WO2014156873A1 - Photosensitive resin composition, method for producing cured film, cured film, organic el display device and liquid crystal display device - Google Patents
Photosensitive resin composition, method for producing cured film, cured film, organic el display device and liquid crystal display device Download PDFInfo
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- WO2014156873A1 WO2014156873A1 PCT/JP2014/057509 JP2014057509W WO2014156873A1 WO 2014156873 A1 WO2014156873 A1 WO 2014156873A1 JP 2014057509 W JP2014057509 W JP 2014057509W WO 2014156873 A1 WO2014156873 A1 WO 2014156873A1
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- WIPO (PCT)
- Prior art keywords
- group
- resin composition
- photosensitive resin
- nitrogen
- cured film
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 109
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- -1 quinonediazide compound Chemical class 0.000 claims abstract description 122
- 229920000642 polymer Polymers 0.000 claims abstract description 45
- 239000002904 solvent Substances 0.000 claims abstract description 41
- 125000003118 aryl group Chemical group 0.000 claims abstract description 34
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 69
- 239000000758 substrate Substances 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 50
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 40
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 239000011229 interlayer Substances 0.000 claims description 25
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 22
- 125000005843 halogen group Chemical group 0.000 claims description 20
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 20
- 125000003277 amino group Chemical group 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 15
- 125000003566 oxetanyl group Chemical group 0.000 claims description 14
- 125000002252 acyl group Chemical group 0.000 claims description 13
- 125000003700 epoxy group Chemical group 0.000 claims description 13
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- 238000011161 development Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 6
- UWWUXWWWOUNMKW-UHFFFAOYSA-N 1h-pteridin-4-one Chemical compound C1=CN=C2C(O)=NC=NC2=N1 UWWUXWWWOUNMKW-UHFFFAOYSA-N 0.000 claims description 5
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 5
- 238000001312 dry etching Methods 0.000 claims description 5
- 229920001187 thermosetting polymer Polymers 0.000 claims description 5
- LGPQRQCYEQNQJV-UHFFFAOYSA-N 2-ethyl-1h-pteridin-4-one Chemical compound C1=CN=C2C(=O)NC(CC)=NC2=N1 LGPQRQCYEQNQJV-UHFFFAOYSA-N 0.000 claims description 4
- UJAQYOZROIFQHO-UHFFFAOYSA-N 5-methyl-1,10-phenanthroline Chemical compound C1=CC=C2C(C)=CC3=CC=CN=C3C2=N1 UJAQYOZROIFQHO-UHFFFAOYSA-N 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 abstract description 17
- 239000000470 constituent Substances 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 167
- 150000001875 compounds Chemical class 0.000 description 47
- 238000009835 boiling Methods 0.000 description 19
- 239000010410 layer Substances 0.000 description 19
- 125000001424 substituent group Chemical group 0.000 description 18
- 239000003963 antioxidant agent Substances 0.000 description 16
- 235000006708 antioxidants Nutrition 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 14
- 239000004094 surface-active agent Substances 0.000 description 14
- 239000011521 glass Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 239000000178 monomer Substances 0.000 description 13
- 239000003431 cross linking reagent Substances 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000001723 curing Methods 0.000 description 8
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 230000003078 antioxidant effect Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 230000018109 developmental process Effects 0.000 description 7
- 239000003822 epoxy resin Substances 0.000 description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- 239000012948 isocyanate Substances 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 7
- 229910052753 mercury Inorganic materials 0.000 description 7
- 229920000647 polyepoxide Polymers 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 5
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 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 4
- 238000007654 immersion Methods 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 3
- 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 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000002981 blocking agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 238000003384 imaging method Methods 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
- 238000012545 processing Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- QYGBYAQGBVHMDD-XQRVVYSFSA-N (z)-2-cyano-3-thiophen-2-ylprop-2-enoic acid Chemical compound OC(=O)C(\C#N)=C/C1=CC=CS1 QYGBYAQGBVHMDD-XQRVVYSFSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 2
- JFWFAUHHNYTWOO-UHFFFAOYSA-N 2-[(2-ethenylphenyl)methoxymethyl]oxirane Chemical compound C=CC1=CC=CC=C1COCC1OC1 JFWFAUHHNYTWOO-UHFFFAOYSA-N 0.000 description 2
- OCKQMFDZQUFKRD-UHFFFAOYSA-N 2-[(3-ethenylphenyl)methoxymethyl]oxirane Chemical compound C=CC1=CC=CC(COCC2OC2)=C1 OCKQMFDZQUFKRD-UHFFFAOYSA-N 0.000 description 2
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- DPTGFYXXFXSRIR-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl prop-2-enoate Chemical compound C1C(COC(=O)C=C)CCC2OC21 DPTGFYXXFXSRIR-UHFFFAOYSA-N 0.000 description 2
- PTRATZCAGVBFIQ-UHFFFAOYSA-N Abametapir Chemical compound N1=CC(C)=CC=C1C1=CC=C(C)C=N1 PTRATZCAGVBFIQ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
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- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- 239000004115 Sodium Silicate Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical group C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
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- 238000004040 coloring Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
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- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 230000002349 favourable effect Effects 0.000 description 2
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- 238000005227 gel permeation chromatography Methods 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
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- 230000001678 irradiating effect Effects 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 2
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- 230000035945 sensitivity Effects 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000001174 sulfone group Chemical group 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- MWMWRSCIFDZZGW-UHFFFAOYSA-N (2-oxooxolan-3-yl) prop-2-enoate Chemical compound C=CC(=O)OC1CCOC1=O MWMWRSCIFDZZGW-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical group CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- PJMXUSNWBKGQEZ-UHFFFAOYSA-N (4-hydroxyphenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=C(O)C=C1 PJMXUSNWBKGQEZ-UHFFFAOYSA-N 0.000 description 1
- ZRDYULMDEGRWRC-UHFFFAOYSA-N (4-hydroxyphenyl)-(2,3,4-trihydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C(O)=C1O ZRDYULMDEGRWRC-UHFFFAOYSA-N 0.000 description 1
- JDVMJFIBTWIYJX-UHFFFAOYSA-N 1,10-phenanthroline-5,6-diol Chemical compound Oc1c(O)c2cccnc2c2ncccc12 JDVMJFIBTWIYJX-UHFFFAOYSA-N 0.000 description 1
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- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
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- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
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- 239000011368 organic material Substances 0.000 description 1
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- 238000000059 patterning Methods 0.000 description 1
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- 239000011574 phosphorus Substances 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
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- 229920001223 polyethylene glycol Polymers 0.000 description 1
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- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- 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
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 150000003536 tetrazoles Chemical group 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical group 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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Images
Classifications
-
- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
-
- 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
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
-
- 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
Definitions
- the present invention relates to a photosensitive resin composition (hereinafter also referred to as “the composition of the present invention”). Moreover, it is related with the manufacturing method of the cured film using the said photosensitive resin composition, the cured film formed by hardening
- Organic EL display devices, liquid crystal display devices, and the like are provided with a patterned interlayer insulating film.
- a photosensitive resin composition is widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained (for example, patents). References 1-2).
- JP-A-5-165214 Japanese Patent Laid-Open No. 11-223937
- Patent Document 2 proposes a positive photosensitive resin composition using a nitrogen-containing heterocyclic compound having a specific structure.
- the inventors of the present application have examined a resist used after forming a cured film. Inferior resistance to the solvent used for the stripping solution and interlayer insulation film, panel display unevenness when incorporated into a liquid crystal display device as a cured film, and severe conditions such as high temperature, high humidity, and high pressure It was found that panel display unevenness was likely to occur under certain conditions.
- interlayer insulating films Since the interlayer insulating film is exposed to a resist stripping solution used for forming a pattern of the transparent electrode film after the interlayer insulating film is formed and a chemical used for forming the liquid crystal alignment film, these interlayer insulating films are used. Sufficient resistance to common chemicals used in the field is required. In addition, panel display unevenness is suppressed in panel evaluation under normal environmental conditions, and it is required to suppress panel display unevenness even when exposed to severe conditions such as high temperature, high humidity, and high pressure.
- the present invention aims to solve the above-mentioned problems, and is excellent in chemical resistance in the state when it is used as a cured film, and is a panel display of a display device when incorporated in a liquid crystal display device or the like as a cured film.
- An object of the present invention is to provide a photosensitive resin composition that can further suppress unevenness and suppress panel display unevenness even when exposed to severe conditions such as high temperature, high humidity, and high pressure. Furthermore, it aims at providing the manufacturing method of a cured film using such a photosensitive resin composition, a cured film, an organic electroluminescence display, and a liquid crystal display device.
- the photosensitive resin composition contains a polymer containing a structural unit having an acid group and a structural unit having a crosslinkable group, and a nitrogen-containing heterocycle having a specific structure.
- the chemical resistance when the photosensitive resin composition is used for an interlayer insulating film is improved, and the panel display unevenness in the display device can be suppressed, such as high temperature, high humidity, and high pressure. It has been found that even when exposed to harsh conditions, panel display unevenness can be suppressed, and the present invention has been completed.
- the nitrogen-containing heterocyclic compound having a specific structure promotes crosslinking of the crosslinkable group in the photosensitive resin composition during post-baking, and forms a strong cured film having a high crosslinking density. Therefore, it is estimated that the cured film has high chemical resistance and can suppress panel display unevenness of the display device.
- the crosslinkable group in the photosensitive resin composition and the nitrogen-containing heterocyclic compound with a specific structure more effectively capture the decomposition products generated in the cured film under severe conditions such as high temperature, high humidity, and high pressure. Therefore, it is estimated that the panel display unevenness can be further suppressed even when exposed to severe conditions such as high temperature, high humidity, and high pressure.
- ⁇ 1> (A) (a1) a polymer having a structural unit having an acid group and (a2) a structural unit having a crosslinkable group, (B) a quinonediazide compound, (C) at least one nitrogen-containing heterocyclic compound, and (D) a solvent,
- the nitrogen-containing heterocyclic compound contains two or more nitrogen-containing aromatic rings, of which two nitrogen-containing aromatic rings are condensed or directly connected, and the nitrogen-containing aromatic ring is condensed or directly connected.
- a photosensitive resin composition containing a structure of the following formula (c-1) or a structure of the following formula (c-2) in the structure.
- R 3 to R 5 each represents a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, an alkyl group, an amino group, a halogen atom, or a mercapto group, and q is 0.
- r and s each represent an integer of 0 to 3.
- R 6 and R 7 are each a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, or an alkyl group.
- the (C) at least one nitrogen-containing heterocyclic compound is a nitrogen-containing heterocyclic compound represented by the following general formula (1-1), the general formula (2), or the general formula (3).
- the photosensitive resin composition according to ⁇ 2> which is at least one selected.
- R 11 and R 21 each represent a hydrogen atom, a hydroxyl group, a sulfonic acid group, or an alkyl group.
- X 1 represents a hydrogen atom, an acyl group, or an alkyl group.
- P1 represents Represents an integer of 0 to 2.
- the nitrogen heterocyclic compound is 4-hydroxypteridine, 2-ethyl-4-hydroxypteridine, 1,10-phenanthroline, 5-methyl-1,10-phenanthroline, 2,2′-bipyridine and 5,5.
- the structural unit (a1) is a structural unit having a carboxyl group and / or a phenolic hydroxyl group.
- the structural unit (a2) is selected from the group consisting of an epoxy group, an oxetanyl group, and a group represented by —NH—CH 2 —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms).
- ⁇ 7> The photosensitive composition according to any one of ⁇ 1> to ⁇ 6>, wherein the blending amount of the (B) quinonediazide compound is 10 to 50 parts by mass with respect to a total of 100 parts by mass of the (A) polymer component. Resin composition.
- ⁇ 10> (1) A step of applying the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 9> on a substrate, (2) a step of removing the solvent from the applied photosensitive resin composition; (3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays, (4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and (5) a post-baking step of thermosetting the developed photosensitive resin composition; The manufacturing method of the cured film containing this.
- the method for producing a cured film according to ⁇ 10> including (6) a step of exposing the entire surface of the developed photosensitive resin composition after the development step and before the post-baking step.
- ⁇ 12> The method for producing a cured film according to ⁇ 10> or ⁇ 11>, including a step of performing dry etching on a substrate having a cured film obtained by thermosetting in the post-baking step.
- ⁇ 13> A cured film obtained by curing the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 9> or a method for producing a cured film according to any one of ⁇ 10> to ⁇ 12> Formed cured film.
- ⁇ 14> The cured film according to ⁇ 13>, which is an interlayer insulating film.
- the present invention it is excellent in chemical resistance in the state when it is used as a cured film, and when it is incorporated in a liquid crystal display device or the like as a cured film, it can further suppress panel display unevenness of the display device, Even when exposed to severe conditions such as high humidity and high pressure, a photosensitive resin composition capable of further suppressing panel display unevenness can be provided.
- FIG. 1 is a conceptual diagram of a configuration of an example of a liquid crystal display device.
- the schematic sectional drawing of the active matrix substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film.
- 1 shows a conceptual diagram of a configuration of an example of an organic EL display device.
- a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
- the photosensitive resin composition of the present invention is preferably used as a positive photosensitive resin composition.
- the photosensitive resin composition of the present invention is (A) (a1) a polymer having a structural unit having an acid group and (a2) a structural unit having a crosslinkable group, (B) a quinonediazide compound, (C) at least one nitrogen-containing heterocyclic compound, and (D) a solvent,
- the nitrogen-containing heterocyclic compound contains two or more nitrogen-containing aromatic rings, and at least two of the nitrogen-containing aromatic rings are condensed or directly connected, and the nitrogen-containing aromatic ring is condensed or directly connected.
- the chemical resistance in a state of being a cured film for example, a resist stripping solution used for forming a pattern of a transparent electrode film after forming an interlayer insulating film or a liquid crystal alignment film is used.
- Resistance to NMP N-methylpyrrolidone
- the photosensitive resin composition which can suppress panel display nonuniformity more even if exposed to various conditions can be provided.
- the (A) polymer used in the present invention is a polymer containing (a1) a structural unit having an acid group and (a2) a structural unit having a crosslinkable group.
- a polymer component becomes a main component of the component except the solvent of the composition of this invention, and it is preferable to occupy 30 mass% or more of a total solid.
- the (A) polymer used by this invention contains the structural unit derived from (meth) acrylic acid.
- Examples of the structural unit derived from (meth) acrylic acid include a structural unit derived from styrene, a structural unit derived from a vinyl compound, and a structural unit derived from (meth) acrylic acid and / or an ester thereof.
- (a1) Structural Unit Having Acid Group By including (a1) the structural unit having an acid group in the polymer component (A), the polymer component is easily dissolved in an alkaline developer, and the effects of the present invention are more effectively exhibited.
- the acid group is usually incorporated into the polymer as a structural unit having an acid group using a monomer capable of forming an acid group. By including such a structural unit having an acid group in the polymer, the polymer tends to be easily dissolved in an alkaline developer.
- Examples of the acid group used in the present invention include a structural unit derived from a carboxylic acid group, a phenolic hydroxyl group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, and a sulfonylimide group, and the carboxylic acid group and / or phenol.
- a structural unit derived from a functional hydroxyl group is more preferred.
- the structural unit (a1) having an acid group used in the present invention is preferably a structural unit having a carboxyl group and / or a phenolic hydroxyl group.
- the structural unit having an acid group used in the present invention is preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, a structural unit derived from (meth) acrylic acid and / or an ester thereof.
- compounds described in JP 2012-88459 A, paragraph numbers 0021 to 0023 and paragraph numbers 0029 to 0044 can be used, the contents of which are incorporated herein.
- acrylic acid, methacrylic acid, maleic anhydride, 4-hydroxyphenyl methacrylate, o-hydroxystyrene, p-hydroxystyrene, ⁇ -methyl-p-hydroxystyrene, etc. are copolymerized and soluble in aqueous alkali solutions. It is more preferable from the viewpoint of availability and availability. These compounds may be used alone or in combination of two or more.
- the structural unit (a1) is preferably contained in an amount of 3 to 70 mol%, more preferably 5 to 60 mol%, more preferably 10 to 50 mol%. More preferably, it is contained.
- the polymer has a structural unit (a2) having a crosslinkable group.
- the crosslinkable group is not particularly limited as long as it is a group that causes a curing reaction by heat treatment.
- Preferred examples of the structural unit having a crosslinkable group include an epoxy group, an oxetanyl group, a group represented by —NH—CH 2 —O—R (where R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) and ethylene.
- a structural unit containing at least one selected from the group consisting of an unsaturated group, an epoxy group, an oxetanyl group, and NH—CH 2 —O—R (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). It is preferably at least one selected from the group represented by In more detail, the following are mentioned.
- the polymer (A) preferably contains a structural unit (a2-1) having an epoxy group and / or an oxetanyl group.
- a2-1 structural unit having an epoxy group
- the radical polymerizable monomer used for forming the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl ⁇ -ethyl acrylate, and glycidyl ⁇ -n-propyl acrylate.
- radical polymerizable monomer used for forming the structural unit (a2-1) having the epoxy group and / or oxetanyl group include a monomer having a methacrylic ester structure and an acrylic ester structure. It is preferable that it is a monomer to contain.
- glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl are preferred.
- Ether, (3-ethyloxetane-3-yl) methyl acrylate, and (3-ethyloxetane-3-yl) methyl methacrylate are preferred from the viewpoints of copolymerization reactivity and improved properties of the cured film.
- These structural units can be used individually by 1 type or in combination of 2 or more types.
- R represents a hydrogen atom or a methyl group.
- Examples of the structural unit (a2) having a crosslinkable group include a structural unit (a2-2) having an ethylenically unsaturated group.
- the structural unit (a2-2) is preferably a structural unit having an ethylenically unsaturated group in the side chain, and a structural unit having an ethylenically unsaturated group at the terminal and having a side chain having 3 to 16 carbon atoms. More preferred.
- Other examples of the structural unit (a2-2) include compounds described in paragraphs 0013 to 0031 of JP-A-2008-256974, and the contents thereof are incorporated in the present specification.
- structural unit having a group represented by (a2-3) -NH—CH 2 —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) As the structural unit (a2) having a crosslinkable group, a structural unit (a2-3) having a group represented by —NH—CH 2 —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). Is also preferred.
- a curing reaction can be caused by a mild heat treatment, and a cured film having excellent characteristics can be obtained.
- R is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
- the alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
- the structural unit (a2-3) is more preferably a structural unit having a group represented by the following general formula (a2-30).
- R 1 represents a hydrogen atom or a methyl group
- R 2 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
- R 2 is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
- the alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
- Specific examples of R 2 include a methyl group, an ethyl group, an n-butyl group, an i-butyl group, a cyclohexyl group, and an n-hexyl group. Of these, i-butyl, n-butyl and methyl are preferred.
- the structural unit (a2) is preferably contained in an amount of 20 to 80 mol%, more preferably 20 to 70 mol%, more preferably 20 to 65 mol%. More preferably it is contained.
- the polymer (A) may have another structural unit (a3) in addition to the structural units (a1) and (a2).
- the monomer that becomes the other structural unit (a3) is not particularly limited as long as it is an unsaturated compound other than the structural units (a1) and (a2).
- Specific examples of the radical polymerizable monomer used for forming the structural unit (a3) include, for example, a methacrylic acid chain alkyl ester, a methacrylic acid cyclic alkyl ester, an acrylic acid chain alkyl ester, and an acrylic acid cyclic alkyl ester.
- Methacrylic acid aryl ester acrylic acid aryl ester, unsaturated dicarboxylic acid diester, bicyclo unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene, tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, pyran skeleton, Examples thereof include unsaturated compounds containing the skeleton represented by 4) and other unsaturated compounds.
- the radical polymerizable monomer used for forming the structural unit (a3) compounds described in paragraph Nos. 0046 to 0065 of JP2012-8859A can be used, and the contents thereof are as follows. It is incorporated herein.
- R 23 is a hydrogen atom or a methyl group. s is an integer of 1 or more.
- An unsaturated compound, an unsaturated aromatic compound, an acrylic acid cyclic alkyl ester, and acryloylmorpholine are preferable.
- These (a3) compounds may be used alone or in admixture of two or more.
- the structural unit (a3) is preferably contained in an amount of 1 to 90 mol%, more preferably 5 to 80 mol%, more preferably 7 to 60 mol%. More preferably, it is contained. By setting the use ratio of the structural unit (a3) within the above range, a cured film having excellent characteristics can be formed.
- the molecular weight of the polymer (A) is a weight average molecular weight in terms of polystyrene, and is preferably 1,000 to 200,000, more preferably 2,000 to 50,000. Various characteristics are favorable in the range of said numerical value.
- the ratio (dispersity) between the number average molecular weight and the weight average molecular weight is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.
- the component (A) is used to form at least the structural units represented by (a1) and (a2). It can be synthesized by polymerizing a radical polymerizable monomer mixture containing a radical polymerizable monomer in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction.
- radical polymerization initiator examples include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4 Azo compounds such as -methoxy-2,4-dimethylvaleronitrile); organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1'-bis- (t-butylperoxy) cyclohexane, and Examples include hydrogen peroxide.
- the method for producing the polymer (A) for example, the method described in JP-A-2012-88549, paragraphs 0067 to 0073 can be used, and the contents thereof are incorporated in the present specification.
- (B) quinonediazide compound used in the composition of the present invention for example, a 1,2-quinonediazide compound that generates a carboxylic acid upon irradiation with actinic rays can be used.
- a 1,2-quinonediazide compound a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as “mother nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide can be used.
- description of paragraphs 0075 to 0078 of JP2012-088459A can be referred to, and the contents thereof are incorporated in the present specification.
- condensation reaction In the condensation reaction of the phenolic compound or alcoholic compound (mother nucleus) and 1,2-naphthoquinonediazide sulfonic acid halide, preferably 30 to 85 moles relative to the number of OH groups in the phenolic compound or alcoholic compound. %, More preferably 1,2-naphthoquinonediazide sulfonic acid halide corresponding to 50 to 70 mol% can be used.
- the condensation reaction can be carried out by a known method.
- 1,2-quinonediazide compound examples include 1,2-naphthoquinonediazidesulfonic acid amides in which the ester bond of the mother nucleus exemplified above is changed to an amide bond, such as 2,3,4-triaminobenzophenone-1,2 -Naphthoquinonediazide-4-sulfonic acid amide is also preferably used.
- the blending amount of the (B) quinonediazide compound in the photosensitive resin composition of the present invention is preferably 1 to 50% by mass, more than 10% by mass and 40% by mass or less, based on the total solid content in the photosensitive resin composition. More preferably, it is more than 12 mass% and 40 mass% or less.
- the blending amount of the (B) quinonediazide compound in the photosensitive resin composition of the present invention is preferably 5 to 100 parts by mass with respect to 100 parts by mass in total of the (A) polymer. More preferably, it is more preferably 10 to 35 parts by mass.
- the composition of the present invention contains at least one nitrogen-containing heterocyclic compound.
- the nitrogen-containing heterocyclic compound contains two or more nitrogen-containing aromatic rings, and at least two of the nitrogen-containing aromatic rings are condensed or directly connected, and the nitrogen-containing aromatic ring is condensed or directly connected.
- the structure of the following formula (c-1) or the structure of the following formula (c-2) is contained.
- * represents a bonding site with another atom.
- the chemical resistance of the cured film obtained by curing the composition of the present invention can be improved by blending at least one nitrogen-containing heterocyclic compound in the composition of the present invention.
- the composition of the present invention is incorporated into a liquid crystal display device or the like as a cured film.
- Panel display unevenness can be further suppressed.
- the nitrogen-containing heterocyclic compound promotes the crosslinking of the crosslinkable group in the photosensitive resin composition during post-baking, and forms a strong cured film having a high crosslinking density. Therefore, it is estimated that the chemical resistance of the cured film is high, and the panel display unevenness of the display device can be suppressed.
- the crosslinkable group in the photosensitive resin composition and the nitrogen-containing heterocyclic compound more effectively capture decomposition products generated in a cured film under severe conditions such as high temperature, high humidity, and high pressure. Even when exposed to severe conditions such as high temperature, high humidity, and high pressure, it is estimated that panel display unevenness can be further suppressed.
- the nitrogen-containing aromatic ring of the nitrogen-containing heterocyclic compound is not particularly limited as long as it is an aromatic ring containing a nitrogen atom, but a 3- to 6-membered nitrogen-containing aromatic ring is preferable, and a 5-membered or 6-membered ring-containing aromatic ring is preferable. Nitrogen aromatic rings are preferred. Examples of the 5-membered nitrogen-containing aromatic ring include a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, and a tetrazole ring.
- Examples of the 6-membered nitrogen-containing aromatic ring include a pyridine ring, a pyridazine ring, a pyrimidine ring, and a pyrazine ring.
- the number of condensation of the nitrogen-containing aromatic ring is 2 or more, and 2 or 3 Is preferred.
- the number of bonds of the nitrogen-containing aromatic ring is two or more, and two preferable.
- the nitrogen-containing heterocyclic compound contains two or more of the nitrogen-containing aromatic rings, and at least two of the nitrogen-containing aromatic rings are condensed or directly connected to each other.
- the other ring may be any ring as long as it contains the structure of c-1) or the structure of the above formula (c-2), but the other rings include a benzene ring and naphthalene.
- An aromatic ring selected from rings is preferred.
- the number of aromatic rings forming the nitrogen-containing heterocyclic compound is preferably 2 or 3 in one molecule.
- the nitrogen-containing heterocyclic compound may or may not have a substituent on the nitrogen-containing aromatic ring, but preferably does not have it.
- the substituent when the substituent is bulky, it is difficult to capture a decomposition product generated in the cured film. Therefore, it is preferable to have a substituent that does not become bulky.
- the substituent is not particularly limited, but is preferably a hydroxyl group, a carboxyl group, a sulfonic acid group, an alkyl group, an amino group, a halogen atom, an acyl group or a mercapto group, and a hydroxyl group, a carboxyl group, a sulfonic acid group, an acyl group or an alkyl group.
- an alkyl group and a hydroxyl group are more preferable, and a methyl group and a hydroxyl group are particularly preferable in that they are not bulky.
- the substituent is an alkyl group, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group and an ethyl group are more preferable.
- the substituent is a halogen atom, a chlorine atom, a bromine atom or an iodine atom is preferable.
- an acyl group an acyl group having 2 to 4 carbon atoms is preferable.
- the number of substituents is not particularly limited, but is preferably 1 to 3 and more preferably 1 or 2 in one molecule of the nitrogen-containing heterocyclic compound.
- the composition of the present invention preferably contains at least one selected from the nitrogen-containing heterocyclic compounds represented by the following general formulas (1) to (3).
- R 1 and R 2 each represent a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, an alkyl group, an amino group, a halogen atom, or a mercapto group. Represents an integer of 2.
- R 3 to R 5 each represents a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, an alkyl group, an amino group, a halogen atom, or a mercapto group
- q is R represents an integer of 0 to 2
- r and s each represents an integer of 0 to 3.
- R 6 and R 7 represent a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, an alkyl group, respectively. Represents a group, an amino group, a halogen atom or a mercapto group, and t and u each represents an integer of 0 to 4.
- R 1 and R 2 each represent a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, an alkyl group, an amino group, a halogen atom or a mercapto group, and a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfone group
- An acid group, an acyl group, and an alkyl group are more preferable, and a hydrogen atom, a hydroxyl group, an alkyl group, and a sulfonic acid group are particularly preferable.
- R 1 represents a hydrogen atom
- R 2 represents an alkyl group or a hydroxyl group.
- a preferred alkyl group is an alkyl group having 1 to 3 carbon atoms. Specifically, a methyl group and an ethyl group are preferable, and an ethyl group is particularly preferable.
- R 1 and R 2 each represent a halogen atom, preferred halogen atoms are a chlorine atom, a bromine atom and an iodine atom.
- R 1 and R 2 each represent an amino group, the amino group may be substituted with 1 or 2 alkyl groups having 1 to 3 carbon atoms.
- R 1 and R 2 each represent an acyl group, an acyl group having 2 to 4 carbon atoms is preferred.
- p and v each represents an integer of 0 to 2. When p and v represent 2, R 1 may not be the same.
- R 3 to R 5 each represent a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, an alkyl group, an amino group, a halogen atom or a mercapto group, and a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfone group
- An acid group and an alkyl group are more preferable, and a hydrogen atom and an alkyl group are particularly preferable.
- R 3 and R 5 represent a hydrogen atom and R 4 represents an alkyl group.
- a preferred alkyl group is an alkyl group having 1 to 3 carbon atoms. Specifically, a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.
- R 3 to R 5 each represent a halogen atom, preferred halogen atoms are a chlorine atom, a bromine atom and an iodine atom.
- R 3 to R 5 each represent an amino group, the amino group may be substituted with 1 or 2 alkyl groups having 1 to 3 carbon atoms.
- q represents an integer of 0-2.
- q is preferably an integer of 0 to 2.
- R 4 may not be the same as each other, but is preferably the same.
- r and s each represent an integer of 0 to 3.
- r and s are each preferably an integer of 0 to 2, more preferably 0.
- R 4 and R 5 may or may not be the same as each other.
- R 6 and R 7 each represent a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, an alkyl group, an amino group, a halogen atom or a mercapto group, and the hydrogen atom, the carboxyl group and the alkyl group are More preferred are a hydrogen atom and an alkyl group. Specifically, it is preferable that R 6 and R 7 each represent a hydrogen atom or an alkyl group. When R 6 and R 7 each represent an alkyl group, a preferred alkyl group is an alkyl group having 1 to 3 carbon atoms.
- a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.
- R 6 and R 7 each represent a halogen atom
- preferred halogen atoms are a chlorine atom, a bromine atom and an iodine atom.
- R 6 and R 7 each represent an amino group
- the amino group may be substituted with one or two alkyl groups having 1 to 3 carbon atoms.
- t and u each represents an integer of 0 to 4.
- t and u are each preferably an integer of 0 to 2, more preferably 0 or 1.
- t and u represent an integer of 2 to 4, t and u may or may not be the same.
- the substituents (R 1 to R 7 ) on the aromatic ring in at least one nitrogen-containing heterocyclic compound selected from the compounds represented by the general formulas (1) to (3) are When it is high, it becomes difficult to capture a decomposition product generated in the cured film. Therefore, it is more preferable to have a substituent that does not have a substituent or does not become bulky. For example, a methyl group and a hydroxyl group are particularly preferable as the substituent that does not become bulky.
- the nitrogen-containing heterocyclic compound represented by the general formula (1) is more preferably represented by the following general formula (1-1).
- R 11 and R 21 each represent a hydrogen atom, a hydroxyl group, a sulfonic acid group, or an alkyl group.
- X 1 represents a hydrogen atom, an acyl group, or an alkyl group.
- P1 represents Represents an integer of 0 to 2.
- R 11 and R 21 each represent a hydrogen atom, a hydroxyl group, a sulfonic acid group, or an alkyl group.
- R 11 and R 21 have the same meanings as R 1 and R 2 in the general formula (1), and preferred ranges thereof are also the same.
- X 1 represents a hydrogen atom, an acyl group or an alkyl group, preferably a hydrogen atom.
- a preferred alkyl group is an alkyl group having 1 to 3 carbon atoms. Specifically, a methyl group and an ethyl group are preferable.
- X 1 represents an acyl group, an acyl group having 2 to 4 carbon atoms is preferred.
- p1 represents an integer of 0 to 2, and has the same meaning as p in general formula (1), and the preferred range is also the same.
- the nitrogen-containing heterocyclic compound includes 4-hydroxypteridine, 2,4-dihydroxypteridine, 4-hydroxypteridine-2-sulfonic acid, 2-ethyl-4-hydroxypteridine, 2-methyl-4-hydroxypteridine.
- 4-hydroxypteridine, 2-ethyl-4-hydroxypteridine, 1,10-phenanthroline, 5-methyl-1,10-phenanthroline, 2,2′-bipyridine, 5,5′-dimethyl-2,2 '-Bipyridine is particularly preferred.
- 4-hydroxypteridine derivatives are obtained by reacting the corresponding 4,5-diaminopyrimidine and glyoxal according to a conventional method.
- 1,10-phenanthroline derivative and 2,2′-bipyridine derivative can also be obtained by adding a substituent to 1,10-phenanthroline and 2,2′-bipyridine, respectively, according to a conventional method.
- the molecular weight of the nitrogen-containing heterocyclic compound is preferably 1000 or less, more preferably 750 or less, and even more preferably 500 or less.
- the amount of the nitrogen-containing heterocyclic compound is preferably 0.001 to 15 parts by mass with respect to 100 parts by mass in total of the polymer component (A), and 0.05 to The amount is more preferably 10 parts by mass, and further preferably 0.01 to 5 parts by mass.
- 1 type may be sufficient as the nitrogen-containing heterocyclic compound contained in the composition of this invention, and 2 or more types may be sufficient as it.
- 2 or more types of the said nitrogen-containing heterocyclic compound are included in the composition of this invention, it is preferable that the sum total of a nitrogen-containing heterocyclic compound is the said range.
- the photosensitive resin composition of the present invention contains (D) a solvent.
- the photosensitive resin composition of the present invention is preferably prepared as a solution in which the essential components of the present invention and further optional components described below are dissolved in the solvent (D).
- a solvent used for the preparation of the composition of the present invention a solvent that uniformly dissolves essential components and optional components and does not react with each component is used.
- known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene.
- Glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol Examples include monoalkyl ether acetates, esters, ketones, amides, lactones and the like.
- Specific examples of the solvent used in the photosensitive resin composition of the present invention include the solvents described in paragraph numbers 0174 to 0178 of JP2011-221494A, and paragraph numbers 0167 to 0168 of JP2012-194290A. And the contents thereof are incorporated herein by reference.
- the solvent that can be used in the present invention is a single type or a combination of two types, more preferably a combination of two types, propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates. And diethylene glycol dialkyl ethers or esters and butylene glycol alkyl ether acetates are more preferably used in combination.
- the solvent is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
- Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), propylene glycol An example is methyl-n-propyl ether (boiling point 131 ° C.).
- Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate.
- the content of the solvent (D) in the photosensitive resin composition of the present invention is preferably 50 to 95 parts by mass, preferably 60 to 90 parts by mass, per 100 parts by mass of all components in the photosensitive resin composition. More preferably.
- the composition of the present invention comprises, in addition to the above components, a crosslinking agent, an antioxidant, a development accelerator, an alkoxysilane compound (silane coupling agent), and a surfactant, as long as the effects of the present invention are not impaired.
- optional components such as an adhesion assistant, a heat resistance improver, and a heat-sensitive acid generator can be contained. These optional components may be used alone or in combination of two or more. As these compounds, for example, the compounds described in JP-A-2012-88459, paragraph numbers 0201 to 0224 can be used, and the contents thereof are incorporated in the present specification.
- the photosensitive resin composition of the present invention preferably contains an alkoxysilane compound as an adhesion improver.
- an alkoxysilane compound is used, the adhesion between the film formed from the photosensitive resin composition of the present invention and the substrate can be improved, or the properties of the film formed from the photosensitive resin composition of the present invention can be adjusted. Can do.
- the alkoxysilane compound that can be used in the photosensitive resin composition of the present invention is a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, molybdenum, titanium, or aluminum.
- the compound improves the adhesion between the insulating film and the insulating film.
- a known silane coupling agent or the like is also effective.
- silane coupling agents include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxypropyltriacoxysilane, ⁇ -glycidoxypropyl dialkoxysilane, and ⁇ -methacryloxy.
- Propyltrialkoxysilane, ⁇ -methacryloxypropyl dialkoxysilane, ⁇ -chloropropyltrialkoxysilane, ⁇ -mercaptopropyltrialkoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane Can be mentioned.
- ⁇ -glycidoxypropyltrialkoxysilane and ⁇ -methacryloxypropyltrialkoxysilane are more preferable, ⁇ -glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is more preferable. Further preferred. These can be used alone or in combination of two or more.
- R 1 is a hydrocarbon group having 1 to 20 carbon atoms having no reactive group
- R 2 is an alkyl group having 1 to 3 carbon atoms or a phenyl group
- n is an integer of 1 to 3 It is. Specific examples thereof include the following compounds.
- Ph is a phenyl group.
- the alkoxysilane compound in the photosensitive resin composition of this invention is not specifically limited to these, A well-known thing can be used.
- the content of the alkoxysilane compound in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass, and 0.5 to 20 parts by mass with respect to 100 parts by mass in total of the polymer component (A). Is more preferable.
- the photosensitive resin composition of the present invention preferably contains a surfactant.
- a surfactant any of anionic, cationic, nonionic or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
- the surfactant used in the composition of the present invention include those described in paragraph Nos. 0201 to 0205 in JP2012-88459A, and paragraphs 0185 to 0188 in JP2011-215580A. Can be used and these descriptions are incorporated herein.
- nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants.
- KP-341, X-22-822 manufactured by Shin-Etsu Chemical Co., Ltd.
- Polyflow No. 99C manufactured by Kyoeisha Chemical Co., Ltd.
- F Top manufactured by Mitsubishi Materials Kasei Co., Ltd.
- MegaFac manufactured by DIC Corporation
- Florard Novec FC-4430 manufactured by Sumitomo 3M Co., Ltd.
- Surflon S-242 Manufactured by AGC Seimi Chemical Co., Ltd.
- PolyFoxPF-6320 manufactured by OMNOVA
- SH-8400 Toray Dow Corning Silicone
- footgent FTX-218G manufactured by Neos
- the addition amount of the surfactant in the photosensitive resin composition of the present invention is preferably 10 parts by mass or less, and preferably 0.001 to 10 parts by mass with respect to 100 parts by mass in total of the polymer (A). More preferred is 0.01 to 5 parts by mass.
- a plurality of surfactants can be used in combination, and in that case, the content is calculated by adding all the surfactants.
- the photosensitive resin composition of this invention may contain a crosslinking agent as needed. By adding a crosslinking agent, the cured film obtained by the photosensitive resin composition of the present invention can be made a stronger film.
- the crosslinking agent is not limited as long as a crosslinking reaction is caused by heat (excluding the component (A)). For example, adding a compound having two or more epoxy groups or oxetanyl groups in the molecule, an alkoxymethyl group-containing crosslinking agent, a compound having at least one ethylenically unsaturated double bond, a blocked isocyanate compound, etc. Can do.
- the addition amount of the crosslinking agent in the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by mass, and preferably 0.1 to 30 parts by mass with respect to 100 parts by mass in total of the polymer (A). More preferably, the amount is 0.5 to 20 parts by mass. By adding in this range, a cured film excellent in mechanical strength and solvent resistance can be obtained.
- a plurality of crosslinking agents may be used in combination. In that case, the content is calculated by adding all the crosslinking agents.
- a blocked isocyanate compound can also be preferably employed as a crosslinking agent.
- the blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group, but is preferably a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability.
- the blocked isocyanate group in this invention is a group which can produce
- the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably.
- Examples of the matrix structure of the blocked isocyanate compound in the photosensitive resin composition of the present invention include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
- Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to.
- a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.
- the blocked isocyanate compound that can be used in the photosensitive resin composition of the present invention is commercially available.
- Coronate AP Stable M Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (or more, Nippon Polyurethane Industry Co., Ltd.), Takenate B-830, B-815N, B-820NSU, B-842N, B-84N, B-870N, B-874N, B-882N (above, manufactured by Mitsui Chemicals, Inc.) ), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000, E402 -B80T (Asahi Kasei Chemicals Corporation) Death Module BL1100, BL1265 MPA / X,
- the photosensitive resin composition of the present invention may contain an antioxidant.
- an antioxidant a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat resistant transparency is excellent.
- antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, Examples thereof include nitrates, sulfites, thiosulfates, and hydroxylamine derivatives.
- phenol-based antioxidants amide-based antioxidants, hydrazide-based antioxidants, and sulfur-based antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness. preferable. These may be used individually by 1 type and may mix 2 or more types. Specific examples include the compounds described in paragraph numbers 0026 to 0031 of JP-A-2005-29515 and the compounds described in paragraph numbers 0106 to 0116 of JP-A-2001-227106. It is incorporated herein.
- Preferred commercially available products include ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-330, IRGANOX 1726, and IRGA Knox 1035 and Irganox 1098 can be mentioned.
- the content of the antioxidant is preferably 0.1 to 10% by mass, more preferably 0.2 to 7% by mass, based on 100 parts by mass of the total amount of the polymer (A). It is particularly preferably 5 to 5% by mass. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation becomes good.
- the composition of the present invention can be prepared by mixing each component at a predetermined ratio and by any method, and stirring and dissolving.
- the resin composition can be prepared by mixing each component in a predetermined ratio after preparing each solution in advance in the above-described solvent.
- the composition solution prepared as described above can be used after being filtered using, for example, a filter having a pore diameter of 0.2 ⁇ m.
- the method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
- substrate (2) removing the solvent from the applied photosensitive resin composition; (3) The process of exposing the photosensitive resin composition from which the solvent was removed with actinic rays; (4) A step of developing the exposed photosensitive resin composition with an aqueous developer; (5) A developed post-baking step for thermosetting.
- the application step (1) it is preferable to apply (preferably apply) the photosensitive resin composition of the present invention onto a substrate to form a wet film containing a solvent. It is preferable to perform substrate cleaning such as alkali cleaning or plasma cleaning before applying the photosensitive resin resin composition to the substrate, and it is more preferable to treat the substrate surface with hexamethyldisilazane after substrate cleaning. By performing this treatment, the adhesiveness of the photosensitive resin composition to the substrate tends to be improved.
- the method for treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method in which the substrate is exposed to hexamethyldisilazane vapor. Examples of the substrate include inorganic substrates, resins, and resin composite materials.
- the inorganic substrate examples include glass, quartz, silicone, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
- the resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic Made of synthetic resin such as aromatic ether, maleimide
- the application method to the substrate is not particularly limited, and for example, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, or the like can be used.
- the wet film thickness when applied is not particularly limited, and can be applied with a film thickness according to the application, but is usually used in the range of 0.5 to 10 ⁇ m.
- the solvent removal step (2) the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate.
- the heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds. When the temperature and time are in the above ranges, the pattern adhesiveness is better and the residue tends to be further reduced.
- the substrate provided with the coating film is irradiated with an actinic ray having a predetermined pattern.
- an exposure light source using actinic light a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, and the like can be used, i-line (365 nm), h-line (405 nm), g-line ( Actinic rays having a wavelength of 300 nm to 450 nm, such as 436 nm), can be preferably used.
- irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
- the exposure amount is preferably 1 to 500 mj / cm 2 .
- various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, a lens scanner, and a laser exposure can be used.
- the copolymer having a carboxyl group or a phenolic hydroxyl group is developed using an alkaline developer.
- a positive image is formed by removing an exposed area containing a resin composition having a carboxyl group or a phenolic hydroxyl group that is easily dissolved in an alkaline developer.
- the developer used in the development step preferably contains a basic compound.
- Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used.
- An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
- a preferred developing solution is a 0.2 to 2.5% aqueous solution of tetramethylammonium hydroxide.
- the pH of the developer is preferably 10.0 to 14.0.
- the development time is preferably 30 to 500 seconds, and the development method may be any of a liquid piling method (paddle method), a shower method, a dipping method, and the like.
- a rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like.
- a known method can be used as the rinsing method. For example, shower rinse and dip rinse can be mentioned.
- the cured film can be formed by crosslinking the acid group with a crosslinkable group, a crosslinking agent, etc. by heating the obtained positive image.
- This heating is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 to 250 ° C. for a predetermined time, for example, 5 to 90 minutes on the hot plate, 30 to 120 minutes for the oven. It is preferable to By proceeding the crosslinking reaction in this way, a protective film and an interlayer insulating film that are superior in heat resistance, hardness, and the like can be formed.
- the heat treatment is performed in a nitrogen atmosphere, the transparency can be further improved.
- post-baking can be performed after baking at a relatively low temperature (addition of a middle baking process).
- middle baking it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes.
- middle baking and post-baking can be heated in three or more stages.
- the taper angle of the pattern can be adjusted by devising such middle baking and post baking.
- These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
- post-exposure Prior to post-baking, it is preferable from the viewpoint of improving transparency that the substrate on which the pattern is formed is re-exposed (post-exposure) with actinic rays.
- the preferred exposure amount in the case of including a post-exposure step preferably 100 ⁇ 3,000mJ / cm 2, particularly preferably 100 ⁇ 2000mJ / cm 2.
- the cured film obtained from the photosensitive resin composition of the present invention can also be used as a dry etching resist.
- dry etching processes such as ashing, plasma etching, and ozone etching can be performed as the etching process.
- the cured film of the present invention is a cured film obtained by curing the above-described photosensitive resin composition of the present invention.
- the cured film of the present invention can be suitably used as an interlayer insulating film.
- the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention mentioned above.
- the photosensitive resin composition of the present invention an interlayer insulating film having excellent insulation and high transparency even when baked at high temperatures can be obtained. Since the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency and excellent cured film properties, it is useful for liquid crystal display devices and organic EL display devices.
- the liquid crystal display device of the present invention comprises the cured film of the present invention.
- the liquid crystal display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and known liquid crystal displays having various structures.
- An apparatus can be mentioned.
- specific examples of TFT (Thin-Film Transistor) included in the liquid crystal display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
- the liquid crystal driving methods that can be adopted by the liquid crystal display device of the present invention include TN (Twisted Nematic) method, VA (Virtual Alignment) method, IPS (In-Place-Switching) method, FFS (Frings Field Switching) method, OCB (Optical). Compensated Bend) method and the like.
- the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device.
- the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method.
- the polymer orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in JP-A Nos. 2003-149647 and 2011-257734.
- the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses.
- a protective film for the color filter in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc.
- FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix liquid crystal display device 10.
- the color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto.
- the elements of the TFT 16 corresponding to are arranged.
- Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17.
- an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
- the light source of the backlight is not particularly limited, and a known light source can be used.
- the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. Further, it can be made flexible, and used as the second interlayer insulating film (48) described in Japanese Patent Application Laid-Open No. 2011-145686 and the interlayer insulating film (520) described in Japanese Patent Application Laid-Open No. 2009-258758. Can do.
- the organic EL display device of the present invention comprises the cured film of the present invention.
- the organic EL display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known structures having various structures. Examples thereof include an organic EL display device and a liquid crystal display device.
- specific examples of TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
- FIG. 2 is a conceptual diagram of an example of an organic EL display device.
- a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
- a bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si 3 N 4 is formed so as to cover the TFT 1.
- a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 ⁇ m) connected to the TFT 1 through the contact hole is formed on the insulating film 3.
- the wiring 2 is used to connect the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
- the flattening layer 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is embedded.
- a bottom emission type organic EL element is formed on the planarizing film 4. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7.
- the first electrode 5 corresponds to the anode of the organic EL element.
- An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do. Further, although not shown in FIG.
- a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a second layer made of Al is formed on the entire surface above the substrate.
- An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it.
- An EL display device is obtained.
- a resist pattern formed using the photosensitive resin composition of the present invention as a structural member of a MEMS device can be used as a partition wall or mechanically driven. Used as part of the part.
- MEMS devices include parts such as SAW filters, BAW filters, gyro sensors, display micro shutters, image sensors, electronic paper, inkjet heads, biochips, sealants, and the like. More specific examples are exemplified in JP-T-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.
- the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the planarization film (57) described in FIG. 2 of JP-A-2011-107476, JP-A-2010-
- a chemical film (12), a pixel isolation insulating film (14), and the like can also be used to form a chemical film (12), a pixel isolation insulating film (14), and the like.
- spacers for maintaining the thickness of the liquid crystal layer in a liquid crystal display device imaging optical systems for on-chip color filters such as facsimiles, electronic copying machines, solid-state image sensors, and micro lenses for optical fiber connectors are also used. It can be used suitably.
- GPC-101 manufactured by Showa Denko KK
- ⁇ Preparation of photosensitive resin composition > (A) component, (B) component, (C) component, alkoxysilane compound, and surfactant so that it may become the solid content ratio of the following table
- a solvent Diethylene glycol ethyl methyl ether: Highsolve EDM (Toho Chemical Industry Co., Ltd.
- B-1 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 -Condensation product with sulfonic acid chloride (3.0 mol)
- B-2 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid Condensate with chloride (2.0 mol)
- B-3 2,3,4,4′-tetrahydroxybenzophenone (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid ester (2.44) Mole)
- Nitrogen heterocyclic compound > The following compounds (C-1) to (C-16) were used as nitrogen heterocyclic compounds.
- Alkoxysilane compound G-1 3-Glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)
- W-1 Silicone-based surfactant (“SH 8400 FLUID” manufactured by Toray Dow Corning Co., Ltd.)
- W-2 Fluorosurfactant FTX-218 (manufactured by Neos Co., Ltd.)
- HMDS hexamethyldisilazane
- each photosensitive resin composition is spin-coated on the substrate, and then pre-baked on a hot plate at 90 ° C. for 120 seconds to volatilize the solvent.
- a photosensitive resin composition layer having a thickness of 3.0 ⁇ m was formed.
- exposure was performed using an ultrahigh pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm 2 (illuminance: 20 mW / cm 2 , i-line), and the substrate was heated in an oven at 230 ° C./30 minutes.
- the film thickness (T1) of the obtained cured film was measured.
- the film thickness (T1) of the obtained cured film was measured. Then, the substrate on which this cured film was formed was immersed in NMP (N-methylpyrrolidone) controlled at 80 ° C. for 10 minutes at 80 ° C., and the thickness (t1) of the cured film after immersion was measured. Then, the film thickness change rate ⁇
- a liquid crystal display device using a thin film transistor (TFT) was manufactured by the following method (see FIGS. 1 and 2).
- a cured film 17 was formed as an interlayer insulating film as follows to obtain a liquid crystal display device. That is, the bottom gate type TFT 1 was formed on the glass substrate 6, and the insulating film 3 made of Si 3 N 4 was formed so as to cover the TFT 1. Next, after forming a contact hole in the insulating film 3, a wiring 2 (height of 1.0 ⁇ m) connected to the TFT 1 through the contact hole was formed on the insulating film 3.
- the planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded.
- the planarizing film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin compositions of Examples and Comparative Examples on a substrate, pre-baking (90 ° C. ⁇ 120 seconds) on a hot plate, After irradiating 25 mJ / cm 2 (energy intensity 20 mW / cm 2 ) with i-line (365 nm) using a high-pressure mercury lamp from above, a pattern is formed by developing with an alkaline aqueous solution, followed by heat treatment at 230 ° C. for 30 minutes. went.
- a drive voltage is applied to the obtained liquid crystal display device, a gray test signal is input, the panel is continuously lit in an environment of 23 ° C., 50%, 1 atm, and the gray display after 1000 hours of lighting is visually observed. Observation was performed and the presence or absence of display unevenness was evaluated according to the following evaluation criteria.
- C Slight unevenness on the display, but practical level (normal)
- D Display is uneven (somewhat bad)
- E Strong unevenness in display (very bad)
- a liquid crystal display device was produced in the same manner as described above in ⁇ Evaluation of display unevenness (panel display unevenness) in the display device>.
- a drive voltage is applied to the obtained liquid crystal display device, a gray test signal is input, the panel is continuously lit in an environment of 60 ° C., 90%, 2 atm, and the gray display after 1000 hours of lighting is visually observed. Observation was performed and the presence or absence of display unevenness was evaluated according to the following evaluation criteria.
- the composition of the present invention comprises (A) (a1) a structural unit having an acid group, (a2) a polymer containing a structural unit having a crosslinkable group, (B) a quinonediazide compound, and (C) Since it contains at least one nitrogen-containing heterocyclic compound, it has excellent chemical resistance in the state of being a cured film, and is a panel of a display device when incorporated in a liquid crystal display device or the like as a cured film It was found that display unevenness can be further suppressed and panel display unevenness can be suppressed even when exposed to severe conditions such as high temperature, high humidity, and high pressure.
- An organic EL display device using a TFT was manufactured by the following method (for example, refer to FIG. 1 of JP 2011-209681 A).
- a bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si 3 N 4 was formed so as to cover the TFT 1.
- a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 ⁇ m) connected to the TFT 1 through the contact hole is formed on the insulating film 3. .
- the wiring 2 is used to connect the TFT 1 to the organic EL element formed between the TFTs 1 or in a later process.
- the flattening layer 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded.
- the planarizing film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 8 on a substrate, pre-baking on a hot plate (90 ° C. ⁇ 2 minutes), and then applying high pressure from above the mask. After irradiating i-line with 100 mJ / cm 2 using a mercury lamp, a pattern was formed by developing with an alkaline aqueous solution, and heat treatment was performed at 220 ° C. for 60 minutes.
- a bottom emission type organic EL element was formed on the obtained flattening film 4.
- a first electrode 5 made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7.
- a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed.
- pattern processing was performed by wet etching using an ITO etchant.
- the resist pattern was stripped using a resist stripping solution (mixed solution of monoethanolamine and DMSO).
- the first electrode thus obtained corresponds to the anode of the organic EL element.
- an insulating layer 8 having a shape covering the periphery of the first electrode was formed.
- the photosensitive resin composition of Example 1 was used, and the insulating film 8 was formed by the same method as described above. By providing this insulating layer, it is possible to prevent a short circuit between the first electrode and the second electrode formed in the subsequent process.
- a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus.
- a second electrode made of Al was formed on the entire surface above the substrate.
- substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin.
- TFT thin film transistor
- 2 wiring
- 3 insulating film
- 4 flattening film
- 5 first electrode
- 6 glass substrate
- 7 contact hole
- 8 insulating film
- 10 liquid crystal display device
- 12 Backlight unit
- 15 Glass substrate
- 16 TFT
- 17 Cured film
- 18 Contact hole
- 19 ITO transparent electrode
- 20 Liquid crystal
- 22 Color filter
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Abstract
Description
さらに詳しくは、液晶表示装置、有機EL表示装置、集積回路素子、固体撮像素子などの電子部品の平坦化膜、保護膜や層間絶縁膜の形成に好適な、感光性樹脂組成物及びそれを用いた硬化膜の製造方法に関する。 The present invention relates to a photosensitive resin composition (hereinafter also referred to as “the composition of the present invention”). Moreover, it is related with the manufacturing method of the cured film using the said photosensitive resin composition, the cured film formed by hardening | curing the photosensitive composition, and various image display apparatuses using the said cured film.
More specifically, a photosensitive resin composition suitable for forming a planarizing film, a protective film, and an interlayer insulating film of an electronic component such as a liquid crystal display device, an organic EL display device, an integrated circuit element, a solid-state imaging device, and the like is used. The present invention relates to a method for producing a cured film.
この理由は推定であるが、特定構造の含窒素ヘテロ環化合物は、ポストベーク中の感光性樹脂組成物中の架橋性基の架橋を促進し、架橋密度の高い強固な硬化膜を形成しているため、硬化膜の耐薬品性が高く、表示装置のパネル表示ムラを抑制することができると推定される。また、感光性樹脂組成物中の架橋性基と特定構造の含窒素ヘテロ環化合物は、高温・高湿・高圧等の過酷な条件下で硬化膜中に発生する分解物をより効果的に捕捉するため、高温・高湿・高圧等の過酷な条件に曝されても、パネル表示ムラをより抑制することができると推定される。
具体的には、以下の解決手段<1>により、好ましくは、<2>~<15>により、上記課題は解決された。
<1>(A)(a1)酸基を有する構成単位及び(a2)架橋性基を有する構成単位を有する重合体、
(B)キノンジアジド化合物、
(C)少なくとも1種の含窒素ヘテロ環化合物、及び
(D)溶剤を含み、
前記含窒素ヘテロ環化合物は、含窒素芳香環を2つ以上含有し、その内2つの含窒素芳香環が縮合しているか直結しており、該含窒素芳香環が縮合しているか直結している構造中に、下記式(c-1)の構造、又は、下記式(c-2)の構造を含有する、感光性樹脂組成物。
<2>前記(C)少なくとも1種の含窒素ヘテロ環化合物が、下記一般式(1)~(3)で表される含窒素ヘテロ環化合物から選ばれる少なくとも1種である、<1>に記載の感光性樹脂組成物。
<3>前記(C)少なくとも1種の含窒素ヘテロ環化合物が、下記一般式(1-1)、前記一般式(2)又は前記一般式(3)で表される含窒素ヘテロ環化合物から選ばれる少なくとも1種である<2>に記載の感光性樹脂組成物。
<4>前記窒素ヘテロ環化合物が、4-ヒドロキシプテリジン、2-エチル-4-ヒドロキシプテリジン、1,10-フェナントロリン、5-メチル-1,10-フェナントロリン、2,2’-ビピリジン及び5,5’-ジメチル-2,2’-ビピリジンの少なくとも1種である、<1>~<3>のいずれかに記載の感光性樹脂組成物。
<5>前記構成単位(a1)が、カルボキシル基及び/又はフェノール性水酸基を有する構成単位である、<1>~<4>のいずれかに記載の感光性樹脂組成物。
<6>前記構成単位(a2)が、エポキシ基、オキセタニル基及び-NH-CH2-O-R(Rは水素原子又は炭素数1~20のアルキル基)で表される基よりなる群から選ばれる少なくとも1つを含む構成単位を含有する、<1>~<5>のいずれかに記載の感光性樹脂組成物。
<7>前記(A)重合体成分の合計100質量部に対し、前記(B)キノンジアジド化合物の配合量が10~50質量部である、<1>~<6>のいずれかに記載の感光性樹脂組成物。
<8>前記(A)重合体が、(メタ)アクリル酸に由来する構成単位を含有する、<1>~<7>のいずれかに記載の感光性樹脂組成物。
<9>ポジ型である、<1>~<8>のいずれかに記載の感光性樹脂組成物。
<10>(1)<1>~<9>のいずれかに記載の感光性樹脂組成物を基板上に塗布する工程、
(2)塗布された感光性樹脂組成物から溶剤を除去する工程、
(3)溶剤が除去された感光性樹脂組成物を活性光線により露光する工程、
(4)露光された感光性樹脂組成物を水性現像液により現像する工程、及び、
(5)現像された感光性樹脂組成物を熱硬化するポストベーク工程、
を含む硬化膜の製造方法。
<11>前記現像工程後、前記ポストベーク工程前に、(6)現像された感光性樹脂組成物を全面露光する工程を含む、<10>に記載の硬化膜の製造方法。
<12>前記ポストベーク工程で熱硬化して得られた硬化膜を有する基板に対し、ドライエッチングを行う工程を含む、<10>又は<11>に記載の硬化膜の製造方法。
<13><1>~<9>のいずれかに記載の感光性樹脂組成物を硬化してなる硬化膜、又は、<10>~<12>のいずれかに記載の硬化膜の製造方法により形成された硬化膜。
<14>層間絶縁膜である、<13>に記載の硬化膜。
<15><13>又は<14>に記載の硬化膜を有する有機EL表示装置又は液晶表示装置。 Under such circumstances, the inventors of the present application have made extensive studies, and as a result, the photosensitive resin composition contains a polymer containing a structural unit having an acid group and a structural unit having a crosslinkable group, and a nitrogen-containing heterocycle having a specific structure. By using the compound, the chemical resistance when the photosensitive resin composition is used for an interlayer insulating film is improved, and the panel display unevenness in the display device can be suppressed, such as high temperature, high humidity, and high pressure. It has been found that even when exposed to harsh conditions, panel display unevenness can be suppressed, and the present invention has been completed.
The reason for this is presumed, but the nitrogen-containing heterocyclic compound having a specific structure promotes crosslinking of the crosslinkable group in the photosensitive resin composition during post-baking, and forms a strong cured film having a high crosslinking density. Therefore, it is estimated that the cured film has high chemical resistance and can suppress panel display unevenness of the display device. In addition, the crosslinkable group in the photosensitive resin composition and the nitrogen-containing heterocyclic compound with a specific structure more effectively capture the decomposition products generated in the cured film under severe conditions such as high temperature, high humidity, and high pressure. Therefore, it is estimated that the panel display unevenness can be further suppressed even when exposed to severe conditions such as high temperature, high humidity, and high pressure.
Specifically, the above problem has been solved by the following means <1>, preferably <2> to <15>.
<1> (A) (a1) a polymer having a structural unit having an acid group and (a2) a structural unit having a crosslinkable group,
(B) a quinonediazide compound,
(C) at least one nitrogen-containing heterocyclic compound, and (D) a solvent,
The nitrogen-containing heterocyclic compound contains two or more nitrogen-containing aromatic rings, of which two nitrogen-containing aromatic rings are condensed or directly connected, and the nitrogen-containing aromatic ring is condensed or directly connected. A photosensitive resin composition containing a structure of the following formula (c-1) or a structure of the following formula (c-2) in the structure.
<2> The above (C), wherein at least one nitrogen-containing heterocyclic compound is at least one selected from nitrogen-containing heterocyclic compounds represented by the following general formulas (1) to (3), The photosensitive resin composition as described.
<3> The (C) at least one nitrogen-containing heterocyclic compound is a nitrogen-containing heterocyclic compound represented by the following general formula (1-1), the general formula (2), or the general formula (3). The photosensitive resin composition according to <2>, which is at least one selected.
<4> The nitrogen heterocyclic compound is 4-hydroxypteridine, 2-ethyl-4-hydroxypteridine, 1,10-phenanthroline, 5-methyl-1,10-phenanthroline, 2,2′-bipyridine and 5,5. The photosensitive resin composition according to any one of <1> to <3>, which is at least one of '-dimethyl-2,2'-bipyridine.
<5> The photosensitive resin composition according to any one of <1> to <4>, wherein the structural unit (a1) is a structural unit having a carboxyl group and / or a phenolic hydroxyl group.
<6> The structural unit (a2) is selected from the group consisting of an epoxy group, an oxetanyl group, and a group represented by —NH—CH 2 —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). The photosensitive resin composition according to any one of <1> to <5>, which contains a structural unit containing at least one selected from the above.
<7> The photosensitive composition according to any one of <1> to <6>, wherein the blending amount of the (B) quinonediazide compound is 10 to 50 parts by mass with respect to a total of 100 parts by mass of the (A) polymer component. Resin composition.
<8> The photosensitive resin composition according to any one of <1> to <7>, wherein the polymer (A) contains a structural unit derived from (meth) acrylic acid.
<9> The photosensitive resin composition according to any one of <1> to <8>, which is a positive type.
<10> (1) A step of applying the photosensitive resin composition according to any one of <1> to <9> on a substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays,
(4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and
(5) a post-baking step of thermosetting the developed photosensitive resin composition;
The manufacturing method of the cured film containing this.
<11> The method for producing a cured film according to <10>, including (6) a step of exposing the entire surface of the developed photosensitive resin composition after the development step and before the post-baking step.
<12> The method for producing a cured film according to <10> or <11>, including a step of performing dry etching on a substrate having a cured film obtained by thermosetting in the post-baking step.
<13> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <9> or a method for producing a cured film according to any one of <10> to <12> Formed cured film.
<14> The cured film according to <13>, which is an interlayer insulating film.
<15> An organic EL display device or a liquid crystal display device having the cured film according to <13> or <14>.
なお、本明細書における基(原子団)の表記において、置換及び無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば「アルキル基」とは、置換基を有さないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含するものである。 Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In addition, in the description of group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
本発明の感光性樹脂組成物は、
(A)(a1)酸基を有する構成単位及び(a2)架橋性基を有する構成単位を有する重合体、
(B)キノンジアジド化合物、
(C)少なくとも1種の含窒素ヘテロ環化合物、及び
(D)溶剤を含み、
前記含窒素ヘテロ環化合物は、含窒素芳香環を2つ以上含有し、少なくとも2つの該含窒素芳香環が縮合しているか直結しており、前記含窒素芳香環が縮合しているか直結している構造中に、下記式(c-1)の構造、又は、下記式(c-2)の構造を含有する、感光性樹脂組成物。
The photosensitive resin composition of the present invention is
(A) (a1) a polymer having a structural unit having an acid group and (a2) a structural unit having a crosslinkable group,
(B) a quinonediazide compound,
(C) at least one nitrogen-containing heterocyclic compound, and (D) a solvent,
The nitrogen-containing heterocyclic compound contains two or more nitrogen-containing aromatic rings, and at least two of the nitrogen-containing aromatic rings are condensed or directly connected, and the nitrogen-containing aromatic ring is condensed or directly connected. A photosensitive resin composition containing a structure of the following formula (c-1) or a structure of the following formula (c-2) in the structure.
本発明で用いる(A)重合体は、(a1)酸基を有する構成単位と、(a2)架橋性基を有する構成単位を含む重合体である。(A)重合体成分は、本発明の組成物の溶剤を除く成分の主成分となるものであり、全固形分の30質量%以上を占めることが好ましい。
また、本発明で用いる(A)重合体は、(メタ)アクリル酸に由来する構成単位を含有することが好ましい。(メタ)アクリル酸に由来する構成単位としては、例えば、スチレンに由来する構成単位や、ビニル化合物に由来する構成単位、(メタ)アクリル酸及び/又はそのエステルに由来する構成単位も含まれるものとする。 <(A) Polymer>
The (A) polymer used in the present invention is a polymer containing (a1) a structural unit having an acid group and (a2) a structural unit having a crosslinkable group. (A) A polymer component becomes a main component of the component except the solvent of the composition of this invention, and it is preferable to occupy 30 mass% or more of a total solid.
Moreover, it is preferable that the (A) polymer used by this invention contains the structural unit derived from (meth) acrylic acid. Examples of the structural unit derived from (meth) acrylic acid include a structural unit derived from styrene, a structural unit derived from a vinyl compound, and a structural unit derived from (meth) acrylic acid and / or an ester thereof. And
(A)重合体成分に、(a1)酸基を有する構成単位を含むことにより、アルカリ性の現像液に溶けやすくなり、本発明の効果がより効果的に発揮される。酸基は、通常、酸基を形成しうるモノマーを用いて、酸基を有する構成単位として、重合体に組み込まれる。このような酸基を有する構成単位を重合体中に含めることにより、アルカリ性の現像液に対して溶けやすくなる傾向にある。
本発明で用いられる酸基としては、カルボン酸基、フェノール性水酸基、スルホンアミド基、ホスホン酸基、スルホン酸基、スルホニルイミド基に由来する構成単位等が例示され、カルボン酸基及び/又はフェノール性水酸基に由来する構成単位がより好ましい。特に、本発明で用いられる(a1)酸基を有する構成単位は、カルボキシル基及び/又はフェノール性水酸基を有する構成単位であることが好ましい。例えば、特開2012-88459号公報の段落番号0021~0023及び段落番号0029~0044記載の化合物を用いることができ、この内容は本願明細書に組み込まれる。
本発明で用いられる酸基を有する構成単位は、スチレンに由来する構成単位や、ビニル化合物に由来する構成単位、(メタ)アクリル酸及び/又はそのエステルに由来する構成単位であることが好ましい。例えば、特開2012-88459号公報の段落番号0021~0023及び段落番号0029~0044記載の化合物を用いることができ、この内容は本願明細書に組み込まれる。 << (a1) Structural Unit Having Acid Group >>
By including (a1) the structural unit having an acid group in the polymer component (A), the polymer component is easily dissolved in an alkaline developer, and the effects of the present invention are more effectively exhibited. The acid group is usually incorporated into the polymer as a structural unit having an acid group using a monomer capable of forming an acid group. By including such a structural unit having an acid group in the polymer, the polymer tends to be easily dissolved in an alkaline developer.
Examples of the acid group used in the present invention include a structural unit derived from a carboxylic acid group, a phenolic hydroxyl group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, and a sulfonylimide group, and the carboxylic acid group and / or phenol. A structural unit derived from a functional hydroxyl group is more preferred. In particular, the structural unit (a1) having an acid group used in the present invention is preferably a structural unit having a carboxyl group and / or a phenolic hydroxyl group. For example, compounds described in JP 2012-88459 A, paragraph numbers 0021 to 0023 and paragraph numbers 0029 to 0044 can be used, the contents of which are incorporated herein.
The structural unit having an acid group used in the present invention is preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, a structural unit derived from (meth) acrylic acid and / or an ester thereof. For example, compounds described in JP 2012-88459 A, paragraph numbers 0021 to 0023 and paragraph numbers 0029 to 0044 can be used, the contents of which are incorporated herein.
(A)重合体は、架橋性基を有する構成単位(a2)を有する。上記架橋性基は、加熱処理で硬化反応を起こす基であれば特に限定はされない。架橋性基を有する構成単位の好ましい態様としては、エポキシ基、オキセタニル基、-NH-CH2-O-R(Rは水素原子又は炭素数1~20のアルキル基)で表される基及びエチレン性不飽和基よりなる群から選ばれた少なくとも1つを含む構成単位が挙げられ、エポキシ基、オキセタニル基及びNH-CH2-O-R(Rは水素原子又は炭素数1~20のアルキル基)で表される基から選ばれる少なくとも1種であることが好ましい。より詳細には、以下のものが挙げられる。 << (a2) Structural Unit Having Crosslinkable Group >>
(A) The polymer has a structural unit (a2) having a crosslinkable group. The crosslinkable group is not particularly limited as long as it is a group that causes a curing reaction by heat treatment. Preferred examples of the structural unit having a crosslinkable group include an epoxy group, an oxetanyl group, a group represented by —NH—CH 2 —O—R (where R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) and ethylene. And a structural unit containing at least one selected from the group consisting of an unsaturated group, an epoxy group, an oxetanyl group, and NH—CH 2 —O—R (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). It is preferably at least one selected from the group represented by In more detail, the following are mentioned.
上記(A)重合体は、エポキシ基及び/又はオキセタニル基を有する構成単位(a2-1)を含有することが好ましい。
エポキシ基を有する構成単位を形成するために用いられるラジカル重合性単量体の具体例としては、例えば、アクリル酸グリシジル、メタクリル酸グリシジル、α-エチルアクリル酸グリシジル、α-n-プロピルアクリル酸グリシジル、α-n-ブチルアクリル酸グリシジル、アクリル酸-3,4-エポキシブチル、メタクリル酸-3,4-エポキシブチル、アクリル酸-3,4-エポキシシクロヘキシルメチル、メタクリル酸-3,4-エポキシシクロヘキシルメチル、α-エチルアクリル酸-3,4-エポキシシクロヘキシルメチル、o-ビニルベンジルグリシジルエーテル、m-ビニルベンジルグリシジルエーテル、p-ビニルベンジルグリシジルエーテル、特許第4168443号公報の段落番号0031~0035に記載の脂環式エポキシ骨格を含有する化合物などが挙げられ、これらの内容は本願明細書に組み込まれる。
オキセタニル基を有する構成単位を形成するために用いられるラジカル重合性単量体の具体例としては、例えば、特開2001-330953号公報の段落番号0011~0016に記載のオキセタニル基を有する(メタ)アクリル酸エステルや、特開2012-088459公報の段落番号0027に記載されている化合物などが挙げられ、これらの内容は本願明細書に組み込まれる。
上記エポキシ基及び/又はオキセタニル基を有する構成単位(a2-1)を形成するために用いられるラジカル重合性単量体の具体例としては、メタクリル酸エステル構造を含有するモノマー、アクリル酸エステル構造を含有するモノマーであることが好ましい。 <<< (a2-1) Structural Unit Having Epoxy Group and / or Oxetanyl Group >>>
The polymer (A) preferably contains a structural unit (a2-1) having an epoxy group and / or an oxetanyl group.
Specific examples of the radical polymerizable monomer used for forming the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, and glycidyl α-n-propyl acrylate. Glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexyl methacrylate Methyl, α-ethylacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, described in paragraph Nos. 0031 to 0035 of Japanese Patent No. 4168443 Alicyclic And compounds containing epoxy backbone can be cited, the contents of which are hereby incorporated herein.
Specific examples of the radical polymerizable monomer used for forming the structural unit having an oxetanyl group include (meth) having an oxetanyl group described in paragraph Nos. 0011 to 0016 of JP-A No. 2001-330953, for example. Examples thereof include acrylate esters and compounds described in paragraph No. 0027 of JP2012-088459A, the contents of which are incorporated herein.
Specific examples of the radical polymerizable monomer used for forming the structural unit (a2-1) having the epoxy group and / or oxetanyl group include a monomer having a methacrylic ester structure and an acrylic ester structure. It is preferable that it is a monomer to contain.
上記架橋性基を有する構成単位(a2)として、エチレン性不飽和基を有する構成単位(a2-2)が挙げられる。上記構成単位(a2-2)としては、側鎖にエチレン性不飽和基を有する構成単位が好ましく、末端にエチレン性不飽和基を有し、炭素数3~16の側鎖を有する構成単位がより好ましい。
その他、構成単位(a2-2)としては、特開2008-256974の段落番号0013~0031に記載の化合物等が好ましいものとして挙げられ、これらの内容は本願明細書に組み込まれる。 <<< (a2-2) Structural unit having an ethylenically unsaturated group >>>
Examples of the structural unit (a2) having a crosslinkable group include a structural unit (a2-2) having an ethylenically unsaturated group. The structural unit (a2-2) is preferably a structural unit having an ethylenically unsaturated group in the side chain, and a structural unit having an ethylenically unsaturated group at the terminal and having a side chain having 3 to 16 carbon atoms. More preferred.
Other examples of the structural unit (a2-2) include compounds described in paragraphs 0013 to 0031 of JP-A-2008-256974, and the contents thereof are incorporated in the present specification.
上記架橋性基を有する構成単位(a2)として、-NH-CH2-O-R(Rは水素原子又は炭素数1~20のアルキル基)で表される基を有する構成単位(a2-3)も好ましい。構成単位(a2-3)を有することで、緩やかな加熱処理で硬化反応を起こすことができ、諸特性に優れた硬化膜を得ることができる。ここで、Rは炭素数1~9のアルキル基が好ましく、炭素数1~4のアルキル基がより好ましい。また、アルキル基は、直鎖、分岐又は環状のアルキル基のいずれであってもよいが、好ましくは、直鎖又は分岐のアルキル基である。構成単位(a2-3)は、より好ましくは、下記一般式(a2-30)で表される基を有する構成単位である。
一般式(a2-30)
R2は、炭素数1~9のアルキル基が好ましく、炭素数1~4のアルキル基がさらに好ましい。また、アルキル基は、直鎖、分岐又は環状のアルキル基のいずれであってもよいが、好ましくは、直鎖又は分岐のアルキル基である。
R2の具体例としては、メチル基、エチル基、n-ブチル基、i-ブチル基、シクロヘキシル基、及びn-ヘキシル基を挙げることができる。中でもi-ブチル基、n-ブチル基、メチル基が好ましい。 <<< structural unit having a group represented by (a2-3) -NH—CH 2 —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) >>
As the structural unit (a2) having a crosslinkable group, a structural unit (a2-3) having a group represented by —NH—CH 2 —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). Is also preferred. By having the structural unit (a2-3), a curing reaction can be caused by a mild heat treatment, and a cured film having excellent characteristics can be obtained. Here, R is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group. The structural unit (a2-3) is more preferably a structural unit having a group represented by the following general formula (a2-30).
Formula (a2-30)
R 2 is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
Specific examples of R 2 include a methyl group, an ethyl group, an n-butyl group, an i-butyl group, a cyclohexyl group, and an n-hexyl group. Of these, i-butyl, n-butyl and methyl are preferred.
本発明において、(A)重合体は、上記構成単位(a1)及び(a2)に加えて、これら以外の他の構成単位(a3)を有していてもよい。その他の構成単位(a3)となるモノマーとしては、上記構成単位(a1)及び(a2)以外の不飽和化合物であれば特に制限されるものではない。構成単位(a3)を形成するために用いられるラジカル重合性単量体の具体例としては、例えばメタクリル酸鎖状アルキルエステル、メタクリル酸環状アルキルエステル、アクリル酸鎖状アルキルエステル、アクリル酸環状アルキルエステル、メタクリル酸アリールエステル、アクリル酸アリールエステル、不飽和ジカルボン酸ジエステル、ビシクロ不飽和化合物、マレイミド化合物、不飽和芳香族化合物、共役ジエン、テトラヒドロフラン骨格、フラン骨格、テトラヒドロピラン骨格、ピラン骨格、下記式(4)で表される骨格を含む不飽和化合物及びその他の不飽和化合物等が挙げられる。構成単位(a3)を形成するために用いられるラジカル重合性単量体の具体例としては、特開2012-88459号公報の段落番号0046~0065記載の化合物等を用いることができ、この内容は本願明細書に組み込まれる。 << (a3) Other structural units >>
In the present invention, the polymer (A) may have another structural unit (a3) in addition to the structural units (a1) and (a2). The monomer that becomes the other structural unit (a3) is not particularly limited as long as it is an unsaturated compound other than the structural units (a1) and (a2). Specific examples of the radical polymerizable monomer used for forming the structural unit (a3) include, for example, a methacrylic acid chain alkyl ester, a methacrylic acid cyclic alkyl ester, an acrylic acid chain alkyl ester, and an acrylic acid cyclic alkyl ester. Methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated dicarboxylic acid diester, bicyclo unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene, tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, pyran skeleton, Examples thereof include unsaturated compounds containing the skeleton represented by 4) and other unsaturated compounds. As specific examples of the radical polymerizable monomer used for forming the structural unit (a3), compounds described in paragraph Nos. 0046 to 0065 of JP2012-8859A can be used, and the contents thereof are as follows. It is incorporated herein.
(A)重合体の分子量は、ポリスチレン換算重量平均分子量で、好ましくは1,000~200,000、より好ましくは2,000~50,000の範囲である。上記の数値の範囲内であると、諸特性が良好である。
数平均分子量と重量平均分子量の比(分散度)は1.0~5.0が好ましく1.5~3.5がより好ましい。 << (A) Molecular Weight of Polymer >>
The molecular weight of the polymer (A) is a weight average molecular weight in terms of polystyrene, and is preferably 1,000 to 200,000, more preferably 2,000 to 50,000. Various characteristics are favorable in the range of said numerical value.
The ratio (dispersity) between the number average molecular weight and the weight average molecular weight is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.
また、(A)成分の合成法についても、様々な方法が知られているが、一例を挙げると、少なくとも上記(a1)及び上記(a2)で表される構成単位を形成するために用いられるラジカル重合性単量体を含むラジカル重合性単量体混合物を有機溶剤中、ラジカル重合開始剤を用いて重合することにより合成することができる。また、いわゆる高分子反応で合成することもできる。
ラジカル重合開始剤としては、例えば、2,2'-アゾビスイソブチロニトリル(AIBN)、2,2'-アゾビス-(2,4-ジメチルバレロニトリル)、2,2'-アゾビス-(4-メトキシ-2,4-ジメチルバレロニトリル)等のアゾ化合物;ベンゾイルペルオキシド、ラウロイルペルオキシド、t-ブチルペルオキシピバレート、1,1'-ビス-(t-ブチルペルオキシ)シクロヘキサン等の有機過酸化物及び過酸化水素が挙げられる。
(A)重合体の製造方法は、例えば、特開2012-88549号公報の段落番号0067~0073の記載の方法を用いることができ、かかる内容は本願明細書に組み込まれる。 << (A) Polymer Production Method >>
Various methods for synthesizing the component (A) are known. To give an example, the component (A) is used to form at least the structural units represented by (a1) and (a2). It can be synthesized by polymerizing a radical polymerizable monomer mixture containing a radical polymerizable monomer in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction.
Examples of the radical polymerization initiator include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4 Azo compounds such as -methoxy-2,4-dimethylvaleronitrile); organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1'-bis- (t-butylperoxy) cyclohexane, and Examples include hydrogen peroxide.
As the method for producing the polymer (A), for example, the method described in JP-A-2012-88549, paragraphs 0067 to 0073 can be used, and the contents thereof are incorporated in the present specification.
本発明の組成物に用いられる(B)キノンジアジド化合物としては、例えば、活性光線の照射によりカルボン酸を発生する1,2-キノンジアジド化合物を用いることができる。1,2-キノンジアジド化合物としては、フェノール性化合物又はアルコール性化合物(以下、「母核」と称する)と1,2-ナフトキノンジアジドスルホン酸ハライドとの縮合物を用いることができる。これらの化合物の具体例としては、例えば特開2012-088459公報の段落番号0075~0078の記載を参酌することができ、この内容は本願明細書に組み込まれる。 <(B) Quinonediazide compound>
As the (B) quinonediazide compound used in the composition of the present invention, for example, a 1,2-quinonediazide compound that generates a carboxylic acid upon irradiation with actinic rays can be used. As the 1,2-quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as “mother nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide can be used. As specific examples of these compounds, for example, description of paragraphs 0075 to 0078 of JP2012-088459A can be referred to, and the contents thereof are incorporated in the present specification.
また、本発明の感光性樹脂組成物における(B)キノンジアジド化合物の配合量は、前記(A)重合体の合計100質量部に対し、5~100質量部であることが好ましく、10~50質量部であることがより好ましく、10~35質量部であることがさらに好ましい。
(B)キノンジアジド化合物の配合量を上記範囲とすることで、現像液となるアルカリ水溶液に対する活性光線の照射部分と未照射部分との溶解度の差が大きく、パターニング性能が良好となり、また得られる硬化膜の耐溶剤性が良好となる。 These (B) quinonediazide compounds can be used alone or in combination of two or more. The blending amount of the (B) quinonediazide compound in the photosensitive resin composition of the present invention is preferably 1 to 50% by mass, more than 10% by mass and 40% by mass or less, based on the total solid content in the photosensitive resin composition. More preferably, it is more than 12 mass% and 40 mass% or less.
The blending amount of the (B) quinonediazide compound in the photosensitive resin composition of the present invention is preferably 5 to 100 parts by mass with respect to 100 parts by mass in total of the (A) polymer. More preferably, it is more preferably 10 to 35 parts by mass.
(B) By making the compounding quantity of a quinonediazide compound into the said range, the difference of the solubility of the irradiation part of the actinic ray with respect to the alkaline aqueous solution used as a developing solution and a non-irradiation part is large, patterning performance becomes favorable, and hardening obtained The solvent resistance of the film is improved.
本発明の組成物は、少なくとも1種の含窒素ヘテロ環化合物を含む。この含窒素ヘテロ環化合物は、含窒素芳香環を2つ以上含有し、少なくとも2つの該含窒素芳香環が縮合しているか直結しており、前記含窒素芳香環が縮合しているか直結している構造中に、下記式(c-1)の構造、又は、下記式(c-2)の構造を含有する。
The composition of the present invention contains at least one nitrogen-containing heterocyclic compound. The nitrogen-containing heterocyclic compound contains two or more nitrogen-containing aromatic rings, and at least two of the nitrogen-containing aromatic rings are condensed or directly connected, and the nitrogen-containing aromatic ring is condensed or directly connected. In the structure, the structure of the following formula (c-1) or the structure of the following formula (c-2) is contained.
この理由については定かではないが、前記含窒素ヘテロ環化合物は、ポストベーク中の感光性樹脂組成物中の架橋性基の架橋を促進し、架橋密度の高い強固な硬化膜を形成しているため、硬化膜の耐薬品性が高く、表示装置のパネル表示ムラを抑制することができると推定される。また、感光性樹脂組成物中の架橋性基と前記含窒素ヘテロ環化合物は、高温・高湿・高圧等の過酷な条件下で硬化膜中に発生する分解物をより効果的に捕捉するため、高温・高湿・高圧等の過酷な条件に曝されても、パネル表示ムラをより抑制することができると推定される。 The chemical resistance of the cured film obtained by curing the composition of the present invention can be improved by blending at least one nitrogen-containing heterocyclic compound in the composition of the present invention. In addition, by incorporating at least one nitrogen-containing heterocyclic compound used in the present invention into the photosensitive resin composition, the composition of the present invention is incorporated into a liquid crystal display device or the like as a cured film. Panel display unevenness can be further suppressed. Furthermore, it is possible to further suppress panel display unevenness when the cured film obtained by curing the composition of the present invention is exposed to severe conditions such as high temperature, high humidity, and high pressure.
Although the reason for this is not clear, the nitrogen-containing heterocyclic compound promotes the crosslinking of the crosslinkable group in the photosensitive resin composition during post-baking, and forms a strong cured film having a high crosslinking density. Therefore, it is estimated that the chemical resistance of the cured film is high, and the panel display unevenness of the display device can be suppressed. In addition, the crosslinkable group in the photosensitive resin composition and the nitrogen-containing heterocyclic compound more effectively capture decomposition products generated in a cured film under severe conditions such as high temperature, high humidity, and high pressure. Even when exposed to severe conditions such as high temperature, high humidity, and high pressure, it is estimated that panel display unevenness can be further suppressed.
前記含窒素ヘテロ環化合物が有する含窒素芳香環において、少なくとも2つの含窒素芳香環が縮合している場合、含窒素芳香環の縮合数は、2つ以上であり、2又は3つであることが好ましい。前記含窒素ヘテロ環化合物が有する含窒素芳香環において、2つ以上の含窒素芳香環が直結している場合、含窒素芳香環の結合数は、2つ以上であり、2つであることが好ましい。
前記含窒素ヘテロ環化合物は、前記含窒素芳香環を2つ以上含有し、少なくとも2つの該含窒素芳香環が縮合しているか直結しており、前記含窒素ヘテロ環化合物中に、前記式(c-1)の構造、又は、前記式(c-2)の構造を含有するものであれば、他の環はどのような環であってもよいが、他の環は、ベンゼン環及びナフタレン環から選択される芳香環であることが好ましい。前記含窒素ヘテロ環化合物を形成する芳香環の数は、1分子中に2又は3つであることが好ましい。
前記含窒素ヘテロ環化合物は、含窒素芳香環上に置換基を有していてもよく、有していなくてもよいが、有していないことが好ましい。置換基としては、置換基が嵩高い場合には硬化膜中に発生する分解物を捕捉しにくくなるため、嵩高くならない置換基を有することが好ましい。
置換基としては、特に限定されないが、水酸基、カルボキシル基、スルホン酸基、アルキル基、アミノ基、ハロゲン原子、アシル基及びメルカプト基が好ましく、水酸基、カルボキシル基、スルホン酸基、アシル基及びアルキル基がより好ましく、アルキル基及び水酸基がさらに好ましく、嵩高くならない点でメチル基及び水酸基が特に好ましい。
置換基がアルキル基である場合、炭素原子数1~3のアルキル基が好ましく、メチル基及びエチル基がより好ましい。
置換基がハロゲン原子である場合、塩素原子、臭素原子又はヨウ素原子が好ましい。
置換基がアシル基である場合、炭素原子数2~4のアシル基が好ましい。
置換基の数は、特に限定されないが、含窒素ヘテロ環化合物1分子中に1~3つであることが好ましく、1又は2つであることがより好ましい。 The nitrogen-containing aromatic ring of the nitrogen-containing heterocyclic compound is not particularly limited as long as it is an aromatic ring containing a nitrogen atom, but a 3- to 6-membered nitrogen-containing aromatic ring is preferable, and a 5-membered or 6-membered ring-containing aromatic ring is preferable. Nitrogen aromatic rings are preferred. Examples of the 5-membered nitrogen-containing aromatic ring include a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, and a tetrazole ring. Examples of the 6-membered nitrogen-containing aromatic ring include a pyridine ring, a pyridazine ring, a pyrimidine ring, and a pyrazine ring.
In the nitrogen-containing aromatic ring possessed by the nitrogen-containing heterocyclic compound, when at least two nitrogen-containing aromatic rings are condensed, the number of condensation of the nitrogen-containing aromatic ring is 2 or more, and 2 or 3 Is preferred. In the nitrogen-containing aromatic ring of the nitrogen-containing heterocyclic compound, when two or more nitrogen-containing aromatic rings are directly connected, the number of bonds of the nitrogen-containing aromatic ring is two or more, and two preferable.
The nitrogen-containing heterocyclic compound contains two or more of the nitrogen-containing aromatic rings, and at least two of the nitrogen-containing aromatic rings are condensed or directly connected to each other. The other ring may be any ring as long as it contains the structure of c-1) or the structure of the above formula (c-2), but the other rings include a benzene ring and naphthalene. An aromatic ring selected from rings is preferred. The number of aromatic rings forming the nitrogen-containing heterocyclic compound is preferably 2 or 3 in one molecule.
The nitrogen-containing heterocyclic compound may or may not have a substituent on the nitrogen-containing aromatic ring, but preferably does not have it. As the substituent, when the substituent is bulky, it is difficult to capture a decomposition product generated in the cured film. Therefore, it is preferable to have a substituent that does not become bulky.
The substituent is not particularly limited, but is preferably a hydroxyl group, a carboxyl group, a sulfonic acid group, an alkyl group, an amino group, a halogen atom, an acyl group or a mercapto group, and a hydroxyl group, a carboxyl group, a sulfonic acid group, an acyl group or an alkyl group. Are more preferable, an alkyl group and a hydroxyl group are more preferable, and a methyl group and a hydroxyl group are particularly preferable in that they are not bulky.
When the substituent is an alkyl group, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group and an ethyl group are more preferable.
When the substituent is a halogen atom, a chlorine atom, a bromine atom or an iodine atom is preferable.
When the substituent is an acyl group, an acyl group having 2 to 4 carbon atoms is preferable.
The number of substituents is not particularly limited, but is preferably 1 to 3 and more preferably 1 or 2 in one molecule of the nitrogen-containing heterocyclic compound.
R1及びR2がそれぞれアルキル基を表す場合、好ましいアルキル基は、炭素原子数1~3のアルキル基である。具体的には、メチル基及びエチル基が好ましく、エチル基が特に好ましい。
R1及びR2がそれぞれハロゲン原子を表す場合、好ましいハロゲン原子は、塩素原子、臭素原子及びヨウ素原子である。
R1及びR2がそれぞれアミノ基を表す場合、アミノ基は、1又は2個の炭素数1~3のアルキル基によって置換されてもよい。
R1及びR2がそれぞれアシル基を表す場合、炭素原子数2~4のアシル基が好ましい。
一般式(1)中、p及びvは、それぞれ0~2の整数を表す。p及びvが2を表す場合、R1は同じでなくてもよい。 In the general formula (1), R 1 and R 2 each represent a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, an alkyl group, an amino group, a halogen atom or a mercapto group, and a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfone group An acid group, an acyl group, and an alkyl group are more preferable, and a hydrogen atom, a hydroxyl group, an alkyl group, and a sulfonic acid group are particularly preferable. Specifically, it is preferable that R 1 represents a hydrogen atom and R 2 represents an alkyl group or a hydroxyl group.
When R 1 and R 2 each represents an alkyl group, a preferred alkyl group is an alkyl group having 1 to 3 carbon atoms. Specifically, a methyl group and an ethyl group are preferable, and an ethyl group is particularly preferable.
When R 1 and R 2 each represent a halogen atom, preferred halogen atoms are a chlorine atom, a bromine atom and an iodine atom.
When R 1 and R 2 each represent an amino group, the amino group may be substituted with 1 or 2 alkyl groups having 1 to 3 carbon atoms.
When R 1 and R 2 each represent an acyl group, an acyl group having 2 to 4 carbon atoms is preferred.
In general formula (1), p and v each represents an integer of 0 to 2. When p and v represent 2, R 1 may not be the same.
R3~R5がそれぞれアルキル基を表す場合、好ましいアルキル基は、炭素原子数1~3のアルキル基である。具体的には、メチル基及びエチル基が好ましく、メチル基が特に好ましい。
R3~R5がそれぞれハロゲン原子を表す場合、好ましいハロゲン原子は、塩素原子、臭素原子及びヨウ素原子である。
R3~R5がそれぞれアミノ基を表す場合、アミノ基は、1又は2個の炭素数1~3のアルキル基によって置換されてもよい。
一般式(2)中、qは、0~2の整数を表す。qは、0~2の整数が好ましい。pが2を表す場合、R4は互いに同じでなくてもよいが、同じであることが好ましい。
一般式(2)中、r及びsは、それぞれ0~3の整数を表す。r及びsは、それぞれ0~2の整数が好ましく、0がより好ましい。r及びsが2又は3を表す場合、R4及びR5は互いに同じであっても同じでなくてもよい。 In the general formula (2), R 3 to R 5 each represent a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, an alkyl group, an amino group, a halogen atom or a mercapto group, and a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfone group An acid group and an alkyl group are more preferable, and a hydrogen atom and an alkyl group are particularly preferable. Specifically, it is preferable that R 3 and R 5 represent a hydrogen atom and R 4 represents an alkyl group.
When R 3 to R 5 each represents an alkyl group, a preferred alkyl group is an alkyl group having 1 to 3 carbon atoms. Specifically, a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.
When R 3 to R 5 each represent a halogen atom, preferred halogen atoms are a chlorine atom, a bromine atom and an iodine atom.
When R 3 to R 5 each represent an amino group, the amino group may be substituted with 1 or 2 alkyl groups having 1 to 3 carbon atoms.
In general formula (2), q represents an integer of 0-2. q is preferably an integer of 0 to 2. When p represents 2, R 4 may not be the same as each other, but is preferably the same.
In general formula (2), r and s each represent an integer of 0 to 3. r and s are each preferably an integer of 0 to 2, more preferably 0. When r and s represent 2 or 3, R 4 and R 5 may or may not be the same as each other.
R6及びR7がそれぞれアルキル基を表す場合、好ましいアルキル基は、炭素原子数1~3のアルキル基である。具体的には、メチル基及びエチル基が好ましく、メチル基が特に好ましい。
R6及びR7がそれぞれハロゲン原子を表す場合、好ましいハロゲン原子は、塩素原子、臭素原子及びヨウ素原子である。
R6及びR7がそれぞれアミノ基を表す場合、アミノ基は、1又は2個の炭素数1~3のアルキル基によって置換されてもよい。
一般式(3)中、t及びuは、それぞれ0~4の整数を表す。t及びuは、それぞれ0~2の整数が好ましく、0又は1がより好ましい。t及びuが2~4の整数を表す場合、t及びuは互いに同じであっても同じでなくてもよい。 In the general formula (3), R 6 and R 7 each represent a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, an alkyl group, an amino group, a halogen atom or a mercapto group, and the hydrogen atom, the carboxyl group and the alkyl group are More preferred are a hydrogen atom and an alkyl group. Specifically, it is preferable that R 6 and R 7 each represent a hydrogen atom or an alkyl group.
When R 6 and R 7 each represent an alkyl group, a preferred alkyl group is an alkyl group having 1 to 3 carbon atoms. Specifically, a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.
When R 6 and R 7 each represent a halogen atom, preferred halogen atoms are a chlorine atom, a bromine atom and an iodine atom.
When R 6 and R 7 each represent an amino group, the amino group may be substituted with one or two alkyl groups having 1 to 3 carbon atoms.
In general formula (3), t and u each represents an integer of 0 to 4. t and u are each preferably an integer of 0 to 2, more preferably 0 or 1. When t and u represent an integer of 2 to 4, t and u may or may not be the same.
一般式(1-1)中、R11及びR21は、それぞれ水素原子、水酸基、スルホン酸基又はアルキル基を表す。R11及びR21は、前記一般式(1)中のR1及びR2と同義であり、好ましい範囲も同様である。
一般式(1-1)中、X1は水素原子、アシル基又はアルキル基を表し、水素原子が好ましい。X1がアルキル基を表す場合、好ましいアルキル基は、炭素原子数1~3のアルキル基である。具体的には、メチル基及びエチル基が好ましい。X1がアシル基を表す場合、炭素原子数2~4のアシル基が好ましい。
一般式(1-1)中、p1は、0~2の整数を表し、前記一般式(1)中のpと同義であり、好ましい範囲も同様である。 The nitrogen-containing heterocyclic compound represented by the general formula (1) is more preferably represented by the following general formula (1-1).
In general formula (1-1), R 11 and R 21 each represent a hydrogen atom, a hydroxyl group, a sulfonic acid group, or an alkyl group. R 11 and R 21 have the same meanings as R 1 and R 2 in the general formula (1), and preferred ranges thereof are also the same.
In general formula (1-1), X 1 represents a hydrogen atom, an acyl group or an alkyl group, preferably a hydrogen atom. When X 1 represents an alkyl group, a preferred alkyl group is an alkyl group having 1 to 3 carbon atoms. Specifically, a methyl group and an ethyl group are preferable. When X 1 represents an acyl group, an acyl group having 2 to 4 carbon atoms is preferred.
In general formula (1-1), p1 represents an integer of 0 to 2, and has the same meaning as p in general formula (1), and the preferred range is also the same.
本発明の組成物中に含まれる含窒素ヘテロ環化合物は、1種のみでもよいし、2種以上であってもよい。本発明の組成物中に前記含窒素ヘテロ環化合物を2種以上含む場合は、含窒素ヘテロ環化合物の合計が上記範囲であることが好ましい。 In the composition of the present invention, the amount of the nitrogen-containing heterocyclic compound is preferably 0.001 to 15 parts by mass with respect to 100 parts by mass in total of the polymer component (A), and 0.05 to The amount is more preferably 10 parts by mass, and further preferably 0.01 to 5 parts by mass.
1 type may be sufficient as the nitrogen-containing heterocyclic compound contained in the composition of this invention, and 2 or more types may be sufficient as it. When 2 or more types of the said nitrogen-containing heterocyclic compound are included in the composition of this invention, it is preferable that the sum total of a nitrogen-containing heterocyclic compound is the said range.
本発明の感光性樹脂組成物は、(D)溶剤を含有する。本発明の感光性樹脂組成物は、本発明の必須成分と、さらに後述の任意の成分を(D)溶剤に溶解した溶液として調製されることが好ましい。本発明の組成物の調製に用いられる溶剤としては、必須成分及び任意成分を均一に溶解し、各成分と反応しないものが用いられる。
本発明の感光性樹脂組成物に使用される(D)溶剤としては、公知の溶剤を用いることができ、エチレングリコールモノアルキルエーテル類、エチレングリコールジアルキルエーテル類、エチレングリコールモノアルキルエーテルアセテート類、プロピレングリコールモノアルキルエーテル類、プロピレングリコールジアルキルエーテル類、プロピレングリコールモノアルキルエーテルアセテート類、ジエチレングリコールジアルキルエーテル類、ジエチレングリコールモノアルキルエーテルアセテート類、ジプロピレングリコールモノアルキルエーテル類、ジプロピレングリコールジアルキルエーテル類、ジプロピレングリコールモノアルキルエーテルアセテート類、エステル類、ケトン類、アミド類、ラクトン類等が例示できる。また、本発明の感光性樹脂組成物に使用される溶剤の具体例としては特開2011-221494号公報の段落番号0174~0178に記載の溶剤、特開2012-194290公報の段落番号0167~0168に記載の溶剤も挙げられ、これらの内容は本願明細書に組み込まれる。 <(D) Solvent>
The photosensitive resin composition of the present invention contains (D) a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution in which the essential components of the present invention and further optional components described below are dissolved in the solvent (D). As a solvent used for the preparation of the composition of the present invention, a solvent that uniformly dissolves essential components and optional components and does not react with each component is used.
As the solvent (D) used in the photosensitive resin composition of the present invention, known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene. Glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol Examples include monoalkyl ether acetates, esters, ketones, amides, lactones and the like. Specific examples of the solvent used in the photosensitive resin composition of the present invention include the solvents described in paragraph numbers 0174 to 0178 of JP2011-221494A, and paragraph numbers 0167 to 0168 of JP2012-194290A. And the contents thereof are incorporated herein by reference.
沸点130℃以上160℃未満の溶剤としては、プロピレングリコールモノメチルエーテルアセテート(沸点146℃)、プロピレングリコールモノエチルエーテルアセテート(沸点158℃)、プロピレングリコールメチル-n-ブチルエーテル(沸点155℃)、プロピレングリコールメチル-n-プロピルエーテル(沸点131℃)が例示できる。
沸点160℃以上の溶剤としては、3-エトキシプロピオン酸エチル(沸点170℃)、ジエチレングリコールメチルエチルエーテル(沸点176℃)、プロピレングリコールモノメチルエーテルプロピオネート(沸点160℃)、ジプロピレングリコールメチルエーテルアセテート(沸点213℃)、3-メトキシブチルエーテルアセテート(沸点171℃)、ジエチレングリコールジエチエルエーテル(沸点189℃)、ジエチレングリコールジメチルエーテル(沸点162℃)、プロピレングリコールジアセテート(沸点190℃)、ジエチレングリコールモノエチルエーテルアセテート(沸点220℃)、ジプロピレングリコールジメチルエーテル(沸点175℃)、1,3-ブチレングリコールジアセテート(沸点232℃)が例示できる。 Further, the solvent is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), propylene glycol An example is methyl-n-propyl ether (boiling point 131 ° C.).
Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate. (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (Boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), 1,3-butylene glycol diacetate (boiling point 232 ° C) It can be.
本発明の組成物は、前記成分に加え、本発明の効果を損なわない範囲で必要に応じて、架橋剤、酸化防止剤、現像促進剤、アルコキシシラン化合物(シランカップリング剤)、界面活性剤、接着助剤、耐熱性向上剤、感熱性酸発生剤等の任意成分を含有できる。これらの任意成分は、単独で使用してもよいし2種以上を混合して使用してもよい。これらの化合物としては、例えば特開2012-88459号公報の段落番号0201~0224の記載の化合物を使用することができ、これらの内容は本願明細書に組み込まれる。 <Other ingredients>
The composition of the present invention comprises, in addition to the above components, a crosslinking agent, an antioxidant, a development accelerator, an alkoxysilane compound (silane coupling agent), and a surfactant, as long as the effects of the present invention are not impaired. In addition, optional components such as an adhesion assistant, a heat resistance improver, and a heat-sensitive acid generator can be contained. These optional components may be used alone or in combination of two or more. As these compounds, for example, the compounds described in JP-A-2012-88459, paragraph numbers 0201 to 0224 can be used, and the contents thereof are incorporated in the present specification.
本発明の感光性樹脂組成物は、密着改良剤としてアルコキシシラン化合物を含有していることが好ましい。アルコキシシラン化合物を用いると、本発明の感光性樹脂組成物により形成された膜と基板との密着性を向上できたり、本発明の感光性樹脂組成物により形成された膜の性質を調整することができる。本発明の感光性樹脂組成物に用いることができるアルコキシシラン化合物は、基材となる無機物、例えば、シリコン、酸化シリコン、窒化シリコン等のシリコン化合物、金、銅、モリブデン、チタン、アルミニウム等の金属と絶縁膜との密着性を向上させる化合物であることが好ましい。具体的には、公知のシランカップリング剤等も有効である。
シランカップリング剤としては、例えば、γ-アミノプロピルトリメトキシシラン、γ-アミノプロピルトリエトキシシラン、γ-グリシドキシプロピルトリアコキシシラン、γ-グリシドキシプロピルジアルコキシシラン、γ-メタクリロキシプロピルトリアルコキシシラン、γ-メタクリロキシプロピルジアルコキシシラン、γ-クロロプロピルトリアルコキシシラン、γ-メルカプトプロピルトリアルコキシシラン、β-(3,4-エポキシシクロヘキシル)エチルトリアルコキシシラン、ビニルトリアルコキシシランが挙げられる。これらのうち、γ-グリシドキシプロピルトリアルコキシシランやγ-メタクリロキシプロピルトリアルコキシシランがより好ましく、γ-グリシドキシプロピルトリアルコキシシランがさらに好ましく、3-グリシドキシプロピルトリメトキシシランがよりさらに好ましい。これらは1種単独又は2種以上を組み合わせて使用することができる。 Alkoxysilane Compound The photosensitive resin composition of the present invention preferably contains an alkoxysilane compound as an adhesion improver. When an alkoxysilane compound is used, the adhesion between the film formed from the photosensitive resin composition of the present invention and the substrate can be improved, or the properties of the film formed from the photosensitive resin composition of the present invention can be adjusted. Can do. The alkoxysilane compound that can be used in the photosensitive resin composition of the present invention is a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, molybdenum, titanium, or aluminum. Preferably, the compound improves the adhesion between the insulating film and the insulating film. Specifically, a known silane coupling agent or the like is also effective.
Examples of silane coupling agents include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropyl dialkoxysilane, and γ-methacryloxy. Propyltrialkoxysilane, γ-methacryloxypropyl dialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane Can be mentioned. Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, γ-glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is more preferable. Further preferred. These can be used alone or in combination of two or more.
(R1)4-n-Si-(OR2)n
一般式中、R1は反応性基を有さない炭素数1~20の炭化水素基であり、R2は炭素数1~3のアルキル基又はフェニル基であり、nは1~3の整数である。
具体例として以下の化合物をあげることができる。
(R 1 ) 4-n -Si- (OR 2 ) n
In the general formula, R 1 is a hydrocarbon group having 1 to 20 carbon atoms having no reactive group, R 2 is an alkyl group having 1 to 3 carbon atoms or a phenyl group, and n is an integer of 1 to 3 It is.
Specific examples thereof include the following compounds.
本発明の感光性樹脂組成物におけるアルコキシシラン化合物の含有量は、前記(A)重合体成分の合計100質量部に対して、0.1~30質量部が好ましく、0.5~20質量部がより好ましい。 The alkoxysilane compound in the photosensitive resin composition of this invention is not specifically limited to these, A well-known thing can be used.
The content of the alkoxysilane compound in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass, and 0.5 to 20 parts by mass with respect to 100 parts by mass in total of the polymer component (A). Is more preferable.
本発明の感光性樹脂組成物は、界面活性剤を含有していることが好ましい。界面活性剤としては、アニオン系、カチオン系、ノニオン系、又は、両性のいずれでも使用することができるが、好ましい界面活性剤はノニオン界面活性剤である。本発明の組成物に用いられる界面活性剤としては、例えば、特開2012-88459号公報の段落番号0201~0205に記載のものや、特開2011-215580号公報の段落番号0185~0188に記載のものを用いることができ、これらの記載は本願明細書に組み込まれる。
ノニオン系界面活性剤の例としては、ポリオキシエチレン高級アルキルエーテル類、ポリオキシエチレン高級アルキルフェニルエーテル類、ポリオキシエチレングリコールの高級脂肪酸ジエステル類、シリコーン系、フッ素系界面活性剤を挙げることができる。また、以下商品名で、KP-341、X-22-822(信越化学工業(株)製)、ポリフローNo.99C(共栄社化学(株)製)、エフトップ(三菱マテリアル化成社製)、メガファック(DIC(株)製)、フロラードノベックFC-4430(住友スリーエム(株)製)、サーフロンS-242(AGCセイミケミカル社製)、PolyFoxPF-6320(OMNOVA社製)、SH-8400(東レ・ダウコーニングシリコーン)、フタージェントFTX-218G(ネオス社製)等を挙げることができる。
本発明の感光性樹脂組成物中における界面活性剤の添加量は、前記(A)重合体の合計100質量部に対し、10質量部以下であることが好ましく、0.001~10質量部であることがより好ましく、0.01~5質量部であることがさらに好ましい。界面活性剤は複数を併用することもでき、その場合は界面活性剤を全て合算して含有量を計算する。 Surfactant The photosensitive resin composition of the present invention preferably contains a surfactant. As the surfactant, any of anionic, cationic, nonionic or amphoteric can be used, but a preferred surfactant is a nonionic surfactant. Examples of the surfactant used in the composition of the present invention include those described in paragraph Nos. 0201 to 0205 in JP2012-88459A, and paragraphs 0185 to 0188 in JP2011-215580A. Can be used and these descriptions are incorporated herein.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . The following trade names are KP-341, X-22-822 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 99C (manufactured by Kyoeisha Chemical Co., Ltd.), F Top (manufactured by Mitsubishi Materials Kasei Co., Ltd.), MegaFac (manufactured by DIC Corporation), Florard Novec FC-4430 (manufactured by Sumitomo 3M Co., Ltd.), Surflon S-242 (Manufactured by AGC Seimi Chemical Co., Ltd.), PolyFoxPF-6320 (manufactured by OMNOVA), SH-8400 (Toray Dow Corning Silicone), and footgent FTX-218G (manufactured by Neos).
The addition amount of the surfactant in the photosensitive resin composition of the present invention is preferably 10 parts by mass or less, and preferably 0.001 to 10 parts by mass with respect to 100 parts by mass in total of the polymer (A). More preferred is 0.01 to 5 parts by mass. A plurality of surfactants can be used in combination, and in that case, the content is calculated by adding all the surfactants.
本発明の感光性樹脂組成物は、必要に応じ、架橋剤を含有してもよい。架橋剤を添加することにより、本発明の感光性樹脂組成物により得られる硬化膜をより強固な膜とすることができる。
架橋剤としては、熱によって架橋反応が起こるものであれば制限は無い(前記(A)成分を除く)。例えば、分子内に2個以上のエポキシ基又はオキセタニル基を有する化合物、アルコキシメチル基含有架橋剤、又は、少なくとも1個のエチレン性不飽和二重結合を有する化合物、ブロックイソシアネート化合物等を添加することができる。 Crosslinking agent The photosensitive resin composition of this invention may contain a crosslinking agent as needed. By adding a crosslinking agent, the cured film obtained by the photosensitive resin composition of the present invention can be made a stronger film.
The crosslinking agent is not limited as long as a crosslinking reaction is caused by heat (excluding the component (A)). For example, adding a compound having two or more epoxy groups or oxetanyl groups in the molecule, an alkoxymethyl group-containing crosslinking agent, a compound having at least one ethylenically unsaturated double bond, a blocked isocyanate compound, etc. Can do.
分子内に2個以上のエポキシ基を有する化合物の具体例としては、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、脂肪族エポキシ樹脂等を挙げることができる。 <Compound having two or more epoxy groups or oxetanyl groups in the molecule>
Specific examples of compounds having two or more epoxy groups in the molecule include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aliphatic epoxy resins, and the like. Can do.
分子内に2個以上のオキセタニル基を有する化合物の具体例としては、アロンオキセタンOXT-121、OXT-221、OX-SQ、PNOX(以上、東亞合成(株)製)を用いることができる。
また、オキセタニル基を含む化合物は、単独で又はエポキシ基を含む化合物と混合して使用することが好ましい。 These are available as commercial products. Examples thereof include commercially available products described in paragraph number 0189 of JP2011-212494, such as JER152, JER157S70, JER157S65, JER806, JER828, JER1007 (manufactured by Mitsubishi Chemical Holdings Corporation).
As specific examples of the compound having two or more oxetanyl groups in the molecule, Aron oxetane OXT-121, OXT-221, OX-SQ, PNOX (manufactured by Toagosei Co., Ltd.) can be used.
Moreover, it is preferable to use the compound containing an oxetanyl group individually or in mixture with the compound containing an epoxy group.
本発明の感光性樹脂組成物では、架橋剤として、ブロックイソシアネート系化合物も好ましく採用できる。ブロックイソシアネート化合物は、ブロックイソシアネート基を有する化合物であれば特に制限はないが、硬化性の観点から、1分子内に2以上のブロックイソシアネート基を有する化合物であることが好ましい。
なお、本発明におけるブロックイソシアネート基とは、熱によりイソシアネート基を生成することが可能な基であり、例えば、ブロック剤とイソシアネート基とを反応させイソシアネート基を保護した基が好ましく例示できる。
本発明の感光性樹脂組成物におけるブロックイソシアネート化合物の母構造としては、ビウレット型、イソシアヌレート型、アダクト型、2官能プレポリマー型等を挙げることができる。
前記ブロックイソシアネート化合物のブロック構造を形成するブロック剤としては、オキシム化合物、ラクタム化合物、フェノール化合物、アルコール化合物、アミン化合物、活性メチレン化合物、ピラゾール化合物、メルカプタン化合物、イミダゾール系化合物、イミド系化合物等を挙げることができる。これらの中でも、オキシム化合物、ラクタム化合物、フェノール化合物、アルコール化合物、アミン化合物、活性メチレン化合物、ピラゾール化合物から選ばれるブロック剤が特に好ましい。 <Block isocyanate compound>
In the photosensitive resin composition of the present invention, a blocked isocyanate compound can also be preferably employed as a crosslinking agent. The blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group, but is preferably a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability.
In addition, the blocked isocyanate group in this invention is a group which can produce | generate an isocyanate group with a heat | fever, For example, the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably.
Examples of the matrix structure of the blocked isocyanate compound in the photosensitive resin composition of the present invention include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to. Among these, a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.
その他の架橋剤としては、例えばメチル化メラミン樹脂(例えば、ニカラックMW-30HM((株)三和ケミカル製)を用いることができる。 The blocked isocyanate compound that can be used in the photosensitive resin composition of the present invention is commercially available. For example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (or more, Nippon Polyurethane Industry Co., Ltd.), Takenate B-830, B-815N, B-820NSU, B-842N, B-84N, B-870N, B-874N, B-882N (above, manufactured by Mitsui Chemicals, Inc.) ), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000, E402 -B80T (Asahi Kasei Chemicals Corporation) Death Module BL1100, BL1265 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumidur BL3175 (above, Sumika Bayer Urethane Co., Ltd.), Karenz MOI-BP, Karenz MOI-BM (manufactured by Showa Denko KK) and the like can be preferably used.
As another crosslinking agent, for example, a methylated melamine resin (for example, Nicalac MW-30HM (manufactured by Sanwa Chemical Co., Ltd.)) can be used.
本発明の感光性樹脂組成物は、酸化防止剤を含有してもよい。酸化防止剤としては、公知の酸化防止剤を含有することができる。酸化防止剤を添加することにより、硬化膜の着色を防止できる、又は、分解による膜厚減少を低減でき、また、耐熱透明性に優れるという利点がある。
このような酸化防止剤としては、例えば、リン系酸化防止剤、アミド類、ヒドラジド類、ヒンダードアミン系酸化防止剤、イオウ系酸化防止剤、フェノール系酸化防止剤、アスコルビン酸類、硫酸亜鉛、糖類、亜硝酸塩、亜硫酸塩、チオ硫酸塩、ヒドロキシルアミン誘導体などを挙げることができる。これらの中では、硬化膜の着色、膜厚減少の観点から特にフェノール系酸化防止剤、アミド系酸化防止剤、ヒドラジド系酸化防止剤、イオウ系酸化防止剤が好ましく、フェノール系酸化防止剤が最も好ましい。これらは1種単独で用いてもよいし、2種以上を混合してもよい。
具体例としては、特開2005-29515号公報の段落番号0026~0031に記載の化合物、特開2001-227106号公報の段落番号0106~0116に記載の化合物を挙げる事ができ、これらの内容は本願明細書に組み込まれる。
好ましい市販品として、アデカスタブAO-20、アデカスタブAO-30、アデカスタブAO-40、アデカスタブAO-50、アデカスタブAO-60、アデカスタブAO-70、アデカスタブAO-80、アデカスタブAO-330、イルガノックス1726、イルガノックス1035、イルガノックス1098を挙げる事ができる。 Antioxidant The photosensitive resin composition of the present invention may contain an antioxidant. As an antioxidant, a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat resistant transparency is excellent.
Examples of such antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, Examples thereof include nitrates, sulfites, thiosulfates, and hydroxylamine derivatives. Of these, phenol-based antioxidants, amide-based antioxidants, hydrazide-based antioxidants, and sulfur-based antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness. preferable. These may be used individually by 1 type and may mix 2 or more types.
Specific examples include the compounds described in paragraph numbers 0026 to 0031 of JP-A-2005-29515 and the compounds described in paragraph numbers 0106 to 0116 of JP-A-2001-227106. It is incorporated herein.
Preferred commercially available products include ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-330, IRGANOX 1726, and IRGA Knox 1035 and Irganox 1098 can be mentioned.
本発明の組成物は、各成分を所定の割合でかつ任意の方法で混合し、撹拌溶解することによって調製することができる。例えば、各成分を、それぞれ予め上述した溶剤に溶解させた溶液とした後、これらを所定の割合で混合して樹脂組成物を調製することもできる。以上のように調製した組成物溶液は、例えば孔径0.2μmのフィルター等を用いてろ過した後に、使用することもできる。 <Method for preparing photosensitive resin composition>
The composition of the present invention can be prepared by mixing each component at a predetermined ratio and by any method, and stirring and dissolving. For example, the resin composition can be prepared by mixing each component in a predetermined ratio after preparing each solution in advance in the above-described solvent. The composition solution prepared as described above can be used after being filtered using, for example, a filter having a pore diameter of 0.2 μm.
次に、本発明の硬化膜の製造方法を説明する。
本発明の硬化膜の製造方法は、以下の(1)~(5)の工程を含むことが好ましい。
(1)本発明の感光性樹脂組成物を基板上に適用する工程;
(2)適用された感光性樹脂組成物から溶剤を除去する工程;
(3)溶剤が除去された感光性樹脂組成物を活性光線により露光する工程;
(4)露光された感光性樹脂組成物を水性現像液により現像する工程;
(5)現像された熱硬化するポストベーク工程。
以下に各工程を順に説明する。 <Method for producing cured film>
Next, the manufacturing method of the cured film of this invention is demonstrated.
The method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
(1) The process of applying the photosensitive resin composition of this invention on a board | substrate;
(2) removing the solvent from the applied photosensitive resin composition;
(3) The process of exposing the photosensitive resin composition from which the solvent was removed with actinic rays;
(4) A step of developing the exposed photosensitive resin composition with an aqueous developer;
(5) A developed post-baking step for thermosetting.
Each step will be described below in order.
上記の基板としては、無機基板、樹脂、樹脂複合材料などが挙げられる。
無機基板としては、例えばガラス、石英、シリコーン、シリコンナイトライド、及び、それらのような基板上にモリブデン、チタン、アルミ、銅などを蒸着した複合基板が挙げられる。
樹脂としては、ポリブチレンテレフタレート、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート、ポリスチレン、ポリカーボネート、ポリスルホン、ポリエーテルスルホン、ポリアリレート、アリルジグリコールカーボネート、ポリアミド、ポリイミド、ポリアミドイミド、ポリエーテルイミド、ポリベンズアゾール、ポリフェニレンサルファイド、ポリシクロオレフィン、ノルボルネン樹脂、ポリクロロトリフルオロエチレン等のフッ素樹脂、液晶ポリマー、アクリル樹脂、エポキシ樹脂、シリコーン樹脂、アイオノマー樹脂、シアネート樹脂、架橋フマル酸ジエステル、環状ポリオレフィン、芳香族エーテル、マレイミドーオレフィン、セルロース、エピスルフィド化合物等の合成樹脂からなる基板が挙げられる。
これらの基板は、上記の形態のまま用いられる場合は少なく、通常、最終製品の形態によって、例えばTFT素子のような多層積層構造が形成されている。
基板への適用方法は特に限定されず、例えば、スリットコート法、スプレー法、ロールコート法、回転塗布法、流延塗布法、スリットアンドスピン法等の方法を用いることができる。
適用したときの湿潤膜厚は特に限定されるものではなく、用途に応じた膜厚で塗布することができるが、通常は0.5~10μmの範囲で使用される。
更に、基板に本発明で用いられる組成物を塗布する前に、特開2009-145395号公報に記載されているような、所謂プリウェット法を適用することも可能である。 In the application step (1), it is preferable to apply (preferably apply) the photosensitive resin composition of the present invention onto a substrate to form a wet film containing a solvent. It is preferable to perform substrate cleaning such as alkali cleaning or plasma cleaning before applying the photosensitive resin resin composition to the substrate, and it is more preferable to treat the substrate surface with hexamethyldisilazane after substrate cleaning. By performing this treatment, the adhesiveness of the photosensitive resin composition to the substrate tends to be improved. The method for treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method in which the substrate is exposed to hexamethyldisilazane vapor.
Examples of the substrate include inorganic substrates, resins, and resin composite materials.
Examples of the inorganic substrate include glass, quartz, silicone, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
The resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic Made of synthetic resin such as aromatic ether, maleimide-olefin, cellulose, episulfide compound And the like.
These substrates are rarely used in the above-described form, and usually a multilayer laminated structure such as a TFT element is formed depending on the form of the final product.
The application method to the substrate is not particularly limited, and for example, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, or the like can be used.
The wet film thickness when applied is not particularly limited, and can be applied with a film thickness according to the application, but is usually used in the range of 0.5 to 10 μm.
Furthermore, before applying the composition used in the present invention to the substrate, it is also possible to apply a so-called prewetting method as described in JP-A-2009-145395.
活性光線による露光光源としては、低圧水銀灯、高圧水銀灯、超高圧水銀灯、ケミカルランプ、LED光源、エキシマレーザー発生装置などを用いることができ、i線(365nm)、h線(405nm)、g線(436nm)などの波長300nm以上450nm以下の波長を有する活性光線が好ましく使用できる。また、必要に応じて長波長カットフィルター、短波長カットフィルター、バンドパスフィルターのような分光フィルターを通して照射光を調整することもできる。露光量は好ましくは1~500mj/cm2である。
露光装置としては、ミラープロジェクションアライナー、ステッパー、スキャナー、プロキシミティ、コンタクト、マイクロレンズアレイ、レンズスキャナ、レーザー露光、など各種方式の露光機を用いることができる。 In the exposure step (3), the substrate provided with the coating film is irradiated with an actinic ray having a predetermined pattern.
As an exposure light source using actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, and the like can be used, i-line (365 nm), h-line (405 nm), g-line ( Actinic rays having a wavelength of 300 nm to 450 nm, such as 436 nm), can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed. The exposure amount is preferably 1 to 500 mj / cm 2 .
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, a lens scanner, and a laser exposure can be used.
現像工程で使用する現像液には、塩基性化合物が含まれることが好ましい。塩基性化合物としては、例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物類;炭酸ナトリウム、炭酸カリウムなどのアルカリ金属炭酸塩類;重炭酸ナトリウム、重炭酸カリウムなどのアルカリ金属重炭酸塩類;テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、コリンヒドロキシド等のアンモニウムヒドロキシド類;ケイ酸ナトリウム、メタケイ酸ナトリウムなどの水溶液を使用することができる。また、上記アルカリ類の水溶液にメタノールやエタノールなどの水溶性有機溶剤や界面活性剤を適当量添加した水溶液を現像液として使用することもできる。
好ましい現像液として、テトラメチルアンモニウムヒドロキシドの0.2~2.5%水溶液を挙げる事ができる。
現像液のpHは、好ましくは10.0~14.0である。
現像時間は、好ましくは30~500秒間であり、また、現像の手法は液盛り法(パドル法)、シャワー法、ディップ法等の何れでもよい。
現像の後に、リンス工程を行うこともできる。リンス工程では、現像後の基板を純水などで洗うことで、付着している現像液除去、現像残渣除去を行う。リンス方法は公知の方法を用いることができる。例えばシャワーリンスやディップリンスなどを挙げる事ができる。 In the developing step (4), the copolymer having a carboxyl group or a phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing an exposed area containing a resin composition having a carboxyl group or a phenolic hydroxyl group that is easily dissolved in an alkaline developer.
The developer used in the development step preferably contains a basic compound. Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
A preferred developing solution is a 0.2 to 2.5% aqueous solution of tetramethylammonium hydroxide.
The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 500 seconds, and the development method may be any of a liquid piling method (paddle method), a shower method, a dipping method, and the like.
A rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like. A known method can be used as the rinsing method. For example, shower rinse and dip rinse can be mentioned.
ポストベークの前に、比較的低温でベークを行った後にポストベークすることもできる(ミドルベーク工程の追加)。ミドルベークを行う場合は、90~150℃で1~60分加熱した後に、200℃以上の高温でポストベークすることが好ましい。また、ミドルベーク、ポストベークを3段階以上の多段階に分けて加熱する事もできる。このようなミドルベーク、ポストベークの工夫により、パターンのテーパー角を調整することができる。これらの加熱は、ホットプレート、オーブン、赤外線ヒーターなど、公知の加熱方法を使用することができる。
なお、ポストベークに先立ち、パターンを形成した基板に活性光線により全面再露光(ポスト露光)することが、透明性向上の観点から好ましい。ポスト露光工程を含む場合の好ましい露光量としては、100~3,000mJ/cm2が好ましく、100~2000mJ/cm2が特に好ましい。 In the post-baking step of (5), the cured film can be formed by crosslinking the acid group with a crosslinkable group, a crosslinking agent, etc. by heating the obtained positive image. This heating is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 to 250 ° C. for a predetermined time, for example, 5 to 90 minutes on the hot plate, 30 to 120 minutes for the oven. It is preferable to By proceeding the crosslinking reaction in this way, a protective film and an interlayer insulating film that are superior in heat resistance, hardness, and the like can be formed. In addition, when the heat treatment is performed in a nitrogen atmosphere, the transparency can be further improved.
Prior to post-baking, post-baking can be performed after baking at a relatively low temperature (addition of a middle baking process). When middle baking is performed, it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes. Moreover, middle baking and post-baking can be heated in three or more stages. The taper angle of the pattern can be adjusted by devising such middle baking and post baking. These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
Prior to post-baking, it is preferable from the viewpoint of improving transparency that the substrate on which the pattern is formed is re-exposed (post-exposure) with actinic rays. The preferred exposure amount in the case of including a post-exposure step, preferably 100 ~ 3,000mJ / cm 2, particularly preferably 100 ~ 2000mJ / cm 2.
本発明の硬化膜は、上述した本発明の感光性樹脂組成物を硬化して得られた硬化膜である。
本発明の硬化膜は、層間絶縁膜として好適に用いることができる。また、本発明の硬化膜は、上述した本発明の硬化膜の形成方法により得られた硬化膜であることが好ましい。
本発明の感光性樹脂組成物により、絶縁性に優れ、高温でベークされた場合においても高い透明性を有する層間絶縁膜が得られる。本発明の感光性樹脂組成物を用いてなる層間絶縁膜は、高い透明性を有し、硬化膜物性に優れるため、液晶表示装置や有機EL表示装置の用途に有用である。 [Curing film]
The cured film of the present invention is a cured film obtained by curing the above-described photosensitive resin composition of the present invention.
The cured film of the present invention can be suitably used as an interlayer insulating film. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention mentioned above.
With the photosensitive resin composition of the present invention, an interlayer insulating film having excellent insulation and high transparency even when baked at high temperatures can be obtained. Since the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency and excellent cured film properties, it is useful for liquid crystal display devices and organic EL display devices.
本発明の液晶表示装置は、本発明の硬化膜を具備することを特徴とする。
本発明の液晶表示装置としては、上記本発明の感光性樹脂組成物を用いて形成される平坦化膜や層間絶縁膜を有すること以外は特に制限されず、様々な構造をとる公知の液晶表示装置を挙げることができる。
例えば、本発明の液晶表示装置が具備するTFT(Thin-Film Transistor)の具体例としては、アモルファスシリコン-TFT、低温ポリシリコンーTFT、酸化物半導体TFT等が挙げられる。本発明の硬化膜は電気特性に優れるため、これらのTFTに組み合わせて好ましく用いることができる。
また、本発明の液晶表示装置が取りうる液晶駆動方式としてはTN(TwistedNematic)方式、VA(Virtical Alignment)方式、IPS(In-Place-Switching)方式、FFS(Frings Field Switching)方式、OCB(Optical Compensated Bend)方式などが挙げられる。
パネル構成においては、COA(Color Filter on Allay)方式の液晶表示装置でも本発明の硬化膜を用いることができ、例えば、特開2005-284291の有機絶縁膜(115)や、特開2005-346054の有機絶縁膜(212)として用いることができる。また、本発明の液晶表示装置が取りうる液晶配向膜の具体的な配向方式としてはラビング配向法、光配向方などが挙げられる。また、特開2003-149647号公報や特開2011-257734号公報に記載のPSA(Polymer Sustained Alignment)技術によってポリマー配向支持されていてもよい。
また、本発明の感光性樹脂組成物及び本発明の硬化膜は、上記用途に限定されず種々の用途に使用することができる。例えば、平坦化膜や層間絶縁膜以外にも、カラーフィルターの保護膜や、液晶表示装置における液晶層の厚みを一定に保持するためのスペーサーや固体撮像素子においてカラーフィルター上に設けられるマイクロレンズ等に好適に用いることができる。
図1は、アクティブマトリックス方式の液晶表示装置10の一例を示す概念的断面図である。このカラー液晶表示装置10は、背面にバックライトユニット12を有する液晶パネルであって、液晶パネルは、偏光フィルムが貼り付けられた2枚のガラス基板14,15の間に配置されたすべての画素に対応するTFT16の素子が配置されている。ガラス基板上に形成された各素子には、硬化膜17中に形成されたコンタクトホール18を通して、画素電極を形成するITO透明電極19が配線されている。ITO透明電極19の上には、液晶20の層とブラックマトリックスを配置したRGBカラーフィルター22が設けられている。
バックライトの光源としては、特に限定されず公知の光源を用いることができる。例えば白色LED、青色・赤色・緑色などの多色LED、蛍光灯(冷陰極管)、有機ELなどを挙げる事ができる。
また、液晶表示装置は、3D(立体視)型のものとしたり、タッチパネル型のものとしたりすることも可能である。さらにフレキシブル型にすることも可能であり、特開2011-145686号公報に記載の第2層間絶縁膜(48)や、特開2009-258758号公報に記載の層間絶縁膜(520)として用いることができる。 [Liquid Crystal Display]
The liquid crystal display device of the present invention comprises the cured film of the present invention.
The liquid crystal display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and known liquid crystal displays having various structures. An apparatus can be mentioned.
For example, specific examples of TFT (Thin-Film Transistor) included in the liquid crystal display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
Further, the liquid crystal driving methods that can be adopted by the liquid crystal display device of the present invention include TN (Twisted Nematic) method, VA (Virtual Alignment) method, IPS (In-Place-Switching) method, FFS (Frings Field Switching) method, OCB (Optical). Compensated Bend) method and the like.
In the panel configuration, the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device. For example, the organic insulating film (115) of Japanese Patent Application Laid-Open No. 2005-284291, or Japanese Patent Application Laid-Open No. 2005-346054. It can be used as an organic insulating film (212). Specific examples of the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method. Further, the polymer orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in JP-A Nos. 2003-149647 and 2011-257734.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses. For example, in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc. Can be suitably used.
FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix liquid
The light source of the backlight is not particularly limited, and a known light source can be used. For example, a white LED, a multicolor LED such as blue, red, and green, a fluorescent lamp (cold cathode tube), and an organic EL can be used.
Further, the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. Further, it can be made flexible, and used as the second interlayer insulating film (48) described in Japanese Patent Application Laid-Open No. 2011-145686 and the interlayer insulating film (520) described in Japanese Patent Application Laid-Open No. 2009-258758. Can do.
本発明の有機EL表示装置は、本発明の硬化膜を具備することを特徴とする。
本発明の有機EL表示装置としては、上記本発明の感光性樹脂組成物を用いて形成される平坦化膜や層間絶縁膜を有すること以外は特に制限されず、様々な構造をとる公知の各種有機EL表示装置や液晶表示装置を挙げることができる。
例えば、本発明の有機EL表示装置が具備するTFT(Thin-Film Transistor)の具体例としては、アモルファスシリコン-TFT、低温ポリシリコンーTFT、酸化物半導体TFT等が挙げられる。本発明の硬化膜は電気特性に優れるため、これらのTFTに組み合わせて好ましく用いることができる。
図2は、有機EL表示装置の一例の構成概念図である。ボトムエミッション型の有機EL表示装置における基板の模式的断面図を示し、平坦化膜4を有している。
ガラス基板6上にボトムゲート型のTFT1を形成し、このTFT1を覆う状態でSi3N4から成る絶縁膜3が形成されている。絶縁膜3に、ここでは図示を省略したコンタクトホールを形成した後、このコンタクトホールを介してTFT1に接続される配線2(高さ1.0μm)が絶縁膜3上に形成されている。配線2は、TFT1間又は、後の工程で形成される有機EL素子とTFT1とを接続するためのものである。
さらに、配線2の形成による凹凸を平坦化するために、配線2による凹凸を埋め込む状態で絶縁膜3上に平坦化層4が形成されている。
平坦化膜4上には、ボトムエミッション型の有機EL素子が形成されている。すなわち、平坦化膜4上に、ITOからなる第一電極5が、コンタクトホール7を介して配線2に接続させて形成されている。また、第一電極5は、有機EL素子の陽極に相当する。
第一電極5の周縁を覆う形状の絶縁膜8が形成されており、この絶縁膜8を設けることによって、第一電極5とこの後の工程で形成する第二電極との間のショートを防止することができる。
さらに、図2には図示していないが、所望のパターンマスクを介して、正孔輸送層、有機発光層、電子輸送層を順次蒸着して設け、次いで、基板上方の全面にAlから成る第二電極を形成し、封止用ガラス板と紫外線硬化型エポキシ樹脂を用いて貼り合わせることで封止し、各有機EL素子にこれを駆動するためのTFT1が接続されてなるアクティブマトリックス型の有機EL表示装置が得られる。 [Organic EL display device]
The organic EL display device of the present invention comprises the cured film of the present invention.
The organic EL display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known structures having various structures. Examples thereof include an organic EL display device and a liquid crystal display device.
For example, specific examples of TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
FIG. 2 is a conceptual diagram of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
A bottom
Further, in order to flatten the unevenness due to the formation of the
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do.
Further, although not shown in FIG. 2, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a second layer made of Al is formed on the entire surface above the substrate. An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a
以下の合成例において、共重合体の重量平均分子量Mwの測定は下記の装置及び条件のもと、ゲルパーミエーションクロマトグラフィー(GPC)によった。
装置:GPC-101(昭和電工(株)製)
カラム:GPC-KF-801、GPC-KF-802、GPC-KF-803及びGPC-KF-804を結合
移動相:テトラヒドロフラン
検出器:示差屈折計
標準物質:単分散ポリスチレン The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
In the following synthesis examples, the weight average molecular weight Mw of the copolymer was measured by gel permeation chromatography (GPC) under the following apparatus and conditions.
Device: GPC-101 (manufactured by Showa Denko KK)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are combined Mobile phase: Tetrahydrofuran Detector: Differential refractometer Standard material: Monodisperse polystyrene
(P-1の合成)
冷却管及び攪拌機を備えたフラスコに、2,2’-アゾビス-(2,4-ジメチルバレロニトリル)7質量部とジエチレングリコールエチルメチルエーテル200質量部とを仕込んだ。引き続き、メタクリル酸12質量部、メタクリル酸グリシジル50質量部、N-シクロヘキシルマレイミド4質量部、メタクリル酸テトラヒドロフルフリル15質量部、アクリロイルモルホリン5質量部、3-(2-メタクリロイルオキシエチル)オキセタン8質量部及びペンタエリスリトールテトラキス(3-メルカプトプロピオネート)2質量部を仕込んで窒素置換した後、ゆるやかに撹拌を始めた。溶液の温度を70℃に上昇させ、反応溶液温度が70℃に達した時点で重合開始とした。その後、重合開始から30分後にN-シクロヘキシルマレイミド3質量部、1時間後にN-シクロヘキシルマレイミド3質量部を反応溶液に滴下した。その後、3時間保持することによって共重合体(P-1)を含む重合体溶液を得た。共重合体P-1のポリスチレン換算重量平均分子量(Mw)は9,000、分子量分布(Mw/Mn)は2.0であった。 <(A) Synthesis of polymer>
(Synthesis of P-1)
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 12 parts by weight of methacrylic acid, 50 parts by weight of glycidyl methacrylate, 4 parts by weight of N-cyclohexylmaleimide, 15 parts by weight of tetrahydrofurfuryl methacrylate, 5 parts by weight of acryloylmorpholine, 8 parts by weight of 3- (2-methacryloyloxyethyl) oxetane And 2 parts by mass of pentaerythritol tetrakis (3-mercaptopropionate) were charged, and the atmosphere was purged with nitrogen. The temperature of the solution was raised to 70 ° C., and the polymerization was started when the reaction solution temperature reached 70 ° C. Thereafter, 3 parts by mass of N-cyclohexylmaleimide 30 minutes after the start of polymerization, and 3 parts by mass of N-cyclohexylmaleimide were added dropwise to the
下記表中の特に単位を付していない数値は、質量部を単位とする。 Other polymers were synthesized in the same manner as P-1 using the monomers listed in the table below (monomer components (raw materials of (a1) to (a3))), a polymerization initiator, a molecular weight regulator, and a solvent. did.
The numerical values in the following table that are not marked with a unit are in parts by mass.
下記表に記載の固形分比となるように、(A)成分、(B)成分、(C)成分、アルコキシシラン化合物及び界面活性剤を溶剤(ジエチレングリコールエチルメチルエーテル:ハイソルブEDM(東邦化学工業社製))に固形分濃度32質量%になるまで溶解混合し、口径0.2μmのポリテトラフルオロエチレン製フィルターで濾過して、各種実施例及び比較例の感光性樹脂組成物を得た。 <Preparation of photosensitive resin composition>
(A) component, (B) component, (C) component, alkoxysilane compound, and surfactant so that it may become the solid content ratio of the following table | surface, a solvent (Diethylene glycol ethyl methyl ether: Highsolve EDM (Toho Chemical Industry Co., Ltd.) To a solid content concentration of 32% by mass, and filtered through a polytetrafluoroethylene filter having a diameter of 0.2 μm to obtain photosensitive resin compositions of various Examples and Comparative Examples.
P-1~P11:前記表に記載の重合体P-1~P11
P-12:特開平11-223937号公報の実施例1に記載のクレゾールノボラック型樹脂 <(A) Polymer>
P-1 to P11: Polymers P-1 to P11 described in the above table
P-12: Cresol novolak type resin described in Example 1 of JP-A-11-223937
B-1:4,4’-[1-[4-[1-[4-ヒドロキシフェニル]-1-メチルエチル]フェニル]エチリデン]ビスフェノール(1.0モル)と1,2-ナフトキノンジアジド-5-スルホン酸クロリド(3.0モル)との縮合物
B-2:1,1,1-トリ(p-ヒドロキシフェニル)エタン(1.0モル)と1,2-ナフトキノンジアジド-5-スルホン酸クロリド(2.0モル)との縮合物
B-3:2,3,4,4’-テトラヒドロキシベンゾフェノン(1.0モル)と1,2-ナフトキノンジアジド-5-スルホン酸エステル(2.44モル) <(B) Quinonediazide compound>
B-1: 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 -Condensation product with sulfonic acid chloride (3.0 mol) B-2: 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid Condensate with chloride (2.0 mol) B-3: 2,3,4,4′-tetrahydroxybenzophenone (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid ester (2.44) Mole)
窒素ヘテロ環化合物として、下記の(C-1)~(C-16)の化合物を用いた。
The following compounds (C-1) to (C-16) were used as nitrogen heterocyclic compounds.
G-1:3-グリシドキシプロピルトリメトキシシラン(KBM-403、信越化学工業(株)製) (Alkoxysilane compound)
G-1: 3-Glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)
W-1:シリコーン系界面活性剤((株)東レ・ダウコーニング製の「SH 8400 FLUID」)
W-2:フッ素系界面活性剤 FTX-218((株)ネオス製) (Surfactant)
W-1: Silicone-based surfactant (“SH 8400 FLUID” manufactured by Toray Dow Corning Co., Ltd.)
W-2: Fluorosurfactant FTX-218 (manufactured by Neos Co., Ltd.)
ガラス基板を、ヘキサメチルジシラザン(HMDS)蒸気下に30秒曝し、該基板に各感光性樹脂組成物をスピンコート塗布した後、90℃/120秒ホットプレート上でプリベークして溶剤を揮発させ、膜厚3.0μmの感光性樹脂組成物層を形成した。続いて超高圧水銀灯を用いて積算照射量が300mJ/cm2(照度:20mW/cm2、i線)となるように露光し、この基板をオーブンにて230℃/30分間加熱した。
得られた硬化膜の膜厚(T1)を測定した。そして、この硬化膜が形成された基板を80℃に温度制御されたモノエタノールアミンに60℃で5分浸漬させた後、浸漬後の硬化膜の膜厚(t1)を測定し、浸漬による膜厚変化率{|t1-T1|/T1}×100〔%〕を算出した。結果を下記表に示す。小さいほど好ましく、A、Bが実用上問題のないレベルである。
A:2%未満
B:2%以上3%未満
C:3%以上4%未満
D:4%以上6%未満
E:6%以上 <Evaluation of stripping solution resistance>
A glass substrate is exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and each photosensitive resin composition is spin-coated on the substrate, and then pre-baked on a hot plate at 90 ° C. for 120 seconds to volatilize the solvent. A photosensitive resin composition layer having a thickness of 3.0 μm was formed. Subsequently, exposure was performed using an ultrahigh pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm 2 (illuminance: 20 mW / cm 2 , i-line), and the substrate was heated in an oven at 230 ° C./30 minutes.
The film thickness (T1) of the obtained cured film was measured. And after immersing the board | substrate with which this cured film was formed in monoethanolamine temperature-controlled at 80 degreeC at 60 degreeC for 5 minutes, the film thickness (t1) of the cured film after immersion was measured, and the film | membrane by immersion The thickness change rate {| t1-T1 | / T1} × 100 [%] was calculated. The results are shown in the table below. A smaller value is preferable, and A and B are at a level causing no problem in practical use.
A: Less than 2% B: 2% or more and less than 3% C: 3% or more and less than 4% D: 4% or more and less than 6% E: 6% or more
ガラス基板を、ヘキサメチルジシラザン(HMDS)蒸気下に30秒曝し、該基板に各感光性樹脂組成物をスピンコート塗布した後、90℃/120秒ホットプレート上でプリベークして溶剤を揮発させ、膜厚3.0μmの感光性樹脂組成物層を形成した。続いて超高圧水銀灯を用いて積算照射量が300mJ/cm2(照度:20mW/cm2、i線)となるように露光し、この基板をオーブンにて230℃/30分間加熱した後、さらにオーブンにて230℃/2時間加熱した。
得られた硬化膜の膜厚(T1)を測定した。そして、この硬化膜が形成された基板を80℃に温度制御されたNMP(N-メチルピロリドン)中に80℃で10分間浸漬させた後、浸漬後の硬化膜の膜厚(t1)を測定し、浸漬による膜厚変化率{|t1-T1|/T1}×100〔%〕を算出した。結果を下記表に示す。小さいほど好ましく、A、Bが実用上問題のないレベルである。
A:2%未満
B:2%以上3%未満
C:3%以上4%未満
D:4%以上6%未満
E:6%以上 <Evaluation of NMP resistance>
A glass substrate is exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and each photosensitive resin composition is spin-coated on the substrate, and then pre-baked on a hot plate at 90 ° C. for 120 seconds to volatilize the solvent. A photosensitive resin composition layer having a thickness of 3.0 μm was formed. Subsequently, using an ultra-high pressure mercury lamp, exposure was performed so that the integrated irradiation amount was 300 mJ / cm 2 (illuminance: 20 mW / cm 2 , i-line), and this substrate was heated in an oven at 230 ° C./30 minutes, Heated in an oven at 230 ° C./2 hours.
The film thickness (T1) of the obtained cured film was measured. Then, the substrate on which this cured film was formed was immersed in NMP (N-methylpyrrolidone) controlled at 80 ° C. for 10 minutes at 80 ° C., and the thickness (t1) of the cured film after immersion was measured. Then, the film thickness change rate {| t1-T1 | / T1} × 100 [%] by immersion was calculated. The results are shown in the table below. A smaller value is preferable, and A and B are at a level causing no problem in practical use.
A: Less than 2% B: 2% or more and less than 3% C: 3% or more and less than 4% D: 4% or more and less than 6% E: 6% or more
薄膜トランジスタ(TFT)を用いた液晶表示装置を以下の方法で作製した(図1、2参照)。特許第3321003号公報の図1及び図2に記載のアクティブマトリクス型液晶表示装置において、層間絶縁膜として硬化膜17を以下のようにして形成し、液晶表示装置を得た。
すなわち、ガラス基板6上にボトムゲート型のTFT1を形成し、このTFT1を覆う状態でSi3N4から成る絶縁膜3を形成した。次に、この絶縁膜3に、コンタクトホールを形成した後、このコンタクトホールを介してTFT1に接続される配線2(高さ1.0μm)を絶縁膜3上に形成した。 <Evaluation of display unevenness (panel display unevenness) in display device>
A liquid crystal display device using a thin film transistor (TFT) was manufactured by the following method (see FIGS. 1 and 2). In the active matrix type liquid crystal display device described in FIG. 1 and FIG. 2 of Japanese Patent No. 3321003, a cured
That is, the bottom
A:まったくムラがみられない(非常に良い)
B:ガラス基板の縁部分にかすかにムラが見られるが、表示部に問題なし(良い)
C:表示部にかすかにムラが見られるが実用レベル(普通)
D:表示部にムラがある(やや悪い)
E:表示部に強いムラがある(非常に悪い) A drive voltage is applied to the obtained liquid crystal display device, a gray test signal is input, the panel is continuously lit in an environment of 23 ° C., 50%, 1 atm, and the gray display after 1000 hours of lighting is visually observed. Observation was performed and the presence or absence of display unevenness was evaluated according to the following evaluation criteria.
A: No unevenness at all (very good)
B: Slight unevenness is observed on the edge of the glass substrate, but there is no problem in the display (good)
C: Slight unevenness on the display, but practical level (normal)
D: Display is uneven (somewhat bad)
E: Strong unevenness in display (very bad)
上述した<表示装置における表示ムラ(パネル表示ムラ)の評価>と同様の方法で液晶表示装置を作製した。得られた液晶表示装置に対して駆動電圧を印加し、グレイのテスト信号を入力させ、60℃、90%、2atmの環境でパネルを連続点灯させ、1000時間点灯後のグレイ表示を目視にて観察し、表示ムラの発生の有無を下記評価基準にしたがって評価した。
A:まったくムラがみられない(非常に良い)
B:ガラス基板の縁部分にかすかにムラが見られるが、表示部に問題なし(良い)
C:表示部にかすかにムラが見られるが実用レベル(普通)
D:表示部にムラがある(やや悪い)
E:表示部に強いムラがある(非常に悪い) <Evaluation of panel display unevenness under severe conditions such as high temperature, high humidity, and high pressure (evaluation of panel reliability of display device)>
A liquid crystal display device was produced in the same manner as described above in <Evaluation of display unevenness (panel display unevenness) in the display device>. A drive voltage is applied to the obtained liquid crystal display device, a gray test signal is input, the panel is continuously lit in an environment of 60 ° C., 90%, 2 atm, and the gray display after 1000 hours of lighting is visually observed. Observation was performed and the presence or absence of display unevenness was evaluated according to the following evaluation criteria.
A: No unevenness at all (very good)
B: Slight unevenness is observed on the edge of the glass substrate, but there is no problem in the display (good)
C: Slight unevenness on the display, but practical level (normal)
D: Display is uneven (somewhat bad)
E: Strong unevenness in display (very bad)
TFTを用いた有機EL表示装置を以下の方法で作製した(例えば、特開2011-209681号公報の図1参照)。
ガラス基板6上にボトムゲート型のTFT1を形成し、このTFT1を覆う状態でSi3N4から成る絶縁膜3を形成した。次に、この絶縁膜3に、ここでは図示を省略したコンタクトホールを形成した後、このコンタクトホールを介してTFT1に接続される配線2(高さ1.0μm)を絶縁膜3上に形成した。この配線2は、TFT1間又は、後の工程で形成される有機EL素子とTFT1とを接続するためのものである。 <Create organic EL display device>
An organic EL display device using a TFT was manufactured by the following method (for example, refer to FIG. 1 of JP 2011-209681 A).
A bottom
Claims (15)
- (A)(a1)酸基を有する構成単位及び(a2)架橋性基を有する構成単位を有する重合体、
(B)キノンジアジド化合物、
(C)少なくとも1種の含窒素ヘテロ環化合物、及び
(D)溶剤を含み、
前記含窒素ヘテロ環化合物は、含窒素芳香環を2つ以上含有し、その内2つの含窒素芳香環が縮合しているか直結しており、該含窒素芳香環が縮合しているか直結している構造中に、下記式(c-1)の構造、又は、下記式(c-2)の構造を含有する、感光性樹脂組成物。
(B) a quinonediazide compound,
(C) at least one nitrogen-containing heterocyclic compound, and (D) a solvent,
The nitrogen-containing heterocyclic compound contains two or more nitrogen-containing aromatic rings, of which two nitrogen-containing aromatic rings are condensed or directly connected, and the nitrogen-containing aromatic ring is condensed or directly connected. A photosensitive resin composition containing a structure of the following formula (c-1) or a structure of the following formula (c-2) in the structure.
- 前記(C)少なくとも1種の含窒素ヘテロ環化合物が、下記一般式(1)~(3)で表される含窒素ヘテロ環化合物から選ばれる少なくとも1種である、請求項1に記載の感光性樹脂組成物。
- 前記(C)少なくとも1種の含窒素ヘテロ環化合物が、下記一般式(1-1)、前記一般式(2)又は前記一般式(3)で表される含窒素ヘテロ環化合物から選ばれる少なくとも1種である、請求項2に記載の感光性樹脂組成物。
- 前記窒素ヘテロ環化合物が、4-ヒドロキシプテリジン、2-エチル-4-ヒドロキシプテリジン、1,10-フェナントロリン、5-メチル-1,10-フェナントロリン、2,2’-ビピリジン及び5,5’-ジメチル-2,2’-ビピリジンの少なくとも1種である、請求項1~3のいずれか1項に記載の感光性樹脂組成物。 The nitrogen heterocyclic compound is 4-hydroxypteridine, 2-ethyl-4-hydroxypteridine, 1,10-phenanthroline, 5-methyl-1,10-phenanthroline, 2,2′-bipyridine and 5,5′-dimethyl. The photosensitive resin composition according to any one of claims 1 to 3, which is at least one of -2,2'-bipyridine.
- 前記構成単位(a1)が、カルボキシル基及び/又はフェノール性水酸基を有する構成単位である、請求項1~4のいずれか1項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 4, wherein the structural unit (a1) is a structural unit having a carboxyl group and / or a phenolic hydroxyl group.
- 前記構成単位(a2)が、エポキシ基、オキセタニル基及び-NH-CH2-O-R(Rは水素原子又は炭素数1~20のアルキル基)で表される基よりなる群から選ばれる少なくとも1つを含む構成単位を含有する、請求項1~5のいずれか1項に記載の感光性樹脂組成物。 The structural unit (a2) is at least selected from the group consisting of an epoxy group, an oxetanyl group, and a group represented by —NH—CH 2 —O—R (where R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). The photosensitive resin composition according to any one of claims 1 to 5, comprising a structural unit containing one.
- 前記(A)重合体成分の合計100質量部に対し、前記(B)キノンジアジド化合物の配合量が10~50質量部である、請求項1~6のいずれか1項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 6, wherein a blending amount of the (B) quinonediazide compound is 10 to 50 parts by mass with respect to a total of 100 parts by mass of the (A) polymer component. object.
- 前記(A)重合体が、(メタ)アクリル酸に由来する構成単位を含有する、請求項1~7のいずれか1項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 7, wherein the polymer (A) contains a structural unit derived from (meth) acrylic acid.
- ポジ型である、請求項1~8のいずれか1項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 8, which is a positive type.
- (1)請求項1~9のいずれか1項に記載の感光性樹脂組成物を基板上に塗布する工程、
(2)塗布された感光性樹脂組成物から溶剤を除去する工程、
(3)溶剤が除去された感光性樹脂組成物を活性光線により露光する工程、
(4)露光された感光性樹脂組成物を水性現像液により現像する工程、及び、
(5)現像された感光性樹脂組成物を熱硬化するポストベーク工程、
を含む硬化膜の製造方法。 (1) a step of applying the photosensitive resin composition according to any one of claims 1 to 9 on a substrate;
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays,
(4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and
(5) a post-baking step of thermosetting the developed photosensitive resin composition;
The manufacturing method of the cured film containing this. - 前記現像工程後、前記ポストベーク工程前に、(6)現像された感光性樹脂組成物を全面露光する工程を含む、請求項10に記載の硬化膜の製造方法。 The manufacturing method of the cured film of Claim 10 including the process of exposing the developed photosensitive resin composition to the whole surface after the said image development process and before the said post-baking process.
- 前記ポストベーク工程で熱硬化して得られた硬化膜を有する基板に対し、ドライエッチングを行う工程を含む、請求項10又は11に記載の硬化膜の製造方法。 The manufacturing method of the cured film of Claim 10 or 11 including the process of dry-etching with respect to the board | substrate which has a cured film obtained by thermosetting at the said post-baking process.
- 請求項1~9のいずれか1項に記載の感光性樹脂組成物を硬化してなる硬化膜、又は、請求項10~12のいずれか1項に記載の硬化膜の製造方法により形成された硬化膜。 A cured film formed by curing the photosensitive resin composition according to any one of claims 1 to 9, or a cured film manufacturing method according to any one of claims 10 to 12. Cured film.
- 層間絶縁膜である、請求項13に記載の硬化膜。 The cured film of Claim 13 which is an interlayer insulation film.
- 請求項13又は14に記載の硬化膜を有する有機EL表示装置又は液晶表示装置。 An organic EL display device or a liquid crystal display device having the cured film according to claim 13 or 14.
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