JP5136744B2 - Thermosetting resin composition for forming a highly planarized film - Google Patents
Thermosetting resin composition for forming a highly planarized film Download PDFInfo
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- JP5136744B2 JP5136744B2 JP2006304114A JP2006304114A JP5136744B2 JP 5136744 B2 JP5136744 B2 JP 5136744B2 JP 2006304114 A JP2006304114 A JP 2006304114A JP 2006304114 A JP2006304114 A JP 2006304114A JP 5136744 B2 JP5136744 B2 JP 5136744B2
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- resin composition
- thermosetting resin
- film
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- 229920001187 thermosetting polymer Polymers 0.000 title claims description 55
- 239000011342 resin composition Substances 0.000 title claims description 49
- 229920000058 polyacrylate Polymers 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 36
- 230000015572 biosynthetic process Effects 0.000 claims description 29
- 125000000524 functional group Chemical group 0.000 claims description 28
- -1 bismaleimide compound Chemical class 0.000 claims description 24
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 24
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 3
- 239000010408 film Substances 0.000 description 123
- 239000011248 coating agent Substances 0.000 description 28
- 238000000576 coating method Methods 0.000 description 28
- 229920001577 copolymer Polymers 0.000 description 23
- 239000000178 monomer Substances 0.000 description 22
- 239000000758 substrate Substances 0.000 description 22
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 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 15
- 230000000052 comparative effect Effects 0.000 description 15
- 239000004973 liquid crystal related substance Substances 0.000 description 11
- 230000001681 protective effect Effects 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 10
- 229920000178 Acrylic resin Polymers 0.000 description 8
- 239000004925 Acrylic resin Substances 0.000 description 8
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 125000000962 organic group Chemical group 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 4
- 239000010703 silicon Substances 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 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- IIQWTZQWBGDRQG-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C(C)=C IIQWTZQWBGDRQG-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- FDYDISGSYGFRJM-UHFFFAOYSA-N (2-methyl-2-adamantyl) 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC1C(OC(=O)C(=C)C)(C)C2C3 FDYDISGSYGFRJM-UHFFFAOYSA-N 0.000 description 1
- YRPLSAWATHBYFB-UHFFFAOYSA-N (2-methyl-2-adamantyl) prop-2-enoate Chemical compound C1C(C2)CC3CC1C(C)(OC(=O)C=C)C2C3 YRPLSAWATHBYFB-UHFFFAOYSA-N 0.000 description 1
- AURQHUVLTRSLGM-UHFFFAOYSA-N (2-propyl-2-adamantyl) prop-2-enoate Chemical compound C1C(C2)CC3CC1C(CCC)(OC(=O)C=C)C2C3 AURQHUVLTRSLGM-UHFFFAOYSA-N 0.000 description 1
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- CNDOSNMFHUSKGN-UHFFFAOYSA-N 1-(2-hydroxyphenyl)pyrrole-2,5-dione Chemical compound OC1=CC=CC=C1N1C(=O)C=CC1=O CNDOSNMFHUSKGN-UHFFFAOYSA-N 0.000 description 1
- ZVEMLYIXBCTVOF-UHFFFAOYSA-N 1-(2-isocyanatopropan-2-yl)-3-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC(C(C)(C)N=C=O)=C1 ZVEMLYIXBCTVOF-UHFFFAOYSA-N 0.000 description 1
- OEUTXEVXKFXZPB-UHFFFAOYSA-N 1-[12-(2,5-dioxopyrrol-1-yl)dodecyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CCCCCCCCCCCCN1C(=O)C=CC1=O OEUTXEVXKFXZPB-UHFFFAOYSA-N 0.000 description 1
- PUKLCKVOVCZYKF-UHFFFAOYSA-N 1-[2-(2,5-dioxopyrrol-1-yl)ethyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CCN1C(=O)C=CC1=O PUKLCKVOVCZYKF-UHFFFAOYSA-N 0.000 description 1
- FJKKJQRXSPFNPM-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)-4-methylphenyl]pyrrole-2,5-dione Chemical compound CC1=CC=C(N2C(C=CC2=O)=O)C=C1N1C(=O)C=CC1=O FJKKJQRXSPFNPM-UHFFFAOYSA-N 0.000 description 1
- SIABDEKAVHRTFN-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)-5-methoxyphenyl]pyrrole-2,5-dione Chemical compound C=1C(OC)=CC(N2C(C=CC2=O)=O)=CC=1N1C(=O)C=CC1=O SIABDEKAVHRTFN-UHFFFAOYSA-N 0.000 description 1
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- XJBSYHZLEOIPEJ-UHFFFAOYSA-N 1-[4-[2,6-dibromo-4-[2-[3,5-dibromo-4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C(Br)=C(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)C(Br)=CC=1C(C(F)(F)F)(C(F)(F)F)C(C=C1Br)=CC(Br)=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O XJBSYHZLEOIPEJ-UHFFFAOYSA-N 0.000 description 1
- OGPFZTQPAAOEAG-UHFFFAOYSA-N 1-[4-[2-bromo-4-[1-[3-bromo-4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]ethyl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)C(Br)=CC=1C(C)C(C=C1Br)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O OGPFZTQPAAOEAG-UHFFFAOYSA-N 0.000 description 1
- QMQYJRMHXYICMD-UHFFFAOYSA-N 1-[4-[2-bromo-4-[2-[3-bromo-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(Br)=CC=1C(C)(C)C(C=C1Br)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O QMQYJRMHXYICMD-UHFFFAOYSA-N 0.000 description 1
- MSMRYSXMPLWMFH-UHFFFAOYSA-N 1-[4-[2-butyl-4-[2-[3-butyl-4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]propan-2-yl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound CCCCC1=CC(C(C)(C)C=2C=C(CCCC)C(OC=3C=CC(=CC=3)N3C(C=CC3=O)=O)=CC=2)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O MSMRYSXMPLWMFH-UHFFFAOYSA-N 0.000 description 1
- LRLKRMWSHCJOQL-UHFFFAOYSA-N 1-[4-[2-chloro-4-[1-[3-chloro-4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]ethyl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)C(Cl)=CC=1C(C)C(C=C1Cl)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O LRLKRMWSHCJOQL-UHFFFAOYSA-N 0.000 description 1
- UTUDZIVGWZEXJH-UHFFFAOYSA-N 1-[4-[2-chloro-4-[2-[3-chloro-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(Cl)=CC=1C(C)(C)C(C=C1Cl)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O UTUDZIVGWZEXJH-UHFFFAOYSA-N 0.000 description 1
- OJDDBNNNPILOKG-UHFFFAOYSA-N 1-[4-[4-[1-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]-3-methylphenyl]ethyl]-2-methylphenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)C(C)=CC=1C(C)C(C=C1C)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O OJDDBNNNPILOKG-UHFFFAOYSA-N 0.000 description 1
- OAQGRJSNFQTHST-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]-3,5-dimethylphenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]-2,6-dimethylphenoxy]phenyl]pyrrole-2,5-dione Chemical compound CC1=CC(C(C=2C=C(C)C(OC=3C=CC(=CC=3)N3C(C=CC3=O)=O)=C(C)C=2)(C(F)(F)F)C(F)(F)F)=CC(C)=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O OAQGRJSNFQTHST-UHFFFAOYSA-N 0.000 description 1
- XRHJTQFPYUPMRJ-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]-3-ethylphenyl]propan-2-yl]-2-ethylphenoxy]phenyl]pyrrole-2,5-dione Chemical compound CCC1=CC(C(C)(C)C=2C=C(CC)C(OC=3C=CC(=CC=3)N3C(C=CC3=O)=O)=CC=2)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O XRHJTQFPYUPMRJ-UHFFFAOYSA-N 0.000 description 1
- YKSGJSKYCBPXDT-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]-3-methoxyphenyl]propan-2-yl]-2-methoxyphenoxy]phenyl]pyrrole-2,5-dione Chemical compound COC1=CC(C(C)(C)C=2C=C(OC)C(OC=3C=CC(=CC=3)N3C(C=CC3=O)=O)=CC=2)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O YKSGJSKYCBPXDT-UHFFFAOYSA-N 0.000 description 1
- OVBYYBVBCLQSQZ-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]-3-propan-2-ylphenyl]propan-2-yl]-2-propan-2-ylphenoxy]phenyl]pyrrole-2,5-dione Chemical compound CC(C)C1=CC(C(C)(C)C=2C=C(C(OC=3C=CC(=CC=3)N3C(C=CC3=O)=O)=CC=2)C(C)C)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O OVBYYBVBCLQSQZ-UHFFFAOYSA-N 0.000 description 1
- IAKITQMGMOKJGX-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]-3-propylphenyl]propan-2-yl]-2-propylphenoxy]phenyl]pyrrole-2,5-dione Chemical compound CCCC1=CC(C(C)(C)C=2C=C(CCC)C(OC=3C=CC(=CC=3)N3C(C=CC3=O)=O)=CC=2)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O IAKITQMGMOKJGX-UHFFFAOYSA-N 0.000 description 1
- PYTZZNUKESXWLN-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]-1,1,1,3,3,3-hexafluoropropan-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(F)(F)F)(C(F)(F)F)C(C=C1)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O PYTZZNUKESXWLN-UHFFFAOYSA-N 0.000 description 1
- PYVHLZLQVWXBDZ-UHFFFAOYSA-N 1-[6-(2,5-dioxopyrrol-1-yl)hexyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CCCCCCN1C(=O)C=CC1=O PYVHLZLQVWXBDZ-UHFFFAOYSA-N 0.000 description 1
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- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、平坦化に優れる平坦化膜形成用熱硬化性樹脂組成物及びそれから得られる硬化膜に関する。より詳しくは、段差被覆時の平坦性が高い平坦化膜形成用熱硬化性樹脂組成物及びその硬化膜、並びに該硬化膜を用いた各種材料に関するものである。この平坦化膜形成用熱硬化性樹脂組成物は特に液晶ディスプレイやＥＬディスプレイにおける層間絶縁膜、カラーフィルタ等のオーバーコート剤に好適である。 The present invention relates to a thermosetting resin composition for forming a flattened film excellent in flattening and a cured film obtained therefrom. More specifically, the present invention relates to a thermosetting resin composition for forming a flattened film having high flatness at the time of step coating, a cured film thereof, and various materials using the cured film. This thermosetting resin composition for flattening film formation is particularly suitable for overcoat agents such as interlayer insulating films and color filters in liquid crystal displays and EL displays.
一般に、液晶表示素子、有機ＥＬ（ｅｌｅｃｔｒｏｌｕｍｉｎｅｓｃｅｎｔ）素子、固体撮像素子などの光デバイスでは、素子表面が製造工程中に溶剤や熱にさらされるのを防ぐために保護膜が設けられる。この保護膜は保護する基板との密着性が高く耐溶剤性が高いだけでなく、透明性、耐熱性等の性能も良好であることが要求される。 In general, in an optical device such as a liquid crystal display element, an organic EL (electroluminescent) element, and a solid-state imaging element, a protective film is provided to prevent the element surface from being exposed to a solvent or heat during the manufacturing process. This protective film is required to have not only high adhesion to the substrate to be protected and high solvent resistance, but also good performance such as transparency and heat resistance.
一方、このような保護膜は、カラー液晶表示装置や固体撮像素子に用いられるカラーフィルタの保護膜として使用する場合には、一般にその下地基板のカラーフィルタあるいはブラックマトリックス樹脂を平坦化する性能、すなわち平坦化膜としての性能を有することが要求される。特にＳＴＮ方式やＴＦＴ方式のカラー液晶表示素子を製造する際には、カラーフィルタ基板と対向基板との張り合わせ精度を非常に厳密に行う必要があり、基板間のセルギャップを均一にすることが必要不可欠である。加えてカラーフィルタを透過する光の透過率を維持するため、その保護膜であるこれら平坦化膜には高い透明性が必要となる。 On the other hand, when such a protective film is used as a protective film for a color filter used in a color liquid crystal display device or a solid-state imaging device, generally the performance of flattening the color filter or black matrix resin of the underlying substrate, that is, It is required to have a performance as a planarizing film. In particular, when manufacturing a color liquid crystal display element of STN method or TFT method, it is necessary to perform the bonding accuracy between the color filter substrate and the counter substrate very strictly, and it is necessary to make the cell gap between the substrates uniform. It is essential. In addition, in order to maintain the transmittance of light passing through the color filter, the planarizing film as the protective film needs to have high transparency.
また、液晶表示素子や有機ＥＬ素子の電極の保護膜として使用する場合には、近年、電極の段差が大きくなっていることもあり、少しでも高い平坦化性能を有する材料が求められている。 Further, when used as a protective film for an electrode of a liquid crystal display element or an organic EL element, in recent years, there is a demand for a material having a high leveling performance even a little because the step of the electrode has become large.
一般に斯様な用途には透明性の高いアクリル樹脂が用いられている。この種のアクリル樹脂は熱硬化あるいは光硬化することで耐熱性及び耐溶剤性を付与することができる性質を有している。
一般的な熱硬化の方法としてはヒドロキシ基を有するアクリル樹脂にメチロール系の架橋剤と酸触媒を添加する方法、並びにカルボキシル基を含有するアクリル樹脂にエポキシ系の架橋剤を添加する方法がよく知られている。また、エポキシ基とカルボキシル基をアクリル樹脂中に導入することで熱硬化させる方法（特許文献１参照）、並びに熱ラジカル開始剤と一分子中に２個以上の不飽和二重結合を有する化合物を用いる方法（特許文献２参照）も従来提案されている。
また、一般的な光硬化の方法としてはアクリル樹脂に一分子中に２個以上の不飽和二重結合を有する化合物と光ラジカル開始剤を添加する方法、ヒドロキシ基を含有するアクリル樹脂にメチロール系の架橋剤と光酸発生剤を添加する方法が知られている。
しかしながら、従来の熱硬化性又は光硬化性のアクリル樹脂から形成された硬化膜の平坦化率は十分に高いものとは言えなかった。
As a general thermosetting method, a method of adding a methylol-based crosslinking agent and an acid catalyst to an acrylic resin having a hydroxy group, and a method of adding an epoxy-based crosslinking agent to an acrylic resin containing a carboxyl group are well known. It has been. In addition, a method of thermosetting by introducing an epoxy group and a carboxyl group into an acrylic resin (see Patent Document 1), and a compound having two or more unsaturated double bonds in one molecule with a thermal radical initiator A method to be used (see Patent Document 2) has also been proposed.
In addition, as a general photocuring method, a method of adding a compound having two or more unsaturated double bonds per molecule and a photo radical initiator to an acrylic resin, a methylol-based acrylic resin containing a hydroxy group There is known a method of adding a crosslinking agent and a photoacid generator.
However, it cannot be said that the flattening rate of a cured film formed from a conventional thermosetting or photocurable acrylic resin is sufficiently high.
本発明は、以上のような事情に基づいてなされたものであり、液晶表示素子及び有機ＥＬ表示素子等に使用される電極及びカラーフィルタの平坦化膜に好適である、高透明性、
高平坦化性を達成する熱硬化性樹脂組成物を提供することにある。
The present invention has been made based on the circumstances as described above, and is suitable for a flattening film of electrodes and color filters used for liquid crystal display elements and organic EL display elements.
It is providing the thermosetting resin composition which achieves high planarization property.
本発明者は、上記の課題を解決するべく鋭意研究を行った結果、本発明を見出すに至った。
すなわち、第１観点として、下記（Ａ）成分、（Ｂ）成分及び（Ｃ）溶剤を含有する平坦化膜形成用熱硬化性樹脂組成物。
（Ａ）成分：炭素原子数が３乃至１６であって末端に不飽和結合を有する側鎖を持ち、数平均分子量が２，０００乃至３０，０００であるアクリル重合体、
（Ｂ）成分：ビスマレイミド化合物、
（Ｃ）溶剤。
第２観点として、上記（Ａ）成分において、末端に不飽和結合を有する側鎖が脂肪族の側鎖である、第１観点に記載の平坦化膜形成用熱硬化性樹脂組成物。
第３観点として、（Ａ）成分が、末端にアクリロイル基又はメタクリロイル基を有する側鎖を持つアクリル重合体である、第１観点又は第２観点に記載の平坦化膜形成用熱硬化性樹脂組成物。
第４観点として、（Ｂ）成分が、芳香族ビスマレイミド化合物である、第１観点乃至第３観点のうちのいずれか一項に記載の平坦化膜形成用熱硬化性樹脂組成物。
第５観点として、（Ａ）成分の１００質量部に基づいて、１０乃至２００質量部の（Ｂ）成分を含有する、第１観点乃至第４観点のうちのいずれか一項に記載の平坦化膜形成用熱硬化性樹脂組成物。
第６観点として、第１観点乃至第５観点のうちのいずれか一項に記載の平坦化膜形成用熱硬化性樹脂組成物から得られる硬化膜。
第７観点として、第６観点に記載の硬化膜を有する表示素子。
As a result of intensive studies to solve the above problems, the present inventors have found the present invention.
That is, as a first aspect, a thermosetting resin composition for forming a flattened film, which contains the following component (A), component (B) and solvent (C).
Component (A): an acrylic polymer having 3 to 16 carbon atoms, having a side chain having an unsaturated bond at the terminal, and having a number average molecular weight of 2,000 to 30,000,
(B) component: bismaleimide compound,
(C) Solvent.
As a second aspect, the thermosetting resin composition for forming a flattened film according to the first aspect, wherein in the component (A), the side chain having an unsaturated bond at the terminal is an aliphatic side chain.
As a third aspect, the thermosetting resin composition for forming a flattened film according to the first aspect or the second aspect, wherein the component (A) is an acrylic polymer having a side chain having an acryloyl group or a methacryloyl group at the terminal. object.
The thermosetting resin composition for planarization film formation as described in any one of the 1st viewpoint thru | or 3rd viewpoint whose (B) component is an aromatic bismaleimide compound as a 4th viewpoint.
As 5th viewpoint, based on 100 mass parts of (A) component, the planarization as described in any one of the 1st viewpoint thru | or 4th viewpoint containing 10-200 mass parts (B) component. A thermosetting resin composition for film formation.
As a sixth aspect, a cured film obtained from the thermosetting resin composition for flattening film formation according to any one of the first aspect to the fifth aspect.
The display element which has a cured film as described in a 6th viewpoint as a 7th viewpoint.
本発明の平坦化膜形成用熱硬化性樹脂組成物は、透明性が高い上に平坦化に優れ、よって高い透明性及び高い平坦性を有する硬化膜を提供できる。そのため、本発明の平坦化膜形成用熱硬化性樹脂組成物から得られる硬化膜は、液晶表示素子、有機ＥＬ表示素子等に使用される電極又はカラーフィルタの保護膜又は平坦化膜として有用である。 The thermosetting resin composition for forming a flattened film of the present invention has high transparency and is excellent in flattening, and thus can provide a cured film having high transparency and high flatness. Therefore, the cured film obtained from the thermosetting resin composition for forming a planarizing film of the present invention is useful as a protective film or a planarizing film for electrodes or color filters used in liquid crystal display elements, organic EL display elements and the like. is there.
本発明の平坦化膜形成用熱硬化性樹脂組成物は、下記（Ａ）成分のアクリル重合体、（Ｂ）成分のビスマレイミド化合物及び（Ｃ）溶剤を含有し、且つ、所望により（Ｄ）成分の界面活性剤を含有する組成物である。
以下、各成分の詳細を説明する。
The thermosetting resin composition for forming a flattened film of the present invention contains an acrylic polymer as the following component (A), a bismaleimide compound as the component (B), and (C) a solvent, and (D) if desired. A composition containing a component surfactant.
Hereinafter, details of each component will be described.
＜（Ａ）成分＞
（Ａ）成分は、アクリル重合体の構造中に、炭素原子数が３乃至１６であって末端に不飽和結合を有する側鎖（以下、特定側鎖と称す。）を持ち、且つポリスチレン換算数平均分子量（以下、数平均分子量と称す。）が２，０００乃至３０，０００であるアクリル重合体である。
本発明において、アクリル重合体とはアクリル酸エステル、メタクリル酸エステル、スチレン等の不飽和二重結合を有するモノマーを用いて単独重合もしくは共重合して得られた重合体を指す。
（Ａ）成分のアクリル重合体は、斯かる構造を有するアクリル重合体であればよく、アクリル重合体を構成する高分子の主鎖の骨格及び側鎖の種類などについて特に限定されない。
<(A) component>
The component (A) has a side chain having 3 to 16 carbon atoms and an unsaturated bond at the end (hereinafter referred to as a specific side chain) in the structure of the acrylic polymer, and the number in terms of polystyrene. An acrylic polymer having an average molecular weight (hereinafter referred to as a number average molecular weight) of 2,000 to 30,000.
In the present invention, the acrylic polymer refers to a polymer obtained by homopolymerization or copolymerization using a monomer having an unsaturated double bond such as acrylic ester, methacrylic ester or styrene.
The acrylic polymer as the component (A) may be an acrylic polymer having such a structure, and is not particularly limited with respect to the main chain skeleton and side chain type of the polymer constituting the acrylic polymer.
然しながら、（Ａ）成分のアクリル重合体は、数平均分子量が３０，０００を超えて過
大なものであると、段差に対する平坦化性能が低下する一方、数平均分子量が２，０００未満で過小なものであると、熱硬化時に硬化不足になり溶剤耐性が低下する場合がある。従って、数平均分子量が２，０００乃至３０，０００の範囲内にあるものである。
またより好ましくは、上記特定側鎖に含まれる不飽和二重結合１ｍｏｌ当量当り、（Ａ）成分のアクリル重合体２００乃至１，３００ｇ当量であることが望ましい。
However, when the number average molecular weight of the acrylic polymer of component (A) is excessively larger than 30,000, the flattening performance with respect to the step is lowered, while the number average molecular weight is less than 2,000 and too small. If it is, it may be insufficiently cured at the time of thermosetting and solvent resistance may be reduced. Therefore, the number average molecular weight is in the range of 2,000 to 30,000.
More preferably, the amount of the acrylic polymer of component (A) is 200 to 1,300 g equivalent per 1 mol equivalent of the unsaturated double bond contained in the specific side chain.
上述のように、（Ａ）成分の特定側鎖は、炭素原子数が３乃至１６であって、末端に不飽和結合を有するものであれば特に限定されない。中でも式（１）のように特定官能基のカルボキシル基に結合された特定側鎖が好ましい。
As described above, the specific side chain of the component (A) is not particularly limited as long as it has 3 to 16 carbon atoms and has an unsaturated bond at the terminal. Among these particular side chain attached to the carboxyl group of good urchin specific functional group of the formula (1) are preferred.
式（１）中、Ｒ1は、炭素原子数が１乃至１４であり、脂肪族基、環式構造を含む脂肪
族基及び芳香族基からなる群から選ばれる有機基又はそれらの群から選ばれる複数の有機基の組み合わせからなる有機基である。そして、Ｒ1には、エステル結合、エーテル結合
、アミド結合、ウレタン結合等の結合を含んでいても良い。
In formula (1), R 1 has 1 to 14 carbon atoms and is selected from an organic group selected from the group consisting of aliphatic groups, aliphatic groups containing cyclic structures, and aromatic groups, or a group thereof. An organic group comprising a combination of a plurality of organic groups. R 1 may contain a bond such as an ester bond, an ether bond, an amide bond, or a urethane bond.
Ｒ1の具体例を挙げると、下記式（Ａ−１）乃至式（Ａ−１０）等が挙げられる。 Specific examples of R 1 include the following formula (A-1) to formula (A-10).
前記式（１）で表されるカルボキシル基に結合された特定側鎖の中でも、特に、脂肪族の側鎖である特定側鎖が好ましい。
より好ましくは、前記特定側鎖の中でも、特に、末端がアクリロイル基又はメタクリロイル基である特定側鎖が好ましい。
またさらに好ましくは、前記式（１）で表される特定側鎖に含まれる不飽和二重結合は、（Ａ）成分のアクリル重合体２００乃至１，３００ｇ当量に対して１ｍｏｌ当量含まれることが望ましい。
Among the specific side chains bonded to the carboxyl group represented by the formula (1), a specific side chain that is an aliphatic side chain is particularly preferable.
More preferably, among the front Kitoku Jogawakusari, in particular, ends are specific side chain is preferably an acryloyl group or a methacryloyl group.
More preferably, the unsaturated double bond contained in the specific side chain represented by the formula (1) is contained in an amount of 1 mol equivalent to 200 to 1,300 g equivalent of the acrylic polymer of the component (A). desirable.
上記のような特定側鎖を有するアクリル重合体を得る方法は、特に限定されないが、例えば、あらかじめラジカル重合等の重合方法によって、特定官能基を有するアクリル重合体を生成し、その特定官能基と、末端に不飽和結合を有する化合物（以下、特定化合物と称す。）とを反応させることによって特定側鎖を生成して、（Ａ）成分であるアクリル重合体とすることができる。 The method for obtaining the acrylic polymer having a specific side chain as described above is not particularly limited. For example, an acrylic polymer having a specific functional group is generated in advance by a polymerization method such as radical polymerization, and the specific functional group and A specific side chain can be generated by reacting a compound having an unsaturated bond at the terminal (hereinafter referred to as a specific compound) to obtain an acrylic polymer as the component (A).
ここで、前記特定官能基とは、カルボキシル基、グリシジル基、ヒドロキシ基、活性水素を有するアミノ基、フェノール性ヒドロキシ基、イソシアネート基等からなる群から選ばれる一種又は複数種の官能基を意味する。
また、前記特定化合物としては、例えば、グリシジルメタクリレート、グリシジルアクリレート、イソシアナートエチルメタクリレート、イソシアナートエチルアクリレート、メタクリル酸クロリド、アクリル酸クロリド、メタクリル酸、アクリル酸等が挙げられる。
Here, the specific functional group means one or more functional groups selected from the group consisting of a carboxyl group, a glycidyl group, a hydroxy group, an amino group having active hydrogen, a phenolic hydroxy group, an isocyanate group, and the like. .
Examples of the specific compound include glycidyl methacrylate, glycidyl acrylate, isocyanate ethyl methacrylate, isocyanate ethyl acrylate, methacrylic acid chloride, acrylic acid chloride, methacrylic acid, and acrylic acid.
このようにして得られるアクリル重合体の中で、好ましい特定側鎖を有するアクリル重合体は、式（１）で表される特定官能基をカルボキシル基に結合された側鎖を有するアクリル重合体であり、即ち、式（２）で表される構造を有するアクリル重合体である。
Among the acrylic polymers thus obtained, an acrylic polymer having a preferred specific side chain is an acrylic polymer having a side chain in which the specific functional group represented by the formula (1) is bonded to a carboxyl group. Yes, that is, an acrylic polymer having a structure represented by the formula (2).
（式（２）中、Ｒ1は前述の式（１）にて定義したように炭素原子数が１乃至１４であり
、脂肪族基、環式構造を含む脂肪族基及び芳香族基からなる群から選ばれる有機基又はそれらの群から選ばれる複数の有機基の組み合わせからなる有機基である。そして、Ｒ1に
は、エステル結合、エーテル結合、アミド結合、ウレタン結合等の結合を含んでいても良い。Ｒ2は水素原子又はメチル基を表す。）
(In Formula (2), R 1 has 1 to 14 carbon atoms as defined in Formula (1) above, and is composed of an aliphatic group, an aliphatic group containing a cyclic structure, and an aromatic group. An organic group selected from the group or a combination of a plurality of organic groups selected from these groups, and R 1 includes a bond such as an ester bond, an ether bond, an amide bond, or a urethane bond. R 2 represents a hydrogen atom or a methyl group.)
上記特定側鎖を生成させる反応において、好ましい前記特定官能基と前記特定化合物の組み合わせは、カルボキシル基とエポキシ基、ヒドロキシ基とイソシアネート基、フェノール性ヒドロキシ基とエポキシ基、カルボキシル基とイソシアネート基、アミノ基とイソシアネート基、ヒドロキシ基と酸クロリド等の組み合わせである。より好ましくは、カルボキシル基とグリシジルメタクリレート、及びヒドロキシ基とイソシアネートエチルメタクリレートである。 In the reaction for generating the specific side chain, preferred combinations of the specific functional group and the specific compound include a carboxyl group and an epoxy group, a hydroxy group and an isocyanate group, a phenolic hydroxy group and an epoxy group, a carboxyl group and an isocyanate group, amino A combination of a group and an isocyanate group, a hydroxy group and an acid chloride, and the like. More preferred are a carboxyl group and glycidyl methacrylate, and a hydroxy group and isocyanate ethyl methacrylate.
上記の特定官能基を有するアクリル重合体は、特定化合物と反応するための官能基（特定官能基）を有するモノマー、すなわち、カルボキシル基、グリシジル基、ヒドロキシ基、活性水素を有するアミノ基、フェノール性ヒドロキシ基又はイソシアネート基等を有するモノマーからなる群から選ばれるモノマーを必須の構成成分として重合して得られる共重合体であって、その数平均分子量が２，０００乃至２５，０００のものである。その際、特定官能基を有するモノマーは、単独でも良いし、重合中に反応しない組み合わせであれば複数種を併用しても良い。
以下に、特定官能基を有するアクリル重合体を得るために必要な、特定官能基を有するモノマーの具体例を挙げるがこれらに限定されるものではない。
The acrylic polymer having the above specific functional group is a monomer having a functional group (specific functional group) for reacting with a specific compound, that is, a carboxyl group, a glycidyl group, a hydroxy group, an amino group having active hydrogen, a phenolic group. A copolymer obtained by polymerizing a monomer selected from the group consisting of monomers having a hydroxy group or an isocyanate group as an essential constituent, and having a number average molecular weight of 2,000 to 25,000 . In that case, the monomer which has a specific functional group may be individual, and if it is a combination which does not react during superposition | polymerization, multiple types may be used together.
Specific examples of the monomer having the specific functional group necessary for obtaining the acrylic polymer having the specific functional group are shown below, but the invention is not limited thereto.
カルボキシル基を有するモノマーとしては、例えば、アクリル酸、メタクリル酸、クロトン酸、モノ−（２−（アクリロイルオキシ）エチル）フタレート、モノ−（２−（メタクリロイルオキシ）エチル）フタレート、Ｎ−（カルボキシフェニル）マレイミド、Ｎ−（カルボキシフェニル）メタクリルアミド、Ｎ−（カルボキシフェニル）アクリルアミド等が挙げられる。 Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, and N- (carboxyphenyl). ) Maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide and the like.
グリシジル基を有するモノマーとしては、例えば、グリシジルメタクリレート、グリシジルアクリレート、アリルグリシジルエーテル、３−エテニル−７−オキサビシクロ［４．１．０］ヘプタン、１，２−エポキシ−５−ヘキセン、１，７−オクタジエンモノエポキサイド、等が挙げられる。 Examples of the monomer having a glycidyl group include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2-epoxy-5-hexene, 1,7. -Octadiene monoepoxide and the like.
ヒドロキシ基を有するモノマーとしては、例えば、２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレート、２−ヒドロキシプロピルアクリレート、２−ヒドロキシプロピルメタクリレート、４−ヒドロキシブチルアクリレート、４−ヒドロキシブチルメタクリレート、２，３−ジヒドロキシプロピルアクリレート、２，３−ジヒドロキシプロピルメタクリレート、ジエチレングリコールモノアクリレート、ジエチレングリコールモノメタクリレート、カプロラクトン２−（アクリロイルオキシ）エチルエステル、カプロラクトン２−（メタクリロイルオキシ）エチルエステル、ポリ（エチレングリコール）エチルエーテルアクリレート、ポリ（エチレングリコール）エチルエーテルメタクリレート、５−アクリロイルオキシ−６−ヒドロキシノルボルネン−２−カルボキシリック−６−ラクトン、５−メタクリロイルオキシ−６−ヒドロキシノルボルネン−２−カルボキシリック−６−ラクトン等が挙げられる。 Examples of the monomer having a hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3- Dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2- (acryloyloxy) ethyl ester, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, poly (Ethylene glycol) ethyl ether methacrylate, 5-acryloyl Shi-6-hydroxy-norbornene-2-carboxylic-6-lactone, 5-methacryloyloxy-6-hydroxy-norbornene-2-carboxylic-6-lactone and the like.
活性水素を有するアミノ基を有するモノマーとしては、２−アミノエチルアクリレート、２−アミノメチルメタクリレート等が挙げられる。 Examples of the monomer having an amino group having active hydrogen include 2-aminoethyl acrylate and 2-aminomethyl methacrylate.
フェノール性ヒドロキシ基を有するモノマーとしては、例えば、ヒドロキシスチレン、Ｎ−（ヒドロキシフェニル）アクリルアミド、Ｎ−（ヒドロキシフェニル）メタクリルアミド、Ｎ−（ヒドロキシフェニル）マレイミド等が挙げられる。 Examples of the monomer having a phenolic hydroxy group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) maleimide and the like.
さらに、イソシアネート基を有するモノマーとしては、例えば、アクリロイルエチルイソシアネート、メタクリロイルエチルイソシアネート、ｍ−テトラメチルキシレンイソシアネート、等が挙げられる。 Furthermore, as a monomer which has an isocyanate group, acryloyl ethyl isocyanate, methacryloyl ethyl isocyanate, m-tetramethyl xylene isocyanate, etc. are mentioned, for example.
また、本発明においては、特定官能基を有するアクリル重合体を得る際に、特定官能基を有するモノマーと共重合可能な、非反応性官能基を有するモノマーを併用することができる。
非反応性官能基を有するモノマーの具体例としては、アクリル酸エステル化合物、メタクリル酸エステル化合物、マレイミド化合物、アクリロニトリル、マレイン酸無水物、スチレン化合物及びビニル化合物等が挙げられる。
以下、上記モノマーの具体例を挙げるが、これらに限定されるものではない。
Moreover, in this invention, when obtaining the acrylic polymer which has a specific functional group, the monomer which has a non-reactive functional group which can be copolymerized with the monomer which has a specific functional group can be used together.
Specific examples of the monomer having a non-reactive functional group include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.
Hereinafter, although the specific example of the said monomer is given, it is not limited to these.
前記アクリル酸エステル化合物としては、例えば、メチルアクリレート、エチルアクリレート、イソプロピルアクリレート、ベンジルアクリレート、ナフチルアクリレート、アントリルアクリレート、アントリルメチルアクリレート、フェニルアクリレート、２，２，２−トリフルオロエチルアクリレート、ｔｅｒｔ−ブチルアクリレート、シクロヘキシルアクリレート、イソボルニルアクリレート、２−メトキシエチルアクリレート、メトキシトリエチレングリコールアクリレート、２−エトキシエチルアクリレート、テトラヒドロフルフリルアクリレート、３−メトキシブチルアクリレート、２−メチル−２−アダマ
ンチルアクリレート、２−プロピル−２−アダマンチルアクリレート、８−メチル−８−トリシクロデシルアクリレート、及び、８−エチル−８−トリシクロデシルアクリレート等が挙げられる。
Examples of the acrylic ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert- Butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2 -Propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate And, like 8-ethyl-8-tricyclodecyl acrylate.
前記メタクリル酸エステル化合物としては、例えば、メチルメタクリレート、エチルメタクリレート、イソプロピルメタクリレート、ベンジルメタクリレート、ナフチルメタクリレート、アントリルメタクリレート、アントリルメチルメタクリレート、フェニルメタクリレート、２，２，２−トリフルオロエチルメタクリレート、ｔｅｒｔ−ブチルメタクリレート、シクロヘキシルメタクリレート、イソボルニルメタクリレート、２−メトキシエチルメタクリレート、メトキシトリエチレングリコールメタクリレート、２−エトキシエチルメタクリレート、テトラヒドロフルフリルメタクリレート、３−メトキシブチルメタクリレート、２−メチル−２−アダマンチルメタクリレート、γ−ブチロラクトンメタクリレート、２−プロピル−２−アダマンチルメタクリレート、８−メチル−８−トリシクロデシルメタクリレート、及び、８−エチル−８−トリシクロデシルメタクリレート等が挙げられる。 Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert- Butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ -Butyrolactone methacrylate, 2-propyl-2 Adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and, 8-ethyl-8-tricyclodecyl methacrylate.
前記ビニル化合物としては、例えば、メチルビニルエーテル、ベンジルビニルエーテル、ビニルナフタレン、ビニルアントラセン、ビニルカルバゾール、２−ヒドロキシエチルビニルエーテル、フェニルビニルエーテル、及び、プロピルビニルエーテル等が挙げられる。 Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl carbazole, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
前記スチレン化合物としては、例えば、スチレン、メチルスチレン、クロロスチレン、ブロモスチレン等が挙げられる。 Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.
前記マレイミド化合物としては、例えば、マレイミド、Ｎ−メチルマレイミド、Ｎ−フェニルマレイミド、及びＮ−シクロヘキシルマレイミド等が挙げられる。 Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
本発明に用いる特定官能基を有するアクリル重合体を得る方法は特に限定されないが、例えば、特定官能基を有するモノマー、それ以外の共重合可能な非反応性官能基を有するモノマー及び所望により重合開始剤等を共存させた溶剤中において、５０乃至１１０℃の温度下で重合反応させることにより、得られる。その際、用いられる溶剤は、特定官能基を有するアクリル重合体を構成するモノマー及び特定官能基を有するアクリル重合体を溶解するものであれば特に限定されない。具体例としては、後述する（Ｃ）溶剤に記載する溶剤が挙げられる。
このようにして得られる特定官能基を有するアクリル重合体は、通常、溶剤に溶解した溶液の状態である。
The method for obtaining an acrylic polymer having a specific functional group used in the present invention is not particularly limited. For example, a monomer having a specific functional group, another monomer having a non-reactive functional group capable of copolymerization, and initiation of polymerization if desired. It can be obtained by carrying out a polymerization reaction at a temperature of 50 to 110 ° C. in a solvent in which an agent or the like is present. In that case, the solvent used will not be specifically limited if it dissolves the monomer which comprises the acrylic polymer which has a specific functional group, and the acrylic polymer which has a specific functional group. As a specific example, the solvent described in the (C) solvent mentioned later is mentioned.
The acrylic polymer having a specific functional group thus obtained is usually in a solution state dissolved in a solvent.
次いで、得られた特定官能基を有するアクリル重合体に特定化合物を反応させて、（Ａ）成分であるアクリル重合体（以下、特定共重合体と称す。）を得ることができる。その際、通常は、特定官能基を有するアクリル重合体の溶液を用いる。
具体的には、例えば、カルボキシル基を有するアクリル重合体の溶液に、グリシジルメタクリレートをベンジルトリエチルアンモニウムクロリド等の触媒存在下、８０℃乃至１５０℃の温度で反応させることにより、特定共重合体を得ることができる。その際、用いられる溶剤は、特定共重合体を構成するモノマー及び特定共重合体を溶解するものであれば特に限定されない。具体例としては、後述する（Ｃ）溶剤に記載する溶剤が挙げられる。
このようにして得られる特定共重合体は、通常、この特定共重合体が溶剤に溶解した溶液の状態である。
Next, a specific compound is reacted with the obtained acrylic polymer having a specific functional group, whereby an acrylic polymer (hereinafter referred to as a specific copolymer) as the component (A) can be obtained. In that case, the solution of the acrylic polymer which has a specific functional group is used normally.
Specifically, for example, a specific copolymer is obtained by reacting a solution of an acrylic polymer having a carboxyl group with glycidyl methacrylate in the presence of a catalyst such as benzyltriethylammonium chloride at a temperature of 80 ° C. to 150 ° C. be able to. In that case, the solvent used will not be specifically limited if the monomer which comprises a specific copolymer, and a specific copolymer are melt | dissolved. As a specific example, the solvent described in the (C) solvent mentioned later is mentioned.
The specific copolymer thus obtained is usually in the form of a solution in which the specific copolymer is dissolved in a solvent.
また、上記のようにして得られた特定共重合体の溶液を、ジエチルエーテルや水等の撹
拌下に投入して再沈殿させ、生成した沈殿物を濾過・洗浄した後、常圧又は減圧下で、常温あるいは加熱乾燥することで、特定共重合体の粉体とすることができる。このような操作により、特定共重合体と共存する重合開始剤や未反応モノマーを除去することができ、その結果、精製した特定共重合体の粉体を得られる。一度の操作で充分に精製できない場合は、得られた粉体を溶剤に再溶解して、上記の操作を繰り返し行えば良い。
本発明においては、上記特定共重合体の粉体をそのまま用いても良く、あるいはその粉体を、たとえば後述する（Ｃ）溶剤に再溶解して溶液の状態として用いても良い。
また、本発明においては、（Ａ）成分のアクリル重合体は、複数種の特定共重合体の混合物であってもよい。
In addition, the solution of the specific copolymer obtained as described above is re-precipitated by stirring with stirring such as diethyl ether or water, and the generated precipitate is filtered and washed, and then under normal pressure or reduced pressure. Thus, the powder of the specific copolymer can be obtained by drying at room temperature or by heating. By such an operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. If sufficient purification cannot be achieved by a single operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
In the present invention, the powder of the specific copolymer may be used as it is, or the powder may be redissolved in a solvent (C) described later and used as a solution.
In the present invention, the acrylic polymer of component (A) may be a mixture of a plurality of types of specific copolymers.
＜（Ｂ）成分＞
本発明の（Ｂ）成分であるビスマレイミド化合物は下記の一般式（３）で示される。
<(B) component>
The bismaleimide compound which is the component (B) of the present invention is represented by the following general formula (3).
式中、Ｒ3は、脂肪族基、環式構造を含む脂肪族基及び芳香族基からなる群から選ばれ
る有機基又はそれらの群から選ばれる複数の有機基の組み合わせからなる有機基である。そして、Ｒ3には、エステル結合、エーテル結合、アミド結合、ウレタン結合等の結合を
含んでいても良い。
In the formula, R 3 is an organic group selected from the group consisting of an aliphatic group, an aliphatic group containing a cyclic structure, and an aromatic group, or an organic group consisting of a combination of a plurality of organic groups selected from these groups. . R 3 may contain a bond such as an ester bond, an ether bond, an amide bond, or a urethane bond.
このようなビスマレイミド化合物の具体例としては、例えば、Ｎ，Ｎ’−３，３−ジフェニルメタンビスマレイミド、Ｎ，Ｎ’−（３，３−ジエチル−５，５−ジメチル）−４，４−ジフェニル−メタンビスマレイミド、Ｎ，Ｎ’−４，４−ジフェニルメタンビスマレイミド、３，３−ジフェニルスルホンビスマレイミド、４，４−ジフェニルスルホンビスマレイミド、Ｎ，Ｎ’−ｐ−ベンゾフェノンビスマレイミド、Ｎ，Ｎ’−ジフェニルエタンビスマレイミド、Ｎ，Ｎ’−ジフェニルエーテルビスマレイミド、Ｎ，Ｎ’−（メチレンジ−ジテトラヒドロフェニル）ビスマレイミド、Ｎ，Ｎ’−（３−エチル）−４，４−ジフェニルメタンビスマレイミド、Ｎ，Ｎ’−（３、３−ジメチル）−４，４−ジフェニルメタンビスマレイミド、Ｎ，Ｎ’−（３、３−ジエチル）−４，４−ジフェニルメタンビスマレイミド、Ｎ，Ｎ’−（３、３−ジクロロ）−４，４−ジフェニルメタンビスマレイミド、Ｎ，Ｎ’−イソホロンビスマレイミド、Ｎ，Ｎ’−トリジンビスマレイミド、Ｎ，Ｎ’−ジフェニルプロパンビスマレイミド、Ｎ，Ｎ’−ナフタレンビスマレイミド、Ｎ，Ｎ’−ｍ−フェニレンビスマレイミド、Ｎ，Ｎ’−５−メトキシ−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、２，２−ビス（３−クロロ−４−（４−マレイミドフェノキシ）フェニル）プロパン、２，２−ビス（３−ブロモ−４−（４−マレイミドフェノキシ）フェニル）プロパン、２，２−ビス（３−エチル−４−（４−マレイミドフェノキシ）フェニル）プロパン、２，２−ビス（３−プロピル−４−（４−マレイミドフェノキシ）フェニル）プロパン、２，２−ビス（３−イソプロピル−４−（４−マレイミドフェノキシ）フェニル）プロパン、２，２−ビス（３−ブチル−４−（４−マレイミドフェノキシ）フェニル）プロパン、２，２−ビス（３−メトキシ−４−（４−マレイミドフェノキシ）フェニル）プロパン、１，１−ビス（４−（４−マレイミドフェノキシ）フェニル）エタン、１，１−ビス（３−メチル−４−（４−マレイミドフェノキシ）フェニル）エタン、１，１−ビス（３−ク
ロロ−４−（４−マレイミドフェノキシ）フェニル）エタン、１，１−ビス（３−ブロモ−４−（４−マレイミドフェノキシ）フェニル）エタン、３，３−ビス（４−（４−マレイミドフェノキシ）フェニル）ペンタン、１，１，１，３，３，３−ヘキサフルオロ−２，２−ビス（４−（４−マレイミドフェノキシ）フェニル）プロパン、１，１，１，３，３，３−ヘキサフルオロ−２，２−ビス（３，５−ジメチル−４−（４−マレイミドフェノキシ）フェニル）プロパン、１，１，１，３，３，３−ヘキサフルオロ−２，２−ビス（３，５−ジブロモ−４−（４−マレイミドフェノキシ）フェニル）プロパン、Ｎ，Ｎ’−エチレンジマレイミド、Ｎ，Ｎ’−ヘキサメチレンビスマレイミド、Ｎ，Ｎ’−ドデカメチレンビスマレイミド、Ｎ，Ｎ’−ｍ−キシレンビスマレイミド、Ｎ，Ｎ’−ｐ−キシレンビスマレイミド、Ｎ，Ｎ’−１，３−ビスメチレンシクロヘキサンビスマレイミド、Ｎ，Ｎ’−２，４−トリレンビスマレイミド、Ｎ，Ｎ’−２，６−トリレンビスマレイミド、等が挙げられる。
Specific examples of such bismaleimide compounds include, for example, N, N′-3,3-diphenylmethane bismaleimide, N, N ′-(3,3-diethyl-5,5-dimethyl) -4,4- Diphenyl-methane bismaleimide, N, N′-4,4-diphenylmethane bismaleimide, 3,3-diphenylsulfone bismaleimide, 4,4-diphenylsulfone bismaleimide, N, N′-p-benzophenone bismaleimide, N, N′-diphenylethane bismaleimide, N, N′-diphenyl ether bismaleimide, N, N ′-(methylenedi-ditetrahydrophenyl) bismaleimide, N, N ′-(3-ethyl) -4,4-diphenylmethane bismaleimide N, N ′-(3,3-dimethyl) -4,4-diphenylmethane bismaleimide, N, N ′-(3, 3-diethyl) -4,4-diphenylmethane bismaleimide, N, N ′-(3,3-dichloro) -4,4-diphenylmethane bismaleimide, N, N′-isophorone bismaleimide, N, N′-tolidine bis Maleimide, N, N′-diphenylpropane bismaleimide, N, N′-naphthalene bismaleimide, N, N′-m-phenylene bismaleimide, N, N′-5-methoxy-1,3-phenylene bismaleimide, 2 , 2-bis (4- (4-maleimidophenoxy) phenyl) propane, 2,2-bis (3-chloro-4- (4-maleimidophenoxy) phenyl) propane, 2,2-bis (3-bromo-4 -(4-maleimidophenoxy) phenyl) propane, 2,2-bis (3-ethyl-4- (4-maleimidophenoxy) phenyl) propane, 2,2-bis (3-propyl-4- (4-maleimidophenoxy) phenyl) propane, 2,2-bis (3-isopropyl-4- (4-maleimidophenoxy) phenyl) propane, 2,2-bis ( 3-butyl-4- (4-maleimidophenoxy) phenyl) propane, 2,2-bis (3-methoxy-4- (4-maleimidophenoxy) phenyl) propane, 1,1-bis (4- (4-maleimide) Phenoxy) phenyl) ethane, 1,1-bis (3-methyl-4- (4-maleimidophenoxy) phenyl) ethane, 1,1-bis (3-chloro-4- (4-maleimidophenoxy) phenyl) ethane, 1,1-bis (3-bromo-4- (4-maleimidophenoxy) phenyl) ethane, 3,3-bis (4- (4-maleimidophenoxy) pheny ) Pentane, 1,1,1,3,3,3-hexafluoro-2,2-bis (4- (4-maleimidophenoxy) phenyl) propane, 1,1,1,3,3,3-hexafluoro -2,2-bis (3,5-dimethyl-4- (4-maleimidophenoxy) phenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,5- Dibromo-4- (4-maleimidophenoxy) phenyl) propane, N, N′-ethylenedimaleimide, N, N′-hexamethylene bismaleimide, N, N′-dodecamethylene bismaleimide, N, N′-m- Xylene bismaleimide, N, N′-p-xylene bismaleimide, N, N′-1,3-bismethylenecyclohexane bismaleimide, N, N′-2,4-tolylene bismaleimide, N, N′-2 , 6-To And rylene bismaleimide.
これらのビスマレイミド化合物は特に上記のものに限定されるものではない。そして、これらは、単独又は２種以上の成分を併用することが可能である。 These bismaleimide compounds are not particularly limited to those described above. These can be used alone or in combination of two or more.
これらのビスマレイミドのうち２，２−ビス（４−（４−マレイミドフェノキシ）フェニル）プロパン、Ｎ，Ｎ’−４，４−ジフェニルメタンビスマレイミド、Ｎ，Ｎ’−（３，３−ジエチル−５，５−ジメチル）−４，４−ジフェニル−メタンビスマレイミド等の芳香族ビスマレイミドが高い耐熱性の点から好ましい。 Among these bismaleimides, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane, N, N′-4,4-diphenylmethane bismaleimide, N, N ′-(3,3-diethyl-5 , 5-dimethyl) -4,4-diphenyl-methane bismaleimide is preferred from the viewpoint of high heat resistance.
また、これらのビスマレイミドのうちにおいては、分子量１０００以下のものが、より高い平坦化性を得るので好ましい。 Among these bismaleimides, those having a molecular weight of 1000 or less are preferable because higher planarity can be obtained.
本発明において（Ｂ）成分のビスマレイミド化合物の使用割合は、（Ａ）成分のアクリル重合体１００質量部に対して１０乃至２００質量部であることが好ましく、より好ましくは２０乃至１５０質量部であり、特に好ましくは５０乃至１３０質量部である。この割合が過小である場合には、平坦化性が低下し、過大である場合には硬化膜の透過率が低下したり塗膜が荒れたりすることがある。 In the present invention, the use ratio of the (B) component bismaleimide compound is preferably 10 to 200 parts by mass, more preferably 20 to 150 parts by mass, relative to 100 parts by mass of the (A) component acrylic polymer. Particularly preferably 50 to 130 parts by mass. When this ratio is too small, the planarization property is lowered, and when it is too large, the transmittance of the cured film may be lowered or the coating film may be roughened.
＜（Ｃ）溶剤＞
本発明に用いる（Ｃ）溶剤は、（Ａ）成分及び（Ｂ）成分を溶解し、且つ所望により添加される後述の（Ｄ）成分などを溶解するものであり、斯様な溶解能を有する溶剤であれば、その種類及び構造などは特に限定されるものでない。
<(C) Solvent>
The (C) solvent used in the present invention dissolves the component (A) and the component (B) and dissolves the component (D) to be added as required, and has such a dissolving ability. If it is a solvent, the kind and structure thereof are not particularly limited.
斯様な（Ｃ）溶剤としては、例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコール、プロピレングリコールモノメチルエーテル、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プロピルエーテルアセテート、トルエン、キシレン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン、シクロヘキサノール、２−ペンタノン、２−ヘプタノン、γ−ブチロラクトン、２−ヒドロキシプロピオン酸エチル、２−ヒドロキシ−２−メチルプロピオン酸エチル、エトキシ酢酸エチル、ヒドロキシ酢酸エチル、２−ヒドロキシ−３−メチルブタン酸メチル、３−メトキシプロピオン酸メチル、３−メトキシプロピオン酸エチル、３−エトキシプロピオン酸エチル、３−エトキシプロピオン酸メチル、ピルビン酸メチル、ピルビン酸エチル、酢酸エチル、酢酸ブチル、乳酸エチル、乳酸ブチル、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、及びＮ−メチルピロリドン等が挙げられる。
これらの溶剤は、一種単独で、又は二種以上の組み合わせで使用することができる。
Examples of such a solvent (C) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol. Monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, cyclohexanol, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, 2-hydroxy-2- Ethyl methyl propionate, ethyl ethoxy acetate, hydroxy vinegar Ethyl, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate Butyl acetate, ethyl lactate, butyl lactate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.
These solvents can be used singly or in combination of two or more.
＜（Ｄ）成分＞
（Ｄ）成分は、界面活性剤である。本発明の平坦化膜形成用熱硬化性樹脂組成物にあっては、その塗布性を向上させるという目的で、本発明の効果を損なわない限りにおいて、更に界面活性剤を含有することができる。
<(D) component>
Component (D) is a surfactant. The thermosetting resin composition for forming a flattened film of the present invention can further contain a surfactant for the purpose of improving the coating properties as long as the effects of the present invention are not impaired.
（Ｄ）成分の界面活性剤としては、特に制限されないが、例えば、フッ素系界面活性剤、シリコン系界面活性剤、ノニオン系界面活性剤などが挙げられ、特にフッ素系界面活性剤を用いることが好ましい。この種の界面活性剤としては、例えば、住友スリーエム（株）製、大日本インキ化学工業（株）製或いは旭硝子（株）製等の市販品を用いることができる。これら市販品は、容易に入手することができるので、好都合である。その具体的な例としては、エフトップＥＦ３０１、ＥＦ３０３、ＥＦ３５２（（株）ジェムコ製）、メガファックＲ−３０、Ｒ−０８、ＢＬ−２０、Ｆ１７１、Ｆ１７３（大日本インキ化学工業（株）製）、フロラードＦＣ４３０、ＦＣ４３１、ＦＣ−４４３２、ＦＣ−４４３０（住友スリーエム（株）製）、アサヒガードＡＧ７１０、サーフロンＳ−３８２、ＳＣ１０１、ＳＣ１０２、ＳＣ１０３、ＳＣ１０４、ＳＣ１０５、ＳＣ１０６（旭硝子（株）製）等のフッ素系界面活性剤が挙げられる。
これら（Ｄ）成分の界面活性剤は、一種単独で、又は二種以上の組み合わせで使用することができる。
The surfactant of the component (D) is not particularly limited, and examples thereof include a fluorine-based surfactant, a silicon-based surfactant, a nonionic surfactant, and the like, and in particular, a fluorine-based surfactant is used. preferable. As this type of surfactant, for example, commercially available products such as those manufactured by Sumitomo 3M Co., Ltd., Dainippon Ink Chemical Co., Ltd., or Asahi Glass Co., Ltd. can be used. These commercial products are convenient because they can be easily obtained. Specific examples thereof include F-top EF301, EF303, EF352 (manufactured by Gemco), MegaFac R-30, R-08, BL-20, F171, F173 (manufactured by Dainippon Ink & Chemicals, Inc.). ), FLORARD FC430, FC431, FC-4432, FC-4430 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) Fluorine-based surfactants such as
These (D) component surfactants can be used singly or in combination of two or more.
界面活性剤が使用される場合、その含有量は、平坦化膜形成用熱硬化性樹脂組成物中に通常１質量％以下であり、好ましくは０．１質量％以下である。（Ｄ）成分の含有量が１質量％を超える量に設定されても、上記塗布性の改良効果は鈍くなり、経済的でなくなる。 When a surfactant is used, its content is usually 1% by mass or less, preferably 0.1% by mass or less, in the thermosetting resin composition for forming a flattened film. Even if the content of the component (D) is set to an amount exceeding 1% by mass, the effect of improving the applicability becomes dull and not economical.
＜その他添加剤＞
更に、本発明の平坦化膜形成用熱硬化性樹脂組成物は、本発明の効果を損なわない限りにおいて、必要に応じて、レオロジー調整剤、シランカップリング剤等の接着補助剤、顔料、染料、保存安定剤、消泡剤、又は多価フェノール、多価カルボン酸等の溶解促進剤等を含有することができる。
<Other additives>
Furthermore, the thermosetting resin composition for flattened film formation according to the present invention can be used as necessary, as long as the effects of the present invention are not impaired, as a bonding aid such as a rheology modifier or a silane coupling agent, a pigment, or a dye. , A storage stabilizer, an antifoaming agent, or a dissolution accelerator such as polyhydric phenol and polycarboxylic acid can be contained.
＜平坦化膜形成用熱硬化性樹脂組成物＞
本発明の平坦化膜形成用樹脂組成物は、（Ａ）成分のアクリル重合体、（Ｂ）成分のビスマレイミド化合物及び（Ｃ）溶剤を含有し、それぞれ所望により、（Ｄ）成分の界面活性剤及びその他添加剤のうち一種以上を更に含有することができる組成物である。
<Thermosetting resin composition for flattening film formation>
The resin composition for forming a flattened film of the present invention comprises (A) an acrylic polymer, (B) a bismaleimide compound, and (C) a solvent. It is the composition which can further contain 1 or more types among an agent and another additive.
中でも、本発明の平坦化膜形成用熱硬化性樹脂組成物の好ましい例は、以下のとおりである。
［１］：（Ａ）成分の１００質量部に基づいて、１０乃至２００質量部の（Ｂ）成分を含有し、それらが（Ｃ）溶剤に溶解した平坦化膜形成用熱硬化性樹脂組成物。
［２］：上記［１］の組成物において、更に（Ｄ）成分を１質量％以下含有する平坦化膜形成用熱硬化性樹脂組成物。
Especially, the preferable example of the thermosetting resin composition for planarization film formation of this invention is as follows.
[1]: A thermosetting resin composition for forming a flattened film, containing 10 to 200 parts by mass of the component (B) based on 100 parts by mass of the component (A) and dissolved in the solvent (C). .
[2]: A thermosetting resin composition for forming a flattened film, further comprising (D) component in an amount of 1% by mass or less in the composition of [1] above.
本発明の平坦化膜形成用熱硬化性樹脂組成物における固形分の割合は、各成分が均一に溶剤に溶解している限り、特に限定されるものではないが、例えば１乃至８０質量％であり、また例えば５乃至６０質量％であり、又は１０乃至５０質量％である。ここで、固形分とは、平坦化膜形成用熱硬化性樹脂組成物の全成分から（Ｃ）溶剤を除いたものを指す。 The ratio of the solid content in the thermosetting resin composition for forming a flattened film of the present invention is not particularly limited as long as each component is uniformly dissolved in a solvent. For example, 5 to 60% by mass, or 10 to 50% by mass. Here, solid content refers to what remove | excluded the (C) solvent from all the components of the thermosetting resin composition for flattening film formation.
本発明の平坦化膜形成用熱硬化性樹脂組成物の調製方法は、特に限定されないが、その調製法としては、例えば、（Ａ）成分を（Ｃ）溶剤に溶解し、この溶液に（Ｂ）成分、及
び所望により（Ｄ）成分を所定の割合で混合し、均一な溶液とする方法、あるいはこの調製法の適当な段階において、必要に応じてその他添加剤を更に添加して混合する方法が挙げられる。
Although the preparation method of the thermosetting resin composition for planarization film formation of this invention is not specifically limited, As the preparation method, (A) component is melt | dissolved in the (C) solvent, for example, (B) ) Component and, if desired, component (D) in a predetermined ratio to make a uniform solution, or a method in which other additives are further added as needed at an appropriate stage of this preparation method. Is mentioned.
本発明の平坦化膜形成用熱硬化性樹脂組成物の調製にあたっては、（Ｃ）溶剤中における重合反応によって得られる特定共重合体の溶液をそのまま使用することができ、この場合、この（Ａ）成分の溶液に前記と同様に（Ｂ）成分、（Ｄ）成分などを入れて均一な溶液とする際に、濃度調整を目的としてさらに（Ｃ）溶剤を追加投入してもよい。このとき、特定共重合体の形成過程で用いられる（Ｃ）溶剤と、平坦化膜形成用熱硬化性樹脂組成物の調製時に濃度調整のために用いられる（Ｃ）溶剤とは同一であってもよいし、異なってもよい。 In preparing the thermosetting resin composition for flattened film formation of the present invention, the solution of the specific copolymer obtained by the polymerization reaction in the solvent (C) can be used as it is. In the same manner as described above, when the component (B), the component (D), etc. are added to the component solution to obtain a uniform solution, a solvent (C) may be additionally added for the purpose of adjusting the concentration. At this time, the (C) solvent used in the process of forming the specific copolymer is the same as the (C) solvent used for concentration adjustment when preparing the thermosetting resin composition for flattening film formation. It may be different or different.
而して、調製された平坦化膜形成用熱硬化性樹脂組成物の溶液は、孔径が０.２μｍ程
度のフィルタなどを用いて濾過した後、使用することが好ましい。
Thus, the prepared solution of the thermosetting resin composition for forming a flattened film is preferably used after being filtered using a filter having a pore diameter of about 0.2 μm.
＜塗膜及び硬化膜＞
本発明の平坦化膜形成用熱硬化性樹脂組成物を半導体で用いられる基板（例えば、シリコン／二酸化シリコン被覆基板、シリコンナイトライド基板、金属例えばアルミニウム、モリブデン、クロムなどが被覆された基板、ガラス基板、石英基板、ＩＴＯ基板等）の上に、回転塗布、流し塗布、ロール塗布、スリット塗布、スリットに続いた回転塗布、インクジェット塗布などによって塗布し、その後、ホットプレート又はオーブン等で予備乾燥することにより、塗膜を形成することができる。その後、この塗膜を加熱処理することにより、平坦化に優れる平坦化膜形成用熱硬化性樹脂膜が形成される。
<Coating film and cured film>
A substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, glass, or the like, which is used as a semiconductor for the planarization film forming thermosetting resin composition of the present invention. On a substrate, quartz substrate, ITO substrate, etc.) by spin coating, flow coating, roll coating, slit coating, spin coating following slit, ink jet coating, etc., and then pre-dried in a hot plate or oven, etc. Thus, a coating film can be formed. Then, the thermosetting resin film for planarization film formation excellent in planarization is formed by heat-processing this coating film.
この加熱処理の条件としては、例えば、温度７０℃乃至１６０℃、時間０．３乃至６０分間の範囲の中から適宜選択された加熱温度及び加熱時間が採用される。加熱温度及び加熱時間は、好ましくは８０℃乃至１４０℃、０．５乃至１０分間である。 As conditions for this heat treatment, for example, a heating temperature and a heating time appropriately selected from the range of a temperature of 70 ° C. to 160 ° C. and a time of 0.3 to 60 minutes are employed. The heating temperature and heating time are preferably 80 to 140 ° C. and 0.5 to 10 minutes.
また、上記平坦化膜形成用熱硬化性樹脂組成物から形成される平坦化膜形成用熱硬化性樹脂膜の膜厚は、例えば０．１乃至３０μｍであり、また例えば０．２乃至１０μｍであり、更に例えば０．２乃至５μｍであり、使用する基板の段差や光学的、電気的性質を考慮し適宜選択することができる。 Moreover, the film thickness of the thermosetting resin film for planarization film formation formed from the said thermosetting resin composition for planarization film formation is 0.1 thru | or 30 micrometers, for example, and is 0.2 thru | or 10 micrometers, for example. In addition, for example, the thickness is 0.2 to 5 μm, and can be appropriately selected in consideration of the level difference of the substrate to be used and optical and electrical properties.
ポストベークとしては、一般に、温度１４０℃乃至２５０℃の範囲の中から選択された加熱温度にて、ホットプレート上の場合には５乃至３０分間、オーブン中の場合には３０乃至９０分間処理するという方法が採られる。 The post-bake is generally processed at a heating temperature selected from the range of 140 ° C. to 250 ° C. for 5 to 30 minutes when on a hot plate and 30 to 90 minutes when in an oven. The method is taken.
以上のように、本発明の平坦化膜形成用熱硬化性樹脂組成物により、十分に基板の段差を平坦化でき、平坦化に優れ、高透明性を有する平坦化膜を形成することができる。 As described above, the level difference of the substrate can be sufficiently flattened by the thermosetting resin composition for flattening film formation of the present invention, and a flattening film having excellent transparency and high transparency can be formed. .
そのため、例えば、本発明による平坦化膜形成用熱硬化性樹脂組成物は、薄膜トランジスタ（ＴＦＴ）型液晶表示素子、有機ＥＬ素子等の各種ディスプレイにおける保護膜、平坦化膜、絶縁膜等の硬化膜を形成する材料として好適であり、特に、ＴＦＴ型液晶素子の層間絶縁膜、カラーフィルタの保護膜、有機ＥＬ素子の絶縁膜等を形成する材料としても好適である。 Therefore, for example, the thermosetting resin composition for flattening film formation according to the present invention is a cured film such as a protective film, a flattening film, and an insulating film in various displays such as thin film transistor (TFT) type liquid crystal display elements and organic EL elements. In particular, it is also suitable as a material for forming an interlayer insulating film of a TFT type liquid crystal element, a protective film of a color filter, an insulating film of an organic EL element, and the like.
以下、実施例を挙げて、本発明を更に詳しく説明するが、本発明は、これら実施例に限定されるものでない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in more detail, this invention is not limited to these Examples.
［実施例で用いる略記号］
以下の実施例で用いる略記号の意味は、次のとおりである。
ＭＡＡ：メタクリル酸
ＭＭＡ：メチルメタクリレート
ＧＭＡ：グリシジルメタクリレート
ＡＩＢＮ：アゾビスイソブチロニトリル
ＢＴＥＡＣ：ベンジルトリエチルアンモニウムクロリド
ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート
ＮＭＰ：Ｎ−メチルピロリドン
ＤＰＨＡ：日本化薬（株）製 ＫＡＹＡＲＡＤ ＤＰＨＡ（商品名）
ＢＭＩ１：Ｎ，Ｎ’−（３，３−ジエチル−５，５−ジメチル）−４，４−ジフェニル−メタンビスマレイミド
ＢＭＩ２：２，２−ビス（４−（４−マレイミドフェノキシ）フェニル）プロパン
ＢＭＩ３：Ｎ，Ｎ’−４，４−ジフェニルメタンビスマレイミド
Ｒ３０：大日本インキ化学工業（株）製 メガファック Ｒ−３０（商品名）
[Abbreviations used in Examples]
The meanings of the abbreviations used in the following examples are as follows.
MAA: methacrylic acid MMA: methyl methacrylate GMA: glycidyl methacrylate AIBN: azobisisobutyronitrile BTEAC: benzyltriethylammonium chloride PGMEA: propylene glycol monomethyl ether acetate NMP: N-methylpyrrolidone DPHA: manufactured by Nippon Kayaku Co., Ltd. KAYARAD DPHA (Product name)
BMI1: N, N ′-(3,3-diethyl-5,5-dimethyl) -4,4-diphenyl-methane bismaleimide BMI2: 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane BMI3 : N, N′-4,4-diphenylmethane bismaleimide R30: Daifuku Ink Chemical Co., Ltd. MegaFuck R-30 (trade name)
［数平均分子量及び重量平均分子量の測定］
以下の合成例に従い得られる特定共重合体及び共重合体の数平均分子量及び重量平均分子量は、日本分光（株）製ＧＰＣ装置（Ｓｈｏｄｅｘ（登録商標）カラムＫＦ８０３Ｌ及びＫＦ８０４Ｌ）を用い、溶出溶媒テトラヒドロフランを流量１ｍｌ／分でカラム中に（カラム温度４０℃）流して溶離させるという条件で測定した。なお、下記の数平均分子量（以下、Ｍｎと称す。）及び重量平均分子量（以下、Ｍｗと称す。）は、ポリスチレン換算値にて表される。
[Measurement of number average molecular weight and weight average molecular weight]
The number average molecular weight and the weight average molecular weight of the specific copolymer and copolymer obtained according to the following synthesis examples were measured using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF804L) manufactured by JASCO Corporation, and the elution solvent tetrahydrofuran. Was flowed through the column at a flow rate of 1 ml / min (
＜合成例１＞
共重合体を構成するモノマー成分として、ＭＡＡ（４０．０ｇ）、ＭＭＡ（４０．０ｇ）を使用し、ラジカル重合開始剤としてＡＩＢＮ（２ｇ）を使用し、これらを溶剤ＰＧＭＥＡ（１２０ｇ）中において重合反応させることにより、Ｍｎ６，３００、Ｍｗ１０，６００である共重合体溶液（共重合体濃度：４０質量％）を得た（Ｐ１）。なお、重合温度は、温度６０℃乃至１００℃に調整した。
<Synthesis Example 1>
MAA (40.0 g) and MMA (40.0 g) are used as monomer components constituting the copolymer, AIBN (2 g) is used as a radical polymerization initiator, and these are polymerized in a solvent PGMEA (120 g). By making it react, the copolymer solution (copolymer density | concentration: 40 mass%) which is Mn6,300 and Mw10,600 was obtained (P1). The polymerization temperature was adjusted to 60 to 100 ° C.
＜合成例２＞
上記共重合体（Ｐ１）２００ｇにＧＭＡ（２６．０ｇ）、ＢＴＥＡＣ（１．１ｇ）、ＰＧＭＥＡ（３９ｇ）を加えて反応させることにより（Ａ）成分の溶液であるＭｎ７，２００、Ｍｗ１３，２００の（Ａ）成分（特定共重合体）の溶液（特定共重合体濃度：４０質量％）を得た（Ｐ２）。なお、反応温度を９０乃至１２０℃に調整した。
<Synthesis Example 2>
By adding GMA (26.0 g), BTEAC (1.1 g), and PGMEA (39 g) to 200 g of the copolymer (P1) and reacting them, the solution of the component (A) Mn7,200, Mw13,200 A solution (specific copolymer concentration: 40% by mass) of the component (A) (specific copolymer) was obtained (P2). The reaction temperature was adjusted to 90 to 120 ° C.
＜実施例１乃至６及び比較例１乃至５＞
次の表１に示す組成に従い、（Ａ）成分の溶液に、（Ｂ）成分、及び（Ｃ）溶剤、更に（Ｄ）成分を所定の割合で混合し、室温で３時間撹拌して均一な溶液とすることにより、各実施例及び各比較例の平坦化膜形成用熱硬化性樹脂組成物を調製した。
<Examples 1 to 6 and Comparative Examples 1 to 5>
According to the composition shown in the following Table 1, the solution of the component (A) is mixed with the component (B), the solvent (C), and the component (D) in a predetermined ratio, and the mixture is stirred at room temperature for 3 hours to be uniform. By using it as a solution, the thermosetting resin composition for planarization film formation of each Example and each comparative example was prepared.
実施例１乃至実施例３並びに比較例１乃至比較例３の各組成物について、それぞれ、塗膜の評価、平坦化性の評価、ＮＭＰ耐性の評価、並びに高温焼成後の光透過率（透明性）の評価を行った。 About each composition of Example 1 thru | or Example 3 and Comparative Example 1 thru | or Comparative Example 3, evaluation of a coating film, evaluation of planarization property, evaluation of NMP resistance, and the light transmittance (transparency after high temperature baking), respectively ) Was evaluated.
［塗膜の評価］
実施例１乃至実施例３並びに比較例１乃至比較例３の平坦化膜形成用熱硬化性樹脂組成物を、それぞれスピンコーターを用いてシリコンウェハに塗布した後、温度１１０℃で１２０秒間ホットプレート上においてプリベークを行い、膜厚２．５μｍの塗膜を形成した。塗膜ができない場合やタックが入る場合を×、正常な塗膜が形成される場合を○とした。結果を表２に示す。
[Evaluation of coating film]
Each of the thermosetting resin compositions for forming a flattened film of Examples 1 to 3 and Comparative Examples 1 to 3 was applied to a silicon wafer using a spin coater, and then hotplate at a temperature of 110 ° C. for 120 seconds. Pre-baking was performed on the top to form a coating film having a thickness of 2.5 μm. The case where the coating film could not be formed or the case where tack was caused was evaluated as x, and the case where a normal coating film was formed was evaluated as ◯. The results are shown in Table 2.
［平坦化性の評価］
実施例１乃至実施例３並びに比較例１乃至比較例３の平坦化膜形成用熱硬化性樹脂組成物を、それぞれ高さ０．５μｍ、ライン幅５０μｍ、ライン間スペース１２０μｍの段差基板（ガラス製）上にスピンコーターを用いて塗布した後、温度１１０℃で１２０秒間ホットプレート上においてプリベークを行い膜厚２．５μｍの塗膜を形成した。膜厚はＦＩＬＭＥＴＲＩＣＳ製 Ｆ２０を用いて測定した。この塗膜を温度２３０℃で３０分間加熱することによりポストベークを行い、膜厚２．１μｍの硬化膜を形成した。
段差基板ライン上の塗膜とスペース上の塗膜の膜厚差を測定した（図１参照）。平坦化率（ＤＯＰ）＝１００×｛１−（塗膜の膜厚差（μｍ））／（段差基板の高さ（０．５μｍ）｝の式を用いて平坦化率を求めた。結果を表２に示す。
[Evaluation of flatness]
The thermosetting resin compositions for flattened film formation of Examples 1 to 3 and Comparative Examples 1 to 3 are stepped substrates (made of glass, each having a height of 0.5 μm, a line width of 50 μm, and a space between lines of 120 μm. After coating using a spin coater, pre-baking was performed on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. The film thickness was measured using F20 manufactured by FILMETRICS. This coating film was post-baked by heating at a temperature of 230 ° C. for 30 minutes to form a cured film having a thickness of 2.1 μm.
The film thickness difference between the coating film on the stepped substrate line and the coating film on the space was measured (see FIG. 1). Planarization rate (DOP) = 100 × {1− (film thickness difference (μm)) / (height of stepped substrate (0.5 μm))} The planarization rate was obtained. It shows in Table 2.
ライン幅（１０μｍ、３０μｍ、５０μｍ）及びライン間スペース（１０〜１００μｍ）を種々に変えた高さ０．５μｍの段差基板を準備し、実施例２及び比較例２の平坦化膜形成熱硬化性樹脂組成物を用いて、上記［平坦化性の評価］の手順に倣って硬化膜を形成し、塗膜の膜厚差より平坦化率（ＤＯＰ）を求めた。
得られた結果を図２（実施例２）及び図３（比較例２）に示す。
Stepped substrates having a height of 0.5 μm with various line widths (10 μm, 30 μm, 50 μm) and inter-line spaces (10-100 μm) were prepared, and the planarized film forming thermosetting properties of Example 2 and Comparative Example 2 were prepared. Using the resin composition, a cured film was formed following the above-mentioned procedure of [Evaluation of planarization], and the planarization rate (DOP) was determined from the difference in film thickness of the coating film.
The obtained results are shown in FIG. 2 (Example 2) and FIG. 3 (Comparative Example 2).
［ＮＭＰ耐性の評価］
実施例１乃至実施例３並びに比較例１乃至比較例３の平坦化膜形成用熱硬化性樹脂組成物を、それぞれシリコンウェハにスピンコーターを用いて塗布した後、温度１１０℃で１
２０秒間ホットプレート上においてプリベークを行い膜厚２．５μｍの塗膜を形成した。膜厚はＦＩＬＭＥＴＲＩＣＳ製 Ｆ２０を用いて測定した。この塗膜を温度２３０℃で３０分間ホットプレート上においてポストベークを行い、膜厚２．２μｍの硬化膜を形成した。この硬化膜をにＮＭＰ中に６０秒間浸漬させた後、１００℃にて６０秒間乾燥し膜厚を測定した。ＮＭＰ浸漬後の膜厚変化がないものを○、浸漬後に膜厚の減少が見られたものを×とした。結果を表２に示す。
[Evaluation of NMP resistance]
Each of the thermosetting resin compositions for forming a flattened film of Examples 1 to 3 and Comparative Examples 1 to 3 was applied to a silicon wafer using a spin coater, and then heated at 110 ° C.
Pre-baking was performed on a hot plate for 20 seconds to form a coating film having a thickness of 2.5 μm. The film thickness was measured using F20 manufactured by FILMETRICS. This coating film was post-baked on a hot plate at a temperature of 230 ° C. for 30 minutes to form a cured film having a thickness of 2.2 μm. The cured film was immersed in NMP for 60 seconds, dried at 100 ° C. for 60 seconds, and the film thickness was measured. The case where there was no change in film thickness after immersion in NMP was marked as ◯, and the case where the film thickness decreased after immersion was marked as x. The results are shown in Table 2.
［高温焼成後の光透過率（透明性）の評価］
実施例１乃至実施例３並びに比較例１乃至比較例３の平坦化膜形成用熱硬化性樹脂組成物を、それぞれ石英基板上にスピンコーターを用いて塗布した後、温度１１０℃で１２０秒間ホットプレート上においてプリベークを行い膜厚２．５μｍの塗膜を形成した。膜厚はＦＩＬＭＥＴＲＩＣＳ製 Ｆ２０を用いて測定した。この膜を温度２３０℃で３０分間ホットプレート上においてポストベークを行い、硬化膜を形成した。この硬化膜を紫外線可視分光光度計（（株）島津製作所製ＳＨＩＭＡＤＳＵ ＵＶ−２５５０型番）を用いて４００ｎｍの波長の透過率を測定した。結果を表２に示す。
なお、高温焼成後の光透過率において、平坦化膜としての要求性能は９０％以上である。
[Evaluation of light transmittance (transparency) after high-temperature firing]
Each of the thermosetting resin compositions for forming a flattened film of Examples 1 to 3 and Comparative Examples 1 to 3 was applied on a quartz substrate using a spin coater, and then hot for 120 seconds at a temperature of 110 ° C. Pre-baking was performed on the plate to form a coating film having a thickness of 2.5 μm. The film thickness was measured using F20 manufactured by FILMETRICS. This film was post-baked on a hot plate at a temperature of 230 ° C. for 30 minutes to form a cured film. The cured film was measured for transmittance at a wavelength of 400 nm using an ultraviolet-visible spectrophotometer (SHIMADSU UV-2550 model number, manufactured by Shimadzu Corporation). The results are shown in Table 2.
In addition, in the light transmittance after high temperature baking, the required performance as a planarization film is 90% or more.
［評価の結果］
以上の評価を行った結果は下記表２の通りとなった。
[Evaluation results]
The results of the above evaluation are as shown in Table 2 below.
実施例１乃至３は、塗膜形成性が良好で、得られた塗膜６０％以上の高い平坦化率を有し、ＮＭＰに対し耐性が見られた。さらに、高温焼成後も平坦化膜として要求される９０％以上の光透過率（透明性）を達成した。
一方、比較例１はプリベーク時、塗膜にタックが入り、硬化膜のＮＭＰ耐性も低かった。比較例２はＮＭＰ耐性が見られたものの平坦化性が低かった。比較例３は均一な塗膜を得ることができず、特性の評価に至らなかった。
Examples 1 to 3 had good coating film formability, had a high flattening rate of 60% or more of the obtained coating film, and were resistant to NMP. Furthermore, the light transmittance (transparency) of 90% or more required as a planarizing film was achieved even after high temperature baking.
On the other hand, when Comparative Example 1 was pre-baked, the coating film had tack and the cured film had low NMP resistance. Although the comparative example 2 showed NMP tolerance, the planarization property was low. In Comparative Example 3, a uniform coating film could not be obtained, and the characteristics could not be evaluated.
また、ライン幅及びライン間スペースを種々に変えて平坦化率を測定した結果（図２及び図３）をみると、実施例２においてはライン幅およびライン間スペースの変化に殆ど依存することなく高い平坦化率（９０％前後）を維持したものの、比較例２においてはライン間スペースの増大とともに平坦化率が減少する傾向を示し、特にライン幅が増大するにつれ、平坦化率の減少傾向は顕著に現れるとする結果を示した。 Further, when the flattening rate was measured by changing the line width and the inter-line space (FIGS. 2 and 3), in Example 2, there was almost no dependence on the change in the line width and the inter-line space. Although a high flattening rate (around 90%) was maintained, Comparative Example 2 showed a tendency for the flattening rate to decrease with an increase in the space between lines, and in particular, as the line width increased, the decreasing trend of the flattening rate was The result is that it appears prominently.
以上のように、本発明の平坦化に優れる平坦化膜形成用熱硬化性樹脂組成物によると、
従来品の優れた性能（光透過性）を維持した上で、平坦化性において実用面で際立った改良となる結果が得られる。
As described above, according to the thermosetting resin composition for flattening film formation excellent in flattening of the present invention,
While maintaining the superior performance (light transmittance) of the conventional product, a result that is a remarkable improvement in terms of flatness can be obtained.
本発明による平坦化に優れる平坦化膜形成用熱硬化性樹脂組成物は、薄膜トランジスタ（ＴＦＴ）型液晶表示素子、有機ＥＬ素子等の各種ディスプレイにおける保護膜、平坦化膜、絶縁膜等の硬化膜を形成する材料として好適であり、特に、ＴＦＴ型液晶素子の層間絶縁膜、カラーフィルタの保護膜、有機ＥＬ素子の絶縁膜等を形成する材料としても好適である。 The thermosetting resin composition for flattening film formation excellent in flattening according to the present invention is a cured film such as a protective film, a flattening film, and an insulating film in various displays such as thin film transistor (TFT) type liquid crystal display elements and organic EL elements. In particular, it is also suitable as a material for forming an interlayer insulating film of a TFT type liquid crystal element, a protective film of a color filter, an insulating film of an organic EL element, and the like.
Claims (7)
（Ａ）成分：特定官能基（特定官能基はカルボキシル基、グリシジル基、ヒドロキシ基、活性水素を有するアミノ基、フェノール性ヒドロキシ基及びイソシアネート基からなる群から選ばれる）を有するアクリル重合体であって、該特定官能基に結合された特定側鎖（特定側鎖とは、炭素原子数が３乃至１６であって末端に不飽和結合を有する側鎖である。）を持ち、数平均分子量が２，０００乃至３０，０００であるアクリル重合体、
（Ｂ）成分：ビスマレイミド化合物、
（Ｃ）溶剤。 A thermosetting resin composition for forming a flattened film, which contains the following component (A), component (B) and solvent (C).
Component (A) is an acrylic polymer having a specific functional group (the specific functional group is selected from the group consisting of a carboxyl group, a glycidyl group, a hydroxy group, an amino group having active hydrogen, a phenolic hydroxy group, and an isocyanate group). And having a specific side chain bonded to the specific functional group (the specific side chain is a side chain having 3 to 16 carbon atoms and having an unsaturated bond at the terminal ) and having a number average molecular weight. An acrylic polymer that is 2,000 to 30,000,
(B) component: bismaleimide compound,
(C) Solvent.
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