WO2015046295A1 - Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device and organic el display device - Google Patents
Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device and organic el display device Download PDFInfo
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- WO2015046295A1 WO2015046295A1 PCT/JP2014/075366 JP2014075366W WO2015046295A1 WO 2015046295 A1 WO2015046295 A1 WO 2015046295A1 JP 2014075366 W JP2014075366 W JP 2014075366W WO 2015046295 A1 WO2015046295 A1 WO 2015046295A1
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- structural unit
- resin composition
- photosensitive resin
- polymer
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- 239000011342 resin composition Substances 0.000 title claims abstract description 141
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 97
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 229
- 239000002253 acid Substances 0.000 claims abstract description 69
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 50
- 239000002904 solvent Substances 0.000 claims abstract description 47
- 238000005904 alkaline hydrolysis reaction Methods 0.000 claims abstract description 9
- -1 oxime sulfonate compound Chemical class 0.000 claims description 129
- 125000000217 alkyl group Chemical group 0.000 claims description 128
- 125000004432 carbon atom Chemical group C* 0.000 claims description 91
- 125000001424 substituent group Chemical group 0.000 claims description 64
- 239000000758 substrate Substances 0.000 claims description 62
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 44
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 claims description 21
- 239000011229 interlayer Substances 0.000 claims description 21
- 125000003700 epoxy group Chemical group 0.000 claims description 20
- 125000003566 oxetanyl group Chemical group 0.000 claims description 20
- 125000003367 polycyclic group Chemical group 0.000 claims description 17
- 125000002950 monocyclic group Chemical group 0.000 claims description 14
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 11
- 238000009413 insulation Methods 0.000 claims description 4
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims 1
- 125000000686 lactone group Chemical group 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 50
- 239000000470 constituent Substances 0.000 abstract description 13
- 239000010408 film Substances 0.000 description 153
- 150000001875 compounds Chemical class 0.000 description 81
- 238000000034 method Methods 0.000 description 65
- 125000003118 aryl group Chemical group 0.000 description 56
- 239000000203 mixture Substances 0.000 description 51
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 40
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 39
- 239000000178 monomer Substances 0.000 description 37
- 150000002596 lactones Chemical group 0.000 description 36
- 238000011161 development Methods 0.000 description 32
- 230000018109 developmental process Effects 0.000 description 32
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 31
- 239000010410 layer Substances 0.000 description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- 125000005843 halogen group Chemical group 0.000 description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 23
- 239000000243 solution Substances 0.000 description 23
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 22
- 230000008569 process Effects 0.000 description 21
- 238000009835 boiling Methods 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 20
- 239000007864 aqueous solution Substances 0.000 description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 125000003545 alkoxy group Chemical group 0.000 description 18
- 239000003513 alkali Substances 0.000 description 17
- 239000003431 cross linking reagent Substances 0.000 description 17
- 239000007787 solid Substances 0.000 description 17
- 239000003963 antioxidant agent Substances 0.000 description 16
- 235000006708 antioxidants Nutrition 0.000 description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 14
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 14
- 230000007062 hydrolysis Effects 0.000 description 14
- 238000006460 hydrolysis reaction Methods 0.000 description 14
- 230000035945 sensitivity Effects 0.000 description 14
- 239000004094 surface-active agent Substances 0.000 description 14
- 125000005647 linker group Chemical group 0.000 description 13
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 13
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 12
- 238000004132 cross linking Methods 0.000 description 12
- 125000004122 cyclic group Chemical group 0.000 description 12
- 229910052731 fluorine Inorganic materials 0.000 description 12
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 12
- 229910052753 mercury Inorganic materials 0.000 description 12
- 150000001241 acetals Chemical class 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000003822 epoxy resin Substances 0.000 description 11
- 229920000647 polyepoxide Polymers 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 150000007514 bases Chemical class 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 125000000623 heterocyclic group Chemical group 0.000 description 10
- 150000003254 radicals Chemical class 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 9
- 125000001309 chloro group Chemical group Cl* 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 125000006165 cyclic alkyl group Chemical group 0.000 description 9
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- 125000001153 fluoro group Chemical group F* 0.000 description 9
- 239000012948 isocyanate Substances 0.000 description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 9
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 9
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 8
- 125000004093 cyano group Chemical group *C#N 0.000 description 8
- 125000000753 cycloalkyl group Chemical group 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 125000004430 oxygen atom Chemical group O* 0.000 description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 7
- 230000003078 antioxidant effect Effects 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 6
- 125000001072 heteroaryl group Chemical group 0.000 description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 6
- 235000019341 magnesium sulphate Nutrition 0.000 description 6
- 239000011976 maleic acid Substances 0.000 description 6
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- HXHCOXPZCUFAJI-UHFFFAOYSA-N prop-2-enoic acid;styrene Chemical compound OC(=O)C=C.C=CC1=CC=CC=C1 HXHCOXPZCUFAJI-UHFFFAOYSA-N 0.000 description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 5
- 125000002723 alicyclic group Chemical group 0.000 description 5
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 5
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- 238000002161 passivation Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 4
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
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- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
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- 238000000354 decomposition reaction Methods 0.000 description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 4
- 230000002349 favourable effect Effects 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
- 238000003384 imaging method Methods 0.000 description 4
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- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
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- 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 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- DVNYTAVYBRSTGK-UHFFFAOYSA-N 5-aminoimidazole-4-carboxamide Chemical compound NC(=O)C=1N=CNC=1N DVNYTAVYBRSTGK-UHFFFAOYSA-N 0.000 description 3
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- 125000005440 p-toluyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C(*)=O)C([H])([H])[H] 0.000 description 3
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- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
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- 238000000926 separation method Methods 0.000 description 3
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- 238000001228 spectrum Methods 0.000 description 3
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- 238000006467 substitution reaction Methods 0.000 description 3
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- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 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
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- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- CSVRUJBOWHSVMA-UHFFFAOYSA-N oxolan-2-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCO1 CSVRUJBOWHSVMA-UHFFFAOYSA-N 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920003050 poly-cycloolefin Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229940116423 propylene glycol diacetate Drugs 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000004007 reversed phase HPLC Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 229940081623 rose bengal Drugs 0.000 description 1
- 229930187593 rose bengal Natural products 0.000 description 1
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 description 1
- VDNLFJGJEQUWRB-UHFFFAOYSA-N rose bengal free acid Chemical compound OC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C(O)=C(I)C=C21 VDNLFJGJEQUWRB-UHFFFAOYSA-N 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000005394 sealing glass Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000005463 sulfonylimide group Chemical group 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- XKXIQBVKMABYQJ-UHFFFAOYSA-M tert-butyl carbonate Chemical group CC(C)(C)OC([O-])=O XKXIQBVKMABYQJ-UHFFFAOYSA-M 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000008027 tertiary esters Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- MCZDHTKJGDCTAE-UHFFFAOYSA-M tetrabutylazanium;acetate Chemical compound CC([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC MCZDHTKJGDCTAE-UHFFFAOYSA-M 0.000 description 1
- JCJNUSDBRRKQPC-UHFFFAOYSA-M tetrahexylazanium;hydroxide Chemical compound [OH-].CCCCCC[N+](CCCCCC)(CCCCCC)CCCCCC JCJNUSDBRRKQPC-UHFFFAOYSA-M 0.000 description 1
- MRYQZMHVZZSQRT-UHFFFAOYSA-M tetramethylazanium;acetate Chemical compound CC([O-])=O.C[N+](C)(C)C MRYQZMHVZZSQRT-UHFFFAOYSA-M 0.000 description 1
- IEVVGBFMAHJELO-UHFFFAOYSA-M tetramethylazanium;benzoate Chemical compound C[N+](C)(C)C.[O-]C(=O)C1=CC=CC=C1 IEVVGBFMAHJELO-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 150000004897 thiazines Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 229950003937 tolonium Drugs 0.000 description 1
- HNONEKILPDHFOL-UHFFFAOYSA-M tolonium chloride Chemical compound [Cl-].C1=C(C)C(N)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 HNONEKILPDHFOL-UHFFFAOYSA-M 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 125000001834 xanthenyl group Chemical class C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
Images
Classifications
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- 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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133345—Insulating layers
-
- 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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- 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
- G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
-
- 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
-
- 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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
- G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/38—Treatment before imagewise removal, e.g. prebaking
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
- H10K59/12—Active-matrix OLED [AMOLED] displays
- H10K59/124—Insulating layers formed between TFT elements and OLED elements
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/87—Passivation; Containers; Encapsulations
- H10K59/873—Encapsulations
Definitions
- the present invention relates to a photosensitive resin composition (hereinafter sometimes simply 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
- the present invention relates to a product and a method for producing a cured film using the product.
- an interlayer insulating film is generally used to insulate between wirings arranged in layers. Is provided.
- a material for forming the interlayer insulating film a photosensitive resin composition is widely used because the number of steps for obtaining a required pattern shape is small and a material having sufficient flatness is preferable (for example, , See Patent Document 1).
- Patent Document 2 discloses a radiation-sensitive material including a copolymer having a repeating unit having a tertiary ester group and a repeating unit having an acid anhydride structure.
- JP 2011-209681 A Japanese Patent Laid-Open No. 7-234511
- the present invention is intended to solve such problems, and is a photosensitive resin composition capable of improving chemical resistance, lowering a relative dielectric constant, and further improving pattern dimension stability.
- the purpose is to provide.
- the polymer component in the photosensitive resin composition has a structural unit having a group in which an acid group is protected by an acid-decomposable group, and a crosslinkable group.
- ⁇ 1> (A) a polymer component, (B) a photoacid generator, and (C) a solvent, (A) the polymer component includes at least one of the following (1) and (2), and Satisfy at least one of the following (3) and (4); (1) (a1) a polymer (A1) comprising a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (a2) a structural unit having a crosslinkable group, (2) a polymer (A2) containing the structural unit (a1) and a polymer (A3) containing the structural unit (a2); (3) At least one of the polymers (A1) to (A3) is a polymer containing (a4) a structural unit having a group that generates a carboxyl group by alkaline hydrolysis.
- a polymer (A4) containing the structural unit (a4) and not containing the structural unit (a1) and the structural unit (a2) is included;
- the photosensitive resin composition according to ⁇ 2>, wherein the carboxylic anhydride structure is a 5-membered or 6-membered cyclic carboxylic anhydride structure.
- R A1a represents a substituent
- n 1a R A1a s are independent and may be the same or different
- Z 1a may be —C ( ⁇ O) —O—C ( Represents a monocyclic or polycyclic structure containing ⁇ O) —
- n 1a represents an integer of 0 or more.
- ⁇ 5> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the structural unit (a4) is represented by the following formula (1A) and / or (1B).
- ⁇ 6> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the structural unit (a4) is represented by the formula (1A).
- ⁇ 7> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 6>, wherein (A) the polymer component includes (a3) a structural unit having an acid group.
- ⁇ 8> The photosensitive resin composition according to ⁇ 7>, wherein the proportion of the structural unit (a3) in the polymer component (A) is 5 to 20 mol%.
- ⁇ 9> Any one of ⁇ 1> to ⁇ 8>, wherein the crosslinkable group contained in the structural unit (a2) is at least one selected from an epoxy group, an oxetanyl group, and —NH—CH 2 —OR 2 Wherein R 2 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
- R 2 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
- the photoacid generator is an oxime sulfonate compound.
- ⁇ 12> (1) A step of applying the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 11> 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) 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.
- ⁇ 13> A cured film obtained by curing the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 11>, or a cured film formed by the method for producing a cured film according to ⁇ 12>.
- ⁇ 14> The cured film according to ⁇ 13>, which is an interlayer insulating film.
- ⁇ 15> A liquid crystal display device or an organic EL display device having the cured film according to ⁇ 13> or ⁇ 14>.
- the present invention it is possible to provide a photosensitive resin composition that can improve chemical resistance, reduce the relative dielectric constant, and improve the dimensional stability of the pattern.
- 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.
- 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 is a conceptual diagram of a configuration of an example of a liquid crystal display device.
- 1 is a conceptual diagram of a configuration of an example of a liquid crystal display device.
- the photosensitive resin composition of the present invention is (A) a polymer component, (B) a photoacid generator, and (C) a solvent, wherein the (A) polymer component includes at least one of the following (1) and (2), and Satisfy at least one of 3) and (4); (1) (a1) a polymer (A1) comprising a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (a2) a structural unit having a crosslinkable group, (2) The polymer (A2) containing the structural unit (a1) and the polymer (A3) containing the structural unit (a2); (3) At least one of the polymers (A1) to (A3) is a polymer containing (a4) a structural unit having a group that generates a carboxyl group by alkaline hydrolysis.
- the polymer (A4) containing the structural unit (a4) and not containing the structural unit (a1) and the structural unit (a2) is included;
- the proportion of the structural unit (a2) is 10 to 40 mol% and the proportion of the structural unit (a4) is 1 to 20 mol% with respect to all the structural units constituting the polymer component (A). It is characterized by that.
- ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which can make chemical-resistance favorable, can make a dielectric constant low, and can make pattern dimension stability favorable can be provided.
- pattern dimension stability refers to development conditions (for example, when developing with a developer (typically an alkaline aqueous solution) after performing an exposure process on a film obtained using a photosensitive resin composition. It means the variability of the pattern dimension with respect to the fluctuation of the development time, the alkali concentration of the developer, etc., and the smaller the fluctuation of the pattern dimension, the better.
- High pattern dimensional stability is one of the important performance issues in practical use. In the present invention, the reason why high pattern dimensional stability can be obtained is presumed, but it is considered that the reason is that the (A) polymer component has the structural unit (a4) at a ratio of a specific ratio or more. It is done.
- the structural unit (a4) is gradually changed to a hydrophilic structural unit under the action of hydrolysis with an alkaline developer, and the affinity of the polymer component (A) for the developer is gradually increased. Therefore, it is estimated that the development speed is controlled to a desired speed and stable development is realized.
- the (A) polymer component is the structural unit (a2). ) And (a4) at a specific ratio. That is, the structural unit (a2) is a structural unit necessary for improving chemical resistance, but if it is too much, it is considered that the relative dielectric constant tends to increase and the dimensional stability tends to decrease. Moreover, although the said structural unit (a4) is a structural unit required in order to obtain favorable pattern dimensional stability, when too large, there exists a tendency to reduce chemical resistance and / or to raise a dielectric constant. Conceivable.
- the polymer means a compound obtained by polymerizing 5 or more of one or more monomers (that is, having 5 or more repeating units) and having a molecular weight of 1,000 or more.
- the polymer component (A) in the present invention refers to a collection of all the polymers contained in the composition. Therefore, the surfactant described later may correspond to the polymer component (A) in the present invention.
- the weight average molecular weight of the polymer component is preferably 1,000 to 200,000, and more preferably 2,000 to 50,000.
- the ratio of the polymer obtained by addition polymerization of the compound having a polymerizable unsaturated bond in the total mass of the polymer component (A) is preferably 60 to 100% by mass, and preferably 90 to 100% by mass. More preferred is 98 to 100% by mass.
- a polymer obtained by addition polymerization of the compound having a polymerizable unsaturated bond is an ⁇ , ⁇ -unsaturated carboxylic acid (for example, (meth) acrylic acid, maleic acid, itaconic acid, etc.), an ester thereof, and an anhydride thereof. It is preferable that it is a polymer containing the structural unit derived from at least 1 sort (s).
- 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 60 mass% or more of a total solid.
- Examples of the polymer constituting the (A) polymer component in the present invention include the following (A1) to (A6).
- any of the polymers (A1) to (A6) is preferably a polymer obtained by addition polymerization of a compound having a polymerizable unsaturated bond. Further, the total ratio of the polymers (A1) to (A5) in the total mass of the polymer component (A) is preferably 60 to 100% by mass, and more preferably 90 to 100% by mass. 98 to 100% by mass is particularly preferable.
- the polymer component is (a1) a structural unit having an acid group protected by an acid-decomposable group, (a2) a structural unit having a crosslinkable group, and (a4) a carboxyl group by alkali hydrolysis. 1 type or more of polymers (henceforth a polymer (A1a)) which has the structural unit which has group are included.
- the polymer (A1a) may contain (a3) a structural unit having an acid group.
- the polymer component (A) may have at least one of the polymers (A2) to (A6). In this embodiment, it is preferable that content of polymers other than a polymer (A1a) is 10 mass% or less in (A) polymer component.
- a polymer component includes (a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group and (a2) a structural unit having a crosslinkable group (hereinafter referred to as polymer (A1b)). And (a4) a structural unit having a group having a carboxyl group by alkali hydrolysis, and (a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (a2) a cross-linking A polymer containing no structural unit having a functional group (hereinafter also referred to as polymer (A4)) is included.
- the polymer (A1b) usually does not contain the structural unit (a4).
- the polymer (A1b) and / or the polymer (A4) may further contain (a3) a structural unit having an acid group.
- the polymer component (A) may have at least one of the polymers (A2), (A3), (A5), and (A6).
- content of polymers other than a polymer (A1b) and a polymer (A4) is 10 mass% or less in (A) polymer component.
- the polymer (A2a) usually does not contain the structural unit (a2).
- the polymer (A3b) usually does not contain the structural unit (a1) and the structural unit (a4).
- the polymer (A2a) and / or the polymer (A3b) may further contain the structural unit (a3).
- the polymer component (A) may have at least one of the polymers (A4) to (A6).
- content of polymers other than a polymer (A2a) and a polymer (A3b) is 10 mass% or less in (A) polymer component.
- a polymer component includes (a1) a polymer containing a structural unit having an acid group protected by an acid-decomposable group (hereinafter also referred to as polymer (A2b)), and (a2) a crosslinkable group And (a4) a polymer (hereinafter, also referred to as polymer (A3a)) containing a structural unit having a group that generates a carboxyl group by alkali hydrolysis.
- the polymer (A2b) usually does not contain the structural unit (a2) and the structural unit (a4). Further, the polymer (A3a) usually does not contain the structural unit (a1).
- the polymer (A2b) and / or the polymer (A3a) may further contain the structural unit (a3).
- the polymer component (A) may have at least one of the polymers (A4) to (A6).
- content of polymers other than a polymer (A2b) and a polymer (A3a) is 10 mass% or less in (A) polymer component.
- a polymer component includes (a1) a polymer containing a structural unit having an acid group protected by an acid-decomposable group (hereinafter also referred to as polymer (A2b)), and (a2) a crosslinkable group A polymer containing a structural unit (hereinafter also referred to as polymer (A3b)), (a4) a structural unit having a group that generates a carboxyl group by alkali hydrolysis, and (a1) an acid group is acid-decomposed. And a polymer having no structural unit having a group protected by a functional group and (a2) a crosslinkable group (hereinafter also referred to as polymer (A4)).
- the polymer (A2b) usually does not contain the structural unit (a2) and the structural unit (a4).
- the polymer (A3b) usually does not contain the structural unit (a1) and the structural unit (a4). At least one of the polymer (A2b), the polymer (A3b) and the polymer (A4) may further contain the structural unit (a3).
- composition ratio of the polymer (A2b) to the polymer (A3b) is (mass ratio (polymer (A2b) / polymer)).
- (A3b)) is preferably 0.2 to 5, and more preferably 0.25 to 5.
- the (A) polymer component may have the said polymer (A5) and / or (A6).
- content of polymers other than a polymer (A2b), a polymer (A3b), and a polymer (A4) is 10 mass% or less in (A) polymer component.
- the content of the structural unit (a1) is preferably 3 to 80 mol%, preferably 8 to 75 mol% in the total structural units of the polymer component (A) from the viewpoint of improving sensitivity. Is more preferable, and 15 to 65 mol% is more preferable.
- the content of the structural unit (a2) is from 10 to 40 mol%, more preferably from 10 to 35 mol%, further preferably from 15 to 35 mol%, based on all the structural units of the polymer component (A). 35 mol% is still more preferable.
- the content of the structural unit (a4) is 1.0 to 20 mol%, more preferably 1.0 to 15 mol%, and more preferably 1.0 to 10 mol% in all the structural units of the polymer component (A).
- the content of the structural unit (a3) is preferably from 5 to 20 mol%, more preferably from 5 to 15 mol%, more preferably from 8 to 15 mol% is more preferable.
- the total content of the structural units (a1), (a2) and (a4) is preferably 20 to 100 mol%, more preferably 30 to 90 mol%, based on the total structural units of the polymer component (A).
- the total content of the structural units (a1), (a2), (a3), and (a4) is preferably 20 to 100 mol%, and preferably 30 to 100 mol%, based on the total structural units of the polymer component (A). Is more preferable.
- the molecular weight of the polymer contained in the polymer component is a weight average molecular weight in terms of polystyrene, preferably in the range of 1,000 to 200,000, more preferably in the range of 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 weight average molecular weight of the compound used in the present invention is defined as a polystyrene converted value by GPC measurement.
- the weight average molecular weight and number average molecular weight are, for example, HLC-8220 (manufactured by Tosoh Corporation), TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6.0 mm ID ⁇ 15.0 cm) as a column, and eluent. It can be determined by using tetrahydrofuran (THF).
- HLC-8220 manufactured by Tosoh Corporation
- TSKgel Super AWM-H manufactured by Tosoh Corporation, 6.0 mm ID ⁇ 15.0 cm
- THF tetrahydrofuran
- (A) Production Method of Polymer Component >> also, various methods are known for the synthesis method of the polymer component (A). For example, in order to form at least the structural units represented by the above (a1) and (a2), It can be synthesized by polymerizing a radical polymerizable monomer mixture containing the radical polymerizable monomer used in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction.
- the polymer component (A) preferably contains 50 mol% or more, more preferably 80 mol% or more of the structural unit derived from (meth) acrylic acid and / or its ester with respect to all the structural units. preferable.
- the polymer component has at least one structural unit (a1) having a group in which an acid group is protected by an acid-decomposable group.
- a polymer component has a structural unit (a1), it can be set as the photosensitive resin composition in which pattern formation by an exposure and image development process is possible.
- the “group in which the acid group is protected with an acid-decomposable group” in the present invention those known as an acid group and an acid-decomposable group can be used, and are not particularly limited.
- Specific examples of the acid group preferably include a carboxyl group and a phenolic hydroxyl group.
- Specific acid-decomposable groups include groups that are relatively easily decomposed by an acid (for example, an acetal functional group such as an ester structure, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group described later) or an acid.
- a group that is relatively difficult to decompose for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group
- a tertiary alkyl group such as a tert-butyl ester group
- a tertiary alkyl carbonate group such as a tert-butyl carbonate group
- the structural unit (a1) is preferably a structural unit having a protected carboxyl group protected with an acid-decomposable group or a structural unit having a protected phenolic hydroxyl group protected with an acid-decomposable group.
- the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group and the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group will be described in order. To do.
- the structural unit (a1-1) is a structural unit having a protected carboxyl group in which the carboxyl group of the structural unit having a carboxyl group is protected by an acid-decomposable group described in detail below.
- the structural unit having a carboxyl group that can be used for the structural unit (a1-1) is not particularly limited, and a known structural unit can be used.
- Examples thereof include a structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, or unsaturated tricarboxylic acid. It is done.
- the structural unit (a1-1-1) used as the structural unit having a carboxyl group will be described.
- ⁇ (a1-1-1) Structural Unit Derived from Unsaturated Carboxylic Acid etc. Having at least One Carboxyl Group in the Molecule >>>>>>>
- the unsaturated carboxylic acid used in the present invention include those listed below. That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, ⁇ -chloroacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acrylic acid. And leuoxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-phthalic acid, and the like.
- the unsaturated dicarboxylic acid examples include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.
- the unsaturated carboxylic acid may be a mono (2- (meth) acryloyloxyalkyl) ester of a polyvalent carboxylic acid.
- succinic acid mono (2-acryloyloxyethyl)
- succinic acid mono 2-methacryloyloxyethyl
- mono (2-acryloyloxyethyl) phthalate mono (2-methacryloyloxyethyl) phthalate and the like.
- the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both ends thereof.
- unsaturated carboxylic acid acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.
- acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyl Roxyethyl hexahydrophthalic acid or 2- (meth) acryloyloxyethyl phthalic acid is preferably used, and acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid is preferably used. More preferred.
- the structural unit (a1-1-1) may be composed of one type alone, or may be composed of two or more types.
- acid-decomposable group that can be used for the structural unit (a1-1) >>>>>
- the acid-decomposable group that can be used for the structural unit (a1-1) the acid-decomposable groups described above can be used.
- the acid-decomposable group is preferably a group having a structure protected in the form of an acetal.
- the carboxyl group is a protected carboxyl group in which the carboxyl group is protected in the form of an acetal, the basic physical properties of the photosensitive resin composition, particularly the sensitivity and pattern shape, the formation of contact holes, the storage stability of the photosensitive resin composition
- the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-10).
- the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-10)
- the entire protected carboxyl group is — (C ⁇ O) —O—CR 101
- the structure is R 102 (OR 103 ).
- R 101 and R 102 each independently represents a hydrogen atom, an alkyl group or an aryl group
- R 103 represents an alkyl group or an aryl group
- R 101 or R 102 and R 103 may be linked to form a cyclic ether.
- R 101 and R 102 each independently represent a hydrogen atom, an alkyl group, or an aryl group.
- R 103 represents an alkyl group or an aryl group.
- R 101 or R 102 may form a cyclic ether linked and the R 103.
- the alkyl group may be linear, branched or cyclic.
- R 101 and R 102 are preferably a hydrogen atom or an alkyl group, and at least one of R 101 and R 102 preferably represents an alkyl group. It is preferable that one of R 101 and R 102 is a hydrogen atom or a methyl group, and particularly preferably one of which is the other is a methyl group with a hydrogen atom.
- R 103 is preferably an alkyl group or an aryl group, and particularly preferably an alkyl group.
- the linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms.
- methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like.
- the cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms.
- Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.
- the alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group.
- R 101 , R 102 and R 103 When it has a halogen atom as a substituent, R 101 , R 102 and R 103 become a haloalkyl group, and when it has an aryl group as a substituent, R 101 , R 102 and R 103 become an aralkyl group.
- the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.
- the aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, an ⁇ -methylphenyl group, and a naphthyl group.
- the alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and more preferably a methoxy group or an ethoxy group.
- the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group is straight.
- the alkyl group is a chain or branched chain, it may have a cycloalkyl group having 3 to 12 carbon atoms as a substituent. These substituents may be further substituted with the above substituents.
- R 101 , R 102 and R 103 represent an aryl group
- the aryl group preferably has 6 to 12 carbon atoms, and preferably 6 to 10 carbon atoms. More preferred.
- the aryl group may have a substituent, and preferred examples of the substituent include an alkyl group having 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a 1-naphthyl group.
- R 101 , R 102 and R 103 can be bonded together to form a ring together with the carbon atom to which they are bonded.
- Examples of the ring structure when R 101 and R 102 , R 101 and R 103 or R 102 and R 103 are bonded include, for example, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, an adamantyl group, and a tetrahydropyrani group. And the like.
- radical polymerizable monomer used for forming the structural unit having a protected carboxyl group represented by the general formula (a1-10) a commercially available one may be used, or it may be synthesized by a known method. Things can also be used. For example, it can be synthesized by the synthesis method described in paragraph Nos. 0037 to 0040 of JP2011-212494A, the contents of which are incorporated herein.
- a first preferred embodiment of the structural unit (a1-1) is a structural unit represented by the following general formula (1-11).
- R 1 and R 2 each represent a hydrogen atom, an alkyl group or an aryl group, at least either one of R 1 and R 2 represent an alkyl group or an aryl group, R 3 Represents an alkyl group or an aryl group, and R 1 or R 2 and R 3 may be linked to form a cyclic ether, R 4 represents a hydrogen atom or a methyl group, and X represents a single bond or Represents an arylene group.
- R 1 and R 2 are alkyl groups, alkyl groups having 1 to 10 carbon atoms are preferred.
- R 1 and R 2 are aryl groups, a phenyl group is preferred.
- R 1 and R 2 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- R 3 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.
- X represents a single bond or an arylene group, and a single bond is preferable.
- a second preferred embodiment of the structural unit (a1-1) is a structural unit represented by the following general formula (1-12).
- Formula (1-12) (In the formula (1-12), R 121 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L 1 represents a carbonyl group or a phenylene group, and R 122 to R 128 each independently represents a hydrogen atom or Represents an alkyl group having 1 to 4 carbon atoms.) R 121 is preferably a hydrogen atom or a methyl group. L 1 is preferably a carbonyl group. R 122 to R 128 are preferably hydrogen atoms.
- R represents a hydrogen atom or a methyl group.
- the structural unit (a1-2) is a structural unit (a1-2-1) having a protected phenolic hydroxyl group in which the structural unit having a phenolic hydroxyl group is protected by an acid-decomposable group described in detail below.
- ⁇ (a1-2-1) Structural Unit Having Phenolic Hydroxyl Group examples include a hydroxystyrene structural unit and a structural unit in a novolac resin.
- a structural unit derived from hydroxystyrene or ⁇ -methylhydroxystyrene includes: It is preferable from the viewpoint of sensitivity.
- a structural unit represented by the following general formula (a1-20) is also preferable from the viewpoint of sensitivity.
- R 220 represents a hydrogen atom or a methyl group
- R 221 represents a single bond or a divalent linking group
- R 222 represents a halogen atom or a straight chain having 1 to 5 carbon atoms or Represents a branched alkyl group
- a represents an integer of 1 to 5
- b represents an integer of 0 to 4
- a + b is 5 or less
- R 222 is 2 or more, these R 222 may be different from each other or the same.
- R 220 represents a hydrogen atom or a methyl group, and is preferably a methyl group.
- R 221 represents a single bond or a divalent linking group. A single bond is preferable because the sensitivity can be improved and the transparency of the cured film can be further improved.
- the divalent linking group of R 221 may be exemplified alkylene groups, specific examples R 221 is an alkylene group, a methylene group, an ethylene group, a propylene group, isopropylene group, n- butylene group, isobutylene group, tert -Butylene group, pentylene group, isopentylene group, neopentylene group, hexylene group and the like.
- R 221 is a single bond, a methylene group, or an ethylene group.
- the divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group.
- A represents an integer of 1 to 5, but a is preferably 1 or 2 and more preferably 1 from the viewpoint of the effects of the present invention and the ease of production.
- the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4-position when the carbon atom bonded to R 221 is defined as the reference (first position).
- R 222 is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. It is done. Among these, a chlorine atom, a bromine atom, a methyl group, or an ethyl group is preferable from the viewpoint of easy production.
- B represents 0 or an integer of 1 to 4;
- acid-decomposable group that can be used for the structural unit (a1-2) >>>>>
- the acid-decomposable group that can be used for the structural unit (a1-2) as with the acid-decomposable group that can be used for the structural unit (a1-1), known ones can be used. It is not limited.
- a structural unit having a protected phenolic hydroxyl group protected with acetal is a basic physical property of the photosensitive resin composition, particularly sensitivity and pattern shape, storage stability of the photosensitive resin composition, contact This is preferable from the viewpoint of hole formability.
- the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of an acetal represented by the above general formula (a1-10).
- the protected phenolic hydroxyl group as a whole is —Ar—O—CR 101 R
- the structure is 102 (OR 103 ).
- Ar represents an arylene group.
- Examples of the radical polymerizable monomer used for forming a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected in the form of an acetal include paragraph number 0042 of JP2011-215590A. And the like.
- a 1-alkoxyalkyl protector of 4-hydroxyphenyl methacrylate and a tetrahydropyranyl protector of 4-hydroxyphenyl methacrylate are preferable from the viewpoint of transparency.
- acetal protecting group for the phenolic hydroxyl group examples include a 1-alkoxyalkyl group, such as a 1-ethoxyethyl group, a 1-methoxyethyl group, a 1-n-butoxyethyl group, and a 1-isobutoxyethyl group.
- 1- (2-chloroethoxy) ethyl group, 1- (2-ethylhexyloxy) ethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, 1- (2-cyclohexylethoxy) ethyl group, 1 -A benzyloxyethyl group etc. can be mentioned, These can be used individually or in combination of 2 or more types.
- the radical polymerizable monomer used for forming the structural unit (a1-2) a commercially available one may be used, or one synthesized by a known method may be used. For example, it can be synthesized by reacting a compound having a phenolic hydroxyl group with vinyl ether in the presence of an acid catalyst. In the above synthesis, a monomer having a phenolic hydroxyl group may be previously copolymerized with another monomer, and then reacted with vinyl ether in the presence of an acid catalyst.
- the structural unit (a1-1) is characterized by faster development than the structural unit (a1-2). Therefore, when it is desired to develop quickly, the structural unit (a1-1) is preferable. Conversely, when it is desired to delay the development, it is preferable to use the structural unit (a1-2).
- the polymer component has a structural unit (a2) having a crosslinkable group, and the structural unit (a2) is 10 to 40 with respect to all the structural units constituting the (A) polymer component. Contains mol%.
- the crosslinkable group is defined as a group that can react with each other by a heat treatment to form a covalent bond, or a functional group that can react with an acid group to form a covalent bond.
- the heat treatment is preferably a step (post-bake step) of thermosetting after development.
- the temperature at which the structural unit having a crosslinkable group starts thermal crosslinking is preferably, for example, 70 to 200 ° C., more preferably 90 to 180 ° C.
- the crosslinking initiation temperature of a structural unit derived from glycidyl methacrylate is 115 ° C.
- the crosslinking initiation temperature of a structural unit derived from 3-ethyl-3-oxetanylmethyl methacrylate described later is 151 ° C.
- These crosslinking initiation temperatures can be measured using, for example, real-time infrared spectroscopy (RT-IR). For example, it can be measured using FTS60A / 896 or FTS7000 manufactured by Digilab. For example, the following measuring methods are mentioned.
- Each photosensitive resin composition is slit-coated on an aluminum plate (mirror finish, thickness: 100 ⁇ m), then pre-baked on a hot plate at 95 ° C. for 140 seconds to volatilize the solvent, and the photosensitive resin composition layer is formed into a film thickness It was formed to 4.0 ⁇ m, a Digilab FTS7000 was equipped with a Digilab Spectra Mono and a reflective heating stage with a temperature controller made by Systems Engineering, and time-resolved FT-IR measurement (integration: 10 Scan / spectra, Time resolution: 10 sec / spectra, detector: TGS).
- Preferred embodiments of the structural unit having a crosslinkable group include an epoxy group, an oxetanyl group, a group represented by —NH—CH 2 —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) and ethylene.
- the (A-1) polymer component preferably contains a structural unit containing at least one of an epoxy group and an oxetanyl group, and a structural unit containing an epoxy group It is more preferable to contain. In more detail, the following are mentioned.
- the (A) polymer component preferably contains a structural unit having an epoxy group and / or an oxetanyl group (hereinafter also referred to as a structural unit (a2-1)).
- the structural unit (a2-1) may have at least one epoxy group or oxetanyl group in one structural unit, and includes one or more epoxy groups, one or more oxetanyl groups, and two or more epoxy groups.
- Group may have two or more oxetanyl groups, and is not particularly limited, but preferably has a total of 1 to 3 epoxy groups and / or oxetanyl groups, and a total of epoxy groups and / or oxetanyl groups It is more preferable to have one or two, and it is even more preferable to have one epoxy group or one oxetanyl group.
- 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 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.
- radical polymerizable monomer used for forming the structural unit (a1-2-1) having an epoxy group and / or oxetanyl group include a monomer having a methacrylate structure and an acrylate ester. A monomer containing a structure is preferred.
- glycidyl methacrylate 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinyl.
- Benzyl glycidyl ether, acrylic acid (3-ethyloxetane-3-yl) methyl, and methacrylic acid (3-ethyloxetane-3-yl) methyl are from the viewpoint of improving the copolymerization reactivity and various properties of the cured film. preferable.
- 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.
- (a2-2) Structural unit having an ethylenically unsaturated group >>>
- the structural unit (a2) having a crosslinkable group there may be mentioned the 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.
- the polymer component (A) used in the present invention is 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 preferable.
- 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) (In general formula (a2-30), R 1 represents a hydrogen atom or a methyl group, and 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.
- 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 polymer component has (a4) one or more structural units having a group that generates a carboxyl group by alkaline hydrolysis, and the structural unit (a4) comprises (A) all of the constituents of the polymer component. It is contained in an amount of 1.0 to 20 mol% based on the structural unit.
- the structural unit (a4) is converted into a structural unit having a carboxyl group by the action of alkali hydrolysis.
- a standard solution JIS standard, aqueous solution containing K0022
- a structural unit having a monomer change rate of 80% or more is defined as a structural unit that satisfies the conditions of the present invention.
- the analytical instrument for example, liquid chromatography can be used, and the reaction rate can be calculated from the measured peak integrated value (area) of the monomer.
- the structural unit represented by the following structural formula (a4-1) has a rate of change of 80% or more when the alkali hydrolyzability of the corresponding monomer (a4-1m) is measured by the above measuring method.
- the structural unit is determined to be a structural unit corresponding to the structural unit (a4).
- the group that generates a carboxyl group by alkali hydrolysis is not limited to a specific structure as long as the above hydrolyzable conditions are satisfied.
- Specific examples include carboxylic anhydrides, cyclic or acyclic esters, and acid halides. , Groups having a structure such as carbamate, sulfonic anhydride, cyclic or acyclic sulfonate, cyclic or acyclic sulfinate, alkoxysilyl, and the like.
- the group that generates a carboxyl group by alkaline hydrolysis is preferably a group having a carboxylic acid anhydride structure or a group having a lactone structure (that is, a cyclic ester structure), and preferably a group having a carboxylic acid anhydride structure. More preferred is a group having a 5-membered or 6-membered cyclic carboxylic acid anhydride structure.
- the carboxylic acid anhydride structure may be either chain or cyclic, but is a cyclic carboxylic acid anhydride structure. It is preferable.
- the number of ring members is preferably a 5- to 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and particularly preferably a 5-membered ring.
- other ring structures may be condensed to the cyclic carboxylic acid anhydride structure to form a polycyclic structure, but it is preferable that no polycyclic structure is formed.
- the other ring structures are condensed in a form that forms a bicyclo structure or a spiro structure, and the number of other ring structures that are condensed. Is preferably 1 to 5, and more preferably 1 to 3.
- examples of other ring structures include a cyclic hydrocarbon group having 3 to 20 carbon atoms, a heterocyclic group having 3 to 20 carbon atoms, and the like.
- the heterocyclic group is not particularly limited, and examples thereof include those having one or more heteroatoms out of the atoms constituting the ring or aromatic heterocyclic groups.
- heterocyclic group a 5-membered ring or a 6-membered ring is preferable, and a 5-membered ring is especially preferable.
- the heterocyclic group preferably contains at least one oxygen atom, and examples thereof include an oxolane ring, an oxane ring, and a dioxane ring.
- the carboxylic anhydride structure used in the present invention may or may not have a substituent, but preferably does not have a substituent.
- substituents include, but are not limited to, for example, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, Examples include a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, and an acid-decomposable group. More preferred are an alkyl group having 1 to 4 carbon atoms and a cyano group.
- the alkyl group a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms is preferable. More preferred are ⁇ 3 alkyl groups.
- the number of substituents is not particularly limited, but is preferably 1 to 4, and more preferably 1 or 2.
- the carboxylic anhydride structure used in the present invention has a plurality of substituents, the plurality of substituents may be the same as or different from each other. Further, when another ring structure is condensed to the carboxylic acid anhydride structure, the other ring structure may have a substituent.
- the structural unit having a carboxylic acid anhydride structure used in the present invention preferably includes a partial structure represented by the following general formula (1).
- General formula (1) (In the general formula (1), R A1a represents a substituent, and n 1a R A1a s are independent and may be the same or different.
- Z 1a is —C ( ⁇ O) —O—C Represents a monocyclic or polycyclic structure containing ( ⁇ O) —, and n 1a represents an integer of 0 or more.)
- R A1a represents a substituent, and n 1a R A1a s are independent and may be the same or different.
- R A1a has the same meaning as the substituent that the carboxylic anhydride structure described above may have, and the preferred range is also the same.
- Z 1a represents a monocyclic or polycyclic structure containing —C ( ⁇ O) —O—C ( ⁇ O) —, and preferably represents a monocyclic structure.
- Z 1a represents a monocyclic structure, it preferably forms a 5- to 7-membered ring, more preferably forms a 5- or 6-membered ring, and particularly preferably forms a 5-membered ring.
- n 1a represents an integer of 0 or more, preferably an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0.
- a plurality of substituents may be the same as or different from each other. A plurality of substituents may be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.
- Rx represents a hydrogen atom, a methyl group, a CH 2 OH group, or a CF 3 group.
- the structural unit (a4) is preferably represented by the following formula (1A) or (1B), and particularly preferably represented by the formula (1A).
- composition of the present invention structural units having two or more carboxylic anhydride structures may be used in combination.
- the lactone structure is not particularly limited as long as the hydrolyzability condition is satisfied.
- the lactone structure used in the present invention is preferably a lactone structure that forms a 5- to 7-membered ring, and more preferably a lactone structure that forms a 5-membered or 6-membered ring.
- a lactone structure forming a 5- to 7-membered ring may be condensed with another ring structure on the lactone structure to form a polycyclic structure.
- other ring structures are not condensed to the lactone structure.
- the lactone structure forming a 5- to 7-membered ring is condensed with another ring structure
- the other ring structure is preferably condensed so as to form a bicyclo structure or a spiro structure.
- examples of other ring structures include a cyclic hydrocarbon group having 3 to 20 carbon atoms, a heterocyclic group having 3 to 20 carbon atoms, and the like.
- the heterocyclic group is not particularly limited, and examples thereof include those having one or more heteroatoms out of the atoms constituting the ring or aromatic heterocyclic groups.
- heterocyclic group a 5-membered ring or a 6-membered ring is preferable, and a 5-membered ring is especially preferable.
- the heterocyclic group preferably contains at least one oxygen atom, and examples thereof include an oxolane ring, an oxane ring, and a dioxane ring.
- the number of the other ring structures condensed to the lactone structure is preferably 1 to 5 1 to 3 are more preferable.
- the lactone structure used in the present invention may or may not have a substituent, but preferably does not have a substituent.
- substituents include, but are not limited to, for example, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, Examples include a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, and an acid-decomposable group. More preferred are an alkyl group having 1 to 4 carbon atoms and a cyano group.
- the alkyl group a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms is preferable. More preferred are ⁇ 3 alkyl groups.
- the number of substituents is not particularly limited, but is preferably 1 to 4, and more preferably 1 or 2.
- the lactone structure used in the present invention has a plurality of substituents, the plurality of substituents may be the same as or different from each other. Further, when another ring structure is condensed to the lactone structure, this other ring structure may have a substituent.
- the structural unit having a lactone structure used in the present invention preferably contains a partial structure represented by the following general formula (2-1).
- Formula (2-1) (In General Formula (2-1), R A1 represents a substituent, and n1 R A1 s are independent and may be the same or different. Z 1 is —O—C ( ⁇ O) — And n1 represents an integer of 0 or more.)
- R A1 represents a substituent, and n1 R A1 s are independent and may be the same or different.
- R A1 has the same meaning as the substituent that the above-mentioned lactone structure may have, and the preferred range is also the same.
- Z 1 represents a monocyclic or polycyclic structure containing —O—C ( ⁇ O) —, and preferably represents a monocyclic structure.
- the monocyclic structure is preferably a lactone structure that forms a 5- to 7-membered ring, and more preferably a lactone structure that forms a 5-membered or 6-membered ring.
- the polycyclic structure preferably has a condensed lactone structure with another cyclic structure forming a bicyclo structure or a spiro structure.
- the other ring structures are synonymous with the other ring structures described above, and the preferred ranges are also the same.
- n1 represents an integer of 0 or more, preferably an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0.
- a plurality of substituents may be the same as or different from each other.
- a plurality of substituents may be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.
- the structural unit (a4) is a structural unit containing a lactone structure, it is preferably represented by the following general formula (2-2).
- Formula (2-2) (In the general formula (2-2), R X1 represents a hydrogen atom or an alkyl group. R A2 represents a substituent, and n2 R A2 s are independent and may be the same or different. 1 represents a single bond or a divalent linking group, Z 2 represents a monocyclic or polycyclic structure containing a group represented by —O—C ( ⁇ O) —, and n2 represents an integer of 0 or more. ) In general formula (2-2), R X1 represents a hydrogen atom or an alkyl group.
- alkyl group a linear or branched alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.
- the alkyl group may have a substituent.
- a hydroxyl group or a halogen atom is preferable.
- R A2 represents a substituent, and n2 R A2 s are independent and may be the same or different.
- R A2 has the same meaning as the substituent that the lactone structure described above may have, and the preferred range is also the same.
- a 1 represents a single bond or a divalent linking group.
- Examples of the divalent linking group include a linear, branched or cyclic alkylene group, an arylene group, —O—, —COO—, —S—, —NR ′′ —, —CO—, and —NR ′′ CO—. , —SO 2 — and the like, or a combination of these groups.
- R ′′ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom.
- Examples of the divalent linking group include —O—, —COO—, —S—, —NH— and At least one of —CO— or a group thereof and — (CH 2 ) m — (m is an integer of 1 to 10, preferably an integer of 1 to 6, more preferably an integer of 1 to 4) Groups consisting of combinations are preferred.
- Z 2 represents a monocyclic or polycyclic structure containing a group represented by —O—C ( ⁇ O) —, and has the same meaning as Z 1 in general formula (2-1). The preferred range is also the same.
- n2 represents an integer of 0 or more, and is synonymous with n1 in general formula (1), and the preferred range is also the same.
- the structural unit (a4) is a structural unit containing a lactone structure, it is preferably represented by the following general formula (2-3).
- General formula (2-3) (In the general formula (2-3), R X2 represents a hydrogen atom or an alkyl group. R A3 represents a substituent, and n3 R A3 s are independent and may be the same or different. 2 represents a single bond or a divalent linking group, Z 3 represents a monocyclic or polycyclic structure containing a group represented by —O—C ( ⁇ O) —, and n3 represents an integer of 0 or more.
- X 1 represents an oxygen atom or —NR ′′ —.
- R ′′ represents a hydrogen atom or an alkyl group.
- R A3 represents a substituent, and n3 R A3 s are independent and may be the same or different.
- R A3 has the same meaning as the substituent that the lactone structure described above may have, and the preferred range is also the same.
- a 2 represents a single bond or a divalent linking group.
- the divalent linking group is synonymous with the case where A 1 in the general formula (2-2) represents a divalent linking group.
- a preferred divalent linking group is at least one of —COO— and —CO—, or these groups, and — (CH 2 ) m — (m is an integer of 1 to 10, preferably 1 to 6.
- a 2 in the general formula (2-3) is preferably a single bond.
- Z 3 represents a monocyclic or polycyclic structure containing a group represented by —O—C ( ⁇ O) —, and has the same meaning as Z 1 in general formula (2-1). The preferred range is also the same.
- n3 represents an integer of 0 or more, and is synonymous with n1 in general formula (2-1), and the preferred range is also the same.
- X 1 represents an oxygen atom or —NR ′′ —, preferably an oxygen atom.
- R ′′ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferable.
- the structure represented by the general formula (2-1) preferably includes a structure represented by any one of the following general formulas (LC1-1) to (LC1-21). More preferred structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), (LC1-17), Particularly preferred structures are (LC1-1), (LC1-4), and (LC1-17).
- the structural unit (a4) includes such a structure, the relative dielectric constant can be further lowered while improving the chemical resistance of the composition of the present invention.
- (Rb 2 ) represents a substituent, which may or may not have ( That is, in the general formulas (LC1-1) to (LC1-21), n4 is 0).
- the preferred substituent (Rb 2 ) is synonymous with the substituent that the above-mentioned lactone structure may have, and the preferred range is also the same.
- n4 has the same meaning as n1 in the general formula (2-1), and the preferred range is also the same.
- the structural unit having a lactone structure usually has an optical isomer, but any optical isomer may be used.
- One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used.
- the optical purity (ee) thereof is preferably 90% or more, more preferably 95% or more.
- the structural unit (a4) when it has a lactone structure, it is preferably represented by the following formula (2A), (2B), (2C) or (2D), and represented by the formula (2A). More preferably.
- the composition of the present invention may have two or more structural units as the structural unit (a4).
- a structural unit having an acid anhydride structure and a structural unit having a lactone structure may be used in combination. it can.
- the total amount is a numerical range of the structural unit (a4) mentioned later.
- the polymer component preferably contains (a3) a structural unit having an acid group.
- the acid group is usually incorporated into the polymer as a structural unit containing an acid group using a monomer capable of forming an acid group. By including such a structural unit containing an acid group in the polymer, the polymer tends to be easily dissolved in an alkaline developer.
- Acid groups used in the present invention include those derived from carboxylic acid groups, those derived from sulfonamide groups, those derived from phosphonic acid groups, those derived from sulfonic acid groups, those derived from phenolic hydroxyl groups, sulfones Examples include amide groups, sulfonylimide groups, and the like, and those derived from carboxylic acid groups and / or those derived from phenolic hydroxyl groups are preferred.
- the structural unit containing an acid group used in the present invention is more 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. .
- the polymer component contains (a3) a structural unit having an acid group
- at least one of the polymers (A1) to (A4) has the above structural unit (a3).
- a polymer having none of the structural units (a1), (a2) and (a4) and having the structural unit (a3) (hereinafter, also referred to as polymer (A5)) can be used as (A ) It may be contained in the polymer component.
- the polymer (A5) is preferably a resin having a carboxyl group in the side chain.
- a resin having a carboxyl group in the side chain For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048
- methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc. and side chain Examples thereof include acidic cellulose derivatives having a carboxyl group, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, and high molecular polymers having a (meth) acryloyl group in the side chain.
- benzyl (meth) acrylate / (meth) acrylic acid copolymer 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / Benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzine Methacrylate / methacrylic acid copolymer and the like.
- Known polymer compounds described in JP-A-2003-233179, JP-A-2009-52020, and the like can be used, and the contents thereof are incorporated herein. These polymers may contain only 1 type and may contain 2 or more types.
- ARUFON UC-3000 commercially available ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above, manufactured by Toagosei Co., Ltd.) Joncryl 690, Joncryl 678, Joncryl 67, Joncryl 586, Joncryl 67 (above, manufactured by BASF) and the like can also be used.
- a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group it is particularly preferable from the viewpoint of sensitivity to contain a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group.
- a structural unit having a carboxyl group or a structural unit having 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 polymer component (A) may have other structural units (a5) in addition to the structural units (a1), (a2), (a4) and (a3). Good.
- the polymer component (A) has the structural unit (a5), at least one of the polymers (A1) to (A5) may have the structural unit (a5).
- a polymer having no structural unit (a1) to (a4) and having the structural unit (a5) also referred to as polymer (A6)
- it is contained in the polymer component (A). Also good.
- the raw material monomer for forming the structural unit (a5) is not particularly limited, and examples thereof include styrenes, (meth) acrylic acid alkyl esters, (meth) acrylic acid cyclic alkyl esters, (meth) acrylic acid aryl esters, and unsaturated compounds. Examples thereof include dicarboxylic acid diesters, bicyclo unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, and other unsaturated compounds.
- the monomer which becomes a structural unit (a5) can be used individually or in combination of 2 or more types.
- the structural unit (a5) is styrene, methyl styrene, ⁇ -methyl styrene, acetoxy styrene, methoxy styrene, ethoxy styrene, chlorostyrene, methyl vinyl benzoate, ethyl vinyl benzoate, or methyl (meth) acrylate.
- styrenes and groups having an aliphatic cyclic skeleton are preferable from the viewpoint of electrical characteristics.
- Specific examples include styrene, methylstyrene, ⁇ -methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and benzyl (meth) acrylate.
- (meth) acrylic acid alkyl ester is preferable as the other structural unit (a5) from the viewpoint of adhesion.
- Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate, and methyl (meth) acrylate is more preferable.
- the photosensitive resin composition of the present invention contains (B) a photoacid generator.
- the photoacid generator used in the present invention is preferably a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but is not limited to its chemical structure.
- a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
- the photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and an acid of 2 or less. Most preferred are photoacid generators that generate.
- photoacid generator examples include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound from the viewpoint of insulation.
- photoacid generators can be used singly or in combination of two or more.
- trichloromethyl-s-triazines diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane derivatives include the compounds described in paragraph numbers 0083 to 0088 of JP2011-212494A. These can be illustrated and their contents are incorporated herein.
- Preferred examples of the oxime sulfonate compound that is, a compound having an oxime sulfonate structure include compounds having an oxime sulfonate structure represented by the following general formula (B1-1).
- General formula (B1-1) (In the general formula (B1-1), R 21 represents an alkyl group or an aryl group. The wavy line represents a bond with another group.)
- any group may be substituted, and the alkyl group in R 21 may be linear, branched or cyclic. Acceptable substituents are described below.
- the alkyl group for R 21 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
- the alkyl group represented by R 21 has a halogen atom, an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group, etc.). It may be substituted with a bridged alicyclic group, preferably a bicycloalkyl group or the like.
- aryl group for R 21 an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable.
- the aryl group of R 21 may be substituted with a lower alkyl group, an alkoxy group, or a halogen atom.
- the compound containing the oxime sulfonate structure represented by the general formula (B1-1) is preferably an oxime sulfonate compound represented by the following general formula (B1-2).
- General formula (B1-2) (In the formula (B1-2), R 42 represents an optionally substituted alkyl group or aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, and m4 represents 0-3. Represents an integer, and when m4 is 2 or 3, a plurality of Xs may be the same or different.
- the alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
- the alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
- the halogen atom as X is preferably a chlorine atom or a fluorine atom.
- m4 is preferably 0 or 1.
- m4 is 1
- X is a methyl group
- substitution position of X is the ortho position
- R 42 is a linear alkyl group having 1 to 10 carbon atoms
- 7,7- A compound that is a dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferred.
- the compound containing an oxime sulfonate structure represented by the general formula (B1-1) is also preferably an oxime sulfonate compound represented by the following general formula (B1-3).
- General formula (B1-3) (In Formula (B1-3), R 43 has the same meaning as R 42 in Formula (B1-2), and X 1 represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. Represents an alkoxy group, a cyano group or a nitro group, and n4 represents an integer of 0 to 5.)
- R 43 in the above general formula (B1-3) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n—.
- a propyl group, a perfluoro-n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferable, and an n-octyl group is particularly preferable.
- X 1 is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
- n4 is preferably from 0 to 2, particularly preferably from 0 to 1.
- description in paragraphs 0080 to 0082 of JP2012-163937A can be referred to, and the contents thereof are described in this application. Incorporated in the description.
- the compound containing an oxime sulfonate structure represented by the general formula (B1-1) is also preferably a compound represented by the following general formula (OS-1).
- R 101 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or Represents a heteroaryl group.
- R102 represents an alkyl group or an aryl group.
- X 101 represents —O—, —S—, —NH—, —NR 105 —, —CH 2 —, —CR 106 H—, or —CR 105 R 107 —, wherein R 105 to R 107 are alkyl groups.
- R 121 ⁇ R 124 are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amido group, a sulfo group, a cyano group, Or an aryl group is represented. Two of R 121 to R 124 may be bonded to each other to form a ring.
- R 121 to R 124 are preferably a hydrogen atom, a halogen atom and an alkyl group, and an embodiment in which at least two of R 121 to R 124 are bonded to each other to form an aryl group is also preferred. Among these, an embodiment in which R 121 to R 124 are all hydrogen atoms is preferable from the viewpoint of sensitivity. Any of the aforementioned functional groups may further have a substituent.
- the compound represented by the general formula (OS-1) is, for example, a compound represented by the general formula (OS-2) described in paragraph numbers 0087 to 0089 of JP2012-163937A Which is incorporated herein by reference.
- the compound represented by the general formula (OS-1) that can be suitably used in the present invention include compounds described in paragraph numbers 0128 to 0132 of JP2011-221494A (exemplified compounds b-1 to b-34), but the present invention is not limited thereto.
- the compound containing the oxime sulfonate structure represented by the general formula (B1-1) is represented by the following general formula (OS-3), the following general formula (OS-4) or the following general formula (OS- The oxime sulfonate compound represented by 5) is preferred.
- R 22 , R 25 and R 28 each independently represents an alkyl group, an aryl group or a heteroaryl group
- R 23 , R 26 and R 29 Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom
- R 24 , R 27 and R 30 each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group.
- X 1 to X 3 each independently represents an oxygen atom or a sulfur atom
- n 1 to n 3 each independently represents 1 or 2
- m 1 to m 3 each independently represents an integer of 0 to 6 Represents.
- the compound containing an oxime sulfonate structure represented by the above general formula (B1-1) is, for example, a compound represented by the general formula (OS-6) described in paragraph 0117 of JP2012-163937A. Particularly preferred is a compound represented by any of (OS-11), the contents of which are incorporated herein. Preferred ranges in the above general formulas (OS-6) to (OS-11) are preferred ranges of (OS-6) to (OS-11) described in paragraph numbers 0110 to 0112 of JP2011-221494A. The contents of which are incorporated herein by reference.
- oxime sulfonate compound represented by the general formula (OS-3) to the general formula (OS-5) include compounds described in paragraph numbers 0114 to 0120 of JP2011-221494A. The contents of which are incorporated herein by reference. The present invention is not limited to these.
- the compound containing an oxime sulfonate structure represented by the general formula (B1-1) is also preferably an oxime sulfonate compound represented by the following general formula (B1-4).
- General formula (B1-4) (In the general formula (B1-4), R 1 represents an alkyl group or an aryl group, R 2 represents an alkyl group, an aryl group, or a heteroaryl group. R 3 to R 6 each represents a hydrogen atom. Represents an alkyl group, an aryl group, or a halogen atom, provided that R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 may combine to form an alicyclic ring or aromatic ring. , -O- or S-).
- R 1 represents an alkyl group or an aryl group.
- the alkyl group is preferably a branched alkyl group or a cyclic alkyl group.
- the alkyl group preferably has 3 to 10 carbon atoms. In particular, when the alkyl group has a branched structure, an alkyl group having 3 to 6 carbon atoms is preferable. When the alkyl group has a cyclic structure, an alkyl group having 5 to 7 carbon atoms is preferable.
- alkyl group examples include propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, 1,1-dimethylpropyl group, hexyl group. 2-ethylhexyl group, cyclohexyl group, octyl group and the like, preferably isopropyl group, tert-butyl group, neopentyl group, and cyclohexyl group.
- the aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms, and still more preferably 6 to 7 carbon atoms.
- Examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferable.
- the alkyl group and aryl group represented by R 1 may have a substituent.
- substituents examples include a halogen atom (a fluorine atom, a chloro atom, a bromine atom, an iodine atom), a linear, branched or cyclic alkyl group (for example, a methyl group, an ethyl group, a propyl group), an alkenyl group, an alkynyl group, Aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, cyano group, carboxyl group, hydroxyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, heterocyclic oxy group, acyloxy group, amino group, A nitro group, a hydrazino group, a heterocyclic group, etc. are mentioned. Further, these groups may be further substituted. Preferably, they are a halogen atom and a methyl group.
- R 1 is preferably an alkyl group from the viewpoint of transparency, and R 1 has a branched structure having 3 to 6 carbon atoms from the viewpoint of achieving both storage stability and sensitivity.
- An alkyl group, an alkyl group having a cyclic structure having 5 to 7 carbon atoms, or a phenyl group is preferable, and an alkyl group having a branched structure having 3 to 6 carbon atoms or an alkyl group having a cyclic structure having 5 to 7 carbon atoms is more preferable. .
- an isopropyl group, a tert-butyl group, a neopentyl group, and a cyclohexyl group are preferable, and a tert-butyl group and a cyclohexyl group are more preferable.
- R 2 represents an alkyl group, an aryl group, or a heteroaryl group.
- the alkyl group represented by R 2 is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.
- Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, and a cyclohexyl group. It is a group.
- As the aryl group an aryl group having 6 to 10 carbon atoms is preferable.
- Examples of the aryl group include a phenyl group, a naphthyl group, a p-toluyl group (p-methylphenyl group), and a phenyl group and a p-toluyl group are preferable.
- Examples of the heteroaryl group include a pyrrole group, an indole group, a carbazole group, a furan group, and a thiophene group.
- the alkyl group, aryl group, and heteroaryl group represented by R 2 may have a substituent. As a substituent, it is synonymous with the substituent which the alkyl group and aryl group which R ⁇ 1 > may have.
- R 2 is preferably an alkyl group or an aryl group, more preferably an aryl group, and more preferably a phenyl group.
- As the substituent for the phenyl group a methyl group is preferred.
- R 3 to R 6 each represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom (a fluorine atom, a chloro atom, a bromine atom, or an iodine atom).
- the alkyl group represented by R 3 to R 6 has the same meaning as the alkyl group represented by R 2 , and the preferred range is also the same.
- the aryl group represented by R 3 to R 6 has the same meaning as the aryl group represented by R 1 , and the preferred range is also the same.
- R 3 to R 6 , R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 may combine to form a ring, and the ring may form an alicyclic ring or an aromatic ring. It is preferable that a benzene ring is more preferable.
- R 3 to R 6 are a hydrogen atom, an alkyl group, a halogen atom (fluorine atom, chloro atom, bromine atom), or R 3 and R 4 , R 4 and R 5 , or R 5 and R 6
- a benzene ring is preferably formed, and a hydrogen atom, a methyl group, a fluorine atom, a chloro atom, a bromine atom, or R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 are combined to form a benzene ring Is more preferable.
- Preferred embodiments of R 3 to R 6 are as follows. (Aspect 1) At least two are hydrogen atoms.
- Ts represents a tosyl group (p-toluenesulfonyl group)
- Me represents a methyl group
- Bu represents an n-butyl group
- Ph represents a phenyl group.
- each R 7 independently represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
- N represents an integer from 0 to 4.
- X represents an integer from 1 to 20
- Y represents an integer from 0 to 20
- Z represents an integer from 0 to 20
- W represents an integer from 0 to 5.
- imide sulfonate compound examples include compounds described in paragraph 0084 of JP2012-155115A, the contents of which are incorporated herein.
- the imidosulfonate compound is also preferably a compound having the following structure.
- each R independently represents a hydrogen atom and an organic group composed of a carbon atom and / or an oxygen atom. Two or more Rs may be bonded to each other to form a ring. The total number of carbon atoms and oxygen atoms in each R is preferably 16 or less. Examples of such imide sulfonate compounds include the following compounds.
- the addition amount of the photoacid generator is preferably 0.1 to 10% by mass relative to the total solid content in the photosensitive resin composition of the present invention. More preferably, the content is 5 to 10% by mass.
- Two or more photoacid generators can be used in combination. When using together 2 or more types of photo-acid generators, it is preferable that the total amount is the said numerical range.
- the photosensitive resin composition of the present invention contains 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 a solvent.
- 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 monomethyl ether.
- Propylene glycol monoalkyl ethers such as acetate, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers such as diethylene glycol ethyl methyl ether, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, Dipropylene glycol dialkyl ethers, dipropylene glycol monoal Ether acetates, esters, ketones, amides, lactones and the like.
- 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 in the photosensitive resin composition of the present invention is preferably 50 to 95 parts by mass and more preferably 60 to 90 parts by mass with respect to 100 parts by mass of all components in the photosensitive resin composition. preferable.
- a sensitizer, a crosslinking agent, an alkoxysilane compound, a basic compound, a surfactant, and an antioxidant can be preferably added to the photosensitive resin composition of the present invention as necessary.
- the photosensitive resin composition of the present invention includes an acid proliferation agent, a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor.
- Known additives such as can be added.
- compounds described in paragraph numbers 0201 to 0224 of JP2012-8859A can be used, and the contents thereof are incorporated in the present specification.
- the photosensitive resin composition of the present invention preferably contains a sensitizer in combination with a photoacid generator in order to promote its decomposition.
- the sensitizer absorbs actinic rays or radiation and enters an electronically excited state.
- the sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur.
- a photo-acid generator raise
- Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm.
- Polynuclear aromatics eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene
- xanthenes Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal
- xanthones eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone
- cyanines eg, thiacarbocyanine, oxacarbocyanine
- merocyanines For example, merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg, thionine, methylene blue, to
- polynuclear aromatics polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable.
- polynuclear aromatics anthracene derivatives are most preferred.
- the addition amount of the sensitizer in the photosensitive resin composition of the present invention is preferably 0 to 100% by mass with respect to the total solid content in the photosensitive resin composition of the present invention, preferably 0.1 to 50%. More preferably, it is more preferably 0.5 to 20% by mass. Two or more sensitizers can be used in combination.
- the photosensitive resin composition of this invention contains 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. However, in the present invention, the crosslinking agent does not include the case where it is a polymer, that is, the case where it is one of the polymer components (A).
- a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, a compound having at least one ethylenically unsaturated double bond, a blocked isocyanate compound, etc. can be added.
- the addition amount of the crosslinking agent in the photosensitive resin composition of the present invention is preferably 0.01 to 50% by mass with respect to the total solid content in the photosensitive resin composition of the present invention, preferably 0.1 to It is more preferably 30% by mass, and further preferably 0.5 to 20% 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.
- JER152, JER157S70, JER157S65, JER806, JER828, JER1007 are commercially available products described in paragraph No. 0189 of JP2011-221494, etc.
- bisphenol A type epoxy resin bisphenol F type epoxy resin, phenol novolac type epoxy resin and aliphatic epoxy resin are more preferable, and bisphenol A type epoxy resin is particularly preferable.
- the compound having two or more oxetanyl groups in the molecule Aron oxetane OXT-121, OXT-221, OX-SQ, and PNOX (manufactured by Toagosei Co., Ltd.) can be used.
- alkoxymethyl group-containing crosslinking agents described in paragraph numbers 0107 to 0108 of JP2012-8223A, and compounds having at least one ethylenically unsaturated double bond are also preferable. These contents can be used and are incorporated herein.
- alkoxymethyl group-containing crosslinking agent alkoxymethylated glycoluril is preferable.
- 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.
- the blocked isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 ° C. to 250 ° C.
- the skeleton of the blocked isocyanate compound is not particularly limited and may be any as long as it has two isocyanate groups in one molecule, and may be aliphatic, alicyclic or aromatic.
- Polyisocyanates may be used, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene Diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2, '-Diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3
- tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are particularly preferable.
- 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.
- 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.
- Examples of the oxime compound include oxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and acetoxime.
- Examples of the lactam compound include ⁇ -caprolactam and ⁇ -butyrolactam.
- Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
- Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
- Examples of the amine compound include primary amines and secondary amines, which may be aromatic amines, aliphatic amines, and alicyclic amines, and examples thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.
- Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
- Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
- Examples of the mercaptan compound include alkyl mercaptans and aryl mercaptans.
- 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 (above , Manufactured by Asahi Kasei Chemicals Corporation, Death Module B 1100, BL1265 MPA / X, BL
- the photosensitive resin composition of the present invention may contain an alkoxysilane compound.
- 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.
- silane coupling agents include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxypropyltriacoxysilane, ⁇ -glycidoxypropyl dialkoxysilane, and ⁇ -methacryloxy.
- ⁇ -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% by mass, and preferably 0.5 to 20% by mass with respect to the total solid content in the photosensitive resin composition of the present invention. Is more preferable.
- the photosensitive resin composition of the present invention may contain a basic compound.
- the basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include the compounds described in JP-A 2011-212494, paragraphs 0204 to 0207, the contents of which are incorporated herein.
- aliphatic amine examples include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and the like.
- examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
- aromatic amine examples include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
- heterocyclic amine examples include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, diazabicyclononene, nicotine, nicotinic acid, nicotinamide, quinoline, 8- Oxyquinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea, 1,5-diazabicyclo [ 4.3.0]- And 5-nonene and
- Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide, and the like.
- Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate and the like.
- the basic compounds that can be used in the present invention may be used singly or in combination of two or more.
- the content of the basic compound in the photosensitive resin composition of the present invention is preferably 0.001 to 3% by mass with respect to the total solid content in the photosensitive resin composition of the present invention, preferably 0.005 to More preferably, it is 1 mass%.
- the photosensitive resin composition of the present invention may contain 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
- a and B represented by the following general formula (I-1-1) as a surfactant and tetrahydrofuran (THF) as a solvent.
- a copolymer having a polystyrene-equivalent weight average molecular weight (Mw) of 1,000 or more and 10,000 or less can be mentioned as a preferred example.
- R 401 and R 403 each independently represent a hydrogen atom or a methyl group
- R 402 represents a linear alkylene group having 1 to 4 carbon atoms
- R 404 represents hydrogen.
- L represents an alkylene group having 3 to 6 carbon atoms
- p and q are mass percentages representing a polymerization ratio
- p is 10 mass% to 80 mass%.
- the following numerical values are represented, q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18, and s represents an integer of 1 to 10.
- L is preferably a branched alkylene group represented by the following general formula (I-1-2).
- R 405 in formula (I-1-2) represents an alkyl group having 1 to 4 carbon atoms, and preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability with respect to the coated surface. And an alkyl group having 2 or 3 carbon atoms is more preferred.
- the weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
- These surfactants can be used individually by 1 type or in mixture of 2 or more types.
- the addition amount of the surfactant in the photosensitive resin composition of the present invention is preferably 10% by mass or less, and preferably 0.001 to 10% by mass with respect to the total solid content in the photosensitive resin composition of the present invention. More preferably, the content is 0.01 to 3% by mass.
- 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.
- phenolic antioxidants hindered amine antioxidants, phosphorus antioxidants, amide antioxidants, hydrazide antioxidants, sulfur oxidations are particularly preferred from the viewpoint of coloring of the cured film and reduction of the film thickness.
- Inhibitors are preferred, and phenolic antioxidants are most preferred. These may be used individually by 1 type and may mix 2 or more types. Specific examples include the compounds described in JP-A-2005-29515, paragraphs 0026 to 0031, the contents of which are incorporated herein.
- Preferred commercial products include ADK STAB AO-60, ADK STAB AO-20, ADK STAB AO-80, ADK STAB LA-52, ADK STAB LA-81, ADK STAB AO-412S, ADK STAB PEP-36, IRGANOX 1035, IRGANOX 1098, and Tinuvin 144. Can be mentioned.
- the content of the antioxidant is preferably 0.1 to 10% by mass, and more preferably 0.2 to 5% by mass, based on the total solid content in the photosensitive resin composition of the present invention. It is particularly preferably 0.5 to 4% 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.
- an acid proliferating agent can be used for the purpose of improving sensitivity.
- the acid proliferating agent that can be used in the present invention is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid. is there.
- Specific examples of such an acid proliferating agent include acid proliferating agents described in paragraph numbers 0226 to 0228 of JP2011-221494A, the contents of which are incorporated herein.
- the photosensitive resin composition of the present invention can contain a development accelerator.
- a development accelerator those described in paragraphs 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification.
- a development accelerator may be used individually by 1 type, and can also use 2 or more types together.
- the addition amount of the development accelerator in the photosensitive resin composition of the present invention is preferably 0 to 30 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive composition, from the viewpoint of sensitivity and residual film ratio. 1 to 20 parts by mass is more preferable, and 0.5 to 10 parts by mass is most preferable.
- thermal radical generators described in paragraphs 0120 to 0121 of JP2012-8223A, nitrogen-containing compounds and thermal acid generators described in WO2011-133604A1 can be used. Is incorporated herein by reference.
- a resin composition can be prepared by preparing a solution in which components are dissolved in a solvent in advance and then mixing them in a predetermined ratio.
- 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) A step of 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 post-baking step of thermosetting the developed photosensitive resin composition.
- Each step will be described below in order.
- the photosensitive resin composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent.
- substrate cleaning such as alkali cleaning or plasma cleaning
- 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.
- 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 coating method on 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 it is usually used in the range of 0.5 to 10 ⁇ m. Further, before applying the composition used in the present invention to the substrate, it is possible to apply a so-called pre-wet method as described in JP-A-2009-145395.
- 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.
- the photoacid generator is decomposed to generate an acid.
- the acid-decomposable group contained in the coating film component is decomposed to generate an acid group such as a carboxyl group or a phenolic hydroxyl group.
- 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, and i-line (365 nm), h-line (405 nm), 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 .
- PEB Post Exposure Bake
- PEB can promote the generation of an acid group such as a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group.
- the temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C.
- the acid-decomposable group in the present invention has low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to generate an acid group such as a carboxyl group or a phenolic hydroxyl group, it is not necessarily PEB. It is not indispensable that a positive image can be formed by development.
- a copolymer having a free carboxyl group or an acid group such as 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 an acid group such as 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; tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline hydroxide, and other ammonium hydroxides; sodium silicate, metasilicic acid An aqueous solution such as sodium can be used.
- 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
- tetramethylammonium hydroxide tetraethylam
- 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 0.4 to 2.5% by mass aqueous solution of tetramethylammonium hydroxide can be mentioned.
- 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 acid-decomposable group is thermally decomposed to generate a carboxyl group or a phenolic hydroxyl group, and then crosslinked with a crosslinkable group, a crosslinking agent or the like.
- a cured film can be formed.
- 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.
- 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.
- the entire surface of the patterned substrate was re-exposed with actinic rays (post-exposure), and then post-baked to generate an acid from the photoacid generator present in the unexposed portion, thereby performing a crosslinking step. It can function as a catalyst to promote, and can accelerate the curing reaction of the film.
- the preferred exposure amount in the case of including a post-exposure step preferably 100 ⁇ 3,000mJ / cm 2, particularly preferably 100 ⁇ 500mJ / 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 method that can be adopted by the liquid crystal display device of the present invention, a TN (Twisted Nematic) method, a VA (Virtual Alignment) method, an IPS (In-Place-Switching) method, an FFS (Frings Field Switching) method, an OCB (Optical) method. 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 organic insulating film (115) of JP-A-2005-284291 It can be used as an organic insulating film (212).
- FIG. 2 is a conceptual cross-sectional view showing an example of the active matrix type 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.
- 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.
- the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type.
- 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. 1 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 for connecting the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
- the flattening film 4 is formed on the insulating film 3 with the unevenness due to the wiring 2 being 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 first 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.
- the photosensitive resin composition of the present invention and the cured film of the present invention are not limited to the above-mentioned applications, and can be used for various applications.
- 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. Can be suitably used.
- 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 liquid crystal display devices 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.
- MATHF 2-tetrahydrofuranyl methacrylate (synthetic product)
- MAEVE 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
- MATHP Tetrahydro-2H-pyran-2-yl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
- OXE-30 3-ethyl-3-oxetanylmethyl methacrylate (manufactured by Osaka Organic Chemical Industry) (thermal crosslinking start temperature 151 ° C.)
- GMA Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) (thermal crosslinking start temperature: 115 ° C.)
- NBMA n-butoxymethylacrylamide (manufactured by Tokyo Chemical Industry)
- MAA Methacrylic acid
- the oily product was distilled under reduced pressure to obtain 125 g of tetrahydro-2H-furan-2-yl methacrylate (MATHF) as a colorless oily product having a boiling point (bp.) Of 54 to 56 ° C./3.5 mmHg (yield: 80%). ).
- MATHF tetrahydro-2H-furan-2-yl methacrylate
- the obtained organic layer was washed with saturated brine (50 mL), dried over magnesium sulfate, concentrated under reduced pressure to remove volatile components, and a yellow oil was obtained.
- Solution B and Solution C were measured by reversed-phase HPLC (* 2), and obtained from the following formula based on the peak area (integrated value) of each monomer obtained by normalization from the peak area (integrated value) of anisole. The obtained value was defined as the hydrolysis rate (%) of each monomer.
- the structural unit derived from AICA, MAAN, and ⁇ BLMA is a structural unit having a group that generates a carboxyl group by (a4) alkaline hydrolysis.
- the structural unit derived from PMMA does not satisfy the hydrolyzable condition, it has a lactone ring as a partial structure, but is not a structural unit corresponding to (a4).
- PGMEA 40 g was placed in a three-necked flask and heated to 75 ° C. in a nitrogen atmosphere.
- MATH in an amount of 30 mol% in all monomer components
- GMA in an amount of 12 mol% in all monomer components
- AICA in an amount of 1.2 mol% in all monomer components
- MAA in an amount of 10 mol% in all monomer components
- MMA in an amount of 36.8 mol% in all monomer components
- St an amount of 10 mol% in all monomer components
- the total mass of the body was 50 g), and a solution in which V-65 (amount corresponding to 4 mol% with respect to the total of all monomer components) was dissolved in PGMEA (10 g) at room temperature was added dropwise over 2 hours.
- B-1 Structure shown below (Synthesis example will be described later)
- B-2 Structure shown below (synthesis example will be described later)
- B-3 Structure shown below (synthesized according to the method described in paragraph 0108 of JP-T-2002-528451)
- B-4 PAG-103 (trade name, structure shown below, manufactured by BASF)
- B-5 GSID-26-1, triarylsulfonium salt (manufactured by BASF)
- B-6 The following compound B-7: Structure shown below (synthesized according to the method described in paragraph No. 0128 of WO2011 / 087011)
- the obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, and the mixture was warmed to room temperature and stirred. The reaction was continued for 1 hour. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered, reslurried with methanol (20 mL), filtered and dried to obtain the compound of B-1 (the above structure) (2.3 g).
- Crude B-2A was purified by silica gel column chromatography to obtain 1.7 g of intermediate B-9A.
- Mix B-2A (1.7 g) and p-xylene (6 mL) add 0.23 g of p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and heat at 140 ° C. with stirring for 2 hours. did.
- water and ethyl acetate were added to the reaction mixture and the phases were separated.
- MEDG diethylene glycol ethyl methyl ether
- Hisolv EDM manufactured by Toho Chemical Industry Co., Ltd.
- PGMEA propylene glycol monomethyl ether acetate
- H-1 Diazabicyclononene (manufactured by Tokyo Chemical Industry Co., Ltd.)
- H-2 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
- H-3 Compound having the following structure
- G-1 ⁇ -glycidoxypropyltrimethoxysilane (KBM-403: manufactured by Shin-Etsu Chemical Co., Ltd.)
- G-2 Bis (triethoxysilylpropyl) tetrasulfide (KBE-846, manufactured by Shin-Etsu Chemical Co., Ltd.)
- G-3 Decyltrimethoxysilane (KBM-3103, manufactured by Shin-Etsu Chemical Co., Ltd.)
- W-1 Perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula (F-554, manufactured by DIC) Since W-1 is a polymer, it is treated as one of the polymer components (A) when calculating the content of each component in the present invention.
- F-1 JER828 (manufactured by Mitsubishi Chemical Holdings Corporation)
- F-2 JER1007 (manufactured by Mitsubishi Chemical Holdings Corporation)
- F-3 JER157S65 (Mitsubishi Chemical Holdings Co., Ltd.)
- F-4 Celoxide 2021P (manufactured by Daicel Corporation)
- F-5 Duranate 17B-60P (Asahi Kasei Chemicals Corporation)
- F-6 Denacol EX-321L (manufactured by Nagase ChemteX Corporation)
- F-7 Takenate B-870N (Mitsui Chemicals, Inc.)
- J-1 ADK STAB AO-60 (manufactured by ADEKA Corporation)
- J-2 Irganox 1098 (BASF)
- J-3 Irganox 1035 (manufactured by BASF)
- K-1 Joncryl 67 (manufactured by BASF)
- K-2 ARUFON UC-3910 (manufactured by Toa Gosei Co., Ltd.)
- ⁇ Adjustment of photosensitive resin composition In each example and each comparative example, polymer components, photoacid generators, sensitizers, crosslinking agents, alkoxysilane compounds, basic compounds, surfactants, and others so that the solid content ratios shown in the following table are obtained. Were dissolved and mixed in PGMEA so that the solid content concentration was 25% by mass and filtered through a polytetrafluoroethylene filter having a diameter of 0.2 ⁇ m to obtain a photosensitive resin composition.
- an alkaline developer (2.38 mass% tetramethylammonium hydroxide aqueous solution) was used at 23 ° C., 60 ° C. After developing for 2 seconds, it was rinsed with ultrapure water for 1 minute. The obtained board
- substrate was observed with the optical microscope, and the dimension of the pattern of 10 micrometers line / 10micrometer space was observed. Next, the same operation and observation were performed except that the same operation as described above was performed with a development time of 180 seconds.
- A, B, and C are practically no problem levels.
- F The dimensional variation is 1.5 ⁇ m or more.
- Each photosensitive resin composition was spin-coated on a bare wafer substrate (N-type low resistance) (manufactured by SUMCO), then pre-baked on a hot plate at 90 ° C. for 120 seconds to volatilize the solvent, and the film thickness was 3.0 ⁇ m.
- a photosensitive resin composition layer was formed. Subsequently, exposure was performed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm 2 (energy intensity: 20 mW / cm 2 , i-line), and the substrate was heated in an oven at 230 ° C./30 minutes.
- the column of parts by mass in the total solid content of the polymer (A) is a mass part when the total solid content is 100 parts by mass.
- the composition of the present invention contains (a2) a crosslinkable group and (a4) a group that generates carboxylic acid by alkali hydrolysis in a specific ratio in the (A) polymer component.
- a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 200 was obtained. That is, using the photosensitive resin composition of Example 1, a cured film 17 was formed as an interlayer insulating film. As a pretreatment for improving the wettability between the substrate of paragraph No. 0058 and the interlayer insulating film 17 of Japanese Patent No. 3321003, the substrate is exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and then the photosensitivity of Example 1 The resin composition was spin-coated and then pre-baked on a hot plate at 90 ° C.
- HMDS hexamethyldisilazane
- the obtained photosensitive resin composition layer was subjected to 40 mJ / cm 2 (energy intensity: 20 mW / cm 2 ) through a hole pattern mask of 10 ⁇ m ⁇ using MPA 5500CF (high pressure mercury lamp) manufactured by Canon Inc. , I-line).
- the exposed photosensitive resin composition layer was subjected to paddle development at 23 ° C./60 seconds with an alkaline developer (0.4% tetramethylammonium hydroxide aqueous solution), and then rinsed with ultrapure water for 20 seconds.
- the whole surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm 2 (energy intensity: 20 mW / cm 2 , i-line), and then the substrate was heated in an oven at 230 ° C. for 30 minutes.
- a cured film was obtained.
- the applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking.
- liquid crystal display device When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
- Example 201 A liquid crystal display device similar to that of Example 200 was changed to obtain the same liquid crystal display device. That is, even when the photosensitive resin composition of Example 1 was applied without the hexamethyldisilazane (HMDS) treatment, which is a pretreatment of the substrate, the resulting cured film was good with no chipping or peeling off of the pattern. It was a state. Further, the performance as a liquid crystal display device was good as in Example 200. This is presumably because the composition of the present invention has excellent adhesion to the substrate. From the viewpoint of improving productivity, it is also preferable to omit the substrate pretreatment step.
- HMDS hexamethyldisilazane
- Example 202 A liquid crystal display device similar to that of Example 200 was changed to obtain the same liquid crystal display device. That is, even if a vacuum drying step (VCD) was introduced after pre-baking, the obtained cured film was in a good state with no pattern chipping or peeling. Further, the performance as a liquid crystal display device was good as in Example 200. It is also preferable to introduce a reduced-pressure drying step from the viewpoint of suppressing coating unevenness according to the solid content concentration and the film thickness of the composition.
- VCD vacuum drying step
- Example 203 A liquid crystal display device similar to that of Example 200 was changed to obtain the same liquid crystal display device. That is, even if the PEB process was introduced between the development process and the mask exposure, the obtained cured film was in a good state with no pattern chipping or peeling. Further, the performance as a liquid crystal display device was good as in Example 200. From the viewpoint of improving dimensional stability, it is also preferable to introduce a PEB process.
- Example 204 A liquid crystal display device similar to that of Example 200 was changed to obtain the same liquid crystal display device. That is, even when the alkaline developer is changed from a 0.4% tetramethylammonium hydroxide aqueous solution to a 2.38% tetramethylammonium hydroxide aqueous solution, the resulting cured film has good pattern free of chipping and peeling. It was a state. Further, the performance as a liquid crystal display device was good as in Example 200. This is presumably because the composition of the present invention has excellent adhesion to the substrate.
- Example 205 A liquid crystal display device similar to that of Example 200 was changed to obtain the same liquid crystal display device. That is, even when the alkali development method was changed from paddle development to shower development, the obtained cured film was in a good state with no pattern chipping or peeling. Further, the performance as a liquid crystal display device was good as in Example 200. This is presumably because the composition of the present invention has excellent adhesion to the substrate.
- Example 206 A liquid crystal display device similar to that of Example 200 was changed to obtain the same liquid crystal display device. That is, even when the alkaline developer was changed from a 0.4% tetramethylammonium hydroxide aqueous solution to a 0.04% KOH aqueous solution, the resulting cured film was in a good state with no pattern chipping or peeling. It was. Further, the performance as a liquid crystal display device was good as in Example 200. This is presumably because the composition of the present invention has excellent adhesion to the substrate.
- Example 207 A liquid crystal display device similar to that of Example 200 was changed to obtain the same liquid crystal display device. That is, the entire surface exposure step after development and rinsing was omitted, and the cured film was obtained by heating in an oven at 230 ° C. for 30 minutes. The performance of the obtained liquid crystal display device was as good as in Example 200. This seems to be because the composition of the present invention is excellent in chemical resistance. From the viewpoint of improving productivity, it is also preferable to omit the entire exposure process.
- Example 208> A liquid crystal display device similar to that of Example 200 was changed to obtain the same liquid crystal display device. That is, a step of heating on a hot plate at 100 ° C. for 3 minutes was added between the entire surface exposure step and the 230 ° C./30 minute heating step in the oven. The performance of the obtained liquid crystal display device was as good as in Example 200. It is also preferable to add this process from the viewpoint of adjusting the shape of the hole pattern.
- Example 209 A liquid crystal display device similar to that of Example 200 was changed to obtain the same liquid crystal display device. That is, a process of heating on a hot plate at 100 ° C. for 3 minutes was added between the development / rinse process and the entire surface exposure process. The performance of the obtained liquid crystal display device was as good as in Example 200. It is also preferable to add this process from the viewpoint of adjusting the shape of the hole pattern.
- An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 2).
- 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 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 composition of Example 1 on a substrate, pre-baking (90 ° C./120 seconds) on a hot plate, and then applying high pressure from above the mask. After irradiation with i-line (365 nm) at 45 mJ / cm 2 (energy intensity 20 mW / cm 2 ) using a mercury lamp, development is performed with an alkaline aqueous solution (0.4% TMAH aqueous solution) to form a pattern.
- the integrated dose was 300 mJ / cm 2 (energy intensity: 20 mW / cm 2 , i-line), and a heat treatment was performed at 230 ° C./30 minutes.
- the applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking.
- the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2,000 nm.
- 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 at 50 ° C. using a resist stripper (remover 100, manufactured by AZ Electronic Materials).
- the first electrode 5 thus obtained corresponds to the anode of the organic EL element.
- an insulating film 8 having a shape covering the periphery of the first electrode 5 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 film 8, it is possible to prevent a short circuit between the first electrode 5 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.
- FIG. 3 is a conceptual diagram of an example of the liquid crystal display device.
- an array substrate formed up to just before the organic passivation film 109 of the liquid crystal display device described in FIG. 2 of Japanese Patent Application Laid-Open No. 2011-59314 was manufactured.
- this substrate was exposed to HMDS vapor for 30 seconds, and then the photosensitive resin composition of Example 1 was slit-coated and then pre-baked on a hot plate at 90 ° C.
- a thick photosensitive resin composition layer was formed.
- the obtained photosensitive resin composition layer was subjected to 40 mJ / cm 2 (energy intensity: 20 mW / cm) through a 10 ⁇ m diameter hole pattern mask using Canon Inc. MPA 7800CF (high pressure mercury lamp). 2 , i-line) exposure.
- the exposed resin composition layer was developed with an alkali developer (0.4% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
- Example 210 a liquid crystal display device was produced in the same manner as in Example 210 except that the photosensitive composition of Example 1 was replaced with the photosensitive composition of Example 19. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
- Example 210 a liquid crystal display device was produced in the same manner as in Example 210 except that the photosensitive composition of Example 1 was replaced with the photosensitive composition of Example 33. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
- Example 210 a liquid crystal display device was produced in the same manner as in Example 210 except that the photosensitive composition of Example 1 was replaced with the photosensitive composition of Example 47. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
- FIG. 4 is a conceptual diagram of an example of the liquid crystal display device.
- an array substrate formed until just before the organic insulating film PAS of the liquid crystal display device described in FIG.
- this substrate was exposed to HMDS vapor for 30 seconds, and then the photosensitive resin composition of Example 1 was slit-coated and then pre-baked on a hot plate at 90 ° C. for 2 minutes to volatilize the solvent.
- a thick photosensitive resin composition layer was formed.
- the obtained photosensitive resin composition layer was subjected to optimum exposure dose mJ / cm 2 (energy intensity: 20 mW / cm 2) through a hole pattern mask having a diameter of 8 ⁇ m using MPA 7800CF manufactured by Canon Inc. , I-line) exposure.
- the exposed resin composition layer was developed with an alkali developer (0.4% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
- the whole surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm 2 (energy intensity: 20 mW / cm 2 , measured by i-line), and then the substrate was heated at 230 ° C. in an oven at 30 ° C. An organic passivation film was obtained by heating for a minute. Thereafter, a liquid crystal display device was obtained according to Japanese Patent Application Laid-Open No. 2007-328210. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
- Example 215 a liquid crystal display device was produced in the same manner as in Example 214 except that the photosensitive composition of Example 1 was replaced with the photosensitive composition of Example 19. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
- Example 214 a liquid crystal display device was produced in the same manner as in Example 214 except that the photosensitive composition of Example 1 was replaced with the photosensitive composition of Example 33. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
- Example 214 a liquid crystal display device was produced in the same manner as in Example 214 except that the photosensitive composition of Example 1 was replaced with the photosensitive composition of Example 47. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
- 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
- 109 Organic passivation film
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Abstract
Description
さらに詳しくは、液晶表示装置、有機EL(有機エレクトロルミネッセンス)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 sometimes simply 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 flattening film, a protective film and an interlayer insulating film of an electronic component such as a liquid crystal display device, an organic EL (organic electroluminescence) display device, an integrated circuit element, and a solid-state imaging element. The present invention relates to a product and a method for producing a cured film using the product.
<1>(A)重合体成分、(B)光酸発生剤、並びに(C)溶剤を含有し、(A)重合体成分が、下記(1)及び(2)の少なくとも一方を含み、かつ下記(3)及び(4)の少なくとも一方を満たし;
(1)(a1)酸基が酸分解性基で保護された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含む重合体(A1)、
(2)構成単位(a1)を含む重合体(A2)、及び構成単位(a2)を含む重合体(A3);
(3)重合体(A1)~(A3)の少なくとも1種が、(a4)アルカリ加水分解によってカルボキシル基を生じる基を有する構成単位を含む重合体である、
(4)さらに、構成単位(a4)を含み、かつ、構成単位(a1)及び構成単位(a2)を含まない重合体(A4)を含む;
(A)重合体成分を構成する全構成単位に対して、構成単位(a2)の割合が10~40モル%であり、構成単位(a4)の割合が1.0~20モル%である感光性樹脂組成物。
<2>構成単位(a4)が、カルボン酸無水物構造またはラクトン構造を含有する構成単位である、<1>に記載の感光性樹脂組成物。
<3>カルボン酸無水物構造が、5員環または6員環の環状カルボン酸無水物構造である、<2>に記載の感光性樹脂組成物。
<4>カルボン酸無水物構造が、下記一般式(1)で表される部分構造を含む、<2>又は<3>に記載の感光性樹脂組成物。
<5>構成単位(a4)が下記式(1A)及び/又は(1B)で表される、<1>~<4>のいずれかに記載の感光性樹脂組成物。
<6>構成単位(a4)が式(1A)で表される、<1>~<4>のいずれかに記載の感光性樹脂組成物。
<7>(A)重合体成分中に(a3)酸基を有する構成単位を含む、<1>~<6>のいずれかに記載の感光性樹脂組成物。
<8>(A)重合体成分における構成単位(a3)の割合が5~20モル%である、<7>に記載の感光性樹脂組成物。
<9>構成単位(a2)が含有する架橋性基が、エポキシ基、オキセタニル基、および-NH-CH2-OR2から選ばれる少なくとも1種である、<1>~<8>のいずれかに記載の感光性樹脂組成物;但し、R2は水素原子又は炭素数1~20のアルキル基を表す。
<10>構成単位(a1)が、酸基がアセタールの形で保護された基を有する構成単位である<1>~<9>のいずれかに記載の感光性樹脂組成物。
<11>(B)光酸発生剤がオキシムスルホネート化合物である、<1>~<10>のいずれかに記載の感光性樹脂組成物。
<12>(1)<1>~<11>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で現像する工程、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。
<13><1>~<11>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、<12>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、液晶表示装置又は有機EL表示装置。 Specifically, the above problem has been solved by the following means <1>, preferably <2> to <15>.
<1> (A) a polymer component, (B) a photoacid generator, and (C) a solvent, (A) the polymer component includes at least one of the following (1) and (2), and Satisfy at least one of the following (3) and (4);
(1) (a1) a polymer (A1) comprising a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (a2) a structural unit having a crosslinkable group,
(2) a polymer (A2) containing the structural unit (a1) and a polymer (A3) containing the structural unit (a2);
(3) At least one of the polymers (A1) to (A3) is a polymer containing (a4) a structural unit having a group that generates a carboxyl group by alkaline hydrolysis.
(4) Further, a polymer (A4) containing the structural unit (a4) and not containing the structural unit (a1) and the structural unit (a2) is included;
(A) Photosensitivity in which the proportion of the structural unit (a2) is 10 to 40 mol% and the proportion of the structural unit (a4) is 1.0 to 20 mol% with respect to all the structural units constituting the polymer component Resin composition.
<2> The photosensitive resin composition according to <1>, wherein the structural unit (a4) is a structural unit containing a carboxylic anhydride structure or a lactone structure.
<3> The photosensitive resin composition according to <2>, wherein the carboxylic anhydride structure is a 5-membered or 6-membered cyclic carboxylic anhydride structure.
<4> The photosensitive resin composition according to <2> or <3>, wherein the carboxylic anhydride structure includes a partial structure represented by the following general formula (1).
<5> The photosensitive resin composition according to any one of <1> to <4>, wherein the structural unit (a4) is represented by the following formula (1A) and / or (1B).
<6> The photosensitive resin composition according to any one of <1> to <4>, wherein the structural unit (a4) is represented by the formula (1A).
<7> The photosensitive resin composition according to any one of <1> to <6>, wherein (A) the polymer component includes (a3) a structural unit having an acid group.
<8> The photosensitive resin composition according to <7>, wherein the proportion of the structural unit (a3) in the polymer component (A) is 5 to 20 mol%.
<9> Any one of <1> to <8>, wherein the crosslinkable group contained in the structural unit (a2) is at least one selected from an epoxy group, an oxetanyl group, and —NH—CH 2 —OR 2 Wherein R 2 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
<10> The photosensitive resin composition according to any one of <1> to <9>, wherein the structural unit (a1) is a structural unit having a group in which an acid group is protected in the form of an acetal.
<11> (B) The photosensitive resin composition according to any one of <1> to <10>, wherein the photoacid generator is an oxime sulfonate compound.
<12> (1) A step of applying the photosensitive resin composition according to any one of <1> to <11> 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) 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.
<13> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <11>, or a cured film formed by the method for producing a cured film according to <12>.
<14> The cured film according to <13>, which is an interlayer insulating film.
<15> A liquid crystal display device or an organic EL 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).
(A)重合体成分、(B)光酸発生剤、並びに(C)溶剤を含有し、上記(A)重合体成分が、下記(1)及び(2)の少なくとも一方を含み、かつ下記(3)及び(4)の少なくとも一方を満たし;
(1)(a1)酸基が酸分解性基で保護された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含む重合体(A1)、
(2)上記構成単位(a1)を含む重合体(A2)、及び上記構成単位(a2)を含む重合体(A3);
(3)上記重合体(A1)~(A3)の少なくとも1種が、(a4)アルカリ加水分解によってカルボキシル基を生じる基を有する構成単位を含む重合体である、
(4)さらに、上記構成単位(a4)を含み、かつ、上記構成単位(a1)及び上記構成単位(a2)を含まない重合体(A4)を含む;
上記(A)重合体成分を構成する全構成単位に対して、上記構成単位(a2)の割合が10~40モル%であり、上記構成単位(a4)の割合が1~20モル%であることを特徴とする。
本発明によれば、耐薬品性を良好にし、比誘電率を低くし、さらにパターン寸法安定性を良好にすることができる感光性樹脂組成物を提供することができる。 The photosensitive resin composition of the present invention is
(A) a polymer component, (B) a photoacid generator, and (C) a solvent, wherein the (A) polymer component includes at least one of the following (1) and (2), and Satisfy at least one of 3) and (4);
(1) (a1) a polymer (A1) comprising a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (a2) a structural unit having a crosslinkable group,
(2) The polymer (A2) containing the structural unit (a1) and the polymer (A3) containing the structural unit (a2);
(3) At least one of the polymers (A1) to (A3) is a polymer containing (a4) a structural unit having a group that generates a carboxyl group by alkaline hydrolysis.
(4) Furthermore, the polymer (A4) containing the structural unit (a4) and not containing the structural unit (a1) and the structural unit (a2) is included;
The proportion of the structural unit (a2) is 10 to 40 mol% and the proportion of the structural unit (a4) is 1 to 20 mol% with respect to all the structural units constituting the polymer component (A). It is characterized by that.
ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which can make chemical-resistance favorable, can make a dielectric constant low, and can make pattern dimension stability favorable can be provided.
本発明において、高いパターン寸法安定性が得られる理由は推定であるが、特に上記(A)重合体成分が上記構成単位(a4)を特定の比率以上の割合で有することに起因するものと考えられる。すなわち、上記構成単位(a4)がアルカリ現像液による加水分解の作用を受けて徐々に親水的な構成単位に変化し、上記重合体成分(A)の現像液への親和性が徐々に高まることにより、現像速度が望ましい速度に制御され、安定的な現像を実現するためと推定される。 In the present invention, pattern dimension stability refers to development conditions (for example, when developing with a developer (typically an alkaline aqueous solution) after performing an exposure process on a film obtained using a photosensitive resin composition. It means the variability of the pattern dimension with respect to the fluctuation of the development time, the alkali concentration of the developer, etc., and the smaller the fluctuation of the pattern dimension, the better. High pattern dimensional stability is one of the important performance issues in practical use.
In the present invention, the reason why high pattern dimensional stability can be obtained is presumed, but it is considered that the reason is that the (A) polymer component has the structural unit (a4) at a ratio of a specific ratio or more. It is done. That is, the structural unit (a4) is gradually changed to a hydrophilic structural unit under the action of hydrolysis with an alkaline developer, and the affinity of the polymer component (A) for the developer is gradually increased. Therefore, it is estimated that the development speed is controlled to a desired speed and stable development is realized.
本発明において重合体とは、1種もしくは2種以上のモノマーが5以上重合してなる化合物(すなわち繰り返し単位を5以上有する)であって、かつ分子量1,000以上の化合物を意味する。本発明における重合体成分(A)とは、組成物中に含まれるすべての重合体を集合をいう。従って、後述する界面活性剤等も、本発明における重合体成分(A)に該当する場合がある。重合体成分の重量平均分子量は1,000~200,000であることが好ましく、2,000~50,000であることがより好ましい。(A)重合体成分の全質量のうち、重合性不飽和結合を有する化合物が付加重合してなる重合体の比率が60~100質量であることが好ましく、90~100質量%であることがより好ましく、98~100質量%であることがとくに好ましい。
上記重合性不飽和結合を有する化合物が付加重合してなる重合体は、α,β-不飽和カルボン酸(例えば(メタ)アクリル酸、マレイン酸、イタコン酸等)、そのエステル、及びその無水物の少なくとも1種に由来する構成単位を含む重合体であることが好ましい。また、それら以外の構成単位、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等を有していてもよい。(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60質量%以上を占めることが好ましい。 <(A) Polymer component>
In the present invention, the polymer means a compound obtained by polymerizing 5 or more of one or more monomers (that is, having 5 or more repeating units) and having a molecular weight of 1,000 or more. The polymer component (A) in the present invention refers to a collection of all the polymers contained in the composition. Therefore, the surfactant described later may correspond to the polymer component (A) in the present invention. The weight average molecular weight of the polymer component is preferably 1,000 to 200,000, and more preferably 2,000 to 50,000. The ratio of the polymer obtained by addition polymerization of the compound having a polymerizable unsaturated bond in the total mass of the polymer component (A) is preferably 60 to 100% by mass, and preferably 90 to 100% by mass. More preferred is 98 to 100% by mass.
A polymer obtained by addition polymerization of the compound having a polymerizable unsaturated bond is an α, β-unsaturated carboxylic acid (for example, (meth) acrylic acid, maleic acid, itaconic acid, etc.), an ester thereof, and an anhydride thereof. It is preferable that it is a polymer containing the structural unit derived from at least 1 sort (s). Moreover, you may have structural units other than those, for example, the structural unit derived from styrene, the structural unit derived from a vinyl compound, etc. (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 60 mass% or more of a total solid.
重合体(A1):(a1)酸基が酸分解性基で保護された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含む重合体
重合体(A2):上記構成単位(a1)を含む重合体(A2)
重合体(A3):上記構成単位(a2)を含む重合体(A3)
重合体(A4):(a4)アルカリ加水分解によってカルボキシル基を生じる基を有する構成単位を含み、かつ上記構成単位(a1)及び上記構成単位(a2)を含まない重合体
重合体(A5):(a3)酸基を有する構成単位を含み、上記構成単位(a1)、(a2)及び(a4)を含まない重合体
重合体(A6):上記構成単位(a1)~(a4)のいずれにも属さない構成単位(a5)を含み、上記構成単位(a1)~(a4)のいずれをも含まない重合体 Examples of the polymer constituting the (A) polymer component in the present invention include the following (A1) to (A6).
Polymer (A1): (a1) A polymer containing a structural unit having an acid group protected by an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group Polymer (A2): the above structural unit Polymer (A2) containing (a1)
Polymer (A3): Polymer (A3) containing the structural unit (a2)
Polymer (A4): (a4) A polymer containing a structural unit having a group that generates a carboxyl group by alkaline hydrolysis and not containing the structural unit (a1) and the structural unit (a2) Polymer (A5): (A3) A polymer containing a structural unit having an acid group and not containing the above structural units (a1), (a2) and (a4) Polymer (A6): Any of the above structural units (a1) to (a4) A polymer containing no structural unit (a5) and not containing any of the structural units (a1) to (a4)
(第1の実施形態)
(A)重合体成分が、(a1)酸基が酸分解性基で保護された基を有する構成単位、(a2)架橋性基を有する構成単位及び(a4)アルカリ加水分解によってカルボキシル基を生じる基を有する構成単位を有する重合体(以下、重合体(A1a)ともいう)を1種以上含む。重合体(A1a)は、(a3)酸基を有する構成単位を含んでいてもよい。本実施形態において、(A)重合体成分は、上記重合体(A2)~(A6)の少なくとも1種を有していてもよい。本実施形態において、重合体(A1a)以外の重合体の含有量は、(A)重合体成分中、10質量%以下であることが好ましい。 Although embodiment regarding the combination of the polymer in (A) polymer component is given to the following, this invention is not limited to these.
(First embodiment)
(A) The polymer component is (a1) a structural unit having an acid group protected by an acid-decomposable group, (a2) a structural unit having a crosslinkable group, and (a4) a carboxyl group by alkali hydrolysis. 1 type or more of polymers (henceforth a polymer (A1a)) which has the structural unit which has group are included. The polymer (A1a) may contain (a3) a structural unit having an acid group. In the present embodiment, the polymer component (A) may have at least one of the polymers (A2) to (A6). In this embodiment, it is preferable that content of polymers other than a polymer (A1a) is 10 mass% or less in (A) polymer component.
(A)重合体成分が、(a1)酸基が酸分解性基で保護された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含む重合体(以下、重合体(A1b)ともいう)と、(a4)アルカリ加水分解によってカルボキシル基を生じる基を有する構成単位を含み、かつ、(a1)酸基が酸分解性基で保護された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含まない重合体(以下、重合体(A4)ともいう)を含む。なお、重合体(A1b)は、構成単位(a4)を通常含んでいない。
重合体(A1b)及び/又は重合体(A4)は、さらに(a3)酸基を有する構成単位を含んでいてもよい。(A)重合体成分中、重合体(A1b)と重合体(A4)との組成比は、質量比で(重合体(A1b)/重合体(A4))=1~40であることが好ましく、2~30であることがより好ましい。
本実施形態において、(A)重合体成分は、上記重合体(A2)、(A3)、(A5)及び(A6)の少なくとも1種を有していてもよい。また、重合体(A1b)及び重合体(A4)以外の重合体の含有量は、(A)重合体成分中、10質量%以下であることが好ましい。 (Second Embodiment)
(A) A polymer component includes (a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group and (a2) a structural unit having a crosslinkable group (hereinafter referred to as polymer (A1b)). And (a4) a structural unit having a group having a carboxyl group by alkali hydrolysis, and (a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (a2) a cross-linking A polymer containing no structural unit having a functional group (hereinafter also referred to as polymer (A4)) is included. The polymer (A1b) usually does not contain the structural unit (a4).
The polymer (A1b) and / or the polymer (A4) may further contain (a3) a structural unit having an acid group. In the polymer component (A), the composition ratio of the polymer (A1b) to the polymer (A4) is preferably (polymer (A1b) / polymer (A4)) = 1 to 40 in terms of mass ratio. 2 to 30 is more preferable.
In this embodiment, the polymer component (A) may have at least one of the polymers (A2), (A3), (A5), and (A6). Moreover, it is preferable that content of polymers other than a polymer (A1b) and a polymer (A4) is 10 mass% or less in (A) polymer component.
(A)重合体成分が、(a1)酸基が酸分解性基で保護された基を有する構成単位及び(a4)アルカリ加水分解によってカルボキシル基を生じる基を有する構成単位を含む重合体(以下、重合体(A2a)ともいう)と、(a2)架橋性基を有する構成単位を含む重合体(以下、重合体(A3b)ともいう)を含む。なお、重合体(A2a)は、構成単位(a2)を通常含んでいない。また、重合体(A3b)は、構成単位(a1)及び構成単位(a4)を通常含んでいない。
重合体(A2a)及び/又は重合体(A3b)は、さらに上記構成単位(a3)を含有していてもよい。
(A)重合体成分中、重合体(A2a)と重合体(A3b)との組成比は、質量比で(重合体(A2a)/重合体(A3b))=0.2~5であることが好ましく、0.25~4であることがより好ましい。本実施形態において、(A)重合体成分は、上記重合体(A4)~(A6)の少なくとも1種を有していてもよい。また、重合体(A2a)及び重合体(A3b)以外の重合体の含有量は、(A)重合体成分中、10質量%以下であることが好ましい。 (Third embodiment)
(A) a polymer component comprising (a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group and (a4) a structural unit having a group that generates a carboxyl group by alkali hydrolysis (hereinafter referred to as a polymer unit) Polymer (A2a)) and (a2) a polymer containing a structural unit having a crosslinkable group (hereinafter also referred to as polymer (A3b)). The polymer (A2a) usually does not contain the structural unit (a2). The polymer (A3b) usually does not contain the structural unit (a1) and the structural unit (a4).
The polymer (A2a) and / or the polymer (A3b) may further contain the structural unit (a3).
(A) In the polymer component, the composition ratio of the polymer (A2a) and the polymer (A3b) is (polymer (A2a) / polymer (A3b)) = 0.2-5 in mass ratio. Is more preferable, and 0.25 to 4 is more preferable. In the present embodiment, the polymer component (A) may have at least one of the polymers (A4) to (A6). Moreover, it is preferable that content of polymers other than a polymer (A2a) and a polymer (A3b) is 10 mass% or less in (A) polymer component.
(A)重合体成分が、(a1)酸基が酸分解性基で保護された基を有する構成単位を含む重合体(以下、重合体(A2b)ともいう)と、(a2)架橋性基を有する構成単位及び(a4)アルカリ加水分解によってカルボキシル基を生じる基を有する構成単位を含む重合体(以下、重合体(A3a)ともいう)を含む。なお、重合体(A2b)は、構成単位(a2)及び構成単位(a4)を通常含んでいない。また、重合体(A3a)は、構成単位(a1)を通常含んでいない。
重合体(A2b)及び/又は重合体(A3a)は、さらに上記構成単位(a3)を含有していてもよい。(A)重合体成分中、重合体(A2b)と重合体(A3a)との組成比は、質量比で(重合体(A2b)/重合体(A3a))=0.2~5であることが好ましく、0.25~4であることがより好ましい。
本実施形態において、(A)重合体成分は、上記重合体(A4)~(A6)の少なくとも1種を有していてもよい。また、重合体(A2b)及び重合体(A3a)以外の重合体の含有量は、(A)重合体成分中、10質量%以下であることが好ましい。 (Fourth embodiment)
(A) a polymer component includes (a1) a polymer containing a structural unit having an acid group protected by an acid-decomposable group (hereinafter also referred to as polymer (A2b)), and (a2) a crosslinkable group And (a4) a polymer (hereinafter, also referred to as polymer (A3a)) containing a structural unit having a group that generates a carboxyl group by alkali hydrolysis. The polymer (A2b) usually does not contain the structural unit (a2) and the structural unit (a4). Further, the polymer (A3a) usually does not contain the structural unit (a1).
The polymer (A2b) and / or the polymer (A3a) may further contain the structural unit (a3). (A) In the polymer component, the composition ratio of the polymer (A2b) to the polymer (A3a) is (polymer (A2b) / polymer (A3a)) = 0.2-5 in mass ratio. Is preferable, and 0.25 to 4 is more preferable.
In the present embodiment, the polymer component (A) may have at least one of the polymers (A4) to (A6). Moreover, it is preferable that content of polymers other than a polymer (A2b) and a polymer (A3a) is 10 mass% or less in (A) polymer component.
(A)重合体成分が、(a1)酸基が酸分解性基で保護された基を有する構成単位を含む重合体(以下、重合体(A2b)ともいう)と、(a2)架橋性基を有する構成単位を含む重合体(以下、重合体(A3b)ともいう)と、(a4)アルカリ加水分解によってカルボキシル基を生じる基を有する構成単位を含み、かつ、(a1)酸基が酸分解性基で保護された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含まない重合体(以下、重合体(A4)ともいう)を含む。なお、重合体(A2b)は、構成単位(a2)及び構成単位(a4)を通常含んでいない。また、重合体(A3b)は、構成単位(a1)及び構成単位(a4)を通常含んでいない。
重合体(A2b)、重合体(A3b)及び重合体(A4)のうち少なくとも1種は、さらに上記構成単位(a3)を含有していてもよい。
重合体(A2b)と重合体(A3b)の総量と、重合体(A4)との組成比は、質量比で((重合体(A2b)+重合体(A3b))/重合体(A4)=1~40であることが好ましく、2~30であることがより好ましい。さらに、重合体(A2b)と重合体(A3b)との組成比は、質量比で(重合体(A2b)/重合体(A3b))=0.2~5であることが好ましく、0.25~5であることがより好ましい。
本実施形態において、(A)重合体成分は、上記重合体(A5)及び/又は(A6)を有していてもよい。本実施形態において、重合体(A2b)、重合体(A3b)及び重合体(A4)以外の重合体の含有量は、(A)重合体成分中、10質量%以下であることが好ましい。 (Fifth embodiment)
(A) a polymer component includes (a1) a polymer containing a structural unit having an acid group protected by an acid-decomposable group (hereinafter also referred to as polymer (A2b)), and (a2) a crosslinkable group A polymer containing a structural unit (hereinafter also referred to as polymer (A3b)), (a4) a structural unit having a group that generates a carboxyl group by alkali hydrolysis, and (a1) an acid group is acid-decomposed. And a polymer having no structural unit having a group protected by a functional group and (a2) a crosslinkable group (hereinafter also referred to as polymer (A4)). The polymer (A2b) usually does not contain the structural unit (a2) and the structural unit (a4). The polymer (A3b) usually does not contain the structural unit (a1) and the structural unit (a4).
At least one of the polymer (A2b), the polymer (A3b) and the polymer (A4) may further contain the structural unit (a3).
The composition ratio of the total amount of the polymer (A2b) and the polymer (A3b) to the polymer (A4) is (mass ratio (polymer (A2b) + polymer (A3b)) / polymer (A4) = It is preferably 1 to 40, and more preferably 2 to 30. Furthermore, the composition ratio of the polymer (A2b) to the polymer (A3b) is (mass ratio (polymer (A2b) / polymer)). (A3b)) is preferably 0.2 to 5, and more preferably 0.25 to 5.
In this embodiment, the (A) polymer component may have the said polymer (A5) and / or (A6). In this embodiment, it is preferable that content of polymers other than a polymer (A2b), a polymer (A3b), and a polymer (A4) is 10 mass% or less in (A) polymer component.
また、構成単位(a2)と構成単位(a4)の比率は、モル比で(構成単位(a2)/構成単位(a4))=0.5~80であることが好ましく、1~40であることがより好ましい。
また、好ましい含有率の組み合わせとしては、構成単位(a2)と構成単位(a3)の比率は、モル比で(構成単位(a2)/構成単位(a3))=0.4~8であることが好ましく、1.0~5であることがより好ましい。
構成単位(a2)と構成単位(a1)の比率は、モル比で(構成単位(a2)/構成単位(a1))=0.1~10であることが好ましく、0.1~5であることがより好ましい。 In the composition of the present invention, the content of the structural unit (a1) is preferably 3 to 80 mol%, preferably 8 to 75 mol% in the total structural units of the polymer component (A) from the viewpoint of improving sensitivity. Is more preferable, and 15 to 65 mol% is more preferable. The content of the structural unit (a2) is from 10 to 40 mol%, more preferably from 10 to 35 mol%, further preferably from 15 to 35 mol%, based on all the structural units of the polymer component (A). 35 mol% is still more preferable. The content of the structural unit (a4) is 1.0 to 20 mol%, more preferably 1.0 to 15 mol%, and more preferably 1.0 to 10 mol% in all the structural units of the polymer component (A). Is more preferable. When the structural unit (a3) is included, the content of the structural unit (a3) is preferably from 5 to 20 mol%, more preferably from 5 to 15 mol%, more preferably from 8 to 15 mol% is more preferable. The total content of the structural units (a1), (a2) and (a4) is preferably 20 to 100 mol%, more preferably 30 to 90 mol%, based on the total structural units of the polymer component (A). The total content of the structural units (a1), (a2), (a3), and (a4) is preferably 20 to 100 mol%, and preferably 30 to 100 mol%, based on the total structural units of the polymer component (A). Is more preferable.
Further, the ratio of the structural unit (a2) to the structural unit (a4) is preferably in the molar ratio (structural unit (a2) / structural unit (a4)) = 0.5-80, preferably 1-40. It is more preferable.
Further, as a preferable combination of the content ratios, the ratio of the structural unit (a2) to the structural unit (a3) is (molar ratio (structural unit (a2) / structural unit (a3))) = 0.4 to 8. Is more preferable, and 1.0 to 5 is more preferable.
The ratio of the structural unit (a2) to the structural unit (a1) is preferably (structural unit (a2) / structural unit (a1)) = 0.1 to 10 in terms of molar ratio, preferably 0.1 to 5. It is more preferable.
(A)重合体成分に含まれる重合体の分子量は、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。
本発明で用いられる化合物の重量平均分子量は、GPC測定によるポリスチレン換算値として定義される。重量平均分子量及び数平均分子量は、例えば、HLC-8220(東ソー(株)製)を用い、カラムとしてTSKgel Super AWM-H(東ソー(株)製、6.0mmID×15.0cmを、溶離液としてテトラヒドロフラン(THF)を用いることによって求めることができる。 << (A) Molecular Weight of Polymer Component >>
(A) The molecular weight of the polymer contained in the polymer component is a weight average molecular weight in terms of polystyrene, preferably in the range of 1,000 to 200,000, more preferably in the range of 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 weight average molecular weight of the compound used in the present invention is defined as a polystyrene converted value by GPC measurement. The weight average molecular weight and number average molecular weight are, for example, HLC-8220 (manufactured by Tosoh Corporation), TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6.0 mm ID × 15.0 cm) as a column, and eluent. It can be determined by using tetrahydrofuran (THF).
また、(A)重合体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。
(A)重合体成分は、(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を、全構成単位に対し、50モル%以上含有することが好ましく、80モル%以上含有することがより好ましい。 << (A) Production Method of Polymer Component >>
Also, various methods are known for the synthesis method of the polymer component (A). For example, in order to form at least the structural units represented by the above (a1) and (a2), It can be synthesized by polymerizing a radical polymerizable monomer mixture containing the radical polymerizable monomer used in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction.
The polymer component (A) preferably contains 50 mol% or more, more preferably 80 mol% or more of the structural unit derived from (meth) acrylic acid and / or its ester with respect to all the structural units. preferable.
(A)重合体成分は、酸基が酸分解性基で保護された基を有する構成単位(a1)を少なくとも1種有する。(A)重合体成分が構成単位(a1)を有することにより、露光、現像工程によるパターン形成が可能な感光性樹脂組成物とすることができる。
本発明における「酸基が酸分解性基で保護された基」は、酸基及び酸分解性基として公知のものを使用でき、特に限定されない。
具体的な酸基としては、カルボキシル基、及び、フェノール性水酸基が好ましく挙げられる。
また、具体的な酸分解性基としては、酸により比較的分解し易い基(例えば、後述するエステル構造、テトラヒドロピラニルエステル基、又は、テトラヒドロフラニルエステル基等のアセタール系官能基)や、酸により比較的分解し難い基(例えば、tert-ブチルエステル基等の第三級アルキル基、tert-ブチルカーボネート基等の第三級アルキルカーボネート基)を用いることができる。 << (a1) Structural unit having a group in which an acid group is protected by an acid-decomposable group >>
(A) The polymer component has at least one structural unit (a1) having a group in which an acid group is protected by an acid-decomposable group. (A) When a polymer component has a structural unit (a1), it can be set as the photosensitive resin composition in which pattern formation by an exposure and image development process is possible.
As the “group in which the acid group is protected with an acid-decomposable group” in the present invention, those known as an acid group and an acid-decomposable group can be used, and are not particularly limited.
Specific examples of the acid group preferably include a carboxyl group and a phenolic hydroxyl group.
Specific acid-decomposable groups include groups that are relatively easily decomposed by an acid (for example, an acetal functional group such as an ester structure, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group described later) or an acid. A group that is relatively difficult to decompose (for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group) can be used.
以下、酸分解性基で保護された保護カルボキシル基を有する構成単位(a1-1)と、酸分解性基で保護された保護フェノール性水酸基を有する構成単位(a1-2)について、順にそれぞれ説明する。 The structural unit (a1) is preferably a structural unit having a protected carboxyl group protected with an acid-decomposable group or a structural unit having a protected phenolic hydroxyl group protected with an acid-decomposable group.
Hereinafter, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group and the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group will be described in order. To do.
構成単位(a1-1)は、カルボキシル基を有する構成単位のカルボキシル基が、以下で詳細に説明する酸分解性基によって保護された保護カルボキシル基を有する構成単位である。
上記構成単位(a1-1)に用いることができる上記カルボキシル基を有する構成単位としては、特に制限はなく公知の構成単位を用いることができる。例えば、不飽和モノカルボン酸、不飽和ジカルボン酸、不飽和トリカルボン酸などの、分子中に少なくとも1個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位(a1-1-1)が挙げられる。
以下、上記カルボキシル基を有する構成単位として用いられる、構成単位(a1-1-1)について説明する。 <<< (a1-1) Structural Unit Having a Protected Carboxyl Group Protected with an Acid-Decomposable Group >>>
The structural unit (a1-1) is a structural unit having a protected carboxyl group in which the carboxyl group of the structural unit having a carboxyl group is protected by an acid-decomposable group described in detail below.
The structural unit having a carboxyl group that can be used for the structural unit (a1-1) is not particularly limited, and a known structural unit can be used. Examples thereof include a structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, or unsaturated tricarboxylic acid. It is done.
Hereinafter, the structural unit (a1-1-1) used as the structural unit having a carboxyl group will be described.
本発明で用いられる不飽和カルボン酸としては、以下に挙げるようなものが用いられる。すなわち、不飽和モノカルボン酸としては、例えば、アクリル酸、メタクリル酸、クロトン酸、α-クロロアクリル酸、けい皮酸、2-(メタ)アクリロイロキシエチル-コハク酸、2-(メタ)アクリロイロキシエチルヘキサヒドロフタル酸、2-(メタ)アクリロイロキシエチル-フタル酸、などが挙げられる。
また、不飽和ジカルボン酸としては、例えば、マレイン酸、フマル酸、イタコン酸、シトラコン酸、メサコン酸などが挙げられる。
また、不飽和カルボン酸は、多価カルボン酸のモノ(2-(メタ)アクリロイロキシアルキル)エステルであってもよく、例えば、コハク酸モノ(2-アクリロイロキシエチル)、コハク酸モノ(2-メタクリロイロキシエチル)、フタル酸モノ(2-アクリロイロキシエチル)、フタル酸モノ(2-メタクリロイロキシエチル)などが挙げられる。さらに、不飽和多価カルボン酸は、その両末端ジカルボキシポリマーのモノ(メタ)アクリレートであってもよい。また、不飽和カルボン酸としては、アクリル酸-2-カルボキシエチルエステル、メタクリル酸-2-カルボキシエチルエステル、マレイン酸モノアルキルエステル、フマル酸モノアルキルエステル、4-カルボキシスチレン等も用いることができる。
中でも、現像性の観点から、上記構成単位(a1-1-1)を形成するためには、アクリル酸、メタクリル酸、2-(メタ)アクリロイロキシエチルコハク酸、2-(メタ)アクリロイロキシエチルヘキサヒドロフタル酸、又は2-(メタ)アクリロイロキシエチルフタル酸等を用いることが好ましく、アクリル酸、メタクリル酸、2-(メタ)アクリロイロキシエチルヘキサヒドロフタル酸、を用いることがより好ましい。
構成単位(a1-1-1)は、1種単独で構成されていてもよいし、2種以上で構成されていてもよい。 <<<<< (a1-1-1) Structural Unit Derived from Unsaturated Carboxylic Acid etc. Having at least One Carboxyl Group in the Molecule >>>>
Examples of the unsaturated carboxylic acid used in the present invention include those listed below. That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acrylic acid. And leuoxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-phthalic acid, and the like.
Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.
The unsaturated carboxylic acid may be a mono (2- (meth) acryloyloxyalkyl) ester of a polyvalent carboxylic acid. For example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono ( 2-methacryloyloxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like. Furthermore, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both ends thereof. As the unsaturated carboxylic acid, acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.
Among them, from the viewpoint of developability, in order to form the structural unit (a1-1-1), acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyl Roxyethyl hexahydrophthalic acid or 2- (meth) acryloyloxyethyl phthalic acid is preferably used, and acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid is preferably used. More preferred.
The structural unit (a1-1-1) may be composed of one type alone, or may be composed of two or more types.
構成単位(a1-1)に用いることができる上記酸分解性基としては、上述の酸分解性基を用いることができる。
これらの酸分解性基の中でも、酸分解性基がアセタールの形で保護された構造を有する基であることが好ましい。例えば、カルボキシル基がアセタールの形で保護された保護カルボキシル基であることが、感光性樹脂組成物の基本物性、特に感度やパターン形状、コンタクトホールの形成性、感光性樹脂組成物の保存安定性の観点から好ましい。さらに、カルボキシル基が下記一般式(a1-10)で表されるアセタールの形で保護された保護カルボキシル基であることが、感度の観点からより好ましい。なお、カルボキシル基が下記一般式(a1-10)で表されるアセタールの形で保護された保護カルボキシル基である場合、保護カルボキシル基の全体としては、-(C=O)-O-CR101R102(OR103)の構造となっている。 <<<< acid-decomposable group that can be used for the structural unit (a1-1) >>>>
As the acid-decomposable group that can be used for the structural unit (a1-1), the acid-decomposable groups described above can be used.
Among these acid-decomposable groups, the acid-decomposable group is preferably a group having a structure protected in the form of an acetal. For example, it is a protected carboxyl group in which the carboxyl group is protected in the form of an acetal, the basic physical properties of the photosensitive resin composition, particularly the sensitivity and pattern shape, the formation of contact holes, the storage stability of the photosensitive resin composition From the viewpoint of Furthermore, it is more preferable from the viewpoint of sensitivity that the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-10). When the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-10), the entire protected carboxyl group is — (C═O) —O—CR 101 The structure is R 102 (OR 103 ).
上記直鎖状又は分岐鎖状のアルキル基としては、炭素数1~12であることが好ましく、炭素数1~6であることがより好ましく、炭素数1~4であることがさらに好ましい。具体的には、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、i-ブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、ネオペンチル基、n-ヘキシル基、テキシル基(2,3-ジメチル-2-ブチル基)、n-ヘプチル基、n-オクチル基、2-エチルヘキシル基、n-ノニル基、n-デシル基等を挙げることができる。
上記環状アルキル基としては、炭素数3~12であることが好ましく、炭素数4~8であることがより好ましく、炭素数4~6であることがさらに好ましい。上記環状アルキル基としては、例えばシクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、ノルボルニル基、イソボルニル基等を挙げることができる。 In the general formula (a1-10), R 101 and R 102 each independently represent a hydrogen atom, an alkyl group, or an aryl group. R 103 represents an alkyl group or an aryl group. And R 101 or R 102, may form a cyclic ether linked and the R 103. The alkyl group may be linear, branched or cyclic. R 101 and R 102 are preferably a hydrogen atom or an alkyl group, and at least one of R 101 and R 102 preferably represents an alkyl group. It is preferable that one of R 101 and R 102 is a hydrogen atom or a methyl group, and particularly preferably one of which is the other is a methyl group with a hydrogen atom. R 103 is preferably an alkyl group or an aryl group, and particularly preferably an alkyl group.
The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n Examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like.
The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.
上記ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が例示され、これらの中でもフッ素原子又は塩素原子が好ましい。
また、上記アリール基としては、炭素数6~20のアリール基が好ましく、より好ましくは炭素数6~12であり、具体的には、フェニル基、α-メチルフェニル基、ナフチル基等が例示でき、アリール基で置換されたアルキル基全体、すなわち、アラルキル基としては、ベンジル基、α-メチルベンジル基、フェネチル基、ナフチルメチル基等が例示できる。
上記アルコキシ基としては、炭素数1~6のアルコキシ基が好ましく、より好ましくは炭素数1~4であり、メトキシ基又はエトキシ基がより好ましい。
また、上記アルキル基がシクロアルキル基である場合、上記シクロアルキル基は、置換基として炭素数1~10の直鎖状又は分岐鎖状のアルキル基を有していてもよく、アルキル基が直鎖状又は分岐鎖状のアルキル基である場合には、置換基として炭素数3~12のシクロアルキル基を有していてもよい。
これらの置換基は、上記置換基でさらに置換されていてもよい。 The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When it has a halogen atom as a substituent, R 101 , R 102 and R 103 become a haloalkyl group, and when it has an aryl group as a substituent, R 101 , R 102 and R 103 become an aralkyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, an α-methylphenyl group, and a naphthyl group. Examples of the entire alkyl group substituted with an aryl group, ie, an aralkyl group, include a benzyl group, an α-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.
The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and more preferably a methoxy group or an ethoxy group.
In addition, when the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group is straight. When the alkyl group is a chain or branched chain, it may have a cycloalkyl group having 3 to 12 carbon atoms as a substituent.
These substituents may be further substituted with the above substituents.
R1及びR2がアルキル基の場合、炭素数は1~10のアルキル基が好ましい。R1及びR2がアリール基の場合、フェニル基が好ましい。R1及びR2は、それぞれ、水素原子又は炭素数1~4のアルキル基が好ましい。
R3は、アルキル基又はアリール基を表し、炭素数1~10のアルキル基が好ましく、1~6のアルキル基がより好ましい。
Xは単結合又はアリーレン基を表し、単結合が好ましい。 A first preferred embodiment of the structural unit (a1-1) is a structural unit represented by the following general formula (1-11).
When R 1 and R 2 are alkyl groups, alkyl groups having 1 to 10 carbon atoms are preferred. When R 1 and R 2 are aryl groups, a phenyl group is preferred. R 1 and R 2 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R 3 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.
X represents a single bond or an arylene group, and a single bond is preferable.
一般式(1-12)
R121は水素原子又はメチル基が好ましい。
L1はカルボニル基が好ましい。
R122~R128は、水素原子が好ましい。 A second preferred embodiment of the structural unit (a1-1) is a structural unit represented by the following general formula (1-12).
Formula (1-12)
R 121 is preferably a hydrogen atom or a methyl group.
L 1 is preferably a carbonyl group.
R 122 to R 128 are preferably hydrogen atoms.
構成単位(a1-2)は、フェノール性水酸基を有する構成単位が、以下で詳細に説明する酸分解性基によって保護された保護フェノール性水酸基を有する構成単位(a1-2-1)である。 <<< (a1-2) Structural unit having a protected phenolic hydroxyl group protected with an acid-decomposable group >>>
The structural unit (a1-2) is a structural unit (a1-2-1) having a protected phenolic hydroxyl group in which the structural unit having a phenolic hydroxyl group is protected by an acid-decomposable group described in detail below.
上記フェノール性水酸基を有する構成単位としては、ヒドロキシスチレン系構成単位やノボラック系の樹脂における構成単位が挙げられるが、これらの中では、ヒドロキシスチレン、又はα-メチルヒドロキシスチレンに由来する構成単位が、感度の観点から好ましい。またフェノール性水酸基を有する構成単位として、下記一般式(a1-20)で表される構成単位も、感度の観点から好ましい。 <<<<< (a1-2-1) Structural Unit Having Phenolic Hydroxyl Group >>>>
Examples of the structural unit having a phenolic hydroxyl group include a hydroxystyrene structural unit and a structural unit in a novolac resin. Among these, a structural unit derived from hydroxystyrene or α-methylhydroxystyrene includes: It is preferable from the viewpoint of sensitivity. As the structural unit having a phenolic hydroxyl group, a structural unit represented by the following general formula (a1-20) is also preferable from the viewpoint of sensitivity.
また、R221は単結合又は二価の連結基を示す。単結合である場合には、感度を向上させることができ、さらに硬化膜の透明性を向上させることができるので好ましい。R221の二価の連結基としてはアルキレン基が例示でき、R221がアルキレン基である具体例としては、メチレン基、エチレン基、プロピレン基、イソプロピレン基、n-ブチレン基、イソブチレン基、tert-ブチレン基、ペンチレン基、イソペンチレン基、ネオペンチレン基、ヘキシレン基等が挙げられる。中でも、R221が単結合、メチレン基、エチレン基であることが好ましい。また、上記二価の連結基は、置換基を有していてもよく、置換基としては、ハロゲン原子、水酸基、アルコキシ基等が挙げられる。また、aは1~5の整数を表すが、本発明の効果の観点や、製造が容易であるという点から、aは1又は2であることが好ましく、aが1であることがより好ましい。
また、ベンゼン環における水酸基の結合位置は、R221と結合している炭素原子を基準(1位)としたとき、4位に結合していることが好ましい。
R222はハロゲン原子又は炭素数1~5の直鎖又は分岐鎖状のアルキル基である。具体的には、フッ素原子、塩素原子、臭素原子、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、tert-ブチル基、ペンチル基、イソペンチル基、ネオペンチル基等が挙げられる。中でも製造が容易であるという点から、塩素原子、臭素原子、メチル基又はエチル基であることが好ましい。
また、bは0又は1~4の整数を表す。 In general formula (a1-20), R 220 represents a hydrogen atom or a methyl group, and is preferably a methyl group.
R 221 represents a single bond or a divalent linking group. A single bond is preferable because the sensitivity can be improved and the transparency of the cured film can be further improved. The divalent linking group of R 221 may be exemplified alkylene groups, specific examples R 221 is an alkylene group, a methylene group, an ethylene group, a propylene group, isopropylene group, n- butylene group, isobutylene group, tert -Butylene group, pentylene group, isopentylene group, neopentylene group, hexylene group and the like. Among these, it is preferable that R 221 is a single bond, a methylene group, or an ethylene group. The divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group. A represents an integer of 1 to 5, but a is preferably 1 or 2 and more preferably 1 from the viewpoint of the effects of the present invention and the ease of production. .
Further, the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4-position when the carbon atom bonded to R 221 is defined as the reference (first position).
R 222 is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. It is done. Among these, a chlorine atom, a bromine atom, a methyl group, or an ethyl group is preferable from the viewpoint of easy production.
B represents 0 or an integer of 1 to 4;
上記構成単位(a1-2)に用いることができる上記酸分解性基としては、上記構成単位(a1-1)に用いることができる酸分解性基と同様に、公知のものを使用でき、特に限定されない。酸分解性基の中でもアセタールで保護された保護フェノール性水酸基を有する構成単位であることが、感光性樹脂組成物の基本物性、特に感度やパターン形状、感光性樹脂組成物の保存安定性、コンタクトホールの形成性の観点から好ましい。さらに、酸分解性基の中でも、フェノール性水酸基が上記一般式(a1-10)で表されるアセタールの形で保護された保護フェノール性水酸基であることが、感度の観点からより好ましい。なお、フェノール性水酸基が上記一般式(a1-10)で表されるアセタールの形で保護された保護フェノール性水酸基である場合、保護フェノール性水酸基の全体としては、-Ar-O-CR101R102(OR103)の構造となっている。なお、Arはアリーレン基を表す。
フェノール性水酸基のアセタールエステル構造の好ましい例は、R101=R102=R103=メチル基やR101=R102=メチル基でR103=ベンジル基の組み合わせが例示できる。
また、フェノール性水酸基がアセタールの形で保護された保護フェノール性水酸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としては、例えば、特開2011-215590号公報の段落番号0042に記載のものなどが挙げられる。
これらの中でも、4-ヒドロキシフェニルメタクリレートの1-アルコキシアルキル保護体、4-ヒドロキシフェニルメタクリレートのテトラヒドロピラニル保護体が透明性の観点から好ましい。 <<<< acid-decomposable group that can be used for the structural unit (a1-2) >>>>
As the acid-decomposable group that can be used for the structural unit (a1-2), as with the acid-decomposable group that can be used for the structural unit (a1-1), known ones can be used. It is not limited. Among the acid-decomposable groups, a structural unit having a protected phenolic hydroxyl group protected with acetal is a basic physical property of the photosensitive resin composition, particularly sensitivity and pattern shape, storage stability of the photosensitive resin composition, contact This is preferable from the viewpoint of hole formability. Furthermore, among the acid-decomposable groups, it is more preferable from the viewpoint of sensitivity that the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of an acetal represented by the above general formula (a1-10). When the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of an acetal represented by the general formula (a1-10), the protected phenolic hydroxyl group as a whole is —Ar—O—CR 101 R The structure is 102 (OR 103 ). Ar represents an arylene group.
Preferable examples of the acetal ester structure of the phenolic hydroxyl group include a combination of R 101 = R 102 = R 103 = methyl group, R 101 = R 102 = methyl group and R 103 = benzyl group.
Examples of the radical polymerizable monomer used for forming a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected in the form of an acetal include paragraph number 0042 of JP2011-215590A. And the like.
Among these, a 1-alkoxyalkyl protector of 4-hydroxyphenyl methacrylate and a tetrahydropyranyl protector of 4-hydroxyphenyl methacrylate are preferable from the viewpoint of transparency.
(A)重合体成分は、架橋性基を有する構成単位(a2)を有し、かつ上記構成単位(a2)は、(A)重合体成分を構成する全構成単位に対して、10~40モル%含まれる。本発明において架橋性基とは、加熱処理によってこの官能基どうしが反応して共有結合を形成しうる基、又は酸基と反応して共有結合を形成しうる官能基と定義される。上記加熱処理とは、現像後に熱硬化する工程(ポストベーク工程)であることが好ましい。
架橋性基を有する構成単位が熱架橋を開始する温度については、例えば、70~200℃であることが好ましく、90~180℃であることがより好ましい。例えば、グリシジルメタクリレートに由来する構成単位の架橋開始温度は115℃であり、後述の3-エチル-3-オキセタニルメチルメタクリレートに由来する構成単位の架橋開始温度は151℃である。これらの架橋開始温度は、例えばリアルタイム赤外分光法(RT-IR)を用いて測定できる。例えばDigilab社製FTS60A/896やFTS7000を用いて測定することができる。例えば、以下のような測定方法が挙げられる。
アルミ板(鏡面仕上げ、厚み:100μm)に、各感光性樹脂組成物をスリット塗布した後、95℃/140秒ホットプレート上でプリベークして溶剤を揮発させ、感光性樹脂組成物層を膜厚4.0μmとなるように形成し、Digilab社製FTS7000にDigilab社製スペクトラモノと、システムズエンジニアリング社製昇温コントローラー付き反射型加熱ステージを取り付け、時間分解FT-IR測定(積算:10Scan/spectra、時間分解能:10sec/spectra、検出器:TGS)を行う。各官能基に由来するIR吸収スペクトルピークの時間ごとの吸光度を読み取り、このとき、架橋基の吸光度が95%以下に減少した時の温度を架橋開始温度として定義する。
好ましい架橋性基を有する構成単位の態様としては、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。その中でも、本発明の感光性樹脂組成物は、上記(A-1)重合体成分が、エポキシ基及びオキセタニル基のうち少なくとも1つを含む構成単位を含むことが好ましく、エポキシ基を含む構成単位を含むことがより好ましい。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 component has a structural unit (a2) having a crosslinkable group, and the structural unit (a2) is 10 to 40 with respect to all the structural units constituting the (A) polymer component. Contains mol%. In the present invention, the crosslinkable group is defined as a group that can react with each other by a heat treatment to form a covalent bond, or a functional group that can react with an acid group to form a covalent bond. The heat treatment is preferably a step (post-bake step) of thermosetting after development.
The temperature at which the structural unit having a crosslinkable group starts thermal crosslinking is preferably, for example, 70 to 200 ° C., more preferably 90 to 180 ° C. For example, the crosslinking initiation temperature of a structural unit derived from glycidyl methacrylate is 115 ° C., and the crosslinking initiation temperature of a structural unit derived from 3-ethyl-3-oxetanylmethyl methacrylate described later is 151 ° C. These crosslinking initiation temperatures can be measured using, for example, real-time infrared spectroscopy (RT-IR). For example, it can be measured using FTS60A / 896 or FTS7000 manufactured by Digilab. For example, the following measuring methods are mentioned.
Each photosensitive resin composition is slit-coated on an aluminum plate (mirror finish, thickness: 100 μm), then pre-baked on a hot plate at 95 ° C. for 140 seconds to volatilize the solvent, and the photosensitive resin composition layer is formed into a film thickness It was formed to 4.0 μm, a Digilab FTS7000 was equipped with a Digilab Spectra Mono and a reflective heating stage with a temperature controller made by Systems Engineering, and time-resolved FT-IR measurement (integration: 10 Scan / spectra, Time resolution: 10 sec / spectra, detector: TGS). The absorbance at each time of the IR absorption spectrum peak derived from each functional group is read, and at this time, the temperature at which the absorbance of the crosslinking group decreases to 95% or less is defined as the crosslinking initiation temperature.
Preferred embodiments of the structural unit having a crosslinkable group include an epoxy group, an oxetanyl group, a group represented by —NH—CH 2 —O—R (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 (where R is a hydrogen atom or a carbon number of 1 to 20). The alkyl group is preferably at least one selected from the group represented by Among them, in the photosensitive resin composition of the present invention, the (A-1) polymer component preferably contains a structural unit containing at least one of an epoxy group and an oxetanyl group, and a structural unit containing an epoxy group It is more preferable to contain. In more detail, the following are mentioned.
上記(A)重合体成分は、エポキシ基及び/又はオキセタニル基を有する構成単位(以下、構成単位(a2-1)ともいう。)を含有することが好ましい。
上記構成単位(a2-1)は、1つの構成単位中にエポキシ基又はオキセタニル基を少なくとも1つ有していればよく、1つ以上のエポキシ基及び1つ以上オキセタニル基、2つ以上のエポキシ基、又は、2つ以上のオキセタニル基を有していてもよく、特に限定されないが、エポキシ基及び/又はオキセタニル基を合計1~3つ有することが好ましく、エポキシ基及び/又はオキセタニル基を合計1又は2つ有することがより好ましく、エポキシ基又はオキセタニル基を1つ有することがさらに好ましい。 <<< (a2-1) Structural Unit Having Epoxy Group and / or Oxetanyl Group >>>
The (A) polymer component preferably contains a structural unit having an epoxy group and / or an oxetanyl group (hereinafter also referred to as a structural unit (a2-1)).
The structural unit (a2-1) may have at least one epoxy group or oxetanyl group in one structural unit, and includes one or more epoxy groups, one or more oxetanyl groups, and two or more epoxy groups. Group, or may have two or more oxetanyl groups, and is not particularly limited, but preferably has a total of 1 to 3 epoxy groups and / or oxetanyl groups, and a total of epoxy groups and / or oxetanyl groups It is more preferable to have one or two, and it is even more preferable to have one epoxy group or one oxetanyl group.
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(a1-2-1)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。 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 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 (a1-2-1) having an epoxy group and / or oxetanyl group include a monomer having a methacrylate structure and an acrylate ester. A monomer containing a structure is preferred.
上記架橋性基を有する構成単位(a2)の1つとして、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)については、特開2011-215580号公報の段落番号0072~0090の記載及び特開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 >>>
As one of the structural unit (a2) having a crosslinkable group, there may be mentioned the 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.
In addition, with respect to the structural unit (a2-2), compounds described in paragraph numbers 0072 to 0090 of JP2011-215580A and paragraph numbers 0013 to 0031 of JP2008-256974A are preferable examples. The contents of which are incorporated herein by reference.
本発明で用いる(A)重合体成分は、-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) >>
The polymer component (A) used in the present invention is 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 preferable. 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.
(A)重合体成分は、(a4)アルカリ加水分解によってカルボキシル基を生じる基を有する構成単位を1種以上有し、かつ上記構成単位(a4)は、(A)重合体成分を構成する全構成単位に対して、1.0~20モル%含まれる。構成単位(a4)はアルカリ加水分解の作用によってカルボキシル基を有する構成単位に変化する。 << (a4) Structural unit having a group that generates a carboxyl group by alkali hydrolysis >>
(A) The polymer component has (a4) one or more structural units having a group that generates a carboxyl group by alkaline hydrolysis, and the structural unit (a4) comprises (A) all of the constituents of the polymer component. It is contained in an amount of 1.0 to 20 mol% based on the structural unit. The structural unit (a4) is converted into a structural unit having a carboxyl group by the action of alkali hydrolysis.
加水分解性の試験方法:アセトニトリル3gとpH=10.01の標準液(JIS規格、K0022を含む水溶液)5gからなる混合液に、この構成単位に対応するモノマー(100mg~200mgの範囲の量)を添加し、25℃で20分混合しモノマーの変化率を測定する。モノマーの変化率が80%以上となる構成単位を、本発明の条件を満たす構成単位とする。
分析機器としては、例えば液体クロマトグラフィーを用いることができ、測定されたモノマーのピーク積分値(面積)から反応率を計算することができる。例えば、下記構造式(a4-1)で表される構成単位は、対応するモノマー(a4-1m)のアルカリ加水分解性を上記測定方法で測定した際の変化率が80%以上であることにより、上記構成単位(a4)に該当する構成単位であると判別される。
Hydrolyzability test method: Monomer corresponding to this structural unit (amount in the range of 100 mg to 200 mg) in a mixed solution consisting of 3 g of acetonitrile and 5 g of a standard solution (JIS standard, aqueous solution containing K0022) of pH = 1.01 Is added and mixed at 25 ° C. for 20 minutes, and the rate of change of the monomer is measured. A structural unit having a monomer change rate of 80% or more is defined as a structural unit that satisfies the conditions of the present invention.
As the analytical instrument, for example, liquid chromatography can be used, and the reaction rate can be calculated from the measured peak integrated value (area) of the monomer. For example, the structural unit represented by the following structural formula (a4-1) has a rate of change of 80% or more when the alkali hydrolyzability of the corresponding monomer (a4-1m) is measured by the above measuring method. The structural unit is determined to be a structural unit corresponding to the structural unit (a4).
上記構成単位(a4)が、カルボン酸無水物構造を有する構成単位である場合、カルボン酸無水物構造としては鎖状、環状のいずれも用いることができるが、環状のカルボン酸無水物構造であることが好ましい。環員数としては5~7員環が好ましく、5員環又は6員環であることがより好ましく、5員環であることが特に好ましい。また、環状カルボン酸無水物構造に他の環構造が縮環して多環構造を形成していてもよいが、多環構造を形成していないことが好ましい。他の環構造が縮環していている場合は、ビシクロ構造又はスピロ構造を形成する形で他の環構造が縮環していていることが好ましく、縮環している他の環構造の数は1~5が好ましく、1~3がより好ましい。他の環構造としては、炭素数3~20の環状の炭化水素基、炭素数3~20のヘテロ環基等が挙げられる。ヘテロ環基としては、特に限定されないが、環を構成する原子のうち1つ以上がヘテロ原子があるもの又は芳香族ヘテロ環基が挙げられる。また、ヘテロ環基としては、5員環又は6員環が好ましく、5員環が特に好ましい。具体的には、ヘテロ環基は、酸素原子を少なくとも一つ含有するものが好ましく、例えば、オキソラン環、オキサン環、ジオキサン環等が挙げられる。 <<< Structural Unit Having Carboxylic Anhydride Structure >>>
When the structural unit (a4) is a structural unit having a carboxylic acid anhydride structure, the carboxylic acid anhydride structure may be either chain or cyclic, but is a cyclic carboxylic acid anhydride structure. It is preferable. The number of ring members is preferably a 5- to 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and particularly preferably a 5-membered ring. Further, other ring structures may be condensed to the cyclic carboxylic acid anhydride structure to form a polycyclic structure, but it is preferable that no polycyclic structure is formed. When other ring structures are condensed, it is preferable that the other ring structures are condensed in a form that forms a bicyclo structure or a spiro structure, and the number of other ring structures that are condensed. Is preferably 1 to 5, and more preferably 1 to 3. Examples of other ring structures include a cyclic hydrocarbon group having 3 to 20 carbon atoms, a heterocyclic group having 3 to 20 carbon atoms, and the like. The heterocyclic group is not particularly limited, and examples thereof include those having one or more heteroatoms out of the atoms constituting the ring or aromatic heterocyclic groups. Moreover, as a heterocyclic group, a 5-membered ring or a 6-membered ring is preferable, and a 5-membered ring is especially preferable. Specifically, the heterocyclic group preferably contains at least one oxygen atom, and examples thereof include an oxolane ring, an oxane ring, and a dioxane ring.
一般式(1)
一般式(1)中、RA1aは置換基を表し、n1a個のRA1aはそれぞれ独立しており、同一でも異なっていてもよい。RA1aは、上述したカルボン酸無水物構造が有していてもよい置換基と同義であり、好ましい範囲も同様である。
一般式(1)中、Z1aは-C(=O)-O-C(=O)-を含む単環又は多環構造を表し、単環構造を表すことが好ましい。Z1aが単環構造を表す場合、5~7員環を形成することが好ましく、5員環又は6員環を形成することがより好ましく、5員環を形成することが特に好ましい。Z1aが多環構造を表す場合、多環構造としては、カルボン酸無水物構造に、ビシクロ構造又はスピロ構造を形成する形で他の環構造が縮環していることが好ましい。他の環構造としては、上述した他の環構造と同義であり、好ましい範囲も同様である。
一般式(1)中、n1aは0以上の整数を表し、0~4の整数が好ましく、0~2の整数が好ましく、0がさらに好ましい。n1aが2以上の整数を表す場合、複数存在する置換基は、互いに同一でも異なっていてもよい。また、複数存在する置換基は、互いに結合して環を形成してもよいが、互いに結合して環を形成していないことが好ましい。 The structural unit having a carboxylic acid anhydride structure used in the present invention preferably includes a partial structure represented by the following general formula (1).
General formula (1)
In General Formula (1), R A1a represents a substituent, and n 1a R A1a s are independent and may be the same or different. R A1a has the same meaning as the substituent that the carboxylic anhydride structure described above may have, and the preferred range is also the same.
In the general formula (1), Z 1a represents a monocyclic or polycyclic structure containing —C (═O) —O—C (═O) —, and preferably represents a monocyclic structure. When Z 1a represents a monocyclic structure, it preferably forms a 5- to 7-membered ring, more preferably forms a 5- or 6-membered ring, and particularly preferably forms a 5-membered ring. When Z 1a represents a polycyclic structure, the polycyclic structure is preferably such that other ring structures are condensed to form a bicyclo structure or a spiro structure in the carboxylic anhydride structure. The other ring structures are synonymous with the other ring structures described above, and the preferred ranges are also the same.
In general formula (1), n 1a represents an integer of 0 or more, preferably an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0. When n 1a represents an integer of 2 or more, a plurality of substituents may be the same as or different from each other. A plurality of substituents may be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.
上記構成単位(a4)がラクトン構造を有する構成単位である場合、ラクトン構造としては、上記の加水分解性の条件を満たす限りにおいて特に限定されない。本発明で用いられるラクトン構造としては、5~7員環を形成するラクトン構造が好ましく、5員環又は6員環を形成するラクトン構造がより好ましい。
また、本発明で用いられるラクトン構造を有する構成単位としては、5~7員環を形成するラクトン構造に、ラクトン構造に他の環構造が縮環して多環構造を形成していてもよいが、ラクトン構造に他の環構造が縮環していないことが好ましい。5~7員環を形成するラクトン構造に、他の環構造が縮環していている場合、ビシクロ構造又はスピロ構造を形成する形で他の環構造が縮環していていることが好ましい。他の環構造としては、炭素数3~20の環状の炭化水素基、炭素数3~20のヘテロ環基等が挙げられる。ヘテロ環基としては、特に限定されないが、環を構成する原子のうち1つ以上がヘテロ原子があるもの又は芳香族ヘテロ環基が挙げられる。また、ヘテロ環基としては、5員環又は6員環が好ましく、5員環が特に好ましい。具体的には、ヘテロ環基は、酸素原子を少なくとも一つ含有するものが好ましく、例えば、オキソラン環、オキサン環、ジオキサン環等が挙げられる。
ラクトン構造を有する構成単位において、ラクトン構造に他の環構造が縮環して多環構造を形成している場合、ラクトン構造に縮環している他の環構造の数は1~5が好ましく、1~3がより好ましい。 <<< Structural Unit Having Lactone Ring Structure >>>
When the structural unit (a4) is a structural unit having a lactone structure, the lactone structure is not particularly limited as long as the hydrolyzability condition is satisfied. The lactone structure used in the present invention is preferably a lactone structure that forms a 5- to 7-membered ring, and more preferably a lactone structure that forms a 5-membered or 6-membered ring.
In addition, as the structural unit having a lactone structure used in the present invention, a lactone structure forming a 5- to 7-membered ring may be condensed with another ring structure on the lactone structure to form a polycyclic structure. However, it is preferable that other ring structures are not condensed to the lactone structure. When the lactone structure forming a 5- to 7-membered ring is condensed with another ring structure, the other ring structure is preferably condensed so as to form a bicyclo structure or a spiro structure. Examples of other ring structures include a cyclic hydrocarbon group having 3 to 20 carbon atoms, a heterocyclic group having 3 to 20 carbon atoms, and the like. The heterocyclic group is not particularly limited, and examples thereof include those having one or more heteroatoms out of the atoms constituting the ring or aromatic heterocyclic groups. Moreover, as a heterocyclic group, a 5-membered ring or a 6-membered ring is preferable, and a 5-membered ring is especially preferable. Specifically, the heterocyclic group preferably contains at least one oxygen atom, and examples thereof include an oxolane ring, an oxane ring, and a dioxane ring.
In the structural unit having a lactone structure, when another ring structure is condensed to the lactone structure to form a polycyclic structure, the number of the other ring structures condensed to the lactone structure is preferably 1 to 5 1 to 3 are more preferable.
アルキル基としては、直鎖状の炭素数1~6のアルキル基、分岐状の炭素数3~6のアルキル基又は環状の炭素数3~6のアルキル基が好ましく、直鎖状の炭素数1~3のアルキル基がより好ましい。
ラクトン構造が置換基を有する場合、置換基の数は、特に限定されないが、1~4が好ましく、1又は2がより好ましい。本発明で用いられるラクトン構造が複数の置換基を有する場合、複数の置換基は、互いに同一でも異なっていてもよい。また、ラクトン構造に他の環構造が縮環していている場合、この他の環構造が置換基を有していてもよい。 The lactone structure used in the present invention may or may not have a substituent, but preferably does not have a substituent. Examples of the substituent include, but are not limited to, for example, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, Examples include a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, and an acid-decomposable group. More preferred are an alkyl group having 1 to 4 carbon atoms and a cyano group.
As the alkyl group, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms is preferable. More preferred are ˜3 alkyl groups.
When the lactone structure has a substituent, the number of substituents is not particularly limited, but is preferably 1 to 4, and more preferably 1 or 2. When the lactone structure used in the present invention has a plurality of substituents, the plurality of substituents may be the same as or different from each other. Further, when another ring structure is condensed to the lactone structure, this other ring structure may have a substituent.
一般式(2-1)
一般式(2-1)中、RA1は置換基を表し、n1個のRA1はそれぞれ独立しており、同一でも異なっていてもよい。RA1は、上述したラクトン構造が有していてもよい置換基と同義であり、好ましい範囲も同様である。
一般式(2-1)中、Z1は-O-C(=O)-を含む単環又は多環構造を表し、単環構造を表すことが好ましい。Z1が単環構造を表す場合、単環構造としては、5~7員環を形成するラクトン構造が好ましく、5員環又は6員環を形成するラクトン構造がより好ましい。Z1が多環構造を表す場合、多環構造としては、ラクトン構造に、ビシクロ構造又はスピロ構造を形成する形で他の環構造が縮環していることが好ましい。他の環構造としては、上述した他の環構造と同義であり、好ましい範囲も同様である。
一般式(2-1)中、n1は0以上の整数を表し、0~4の整数が好ましく、0~2の整数が好ましく、0がさらに好ましい。n1が2以上の整数を表す場合、複数存在する置換基は、互いに同一でも異なっていてもよい。また、複数存在する置換基は、互いに結合して環を形成してもよいが、互いに結合して環を形成していないことが好ましい。 The structural unit having a lactone structure used in the present invention preferably contains a partial structure represented by the following general formula (2-1).
Formula (2-1)
In general formula (2-1), R A1 represents a substituent, and n1 R A1 s are independent and may be the same or different. R A1 has the same meaning as the substituent that the above-mentioned lactone structure may have, and the preferred range is also the same.
In general formula (2-1), Z 1 represents a monocyclic or polycyclic structure containing —O—C (═O) —, and preferably represents a monocyclic structure. When Z 1 represents a monocyclic structure, the monocyclic structure is preferably a lactone structure that forms a 5- to 7-membered ring, and more preferably a lactone structure that forms a 5-membered or 6-membered ring. When Z 1 represents a polycyclic structure, the polycyclic structure preferably has a condensed lactone structure with another cyclic structure forming a bicyclo structure or a spiro structure. The other ring structures are synonymous with the other ring structures described above, and the preferred ranges are also the same.
In general formula (2-1), n1 represents an integer of 0 or more, preferably an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0. When n1 represents an integer of 2 or more, a plurality of substituents may be the same as or different from each other. A plurality of substituents may be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.
一般式(2-2)
一般式(2-2)中、RX1は水素原子又はアルキル基を表す。アルキル基としては、直鎖状又は分岐状の炭素数1~3のアルキル基が好ましく、メチル基がより好ましい。アルキル基は、置換基を有していてもよい。置換基としては、ヒドロキシル基又はハロゲン原子(特にフッ素原子)が好ましい。
一般式(2-2)中、RA2は置換基を表し、n2個のRA2はそれぞれ独立しており、同一でも異なっていてもよい。RA2は、上述したラクトン構造が有していてもよい置換基と同義であり、好ましい範囲も同様である。
一般式(2-2)中、A1は単結合又は2価の連結基を表す。2価の連結基としては、直鎖状、分岐鎖状又は環状のアルキレン基、アリーレン基、-O-、-COO-、-S-、-NR”-、-CO-、-NR”CO-、-SO2-等の二価の基、又はこれらの基の組み合わせからなるものが挙げられる。ここで、R”は、水素原子又は炭素数1~4のアルキル基を表し、水素原子が好ましい。二価の連結基としては、-O-、-COO-、-S-、-NH-及び-CO-の少なくとも1つ、又は、これらの基と、-(CH2)m-(mは1~10の整数、好ましくは1~6の整数、より好ましくは1~4の整数)との組み合わせからなる基が好ましい。
一般式(2-2)中、Z2は-O-C(=O)-で表される基を含む単環又は多環構造を表し、一般式(2-1)中のZ1と同義であり、好ましい範囲も同様である。
一般式(2-2)中、n2は0以上の整数を表し、一般式(1)中のn1と同義であり、好ましい範囲も同様である。 When the structural unit (a4) is a structural unit containing a lactone structure, it is preferably represented by the following general formula (2-2).
Formula (2-2)
In general formula (2-2), R X1 represents a hydrogen atom or an alkyl group. As the alkyl group, a linear or branched alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable. The alkyl group may have a substituent. As the substituent, a hydroxyl group or a halogen atom (particularly a fluorine atom) is preferable.
In general formula (2-2), R A2 represents a substituent, and n2 R A2 s are independent and may be the same or different. R A2 has the same meaning as the substituent that the lactone structure described above may have, and the preferred range is also the same.
In general formula (2-2), A 1 represents a single bond or a divalent linking group. Examples of the divalent linking group include a linear, branched or cyclic alkylene group, an arylene group, —O—, —COO—, —S—, —NR ″ —, —CO—, and —NR ″ CO—. , —SO 2 — and the like, or a combination of these groups. Here, R ″ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom. Examples of the divalent linking group include —O—, —COO—, —S—, —NH— and At least one of —CO— or a group thereof and — (CH 2 ) m — (m is an integer of 1 to 10, preferably an integer of 1 to 6, more preferably an integer of 1 to 4) Groups consisting of combinations are preferred.
In general formula (2-2), Z 2 represents a monocyclic or polycyclic structure containing a group represented by —O—C (═O) —, and has the same meaning as Z 1 in general formula (2-1). The preferred range is also the same.
In general formula (2-2), n2 represents an integer of 0 or more, and is synonymous with n1 in general formula (1), and the preferred range is also the same.
一般式(2-3)
一般式(2-3)中、RA3は置換基を表し、n3個のRA3はそれぞれ独立しており、同一でも異なっていてもよい。RA3は、上述したラクトン構造が有していてもよい置換基と同義であり、好ましい範囲も同様である。
一般式(2-3)中、A2は単結合又は2価の連結基を表す。2価の連結基としては、一般式(2-2)中のA1が2価の連結基を表す場合と同義である。好ましい2価の連結基としては、-COO-、-CO-の少なくとも1つ、又は、これらの基と、-(CH2)m-(mは1~10の整数、好ましくは1~6の整数、より好ましくは1~4の整数)との組み合わせからなる基が好ましい。特に、一般式(2-3)中のA2としては、単結合が好ましい。
一般式(2-3)中、Z3は-O-C(=O)-で表される基を含む単環又は多環構造を表し、一般式(2-1)中のZ1と同義であり、好ましい範囲も同様である。
一般式(2-3)中、n3は0以上の整数を表し、一般式(2-1)中のn1と同義であり、好ましい範囲も同様である。
一般式(2-3)中、X1は酸素原子又は-NR”-を表し、酸素原子であることが好ましい。R”は水素原子又は炭素数1~4のアルキル基を表し、水素原子が好ましい。 When the structural unit (a4) is a structural unit containing a lactone structure, it is preferably represented by the following general formula (2-3).
General formula (2-3)
In general formula (2-3), R A3 represents a substituent, and n3 R A3 s are independent and may be the same or different. R A3 has the same meaning as the substituent that the lactone structure described above may have, and the preferred range is also the same.
In general formula (2-3), A 2 represents a single bond or a divalent linking group. The divalent linking group is synonymous with the case where A 1 in the general formula (2-2) represents a divalent linking group. A preferred divalent linking group is at least one of —COO— and —CO—, or these groups, and — (CH 2 ) m — (m is an integer of 1 to 10, preferably 1 to 6. A group consisting of a combination with an integer, more preferably an integer of 1 to 4, is preferred. In particular, A 2 in the general formula (2-3) is preferably a single bond.
In general formula (2-3), Z 3 represents a monocyclic or polycyclic structure containing a group represented by —O—C (═O) —, and has the same meaning as Z 1 in general formula (2-1). The preferred range is also the same.
In general formula (2-3), n3 represents an integer of 0 or more, and is synonymous with n1 in general formula (2-1), and the preferred range is also the same.
In general formula (2-3), X 1 represents an oxygen atom or —NR ″ —, preferably an oxygen atom. R ″ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferable.
より好ましい構造としては、(LC1-1)、(LC1-4)、(LC1-5)、(LC1-6)、(LC1-13)、(LC1-14)、(LC1-17)であり、特に好ましい構造としては、(LC1-1)、(LC1-4)、(LC1-17)である。上記構成単位(a4)が、このような構造を含むことにより、本発明の組成物の耐薬品性を良好にしつつ、比誘電率をより低くすることができる。
More preferred structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), (LC1-17), Particularly preferred structures are (LC1-1), (LC1-4), and (LC1-17). When the structural unit (a4) includes such a structure, the relative dielectric constant can be further lowered while improving the chemical resistance of the composition of the present invention.
また、上記一般式(LC1-1)~(LC1-21)で表される構造において、n4は、上記一般式(2-1)中のn1と同義であり、好ましい範囲も同様である。 In the structures represented by the above general formulas (LC1-1) to (LC1-21), (Rb 2 ) represents a substituent, which may or may not have ( That is, in the general formulas (LC1-1) to (LC1-21), n4 is 0). The preferred substituent (Rb 2 ) is synonymous with the substituent that the above-mentioned lactone structure may have, and the preferred range is also the same.
In the structures represented by the general formulas (LC1-1) to (LC1-21), n4 has the same meaning as n1 in the general formula (2-1), and the preferred range is also the same.
(A)重合体成分は、(a3)酸基を有する構成単位を含んでいることが好ましい。酸基を含むことにより、アルカリ性の現像液との親和性が高まり、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、酸基を含む構成単位として、重合体に組み込まれる。このような酸基を含む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、カルボン酸基由来のもの、スルホンアミド基に由来のもの、ホスホン酸基に由来のもの、スルホン酸基に由来のもの、フェノール性水酸基に由来するもの、スルホンアミド基、スルホニルイミド基等が例示され、カルボン酸基由来のもの及び/又はフェノール性水酸基に由来のものが好ましい。
本発明で用いられる酸基を含む構成単位は、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より好ましい。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。なかでも、p-ヒドロキシスチレン、(メタ)アクリル酸、マレイン酸に由来する構成単位が好ましく、(メタ)アクリル酸に由来する構成単位が特に好ましい。 << (a3) Structural Unit Having Acid Group >>
(A) The polymer component preferably contains (a3) a structural unit having an acid group. By containing an acid group, the affinity with an alkaline developer is increased, and the effects of the present invention are more effectively exhibited. The acid group is usually incorporated into the polymer as a structural unit containing an acid group using a monomer capable of forming an acid group. By including such a structural unit containing an acid group in the polymer, the polymer tends to be easily dissolved in an alkaline developer.
Acid groups used in the present invention include those derived from carboxylic acid groups, those derived from sulfonamide groups, those derived from phosphonic acid groups, those derived from sulfonic acid groups, those derived from phenolic hydroxyl groups, sulfones Examples include amide groups, sulfonylimide groups, and the like, and those derived from carboxylic acid groups and / or those derived from phenolic hydroxyl groups are preferred.
The structural unit containing an acid group used in the present invention is more 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. Of these, structural units derived from p-hydroxystyrene, (meth) acrylic acid and maleic acid are preferred, and structural units derived from (meth) acrylic acid are particularly preferred.
その他にも、特開平7-207211号公報、特開平8-259876号公報、特開平10-300922号公報、特開平11-140144号公報、特開平11-174224号公報、特開2000-56118号公報、特開2003-233179号公報、特開2009-52020号公報等に記載の公知の高分子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。
これらの重合体は、1種類のみ含んでいてもよいし、2種類以上含んでいてもよい。 More specifically, as the polymer (A5), benzyl (meth) acrylate / (meth) acrylic acid copolymer, 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / Benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzine Methacrylate / methacrylic acid copolymer and the like.
In addition, JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118 Known polymer compounds described in JP-A-2003-233179, JP-A-2009-52020, and the like can be used, and the contents thereof are incorporated herein.
These polymers may contain only 1 type and may contain 2 or more types.
本発明において、(A)重合体成分は、上記構成単位(a1)、(a2)、(a4)及び(a3)に加えて、これら以外の他の構成単位(a5)を有していてもよい。(A)重合体成分が構成単位(a5)を有する場合は、上記重合体(A1)~(A5)のうち少なくとも1つの重合体が上記構成単位(a5)を有していてもよいし、上記構成単位(a1)~(a4)のいずれをも有さず、構成単位(a5)を有する重合体(重合体(A6)ともいう)として、(A)重合体成分中に含まれていてもよい。
構成単位(a5)を形成する原料モノマーとしては、特に制限はなく、例えば、スチレン類、(メタ)アクリル酸アルキルエステル、(メタ)アクリル酸環状アルキルエステル、(メタ)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類、マレイミド化合物類、不飽和芳香族化合物、共役ジエン系化合物、その他の不飽和化合物を挙げることができる。構成単位(a5)となるモノマーは、単独又は2種類以上を組み合わせて使用することができる。 << Other structural units >>
In the present invention, the polymer component (A) may have other structural units (a5) in addition to the structural units (a1), (a2), (a4) and (a3). Good. When the polymer component (A) has the structural unit (a5), at least one of the polymers (A1) to (A5) may have the structural unit (a5). As a polymer having no structural unit (a1) to (a4) and having the structural unit (a5) (also referred to as polymer (A6)), it is contained in the polymer component (A). Also good.
The raw material monomer for forming the structural unit (a5) is not particularly limited, and examples thereof include styrenes, (meth) acrylic acid alkyl esters, (meth) acrylic acid cyclic alkyl esters, (meth) acrylic acid aryl esters, and unsaturated compounds. Examples thereof include dicarboxylic acid diesters, bicyclo unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, and other unsaturated compounds. The monomer which becomes a structural unit (a5) can be used individually or in combination of 2 or more types.
本発明の感光性樹脂組成物は、(B)光酸発生剤を含有する。本発明で使用される光酸発生剤としては、波長300nm以上、好ましくは波長300~450nmの活性光線に感応し、酸を発生する化合物が好ましいが、その化学構造に制限されるものではない。また、波長300nm以上の活性光線に直接感応しない光酸発生剤についても、増感剤と併用することによって波長300nm以上の活性光線に感応し、酸を発生する化合物であれば、増感剤と組み合わせて好ましく用いることができる。本発明で使用される光酸発生剤としては、pKaが4以下の酸を発生する光酸発生剤が好ましく、pKaが3以下の酸を発生する光酸発生剤がより好ましく、2以下の酸を発生する光酸発生剤が最も好ましい。 <(B) Photoacid generator>
The photosensitive resin composition of the present invention contains (B) a photoacid generator. The photoacid generator used in the present invention is preferably a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but is not limited to its chemical structure. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination. The photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and an acid of 2 or less. Most preferred are photoacid generators that generate.
一般式(B1-1)
General formula (B1-1)
R21のアルキル基としては、炭素数1~10の、直鎖状又は分岐状アルキル基が好ましい。R21のアルキル基は、ハロゲン原子、炭素数6~11のアリール基、炭素数1~10のアルコキシ基、又は、シクロアルキル基(7,7-ジメチル-2-オキソノルボルニル基などの有橋式脂環基を含む、好ましくはビシクロアルキル基等)で置換されてもよい。
R21のアリール基としては、炭素数6~11のアリール基が好ましく、フェニル基又はナフチル基がより好ましい。R21のアリール基は、低級アルキル基、アルコキシ基あるいはハロゲン原子で置換されてもよい。 In general formula (B1-1), any group may be substituted, and the alkyl group in R 21 may be linear, branched or cyclic. Acceptable substituents are described below.
The alkyl group for R 21 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group represented by R 21 has a halogen atom, an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group, etc.). It may be substituted with a bridged alicyclic group, preferably a bicycloalkyl group or the like.
As the aryl group for R 21, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R 21 may be substituted with a lower alkyl group, an alkoxy group, or a halogen atom.
一般式(B1-2)
General formula (B1-2)
Xとしてのアルキル基は、炭素数1~4の直鎖状又は分岐状アルキル基が好ましい。また、Xとしてのアルコキシ基は、炭素数1~4の直鎖状又は分岐状アルコキシ基が好ましい。また、Xとしてのハロゲン原子は、塩素原子又はフッ素原子が好ましい。
m4は、0又は1が好ましい。上記一般式(B2)中、m4が1であり、Xがメチル基であり、Xの置換位置がオルト位であり、R42が炭素数1~10の直鎖状アルキル基、7,7-ジメチル-2-オキソノルボルニルメチル基、又はp-トルイル基である化合物が特に好ましい。 Preferred ranges of R 42, the same as the preferable range of the R 21.
The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. Further, the alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom as X is preferably a chlorine atom or a fluorine atom.
m4 is preferably 0 or 1. In the above general formula (B2), m4 is 1, X is a methyl group, the substitution position of X is the ortho position, R 42 is a linear alkyl group having 1 to 10 carbon atoms, 7,7- A compound that is a dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferred.
一般式(B1-3)
General formula (B1-3)
X1としては、炭素数1~5のアルコキシ基が好ましく、メトキシ基がより好ましい。
n4としては、0~2が好ましく、0~1が特に好ましい。
上記一般式(B1-3)で表される化合物の具体例及び好ましいオキシムスルホネート化合物の具体例としては、特開2012-163937号公報の段落番号0080~0082の記載を参酌でき、この内容は本願明細書に組み込まれる。 R 43 in the above general formula (B1-3) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n—. A propyl group, a perfluoro-n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferable, and an n-octyl group is particularly preferable.
X 1 is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
n4 is preferably from 0 to 2, particularly preferably from 0 to 1.
As specific examples of the compound represented by the above general formula (B1-3) and preferable examples of the oxime sulfonate compound, description in paragraphs 0080 to 0082 of JP2012-163937A can be referred to, and the contents thereof are described in this application. Incorporated in the description.
X101は-O-、-S-、-NH-、-NR105-、-CH2-、-CR106H-、又は、-CR105R107-を表し、R105~R107はアルキル基、又は、アリール基を表す。
R121~R124は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルケニル基、アルコキシ基、アミノ基、アルコキシカルボニル基、アルキルカルボニル基、アリールカルボニル基、アミド基、スルホ基、シアノ基、又は、アリール基を表す。R121~R124のうち2つは、それぞれ互いに結合して環を形成してもよい。 R121~R124としては、水素原子、ハロゲン原子、及び、アルキル基が好ましく、また、R121~R124のうち少なくとも2つが互いに結合してアリール基を形成する態様もまた、好ましく挙げられる。中でも、R121~R124がいずれも水素原子である態様が感度の観点から好ましい。
既述の官能基は、いずれも、さらに置換基を有していてもよい。
上記一般式(OS-1)で表される化合物は、例えば、特開2012-163937号公報の段落番号0087~0089に記載されている一般式(OS-2)で表される化合物であることが好ましく、この内容は本願明細書に組み込まれる。 In the general formula (OS-1), R 101 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or Represents a heteroaryl group. R102 represents an alkyl group or an aryl group.
X 101 represents —O—, —S—, —NH—, —NR 105 —, —CH 2 —, —CR 106 H—, or —CR 105 R 107 —, wherein R 105 to R 107 are alkyl groups. Or an aryl group.
R 121 ~ R 124 are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amido group, a sulfo group, a cyano group, Or an aryl group is represented. Two of R 121 to R 124 may be bonded to each other to form a ring. R 121 to R 124 are preferably a hydrogen atom, a halogen atom and an alkyl group, and an embodiment in which at least two of R 121 to R 124 are bonded to each other to form an aryl group is also preferred. Among these, an embodiment in which R 121 to R 124 are all hydrogen atoms is preferable from the viewpoint of sensitivity.
Any of the aforementioned functional groups may further have a substituent.
The compound represented by the general formula (OS-1) is, for example, a compound represented by the general formula (OS-2) described in paragraph numbers 0087 to 0089 of JP2012-163937A Which is incorporated herein by reference.
本発明では、上記一般式(B1-1)で表されるオキシムスルホネート構造を含有する化合物としては、下記一般式(OS-3)、下記一般式(OS-4)又は下記一般式(OS-5)で表されるオキシムスルホネート化合物であることが好ましい。
上記一般式(OS-3)~(OS-5)については、例えば、特開2012-163937号公報の段落番号0098~0115の記載を参酌でき、この内容は本願明細書に組み込まれる。 Specific examples of the compound represented by the general formula (OS-1) that can be suitably used in the present invention include compounds described in paragraph numbers 0128 to 0132 of JP2011-221494A (exemplified compounds b-1 to b-34), but the present invention is not limited thereto.
In the present invention, the compound containing the oxime sulfonate structure represented by the general formula (B1-1) is represented by the following general formula (OS-3), the following general formula (OS-4) or the following general formula (OS- The oxime sulfonate compound represented by 5) is preferred.
Regarding the general formulas (OS-3) to (OS-5), for example, the description of paragraph numbers 0098 to 0115 of JP2012-163937A can be referred to, and the contents thereof are incorporated in the present specification.
上記一般式(OS-6)~(OS-11)における好ましい範囲は、特開2011-221494号公報の段落番号0110~0112に記載される(OS-6)~(OS-11)の好ましい範囲と同様であり、この内容は本願明細書に組み込まれる。
上記一般式(OS-3)~上記一般式(OS-5)で表されるオキシムスルホネート化合物の具体例としては、特開2011-221494号公報の段落番号0114~0120に記載の化合物が挙げられ、この内容は本願明細書に組み込まれる。本発明は、これらに限定されるものではない。 In addition, the compound containing an oxime sulfonate structure represented by the above general formula (B1-1) is, for example, a compound represented by the general formula (OS-6) described in paragraph 0117 of JP2012-163937A. Particularly preferred is a compound represented by any of (OS-11), the contents of which are incorporated herein.
Preferred ranges in the above general formulas (OS-6) to (OS-11) are preferred ranges of (OS-6) to (OS-11) described in paragraph numbers 0110 to 0112 of JP2011-221494A. The contents of which are incorporated herein by reference.
Specific examples of the oxime sulfonate compound represented by the general formula (OS-3) to the general formula (OS-5) include compounds described in paragraph numbers 0114 to 0120 of JP2011-221494A. The contents of which are incorporated herein by reference. The present invention is not limited to these.
一般式(B1-4)
General formula (B1-4)
アルキル基の炭素数は、好ましくは3~10である。特にアルキル基が分岐構造を有する場合、炭素数3~6のアルキル基が好ましく、環状構造を有する場合、炭素数5~7のアルキル基が好ましい。
アルキル基としては、例えば、プロピル基、イソプロピル基、n-ブチル基、s-ブチル基、イソブチル基、tert-ブチル基、ペンチル基、イソペンチル基、ネオペンチル基、1,1-ジメチルプロピル基、ヘキシル基、2-エチルヘキシル基、シクロヘキシル基、オクチル基などが挙げられ、好ましくは、イソプロピル基、tert-ブチル基、ネオペンチル基、シクロヘキシル基である。
アリール基の炭素数は、好ましくは6~12であり、より好ましくは6~8であり、さらに好ましくは6~7である。上記アリール基としては、フェニル基、ナフチル基などが挙げられ、好ましくは、フェニル基である。
R1が表すアルキル基及びアリール基は、置換基を有していてもよい。置換基としては、例えばハロゲン原子(フッ素原子、クロロ原子、臭素原子、ヨウ素原子)、直鎖、分岐又は環状のアルキル基(例えばメチル基、エチル基、プロピル基など)、アルケニル基、アルキニル基、アリール基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、カルバモイル基、シアノ基、カルボキシル基、水酸基、アルコキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基、ヘテロ環オキシ基、アシルオキシ基、アミノ基、ニトロ基、ヒドラジノ基、ヘテロ環基などが挙げられる。また、これらの基によってさらに置換されていてもよい。好ましくは、ハロゲン原子、メチル基である。 R 1 represents an alkyl group or an aryl group. The alkyl group is preferably a branched alkyl group or a cyclic alkyl group.
The alkyl group preferably has 3 to 10 carbon atoms. In particular, when the alkyl group has a branched structure, an alkyl group having 3 to 6 carbon atoms is preferable. When the alkyl group has a cyclic structure, an alkyl group having 5 to 7 carbon atoms is preferable.
Examples of the alkyl group include propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, 1,1-dimethylpropyl group, hexyl group. 2-ethylhexyl group, cyclohexyl group, octyl group and the like, preferably isopropyl group, tert-butyl group, neopentyl group, and cyclohexyl group.
The aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms, and still more preferably 6 to 7 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferable.
The alkyl group and aryl group represented by R 1 may have a substituent. Examples of the substituent include a halogen atom (a fluorine atom, a chloro atom, a bromine atom, an iodine atom), a linear, branched or cyclic alkyl group (for example, a methyl group, an ethyl group, a propyl group), an alkenyl group, an alkynyl group, Aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, cyano group, carboxyl group, hydroxyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, heterocyclic oxy group, acyloxy group, amino group, A nitro group, a hydrazino group, a heterocyclic group, etc. are mentioned. Further, these groups may be further substituted. Preferably, they are a halogen atom and a methyl group.
かさ高い置換基の中でも、イソプロピル基、tert-ブチル基、ネオペンチル基、シクロヘキシル基が好ましく、tert-ブチル基、シクロヘキシル基がより好ましい。 In the photosensitive resin composition of the present invention, R 1 is preferably an alkyl group from the viewpoint of transparency, and R 1 has a branched structure having 3 to 6 carbon atoms from the viewpoint of achieving both storage stability and sensitivity. An alkyl group, an alkyl group having a cyclic structure having 5 to 7 carbon atoms, or a phenyl group is preferable, and an alkyl group having a branched structure having 3 to 6 carbon atoms or an alkyl group having a cyclic structure having 5 to 7 carbon atoms is more preferable. . By adopting such a bulky group (particularly a bulky alkyl group) as R 1 , it becomes possible to further improve the transparency.
Among the bulky substituents, an isopropyl group, a tert-butyl group, a neopentyl group, and a cyclohexyl group are preferable, and a tert-butyl group and a cyclohexyl group are more preferable.
アリール基としては、炭素数6~10のアリール基が好ましい。上記アリール基としては、フェニル基、ナフチル基、p-トルイル基(p-メチルフェニル基)などが挙げられ、好ましくは、フェニル基、p-トルイル基である。
ヘテロアリール基としては、例えば、ピロール基、インドール基、カルバゾール基、フラン基、チオフェン基などが挙げられる。
R2が表すアルキル基、アリール基、及びヘテロアリール基は、置換基を有していてもよい。置換基としては、R1が表すアルキル基及びアリール基が有していてもよい置換基と同義である。
R2は、アルキル基又はアリール基が好ましく、アリール基がより好ましく、フェニル基がより好ましい。フェニル基の置換基としてはメチル基が好ましい。 R 2 represents an alkyl group, an aryl group, or a heteroaryl group. The alkyl group represented by R 2 is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, and a cyclohexyl group. It is a group.
As the aryl group, an aryl group having 6 to 10 carbon atoms is preferable. Examples of the aryl group include a phenyl group, a naphthyl group, a p-toluyl group (p-methylphenyl group), and a phenyl group and a p-toluyl group are preferable.
Examples of the heteroaryl group include a pyrrole group, an indole group, a carbazole group, a furan group, and a thiophene group.
The alkyl group, aryl group, and heteroaryl group represented by R 2 may have a substituent. As a substituent, it is synonymous with the substituent which the alkyl group and aryl group which R < 1 > may have.
R 2 is preferably an alkyl group or an aryl group, more preferably an aryl group, and more preferably a phenyl group. As the substituent for the phenyl group, a methyl group is preferred.
R3~R6のうち、R3とR4、R4とR5、又はR5とR6が結合して環を形成してもよく、環としては、脂環又は芳香環を形成していることが好ましく、ベンゼン環がより好ましい。
R3~R6は、水素原子、アルキル基、ハロゲン原子(フッ素原子、クロロ原子、臭素原子)、又は、R3とR4、R4とR5、又はR5とR6が結合してベンゼン環を構成していることが好ましく、水素原子、メチル基、フッ素原子、クロロ原子、臭素原子又はR3とR4、R4とR5、又はR5とR6が結合してベンゼン環を構成していることがより好ましい。
R3~R6の好ましい態様は以下の通りである。
(態様1)少なくとも2つは水素原子である。
(態様2)アルキル基、アリール基、又はハロゲン原子の数は、1つ以下である。
(態様3)R3とR4、R4とR5、又はR5とR6が結合してベンゼン環を構成している。
(態様4)上記態様1と2を満たす態様、及び/又は、上記態様1と3を満たす態様。
Xは、-O-又はS-を表す。 R 3 to R 6 each represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom (a fluorine atom, a chloro atom, a bromine atom, or an iodine atom). The alkyl group represented by R 3 to R 6 has the same meaning as the alkyl group represented by R 2 , and the preferred range is also the same. The aryl group represented by R 3 to R 6 has the same meaning as the aryl group represented by R 1 , and the preferred range is also the same.
Among R 3 to R 6 , R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 may combine to form a ring, and the ring may form an alicyclic ring or an aromatic ring. It is preferable that a benzene ring is more preferable.
R 3 to R 6 are a hydrogen atom, an alkyl group, a halogen atom (fluorine atom, chloro atom, bromine atom), or R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 A benzene ring is preferably formed, and a hydrogen atom, a methyl group, a fluorine atom, a chloro atom, a bromine atom, or R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 are combined to form a benzene ring Is more preferable.
Preferred embodiments of R 3 to R 6 are as follows.
(Aspect 1) At least two are hydrogen atoms.
(Aspect 2) The number of alkyl groups, aryl groups, or halogen atoms is one or less.
(Aspect 3) R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 are combined to form a benzene ring.
(Aspect 4) An aspect satisfying the
X represents —O— or S—.
本発明の感光性樹脂組成物は、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メチルエーテルアセテート等のプロピレングリコールモノアルキルエーテル類、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エチルメチルエーテル等の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。 <Solvent>
The photosensitive resin composition of the present invention contains 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 a solvent. 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 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 monomethyl ether. Propylene glycol monoalkyl ethers such as acetate, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers such as diethylene glycol ethyl methyl ether, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, Dipropylene glycol dialkyl ethers, dipropylene glycol monoal 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.
本発明の感光性樹脂組成物には、上記成分に加えて、必要に応じて、増感剤、架橋剤、アルコキシシラン化合物、塩基性化合物、界面活性剤、酸化防止剤を好ましく加えることができる。さらに本発明の感光性樹脂組成物には、酸増殖剤、現像促進剤、可塑剤、熱ラジカル発生剤、熱酸発生剤、紫外線吸収剤、増粘剤、及び、有機又は無機の沈殿防止剤などの公知の添加剤を加えることができる。また、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>
In addition to the above components, a sensitizer, a crosslinking agent, an alkoxysilane compound, a basic compound, a surfactant, and an antioxidant can be preferably added to the photosensitive resin composition of the present invention as necessary. . Furthermore, the photosensitive resin composition of the present invention includes an acid proliferation agent, a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor. Known additives such as can be added. Further, as these compounds, for example, compounds described in paragraph numbers 0201 to 0224 of JP2012-8859A 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、光酸発生剤との組み合わせにおいて、その分解を促進させるために、増感剤を含有することが好ましい。増感剤は、活性光線又は放射線を吸収して電子励起状態となる。電子励起状態となった増感剤は、光酸発生剤と接触して、電子移動、エネルギー移動、発熱などの作用が生じる。これにより光酸発生剤は化学変化を起こして分解し、酸を生成する。好ましい増感剤の例としては、以下の化合物類に属しており、かつ350nmから450nmの波長域のいずれかに吸収波長を有する化合物を挙げることができる。 Sensitizer The photosensitive resin composition of the present invention preferably contains a sensitizer in combination with a photoacid generator in order to promote its decomposition. The sensitizer absorbs actinic rays or radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise | generates a chemical change and decomposes | disassembles and produces | generates an acid. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm.
これら増感剤の中でも、多核芳香族類、アクリドン類、スチリル類、ベーススチリル類、クマリン類が好ましく、多核芳香族類がより好ましい。多核芳香族類の中でもアントラセン誘導体が最も好ましい。 Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene), xanthenes (Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines ( For example, merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine oleoresin) Di, chloroflavin, acriflavine), acridones (eg, acridone, 10-butyl-2-chloroacridone), anthraquinones (eg, anthraquinone), squaliums (eg, squalium), styryls, base styryls ( For example, 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (for example, 7-diethylamino 4-methylcoumarin, 7-hydroxy 4-methylcoumarin, 2,3,6,7 -Tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinolizine-11-non).
Among these sensitizers, polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable. Of the polynuclear aromatics, anthracene derivatives are most preferred.
本発明の感光性樹脂組成物は、必要に応じ、架橋剤を含有することが好ましい。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。ただし、本発明において架橋剤とは、重合体である場合、すなわち(A)重合体成分の1つである場合を含まない。例えば、以下に述べる分子内に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。
本発明の感光性樹脂組成物中における架橋剤の添加量は、本発明の感光性樹脂組成物中の全固形分に対し、0.01~50質量%であることが好ましく、0.1~30質量%であることがより好ましく、0.5~20質量%であることがさらに好ましい。この範囲で添加することにより、機械的強度及び耐溶剤性に優れた硬化膜が得られる。架橋剤は複数を併用することもでき、その場合は架橋剤を全て合算して含有量を計算する。 Crosslinking agent It is preferable that the photosensitive resin composition of this invention contains 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. However, in the present invention, the crosslinking agent does not include the case where it is a polymer, that is, the case where it is one of the polymer components (A). For example, a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, a compound having at least one ethylenically unsaturated double bond, a blocked isocyanate compound, etc. Can be added.
The addition amount of the crosslinking agent in the photosensitive resin composition of the present invention is preferably 0.01 to 50% by mass with respect to the total solid content in the photosensitive resin composition of the present invention, preferably 0.1 to It is more preferably 30% by mass, and further preferably 0.5 to 20% 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.
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.
これらの中でも、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及び脂肪族エポキシ樹脂がより好ましく挙げられ、ビスフェノールA型エポキシ樹脂が特に好ましく挙げられる。
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. For example, JER152, JER157S70, JER157S65, JER806, JER828, JER1007 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.), and the like are commercially available products described in paragraph No. 0189 of JP2011-221494, etc. EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX- 321L, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX-214L, X-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 (manufactured by Nagase Chemtech), YH-300 YH-301, YH-302, YH-315, YH-324, YH-325 (manufactured by Nippon Steel Chemical Co., Ltd.), Celoxide 2021P (manufactured by Daicel Corporation), and the like. These can be used alone or in combination of two or more.
Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin and aliphatic epoxy resin are more preferable, and bisphenol A type epoxy resin is particularly preferable.
As specific examples of the compound having two or more oxetanyl groups in the molecule, Aron oxetane OXT-121, OXT-221, OX-SQ, and 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。また、上記ブロックイソシアネート基は、90℃~250℃の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ることが好ましい。
また、ブロックイソシアネート化合物としては、その骨格は特に限定されるものではなく、1分子中にイソシアネート基を2個有するものであればどのようなものでもよく、脂肪族、脂環族又は芳香族のポリイソシアネートであってよいが、例えば2,4-トリレンジイソシアネート、2,6-トリレンジイソシアネート、イソホロンジイソシアネート、1,6-ヘキサメチレンジイソシアネート、1,3-トリメチレンジイソシアネート、1,4-テトラメチレンジイソシアネート、2,2,4-トリメチルヘキサメチレンジイソシアネート、2,4,4-トリメチルヘキサメチレンジイソシアネート、1,9-ノナメチレンジイソシアネート、1,10-デカメチレンジイソシアネート、1,4-シクロヘキサンジイソシアネート、2,2'-ジエチルエーテルジイソシアネート、ジフェニルメタン-4,4'-ジイソシアネート、o-キシレンジイソシアネート、m-キシレンジイソシアネート、p-キシレンジイソシアネート、メチレンビス(シクロヘキシルイソシアネート)、シクロヘキサン-1,3-ジメチレンジイソシアネート、シクロヘキサン-1,4-ジメチレレンジイソシアネート、1,5-ナフタレンジイソシアネート、p-フェニレンジイソシアネート、3,3'-メチレンジトリレン-4,4'-ジイソシアネート、4,4'-ジフェニルエーテルジイソシアネート、テトラクロロフェニレンジイソシアネート、ノルボルナンジイソシアネート、水素化1,3-キシリレンジイソシアネート、水素化1,4-キシリレンジイソシアネート等のイソシアネート化合物及びこれらの化合物から派生するプレポリマー型の骨格の化合物を好適に用いることができる。これらの中でも、トリレンジイソシアネート(TDI)やジフェニルメタンジイソシアネート(MDI)、ヘキサメチレンジイソシアネート(HDI)、イソホロンジイソシアネート(IPDI)が特に好ましい。
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。
上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. The blocked isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 ° C. to 250 ° C.
Further, the skeleton of the blocked isocyanate compound is not particularly limited and may be any as long as it has two isocyanate groups in one molecule, and may be aliphatic, alicyclic or aromatic. Polyisocyanates may be used, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene Diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2, '-Diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1, 4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3′-methylene ditolylene-4,4′-diisocyanate, 4,4′-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate, Isocyanate compounds such as hydrogenated 1,3-xylylene diisocyanate and hydrogenated 1,4-xylylene diisocyanate And prepolymer-type skeleton compounds derived from these compounds can be suitably used. Among these, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are particularly preferable.
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.
上記ラクタム化合物としてはε-カプロラクタム、γ-ブチロラクタム等が例示できる。
上記フェノール化合物としては、フェノール、ナフトール、クレゾール、キシレノール、ハロゲン置換フェノール等が例示できる。
上記アルコール化合物としては、メタノール、エタノール、プロパノール、ブタノール、シクロヘキサノール、エチレングリコールモノアルキルエーテル、プロピレングリコールモノアルキルエーテル、乳酸アルキル等が例示できる。
上記アミン化合物としては、1級アミン及び2級アミンが上げられ、芳香族アミン、脂肪族アミン、脂環族アミンいずれでもよく、アニリン、ジフェニルアミン、エチレンイミン、ポリエチレンイミン等が例示できる。
上記活性メチレン化合物としては、マロン酸ジエチル、マロン酸ジメチル、アセト酢酸エチル、アセト酢酸メチル等が例示できる。
上記ピラゾール化合物としては、ピラゾール、メチルピラゾール、ジメチルピラゾール等が例示できる。
上記メルカプタン化合物としては、アルキルメルカプタン、アリールメルカプタン等が例示できる。 Examples of the oxime compound include oxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and acetoxime.
Examples of the lactam compound include ε-caprolactam and γ-butyrolactam.
Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
Examples of the amine compound include primary amines and secondary amines, which may be aromatic amines, aliphatic amines, and alicyclic amines, and examples thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.
Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
Examples of the mercaptan compound include alkyl mercaptans and aryl mercaptans.
本発明の感光性樹脂組成物は、アルコキシシラン化合物を含有してもよい。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、ビス(トリエトキシシリルプロピル)テトラスルフィド、デシルトリメト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 may contain an alkoxysilane compound. 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, Bis (triethoxysilylpropyl) tetrasulfide and decyltrimethoxysilane are 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、本発明の感光性樹脂組成物中の全固形分に対し、0.1~30質量%が好ましく、0.5~20質量%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% by mass, and preferably 0.5 to 20% by mass with respect to the total solid content in the photosensitive resin composition of the present invention. Is more preferable.
本発明の感光性樹脂組成物は、塩基性化合物を含有してもよい。塩基性化合物としては、化学増幅レジストで用いられるものの中から任意に選択して使用することができる。例えば、脂肪族アミン、芳香族アミン、複素環式アミン、第四級アンモニウムヒドロキシド、カルボン酸の第四級アンモニウム塩等が挙げられる。これらの具体例としては、特開2011-221494号公報の段落番号0204~0207に記載の化合物が挙げられ、これらの内容は本願明細書に組み込まれる。 Basic Compound The photosensitive resin composition of the present invention may contain a basic compound. The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include the compounds described in JP-A 2011-212494, paragraphs 0204 to 0207, the contents of which are incorporated herein.
芳香族アミンとしては、例えば、アニリン、ベンジルアミン、N,N-ジメチルアニリン、ジフェニルアミンなどが挙げられる。
複素環式アミンとしては、例えば、ピリジン、2-メチルピリジン、4-メチルピリジン、2-エチルピリジン、4-エチルピリジン、2-フェニルピリジン、4-フェニルピリジン、N-メチル-4-フェニルピリジン、4-ジメチルアミノピリジン、イミダゾール、ベンズイミダゾール、4-メチルイミダゾール、2-フェニルベンズイミダゾール、2,4,5-トリフェニルイミダゾール、ジアザビシクロノネン、ニコチン、ニコチン酸、ニコチン酸アミド、キノリン、8-オキシキノリン、ピラジン、ピラゾール、ピリダジン、プリン、ピロリジン、ピペリジン、ピペラジン、モルホリン、4-メチルモルホリン、N-シクロヘキシル-N’-[2-(4-モルホリニル)エチル]チオ尿素、1,5-ジアザビシクロ[4.3.0]-5-ノネン、1,8-ジアザビシクロ[5.3.0]-7-ウンデセンなどが挙げられる。
第四級アンモニウムヒドロキシドとしては、例えば、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、テトラ-n-ブチルアンモニウムヒドロキシド、テトラ-n-ヘキシルアンモニウムヒドロキシドなどが挙げられる。
カルボン酸の第四級アンモニウム塩としては、例えば、テトラメチルアンモニウムアセテート、テトラメチルアンモニウムベンゾエート、テトラ-n-ブチルアンモニウムアセテート、テトラ-n-ブチルアンモニウムベンゾエートなどが挙げられる。
本発明に用いることができる塩基性化合物は、1種単独で使用しても、2種以上を併用してもよい。 Specific examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and the like. Examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, diazabicyclononene, nicotine, nicotinic acid, nicotinamide, quinoline, 8- Oxyquinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea, 1,5-diazabicyclo [ 4.3.0]- And 5-nonene and 1,8-diazabicyclo [5.3.0] -7-undecene.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide, and the like.
Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate and the like.
The basic compounds that can be used in the present invention may be used singly or in combination of two or more.
本発明の感光性樹脂組成物は、界面活性剤を含有してもよい。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。
また、界面活性剤として、下記一般式(I-1-1)で表される構成単位A及び構成単位Bを含み、テトラヒドロフラン(THF)を溶媒とした場合のゲルパーミエーションクロマトグラフィーで測定されるポリスチレン換算の重量平均分子量(Mw)が1,000以上10,000以下である共重合体を好ましい例として挙げることができる。 Surfactant The photosensitive resin composition of the present invention may contain 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).
Further, it is measured by gel permeation chromatography using a structural unit A and a structural unit B represented by the following general formula (I-1-1) as a surfactant and tetrahydrofuran (THF) as a solvent. A copolymer having a polystyrene-equivalent weight average molecular weight (Mw) of 1,000 or more and 10,000 or less can be mentioned as a preferred example.
これらの界面活性剤は、1種単独で又は2種以上を混合して使用することができる。
本発明の感光性樹脂組成物における界面活性剤の添加量は、本発明の感光性樹脂組成物中の全固形分に対し、10質量%以下であることが好ましく、0.001~10質量%であることがより好ましく、0.01~3質量%であることがさらに好ましい。 The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
These surfactants can be used individually by 1 type or in mixture of 2 or more types.
The addition amount of the surfactant in the photosensitive resin composition of the present invention is preferably 10% by mass or less, and preferably 0.001 to 10% by mass with respect to the total solid content in the photosensitive resin composition of the present invention. More preferably, the content is 0.01 to 3% by mass.
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、ヒンダードアミン系酸化防止剤、リン系酸化防止剤、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-60、アデカスタブAO-20、アデカスタブAO-80、アデカスタブLA-52、アデカスタブLA-81、アデカスタブAO-412S、アデカスタブPEP-36、イルガノックス1035、イルガノックス1098、チヌビン144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. Among them, phenolic antioxidants, hindered amine antioxidants, phosphorus antioxidants, amide antioxidants, hydrazide antioxidants, sulfur oxidations are particularly preferred from the viewpoint of coloring of the cured film and reduction of the film thickness. Inhibitors are preferred, and phenolic antioxidants are most preferred. These may be used individually by 1 type and may mix 2 or more types.
Specific examples include the compounds described in JP-A-2005-29515, paragraphs 0026 to 0031, the contents of which are incorporated herein.
Preferred commercial products include ADK STAB AO-60, ADK STAB AO-20, ADK STAB AO-80, ADK STAB LA-52, ADK STAB LA-81, ADK STAB AO-412S, ADK STAB PEP-36, IRGANOX 1035, IRGANOX 1098, and Tinuvin 144. Can be mentioned.
本発明の感光性樹脂組成物は、感度向上を目的に、酸増殖剤を用いることができる。
本発明に用いることができる酸増殖剤は、酸触媒反応によってさらに酸を発生して反応系内の酸濃度を上昇させることができる化合物であり、酸が存在しない状態では安定に存在する化合物である。
このような酸増殖剤の具体例としては、特開2011-221494の段落番号0226~0228に記載の酸増殖剤が挙げられ、この内容は本願明細書に組み込まれる。 [Acid multiplication agent]
In the photosensitive resin composition of the present invention, an acid proliferating agent can be used for the purpose of improving sensitivity.
The acid proliferating agent that can be used in the present invention is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid. is there.
Specific examples of such an acid proliferating agent include acid proliferating agents described in paragraph numbers 0226 to 0228 of JP2011-221494A, the contents of which are incorporated herein.
本発明の感光性樹脂組成物は、現像促進剤を含有することができる。
現像促進剤としては、特開2012-042837号公報の段落番号0171~0172に記載されているものを参酌でき、この内容は本願明細書に組み込まれる。
現像促進剤は、1種を単独で用いてもよいし、2種以上を併用することも可能である。
本発明の感光性樹脂組成物における現像促進剤の添加量は、感度と残膜率の観点から、感光性組成物の全固形分100質量部に対し、0~30質量部が好ましく、0.1~20質量部がより好ましく、0.5~10質量部であることが最も好ましい。
また、その他の添加剤としては特開2012-8223号公報の段落番号0120~0121に記載の熱ラジカル発生剤、WO2011/136074A1に記載の窒素含有化合物及び熱酸発生剤も用いることができ、これらの内容は本願明細書に組み込まれる。 [Development accelerator]
The photosensitive resin composition of the present invention can contain a development accelerator.
As the development accelerator, those described in paragraphs 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification.
A development accelerator may be used individually by 1 type, and can also use 2 or more types together.
The addition amount of the development accelerator in the photosensitive resin composition of the present invention is preferably 0 to 30 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive composition, from the viewpoint of sensitivity and residual film ratio. 1 to 20 parts by mass is more preferable, and 0.5 to 10 parts by mass is most preferable.
In addition, as other additives, thermal radical generators described in paragraphs 0120 to 0121 of JP2012-8223A, nitrogen-containing compounds and thermal acid generators described in WO2011-133604A1, can be used. Is incorporated herein by reference.
各成分を所定の割合でかつ任意の方法で混合し、撹拌溶解して感光性樹脂組成物を調製する。例えば、成分を、それぞれ予め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>
Each component is mixed in a predetermined ratio and by any method, stirred and dissolved to prepare a photosensitive resin composition. For example, a resin composition can be prepared by preparing a solution in which components are dissolved in a solvent in advance and then mixing them in a predetermined ratio. 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;
(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。
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 apply | coating the photosensitive resin composition of this invention on a board | substrate;
(2) A step of 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 post-baking step of thermosetting the developed photosensitive resin composition.
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。
基板への塗布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。
塗布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。
さらに、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塗布することも可能である。 In the application step (1), the photosensitive resin composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent. Before applying the photosensitive resin composition to the substrate, it is preferable to perform substrate cleaning such as alkali cleaning or plasma cleaning, 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 coating method on 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 it is usually used in the range of 0.5 to 10 μm.
Further, before applying the composition used in the present invention to the substrate, it is possible to apply a so-called pre-wet 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。
酸触媒の生成した領域において、上記の分解反応を加速させるために、露光後加熱処理:Post Exposure Bake(以下、「PEB」ともいう。)を行うことができる。PEBにより、酸分解性基からのカルボキシル基又はフェノール性水酸基などの酸基の生成を促進させることができる。PEBを行う場合の温度は、30℃以上130℃以下であることが好ましく、40℃以上110℃以下がより好ましく、50℃以上100℃以下が特に好ましい。
ただし、本発明における酸分解性基は、酸分解の活性化エネルギーが低く、露光による酸発生剤由来の酸により容易に分解し、カルボキシル基又はフェノール性水酸基などの酸基を生じるため、必ずしもPEBを行うことは必須ではなく、現像によりポジ画像を形成することもできる。 In the exposure step (3), the substrate provided with the coating film is irradiated with an actinic ray having a predetermined pattern. In this step, the photoacid generator is decomposed to generate an acid. By the catalytic action of the generated acid, the acid-decomposable group contained in the coating film component is decomposed to generate an acid group such as a carboxyl group or a phenolic hydroxyl group.
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, and i-line (365 nm), h-line (405 nm), 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.
In order to accelerate the decomposition reaction in the region where the acid catalyst is generated, post-exposure heat treatment: Post Exposure Bake (hereinafter also referred to as “PEB”) can be performed. PEB can promote the generation of an acid group such as a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. The temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 100 ° C. or lower.
However, since the acid-decomposable group in the present invention has low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to generate an acid group such as a carboxyl group or a phenolic hydroxyl group, it is not necessarily PEB. It is not indispensable that a positive image can be formed by development.
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0.4~2.5質量%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), a copolymer having a free carboxyl group or an acid group such as 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 an acid group such as 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; tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline hydroxide, and other ammonium hydroxides; sodium silicate, metasilicic acid An aqueous solution such as sodium 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.
As a preferred developing solution, a 0.4 to 2.5% by mass aqueous solution of tetramethylammonium hydroxide can be mentioned.
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)した後、ポストベークすることにより未露光部分に存在する光酸発生剤から酸を発生させ、架橋工程を促進する触媒として機能させることができ、膜の硬化反応を促進することができる。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、100~500mJ/cm2が特に好ましい。 In the post-baking step of (5), by heating the obtained positive image, the acid-decomposable group is thermally decomposed to generate a carboxyl group or a phenolic hydroxyl group, and then crosslinked with a crosslinkable group, a crosslinking agent or the like. A cured film can be formed. 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, the entire surface of the patterned substrate was re-exposed with actinic rays (post-exposure), and then post-baked to generate an acid from the photoacid generator present in the unexposed portion, thereby performing a crosslinking step. It can function as a catalyst to promote, and can accelerate the curing reaction of the film. The preferred exposure amount in the case of including a post-exposure step, preferably 100 ~ 3,000mJ / cm 2, particularly preferably 100 ~ 500mJ / 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。
図2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.
In addition, as a liquid crystal driving method that can be adopted by the liquid crystal display device of the present invention, a TN (Twisted Nematic) method, a VA (Virtual Alignment) method, an IPS (In-Place-Switching) method, an FFS (Frings Field Switching) method, an OCB (Optical) method. 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 JP-A-2005-284291, 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.
FIG. 2 is a conceptual cross-sectional view showing an example of the active matrix type 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1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間または、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上に平坦化膜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1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. 1 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
A bottom
Further, in order to flatten the unevenness due to the formation of the
On 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. 1, 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 first 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
以下に実施例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。なお、特に断りのない限り、「部」、「%」は質量基準である。 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.
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. Unless otherwise specified, “part” and “%” are based on mass.
以下の合成例、において、以下の略語はそれぞれ以下の化合物を表す。
MATHF:2-テトラヒドロフラニルメタクリレート(合成品)
MAEVE:1-エトキシエチルメタクリレート(和光純薬工業社製)
MATHP:テトラヒドロ-2H-ピラン-2-イルメタクリレート(新中村化学工業社製)
OXE-30:3-エチル-3-オキセタニルメチルメタクリレート(大阪有機化学工業社製)(熱架橋開始温度151℃)
GMA:グリシジルメタクリレート(和光純薬工業社製)(熱架橋開始温度:115℃)
NBMA:n-ブトキシメチルアクリルアミド(東京化成製)
MAA:メタクリル酸(和光純薬工業社製)
MMA:メチルメタクリレート(和光純薬工業社製)
St:スチレン(和光純薬工業社製)
DCPM:ジシクロペンタニルメタクリレート
HEMA:ヒドロキシエチルメタクリレート(和光純薬社製)
AICA:イタコン酸無水物(東京化成製)
MAAN:マレイン酸無水物(東京化成製)
γBLMA:γ-ブチロラクトンメタクリレート(大阪有機化学工業社製)
PLMA:パントラクトンメタクリレート(合成品)
MEDG(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)
PGMEA(プロピレングリコールモノメチルエーテルアセテート):(昭和電工社製)
V-601:ジメチル 2,2’-アゾビス(2-メチルプロピオネート)(和光純薬工業社製)
V-65:2,2’-アゾビス(2,4-ジメチルバレロニトリル)(和光純薬工業社製) [(A) Polymer component]
In the following synthesis examples, the following abbreviations represent the following compounds, respectively.
MATHF: 2-tetrahydrofuranyl methacrylate (synthetic product)
MAEVE: 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
MATHP: Tetrahydro-2H-pyran-2-yl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
OXE-30: 3-ethyl-3-oxetanylmethyl methacrylate (manufactured by Osaka Organic Chemical Industry) (thermal crosslinking start temperature 151 ° C.)
GMA: Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) (thermal crosslinking start temperature: 115 ° C.)
NBMA: n-butoxymethylacrylamide (manufactured by Tokyo Chemical Industry)
MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries)
MMA: Methyl methacrylate (Wako Pure Chemical Industries, Ltd.)
St: Styrene (Wako Pure Chemical Industries, Ltd.)
DCPM: Dicyclopentanyl methacrylate HEMA: Hydroxyethyl methacrylate (Wako Pure Chemical Industries, Ltd.)
AICA: Itaconic anhydride (manufactured by Tokyo Chemical Industry)
MAAN: Maleic anhydride (manufactured by Tokyo Chemical Industry)
γBLMA: γ-butyrolactone methacrylate (manufactured by Osaka Organic Chemical Industry)
PMMA: Pantolactone methacrylate (synthetic product)
MEDG (diethylene glycol ethyl methyl ether): Hisolv EDM (manufactured by Toho Chemical Industry Co., Ltd.)
PGMEA (propylene glycol monomethyl ether acetate): (Showa Denko)
V-601:
V-65: 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)
300mLのナスフラスコ中に、メタクリル酸(86g、1mol)を15℃に冷却しておき、カンファースルホン酸(4.6g、0.02mol)を添加した。その溶液に、2-ジヒドロフラン(71g、1mol、1.0当量)を撹拌しながら滴下した。滴下終了後1時間撹拌した後に、飽和炭酸水素ナトリウム(500mL)を加え、酢酸エチル(500mL)で抽出し、硫酸マグネシウムで乾燥後、不溶物を濾過後40℃以下で減圧濃縮し、残渣の黄色油状物を減圧蒸留して沸点(bp.)54~56℃/3.5mmHg留分のメタクリル酸テトラヒドロ-2H-フラン-2-イル(MATHF)125gを無色油状物として得た(収率80%)。 <Synthesis of MATHF>
Methacrylic acid (86 g, 1 mol) was cooled to 15 ° C. in a 300 mL eggplant flask, and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution, 2-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise with stirring. After stirring for 1 hour after completion of the dropwise addition, saturated sodium hydrogen carbonate (500 mL) was added, extracted with ethyl acetate (500 mL), dried over magnesium sulfate, insolubles were filtered and concentrated under reduced pressure at 40 ° C. or lower to give a yellow residue. The oily product was distilled under reduced pressure to obtain 125 g of tetrahydro-2H-furan-2-yl methacrylate (MATHF) as a colorless oily product having a boiling point (bp.) Of 54 to 56 ° C./3.5 mmHg (yield: 80%). ).
ナスフラスコ中に、アセトニトリル50mLを加え、さらにパントラクトン(13g、100mmol)、トリエチルアミン(12.1g、120mmol)を溶解させた。この溶液を0℃に冷却した後、メタクリル酸クロリド(11.5g、100mmol)を10分かけて攪拌しながら滴下した。滴下終了後、0℃で1時間撹拌した後に、飽和炭酸水素ナトリウム(50mL)を加え、酢酸エチル(50mL)で抽出した。得られた有機層を飽和食塩水(50mL)で洗浄した後、硫酸マグネシウムで乾燥後、減圧濃縮し揮発成分を除去することで、黄色油状物を得た。得られた黄色油状物を順相カラムクロマトグラフィー(展開溶媒 酢酸エチル/ヘキサン=1/7)で精製することで、パントラクトンメタクリレート(PLMA)18.6gを無色油状物として得た(収率93%)。 <Synthesis of PMMA>
In an eggplant flask, 50 mL of acetonitrile was added, and further pantolactone (13 g, 100 mmol) and triethylamine (12.1 g, 120 mmol) were dissolved. After this solution was cooled to 0 ° C., methacrylic acid chloride (11.5 g, 100 mmol) was added dropwise over 10 minutes with stirring. After completion of the dropwise addition, the mixture was stirred at 0 ° C. for 1 hour, saturated sodium hydrogen carbonate (50 mL) was added, and the mixture was extracted with ethyl acetate (50 mL). The obtained organic layer was washed with saturated brine (50 mL), dried over magnesium sulfate, concentrated under reduced pressure to remove volatile components, and a yellow oil was obtained. The obtained yellow oil was purified by normal phase column chromatography (developing solvent: ethyl acetate / hexane = 1/7) to obtain 18.6 g of pantolactone methacrylate (PLMA) as a colorless oil (yield 93 %).
モノマー200mgとアニソール20mg(HPLC測定用の内部標準物質)を含むアセトニトリル溶液25mLを調製した(溶液A)。溶液Aを0.5gにアセトニトリル8gを加えた溶液(溶液B)を調製し、次に溶液A0.5g、アセトニトリル3g、及び炭酸塩pH標準液(*1)5gの混合液を調整し、25℃にて20分経過させて測定サンプル(溶液C)とした。溶液B及び溶液Cを逆相HPLC(*2)で測定し、アニソールのピーク面積(積分値)から規格化して得られた各モノマーのピーク面積(積分値)を元に、下記計算式より得られた値を各モノマーの加水分解率(%)とした。
計算式
[100-(溶液Cのモノマーのピーク面積)×100/(溶液Bのモノマーのピーク面積)]
表1にその結果を示す。 <Hydrolysis test>
25 mL of an acetonitrile solution containing 200 mg of monomer and 20 mg of anisole (an internal standard substance for HPLC measurement) was prepared (Solution A). A solution (solution B) obtained by adding 8 g of acetonitrile to 0.5 g of solution A is prepared, and then a mixed solution of 0.5 g of solution A, 3 g of acetonitrile, and 5 g of carbonate pH standard solution (* 1) is prepared. A measurement sample (solution C) was obtained after 20 minutes at 0 ° C. Solution B and Solution C were measured by reversed-phase HPLC (* 2), and obtained from the following formula based on the peak area (integrated value) of each monomer obtained by normalization from the peak area (integrated value) of anisole. The obtained value was defined as the hydrolysis rate (%) of each monomer.
Formula [100- (Peak Area of Monomer of Solution C) × 100 / (Peak Area of Monomer of Solution B)]
Table 1 shows the results.
(*2) 測定機器: Waters 3000、カラム:Shim-Pack CLC-ODS 4.6mm×150mm(東ソー製)、カラム温度:40℃、流速1mL/min、検出波長:210nm、溶離液:アセトニトリル/Buffer(リン酸/トリエチルアミン/水=1/1/998)=60/40、注入量 10μL (* 1) pH = 10.01 JISK0022 standard carbonate pH standard solution (manufactured by Tokyo Chemical Industry)
(* 2) Measuring equipment: Waters 3000, column: Shim-Pack CLC-ODS 4.6 mm × 150 mm (manufactured by Tosoh), column temperature: 40 ° C.,
3つ口フラスコにPGMEA(40g)を入れ、窒素雰囲気下において75℃に昇温した。その溶液に、全単量体成分中の30mol%となる量のMATHF、全単量体成分中の12mol%となる量のGMA、全単量体成分中の1.2mol%となる量のAICA、全単量体成分中の10mol%となる量のMAA、全単量体成分中の36.8mol%となる量のMMA、全単量体成分中の10mol%となる量のSt(単量体の総質量は50g)並びに、V-65(全単量体成分の合計に対して4mol%に相当する量)をPGMEA(10g)に室温で溶解させた溶液を、2時間かけて滴下した。滴下終了後、75℃で2時間攪拌し重合体A-1を得た。その後、固形分濃度が40質量%になるようにPGMEAを加えて重合体溶液を調製した。固形分濃度は、単量体の合計質量/(単量体の合計質量+溶剤質量)×100(単位質量%)とした。 <Synthesis Example of Polymer A-1>
PGMEA (40 g) was placed in a three-necked flask and heated to 75 ° C. in a nitrogen atmosphere. In the solution, MATH in an amount of 30 mol% in all monomer components, GMA in an amount of 12 mol% in all monomer components, and AICA in an amount of 1.2 mol% in all monomer components MAA in an amount of 10 mol% in all monomer components, MMA in an amount of 36.8 mol% in all monomer components, St (an amount of 10 mol% in all monomer components) The total mass of the body was 50 g), and a solution in which V-65 (amount corresponding to 4 mol% with respect to the total of all monomer components) was dissolved in PGMEA (10 g) at room temperature was added dropwise over 2 hours. . After completion of dropping, the mixture was stirred at 75 ° C. for 2 hours to obtain a polymer A-1. Then, PGMEA was added so that solid content concentration might be 40 mass%, and the polymer solution was prepared. Solid content concentration was made into the total mass of the monomer / (total mass of the monomer + solvent mass) × 100 (unit mass%).
モノマーの種類等を下記表に示す通りに変更し、A-2~A-81については重合溶剤をMEDGに変更し、その他の条件については、A-1と同様の方法で合成した。重合体の固形分濃度は、40質量%とした。表のモノマーはモル比で示している。
また、その他の重合体として、下記K-1およびK-2を用いた。
K-1:Joncryl 67(BASF製)
K-2:ARUFON UC-3910(東亜合成(株)製 <Synthesis Example of Polymers A-2 to A-81>
The monomer type and the like were changed as shown in the following table, the polymerization solvent for A-2 to A-81 was changed to MEDG, and the other conditions were synthesized by the same method as A-1. The solid content concentration of the polymer was 40% by mass. The monomers in the table are shown in molar ratios.
Further, as other polymers, the following K-1 and K-2 were used.
K-1: Joncryl 67 (manufactured by BASF)
K-2: ARUFON UC-3910 (manufactured by Toa Gosei Co., Ltd.)
B-1:下記に示す構造(合成例を後述する)
B-1: Structure shown below (Synthesis example will be described later)
2-ナフトール(10g)とクロロベンゼン(30mL)の懸濁液に塩化アルミニウム(10.6g)と、2-クロロプロピオニルクロリド(10.1g)を添加し、混合液を40℃に加熱して攪拌しながら2時間反応させた。氷冷下、反応液に4NのHCl水溶液(60mL)を滴下し、酢酸エチル(50mL)を添加して分液した。有機層に炭酸カリウム(19.2g)を加え、40℃で1時間反応させた後、2NのHCl水溶液(60mL)を添加して分液し、有機層を濃縮後、結晶をジイソプロピルエーテル(10mL)でリスラリーし、ろ過、乾燥してケトン化合物(6.5g)を得た。
得られたケトン化合物(3.0g)、メタノール(30mL)の懸濁液に酢酸(7.3g)、50質量%ヒドロキシルアミン水溶液(8.0g)を添加し、加熱還流した。放冷後、水(50mL)を加え、析出した結晶をろ過、冷メタノール洗浄後、乾燥してオキシム化合物(2.4g)を得た。
得られたオキシム化合物(1.8g)をアセトン(20mL)に溶解させ、氷冷下トリエチルアミン(1.5g)、p-トルエンスルホニルクロリド(2.4g)を添加し、室温に昇温して攪拌しながら1時間反応させた。反応液に水(50mL)を添加し、析出した結晶をろ過後、メタノール(20mL)でリスラリーし、ろ過、乾燥してB-1の化合物(上述の構造)(2.3g)を得た。
なお、B-1の1H-NMRスペクトル(300MHz、CDCl3)は、δ=8.3(d,1H),8.0(d,2H),7.9(d,1H),7.8(d,1H),7.6(dd,1H),7.4(dd,1H)7.3(d,2H),7.1(d.1H),5.6(q,1H),2.4(s,3H),1.7(d,3H)であった。 <Synthesis example of B-1>
Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture was heated to 40 ° C. and stirred. The reaction was continued for 2 hours. Under ice-cooling, 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution, and ethyl acetate (50 mL) was added for liquid separation. After adding potassium carbonate (19.2 g) to the organic layer and reacting at 40 ° C. for 1 hour, 2N HCl aqueous solution (60 mL) was added and liquid-separated. The organic layer was concentrated, and the crystal was converted to diisopropyl ether (10 mL). ), Followed by filtration and drying to obtain a ketone compound (6.5 g).
Acetic acid (7.3 g) and 50% by mass hydroxylamine aqueous solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (30 mL), and the mixture was heated to reflux. After allowing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).
The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, and the mixture was warmed to room temperature and stirred. The reaction was continued for 1 hour. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered, reslurried with methanol (20 mL), filtered and dried to obtain the compound of B-1 (the above structure) (2.3 g).
The 1H-NMR spectrum (300 MHz, CDCl3) of B-1 is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 ( d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (q, 1H), 2 .4 (s, 3H), 1.7 (d, 3H).
1-アミノー2-ナフトール塩酸塩(東京化成製)4.0gをN-メチルピロリドン(和光純薬製)16gに懸濁させ、炭酸水素ナトリウム(和光純薬製)3.4gを添加後、4,4-ジメチルー3-オキソ吉草酸メチル(和光純薬製)4.9gを滴下し、窒素雰囲気下120℃で攪拌しながら2時間加熱した。放冷後、反応混合液に水、酢酸エチルを添加して分液し、有機相を硫酸マグネシウムで乾燥し、ろ過、濃縮して粗B-2Aを得た。粗B-2Aをシリカゲルカラムクロマトグラフィー精製して、中間体B-9Aを1.7g得た。
B-2A(1.7g)とp-キシレン(6mL)を混合し、p-トルエンスルホン酸一水和物(和光純薬製)0.23gを添加して140℃で攪拌しながら2時間加熱した。放冷後、反応混合液に水、酢酸エチルを添加して分液し、有機相を硫酸マグネシウムで乾燥後、ろ過、濃縮して粗B-2Bを得た。
THF(2mL)と粗B-2B全量を混合し、氷冷下2M塩酸のテトラヒドロフラン溶液6.0mL、次いで亜硝酸イソペンチル(和光純薬製)(0.84g)を滴下し、室温に昇温後2時間攪拌した。得られた混合物に水、酢酸エチルを添加して分液し、有機層を水で洗浄後、硫酸マグネシウムで乾燥し、ろ過、濃縮して中間体粗B-2Cを得た。
中間体粗B-2C全量をアセトン(10mL)と混合し、氷冷下でトリエチルアミン(和光純薬製)(1.2g)、p-トルエンスルホニルクロリド(東京化成製)(1.4g)を添加後、室温に昇温して1時間攪拌した。得られた混合液に水、酢酸エチルを添加して分液し、有機相を硫酸マグネシウムで乾燥後、ろ過、濃縮して粗B-2を得た。粗B-2を冷メタノールでリスラリー後、ろ過、乾燥してB-2(1.2g)を得た。 <Synthesis example of B-2>
4.0 g of 1-amino-2-naphthol hydrochloride (manufactured by Tokyo Chemical Industry) is suspended in 16 g of N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries), and 3.4 g of sodium hydrogen carbonate (manufactured by Wako Pure Chemical Industries) is added. , 4-dimethyl-3-oxovalerate methyl (manufactured by Wako Pure Chemical Industries, Ltd.) (4.9 g) was added dropwise, and the mixture was heated for 2 hours with stirring at 120 ° C. in a nitrogen atmosphere. After allowing to cool, water and ethyl acetate were added to the reaction mixture and the phases were separated, and the organic phase was dried over magnesium sulfate, filtered and concentrated to obtain crude B-2A. Crude B-2A was purified by silica gel column chromatography to obtain 1.7 g of intermediate B-9A.
Mix B-2A (1.7 g) and p-xylene (6 mL), add 0.23 g of p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and heat at 140 ° C. with stirring for 2 hours. did. After allowing to cool, water and ethyl acetate were added to the reaction mixture and the phases were separated. The organic phase was dried over magnesium sulfate, filtered and concentrated to obtain crude B-2B.
THF (2 mL) and the entire amount of crude B-2B were mixed, and 6.0 mL of 2M hydrochloric acid in tetrahydrofuran and then isopentyl nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) (0.84 g) were added dropwise under ice cooling. Stir for 2 hours. Water and ethyl acetate were added to the obtained mixture for liquid separation, and the organic layer was washed with water, dried over magnesium sulfate, filtered and concentrated to obtain a crude intermediate B-2C.
The whole amount of intermediate crude B-2C was mixed with acetone (10 mL), and triethylamine (Wako Pure Chemicals) (1.2 g) and p-toluenesulfonyl chloride (Tokyo Kasei) (1.4 g) were added under ice cooling. Then, it heated up to room temperature and stirred for 1 hour. Water and ethyl acetate were added to the obtained mixed solution for liquid separation, and the organic phase was dried over magnesium sulfate, filtered and concentrated to obtain crude B-2. Crude B-2 was reslurried with cold methanol, filtered and dried to obtain B-2 (1.2 g).
MEDG(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)
PGMEA(プロピレングリコールモノメチルエーテルアセテート):(昭和電工社製) [(C) Solvent]
MEDG (diethylene glycol ethyl methyl ether): Hisolv EDM (manufactured by Toho Chemical Industry Co., Ltd.)
PGMEA (propylene glycol monomethyl ether acetate): (Showa Denko)
(増感剤)
E-1:9,10-ジブトキシアントラセン(川崎化成社製) [Other ingredients]
(Sensitizer)
E-1: 9,10-dibutoxyanthracene (manufactured by Kawasaki Kasei Co., Ltd.)
H-1:ジアザビシクロノネン(東京化成社製)
H-2:2,4,5-トリフェニルイミダゾール(東京化成社製)
H-3:下記構造の化合物
H-1: Diazabicyclononene (manufactured by Tokyo Chemical Industry Co., Ltd.)
H-2: 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
H-3: Compound having the following structure
G-1:γ-グリシドキシプロピルトリメトキシシラン(KBM-403:信越化学工業社製)
G-2:ビス(トリエトキシシリルプロピル)テトラスルフィド(KBE-846、信越化学工業社製)
G-3:デシルトリメトキシシラン(KBM-3103、信越化学工業社製) (Alkoxysilane compound)
G-1: γ-glycidoxypropyltrimethoxysilane (KBM-403: manufactured by Shin-Etsu Chemical Co., Ltd.)
G-2: Bis (triethoxysilylpropyl) tetrasulfide (KBE-846, manufactured by Shin-Etsu Chemical Co., Ltd.)
G-3: Decyltrimethoxysilane (KBM-3103, manufactured by Shin-Etsu Chemical Co., Ltd.)
W-1:下記構造式で示されるパーフルオロアルキル基含有ノニオン界面活性剤(F-554,DIC製)
W-1: Perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula (F-554, manufactured by DIC)
F-1:JER828((株)三菱ケミカルホールディングス製)
F-2:JER1007((株)三菱ケミカルホールディングス製)
F-3:JER157S65((株)三菱ケミカルホールディングス社製)
F-4:セロキサイド2021P((株)ダイセル社製)
F-5:デュラネート17B-60P(旭化成ケミカルズ(株)社製)
F-6:デナコールEX-321L(ナガセケムテックス(株)社製)
F-7:タケネートB-870N(三井化学(株)社製) (Crosslinking agent)
F-1: JER828 (manufactured by Mitsubishi Chemical Holdings Corporation)
F-2: JER1007 (manufactured by Mitsubishi Chemical Holdings Corporation)
F-3: JER157S65 (Mitsubishi Chemical Holdings Co., Ltd.)
F-4: Celoxide 2021P (manufactured by Daicel Corporation)
F-5: Duranate 17B-60P (Asahi Kasei Chemicals Corporation)
F-6: Denacol EX-321L (manufactured by Nagase ChemteX Corporation)
F-7: Takenate B-870N (Mitsui Chemicals, Inc.)
J-1:アデカスタブAO-60((株)ADEKA製)
J-2:イルガノックス1098(BASF社製)
J-3:イルガノックス1035(BASF社製)
K-1:Joncryl 67(BASF製)
K-2:ARUFON UC-3910(東亜合成(株)製 (Other additives)
J-1: ADK STAB AO-60 (manufactured by ADEKA Corporation)
J-2: Irganox 1098 (BASF)
J-3: Irganox 1035 (manufactured by BASF)
K-1: Joncryl 67 (manufactured by BASF)
K-2: ARUFON UC-3910 (manufactured by Toa Gosei Co., Ltd.)
各実施例及び各比較例では、下記表に示す固形分比となるように、重合体成分、光酸発生剤、増感剤、架橋剤、アルコキシシラン化合物、塩基性化合物、界面活性剤及びその他の成分をPGMEAに固形分濃度25質量%になるように溶解混合し、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、感光性樹脂組成物を得た。 <Adjustment of photosensitive resin composition>
In each example and each comparative example, polymer components, photoacid generators, sensitizers, crosslinking agents, alkoxysilane compounds, basic compounds, surfactants, and others so that the solid content ratios shown in the following table are obtained. Were dissolved and mixed in PGMEA so that the solid content concentration was 25% by mass and filtered through a polytetrafluoroethylene filter having a diameter of 0.2 μm to obtain a photosensitive resin composition.
ガラス基板(コーニング1737、0.7mm厚(コーニング社製))を、ヘキサメチルジシラザン(HMDS)蒸気下に30秒曝し、基板にスピンコーターを用いて乾燥膜厚が3μmとなるように塗布したのち、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。その後、10μmライン/10μmスペースを再現することのできるマスクを介して、超高圧水銀灯で40mJ露光した後、アルカリ現像液(2.38質量%のテトラメチルアンモニウムヒドロキシド水溶液)で、23℃、60秒間現像した後、超純水で1分間リンスした。得られた基板を光学顕微鏡で観察し、10μmライン/10μmスペースのパターンの寸法を観察した。
次に、上記と同様の操作を現像時間を180秒にしたこと以外は同様の操作及び観察を行った。現像時間の違いによって寸法が変動しないほど好ましく、A、B、Cが実用上問題のないレベルである。
A:寸法変動が0.3μm未満である。
B:寸法変動が0.3μm以上、0.5μm未満である。
C:寸法変動が0.5μm以上、0.8μm未満である。
D:寸法変動が0.8μm以上、1.0μm未満である。
E:寸法変動が1.0μm以上、1.5μm未満である。
F:寸法変動が1.5μm以上である。 <Evaluation of dimensional stability of pattern>
A glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)) was exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds and applied to the substrate using a spin coater so that the dry film thickness was 3 μm. Then, it prebaked on a 90 degreeC / 120 second hotplate, the solvent was volatilized, and the photosensitive resin composition layer with a film thickness of 3.0 micrometers was formed. Then, after 40 mJ exposure with an ultra-high pressure mercury lamp through a mask capable of reproducing a 10 μm line / 10 μm space, an alkaline developer (2.38 mass% tetramethylammonium hydroxide aqueous solution) was used at 23 ° C., 60 ° C. After developing for 2 seconds, it was rinsed with ultrapure water for 1 minute. The obtained board | substrate was observed with the optical microscope, and the dimension of the pattern of 10 micrometers line / 10micrometer space was observed.
Next, the same operation and observation were performed except that the same operation as described above was performed with a development time of 180 seconds. It is preferable that the dimensions do not fluctuate due to the difference in development time, and A, B, and C are practically no problem levels.
A: The dimensional variation is less than 0.3 μm.
B: The dimensional variation is 0.3 μm or more and less than 0.5 μm.
C: The dimensional variation is 0.5 μm or more and less than 0.8 μm.
D: The dimensional variation is 0.8 μm or more and less than 1.0 μm.
E: The dimensional variation is 1.0 μm or more and less than 1.5 μm.
F: The dimensional variation is 1.5 μm 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、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(エネルギー強度: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NMP(N-メチルピロリドン)溶液中に5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。
膜厚変化率は小さいほど好ましく、A、B、C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5.5%未満
E:5.5%以上7%未満
F:7%以上 <Evaluation of chemical resistance>
The glass substrate was exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and each photosensitive resin composition was spin coated on the substrate, and then pre-baked on a hot plate at 90 ° C./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 ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm 2 (energy intensity: 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. Then, the substrate on which this cured film was formed was immersed in an NMP (N-methylpyrrolidone) solution whose temperature was controlled at 80 ° C. for 5 minutes, and then the thickness (t1) of the cured film after immersion was measured. The film thickness change rate {| t1-T1 | / T1} × 100 [%] by immersion was calculated. The results are shown in the table below.
The smaller the change rate of the film thickness, the better.
A: Less than 2% B: 2% or more and less than 3% C: 3% or more and less than 4
ベアウエハ基板(N型低抵抗)(SUMCO社製)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(エネルギー強度: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。この硬化膜について、CVmap92A(Four Dimensions Inc.社製)を用い、測定周波数1MHzで比誘電率を測定した。
その結果を下記表に示した。数値としては小さいほど良く、A、BまたはCが実用範囲内である。
A:3.6未満
B:3.6以上4.0未満
C:4.0以上4.4未満
D:4.4以上4.7未満
E:4.7以上4.9未満
F:4.9以上 <Evaluation of relative dielectric constant>
Each photosensitive resin composition was spin-coated on a bare wafer substrate (N-type low resistance) (manufactured by SUMCO), then pre-baked on a hot plate at 90 ° C. for 120 seconds to volatilize the solvent, and the film thickness was 3.0 μm. A photosensitive resin composition layer was formed. Subsequently, exposure was performed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm 2 (energy intensity: 20 mW / cm 2 , i-line), and the substrate was heated in an oven at 230 ° C./30 minutes. With respect to this cured film, the relative dielectric constant was measured at a measurement frequency of 1 MHz using CVmap92A (made by Four Dimensions Inc.).
The results are shown in the following table. The smaller the numerical value, the better, and A, B, or C is within the practical range.
A: Less than 3.6 B: 3.6 or more and less than 4.0 C: 4.0 or more and less than 4.4 D: 4.4 or more and less than 4.7 E: 4.7 or more and less than 4.9 F: 4. 9 or more
各評価におけるA~Fに、それぞれ5~0点を割り振ったときの評価の合計値で評価した。ただし、各評価においてD以下の項目(実用範囲外)があった場合には、総合評価の値は各評価の最低評価項目と同等とした。
A:14~15点
B:12点以上14点未満
C:7点以上12点未満
D:総合点が6点以下であるか、またはいずれかの評価項目にDがある
E:いずれかの評価項目にEがある
F:いずれかの評価項目にFがある <Comprehensive evaluation>
Evaluation was made using the total evaluation value when 5 to 0 points were assigned to A to F in each evaluation. However, when there were items of D or less (out of the practical range) in each evaluation, the value of the comprehensive evaluation was made equal to the lowest evaluation item of each evaluation.
A: 14 to 15 points B: 12 points or more and less than 14 points C: 7 points or more and less than 12 points D: Total score is 6 points or less, or D is in any evaluation item E: Any evaluation F with item: F in any evaluation item
特許第3321003号公報の図1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、実施例200の液晶表示装置を得た。すなわち、実施例1の感光性樹脂組成物を用い、層間絶縁膜として硬化膜17を形成した。
特許第3321003号公報の段落番号0058の基板と層間絶縁膜17の濡れ性を向上させる前処理として、基板をヘキサメチルジシラザン(HMDS)蒸気下に30秒曝し、その後、実施例1の感光性樹脂組成物をスピンコート塗布した後、90℃で2分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3μmの感光性樹脂組成物層を形成した。次に、得られた感光性樹脂組成物層を、キヤノン(株)製 MPA 5500CF(高圧水銀灯)を用いて、10μmφのホールパターンのマスクを介して40mJ/cm2(エネルギー強度:20mW/cm2、i線)となるよう露光した。そして、露光後の感光性樹脂組成物層を、アルカリ現像液(0.4%のテトラメチルアンモニウムヒドロキシド水溶液)で23℃/60秒間パドル現像した後、超純水で20秒リンスした。続いて超高圧水銀灯を用いて積算照射量が300mJ/cm2(エネルギー強度:20mW/cm2、i線)となるように全面露光し、その後、この基板をオーブンにて230℃で30分加熱して硬化膜を得た。
上記感光性樹脂組成物を塗布する際の塗布性は良好で、露光、現像、焼成の後に得られた硬化膜には、しわやクラックの発生は認められなかった。 <Example 200>
In the active matrix liquid crystal display device described in FIG. 1 of Japanese Patent No. 3321003, a cured
As a pretreatment for improving the wettability between the substrate of paragraph No. 0058 and the
The applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking.
実施例200と以下のプロセスのみ変更して、同様の液晶表示装置を得た。すなわち、基板の前処理であるヘキサメチルジシラザン(HMDS)処理を省いて、実施例1の感光性樹脂組成物を塗布した場合でも、得られた硬化膜として、パターンの欠けや剥がれの無い良好な状態であった。また液晶表示装置としての性能も実施例200と同様に良好であった。これは本発明の組成物が基板との密着性に優れるためであると思われる。生産性を向上させる観点では、上記基板の前処理の工程を省くことも好ましい。 <Example 201>
A liquid crystal display device similar to that of Example 200 was changed to obtain the same liquid crystal display device. That is, even when the photosensitive resin composition of Example 1 was applied without the hexamethyldisilazane (HMDS) treatment, which is a pretreatment of the substrate, the resulting cured film was good with no chipping or peeling off of the pattern. It was a state. Further, the performance as a liquid crystal display device was good as in Example 200. This is presumably because the composition of the present invention has excellent adhesion to the substrate. From the viewpoint of improving productivity, it is also preferable to omit the substrate pretreatment step.
実施例200と以下のプロセスのみ変更して、同様の液晶表示装置を得た。すなわち、プリベーク後に減圧乾燥工程(VCD)を導入しても、得られた硬化膜として、パターンの欠けや剥がれの無い良好な状態であった。また液晶表示装置としての性能も実施例200と同様に良好であった。組成物の固形分濃度や膜厚に応じて、塗布ムラを抑制する観点から、減圧乾燥工程を導入することも好ましい。 <Example 202>
A liquid crystal display device similar to that of Example 200 was changed to obtain the same liquid crystal display device. That is, even if a vacuum drying step (VCD) was introduced after pre-baking, the obtained cured film was in a good state with no pattern chipping or peeling. Further, the performance as a liquid crystal display device was good as in Example 200. It is also preferable to introduce a reduced-pressure drying step from the viewpoint of suppressing coating unevenness according to the solid content concentration and the film thickness of the composition.
実施例200と以下のプロセスのみ変更して、同様の液晶表示装置を得た。すなわち、マスク露光してから現像工程の間にPEB工程を導入しても、得られた硬化膜として、パターンの欠けや剥がれの無い良好な状態であった。また液晶表示装置としての性能も実施例200と同様に良好であった。寸法安定性を高める観点では、PEB工程を導入することも好ましい。 <Example 203>
A liquid crystal display device similar to that of Example 200 was changed to obtain the same liquid crystal display device. That is, even if the PEB process was introduced between the development process and the mask exposure, the obtained cured film was in a good state with no pattern chipping or peeling. Further, the performance as a liquid crystal display device was good as in Example 200. From the viewpoint of improving dimensional stability, it is also preferable to introduce a PEB process.
実施例200と以下のプロセスのみ変更して、同様の液晶表示装置を得た。すなわち、アルカリ現像液を0.4%のテトラメチルアンモニウムヒドロキシド水溶液から2.38%のテトラメチルアンモニウムヒドロキシド水溶液に変更しても、得られた硬化膜として、パターンの欠けや剥がれの無い良好な状態であった。また液晶表示装置としての性能も実施例200と同様に良好であった。これは本発明の組成物が基板との密着性に優れるためであると思われる。 <Example 204>
A liquid crystal display device similar to that of Example 200 was changed to obtain the same liquid crystal display device. That is, even when the alkaline developer is changed from a 0.4% tetramethylammonium hydroxide aqueous solution to a 2.38% tetramethylammonium hydroxide aqueous solution, the resulting cured film has good pattern free of chipping and peeling. It was a state. Further, the performance as a liquid crystal display device was good as in Example 200. This is presumably because the composition of the present invention has excellent adhesion to the substrate.
実施例200と以下のプロセスのみ変更して、同様の液晶表示装置を得た。すなわち、アルカリ現像方法をパドル現像からシャワー現像に変更しても、得られた硬化膜として、パターンの欠けや剥がれの無い良好な状態であった。また液晶表示装置としての性能も実施例200と同様に良好であった。これは本発明の組成物が基板との密着性に優れるためであると思われる。 <Example 205>
A liquid crystal display device similar to that of Example 200 was changed to obtain the same liquid crystal display device. That is, even when the alkali development method was changed from paddle development to shower development, the obtained cured film was in a good state with no pattern chipping or peeling. Further, the performance as a liquid crystal display device was good as in Example 200. This is presumably because the composition of the present invention has excellent adhesion to the substrate.
実施例200と以下のプロセスのみ変更して、同様の液晶表示装置を得た。すなわち、アルカリ現像液を0.4%のテトラメチルアンモニウムヒドロキシド水溶液から0.04%のKOH水溶液に変更しても、得られた硬化膜として、パターンの欠けや剥がれの無い良好な状態であった。また液晶表示装置としての性能も実施例200と同様に良好であった。これは本発明の組成物が基板との密着性に優れるためであると思われる。 <Example 206>
A liquid crystal display device similar to that of Example 200 was changed to obtain the same liquid crystal display device. That is, even when the alkaline developer was changed from a 0.4% tetramethylammonium hydroxide aqueous solution to a 0.04% KOH aqueous solution, the resulting cured film was in a good state with no pattern chipping or peeling. It was. Further, the performance as a liquid crystal display device was good as in Example 200. This is presumably because the composition of the present invention has excellent adhesion to the substrate.
実施例200と以下のプロセスのみ変更して、同様の液晶表示装置を得た。すなわち、現像・リンス後の全面露光の工程を省いて、オーブンにて230℃で30分加熱して硬化膜を得た。得られた液晶表示装置としての性能は実施例200と同様に良好であった。これは本発明の組成物が薬品耐性に優れるためであると思われる。生産性を向上させる観点では、全面露光の工程を省くことも好ましい。 <Example 207>
A liquid crystal display device similar to that of Example 200 was changed to obtain the same liquid crystal display device. That is, the entire surface exposure step after development and rinsing was omitted, and the cured film was obtained by heating in an oven at 230 ° C. for 30 minutes. The performance of the obtained liquid crystal display device was as good as in Example 200. This seems to be because the composition of the present invention is excellent in chemical resistance. From the viewpoint of improving productivity, it is also preferable to omit the entire exposure process.
実施例200と以下のプロセスのみ変更して、同様の液晶表示装置を得た。すなわち、全面露光の工程とオーブンでの230℃/30分加熱工程の間に、100℃で3分ホットプレート上で加熱する工程を追加した。得られた液晶表示装置としての性能は実施例200と同様に良好であった。ホールパターンの形状を整えるという観点で、本工程を追加することも好ましい。 <Example 208>
A liquid crystal display device similar to that of Example 200 was changed to obtain the same liquid crystal display device. That is, a step of heating on a hot plate at 100 ° C. for 3 minutes was added between the entire surface exposure step and the 230 ° C./30 minute heating step in the oven. The performance of the obtained liquid crystal display device was as good as in Example 200. It is also preferable to add this process from the viewpoint of adjusting the shape of the hole pattern.
実施例200と以下のプロセスのみ変更して、同様の液晶表示装置を得た。すなわち、現像・リンスの工程と全面露光の工程の間に、100℃で3分ホットプレート上で加熱する工程を追加した。得られた液晶表示装置としての性能は実施例200と同様に良好であった。ホールパターンの形状を整えるという観点で、本工程を追加することも好ましい。 <Example 209>
A liquid crystal display device similar to that of Example 200 was changed to obtain the same liquid crystal display device. That is, a process of heating on a hot plate at 100 ° C. for 3 minutes was added between the development / rinse process and the entire surface exposure process. The performance of the obtained liquid crystal display device was as good as in Example 200. It is also preferable to add this process from the viewpoint of adjusting the shape of the hole pattern.
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。 An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 2).
A bottom
感光性樹脂組成物を塗布する際の塗布性は良好で、露光、現像、焼成の後に得られた硬化膜には、しわやクラックの発生は認められなかった。さらに、配線2の平均段差は500nm、作製した平坦化膜4の膜厚は2,000nmであった。 Further, in order to flatten the unevenness due to the formation of the
The applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking. Furthermore, the average step of the
特開2011-59314号公報の図2に記載の液晶表示装置において、有機パッシベーション膜109を以下の方法で形成し、液晶表示装置を得た。図3は、この液晶表示装置の一例の構成概念図を示す。
先ず、特開2011-59314号公報に従って、特開2011-59314号公報の図2に記載の液晶表示装置の有機パッシベーション膜109の直前まで形成したアレイ基板を作製した。
次に、この基板をHMDS蒸気下に30秒曝し、その後、実施例1の感光性樹脂組成物をスリット塗布した後、90℃で2分ホットプレート上でプリベークして溶剤を揮発させ、所定膜厚の感光性樹脂組成物層を形成した。次に、得られた感光性樹脂組成物層を、キヤノン(株)製 MPA 7800CF(高圧水銀灯)を用いて、10μm径のホールパターンのマスクを介して40mJ/cm2(エネルギー強度:20mW/cm2、i線)露光した。そして、露光後の樹脂組成物層を、アルカリ現像液(0.4%のテトラメチルアンモニウムヒドロキシド水溶液)で23℃/60秒間現像した後、超純水で20秒リンスした。続いて超高圧水銀灯を用いて積算照射量が300mJ/cm2(エネルギー強度:20mW/cm2、i線)となるように全面露光し、その後、この基板をオーブンにて230℃で30分加熱して有機パッシベーション膜を得た。
以降は特開2011-59314号公報に従って液晶表示装置を得た。得られた液晶表示装置に対して、駆動電圧を印加したところ、良好な表示特性を示し、信頼性の高い液晶表示装置であることが分かった。 <Example 210>
In the liquid crystal display device shown in FIG. 2 of JP 2011-59314 A, an organic passivation film 109 was formed by the following method to obtain a liquid crystal display device. FIG. 3 is a conceptual diagram of an example of the liquid crystal display device.
First, according to Japanese Patent Application Laid-Open No. 2011-59314, an array substrate formed up to just before the organic passivation film 109 of the liquid crystal display device described in FIG. 2 of Japanese Patent Application Laid-Open No. 2011-59314 was manufactured.
Next, this substrate was exposed to HMDS vapor for 30 seconds, and then the photosensitive resin composition of Example 1 was slit-coated and then pre-baked on a hot plate at 90 ° C. for 2 minutes to volatilize the solvent. A thick photosensitive resin composition layer was formed. Next, the obtained photosensitive resin composition layer was subjected to 40 mJ / cm 2 (energy intensity: 20 mW / cm) through a 10 μm diameter hole pattern mask using Canon Inc. MPA 7800CF (high pressure mercury lamp). 2 , i-line) exposure. The exposed resin composition layer was developed with an alkali developer (0.4% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds. Subsequently, the whole surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm 2 (energy intensity: 20 mW / cm 2 , i-line), and then the substrate was heated in an oven at 230 ° C. for 30 minutes. Thus, an organic passivation film was obtained.
Thereafter, a liquid crystal display device was obtained in accordance with Japanese Patent Application Laid-Open No. 2011-59314. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
実施例210において、実施例1の感光性組成物を実施例19の感光性組成物に代えた以外は、実施例210と同様に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、駆動電圧を印加したところ、良好な表示特性を示し、信頼性の高い液晶表示装置であることが分かった。 <Example 211>
In Example 210, a liquid crystal display device was produced in the same manner as in Example 210 except that the photosensitive composition of Example 1 was replaced with the photosensitive composition of Example 19. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
実施例210において、実施例1の感光性組成物を実施例33の感光性組成物に代えた以外は、実施例210と同様に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、駆動電圧を印加したところ、良好な表示特性を示し、信頼性の高い液晶表示装置であることが分かった。 <Example 212>
In Example 210, a liquid crystal display device was produced in the same manner as in Example 210 except that the photosensitive composition of Example 1 was replaced with the photosensitive composition of Example 33. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
実施例210において、実施例1の感光性組成物を実施例47の感光性組成物に代えた以外は、実施例210と同様に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、駆動電圧を印加したところ、良好な表示特性を示し、信頼性の高い液晶表示装置であることが分かった。 <Example 213>
In Example 210, a liquid crystal display device was produced in the same manner as in Example 210 except that the photosensitive composition of Example 1 was replaced with the photosensitive composition of Example 47. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
特開2007-328210号公報の図1に記載の液晶表示装置において、有機絶縁膜PASを以下の方法で形成し、液晶表示装置を得た。図4は、この液晶表示装置の一例の構成概念図を示す。
先ず、特開2007-328210号公報に従って、特開2007-328210号公報の図1に記載の液晶表示装置の有機絶縁膜PAS直前まで形成したアレイ基板を作製した。
次に、この基板をHMDS蒸気下に30秒曝し、その後、実施例1の感光性樹脂組成物をスリット塗布した後、90℃で2分ホットプレート上でプリベークして溶剤を揮発させ、所定膜厚の感光性樹脂組成物層を形成した。次に、得られた感光性樹脂組成物層を、キヤノン(株)製 MPA 7800CFを用いて、8μm径のホールパターンのマスクを介して最適露光量mJ/cm2(エネルギー強度:20mW/cm2、i線)露光した。そして、露光後の樹脂組成物層を、アルカリ現像液(0.4%のテトラメチルアンモニウムヒドロキシド水溶液)で23℃/60秒間現像した後、超純水で20秒リンスした。続いて超高圧水銀灯を用いて積算照射量が300mJ/cm2(エネルギー強度:20mW/cm2、i線で計測)となるように全面露光し、その後、この基板をオーブンにて230℃で30分加熱して有機パッシベーション膜を得た。
以降は特開2007-328210号公報に従って液晶表示装置を得た。
得られた液晶表示装置に対して、駆動電圧を印加したところ、良好な表示特性を示し、信頼性の高い液晶表示装置であることが分かった。 <Example 214>
In the liquid crystal display device described in FIG. 1 of JP-A-2007-328210, the organic insulating film PAS was formed by the following method to obtain a liquid crystal display device. FIG. 4 is a conceptual diagram of an example of the liquid crystal display device.
First, according to Japanese Patent Application Laid-Open No. 2007-328210, an array substrate formed until just before the organic insulating film PAS of the liquid crystal display device described in FIG.
Next, this substrate was exposed to HMDS vapor for 30 seconds, and then the photosensitive resin composition of Example 1 was slit-coated and then pre-baked on a hot plate at 90 ° C. for 2 minutes to volatilize the solvent. A thick photosensitive resin composition layer was formed. Next, the obtained photosensitive resin composition layer was subjected to optimum exposure dose mJ / cm 2 (energy intensity: 20 mW / cm 2) through a hole pattern mask having a diameter of 8 μm using MPA 7800CF manufactured by Canon Inc. , I-line) exposure. The exposed resin composition layer was developed with an alkali developer (0.4% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds. Subsequently, the whole surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm 2 (energy intensity: 20 mW / cm 2 , measured by i-line), and then the substrate was heated at 230 ° C. in an oven at 30 ° C. An organic passivation film was obtained by heating for a minute.
Thereafter, a liquid crystal display device was obtained according to Japanese Patent Application Laid-Open No. 2007-328210.
When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
実施例214において、実施例1の感光性組成物を実施例19の感光性組成物に代えた以外は、実施例214と同様に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、駆動電圧を印加したところ、良好な表示特性を示し、信頼性の高い液晶表示装置であることが分かった。 <Example 215>
In Example 214, a liquid crystal display device was produced in the same manner as in Example 214 except that the photosensitive composition of Example 1 was replaced with the photosensitive composition of Example 19. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
実施例214において、実施例1の感光性組成物を実施例33の感光性組成物に代えた以外は、実施例214と同様に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、駆動電圧を印加したところ、良好な表示特性を示し、信頼性の高い液晶表示装置であることが分かった。 <Example 216>
In Example 214, a liquid crystal display device was produced in the same manner as in Example 214 except that the photosensitive composition of Example 1 was replaced with the photosensitive composition of Example 33. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
実施例214において、実施例1の感光性組成物を実施例47の感光性組成物に代えた以外は、実施例214と同様に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、駆動電圧を印加したところ、良好な表示特性を示し、信頼性の高い液晶表示装置であることが分かった。 <Example 217>
In Example 214, a liquid crystal display device was produced in the same manner as in Example 214 except that the photosensitive composition of Example 1 was replaced with the photosensitive composition of Example 47. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
Claims (16)
- (A)重合体成分、(B)光酸発生剤、並びに(C)溶剤を含有し、前記(A)重合体成分が、下記(1)及び(2)の少なくとも一方を含み、かつ下記(3)及び(4)の少なくとも一方を満たし;
(1)(a1)酸基が酸分解性基で保護された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含む重合体(A1)、
(2)前記構成単位(a1)を含む重合体(A2)、及び前記構成単位(a2)を含む重合体(A3);
(3)前記重合体(A1)~(A3)の少なくとも1種が、(a4)アルカリ加水分解によってカルボキシル基を生じる基を有する構成単位を含む重合体である、
(4)さらに、前記構成単位(a4)を含み、かつ、前記構成単位(a1)及び前記構成単位(a2)を含まない重合体(A4)を含む;
前記(A)重合体成分を構成する全構成単位に対して、前記構成単位(a2)の割合が10~40モル%であり、前記構成単位(a4)の割合が1.0~20モル%である感光性樹脂組成物。 (A) a polymer component, (B) a photoacid generator, and (C) a solvent, wherein the (A) polymer component includes at least one of the following (1) and (2), and Satisfy at least one of 3) and (4);
(1) (a1) a polymer (A1) comprising a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (a2) a structural unit having a crosslinkable group,
(2) A polymer (A2) containing the structural unit (a1) and a polymer (A3) containing the structural unit (a2);
(3) At least one of the polymers (A1) to (A3) is a polymer containing (a4) a structural unit having a group that generates a carboxyl group by alkaline hydrolysis.
(4) Furthermore, the polymer (A4) containing the structural unit (a4) and not containing the structural unit (a1) and the structural unit (a2) is included;
The proportion of the structural unit (a2) is 10 to 40 mol% and the proportion of the structural unit (a4) is 1.0 to 20 mol% with respect to all the structural units constituting the polymer component (A). A photosensitive resin composition. - 前記構成単位(a4)が、カルボン酸無水物構造またはラクトン構造を含有する構成単位である、請求項1に記載の感光性樹脂組成物。 The photosensitive resin composition of Claim 1 whose said structural unit (a4) is a structural unit containing a carboxylic anhydride structure or a lactone structure.
- 前記カルボン酸無水物構造が、5員環または6員環の環状カルボン酸無水物構造である、請求項2に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 2, wherein the carboxylic acid anhydride structure is a 5-membered or 6-membered cyclic carboxylic acid anhydride structure.
- 前記カルボン酸無水物構造が、下記一般式(1)で表される部分構造を含む、請求項2又は請求項3に記載の感光性樹脂組成物;
- 前記構成単位(a4)が前記式(1A)で表される、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 (a4) is represented by the formula (1A).
- 前記(A)重合体成分中に(a3)酸基を有する構成単位を含む、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 the (A) polymer component contains (a3) a structural unit having an acid group.
- 前記(A)重合体成分における前記構成単位(a3)の割合が5~20モル%である、請求項7に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 7, wherein the proportion of the structural unit (a3) in the polymer component (A) is 5 to 20 mol%.
- 前記構成単位(a2)が含有する架橋性基が、エポキシ基、オキセタニル基、および-NH-CH2-OR2から選ばれる少なくとも1種である、請求項1~8のいずれか1項に記載の感光性樹脂組成物;但し、R2は水素原子又は炭素数1~20のアルキル基を表す。 The crosslinkable group contained in the structural unit (a2) is at least one selected from an epoxy group, an oxetanyl group, and —NH—CH 2 —OR 2. Wherein R 2 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
- 前記構成単位(a1)が、酸基がアセタールの形で保護された基を有する構成単位である請求項1~9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 9, wherein the structural unit (a1) is a structural unit having a group in which an acid group is protected in the form of an acetal.
- 前記(B)光酸発生剤がオキシムスルホネート化合物である、請求項1~10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 10, wherein the photoacid generator (B) is an oxime sulfonate compound.
- (1)請求項1~11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で現像する工程、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 11 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) 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. - 請求項1~11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12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 obtained by curing the photosensitive resin composition according to any one of claims 1 to 11, or a cured film formed by the method for producing a cured film according to claim 12.
- 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、液晶表示装置。 A liquid crystal display device comprising the cured film according to claim 13 or 14.
- 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。 An organic EL display device comprising the cured film according to claim 13.
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KR1020167007212A KR101819625B1 (en) | 2013-09-25 | 2014-09-25 | Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device and organic el display device |
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JP2017134355A (en) * | 2016-01-29 | 2017-08-03 | 富士フイルム株式会社 | Photosensitive resin composition, cured film, liquid crystal display device, organic electroluminescence display device and production method of cured film |
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DE102019134535B4 (en) * | 2019-08-05 | 2023-09-07 | Taiwan Semiconductor Manufacturing Co., Ltd. | MATERIALS FOR LOWER ANTI-REFLECTIVE PLATING |
TWI830850B (en) * | 2019-12-30 | 2024-02-01 | 奇美實業股份有限公司 | Chemically amplified positive photosensitive resin composition and uses thereof |
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JP2012173438A (en) * | 2011-02-18 | 2012-09-10 | Fujifilm Corp | Pattern forming method, actinic ray-sensitive or radiation-sensitive resin composition, and resist film |
JP2013011866A (en) * | 2011-05-30 | 2013-01-17 | Shin Etsu Chem Co Ltd | Pattern forming method and resist composition |
JP2013187408A (en) * | 2012-03-08 | 2013-09-19 | Tokyo Ohka Kogyo Co Ltd | Block copolymer-containing composition and method for reduction of pattern |
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JP5451570B2 (en) | 2009-10-16 | 2014-03-26 | 富士フイルム株式会社 | Photosensitive resin composition, method for forming cured film, cured film, organic EL display device, and liquid crystal display device |
JP5528314B2 (en) * | 2010-01-20 | 2014-06-25 | 富士フイルム株式会社 | Method for producing cured film, photosensitive resin composition, cured film, organic EL display device, and liquid crystal display device |
JP2012042837A (en) * | 2010-08-20 | 2012-03-01 | Fujifilm Corp | Positive photosensitive composition, method for forming cured film, cured film, liquid crystal display device and organic el display device |
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WO2011065207A1 (en) * | 2009-11-30 | 2011-06-03 | Jsr株式会社 | Radiation-sensitive composition and method for forming resist pattern |
JP2012173438A (en) * | 2011-02-18 | 2012-09-10 | Fujifilm Corp | Pattern forming method, actinic ray-sensitive or radiation-sensitive resin composition, and resist film |
JP2013011866A (en) * | 2011-05-30 | 2013-01-17 | Shin Etsu Chem Co Ltd | Pattern forming method and resist composition |
JP2013187408A (en) * | 2012-03-08 | 2013-09-19 | Tokyo Ohka Kogyo Co Ltd | Block copolymer-containing composition and method for reduction of pattern |
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CN105917274A (en) | 2016-08-31 |
KR101819625B1 (en) | 2018-01-17 |
JPWO2015046295A1 (en) | 2017-03-09 |
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TWI649615B (en) | 2019-02-01 |
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