [4- (3-maleimide phenoxy) phenyl] ethane, 1,2-bis [4- (4-maleimide phenoxy) phenyl] ethane, 2, 2-Bis [4- (3-maleimide phenoxy) phenyl] propane, 2,2-bis [4- (4-maleimide phenoxy) phenyl] propane, 2,2-bis [4- (3-maleimide phenoxy) phenyl] Butane, 2,2-bis [4- (4-maleimide phenoxy) phenyl] butane, 2,2-bis [[4- (3-maleimide phenoxy) phenyl] -1,1,1,3,3,3- Hexafluoropropane, 2,2-bis [4- (4-maleimide phenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4-bis (3-maleimide phenoxy) biphenyl, 4,4-Bis (4-maleimide phenyloxy) biphenyl, bis [4- (3-maleimide phenoxy) phenyl] ketone, bis [4- (4-maleimide phenoxy) phenyl] Ketone, 2,2'-bis (4-maleimidephenyl) disulfide, bis (4-maleimidephenyl) disulfide, bis [4- (3-maleimidephenoxy) phenyl] sulfide, bis [4- (4-maleimidephenoxy) phenyl ] Sulphide, bis [4- (3-maleimidephenoxy) phenyl] sulfoxide, bis [4- (4-maleimidephenoxy) phenyl] sulfoxide, bis [4- (3-maleimidephenoxy) phenyl] sulfone, bis [4- ( 4-Maleimidephenoxy) Benzene] Benzene, Bis [4- (3-maleimidephenoxy) phenyl] ether, Bis [4- (4-maleimidephenoxy) phenyl] ether, 1,4-Bis [4- (4-maleimidephenoxy)] ) -Α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-maleimidephenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidephenoxy)- α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidephenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-maleimidephenoxy) -3, 5-Dimethyl-α, α-Dimethylbenzyl] Benzene, 1,3-bis [4- (4-maleimidephenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,4-bis [4 -(3-Maleimidephenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidephenoxy) -3,5-dimethyl-α, α-dimethylbenzyl ] Benzene, 4-methyl-1,3-phenylenebismaleimide, polyphenylmethanemaleimide and the like can be mentioned, and these maleimide compounds may be used alone or in combination of two or more.
これらの中で、2,2−ビス〔4−(4−マレイミドフェノキシ)フェニル〕プロパン、ビス(4−マレイミドフェニル)メタン、4−メチル−1,3−フェニレンビスマレイミド、ポリフェニルメタンマレイミド、およびビス(4−マレイミドフェニル)スルホンが好ましい。なお、反応率が高く、より高耐熱性化できる点からは、ビス(4−マレイミドフェニル)メタン、ビス(4−マレイミドフェニル)スルホン、ビス(4−マレイミドフェニル〕スルフィド、ビス(4−マレイミドフェニル)ジスルフィド、N,N’−(1,3−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)プロパンが好ましく、安価である点からビス(4−マレイミドフェニル)メタン、N,N’−(1,3−フェニレン)ビスマレイミドがより好ましく、溶剤への溶解性の点から、ビス(4−マレイミドフェニル)メタンが特に好ましい。 Among these, 2,2-bis [4- (4-maleimidephenoxy) phenyl] propane, bis (4-maleimidephenyl) methane, 4-methyl-1,3-phenylene bismaleimide, polyphenylmethanemaleimide, and Bis (4-maleimidephenyl) sulfone is preferred. In addition, from the viewpoint of high reaction rate and higher heat resistance, bis (4-maleimidephenyl) methane, bis (4-maleimidephenyl) sulfone, bis (4-maleimidephenyl) sulfide, bis (4-maleimidephenyl) ) Disulfide, N, N'-(1,3-phenylene) bismaleimide, 2,2-bis (4- (4-maleimidephenoxy) phenyl) propane is preferable, and bis (4-maleimidephenyl) is inexpensive. Methane, N, N'-(1,3-phenylene) bismaleimide is more preferable, and bis (4-maleimidephenyl) methane is particularly preferable from the viewpoint of solubility in a solvent.
また、1分子中にN−置換マレイミド基を3つ以上有するマレイミド樹脂の具体例としては、例えば、下記構造式(a2)〜(a4)の何れかで表されるものが挙げられる。 Further, specific examples of the maleimide resin having three or more N-substituted maleimide groups in one molecule include those represented by any of the following structural formulas (a2) to (a4).
これらの中でも、酸変性を行う際の反応の制御が容易である観点および、得られる硬化物の耐熱性により優れる観点より、前記構造式(a2)で表される樹脂を用いることが好ましく、特にVが炭素原子数1〜4のアルキレン基であり、pおよびqが0である樹脂を用いることがより好ましい。 Among these, it is preferable to use the resin represented by the structural formula (a2) from the viewpoint that the reaction at the time of acid denaturation can be easily controlled and the heat resistance of the obtained cured product is superior. It is more preferable to use a resin in which V is an alkylene group having 1 to 4 carbon atoms and p and q are 0.
これらマレイミドとしては、市販されているものをそのまま使用してもよく、例えば、大和化成工業株式会社製BMIシリーズ(BMI−1000、2000、2300、3000、4000、6000、7000、8000、TMH等)、ケイ・アイ化成株式会社製BMI、BMI−70、BMI−80等、東京化成工業株式会社製B1109、B4807、P0778、P0976等が挙げられる。 As these maleimides, commercially available ones may be used as they are. For example, BMI series manufactured by Daiwa Kasei Kogyo Co., Ltd. (BMI-1000, 2000, 2300, 3000, 4000, 6000, 7000, 8000, TMH, etc.) , BMI, BMI-70, BMI-80 manufactured by KI Kasei Co., Ltd., B1109, B4807, P0778, P0976, etc. manufactured by Tokyo Chemical Industry Co., Ltd.
本発明で用いる共役ジエンを有する脂肪酸又はその誘導体(a1)は、前記N−置換マレイミド基に対してディールス・アルダー反応が可能な共役ジエンを有しており、かつ、カルボキシ基又はその誘導体を有する化合物であればよく、特に限定されない。なお、誘導体は、カルボキシ基が塩構造となっているものやハライドになっているものを示し、ディールス・アルダー反応を阻害することがないものであって、かつ付加反応後、カルボキシ基とすることが可能なものをいう。反応の制御が容易である観点からは、脂肪酸を原料して用いることが好ましい。 The fatty acid having a conjugated diene or a derivative thereof (a1) used in the present invention has a conjugated diene capable of a Diels-Alder reaction with the N-substituted maleimide group, and also has a carboxy group or a derivative thereof. It may be a compound and is not particularly limited. The derivative indicates that the carboxy group has a salt structure or a halide, does not inhibit the Diels-Alder reaction, and is converted to a carboxy group after the addition reaction. Is possible. From the viewpoint of easy control of the reaction, it is preferable to use a fatty acid as a raw material.
前記共役ジエンを有する脂肪酸としては、例えば、ソルビン酸、2,4−デカジエン酸、2,4−ドデカジエン酸、10,12−オクタデカジエン酸、9−ヒドロキシ−10,12−オクタデカジエン酸、13−ヒドロキシ−9,11−オクタデカジエン酸、9,14−ジヒドロキシ−10,12−オクタデカジエン酸、9,12,14−オクタデカトリエン酸、8,10,12−オクタデカトリエン酸、エレオステアリン酸等、或いは各種アルキル基を有する脂肪酸を選択的水素化してなる共役ジエン脂肪酸が挙げられ、単独でも2種以上を併用してもよい。とくに付加反応の制御が容易であり、また得られる硬化物の耐熱性により優れる観点からは、炭素原子数が8以下の共役ジエン脂肪酸を用いることが好ましく、原料入手の容易性も鑑みれば、ソルビン酸を用いることがより好ましい。 Examples of the fatty acid having a conjugated diene include sorbic acid, 2,4-decadiene acid, 2,4-dodecadiene acid, 10,12-octadecadiene acid, 9-hydroxy-10,12-octadecadiene acid, and the like. 13-Hydroxy-9,11-octadecadienoic acid, 9,14-dihydroxy-10,12-octadecadienoic acid, 9,12,14-octadecatrienoic acid, 8,10,12-octadecatrienoic acid, Examples thereof include conjugated diene fatty acids obtained by selectively hydrogenating fatty acids having various alkyl groups such as eleostearic acid, and may be used alone or in combination of two or more. In particular, from the viewpoint that the addition reaction can be easily controlled and the heat resistance of the obtained cured product is superior, it is preferable to use a conjugated diene fatty acid having 8 or less carbon atoms, and sorbin is also considered from the viewpoint of easy availability of raw materials. It is more preferable to use an acid.
前記ディールス・アルダー反応は、公知の反応であり、特段本発明において限定されるものではなく、例えば、反応温度20〜150℃、反応時間1〜80時間で行うことができる。この時、N−置換マレイミド基1モルに対して、共役ジエンを有する脂肪酸又はその誘導体(a1)のモル数を0.01〜1.5モルの範囲で用いることが好ましく、0.02〜1.1モルの範囲で用いることがより好ましい。 The Diels-Alder reaction is a known reaction and is not particularly limited in the present invention, and can be carried out, for example, at a reaction temperature of 20 to 150 ° C. and a reaction time of 1 to 80 hours. At this time, it is preferable to use the number of moles of the fatty acid having a conjugated diene or its derivative (a1) in the range of 0.01 to 1.5 mol with respect to 1 mol of the N-substituted maleimide group, and 0.02 to 1 It is more preferable to use it in the range of 1 mol.
ディールス・アルダー反応を行う際に、有機溶剤を用いることもできる。使用できる有機溶剤としては、例えば、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剤;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剤;テトラヒドロフラン等のエーテル系溶剤;トルエン、キシレン、メシチレン等の芳香族系溶剤;ジメチルスルホキシド等のS原子含有溶剤;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N原子含有溶剤;エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールジブチルエーテル等のエチレングリコールジアルキルエーテル類;ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、トリエチレングリコールジメチルエーテル、トリエチレングリコールジエチルエーテル、トリエチレングリコールジブチルエーテル等のポリエチレングリコールジアルキルエーテル類;エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート等のエチレングリコールモノアルキルエーテルアセテート類;ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、トリエチレングリコールモノメチルエーテルアセテート、トリエチレングリコールモノエチルエーテルアセテート、トリエチレングリコールモノブチルエーテルアセテート等のポリエチレングリコールモノアルキルエーテルアセテート類;プロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル、プロピレングリコールジブチルエーテル等のプロピレングリコールジアルキルエーテル類;ジプロピレングリコールジメチルエーテル、ジプロピレングリコールジエチルエーテル、ジプロピレングリコールジブチルエーテル、トリプロピレングリコールジメチルエーテル、トリプロピレングリコールジエチルエーテル、トリプロピレングリコールジブチルエーテル等のポリプロピレングリコールジアルキルエーテル類;プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート等のプロピレングリコールモノアルキルエーテルアセテート類;ジプロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノエチルエーテルアセテート、ジプロピレングリコールモノブチルエーテルアセテート、トリプロピレングリコールモノメチルエーテルアセテート、トリプロピレングリコールモノエチルエーテルアセテート、トリプロピレングリコールモノブチルエーテルアセテート等のポリプロピレングリコールモノアルキルエーテルアセテート類;低分子のエチレン−プロピレン共重合体等の共重合ポリエーテルグリコールのジアルキルエーテル類;共重合ポリエーテルグリコールのモノアセテートモノアルキルエーテル類;共重合ポリエーテルグリコールのアルキルエステル類;および共重合ポリエーテルグリコールのモノアルキルエステルモノアルキルエーテル類等が挙げられる。これら有機溶剤は1種又は2種以上を混合して使用できる。これらの中で、副反応を抑制する観点から、アルコール性水酸基を含有しない溶剤が好ましい。更に溶解性の点からシクロヘキサノン、メチルエチルケトン等のケトン系溶剤や、エステル系溶剤が好ましい。有機溶剤の使用量としては、特に制限はないが、原料のマレイミドと共役ジエンを有する脂肪酸又はその誘導体(a1)を合わせた総質量100質量部に対して、通常0.5〜100質量部であり、好ましくは0.5〜70質量部、より好ましくは0.5〜50質量部である。 An organic solvent can also be used when carrying out the Diels-Alder reaction. Examples of the organic solvent that can be used include alcohol-based 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; and ether-based solvents such as tetrahydrofuran. Solvents: Aromatic solvents such as toluene, xylene, mesityrene; S atom-containing solvents such as dimethylsulfoxide; N atom-containing solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene Ethylene glycol dialkyl ethers such as glycol dibutyl ether; polyethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, and triethylene glycol dibutyl ether; ethylene glycol monomethyl ether Ethethylene glycol monoalkyl ether acetates such as acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate; diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol Polyethylene glycol monoalkyl ether acetates such as monoethyl ether acetate and triethylene glycol monobutyl ether acetate; propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether and propylene glycol dibutyl ether; dipropylene glycol dimethyl ether and dipropylene glycol Polypropylene glycol dialkyl ethers such as diethyl ether, dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, and tripropylene glycol dibutyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether. Propropylene glycol monoalkyl ether acetates such as acetate and propylene glycol monobutyl ether acetate; dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol mono Polypropylene glycol monoalkyl ether acetates such as ethyl ether acetate and tripropylene glycol monobutyl ether acetate; Dialkyl ethers of copolymerized polyether glycols such as low molecular weight ethylene-propylene copolymer; Monoacetate monoacetate of copolymerized polyether glycol Examples thereof include alkyl ethers; alkyl esters of copolymerized polyether glycols; and monoalkyl esters of copolymerized polyether glycols, such as monoalkyl ethers. These organic solvents can be used alone or in admixture of two or more. Among these, a solvent containing no alcoholic hydroxyl group is preferable from the viewpoint of suppressing side reactions. Further, from the viewpoint of solubility, a ketone solvent such as cyclohexanone or methyl ethyl ketone or an ester solvent is preferable. The amount of the organic solvent used is not particularly limited, but is usually 0.5 to 100 parts by mass with respect to 100 parts by mass of the total mass of the raw material maleimide and the fatty acid having conjugated diene or its derivative (a1). Yes, preferably 0.5 to 70 parts by mass, more preferably 0.5 to 50 parts by mass.
本発明での酸変性マレイミド樹脂(A)は、前記の付加反応で得られるものであり、分子中に下記構造式(1) The acid-modified maleimide resin (A) in the present invention is obtained by the above addition reaction, and has the following structural formula (1) in the molecule.
で表される構造を有することが好ましく、特に、この構造を、1分子中に2個以上有するものであることが、得られる硬化物の耐熱性の観点からより好ましいものである。
It is preferable to have a structure represented by, and in particular, it is more preferable to have two or more of these structures in one molecule from the viewpoint of heat resistance of the obtained cured product.
特に前述のビスマレイミド樹脂を用いた場合には、下記構造式(ii) In particular, when the above-mentioned bismaleimide resin is used, the following structural formula (ii)
で表される樹脂であることが好ましい。
It is preferable that the resin is represented by.
更に前述の構造式(a2)で表されるマレイミド樹脂を原料とした場合には、下記構造式(iii) Further, when the maleimide resin represented by the above-mentioned structural formula (a2) is used as a raw material, the following structural formula (iii) is used.
で表される樹脂であることが好ましい。これらの中でも、特に共役ジエンを有する脂肪酸又はその誘導体(a1)の付加の割合が、N−置換マレイミド基1モルに対し、0.02〜1モルである樹脂であることが、得られる硬化物の耐熱性の観点から好ましいものである。
It is preferable that the resin is represented by. Among these, the cured product obtained is a resin in which the addition ratio of the fatty acid having a conjugated diene or its derivative (a1) is 0.02 to 1 mol with respect to 1 mol of the N-substituted maleimide group. It is preferable from the viewpoint of heat resistance.
このようにして得られる本発明の酸変性マレイミド樹脂(A)は、通常、無色〜褐色の固形の樹脂状または液状を示し、場合によっては結晶化する。 The acid-modified maleimide resin (A) of the present invention thus obtained usually exhibits a colorless to brown solid resinous or liquid form, and in some cases crystallizes.
本発明での酸変性マレイミド樹脂の色相が悪い場合は、水素化触媒存在下で水素化することで色相改善を行っても良い。その際に用いる水素化触媒としては、ニッケルなどの鉄族元素またはパラジウム、ロジウム、白金などの白金族元素を活性成分として含むものが好ましく、活性成分を担体に保持させた形態のものがより好ましい。 When the hue of the acid-modified maleimide resin in the present invention is poor, the hue may be improved by hydrogenating in the presence of a hydrogenation catalyst. The hydrogenation catalyst used at that time is preferably one containing an iron group element such as nickel or a platinum group element such as palladium, rhodium or platinum as an active ingredient, and more preferably a catalyst in which the active ingredient is retained in a carrier. ..
また本発明での酸変性マレイミド樹脂のカルボキシ基当量は特に制限されるものではないが、後述する硬化剤として用いる際、得られる硬化物の耐熱性の観点から200〜10000〔g/eq〕の範囲であることが好ましく、さらに配合物のアルカリ現像性の観点から350〜2000〔g/eq〕の範囲であることが好ましい。 The carboxy group equivalent of the acid-modified maleimide resin in the present invention is not particularly limited, but when used as a curing agent described later, it is 200 to 10,000 [g / eq] from the viewpoint of heat resistance of the obtained cured product. The range is preferably in the range of 350 to 2000 [g / eq] from the viewpoint of alkali developability of the formulation.
また本発明での酸変性マレイミド樹脂の分子量は、特に制限されるものではないが、後述する硬化剤として用いる際、硬化物の成形時間の短縮と、任意の形状を付与させることができる観点から、重量平均分子量が、300〜10000であることが好ましく、さらに330〜5000であることがより好ましい。この重量平均分子量は実施例中に記載の方法で測定したポリスチレン換算値である。 The molecular weight of the acid-modified maleimide resin in the present invention is not particularly limited, but from the viewpoint of shortening the molding time of the cured product and imparting an arbitrary shape when used as a curing agent described later. The weight average molecular weight is preferably 300 to 10000, and more preferably 330 to 5000. This weight average molecular weight is a polystyrene-equivalent value measured by the method described in the examples.
当該酸変性マレイミド樹脂は、硬化性樹脂の硬化剤として使用することができ、例えば、以下の成分とともに使用することができる。 The acid-modified maleimide resin can be used as a curing agent for a curable resin, and can be used, for example, with the following components.
本発明で用いる硬化性樹脂(B)としては加熱または活性エネルギー線により硬化性を示す樹脂であれば特に制限されることなく用いることができるが、例えば、エポキシ樹脂、メラミン樹脂、ベンゾグアナミン樹脂、メラミン誘導体、ベンゾグアナミン誘導体等のアミノ樹脂、ブロックイソシアネート化合物、シクロカーボネート化合物、多官能オキセタン化合物、エピスルフィド樹脂、ビスマレイミド、カルボジイミド樹脂、シアネート樹脂等の公知の硬化性樹脂を好ましいものとして例示することができ、このうちエポキシ樹脂が好ましいものとして挙げられる。 The curable resin (B) used in the present invention can be used without particular limitation as long as it is a resin that exhibits curability by heating or active energy rays. For example, an epoxy resin, a melamine resin, a benzoguanamine resin, or a melamine can be used. Known curable resins such as derivatives, amino resins such as benzoguanamine derivatives, blocked isocyanate compounds, cyclocarbonate compounds, polyfunctional oxetane compounds, episulfide resins, bismaleimides, carbodiimide resins, and cyanate resins can be exemplified as preferable ones. Of these, epoxy resin is preferred.
さらに具体的にエポキシ樹脂としては、ノボラック型エポキシ樹脂、ビスフェノールA型エポキシ樹脂、ビフェニル型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂などが挙げられる。具体的には、ビスフェノールA、ビスフェノールS、チオジフェノール、フルオレンビスフェノール、テルペンジフェノール、4,4’−ビフェノール、2,2’−ビフェノール、3,3’,5,5’−テトラメチル−[1,1’−ビフェニル]−4,4’−ジオール、ハイドロキノン、レゾルシン、ナフタレンジオール、トリス−(4−ヒドロキシフェニル)メタン、1,1,2,2−テトラキス(4−ヒドロキシフェニル)エタン、フェノール類(フェノール、アルキル置換フェノール、ナフトール、アルキル置換ナフトール、ジヒドロキシベンゼン、ジヒドロキシナフタレン等)とホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド、p−ヒドロキシベンズアルデヒド、o−ヒドロキシベンズアルデヒド、p−ヒドロキシアセトフェノン、o−ヒドロキシアセトフェノン、ジシクロペンタジエン、フルフラール、4,4’−ビス(クロルメチル)−1,1’−ビフェニル、4,4’−ビス(メトキシメチル)−1,1’−ビフェニル、1,4−ビス(クロロメチル)ベンゼン、1,4−ビス(メトキシメチル)ベンゼン等との重縮合物及びこれらの変性物、テトラブロモビスフェノールA等のハロゲン化ビスフェノール類、アルコール類から誘導されるグリシジルエーテル化物、脂環式エポキシ樹脂、グリシジルアミン系エポキシ樹脂、グリシジルエステル系エポキシ樹脂、シルセスキオキサン系のエポキシ樹脂(鎖状、環状、ラダー状、あるいはそれら少なくとも2種以上の混合構造のシロキサン構造にグリシジル基、および/またはエポキシシクロヘキサン構造を有するエポキシ樹脂)等の固形または液状エポキシ樹脂が挙げられるが、これらに限定されるものではない。 More specific examples of the epoxy resin include novolak type epoxy resin, bisphenol A type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol aralkyl type epoxy resin and the like. Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpendiphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3', 5,5'-tetramethyl- [ 1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol Classes (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclo Pentaziene, furfural, 4,4'-bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis (methoxymethyl) -1,1'-biphenyl, 1,4-bis (chloromethyl) benzene, Polycondensate with 1,4-bis (methoxymethyl) benzene and their modifications, halogenated bisphenols such as tetrabromobisphenol A, glycidyl etherified products derived from alcohols, alicyclic epoxy resin, glycidyl Amin-based epoxy resin, glycidyl ester-based epoxy resin, silsesquioxane-based epoxy resin (chain, cyclic, ladder-like, or a siloxane structure having a mixed structure of at least two of them, a glycidyl group, and / or an epoxycyclohexane structure. Solid or liquid epoxy resin such as epoxy resin), but the present invention is not limited thereto.
本発明の硬化性樹脂組成物において、酸変性マレイミド樹脂(A)と硬化性樹脂(B)との組成比率は特に限定されるものではないが、耐熱性、耐湿熱性に優れる点から、エポキシ樹脂を用いる場合、酸変性マレイミド樹脂(A)のカルボキシル基1当量に対して、硬化性樹脂(B)のエポキシ基が1.0〜2.0当量となる範囲であることが好ましく、さらにアルカリ現像性の観点から1.0〜1.5当量の範囲であることがより好ましい。 In the curable resin composition of the present invention, the composition ratio of the acid-modified maleimide resin (A) and the curable resin (B) is not particularly limited, but the epoxy resin is excellent in heat resistance and moisture heat resistance. Is preferably in the range of 1.0 to 2.0 equivalents of the epoxy group of the curable resin (B) with respect to 1 equivalent of the carboxyl group of the acid-modified maleimide resin (A), and further subjected to alkali development. From the viewpoint of sex, it is more preferably in the range of 1.0 to 1.5 equivalents.
本発明の硬化性樹脂組成物は、必要に応じて公知の光重合開始剤(C)を適宜添加することができる。光重合開始剤としては、オキシムエステル基を有するオキシムエステル系光重合開始剤、アルキルフェノン系光重合開始剤、α−アミノアセトフェノン系光重合開始剤、アシルホスフィンオキサイド系光重合開始剤、チタノセン系光重合開始剤からなる群から選択される1種以上の光重合開始剤を好適に使用することができる。 The known photopolymerization initiator (C) can be appropriately added to the curable resin composition of the present invention, if necessary. Examples of the photopolymerization initiator include an oxime ester-based photopolymerization initiator having an oxime ester group, an alkylphenone-based photopolymerization initiator, an α-aminoacetophenone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, and a titanosen-based photoinitiator. One or more photopolymerization initiators selected from the group consisting of polymerization initiators can be preferably used.
このようなオキシムエステル系光重合開始剤を用いる場合の配合量は、光硬化性および解像性に優れ、密着性やPCT耐性も向上し、さらには無電解金めっき耐性などの耐薬品性にも優れるソルダーレジストを得ることができる点から、組成物全体の0.01〜5質量%とすることが好ましく、0.25〜3質量%とすることがより好ましい。 When such an oxime ester-based photopolymerization initiator is used, the blending amount is excellent in photocurability and resolution, improves adhesion and PCT resistance, and further improves chemical resistance such as electroless gold plating resistance. From the viewpoint that an excellent solder resist can be obtained, the content is preferably 0.01 to 5% by mass, more preferably 0.25 to 3% by mass of the entire composition.
アルキルフェノン系光重合開始剤を用いる場合の配合量は、同様の点から、組成物全体の0.2〜30質量%とすることが好ましく、2〜20質量%とすることがより好ましい。 From the same point of view, when the alkylphenone-based photopolymerization initiator is used, the blending amount is preferably 0.2 to 30% by mass, more preferably 2 to 20% by mass of the entire composition.
α−アミノアセトフェノン系光重合開始剤またはアシルホスフィンオキサイド系光重合開始剤を用いる場合の配合量は、同様の点から、組成物全体の0.1〜25質量%であることが好ましく、1〜20質量%であることがより好ましい。 When an α-aminoacetophenone-based photopolymerization initiator or an acylphosphine oxide-based photopolymerization initiator is used, the blending amount is preferably 0.1 to 25% by mass of the entire composition from the same point of view, and 1 to 1 It is more preferably 20% by mass.
また光重合開始剤としてはBASFジャパン製のイルガキュア389も好適に用いることができる。イルガキュア389の好適な配合量は、組成物全体の0.1〜20質量%であり、さらに1〜15質量%が好適である。 Further, as the photopolymerization initiator, Irgacure 389 manufactured by BASF Japan can also be preferably used. A suitable blending amount of Irgacure 389 is 0.1 to 20% by mass of the entire composition, and more preferably 1 to 15% by mass.
そして、イルガキュア784等のチタノセン系光重合開始剤も好適に用いることができる。チタノセン系光重合開始剤の好適な配合量は、組成物全体の0.01〜5質量%であり、さらに、0.01〜3質量%が好適である。 A titanocene-based photopolymerization initiator such as Irgacure 784 can also be preferably used. The suitable blending amount of the titanocene-based photopolymerization initiator is 0.01 to 5% by mass of the entire composition, and more preferably 0.01 to 3% by mass.
これらの光重合開始剤を好適な配合量とすることにより、光硬化性および解像性に優れ、密着性やPCT耐性も向上し、さらには無電解金めっき耐性などの耐薬品性にも優れたソルダーレジストとすることができる。 By adjusting the amount of these photopolymerization initiators to a suitable level, the photocurability and resolution are excellent, the adhesion and PCT resistance are improved, and the chemical resistance such as electroless gold plating resistance is also excellent. It can be a solder resist.
本発明の硬化性樹脂組成物には、光重合開始剤の他に、さらに必要に応じて光開始助剤、増感剤を用いることができる。硬化性樹脂組成物に好適に用いることができる光開始助剤および増感剤としては、ベンゾイン化合物、アセトフェノン化合物、アントラキノン化合物、チオキサントン化合物、ケタール化合物、ベンゾフェノン化合物、3級アミン化合物、およびキサントン化合物などを挙げることができる。 In addition to the photopolymerization initiator, a photoinitiator aid and a sensitizer can be used in the curable resin composition of the present invention, if necessary. Examples of the photoinitiator aid and sensitizer that can be suitably used in the curable resin composition include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds. Can be mentioned.
これらの光開始助剤および増感剤は、単独でまたは2種類以上の混合物として使用することができる。このような光開始助剤、および増感剤の総量は、組成物全体の30質量%以下であることが好ましい。30質量%を超えると、これらの光吸収により深部硬化性が低下する傾向にある。 These photoinitiator aids and sensitizers can be used alone or as a mixture of two or more. The total amount of such a photoinitiator aid and a sensitizer is preferably 30% by mass or less of the total composition. If it exceeds 30% by mass, the deep curability tends to decrease due to these light absorptions.
硬化性樹脂組成物は、必要に応じて希釈剤(D)を適宜添加することができる。希釈剤(D)として、分子中にエチレン性不飽和基を有する化合物を配合することが好ましい。分子中にエチレン性不飽和基を有する化合物は、活性エネルギー線の照射により光硬化して、本発明の樹脂組成物をアルカリ水溶液に不溶化し、または不溶化を助けることができる。このような化合物としては、慣用公知のポリエステル(メタ)アクリレート、ポリエーテル(メタ)アクリレート、ウレタン(メタ)アクリレート、カーボネート(メタ)アクリレート、エポキシ(メタ)アクリレート、ウレタン(メタ)アクリレートが使用でき、具体的には、2−ヒドロキシエチルアクリレート、2−ヒドロキシプロピルアクリレートなどのヒドロキシアルキルアクリレート類;エチレングリコール、メトキシテトラエチレングリコール、ポリエチレングリコール、プロピレングリコールなどのグリコールのジアクリレート類;N,N−ジメチルアクリルアミド、N−メチロールアクリルアミド、N,N−ジメチルアミノプロピルアクリルアミドなどのアクリルアミド類;N,N−ジメチルアミノエチルアクリレート、N,N−ジメチルアミノプロピルアクリレートなどのアミノアルキルアクリレート類;ヘキサンジオール、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリス−ヒドロキシエチルイソシアヌレートなどの多価アルコールまたはこれらのエチレオキサイド付加体、プロピレンオキサイド付加体、もしくはε−カプロラクトン付加体などの多価アクリレート類;フェノキシアクリレート、ビスフェノールAジアクリレート、およびこれらのフェノール類のエチレンオキサイド付加体もしくはプロピレンオキサイド付加体などの多価アクリレート類;グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、トリグリシジルイソシアヌレートなどのグリシジルエーテルの多価アクリレート類;上記に限らず、ポリエーテルポリオール、ポリカーボネートジオール、水酸基末端ポリブタジエン、ポリエステルポリオールなどのポリオールを直接アクリレート化、もしくは、ジイソシアネートを介してウレタンアクリレート化したアクリレート類およびメラミンアクリレート、および上記アクリレートに対応する各メタクリレート類の少なくとも何れか1種などを挙げることができる。 A diluent (D) can be appropriately added to the curable resin composition, if necessary. As the diluent (D), it is preferable to add a compound having an ethylenically unsaturated group in the molecule. The compound having an ethylenically unsaturated group in the molecule can be photocured by irradiation with active energy rays to insolubilize the resin composition of the present invention in an alkaline aqueous solution or assist in insolubilization. As such a compound, commonly known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, and urethane (meth) acrylate can be used. Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; N, N-dimethylacrylamide. , N-methylol acrylamide, acrylamides such as N, N-dimethylaminopropyl acrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate; hexanediol, trimetyl propane, Polyhydric alcohols such as pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or polyhydric acrylates such as their ethireoxyside adducts, propylene oxide adducts, or ε-caprolactone adducts; phenoxyacrylates, bisphenol A di. Polyvalent acrylates such as acrylates and ethylene oxide adducts or propylene oxide adducts of these phenols; glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropan triglycidyl ether, triglycidyl isocyanurate. Polyvalent acrylates; Not limited to the above, acrylates and melamine acrylates obtained by directly acrylated polyols such as polyether polyols, polycarbonate diols, hydroxyl group-terminated polybutadienes, polyester polyols, or urethane acrylates via diisocyanates, and the above acrylates. At least one of each methacrylate corresponding to the above can be mentioned.
さらに、クレゾールノボラック型エポキシ樹脂等の多官能エポキシ樹脂に、アクリル酸を反応させたエポキシアクリレート樹脂や、さらにそのエポキシアクリレート樹脂の水酸基に、ペンタエリスリトールトリアクリレート等のヒドロキシアクリレートとイソホロンジイソシアネート等のジイソシアネートのハーフウレタン化合物を反応させたエポキシウレタンアクリレート化合物等、又は同様に酸無水物を反応させてカルボン酸基を含有させた酸変性エポキシアクリレート樹脂等を挙げることができる。このようなエポキシアクリレート系樹脂は、指触乾燥性を低下させることなく、光硬化性を向上させることができる。 Further, an epoxy acrylate resin obtained by reacting a polyfunctional epoxy resin such as cresol novolac type epoxy resin with acrylic acid, and a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate are added to the hydroxyl group of the epoxy acrylate resin. Examples thereof include an epoxy urethane acrylate compound obtained by reacting a half urethane compound, and an acid-modified epoxy acrylate resin obtained by reacting an acid anhydride and containing a carboxylic acid group. Such an epoxy acrylate-based resin can improve the photocurability without lowering the dryness to the touch.
上記のような分子中にエチレン性不飽和基を有する化合物は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。特に1分子内に4個から6個のエチレン性不飽和基を有する化合物が光反応性と解像性の観点から好ましく、さらに1分子内に2個のエチレン性不飽和基を有する化合物を用いると、硬化物の線熱膨張係数が低下し、PCT時における剥がれの発生が低減されることから好ましい。 As the compound having an ethylenically unsaturated group in the molecule as described above, one kind may be used alone, or two or more kinds may be used in combination. In particular, a compound having 4 to 6 ethylenically unsaturated groups in one molecule is preferable from the viewpoint of photoreactivity and resolution, and a compound having two ethylenically unsaturated groups in one molecule is used. This is preferable because the linear thermal expansion coefficient of the cured product is lowered and the occurrence of peeling during PCT is reduced.
本発明の硬化性樹脂組成物に希釈剤を用いる場合の配合量は、光硬化性が向上し、活性エネルギー線照射後のアルカリ現像により、パターン形成が良好となり、かつ、希アルカリ水溶液に対する溶解性が向上して、塗膜の耐衝撃性が向上する傾向にあることから、組成物全体の2〜50質量%が好ましい。 When a diluent is used in the curable resin composition of the present invention, the amount of the diluent is improved, the photocurability is improved, the pattern formation is improved by alkaline development after irradiation with active energy rays, and the solubility in a dilute alkaline aqueous solution is improved. Is improved, and the impact resistance of the coating film tends to be improved. Therefore, 2 to 50% by mass of the entire composition is preferable.
本発明の硬化性樹脂組成物は、必要に応じて硬化促進剤を適宜添加することができる。硬化促進剤としては、例えば2−エチル−4−メチルイミダゾール、1−メチルイミダゾール等のイミダゾール類、ベンジルジメチルアミン、N,N−ジメチルアニリン等の三級アミン、テトラメチルアンモニウムクロライド、ベンジルトリエチルアンモニウムクロライド等の四級アンモニウム塩、テトラ−n−ブチルホスホニウム、o,o−ジエチルホスホロジチオネート、テトラブチルホスホニウムベンゾトリアゾラート等のホスホニウム塩、オクチル酸亜鉛、ステアリン酸亜鉛等の金属塩、アセチルアセトン亜鉛、ベンゾイルアセトン亜鉛等の金属錯体などが挙げられる。 In the curable resin composition of the present invention, a curing accelerator can be appropriately added as needed. Examples of the curing accelerator include imidazoles such as 2-ethyl-4-methylimidazole and 1-methylimidazole, tertiary amines such as benzyldimethylamine and N, N-dimethylaniline, tetramethylammonium chloride and benzyltriethylammonium chloride. Quaternary ammonium salts such as, tetra-n-butylphosphonium, o, o-diethylphosphorodithionate, phosphonium salts such as tetrabutylphosphonium benzotriazolate, metal salts such as zinc octylate, zinc stearate, zinc acetylacetone. , Metal complexes such as benzoylacetone zinc and the like.
本発明の硬化性樹脂組成物に硬化促進剤を用いる場合の配合量は、0.01〜8質量%とするのが好ましく、0.1〜5質量%とするのがより好ましい。硬化促進剤の配合量が0.01質量%以上であると、十分な効果が得られるため好ましい。また、硬化促進剤の配合量が8質量%以下であれば、得られる硬化物の、透明度や耐熱性を維持することができるため好ましい。 When a curing accelerator is used in the curable resin composition of the present invention, the blending amount is preferably 0.01 to 8% by mass, more preferably 0.1 to 5% by mass. It is preferable that the blending amount of the curing accelerator is 0.01% by mass or more because a sufficient effect can be obtained. Further, when the blending amount of the curing accelerator is 8% by mass or less, the transparency and heat resistance of the obtained cured product can be maintained, which is preferable.
本発明の硬化性樹脂組成物は、必要に応じて無機フィラーを適宜添加することができる。無機フィラーは、硬化性樹脂組成物の硬化物の硬化収縮を抑制し、密着性、硬度などの特性を向上させるために使用される。無機フィラーとしては、例えば、硫酸バリウム、チタン酸バリウム、無定形シリカ、結晶性シリカ、ノイブルグ珪土、溶融シリカ、球状シリカ、タルク、クレー、炭酸マグネシウム、炭酸カルシウム、酸化アルミニウム、水酸化アルミニウム、窒化ケイ素、窒化アルミニウム、等を挙げることができる。 Inorganic fillers can be appropriately added to the curable resin composition of the present invention, if necessary. Inorganic fillers are used to suppress curing shrinkage of cured products of curable resin compositions and improve properties such as adhesion and hardness. Examples of the inorganic filler include barium sulfate, barium titanate, amorphous silica, crystalline silica, Neuburg silica soil, molten silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and silicon nitride. Examples thereof include silicon and aluminum nitride.
上記無機フィラーの平均粒子径は5μm以下であることが好ましい。配合割合は、組成物全体の75質量%以下が好ましく、より好ましくは0.1〜60質量%である。無機フィラーの配合割合が75質量%を超えると、組成物の粘度が高くなり、塗布性が低下したり、硬化性樹脂組成物の硬化物が脆くなることがある。 The average particle size of the inorganic filler is preferably 5 μm or less. The blending ratio is preferably 75% by mass or less, more preferably 0.1 to 60% by mass, based on the whole composition. If the blending ratio of the inorganic filler exceeds 75% by mass, the viscosity of the composition may increase, the coatability may decrease, or the cured product of the curable resin composition may become brittle.
本発明の硬化性樹脂組成物には、さらに、任意成分として、有機溶剤、エラストマー、メルカプト化合物、着色剤、酸化防止剤、紫外線吸収剤、密着促進剤、重合禁止剤、微粉シリカ、有機ベントナイト、モンモリロナイト等の増粘剤、シリコーン系、フッ素系、高分子系等の消泡剤およびレベリング剤の少なくとも何れか1種、イミダゾール系、チアゾール系、トリアゾール系等のシランカップリング剤、防錆剤、ホスフィン酸塩、燐酸エステル誘導体、フォスファゼン化合物等のリン化合物等の難燃剤、ブロック共重合体といった公知の添加剤類を配合してもよい。 The curable resin composition of the present invention further contains, as optional components, an organic solvent, an elastomer, a mercapto compound, a colorant, an antioxidant, an ultraviolet absorber, an adhesion accelerator, a polymerization inhibitor, a fine powder silica, and an organic bentonite. Thickeners such as montmorillonite, at least one of silicone-based, fluorine-based, polymer-based defoaming agents and leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, rust preventives, etc. Known additives such as phosphinates, phosphoric acid ester derivatives, flame retardants such as phosphorus compounds such as phosphazene compounds, and block copolymers may be blended.
本発明の硬化性樹脂組成物において、上記樹脂組成物の調製のため、または基材やキャリアフィルムに塗布するための粘度調整のため、有機溶剤を使用することができる。このような上記樹脂組成物の調製のための、または基材やキャリアフィルムに塗布するための粘度調整のための有機溶剤としては、ケトン類、芳香族炭化水素類、グリコールエーテル類、グリコールエーテルアセテート類、エステル類、アルコール類、脂肪族炭化水素、石油系溶剤などを挙げることができる。より詳細には、例えば、メチルエチルケトン、シクロヘキサノン等のケトン類;トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類;セロソルブ、メチルセロソルブ、ブチルセロソルブ、カルビトール、メチルカルビトール、ブチルカルビトール、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールジエチルエーテル、トリエチレングリコールモノエチルエーテル等のグリコールエーテル類;酢酸エチル、酢酸ブチル、ジプロピレングリコールメチルエーテルアセテート、プロピレングリコールメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテート、プロピレングリコールブチルエーテルアセテートなどのエステル類;エタノール、プロパノール、エチレングリコール、プロピレングリコール等のアルコール類;オクタン、デカン等の脂肪族炭化水素;石油エーテル、石油ナフサ、水添石油ナフサ、ソルベントナフサ等の石油系溶剤などを挙げることができる。このような有機溶剤は、1種を単独で用いてもよく、2種以上を混合物として用いてもよい。 In the curable resin composition of the present invention, an organic solvent can be used for preparing the above resin composition or for adjusting the viscosity for coating on a base material or a carrier film. Examples of the organic solvent for preparing the above resin composition or adjusting the viscosity for coating on a base material or a carrier film include ketones, aromatic hydrocarbons, glycol ethers, and glycol ether acetate. Kinds, esters, alcohols, aliphatic hydrocarbons, petroleum solvents and the like. More specifically, for example, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol and propylene glycol. Glycol ethers such as monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether Esters such as acetate, propylene glycol butyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol, propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, etc. Petroleum-based solvents and the like can be mentioned. As such an organic solvent, one kind may be used alone, or two or more kinds may be used as a mixture.
本発明のドライフィルムは、本発明の硬化性樹脂組成物を塗布・乾燥して形成される硬化性樹脂層を有する。本発明のドライフィルムは、硬化性樹脂層を、基材に接するようにラミネートして使用することができる。 The dry film of the present invention has a curable resin layer formed by applying and drying the curable resin composition of the present invention. The dry film of the present invention can be used by laminating a curable resin layer so as to be in contact with a base material.
本発明のドライフィルムは、キャリアフィルムに硬化性樹脂組成物をブレードコーター、リップコーター、コンマコーター、フィルムコーター等の適宜の方法により均一に塗布し、乾燥して、前記した硬化性樹脂層を形成し、好ましくはその上にカバーフィルムを積層することにより、製造することができる。カバーフィルムとキャリアフィルムは同一のフィルム材料であっても、異なるフィルムを用いてもよい。 In the dry film of the present invention, the curable resin composition is uniformly applied to the carrier film by an appropriate method such as a blade coater, a lip coater, a comma coater, and a film coater, and dried to form the above-mentioned curable resin layer. However, it can be produced by laminating a cover film on the cover film. The cover film and the carrier film may be the same film material or different films may be used.
本発明のドライフィルムにおいてキャリアフィルム、カバーフィルムのフィルム材料は、ドライフィルムに用いられるものとして公知のものをいずれも使用することができる。 In the dry film of the present invention, as the film material of the carrier film and the cover film, any known one as used for the dry film can be used.
キャリアフィルムとしては、例えば2〜150μmの厚さのポリエチレンテレフタレート等のポリエステルフィルムなどの熱可塑性フィルムが用いられる。 As the carrier film, for example, a thermoplastic film such as a polyester film such as polyethylene terephthalate having a thickness of 2 to 150 μm is used.
カバーフィルムとしては、ポリエチレンフィルム、ポリプロピレンフィルム等を使用することができるが、硬化性樹脂層との接着力が、キャリアフィルムよりも小さいものが良い。 As the cover film, a polyethylene film, a polypropylene film or the like can be used, but one having a smaller adhesive force with the curable resin layer than the carrier film is preferable.
本発明のキャリアフィルム上の硬化性樹脂層の膜厚は、100μm以下が好ましく、5〜50μmの範囲がより好ましい。 The film thickness of the curable resin layer on the carrier film of the present invention is preferably 100 μm or less, more preferably 5 to 50 μm.
本発明のプリント配線板は、本発明のドライフィルムを構成する本発明の硬化性樹脂層を用いて作製されることが好ましい。例えば、硬化性樹脂層を含むドライフィルムをラミネートし、例えば約140〜180℃の温度に加熱して熱硬化させることにより、樹脂絶縁層を形成することが好ましい。 The printed wiring board of the present invention is preferably manufactured by using the curable resin layer of the present invention constituting the dry film of the present invention. For example, it is preferable to form a resin insulating layer by laminating a dry film containing a curable resin layer and heating it to a temperature of, for example, about 140 to 180 ° C. for thermosetting.
なお、本発明のプリント配線板は、ブレードコーター、リップコーター、コンマコーター、フィルムコーター等の適宜の方法により、基材に硬化性樹脂組成物を直接塗布・乾燥して樹脂絶縁層を形成することにより得ることができる。 The printed wiring board of the present invention is formed by directly applying and drying a curable resin composition to a base material by an appropriate method such as a blade coater, a lip coater, a comma coater, or a film coater to form a resin insulating layer. Can be obtained by
本発明のプリント配線板の樹脂絶縁層は、CO2レーザーやUV−YAGレーザー等の半導体レーザーを照射することによりパターニングが可能である。また、CO2レーザーやUV−YAGレーザー、またはドリルにより、穴を開けることができる。樹脂絶縁層が複数からなる場合、穴は樹脂絶縁層の任意の層と導通が可能な貫通穴(スルーホール)でも内層の回路と樹脂絶縁層表面の導通を目的とする部分穴(コンフォーマルビア)のどちらもあけることができる。The resin insulating layer of the printed wiring board of the present invention can be patterned by irradiating it with a semiconductor laser such as a CO 2 laser or a UV-YAG laser. In addition, a hole can be drilled with a CO 2 laser, a UV-YAG laser, or a drill. When there are multiple resin insulating layers, the holes are through holes that can conduct with any layer of the resin insulating layer (through holes), but partial holes (conformal vias) for the purpose of conducting the circuit of the inner layer and the surface of the resin insulating layer. ) Both can be opened.
穴あけ加工後、穴の内壁や底部に存在する残渣(スミヤ)を除去することと、導体層(その後に形成する金属めっき層)とのアンカー効果を発現させるために表面に微細な凹凸状の粗化面を形成することを目的として、市販のデスミヤ液(粗化剤)または過マンガン酸塩、重クロム酸塩、オゾン、過酸化水素/硫酸、硝酸等の酸化剤を含有する液で処理を行う。 After drilling, the surface is rough with fine irregularities in order to remove the residue (sulfuric acid) existing on the inner wall and bottom of the hole and to exhibit the anchor effect with the conductor layer (the metal plating layer formed thereafter). Treatment with a commercially available desmiya solution (roughening agent) or a solution containing an oxidizing agent such as permanganate, dichromate, ozone, hydrogen peroxide / sulfuric acid, or nitric acid for the purpose of forming a plated surface. Do.
次に、デスミヤ液で残渣を除去した穴や、微細な凹凸状に粗化した皮膜表面にサブトラクティブ法やセミアディティブ法により、回路を形成する。いずれの方法においても、無電解めっき、または電解めっき後、或いは両方のめっきを施した後に、金属のストレス除去、強度向上の目的で約80℃〜180℃で10分〜60分程度の熱処理(アニール処理)を施しても良い。 Next, a circuit is formed by a subtractive method or a semi-additive method on a hole from which a residue has been removed with a desmiya liquid or a film surface roughened into fine irregularities. In either method, after electroless plating, electroplating, or both platings, heat treatment at about 80 ° C. to 180 ° C. for about 10 to 60 minutes for the purpose of stress relief and strength improvement of the metal ( Annealing treatment) may be performed.
ここで用いる金属めっきとしては、銅、錫、はんだ、ニッケル等特に制限は無く、複数組み合わせて使用することもできる。また、ここで用いるめっきの代わりに金属のスパッタリング等で代用することも可能である。 The metal plating used here is not particularly limited to copper, tin, solder, nickel and the like, and a plurality of combinations can be used. Further, instead of the plating used here, it is also possible to substitute metal sputtering or the like.
また、樹脂絶縁層を、感光性の硬化性樹脂層や硬化性樹脂組成物を塗布・乾燥した乾燥塗膜により形成する場合、基材(基板)上に形成された硬化性樹脂層や乾燥塗膜を、接触式(または非接触方式)により、パターンを形成したフォトマスクを通して、選択的に活性エネルギー線により露光もしくはレーザーダイレクト露光機により直接パターン露光する。硬化性樹脂層や乾燥塗膜は、露光部(活性エネルギー線により照射された部分)が硬化する。 When the resin insulating layer is formed by a photosensitive curable resin layer or a dry coating film to which a curable resin composition is applied and dried, the curable resin layer or dry coating formed on the base material (subject) is used. The film is selectively exposed to active energy rays or directly patterned by a laser direct exposure machine through a photomask in which a pattern is formed by a contact method (or a non-contact method). In the curable resin layer and the dry coating film, the exposed portion (the portion irradiated with the active energy ray) is cured.
活性エネルギー線照射に用いられる露光機としては、直接描画装置(例えばコンピューターからのCADデータにより直接レーザーで画像を描くレーザーダイレクトイメージング装置)、メタルハライドランプを搭載した露光機、(超)高圧水銀ランプを搭載した露光機、LEDを搭載した露光機、水銀ショートアークランプを搭載した露光装置を用いることができる。 As the exposure machine used for active energy ray irradiation, a direct drawing device (for example, a laser direct imaging device that directly draws an image with a laser based on CAD data from a computer), an exposure machine equipped with a metal halide lamp, and an (ultra) high pressure mercury lamp are used. An on-board exposure machine, an exposure machine equipped with an LED, and an exposure apparatus equipped with a mercury short arc lamp can be used.
活性エネルギー線としては、最大波長が350〜410nmの範囲にある光を用いることが好ましい。最大波長をこの範囲とすることにより、光重合開始剤から効率よくラジカルを生成することができる。また、その露光量は膜厚等によって異なるが、一般には5〜500mJ/cm2、好ましくは10〜300mJ/cm2の範囲内とすることができる。As the active energy ray, it is preferable to use light having a maximum wavelength in the range of 350 to 410 nm. By setting the maximum wavelength in this range, radicals can be efficiently generated from the photopolymerization initiator. The exposure amount varies depending on the film thickness and the like, but can be generally in the range of 5 to 500 mJ / cm 2 , preferably 10 to 300 mJ / cm 2 .
直接描画装置としては、例えば、日本オルボテック株式会社製、ペンタックス株式会社製、オーク株式会社製、大日本スクリーン株式会社製等のものを使用することができ、最大波長が350〜410nmの活性エネルギー線を照射する装置であればいずれの装置を用いてもよい。 As the direct drawing device, for example, one manufactured by Nippon Orbotech Co., Ltd., Pentax Co., Ltd., Oak Co., Ltd., Dainippon Screen Co., Ltd., etc. can be used, and an active energy ray having a maximum wavelength of 350 to 410 nm can be used. Any device may be used as long as it is a device for irradiating.
そして、このようにして硬化性樹脂層や乾燥塗膜を露光することにより、露光部(活性エネルギー線により照射された部分)を硬化させた後、未露光部を希アルカリ水溶液(例えば、0.3〜3wt%炭酸ソーダ水溶液)により現像して、硬化性樹脂層や乾燥塗膜にパターンが形成される。 Then, by exposing the curable resin layer and the dry coating film in this way, the exposed portion (the portion irradiated with the active energy rays) is cured, and then the unexposed portion is subjected to a dilute alkaline aqueous solution (for example, 0. It is developed with a 3 to 3 wt% sodium carbonate aqueous solution) to form a pattern on the curable resin layer and the dry coating film.
このとき、現像方法としては、ディッピング法、シャワー法、スプレー法、ブラシ法等によることができる。また、現像液としては、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、リン酸ナトリウム、ケイ酸ナトリウム、アンモニア、アミン類等のアルカリ水溶液を用いることができる。 At this time, the developing method can be a dipping method, a shower method, a spray method, a brush method, or the like. Further, as the developing solution, an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia and amines can be used.
さらに、硬化性樹脂層を、例えば約140〜180℃の温度に加熱して熱硬化させることにより、酸変性マレイミド樹脂(A)のカルボキシ基と、硬化性樹脂(B)が反応し、耐熱性、耐薬品性、耐吸湿性、密着性、絶縁信頼性等の諸特性に優れた樹脂絶縁層(パターン)を形成することができる。 Further, by heating the curable resin layer to a temperature of, for example, about 140 to 180 ° C. and heat-curing it, the carboxy group of the acid-modified maleimide resin (A) reacts with the curable resin (B), resulting in heat resistance. It is possible to form a resin insulating layer (pattern) having excellent various characteristics such as chemical resistance, moisture absorption resistance, adhesion, and insulation reliability.
本発明のプリント配線板中の樹脂絶縁層の全膜厚は、100μm以下が好ましく、5〜50μmの範囲がより好ましい。 The total film thickness of the resin insulating layer in the printed wiring board of the present invention is preferably 100 μm or less, more preferably 5 to 50 μm.
前記基材としては、予め回路形成されたプリント配線板やフレキシブルプリント配線板の他、紙−フェノール樹脂、紙−エポキシ樹脂、ガラス布−エポキシ樹脂、ガラス−ポリイミド、ガラス布/不繊布−エポキシ樹脂、ガラス布/紙−エポキシ樹脂、合成繊維−エポキシ樹脂、フッ素樹脂・ポリエチレン・ポリフェニレンエーテル,ポリフェニレンオキシド・シアネートエステル等の複合材を用いた全てのグレード(FR−4等)の銅張積層板、ポリイミドフィルム、PETフィルム、ガラス基板、セラミック基板、ウエハ板等を用いることができる。 As the base material, in addition to a pre-circuit-formed printed wiring board and a flexible printed wiring board, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / non-woven cloth-epoxy resin. , Glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin, fluororesin / polyethylene / polyimideene ether, polyphenylene oxide / cyanate ester, and other composite materials of all grades (FR-4, etc.) copper-clad laminates, Polyimide film, PET film, glass substrate, ceramic substrate, wafer plate and the like can be used.
本発明のプリント配線板が有する樹脂絶縁層は、永久被膜として好適であり、中でもソルダーレジストや層間絶縁材料として好適である。 The resin insulating layer contained in the printed wiring board of the present invention is suitable as a permanent coating, and is particularly suitable as a solder resist or an interlayer insulating material.
本発明の積層構造体は、基材と、該基材上に形成された複数の樹脂絶縁層を有し、複数の樹脂絶縁層のうちの少なくとも一層が、本発明の硬化性樹脂組成物から形成された絶縁樹脂層であればよい。 The laminated structure of the present invention has a base material and a plurality of resin insulating layers formed on the base material, and at least one of the plurality of resin insulating layers is derived from the curable resin composition of the present invention. Any formed insulating resin layer may be used.
本発明の積層構造体の基本構成としては、一般なものであればよく、例えば、基材(S)に接して設けられた絶縁樹脂層(L1)と、表面層、即ち最外層との2層を有する物が挙げられる。絶縁樹脂層(L1)と、表面層の間に、さらに他の層を設けても良い。他の層を設けなくても、例えば絶縁樹脂層(L1)と樹脂絶縁層(L2)との交互層としても良い。例えば、絶縁樹脂層(L1)/樹脂絶縁層(L2)/絶縁樹脂層(L1)/樹脂絶縁層(L2)とすることもできる。 The basic structure of the laminated structure of the present invention may be a general one, for example, an insulating resin layer (L1) provided in contact with the base material (S) and a surface layer, that is, an outermost layer. Examples include those having a layer. Another layer may be further provided between the insulating resin layer (L1) and the surface layer. Even if another layer is not provided, for example, it may be an alternating layer of the insulating resin layer (L1) and the resin insulating layer (L2). For example, it may be an insulating resin layer (L1) / a resin insulating layer (L2) / an insulating resin layer (L1) / a resin insulating layer (L2).
以下に実施例および比較例を示して本発明について具体的に説明するが、本発明が下記実施例に限定されるものではない。尚、以下において「部」および「%」とあるのは、特に断りのない限り全て質量基準である。 The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following, "part" and "%" are all based on mass unless otherwise specified.
GPCの測定条件
測定機器:HLC8320GPC(東ソー株式会社製)
検出器:屈折率
溶媒:テトラヒドロフラン(THF)
カラム構成:TSKguardcolumn HxL−L,TSKgel−G4000HxL,G3000HxL,G2000HxL, G1000HxL
温度:40℃
流速:1.0ml/分GPC measurement conditions Measuring equipment: HLC8320 GPC (manufactured by Tosoh Corporation)
Detector: Refractive index Solvent: Tetrahydrofuran (THF)
Column configuration: TSKguardcolum HxL-L, TSKgel-G4000HxL, G3000HxL, G2000HxL, G1000HxL
Temperature: 40 ° C
Flow velocity: 1.0 ml / min
FT−IRの測定条件
測定機器:FT/IR−4100(日本分光株式会社)
サンプル作成条件:KBr板に溶液を塗布し、温風乾燥したものを測定サンプルとした。FT-IR measurement conditions Measuring equipment: FT / IR-4100 (JASCO Corporation)
Sample preparation conditions: A solution was applied to a KBr plate and dried with warm air to prepare a measurement sample.
実施例1
温度計、冷却管、撹拌器を取り付けたフラスコに窒素ガスパージを施しながら、マレイミド化合物(大和化成製BMI−2300)30部、ソルビン酸5.7部、シクロヘキサノン35.7部を仕込み、60℃で5時間保持した。GPCにてソルビン酸の消失を確認した後、取り出して酸変性マレイミド樹脂(A−1)を得た。得られた樹脂の固形分酸価は77mgKOH/g、カルボキシ基当量は729g/eqであった。Example 1
While purging the flask equipped with a thermometer, a cooling tube, and a stirrer with nitrogen gas, 30 parts of a maleimide compound (BMI-2300 manufactured by Daiwa Kasei), 5.7 parts of sorbic acid, and 35.7 parts of cyclohexanone were charged at 60 ° C. It was held for 5 hours. After confirming the disappearance of sorbic acid by GPC, it was taken out to obtain an acid-modified maleimide resin (A-1). The solid acid value of the obtained resin was 77 mgKOH / g, and the carboxy group equivalent was 729 g / eq.
実施例2
温度計、冷却管、撹拌器を取り付けたフラスコに窒素ガスパージを施しながら、マレイミド化合物(大和化成製BMI−1000)30部、ソルビン酸5.7部シクロヘキサノン35.7部を仕込み、60℃で5時間保持した。GPCにてソルビン酸の消失を確認した後、取り出して酸変性マレイミド樹脂(A−1)を得た。得られた樹脂の固形分酸価は77mgKOH/g、カルボキシ基当量は729g/eqであった。Example 2
While performing nitrogen gas purging on a flask equipped with a thermometer, a cooling tube and a stirrer, 30 parts of a maleimide compound (BMI-1000 manufactured by Daiwa Kasei), 5.7 parts of sorbic acid and 35.7 parts of cyclohexanone were charged, and 5 at 60 ° C. I kept the time. After confirming the disappearance of sorbic acid by GPC, it was taken out to obtain an acid-modified maleimide resin (A-1). The solid acid value of the obtained resin was 77 mgKOH / g, and the carboxy group equivalent was 729 g / eq.
比較例1
温度計、攪拌機、還流冷却器および窒素導入口を備えた2Lの反応容器に、エチルジグリコールアセテート(以下EDGAc)294.8部、N,N−ジメチルアセトアミド(以下DMAc)196.5部、BMI−1000(大和化成工業社製、4,4’−ジフェニルメタンビスマレイミド)400.0部、p−アミノフェノール243.3部を入れ、液中窒素流下にて120℃まで150分間かけて昇温した。この反応容器に、リカシッドTH(新日本理化社製、1,2,3,6−テトラヒドロ無水フタル酸)339.3部を入れ、120℃にて反応を継続した。150℃昇温から4.5時間後、樹脂のFT−IRスペクトルに変化がなくなった事を確認した後、EDGAcを709.7部加え、140℃にて減圧操作を行い、DMAcを留去した。留出が終了した後、EDGAc196.5部を加え冷却し、不揮発分50%のイミド樹脂溶液(A’−1)を得た。Comparative Example 1
294.8 parts of ethyl diglycol acetate (hereinafter EDGAc), 196.5 parts of N, N-dimethylacetamide (hereinafter DMAc), BMI in a 2 L reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet. 400.0 parts of −1000 (manufactured by Daiwa Kasei Kogyo Co., Ltd., 4,4'-diphenylmethanebismaleimide) and 243.3 parts of p-aminophenol were added, and the temperature was raised to 120 ° C. over 150 minutes under a flow of nitrogen in the liquid. .. 339.3 parts of Ricacid TH (manufactured by New Japan Chemical Co., Ltd., 1,2,3,6-tetrahydrophthalic anhydride) was placed in this reaction vessel, and the reaction was continued at 120 ° C. 4.5 hours after the temperature was raised to 150 ° C., after confirming that there was no change in the FT-IR spectrum of the resin, 709.7 parts of EDGAc was added, and a depressurization operation was performed at 140 ° C. to distill off DMAc. .. After the distillation was completed, 196.5 parts of EDGAc was added and cooled to obtain an imide resin solution (A'-1) having a non-volatile content of 50%.
比較例2
温度計、撹拌機、窒素導入口を備えた反応容器に、ジエチレングリコールモノエチルエーテルアセテート(EDGAc)563質量部、4,4’−ジフェニルメタンビスマレイミド(大和化成工業株式会社、「BMI−1000」)400質量部、p−アミノフェノール60.9質量部を入れ、液中窒素流通下にて120℃まで150分間かけて昇温し、3時間反応を行い、不揮発分45%の樹脂溶液(A’−2)を得た。Comparative Example 2
Diethylene glycol monoethyl ether acetate (EDGAc) 563 parts by mass, 4,4'-diphenylmethanebismaleimide (Daiwa Kasei Kogyo Co., Ltd., "BMI-1000") 400 in a reaction vessel equipped with a thermometer, a stirrer, and a nitrogen inlet. A resin solution (A'-) having a non-volatile content of 45% was added by mass and 60.9 parts by mass of p-aminophenol, heated to 120 ° C. over 150 minutes under liquid nitrogen flow, and reacted for 3 hours. 2) was obtained.
樹脂組成物の調製
表1に示す組成割合で、最終的に不揮発分(N.V)が50質量%となるように、EDGAcを配合して、硬化性樹脂組成物を調製した。Preparation of Resin Composition A curable resin composition was prepared by blending EDGAc so that the non-volatile content (NV) was finally 50% by mass at the composition ratio shown in Table 1.
フィルムのガラス転移温度(Tg)の測定
上記の割合で配合した硬化性樹脂組成物を、ガラス基材の上に6MILのアプリケータで塗工し、熱風乾燥機に入れ、80℃30分、120℃30分、200℃2時間加熱した。その後基板から硬化フィルムを単離し、試験片とした。下記条件で、測定用試料の動的粘弾性を測定し、得られたスペクトルのTanδの最大値の温度をガラス転移温度(Tg)とした。得られた結果を表1に「フィルムのTg(℃)」として示した。
測定機器:レオバイブロンRSA−II(レオメトリック社製)
治具:引っ張り
チャック間:20mm
測定温度:25℃〜400℃
測定周波数:1Hz
昇温速度:3℃/minMeasurement of glass transition temperature (Tg) of film The curable resin composition blended in the above ratio is coated on a glass substrate with a 6 MIL applicator, placed in a hot air dryer, and placed at 80 ° C. for 30 minutes at 120. It was heated at ° C. for 30 minutes and at 200 ° C. for 2 hours. Then, the cured film was isolated from the substrate and used as a test piece. The dynamic viscoelasticity of the measurement sample was measured under the following conditions, and the temperature of the maximum value of Tan δ in the obtained spectrum was defined as the glass transition temperature (Tg). The obtained results are shown in Table 1 as "Tg (° C.) of film".
Measuring equipment: Leovibron RSA-II (manufactured by Leometric)
Jig: Pull between chucks: 20 mm
Measurement temperature: 25 ° C to 400 ° C
Measurement frequency: 1Hz
Heating rate: 3 ° C / min
アルカリ現像性
硬化性樹脂組成物を乾燥後の膜厚が25〜35μmになるように、ブリキ基板上に塗装した。次いでこの塗装板を80℃の乾燥機で30分乾燥して試験片を作成した。これを、30℃の1%炭酸カリウム水溶液に3分間浸積振とうした後、水道水で洗浄し、塗膜の残存状況を目視観察してアルカリ現像性を評価した。塗膜が全て溶解した場合「○」、一部でも残存した場合「×」とした。The alkaline developable curable resin composition was coated on a tin substrate so that the film thickness after drying was 25 to 35 μm. Next, this coated plate was dried in a dryer at 80 ° C. for 30 minutes to prepare a test piece. This was immersed in a 1% potassium carbonate aqueous solution at 30 ° C. for 3 minutes, washed with tap water, and the residual state of the coating film was visually observed to evaluate the alkali developability. When all the coating film was dissolved, it was evaluated as "○", and when even a part of it remained, it was evaluated as "×".
なお、表中の語は以下の通り
N−680:DIC株式会社、クレゾールノボラック型エポキシ樹脂、エポキシ当量212g/eq
2E4MZ:2−エチル−4−メチルイミダゾールThe words in the table are as follows: N-680: DIC Corporation, cresol novolac type epoxy resin, epoxy equivalent 212 g / eq
2E4MZ: 2-ethyl-4-methylimidazole
Claims (19)
で表される構造である請求項1〜4の何れか1項記載の硬化性樹脂組成物。 The structure (1) formed by adding a fatty acid having a conjugated diene or a derivative (a1) thereof to the N-substituted maleimide group has the following structural formula (i).
The curable resin composition according to any one of claims 1 to 4, which has a structure represented by.
で表されるものである請求項1〜6の何れか1項記載の硬化性樹脂組成物。 The acid-modified maleimide resin (A) has the following structural formula (ii).
The curable resin composition according to any one of claims 1 to 6 , which is represented by.
で表されるものである請求項1〜6の何れか1項記載の硬化性樹脂組成物。 The acid-modified maleimide resin (A) has the following structural formula (iii).
The curable resin composition according to any one of claims 1 to 6 , which is represented by.
で表されることを特徴とする酸変性マレイミド樹脂。 The following structural formula (ii) or (iii)
An acid-modified maleimide resin, which is represented by.
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PCT/JP2019/050507 WO2020166212A1 (en) | 2019-02-14 | 2019-12-24 | Curable resin composition, cured product, acid-modified maleimide resin, and curing agent |
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KR (1) | KR102570940B1 (en) |
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CH407097A (en) * | 1960-12-16 | 1966-02-15 | Ciba Geigy | Process for the production of new dicarboxylic acid anhydrides |
EP0175648B1 (en) * | 1984-09-14 | 1991-05-22 | Ciba-Geigy Ag | Heat-hardenable compositions containing a polymaleinimide and a bicyclo[2.2.1]heptene-5-2,3-dicarboximide, and their use |
DE3872596D1 (en) * | 1987-05-22 | 1992-08-13 | Ciba Geigy Ag | UNSATURATED BISIMIDES AND THEIR POLYMERS. |
US5728501A (en) * | 1995-10-17 | 1998-03-17 | Sanyo Chemical Industries, Ltd. | Charge controller, toner binder composition and electrophotographic toner |
JP4087602B2 (en) | 2001-12-14 | 2008-05-21 | 横浜ゴム株式会社 | Curable compound and curable resin composition containing the same |
JP4735410B2 (en) | 2006-05-15 | 2011-07-27 | 日立化成工業株式会社 | Method for producing curing agent, and thermosetting resin composition using the same |
JP2009079189A (en) * | 2007-09-27 | 2009-04-16 | Kansai Paint Co Ltd | Thermosetting composition |
JP5521939B2 (en) | 2010-09-22 | 2014-06-18 | 住友ベークライト株式会社 | Photosensitive resin composition, cured film, protective film, insulating film, and semiconductor device and display device using the same |
JP5728998B2 (en) | 2011-02-16 | 2015-06-03 | 日立化成株式会社 | Insulating resin material for wiring board, multilayer wiring board, and method for manufacturing multilayer wiring board |
TW201245337A (en) * | 2011-05-11 | 2012-11-16 | Mitsubishi Rayon Co | Active energy ray-hardenable composition, layered body and manufacturing method thereof |
WO2016097404A1 (en) * | 2014-12-19 | 2016-06-23 | Dsm Ip Assets B.V. | Alkyd resin compositions of polyfunctional hydrophthalimide monomer compounds |
US10519279B2 (en) * | 2015-04-30 | 2019-12-31 | Hitachi Chemical Company, Ltd. | Thermosetting resin composition, prepreg, laminate and multilayer printed wiring board |
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