CN109970953B - Curable resin composition, dry film, cured product, and printed wiring board - Google Patents
Curable resin composition, dry film, cured product, and printed wiring board Download PDFInfo
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- CN109970953B CN109970953B CN201711447768.3A CN201711447768A CN109970953B CN 109970953 B CN109970953 B CN 109970953B CN 201711447768 A CN201711447768 A CN 201711447768A CN 109970953 B CN109970953 B CN 109970953B
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- CN
- China
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- resin composition
- curable resin
- component
- group
- ethylenically unsaturated
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 49
- 229920005989 resin Polymers 0.000 claims abstract description 62
- 239000011347 resin Substances 0.000 claims abstract description 62
- 239000003822 epoxy resin Substances 0.000 claims abstract description 59
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 59
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 49
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 239000003999 initiator Substances 0.000 claims abstract description 24
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 19
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 16
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 9
- 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 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229930185605 Bisphenol Natural products 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical group C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 5
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 238000005476 soldering Methods 0.000 abstract description 7
- 238000005452 bending Methods 0.000 abstract description 6
- 239000010408 film Substances 0.000 description 39
- -1 ester compound Chemical class 0.000 description 26
- 239000000047 product Substances 0.000 description 25
- 239000000203 mixture Substances 0.000 description 22
- 238000000576 coating method Methods 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 14
- 239000010410 layer Substances 0.000 description 14
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 229910000679 solder Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229920001721 polyimide Polymers 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 125000001033 ether group Chemical group 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 5
- 239000004642 Polyimide Substances 0.000 description 5
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920005862 polyol Polymers 0.000 description 5
- 229920005749 polyurethane resin Polymers 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- WTFAGPBUAGFMQX-UHFFFAOYSA-N 1-[2-[2-(2-aminopropoxy)propoxy]propoxy]propan-2-amine Chemical compound CC(N)COCC(C)OCC(C)OCC(C)N WTFAGPBUAGFMQX-UHFFFAOYSA-N 0.000 description 4
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000013039 cover film Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- 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 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000012644 addition polymerization Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- HEQOJEGTZCTHCF-UHFFFAOYSA-N 2-amino-1-phenylethanone Chemical compound NCC(=O)C1=CC=CC=C1 HEQOJEGTZCTHCF-UHFFFAOYSA-N 0.000 description 2
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- UMLWXYJZDNNBTD-UHFFFAOYSA-N alpha-dimethylaminoacetophenone Natural products CN(C)CC(=O)C1=CC=CC=C1 UMLWXYJZDNNBTD-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 150000008365 aromatic ketones 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
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 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
- 150000002009 diols Chemical class 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- LMGYOBQJBQAZKC-UHFFFAOYSA-N 1-(2-ethylphenyl)-2-hydroxy-2-phenylethanone Chemical compound CCC1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 LMGYOBQJBQAZKC-UHFFFAOYSA-N 0.000 description 1
- ZIKLJUUTSQYGQI-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxypropoxy)propane Chemical compound CCOCC(C)OCC(C)OCC ZIKLJUUTSQYGQI-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- UALAKBZSBJIXBP-UHFFFAOYSA-N 1-phenylethane-1,1,2,2-tetrol Chemical compound OC(O)C(O)(O)C1=CC=CC=C1 UALAKBZSBJIXBP-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- MDKSQNHUHMMKPP-UHFFFAOYSA-N 2,5-bis(4-methoxyphenyl)-4-phenyl-1h-imidazole Chemical class C1=CC(OC)=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC(OC)=CC=2)N1 MDKSQNHUHMMKPP-UHFFFAOYSA-N 0.000 description 1
- CTWRMVAKUSJNBK-UHFFFAOYSA-N 2-(2,4-dimethoxyphenyl)-4,5-diphenyl-1h-imidazole Chemical class COC1=CC(OC)=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 CTWRMVAKUSJNBK-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- RXAYEPUDXSKVHS-UHFFFAOYSA-N 2-(2-chlorophenyl)-4,5-bis(3-methoxyphenyl)-1h-imidazole Chemical class COC1=CC=CC(C2=C(NC(=N2)C=2C(=CC=CC=2)Cl)C=2C=C(OC)C=CC=2)=C1 RXAYEPUDXSKVHS-UHFFFAOYSA-N 0.000 description 1
- NSWNXQGJAPQOID-UHFFFAOYSA-N 2-(2-chlorophenyl)-4,5-diphenyl-1h-imidazole Chemical class ClC1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 NSWNXQGJAPQOID-UHFFFAOYSA-N 0.000 description 1
- UIHRWPYOTGCOJP-UHFFFAOYSA-N 2-(2-fluorophenyl)-4,5-diphenyl-1h-imidazole Chemical class FC1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 UIHRWPYOTGCOJP-UHFFFAOYSA-N 0.000 description 1
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- XIOGJAPOAUEYJO-UHFFFAOYSA-N 2-(2-methoxyphenyl)-4,5-diphenyl-1h-imidazole Chemical class COC1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 XIOGJAPOAUEYJO-UHFFFAOYSA-N 0.000 description 1
- DRLRGHZJOQGQEC-UHFFFAOYSA-N 2-(2-methoxypropoxy)propyl acetate Chemical compound COC(C)COC(C)COC(C)=O DRLRGHZJOQGQEC-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
-
- 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
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
-
- 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
- C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
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- 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
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- 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
Abstract
Provided are a curable resin composition, a dry film, a cured product, and a printed wiring board, wherein the curable resin composition can provide a cured product having excellent bending properties and warping properties as well as excellent soldering heat resistance. A curable resin composition comprising (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, and (C) an ethylenically unsaturated group-containing compound having 5 or more alkylene oxide skeletons, wherein the component (A) comprises (A1) a carboxyl group-containing photosensitive resin obtained by reacting an epoxy resin with a carboxylic acid having an ethylenically unsaturated group, reacting the resulting hydroxyl group with an acid anhydride, and adding a compound having a glycidyl group and an ethylenically unsaturated group to the carboxyl group-containing resin obtained by the reaction, and the component (C) comprises at least 2 ethylenically unsaturated group-containing compounds.
Description
Technical Field
The invention relates to a curable resin composition, a dry film, a cured product and a printed circuit board.
Background
In recent years, the popularization and performance improvement of smart phones and tablet terminals have been rapidly promoted. In information device terminals represented by these, there is a high demand for size reduction and thickness reduction by consumers, and in response to this demand, it is necessary to increase the density of circuit boards inside products and save space. Therefore, flexible printed circuit boards that can be stored in a flexible manner and have a high degree of freedom in circuit arrangement have been used in a wide range of applications, and the reliability of flexible printed circuit boards has been required to be higher than ever.
In a process of manufacturing a printed wiring board, a protective layer called a coverlay layer or a solder resist layer is coated on the printed wiring board in order to protect a wiring (circuit) pattern formed on a substrate by a method such as screen printing from an external environment or to protect solder from adhering to an unnecessary portion in a soldering process performed when an electronic component is surface-mounted on the printed wiring board. Conventionally, epoxy carboxyl group-containing photosensitive resins have been mainly used in curable resin compositions for solder resists used in the above applications.
For example, jp-a-10-282665 proposes a photosolder resist ink composition using an ultraviolet-curable resin obtained by reacting a carboxyl group of a resin having a radical-polymerizable unsaturated acyl group and a carboxyl group with a compound having 1 epoxy group and 1 or more radical-polymerizable unsaturated groups in 1 molecule.
Further, japanese patent No. 5556990 proposes a photosensitive resin composition containing: a photosensitive prepolymer obtained by reacting a reaction product of a polyfunctional epoxy resin and an ester compound of an unsaturated monocarboxylic acid or an ester compound of a saturated or unsaturated polybasic acid with a saturated or unsaturated polybasic acid anhydride and then further adding a compound having 1 glycidyl group and at least 1 ethylenically unsaturated group in 1 molecule; a photopolymerizable monomer having at least 1 or more ethylenically unsaturated groups in the molecule; a photopolymerization initiator; blocked isocyanates; a bismaleimide compound.
Disclosure of Invention
Problems to be solved by the invention
However, a cured film obtained from a resin composition using a carboxyl group-containing photosensitive resin as described above has a problem of low bendability or large warpage although it has good resistance to soldering heat, and there is room for improvement.
The purpose of the present invention is to provide a curable resin composition that can give a cured product that has excellent bending properties and low warpage in addition to excellent solder heat resistance, and a dry film, a cured product, and a printed wiring board that use the curable resin composition.
Means for solving the problems
The present inventors have conducted intensive studies and, as a result, succeeded in obtaining a curable resin composition which can give a cured product excellent not only in resistance to welding heat but also in bendability and low warpage by blending at least 2 ethylenically unsaturated group-containing compounds having 5 or more alkylene oxide skeletons in a curable resin composition containing a specific carboxyl group-containing photosensitive resin, and thus completed the present invention.
Namely, the present invention is as follows.
[ item 1] to
A curable resin composition characterized by comprising:
(A) a carboxyl group-containing resin,
(B) Photopolymerization initiator, and
(C) an ethylenically unsaturated group-containing compound having 5 or more alkylene oxide skeletons,
the component (A) includes (A1) a carboxyl group-containing photosensitive resin obtained by reacting an epoxy resin with a carboxylic acid having an ethylenically unsaturated group to react the resulting hydroxyl group with an acid anhydride and adding a compound having a glycidyl group and an ethylenically unsaturated group to the resulting carboxyl group-containing resin,
the component (C) contains at least 2 ethylenically unsaturated group-containing compounds.
[ item 2 ] A method for producing a semiconductor device
The curable resin composition according to claim 1, wherein the component (C) has 5 or more and 30 or less alkylene oxide skeletons.
[ item 3 ] A method for producing a semiconductor device
The curable resin composition according to claim 1 or 2, further comprising, as the component (A), at least one of (A2) a carboxyl group-containing photosensitive resin obtained by reacting a bisphenol epoxy resin with a carboxylic acid having an ethylenically unsaturated group and reacting the resulting hydroxyl group with an acid anhydride, and (A3) a carboxyl group-containing resin having a urethane skeleton.
[ item 4 ] A
The curable resin composition according to any one of claims 1 to 3, wherein the content of the component (A1) is 10 to 30 parts by weight based on 100 parts by weight of the component (A).
[ item 5 ] A method for producing a semiconductor device
The curable resin composition according to any one of claims 1 to 4, further comprising (D) an epoxy resin having a structure represented by the following general formula (1).
(in the formula (1), X represents an alicyclic skeleton or aromatic skeleton with 7 or more carbon atoms, and n represents a number of 0 or more.)
[ item 6 ] A composition for treating a tumor
The curable resin composition according to claim 5, wherein the component (D) is an epoxy resin having a dicyclopentadiene skeleton as X in the general formula (1).
[ item 7 ] A composition for treating a tumor
The curable resin composition according to any one of claims 1 to 6, which is used for production of a flexible printed wiring board.
[ item 8 ] to
A dry film comprising a resin layer obtained from the curable resin composition according to any one of items 1 to 7.
[ item 9 ] to
A cured product obtained by curing the curable resin composition according to any one of items 1 to 7 or the resin layer of the dry film according to item 8.
[ item 10 ] A method for producing a semiconductor device
A printed wiring board characterized by having the cured product according to item 9.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a curable resin composition capable of providing a cured product excellent not only in soldering heat resistance but also in bendability and low warpage, and a dry film, a cured product, and a printed wiring board using the same can be provided.
Detailed Description
The present invention relates to a curable resin composition. The photosensitive resin composition is characterized by comprising (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, and (C) an ethylenically unsaturated group-containing compound having 5 or more alkylene oxide skeletons, wherein the component (A) comprises (A1) a carboxyl group-containing photosensitive resin (also referred to simply as component (A1)) which is obtained by reacting an epoxy resin with a carboxylic acid having an ethylenically unsaturated group, reacting the resulting hydroxyl group with an acid anhydride, and adding a compound having a glycidyl group and an ethylenically unsaturated group to the carboxyl group-containing resin thus formed, and the component (C) comprises at least 2 ethylenically unsaturated group-containing compounds.
Hereinafter, each component of the curable resin composition of the present invention will be described. It should be noted that the term (meth) acrylate refers to a general term of acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions below.
(A) Carboxyl group-containing resin
The composition of the present invention contains, as the carboxyl group-containing resin (a), a carboxyl group-containing photosensitive resin (a1) which is obtained by reacting an epoxy resin with a carboxylic acid having an ethylenically unsaturated group, reacting the resulting hydroxyl group with an acid anhydride, and adding a compound having a glycidyl group and an ethylenically unsaturated group to the carboxyl group-containing resin thus formed, as an essential component.
The carboxylic acid having an ethylenically unsaturated group preferably includes (meth) acrylic acid and the like.
As the acid anhydride, a dibasic acid anhydride such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, or the like; aromatic polycarboxylic acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, and benzophenone tetracarboxylic dianhydride; and a polyvalent carboxylic acid anhydride derivative such as 5- (2, 5-dioxotetrahydrofuran) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride attached thereto, preferably a dibasic acid anhydride.
The epoxy resin is a resin having an epoxy group, and a known epoxy resin can be used as desired. Examples thereof include a 2-functional epoxy resin having 2 epoxy groups in the molecule, a polyfunctional epoxy resin having a plurality of epoxy groups in the molecule, and the like.
Examples of the epoxy resin which becomes the raw material of the component (a1) include bisphenol a type epoxy resin, brominated epoxy resin, novolac type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol a type epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin, alicyclic type epoxy resin, trishydroxyphenylmethane type epoxy resin, bisdiphenol type or diphenol type epoxy resin, and mixtures thereof; bisphenol S type epoxy resins, bisphenol a novolac type epoxy resins, tetrahydroxyphenylethane type epoxy resins, heterocyclic epoxy resins, phthalic acid diglycidyl ester resins, tetraglycidyl ditoluoylethane resins, naphthyl-containing epoxy resins, epoxy resins having a dicyclopentadiene skeleton, and the like. Among them, bisphenol type epoxy resins such as bisphenol a type epoxy resins, hydrogenated bisphenol a type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, and the like, biphenol type epoxy resins, and biphenol type epoxy resins are preferable.
Examples of the compound having a glycidyl group and an ethylenically unsaturated group include compounds having 1 glycidyl group and 1 or more (meth) acryloyl groups in the molecule, such as glycidyl (meth) acrylate and α -methylglycidyl (meth) acrylate.
As the component (a1), a carboxyl group-containing photosensitive resin obtained by further adding a compound having 1 glycidyl group and 1 or more (meth) acryloyl groups in the molecule, such as glycidyl (meth) acrylate or α -methylglycidyl (meth) acrylate, to the following resins (1) to (2) is more preferable.
(1) A carboxyl group-containing photosensitive resin obtained by reacting a 2-functional or 2-or more-functional epoxy resin with (meth) acrylic acid to add a dibasic acid anhydride to a hydroxyl group present in a side chain.
(2) A carboxyl group-containing photosensitive resin is obtained by reacting a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of a 2-functional epoxy resin with epichlorohydrin with (meth) acrylic acid and adding a dibasic acid anhydride to the resulting hydroxyl group.
In the composition of the present invention, it is preferable from the viewpoint of soldering heat resistance, bendability, and warping property that the composition further contains, as the carboxyl group-containing resin (a), at least one of (a2) a carboxyl group-containing photosensitive resin formed by reacting a bisphenol epoxy resin with a carboxylic acid having an ethylenically unsaturated group and reacting the generated hydroxyl group with an acid anhydride, and (A3) a carboxyl group-containing resin having a urethane skeleton.
As the component (a2), a carboxyl group-containing photosensitive resin obtained by reacting a bisphenol epoxy resin with (meth) acrylic acid to add a dibasic acid anhydride to a hydroxyl group present in a side chain is more preferable.
The carboxyl group-containing resin having a urethane skeleton (a3) includes any of the following resins (3) to (6).
(3) A carboxyl group-containing polyurethane resin obtained by addition polymerization of a diisocyanate with a carboxyl group-containing diol compound.
(4) The carboxyl group-containing photosensitive polyurethane resin is obtained by addition polymerization of a diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, or an aromatic diisocyanate, and a diol compound such as a carboxyl group-containing diol compound such as dimethylolpropionic acid or dimethylolbutyric acid, a polycarbonate-based polyol, a polyether-based polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol a-based alkylene oxide adduct diol, or a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
(5) A carboxyl group-containing photosensitive polyurethane resin obtained by addition polymerization of a diisocyanate, a (meth) acrylate ester of a 2-functional epoxy resin such as a bisphenol A epoxy resin, a hydrogenated bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, a biphenol epoxy resin, a bisphenol epoxy resin, or a partial acid anhydride modification thereof, and a carboxyl group-containing diol compound.
(6) A carboxyl group-containing photosensitive polyurethane resin obtained by adding a compound having 1 hydroxyl group and 1 or more (meth) acryloyl groups in the molecule, such as hydroxyalkyl (meth) acrylate, to the synthesis of the resin (4) or (5) above and (meth) acrylating the terminal.
(7) The carboxyl group-containing photosensitive polyurethane resin obtained by (meth) acrylating the terminal of a compound having 1 isocyanate group and 1 or more (meth) acryloyl groups in a molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, is added to the synthesis of the resin of (5) or (6).
When the component (a2) is contained, the flexibility of the cured product is improved and the flexibility of the cured product is excellent, and when the component (A3) is contained, the flexibility and heat resistance of the cured product can be improved.
The content ratio of the component (a1) in the carboxyl group-containing resin (a) is not particularly limited. However, if the content of the component (a1) is too low, the effect of improving heat resistance by the component (a1) may be insufficient, and if it is too high, bendability may be poor and warpage may be increased. The content of the component (a1) is preferably 10 to 30 parts by weight, more preferably 10 to 20 parts by weight, based on 100 parts by weight of the component (a), from the viewpoint of balance between heat resistance and bendability and low warpage.
(B) Photopolymerization initiator
In the present invention, the photopolymerization initiator used as the component (B) is not particularly limited as long as it is a photopolymerization initiator generally used for curable resin compositions.
Examples thereof include aromatic ketones such as benzophenone, N ' -tetraalkyl-4, 4 ' -diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinoacetone-1, 4 ' -bis (dimethylamino) benzophenone (mikimone), 4 ' -bis (diethylamino) benzophenone, 4-methoxy-4 ' -dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (morpholinophenyl) -butanone-1, 2-ethylanthraquinone, and the like, Aromatic ketones such as phenanthrenequinone, benzoin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether, benzoin derivatives such as benzoin methyl benzoin and ethyl benzoin, benzoin derivatives such as benzil dimethyl ketal, 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4, 5-bis (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer, 2, 4-bis (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2, 4-dimethoxyphenyl) -4, 5-diphenylimidazole dimer, 2,4, 5-triarylimidazole dimer, Acridine derivatives such as 9-phenylacridine and 1, 7-bis (9, 9' -acridinyl) heptane, N-phenylglycine derivatives, coumarin-based compounds, and the like.
These can be used alone in 1 kind, also can be combined with more than 2 kinds.
As the component (B), 1 or more kinds of photopolymerization initiators selected from the group consisting of oxime ester type photopolymerization initiators having an oxime ester group, alkylphenone type photopolymerization initiators, α -aminoacetophenone type photopolymerization initiators, acylphosphine oxide type photopolymerization initiators, and titanocene type photopolymerization initiators can be suitably used.
Examples of oxime ester photopolymerization initiators that are commercially available include CGI-325, IRGACURE OXE01, IRGACURE OXE02, N-1919, and NCI-831 manufactured by ADEKA corporation, manufactured by BASF Japan Ltd. Further, a photopolymerization initiator having 2 oxime ester groups in the molecule can also be suitably used. The oxime ester photopolymerization initiator is preferably an oxime ester compound having a carbazole structure.
Commercially available alkylphenyl ketone photopolymerization initiators include α -hydroxyalkylphenyl ketone types such as IRGACURE184, Dalocure1173, IRGACURE2959, and IRGACURE127 manufactured by BASF Japan ltd.
Specific examples of the α -aminoacetophenone-based photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone, and N, N-dimethylaminoacetophenone. Examples of commercially available products include IRGACURE907, IRGACURE369, and IRGACURE379 manufactured by BASF Japan ltd.
Specific examples of the acylphosphine oxide-based photopolymerization initiator include 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethyl-pentylphosphine oxide, and the like. Examples of commercially available products include LUCIRIN TPO manufactured by BASF corporation and IRGACURE819 manufactured by BASF Japan Ltd.
Further, as the photopolymerization initiator, titanocene-based photopolymerization initiators such as IRGACURE389 and IRGACURE784 manufactured by BASF Japan ltd. can be suitably used.
(B) The amount of the photopolymerization initiator is preferably 0.1 to 25 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (A). When the amount of the metal compound is 0.1 to 25 parts by mass, a cured film having excellent photocurability and resolution, improved adhesion and PCT resistance, and further excellent chemical resistance such as electroless gold plating resistance can be obtained. In particular, when the amount is 25 parts by mass or less, the effect of reducing outgas can be obtained, and further, the decrease in deep-part curability due to the drastic absorption of light on the surface of the coating film can be suppressed.
(C) Compounds containing ethylenically unsaturated groups having more than 5 alkylene oxide skeletons
In the present invention, the component (C) is not particularly limited as long as it has 5 or more alkylene oxide skeletons and contains an ethylenically unsaturated group. Preferred are compounds having 5 or more EO or PO in the molecule and 2 or more ethylenically unsaturated groups. The component (C) preferably has a structure having a (meth) acryloyl group at the end of the alkylene oxide skeleton. The number of ethylenically unsaturated groups is more preferably 2 or more and 4 or less, most preferably 2 or more and 3 or less.
It is to be noted that "EO" means "ethylene oxide" and "PO" means "propylene oxide". In addition, hereinafter, "EO-modified" means having an ethylene oxide unit (-CH)2-CH2-O-, - "PO modification" means having propylene oxide units (-CH)2-CH2-CH2-O-、-CH(CH3)-CH2-O-、-CH2-CH(CH3) of-O-)A block structure.
As the component (C), for example, an EO-modified polyacrylate is more preferable, and a compound represented by the following general formula (1) or (2) is further preferable.
(wherein the sum of l + m + n represents the modification number, and l + m + n is 5.)
CH2＝CH-CO-O(CH2-CH2O)nOC-CH＝CH2Formula (2)
(wherein n represents a modification number, and n.gtoreq.5.)
"having 5 or more alkylene oxide skeletons" means that, when two or more alkylene oxide skeletons are contained, all kinds of alkylene oxide skeletons have 5 or more in total. If the number is less than 5, the excellent bendability and low warpage of the present invention cannot be achieved.
The component (C) preferably has 5 or more and 30 or less alkylene oxide skeletons, more preferably 5 or more and 20 or less alkylene oxide skeletons, from the viewpoint of balance with other properties. When the number of alkylene oxide skeletons is 30 or less, the thickness of the cured film can be easily ensured without adjusting the viscosity of the composition.
In the present invention, it is necessary to contain at least 2 ethylenically unsaturated group-containing compounds as the component (C). (C) When the component (C) is only one type of ethylenically unsaturated group-containing compound, not only the warpage of the cured product of the present invention is not obtained, but also the bendability and the solder heat resistance may be lowered.
(C) The total amount of the component (A) is preferably 1 to 40 parts by mass, more preferably 10 to 35 parts by mass, and still more preferably 15 to 30 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin (A).
Other ingredients
In the present invention, the epoxy resin composition may further contain (D) an epoxy resin having a structure represented by the following general formula (1) in addition to the components (a) to (C).
(in the formula (1), X represents an alicyclic skeleton or aromatic skeleton with 7 or more carbon atoms, and n represents a number of 0 or more.)
When X in the general formula (1) is a dicyclopentadiene skeleton, it is preferable from the viewpoint of remarkably exerting the effect of the present invention.
In the present invention, an epoxy resin other than the component (D), for example, the above-mentioned bisphenol a type epoxy resin, may be contained.
In the present invention, in addition to the above components (a) to (C), a diamine having an ether skeleton (E) may be contained. Examples of the component (E) include JEFFAMINE D-230 and JEFFAMINE D-2000 (manufactured by Huntsman corporation).
The component (E) preferably contains polyetheramine (also referred to as polyetherdiamine) having an ether skeleton number of 15 or more from the viewpoint of developability and pot life of the curable resin composition of the present invention, and more preferably contains both diamine having an ether skeleton number of 1 or more and 10 or less and polyetheramine having an ether skeleton number of 20 or more and 40 or less from the viewpoint of pot life and heat resistance. The content of the diamine having 1 or more and 10 or less ether skeletons is preferably 1 to 40 parts by weight based on 100 parts by weight of the total weight of the component (E), and the content of the polyetheramine having 15 or more ether skeletons is preferably 60 to 99 parts by weight based on 100 parts by weight of the total weight of the component (E).
The curable resin composition of the present invention may contain (F) an ethylenically unsaturated group-containing compound having 3 or more functions for increasing the crosslinking density (excluding the component (C)) within a range not to impair the effects of the present invention. Examples of the component (F) include trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO-PO-modified trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.
Further, in the curable resin composition of the present invention, various additives such as known and conventional fillers such as barium sulfate, silica, talc, clay, calcium carbonate, silica, bentonite, kaolin, glass fiber, carbon fiber, mica and the like, known and conventional dyes such as phthalocyanine blue, phthalocyanine green, titanium oxide, carbon black and the like, coloring pigments, antifoaming agents, flame retardants, adhesion imparting agents, leveling agents and the like, known and conventional polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, phenothiazine and the like may be added depending on the desired physical properties.
The curable resin composition of the present invention may further contain an organic solvent for preparing the composition and adjusting the viscosity. As the organic solvent, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether (DPM), dipropylene glycol diethyl ether, and tripropylene glycol monomethyl ether; esters such as ethyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, naphtha and solvent naphtha. These organic solvents may be used alone or in combination of 2 or more.
The curable resin composition of the present invention is preferably used for the production of flexible printed wiring boards because it can give a cured product having excellent bending properties and low warpage in addition to excellent solder heat resistance.
Another embodiment of the present invention provides a dry film having a resin layer obtained from the curable resin composition.
The dry film of the present invention can be obtained by coating on a carrier film (support) and drying it. In the case of dry coating, the composition of the present invention is diluted with the organic solvent as necessary to adjust the viscosity to an appropriate level, and the composition is coated on a carrier film in a uniform thickness by a comma coater, a knife coater, a lip coater, a bar coater, a squeeze coater, a reverse coater, a transfer roll coater, a gravure coater, a spray coater, or the like, and dried at a temperature of usually 50 to 130 ℃ for 1 to 30 minutes to prepare a resin layer as a dry coating film. The thickness of the resin layer is not particularly limited, and is usually appropriately selected within a range of 0.1 to 100 μm, preferably 0.5 to 50 μm, in terms of the thickness after drying.
As the carrier film, a plastic film is used, and preferably a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, or the like is used. The thickness of the carrier film is not particularly limited, and is usually appropriately selected within a range of 0.1 to 150 μm.
In this case, after the resin layer is formed on the carrier film, a peelable cover film is preferably further laminated on the surface of the resin layer for the purpose of preventing adhesion of dust and the like to the surface of the resin layer. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used, and when peeling the cover film, the adhesion between the resin layer and the cover film is smaller than the adhesion between the resin layer and the carrier film.
Another embodiment of the present invention provides a cured product obtained from the curable resin composition.
The curable resin composition of the present invention is adjusted to a viscosity suitable for a coating method as needed, and is applied to, for example, a printed wiring board on which a circuit is formed by a screen printing method, a curtain coating method, a spray coating method, a roll coating method, or the like, and an organic solvent contained in the composition is evaporated and dried at, for example, 60 to 100 ℃ as needed, thereby forming a non-tacky coating film. Then, the obtained coating film or the resin layer of the dry film is selectively exposed to an active energy ray through a photomask having a predetermined exposure pattern formed thereon, and the unexposed portion is developed with a developer to form a resist pattern, and further heated to, for example, 140 to 180 ℃ to be thermally cured, whereby a cured product having excellent soldering heat resistance, bendability, and low warpage can be obtained as a resist film.
The evaporation drying after application of the composition of the present invention can be carried out by the following method: a method of bringing hot air in a dryer into convective contact using a device having a heat source of an air heating system using steam, such as a hot air circulation drying furnace, an IR furnace, a hot plate, or a convection oven, and a method of blowing the hot air to a support body using a nozzle.
As an exposure machine used for the irradiation with active energy rays, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, or the like may be mounted and an ultraviolet ray may be irradiated in a range of 350 to 450nm, and further, a direct drawing device (for example, a direct imaging device that directly irradiates active energy rays from CAD data from a computer to draw an image) may be used. As the light source of the line drawing machine, a light source of light having a maximum wavelength in the range of 350 to 410nm may be used. The exposure amount for forming an image varies depending on the film thickness, etc., and is usually 20 to 1000mJ/cm2Preferably 20 to 800mJ/cm2Within the range of (1).
The developing method may be a dipping method, a shower method, a spray method, a brush method, or the like, and the developing solution may be a dilute aqueous alkali solution of potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, or the like.
The present invention also provides a printed wiring board having the cured product.
[ examples ] A method for producing a compound
The present invention will be specifically described below by way of examples and comparative examples, but the present invention is not limited to the following examples. In the following, unless otherwise specified, "parts" and "%" are based on mass.
The components shown in table 1 were mixed at the solid content mixing ratios (mass basis) shown therein to obtain a curable resin composition.
Synthesis example 1 of [ (A1) component ]
To 700g of diethylene glycol monoethyl ether acetate, 1070g of an o-cresol novolak type epoxy resin (EPICLON N-695 manufactured by DIC Co., Ltd., softening point 95 ℃, epoxy equivalent 214, average number of functional groups 7.6) (number of glycidyl groups (total number of aromatic rings): 5.0 mol), 360g (5.0 mol) of acrylic acid and 1.5g of hydroquinone were charged, and the mixture was heated and stirred to 100 ℃ to dissolve uniformly.
Subsequently, 4.3g of triphenylphosphine was charged, the mixture was heated to 110 ℃ for 2 hours to effect a reaction, 1.6g of triphenylphosphine was added thereto, and the temperature was raised to 120 ℃ for a further 12 hours to effect a reaction. 562g of an aromatic hydrocarbon (SOLVESSO150) and 684g (4.5 moles) of tetrahydrophthalic anhydride were charged into the obtained reaction solution, and a reaction was carried out at 110 ℃ for 4 hours. Further, 142.0g (1.0 mol) of glycidyl methacrylate was added to the obtained reaction solution, and the reaction was carried out at 115 ℃ for 4 hours to obtain a carboxyl group-containing photosensitive resin solution as the component (A1). The resin solution thus obtained had a solid content of 65% and an acid value of the solid content of 87 mgKOH/g.
Synthesis example of [ (A2) component ]
400 parts of a bisphenol F type solid epoxy resin having an epoxy equivalent of 800 and a softening point of 79 ℃ was dissolved in 925 parts of epichlorohydrin and 462.5 parts of dimethyl sulfoxide, and 81.2 parts of 98.5% NaOH was added to the solution at 70 ℃ over 100 minutes with stirring. After the addition, the reaction was further carried out at 70 ℃ for 3 hours.
Subsequently, most of the excess unreacted epichlorohydrin and dimethyl sulfoxide were distilled off under reduced pressure to dissolve the reaction product containing the by-product salt and dimethyl sulfoxide in 750 parts of methyl isobutyl ketone, and 10 parts of 30% NaOH was added thereto, and the reaction was carried out at 70 ℃ for 1 hour. After the reaction was completed, the reaction mixture was washed with 200 parts of water 2 times. After oil-water separation, methyl isobutyl ketone was recovered from the oil layer by distillation to obtain 370 parts of an epoxy resin (a-1) having an epoxy equivalent of 290 and a softening point of 62 ℃.
2900 parts (10 equivalents (10 moles based on the epoxy group)) of the obtained epoxy resin (a-1), 720 parts (10 equivalents (10 moles based on the carboxyl group)) of acrylic acid, 2.8 parts of methylhydroquinone, and 1950 parts of carbitol acetate were charged, heated to 90 ℃ and stirred to dissolve the reaction mixture. Then, the reaction mixture was cooled to 60 ℃ and 16.7 parts of triphenylphosphine were added thereto, and the mixture was heated to 100 ℃ to conduct a reaction for about 32 hours, thereby obtaining a reaction product having an acid value of 1.0 mgKOH/g. Then, 786 parts of maleic anhydride (7.86 mol in terms of an acid anhydride structure) and 423 parts of carbitol acetate were put into the solution, and the mixture was heated to 95 ℃ to perform a reaction for about 6 hours, thereby obtaining a photosensitive carboxyl group-containing resin solution.
The resin solution thus obtained had a solid content of 65% and an acid value of the solid content of 100 mgKOH/g.
Synthesis example of [ (A3) component ]
Into a reaction vessel equipped with a stirrer, a thermometer and a condenser were charged 3600g (4.5 mol) of a polycarbonate diol (T5650J, number average molecular weight 800, manufactured by asahi chemicals co., ltd.), 3600g (5.5 mol) of dimethylolbutyric acid and 118g (1.6 mol) of n-butanol as a molecular weight modifier (reaction terminator) which were derived from 1, 5-pentanediol and 1, 6-hexanediol which were compounds having a plurality of alcoholic hydroxyl groups. Next, 2009g (10.8 mol) of trimethylhexamethylene diisocyanate as an isocyanate compound having no aromatic ring was charged, the mixture was heated to 60 ℃ with stirring, the heating was stopped, the mixture was heated again when the temperature in the reaction vessel started to decrease, the stirring was continued at 80 ℃, and the absorption spectrum (2280 cm) of the isocyanate group was confirmed by infrared absorption spectrum-1) Disappeared and the reaction was terminated. Next, carbitol acetate was added so that the solid content became 60 wt%, to obtain a carboxyl group-containing resin as a viscous liquid containing a diluent. The solid content of the obtained carboxyl group-containing resin (A3) having a urethane skeleton had an acid value of 49.8 mgKOH/g.
As commercially available materials, IRGACURE784, IRGACURE369, 4' -bis (diethylamino) benzophenone (EAB) manufactured by BASF Japan Ltd. was used as a photopolymerization initiator, XD-1000 manufactured by Nippon Kagaku K.K. was used as a dicyclopentadiene type solid epoxy resin, NC-3000 manufactured by Nippon Kagaku K.K. was used as a diphenolaldehyde varnish type epoxy resin, and A-600, A-400, and A-GLY-20E manufactured by Nippon Kasei chemical Co., Ltd. were used as EO-modified acrylic monomers. DPHA (dipentaerythritol triacrylate, manufactured by Nippon Kabushiki Kaisha), JEFFAMINE D-230 and JEFFAMINE D-2000 (manufactured by Huntsman corporation) were used.
In the presence of copper circuitsThe compositions of examples 1 to 8 and comparative examples 1 to 3 were applied to the entire surface of a polyimide substrate (thickness of polyimide film: 25 μm, copper circuit: 1/3 ounce) by screen printing so as to be 10 μm after drying, and dried at 160 ℃ for 30 minutes in a hot air circulation type drying oven to form a dried coating film, and then exposed to an exposure machine equipped with a metal halide lamp manufactured by ORC Manufacturing co., Ltd at an exposure dose of 7-order sensitivity. Then, 1 wt% Na was added2CO3The aqueous solution was developed at a jet pressure of 0.1MPa for 1 minute, and then thermally cured at 150 ℃ for 60 minutes in a hot air circulation drying oven to form a cured coating film having a thickness of 10 μm on the polyimide substrate.
The evaluation results of the cured coating film of each of the obtained curable resin compositions are shown in table 1. The evaluation methods and evaluation criteria are as follows.
(evaluation of cured product-Low warpage)
The polyimide substrate having the cured coating film was cut into 5cm × 5cm to prepare an evaluation sample. The warpage of each corner was measured with a straight ruler with the surface of the cured coating film as the upper surface, and the average value of 4 points was evaluated.
O: the average value of the warpage of each corner is 2mm or less
And (delta): the average value of the warpage of each corner is 3mm or less
X: the average value of the warpage of each corner is 4mm or less
(flexibility)
The polyimide substrate having the cured coating film was cut into a width of 10mm × a length of 70mm to prepare an evaluation sample. The cured coating film was folded into a mountain shape, and a weight of 1Kg was placed thereon for 10 seconds to unfold the bent portion. Then, the weight was placed on the curved portion again for 10 seconds as 1 time. The bent portion was observed with a microscope, and the number of times until copper could be observed was evaluated.
O: number of bending-2 times
And (delta): number of bending times-1
X: number of bending times-0
(test for solder Heat resistance)
The polyimide substrate having the cured coating film was cut into 20mm in the longitudinal direction by 20mm in the transverse direction to prepare an evaluation sample. The temperature of the solder bath was set at 320 ℃, the sample substrate was placed therein, and after 10 seconds, the substrate was taken out, and the swelling of the cured coating film on the substrate surface was confirmed, and the number of times until the swelling occurred was evaluated.
O: 320 ℃ for more than 3 times in 10 seconds
And (delta): 320 ℃ for 10 seconds 2 times
X: 320 ℃ for 10 seconds for 1 time
[ TABLE 1]
As is apparent from Table 1, examples 1 to 8 using the component (A1) in combination with 2 types of ethylenically unsaturated group-containing compounds having 5 or more alkylene oxide skeletons all gave excellent results in the evaluation of the low warpage, bendability and solder heat resistance of the cured product. On the other hand, comparative examples 1 to 2 using only one kind of ethylenically unsaturated group-containing compound having 5 or more alkylene oxide skeletons and comparative example 3 containing no component (a1) were insufficient in performance. Specifically, in comparative example 1, the cured product was slightly inferior in all of low warpage, bendability, and solder heat resistance. In comparative example 2, the cured product had slightly poor low warpage properties. In comparative example 3, the cured product was slightly inferior in low warpage and bendability, and poor in soldering heat resistance.
These results demonstrate that the curable resin composition of the present invention can form a cured product having excellent bending properties and low warpage properties as well as excellent welding heat resistance. The resin composition is also suitable for flexible printed circuit boards as a result of excellent bendability and low warpage.
Claims (10)
1. A curable resin composition characterized by comprising:
(A) a carboxyl group-containing resin,
(B) Photopolymerization initiator, and
(C) an ethylenically unsaturated group-containing compound having 5 or more alkylene oxide skeletons,
the component (A) includes (A1) a carboxyl group-containing photosensitive resin obtained by reacting an epoxy resin with a carboxylic acid having an ethylenically unsaturated group to react the resulting hydroxyl group with an acid anhydride and adding a compound having a glycidyl group and an ethylenically unsaturated group to the resulting carboxyl group-containing resin,
as the component (C), at least 2 ethylenically unsaturated group-containing compounds are contained.
2. The curable resin composition according to claim 1, wherein the component (C) has 5 or more and 30 or less alkylene oxide skeletons.
3. The curable resin composition according to claim 1 or 2, wherein the curable resin composition is
(A) The component (A) further contains at least one of (A2) a carboxyl group-containing photosensitive resin obtained by reacting a bisphenol epoxy resin with a carboxylic acid having an ethylenically unsaturated group and reacting the resulting hydroxyl group with an acid anhydride, and (A3) a carboxyl group-containing resin having a urethane skeleton.
4. The curable resin composition according to claim 1 or 2, wherein the content of the component (A1) is 10 to 30 parts by weight based on 100 parts by weight of the component (A).
5. The curable resin composition according to claim 1 or 2, further comprising (D) an epoxy resin having a structure represented by the following general formula (1),
in the formula (1), X represents an alicyclic skeleton or aromatic skeleton having 7 or more carbon atoms, and n represents a number of 0 or more.
6. The curable resin composition according to claim 5, wherein the component (D) comprises an epoxy resin having a dicyclopentadiene skeleton as X in the general formula (1).
7. The curable resin composition according to claim 1 or 2, which is used for production of a flexible printed wiring board.
8. A dry film comprising a resin layer obtained from the curable resin composition according to any one of claims 1 to 7.
9. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 7 or the resin layer of the dry film according to claim 8.
10. A printed wiring board comprising the cured product according to claim 9.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711447768.3A CN109970953B (en) | 2017-12-27 | 2017-12-27 | Curable resin composition, dry film, cured product, and printed wiring board |
| JP2020535591A JP7248682B2 (en) | 2017-12-27 | 2018-08-15 | Curable resin composition, dry film, cured product, and printed wiring board |
| PCT/CN2018/100676 WO2019128257A1 (en) | 2017-12-27 | 2018-08-15 | Curable resin composition, dry film, cured article, and printed circuit board |
| PH12020550991A PH12020550991A1 (en) | 2017-12-27 | 2020-06-26 | Curable resin composition, dry film, cured article, and printed circuit board |
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| CN201711447768.3A CN109970953B (en) | 2017-12-27 | 2017-12-27 | Curable resin composition, dry film, cured product, and printed wiring board |
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| JPWO2022045237A1 (en) * | 2020-08-31 | 2022-03-03 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000068740A1 (en) * | 1999-05-06 | 2000-11-16 | Taiyo Ink Manufacturing Co., Ltd. | Solder resist ink composition |
| CN101220225A (en) * | 2008-01-30 | 2008-07-16 | 深圳市容大电子材料有限公司 | Light sensitive anti-solder ink composition, application and circuit board containing the same |
| CN101846882A (en) * | 2009-03-23 | 2010-09-29 | 太阳油墨制造株式会社 | Light solidifying/heat solidifying resin composition, dry film, solidfied material, printed circuit board (PCB) |
| CN107250198A (en) * | 2015-01-28 | 2017-10-13 | 互应化学工业株式会社 | Containing carboxy resin, photosensitive polymer combination, dry film, printed wiring board and manufacture method containing carboxy resin |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4655362B2 (en) | 1999-12-28 | 2011-03-23 | Ｄｉｃ株式会社 | Method for producing photosensitive resin |
| EP1276011B1 (en) * | 2000-03-29 | 2004-05-26 | Kanagawa University | Photocurable/thermosetting resin composition, photosensitive dry film formed therefrom, and method of forming pattern with the same |
| JP2004062057A (en) * | 2002-07-31 | 2004-02-26 | Showa Denko Kk | Photosensitive thermosetting resin composition and its hardened product |
| JP2017116787A (en) | 2015-12-25 | 2017-06-29 | 三洋化成工業株式会社 | Photosensitive resin composition |
-
2017
- 2017-12-27 CN CN201711447768.3A patent/CN109970953B/en active Active
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2018
- 2018-08-15 JP JP2020535591A patent/JP7248682B2/en active Active
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000068740A1 (en) * | 1999-05-06 | 2000-11-16 | Taiyo Ink Manufacturing Co., Ltd. | Solder resist ink composition |
| CN101220225A (en) * | 2008-01-30 | 2008-07-16 | 深圳市容大电子材料有限公司 | Light sensitive anti-solder ink composition, application and circuit board containing the same |
| CN101846882A (en) * | 2009-03-23 | 2010-09-29 | 太阳油墨制造株式会社 | Light solidifying/heat solidifying resin composition, dry film, solidfied material, printed circuit board (PCB) |
| CN107250198A (en) * | 2015-01-28 | 2017-10-13 | 互应化学工业株式会社 | Containing carboxy resin, photosensitive polymer combination, dry film, printed wiring board and manufacture method containing carboxy resin |
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| WO2019128257A1 (en) | 2019-07-04 |
| CN109970953A (en) | 2019-07-05 |
| JP2021508849A (en) | 2021-03-11 |
| PH12020550991A1 (en) | 2021-04-19 |
| JP7248682B2 (en) | 2023-03-29 |
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