WO2013008652A1 - Photopolymerization initiator, photosensitive composition, and cured article - Google Patents
Photopolymerization initiator, photosensitive composition, and cured article Download PDFInfo
- Publication number
- WO2013008652A1 WO2013008652A1 PCT/JP2012/066763 JP2012066763W WO2013008652A1 WO 2013008652 A1 WO2013008652 A1 WO 2013008652A1 JP 2012066763 W JP2012066763 W JP 2012066763W WO 2013008652 A1 WO2013008652 A1 WO 2013008652A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- photopolymerization initiator
- photosensitive composition
- indole skeleton
- substituent
- Prior art date
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- 239000003999 initiator Substances 0.000 title claims abstract description 60
- 239000000203 mixture Substances 0.000 title claims abstract description 52
- 125000001041 indolyl group Chemical group 0.000 claims abstract description 20
- 125000001424 substituent group Chemical group 0.000 claims abstract description 17
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims description 21
- 229920006395 saturated elastomer Polymers 0.000 claims description 13
- 125000000962 organic group Chemical group 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 10
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 40
- 230000035945 sensitivity Effects 0.000 abstract description 12
- 239000000047 product Substances 0.000 description 27
- -1 oxime ester compounds Chemical class 0.000 description 23
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 238000011161 development Methods 0.000 description 11
- 239000011159 matrix material Substances 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 229920002120 photoresistant polymer Polymers 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000000016 photochemical curing Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- QDBBTFGVXWTAFD-UHFFFAOYSA-N CCN1C=C(C2=C1C=CC(=C2)[N+](=O)[O-])C(=O)C Chemical compound CCN1C=C(C2=C1C=CC(=C2)[N+](=O)[O-])C(=O)C QDBBTFGVXWTAFD-UHFFFAOYSA-N 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
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- OZFPSOBLQZPIAV-UHFFFAOYSA-N 5-nitro-1h-indole Chemical compound [O-][N+](=O)C1=CC=C2NC=CC2=C1 OZFPSOBLQZPIAV-UHFFFAOYSA-N 0.000 description 4
- BQJIFHXNAZMXFI-UHFFFAOYSA-N CCC(=O)C1=CN(C2=C1C=C(C=C2)[N+](=O)[O-])CC Chemical compound CCC(=O)C1=CN(C2=C1C=C(C=C2)[N+](=O)[O-])CC BQJIFHXNAZMXFI-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
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- 125000000524 functional group Chemical group 0.000 description 4
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 3
- 239000012346 acetyl chloride Substances 0.000 description 3
- 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 3
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 150000002923 oximes Chemical class 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 2
- CWRBWLKXTXSMEH-UHFFFAOYSA-N 1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethanone Chemical compound C=1C=C2N(CC)C3=CC=C(C(C)=O)C=C3C2=CC=1C(=O)C1=CC=CC=C1C CWRBWLKXTXSMEH-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical class OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 2
- SKJLUKCXRQYDMG-UHFFFAOYSA-N C(CCC)N1C=C(C2=CC(=CC=C12)[N+](=O)[O-])C(C)=O Chemical compound C(CCC)N1C=C(C2=CC(=CC=C12)[N+](=O)[O-])C(C)=O SKJLUKCXRQYDMG-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000008062 acetophenones Chemical class 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- PESYEWKSBIWTAK-UHFFFAOYSA-N cyclopenta-1,3-diene;titanium(2+) Chemical class [Ti+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 PESYEWKSBIWTAK-UHFFFAOYSA-N 0.000 description 2
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- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
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- 238000000034 method Methods 0.000 description 2
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- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
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- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
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- VQYUAFDBUVMFKD-UHFFFAOYSA-N 1-(4-phenylsulfanylphenyl)octane-1,2-dione Chemical compound C1=CC(C(=O)C(=O)CCCCCC)=CC=C1SC1=CC=CC=C1 VQYUAFDBUVMFKD-UHFFFAOYSA-N 0.000 description 1
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- XOJVXYVKUFVBQE-UHFFFAOYSA-N 1-ethyl-5-nitroindole Chemical compound [O-][N+](=O)C1=CC=C2N(CC)C=CC2=C1 XOJVXYVKUFVBQE-UHFFFAOYSA-N 0.000 description 1
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- SDSMQJYIBMHORW-UHFFFAOYSA-N 2,4,6-tris(trichloromethyl)-1h-triazine Chemical class ClC(Cl)(Cl)N1NC(C(Cl)(Cl)Cl)=CC(C(Cl)(Cl)Cl)=N1 SDSMQJYIBMHORW-UHFFFAOYSA-N 0.000 description 1
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- BFQFFNWLTHFJOZ-UHFFFAOYSA-N 2-(1,3-benzodioxol-5-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(C=2C=C3OCOC3=CC=2)=N1 BFQFFNWLTHFJOZ-UHFFFAOYSA-N 0.000 description 1
- MHDULSOPQSUKBQ-UHFFFAOYSA-N 2-(2-chlorophenyl)-1-[2-(2-chlorophenyl)-4,5-diphenylimidazol-2-yl]-4,5-diphenylimidazole Chemical compound ClC1=CC=CC=C1C(N1C2(N=C(C(=N2)C=2C=CC=CC=2)C=2C=CC=CC=2)C=2C(=CC=CC=2)Cl)=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 MHDULSOPQSUKBQ-UHFFFAOYSA-N 0.000 description 1
- CQDMETPQGYKYJG-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC(C)(C)C)C(=O)C1=CC=CC=C1 CQDMETPQGYKYJG-UHFFFAOYSA-N 0.000 description 1
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- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
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- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
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- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
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- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- FZENGILVLUJGJX-UHFFFAOYSA-N acetaldehyde oxime Chemical compound CC=NO FZENGILVLUJGJX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229930006711 bornane-2,3-dione Natural products 0.000 description 1
- 125000004555 carbazol-3-yl group Chemical group C1=CC(=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001851 cinnamic acid derivatives Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical class C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 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 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- ZOOSILUVXHVRJE-UHFFFAOYSA-N cyclopropanecarbonyl chloride Chemical compound ClC(=O)C1CC1 ZOOSILUVXHVRJE-UHFFFAOYSA-N 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000005022 dithioester group Chemical group 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 125000002632 imidazolidinyl group Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical class OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 125000005439 maleimidyl group Chemical class C1(C=CC(N1*)=O)=O 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-UHFFFAOYSA-N 0.000 description 1
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000001749 primary amide group Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- MVQLEZWPIWKLBY-UHFFFAOYSA-N tert-butyl 2-benzoylbenzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 MVQLEZWPIWKLBY-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000005958 tetrahydrothienyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 150000007970 thio esters Chemical group 0.000 description 1
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/14—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/06—Peri-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
Definitions
- the present invention relates to a novel photopolymerization initiator, a photosensitive composition containing the same, and a cured product thereof.
- Photosensitive compositions are widely used in a form in which a photopolymerization initiator is blended with a polymerizable compound having an olefinic bond.
- Photoresist, photocurable ink, photocurable paint, photocurable adhesive, photofabrication Have been put to practical use in applications such as photosensitive resins, photosensitive printing plates, and recording materials.
- Such a photosensitive composition can be cured by causing a polymerization reaction by irradiating with ultraviolet light or visible light using a mercury lamp, xenon lamp, laser or the like as a light source (referred to as exposure), but can be cured efficiently with a small exposure amount.
- a highly sensitive photosensitive composition is desired, and a highly sensitive photopolymerization initiator for that purpose is required.
- a number of compounds have been proposed as photopolymerization initiators so far, including acetophenone compounds, benzophenone compounds, benzoin ether compounds, ⁇ -aminoalkylphenone compounds, thioxanthone compounds, organic peroxides, biimidazole compounds, titanocene compounds, Triazine compounds, acylphosphine oxide compounds, quinone compounds, oxime ester compounds and the like are known. However, none of these has sufficient sensitivity.
- Another problem is that the solubility in propylene glycol monomethyl ether acetate is low. Furthermore, many of the oxime ester compounds having a carbazole skeleton also have the disadvantage that the molecular structure is relatively complex and the production cost is high.
- the present invention has been made in view of the problems of the prior art, and an object thereof is to provide a photopolymerization initiator having high sensitivity and excellent solubility and a photosensitive composition using the photopolymerization initiator.
- the present inventors focused on an oxime ester compound having an indole skeleton having one less condensed ring than the carbazole skeleton, and further replacing the indole skeleton with a specific functional group.
- the present invention has been completed by finding that the object can be achieved.
- the present invention provides a light having a group having an oxime ester bond bonded to an indole skeleton which may have a substituent, and the indole skeleton is substituted with at least one nitro group. It is a polymerization initiator.
- a group having an oxime ester bond represented by the following general formula (1) is bonded directly or via a carbonyl group to the 3-position of the indole skeleton, and the indole skeleton 5 It is preferred that the position is substituted with a nitro group.
- R 11 and R 12 each represent a saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms which may have a substituent.
- R 11 and R 12 represent a branched structure or a ring structure.
- a hetero atom may be present at any position, R 11 may be bonded to a substituent on the indole skeleton, and R 11 may be a hydrogen atom.
- the present invention is a photosensitive composition containing a polymerizable compound having an olefin bond and the photopolymerization initiator, and a cured product obtained by curing the photosensitive composition.
- the photosensitive composition preferably contains propylene glycol monomethyl ether acetate as a solvent.
- the photopolymerization initiator of the present invention is formed by bonding a group having an oxime ester bond to an indole skeleton which may have a substituent.
- the indole skeleton needs to be substituted with at least one nitro group, and the substitution position is preferably the 5-position.
- the group having an oxime ester bond a group represented by the following general formula (1) is advantageous, and the group having the oxime ester bond is bonded directly to the 3-position of the indole skeleton or via a carbonyl group. Preferably it is.
- R 11 and R 12 each represent a saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms which may have a substituent.
- R 11 and R 12 represent a branched structure or a ring structure. And a hetero atom may be present at any position, R 11 may be bonded to a substituent on the indole skeleton, and R 11 may be a hydrogen atom.
- the oxime moiety of the structure represented by the general formula (1) and the formula described later represents a mixture of these geometric isomers or any one of them.
- a preferable structure is the following general formula (2), It is represented by
- R 1 , R 2 , R 4 , R 6 and R 7 may be any substituent, but may be a saturated or unsaturated group having 1 to 20 carbon atoms which may have a substituent. It is preferably a valent organic group, or a hydrogen atom, a halogen atom or a nitro group. In the case of such a monovalent organic group, R 1 , R 2 , R 4 , R 6 and R 7 may form a branched structure or a ring structure, and a hetero atom may exist at an arbitrary position. Or may be bonded to each other.
- R 11 and R 12 are the same as those in the general formula (1).
- saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms which may have a substituent in the general formulas (1) and (2) include a methyl group and an ethyl group.
- a halogen atom a hydroxy group, a sulfanyl group, a carbonyl group, a thiocarbonyl group, a carboxy group, a thiocarboxy group, a dithiocarboxy group, a formyl group, a cyano group , Nitro group, nitroso group, sulfo group, amino group, imino group, silyl group, ether group, thioether group, ester group, thioester group, dithioester group, amide group, thioamide group, urethane group, thiourethane group, ureido group Moreover, the structure which introduce
- the monovalent organic group includes not only a monovalent organic group on a carbon atom such as a methyl group, but also a monovalent organic group on a heteroatom such as a methoxy group, a methylsulfanyl group, or a dimethylamino group. Groups are also included.
- the monovalent organic group carboxy group, thiocarboxy group, dithiocarboxy group, formyl group, cyano group, primary amide group, primary thioamide group, ureido group, thioureido group, etc.
- the functional group may be directly bonded.
- the monovalent organic group may be appropriately selected according to the molecular weight, sensitivity, solubility, etc. of the target photopolymerization initiator, but is saturated or saturated with 1 to 20 carbon atoms from the viewpoint of performance and economy.
- An unsaturated monovalent hydrocarbon group is preferable, a saturated or unsaturated monovalent hydrocarbon group having 1 to 12 carbon atoms is more preferable, and further, a saturated one having 1 to 4 carbon atoms. Or, it is most preferably an unsaturated monovalent hydrocarbon group.
- the monovalent hydrocarbon group can be used regardless of the presence or absence of a saturated or unsaturated, branched structure or ring structure.
- the photopolymerization initiator of the present invention may be obtained by multiplying it through an appropriate substituent as in the structures represented by the following general formulas (19) and (20).
- R 1a and R 11a represent a saturated or unsaturated divalent organic group having 1 to 20 carbon atoms which may have a substituent.
- R 1 , R 2 , R 4 , R 6 , R 7 , R 11 and R 12 are the same as those in the general formulas (1) and (2).
- the photopolymerization initiator of the present invention may have a structure represented by the following general formulas (21), (22), and (23).
- R 1 , R 2 , R 4 , R 6 , R 7 , R 11 and R 12 are the same as those in the general formulas (1) and (2), and R 1a and R 11a are the same as those in the general formula (19) and (Same as (20).)
- the production method of the photopolymerization initiator of the present invention is not particularly limited.
- the following procedure is applied using commercially available 5-nitroindole as a raw material. It is economically advantageous to do.
- R 1 is introduced into the 1-position of 5-nitroindole by a nucleophilic substitution reaction or the like
- R 11 CO is introduced into the 3-position by Friedel-Crafts acylation reaction to obtain a ketone body. This is converted into an oxime with hydroxylamine, and further esterified with an acid halide or acid anhydride of R 12 COOH to lead to a target photopolymerization initiator.
- a nitrite is allowed to act on the ketone body to form an ⁇ -oxooxime, and the oxime is esterified in the same manner.
- 5-nitroindole may not be used as a starting material, and R 1 or R 11 CO may be first introduced into the indole, followed by nitration.
- the photopolymerization initiator of the present invention has an indole skeleton, which is a skeleton having a smaller number of condensed rings and a smaller plane spread than the carbazole skeleton. Therefore, the photopolymerization initiator of the present invention is excellent in solubility and has an effect of improving the degree of freedom in designing the photosensitive composition. For example, even in applications where photocuring is difficult, such as a light-shielding photoresist used in the production of a black matrix for a color filter, good sensitivity can be obtained by being present at a high concentration in the photosensitive composition. It becomes like this. On the other hand, in order for the photopolymerization initiator to exhibit its function, it needs to absorb light and be in an excited state.
- the photopolymerization initiator of the present invention can overcome this problem by substituting the indole skeleton with at least one nitro group, and can cause light absorption in a wide wavelength range from ultraviolet light to visible light.
- the photosensitive composition of the present invention contains a polymerizable compound having an olefin bond in addition to the above photopolymerization initiator.
- a polymerizable compound having an olefin bond known compounds conventionally used in photosensitive compositions can be used without particular limitation, but acrylic acid and methacrylic acid (hereinafter referred to as “(meth)” Acrylic acid "etc.) derivatives are advantageous, for example, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipenta (Meth) acrylic acid ester derivatives such as erythritol hexa (meth) acrylate, bisphenol A type epoxy di (meth) acrylate, bisphenol F type epoxy di (meth) acrylate, bisphenol fluorene type epoxy di (meth)
- a reaction product of the (meth) acrylic acid derivative and a compound having an (preferably plural) isocyanate group or an acid anhydride group in the structure is also suitable.
- vinyl resins acrylic acid (co) polymer, methacrylic acid (co) polymer, maleic acid (co) polymer, styrene (co) polymer, etc.
- polyester resins which are known resins
- polyamide resins Resins in which a (meth) acryloyl group is introduced into the main chain or side chain of a polyimide resin, polyurethane resin, polyether resin or the like by an ester bond, an amide bond, a urethane bond, or the like can also be used.
- (meth) acrylic acid derivatives maleic acid derivatives, maleimide derivatives, crotonic acid derivatives, itaconic acid derivatives, cinnamic acid derivatives, vinyl derivatives, vinyl alcohol derivatives, vinyl ketone derivatives, vinyl aromatic derivatives, etc. it can.
- These polymerizable compounds having an olefinic bond may further have a heat-functional functional group such as an epoxy group, an alkali-soluble functional group such as a carboxy group, etc., and a composite function. .
- These polymerizable compounds having an olefinic bond may be used alone or in combination.
- the mixing ratio of the photopolymerization initiator in the photosensitive composition of the present invention is not particularly limited, but the photopolymerization initiator is 0.01 to 50 parts by weight with respect to 100 parts by weight of the polymerizable compound having an olefin bond.
- the amount is preferably 0.1 to 20 parts by weight.
- the photosensitive composition of the present invention may contain a solvent, and in particular, propylene glycol monomethyl ether acetate can be preferably used.
- Propylene glycol monomethyl ether acetate is a safe solvent having moderate solubility and drying properties, and is widely used in photoresists and the like used in the production of color filters, but the photopolymerization initiator of the present invention is used in the solvent system. It is difficult to cause problems such as poor dissolution, and a photosensitive composition can be advantageously produced.
- solvent known compounds other than propylene glycol monomethyl ether acetate can also be used, for example, ester solvents, ketone solvents, ether solvents, alcohol solvents, aromatic solvents, aliphatic solvents, amine solvents, An amide solvent or the like can be used without any particular limitation.
- the photosensitive composition of the present invention may contain other optional components as necessary.
- a coloring material a filler, a resin, an additive and the like can be blended.
- coloring materials dyes, organic pigments, inorganic pigments, carbon black pigments, etc., as fillers, silica, talc, etc.
- resins vinyl resins (acrylic acid (co) polymer, methacrylic acid (co) heavy) Coalesce, maleic acid (co) polymer, styrene (co) polymer, etc.), polyester resin, polyamide resin, polyimide resin, polyurethane resin, polyether resin, epoxy resin, melamine resin, etc.
- Crosslinking agents, dispersants, surfactants, silane coupling agents, viscosity modifiers, wetting agents, antifoaming agents, antioxidants and the like can be mentioned.
- known compounds can be used without particular limitation.
- a well-known photoinitiator, a dye sensitizer, etc. can also be used together for the photosensitive composition of this invention.
- acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, benzophenone, 2,4,6-trimethylbenzophenone, 4,4′-bis (N, N Benzophenone compounds such as -diethylamino) benzophenone, benzoin ether compounds such as benzoin ethyl ether and benzoin-tert-butyl ether, 2-methyl-1- [4- (methylsulfanyl) phenyl] -2-morpholinopropan-1-one, ⁇ -aminoalkylphenone compounds such as benzyl-2- (N, N-dimethylamino) -1- (4-morpholinophenyl) butan-1-one,
- a method for producing a cured product of the photosensitive composition of the present invention a known method can be used. After the photosensitive composition is applied or injected onto an appropriate substrate or mold suitable for the purpose or application, it is cured by exposure. Should just be done. Here, by performing selective exposure using a photomask or the like, and further performing development, processing such as image formation or modeling can be performed. Since the photopolymerization initiator of the present invention is excellent in solubility in a developer, it has an effect of shortening the time required for developing the photosensitive composition, and is preferable in terms of improving production efficiency. After performing exposure and development, a treatment such as baking may be further performed as necessary.
- the photopolymerization initiator of the present invention is extremely useful because it is excellent in sensitivity and can provide a highly sensitive photosensitive composition that can be cured efficiently with a small amount of exposure.
- the photopolymerization initiator of the present invention absorbs ultraviolet light and visible light and enters an excited state, the oxime ester bond is rapidly cleaved to generate a highly active radical species, and the olefin bond contained in the photosensitive composition It is considered that a polymerizable compound having a high molecular weight undergoes a polymerization reaction at high speed.
- the photopolymerization initiator of the present invention is excellent in solubility and can be suitably used in a solvent system such as propylene glycol monomethyl ether acetate.
- Step 1 Using N, N-dimethylformamide as a solvent, 0.100 mol of 5-nitroindole, 0.110 mol of bromoethane and 0.110 mol of potassium hydroxide were reacted at 35 ° C. for 2 hours. After cooling, the reaction solution was dropped into water, and the precipitated solid was collected, washed thoroughly and dried to obtain 0.099 mol of 1-ethyl-5-nitroindole.
- Step 2 Using nitromethane as a solvent, the total amount of the product of Step 1, 0.120 mol of acetyl chloride and 0.120 mol of aluminum chloride were reacted at room temperature for 2 hours. The reaction solution was dropped into ice water, and the precipitated solid was collected, washed thoroughly and dried to obtain 0.095 mol of 1- (1-ethyl-5-nitroindol-3-yl) ethanone.
- ⁇ 9.29 (d, 1H, R 4 ), 8.19 (dd, 1H, R 6 ), 7.57 (s, 1H, R 2 ), 7.37 (d, 1H, R 7 ), 6.01 (ddt, 1H, R 1 ), 5.33 (ddt, 1H, R 1 ), 5.15 (ddt, 1H, R 1 ), 4.81 (ddd, 2H, R 1 ), 2. 42 (s, 3H, R 11 ), 2.39 (s, 3H, R 12 ).
- Step 1 The product of Step 1 is 1-allyl-5-nitroindole, the product of Step 2 is 1- (1-allyl-5-nitroindol-3-yl) ethanone, and the product of Step 3 is 1- ( 1-allyl-5-nitroindol-3-yl) ethanone oxime.
- ⁇ 9.27 (d, 1H, R 4 ), 8.19 (dd, 1H, R 6 ), 7.56 (s, 1H, R 2 ), 7.38 (d, 1H, R 7 ), 4.19 (t, 2H, R 1 ), 2.42 (s, 3H, R 11 ), 2.39 (s, 3H, R 12 ), 1.87 (tt, 2H, R 1 ), 1. 37 (tq, 2H, R 1 ), 0.97 (t, 3H, R 1 ).
- Step 1 is 1-butyl-5-nitroindole
- the product of Step 2 is 1- (1-butyl-5-nitroindol-3-yl) ethanone
- the product of Step 3 is 1- ( 1-butyl-5-nitroindol-3-yl) ethanone oxime.
- Step 2 is 1- (1-ethyl-5-nitroindol-3-yl) propan-1-one
- the product of Step 3 is 1- (1-ethyl-5-nitroindole-3- Yl) propan-1-one oxime.
- ⁇ 9.28 (d, 1H, R 4 ), 8.19 (dd, 1H, R 6 ), 7.59 (s, 1H, R 2 ), 7.38 (d, 1H, R 7 ), 4.25 (q, 2H, R 1 ), 2.68 (q, 2H, R 12 ), 2.41 (s, 3H, R 11 ), 1.54 (t, 3H, R 1 ), 1. 31 (t, 3H, R 12 ).
- ⁇ 9.30 (d, 1H, R 4 ), 8.18 (dd, 1H, R 6 ), 7.59 (s, 1H, R 2 ), 7.37 (d, 1H, R 7 ), 4.25 (q, 2H, R 1 ), 2.44 (s, 3H, R 11 ), 1.96 (tt, 1H, R 12 ), 1.54 (t, 3H, R 1 ), 1. 21 (dt, 2H, R 12 ), 1.03 (dt, 2H, R 12 ).
- ⁇ 9.32 (d, 1H, R 4 ), 8.18 (dd, 1H, R 6 ), 7.59 (s, 1H, R 2 ), 7.37 (d, 1H, R 7 ), 4.24 (q, 2H, R 1 ), 2.41 (s, 3H, R 11 ), 1.54 (t, 3H, R 1 ), 1.37 (s, 9H, R 12 ).
- ⁇ 9.32 (d, 1H, R 4 ), 8.19 (dd, 1H, R 6 ), 7.60 (s, 1H, R 2 ), 7.38 (d, 1H, R 7 ), 6.61 (dd, 1H, R 12 ), 6.40 (dd, 1 H, R 12 ), 5.98 (dd, 1 H, R 12 ), 4.26 (q, 2H, R 1 ), 2. 86 (q, 2H, R 11 ), 1.55 (t, 3H, R 1 ), 1.31 (t, 3H, R 11 ).
- Step 2 is 1- (1-ethyl-5-nitroindol-3-yl) propan-1-one
- the product of Step 3 is 1- (1-ethyl-5-nitroindole-3- Yl) propan-1-one oxime.
- Example 11 (Preparation of photosensitive composition) 56.5% by weight of propylene glycol monomethyl ether of 0.10% by weight of the photopolymerization initiator synthesized in Example 1 and 56.5% by weight of an alkali-developable photosensitive resin (polymerizable compound having an olefin bond) having a bisphenolfluorene type epoxy diacrylate structure Acetate solution (“V-259ME” manufactured by Nippon Steel Chemical Co., Ltd.) 26.20% by weight, pentaerythritol tetraacrylate (polymerizable compound having an olefin bond) 5.00% by weight, silicone surfactant (Toray Dow Corning) "FZ-2122" manufactured by the company) 0.05 wt%, 3- (glycidyloxy) propyltrimethoxysilane (silane coupling agent) 0.05 wt% and propylene glycol monomethyl ether acetate (solvent) 68.60 wt% Mix in proportion and
- the photosensitive composition was applied to an alkali-free glass substrate using a spin coater, and dried on an 80 ° C. hot plate for 1 minute to prepare a test piece. At this time, the coating conditions (spin rotation speed) were adjusted so that a cured film having a thickness of 1.0 ⁇ m was obtained. Next, an ultra-high pressure mercury lamp with an illuminance of 30 mW / cm 2 (based on i-line) through a photomask whose transmittance is changed stepwise between 0 and 100% and a cut filter that absorbs light of 350 nm or less And 100 mJ / cm 2 (i-line basis) was irradiated with ultraviolet rays to perform image exposure on the test piece.
- test piece was treated with an alkaline developer at 23 ° C. (10-fold diluted solution of “V-2401ID” manufactured by Nippon Steel Chemical Co., Ltd.) for 1 minute, and further washed with water to develop the image. This image can read the exposure amount required for photocuring. Finally, the test piece was baked in a hot air oven at 230 ° C. for 30 minutes to obtain a cured film of the photosensitive composition. The exposure necessary for photocuring determined from the image was 23 mJ / cm 2 (i-line reference).
- Example 12 The photopolymerization initiator in Example 11 was changed to the photopolymerization initiator synthesized in Example 2, and the others were prepared and evaluated in the same manner as in Example 11.
- the exposure necessary for photocuring determined from the image was 23 mJ / cm 2 (i-line reference).
- Example 13 The photopolymerization initiator in Example 11 was changed to the photopolymerization initiator synthesized in Example 3, and the others were prepared and evaluated in the same manner as in Example 11.
- the exposure amount required for photocuring determined from the image was 26 mJ / cm 2 (i-line reference).
- Example 14 The photopolymerization initiator in Example 11 was changed to the photopolymerization initiator synthesized in Example 4, and the others were prepared and evaluated in the same manner as in Example 11.
- the exposure necessary for photocuring determined from the image was 23 mJ / cm 2 (i-line reference).
- the exposure amount required for photocuring determined from the image was 37 mJ / cm 2 (i-line basis), and it was shown that the sensitivity was lower than in Examples 11 to 14 (exposure amount necessary for curing). The smaller the number, the higher the sensitivity.)
- a photosensitive composition was prepared and evaluated. As a result, the photosensitive composition was completely undissolved in the alkali developer without being photocured, indicating that the sensitivity was lower than in Examples 11-14.
- Example 21 (Preparation of photosensitive composition) 0.60% by weight of the photopolymerization initiator synthesized in Example 1, 56.5% by weight of propylene glycol monomethyl ether of an alkali development type photosensitive resin (polymerizable compound having an olefin bond) having a bisphenolfluorene type epoxy diacrylate structure Acetate solution (“V-259ME” manufactured by Nippon Steel Chemical Co., Ltd.) 8.23 wt%, pentaerythritol tetraacrylate (polymerizable compound having an olefin bond) 1.35 wt%, carbon black pigment (colorant) cationic 26.69 wt% dispersion (carbon black pigment concentration 30.0 wt%, solid content concentration 34.5 wt%) dispersed in propylene glycol monomethyl ether acetate with a polymer dispersant, fluorosurfactant (manufactured by DIC) “Megafuck F-556”) 0.05% by weight,
- the said photosensitive composition was apply
- test piece was treated with an alkaline developer at 23 ° C. (10-fold diluted solution of “V-2401ID” manufactured by Nippon Steel Chemical Co., Ltd.) for 1 minute, and further washed with water to develop the image. Finally, the test piece was baked in a hot air oven at 230 ° C. for 30 minutes to obtain a cured film of the photosensitive composition.
- a high-quality black matrix having a line width of 5 ⁇ m with good linearity and no development residue was formed on the test piece.
- the optical density of the black matrix was 4.4 / ⁇ m and had high light shielding properties.
- Example 22 The photopolymerization initiator in Example 21 was changed to the photopolymerization initiator synthesized in Example 2, and the others were prepared and evaluated in the same manner as in Example 21. A high-quality black matrix having a line width of 5 ⁇ m with good linearity and no development residue was formed on the test piece. The optical density of the black matrix was 4.4 / ⁇ m and had high light shielding properties.
- Example 23 The photopolymerization initiator in Example 21 was changed to the photopolymerization initiator synthesized in Example 3, and the others were prepared and evaluated in the same manner as in Example 21. A high-quality black matrix having a line width of 5 ⁇ m with good linearity and no development residue was formed on the test piece. The optical density of the black matrix was 4.4 / ⁇ m and had high light shielding properties.
- Example 24 The photopolymerization initiator in Example 21 was changed to the photopolymerization initiator synthesized in Example 4, and the others were prepared and evaluated in the same manner as in Example 21. A high-quality black matrix having a line width of 5 ⁇ m with good linearity and no development residue was formed on the test piece. The optical density of the black matrix was 4.4 / ⁇ m and had high light shielding properties.
- a photosensitive composition was prepared and evaluated.
- the foreign matter was an undissolved photopolymerization initiator.
- the photopolymerization initiator of the present invention is highly sensitive and excellent in solubility, a photoresist, a photocurable ink, a photocurable paint, a photocurable adhesive, a photopolymerization photosensitive resin, a photosensitive printing plate, It can be used suitably for recording materials and the like. In particular, it is optimal for applications that require high performance, such as photoresists used in the manufacture of color filters.
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Abstract
The purpose of the present invention is to provide: a photopolymerization initiator having high sensitivity and excellent solubility; a photosensitive composition containing the photopolymerization initiator; and a cured article produced by curing the photosensitive composition.
A photopolymerization initiator characterized in that a group having an oxime ester bond is bound to an indole skeleton that may have a substituent and the indole skeleton is substituted by at least one nitro group; a photosensitive composition comprising a polymerizable compound having an olefin bond and the photopolymerization initiator; and a cured article produced by curing the photosensitive composition.
Description
本発明は、新規な光重合開始剤、これを含有する感光性組成物、及びその硬化物に関する。
The present invention relates to a novel photopolymerization initiator, a photosensitive composition containing the same, and a cured product thereof.
感光性組成物は、オレフィン結合を有する重合性化合物に光重合開始剤を配合した形態で広く使用されており、フォトレジスト、光硬化型インキ、光硬化型塗料、光硬化型接着剤、光造形用感光性樹脂、感光性印刷版、記録材料等の用途で実用化されている。かかる感光性組成物は、水銀ランプ、キセノンランプ、レーザー等を光源として紫外光や可視光を照射すること（露光という）により重合反応を起こさせて硬化できるが、少ない露光量で効率よく硬化できる高感度な感光性組成物が望まれており、そのための高感度な光重合開始剤が必要とされている。
Photosensitive compositions are widely used in a form in which a photopolymerization initiator is blended with a polymerizable compound having an olefinic bond. Photoresist, photocurable ink, photocurable paint, photocurable adhesive, photofabrication Have been put to practical use in applications such as photosensitive resins, photosensitive printing plates, and recording materials. Such a photosensitive composition can be cured by causing a polymerization reaction by irradiating with ultraviolet light or visible light using a mercury lamp, xenon lamp, laser or the like as a light source (referred to as exposure), but can be cured efficiently with a small exposure amount. A highly sensitive photosensitive composition is desired, and a highly sensitive photopolymerization initiator for that purpose is required.
光重合開始剤としてはこれまでに数多くの化合物が提案されており、アセトフェノン化合物、ベンゾフェノン化合物、ベンゾインエーテル化合物、α－アミノアルキルフェノン化合物、チオキサントン化合物、有機過酸化物、ビイミダゾール化合物、チタノセン化合物、トリアジン化合物、アシルホスフィンオキシド化合物、キノン化合物、オキシムエステル化合物等が知られている。しかし、これらはいずれも十分な感度を有するものではなかった。
A number of compounds have been proposed as photopolymerization initiators so far, including acetophenone compounds, benzophenone compounds, benzoin ether compounds, α-aminoalkylphenone compounds, thioxanthone compounds, organic peroxides, biimidazole compounds, titanocene compounds, Triazine compounds, acylphosphine oxide compounds, quinone compounds, oxime ester compounds and the like are known. However, none of these has sufficient sensitivity.
近年、カルバゾール骨格を有するオキシムエステル化合物が多数開示されており（例えば特許文献１～１２参照）、従来の光重合開始剤を大きく上回る感度が報告されている。ところが、これらの化合物をもってしても、カラーフィルターの製造に用いられるフォトレジストのように高性能を要求される用途に関しては、その感度は必ずしも満足な水準に達していないという問題があった。また、カルバゾール骨格は芳香環及びヘテロ芳香環が合計３つ縮合して平面に広がった構造を有することから、当該骨格のオキシムエステル化合物はカラーフィルターの製造に用いられるフォトレジストで広く使用される溶剤であるプロピレングリコールモノメチルエーテルアセテートへの溶解性が低いという課題も有していた。更に、カルバゾール骨格を有するオキシムエステル化合物の多くは、分子構造が比較的複雑で製造コストが高いという不経済性も抱えていた。
In recent years, a large number of oxime ester compounds having a carbazole skeleton have been disclosed (see, for example, Patent Documents 1 to 12), and sensitivity far exceeding that of conventional photopolymerization initiators has been reported. However, even with these compounds, there is a problem that the sensitivity does not necessarily reach a satisfactory level for applications that require high performance such as photoresists used in the production of color filters. In addition, since the carbazole skeleton has a structure in which a total of three aromatic rings and heteroaromatic rings are condensed and spread in a plane, the oxime ester compound of the skeleton is a solvent widely used in photoresists used in the production of color filters. Another problem is that the solubility in propylene glycol monomethyl ether acetate is low. Furthermore, many of the oxime ester compounds having a carbazole skeleton also have the disadvantage that the molecular structure is relatively complex and the production cost is high.
また、カルバゾール以外の骨格を有するオキシムエステル化合物も開示されているが（例えば特許文献１３、１４参照）、それらの性能も十分なものとは言えなかった。
Moreover, although oxime ester compounds having a skeleton other than carbazole have been disclosed (see, for example, Patent Documents 13 and 14), their performance has not been sufficient.
本発明は、かかる従来技術の課題に鑑みてなされたものであり、高感度かつ溶解性に優れる光重合開始剤及びそれを用いた感光性組成物を提供することを目的とする。
The present invention has been made in view of the problems of the prior art, and an object thereof is to provide a photopolymerization initiator having high sensitivity and excellent solubility and a photosensitive composition using the photopolymerization initiator.
上記課題を解決するために検討した結果、本発明者等はカルバゾール骨格よりも縮合環が１つ少ないインドール骨格を有するオキシムエステル化合物に着目し、更にインドール骨格を特定の官能基で置換することで目的を達成できることを見出し、本発明を完成した。
As a result of studies to solve the above problems, the present inventors focused on an oxime ester compound having an indole skeleton having one less condensed ring than the carbazole skeleton, and further replacing the indole skeleton with a specific functional group. The present invention has been completed by finding that the object can be achieved.
すなわち、本発明は、置換基を有していてもよいインドール骨格にオキシムエステル結合を有する基が結合しており、かつインドール骨格が少なくとも１つのニトロ基で置換されていることを特徴とする光重合開始剤である。
That is, the present invention provides a light having a group having an oxime ester bond bonded to an indole skeleton which may have a substituent, and the indole skeleton is substituted with at least one nitro group. It is a polymerization initiator.
ここで、本発明の光重合開始剤は、インドール骨格の３位に下記一般式（１）で表されるオキシムエステル結合を有する基が直接又はカルボニル基を介して結合し、かつインドール骨格の５位がニトロ基で置換されていることが好ましい。
－Ｃ（Ｒ１１）＝Ｎ－Ｏ－Ｃ（Ｒ１２）＝Ｏ （１）
（ただし、Ｒ１１及びＲ１２は置換基を有していてもよい炭素原子数１～２０の飽和又は不飽和の一価の有機基を表す。Ｒ１１及びＲ１２は分岐構造や環構造を形成していてもよく、任意の位置にヘテロ原子が存在していてもよい。また、Ｒ１１はインドール骨格上の置換基と結合していてもよい。更に、Ｒ１１は水素原子でもよい。） Here, in the photopolymerization initiator of the present invention, a group having an oxime ester bond represented by the following general formula (1) is bonded directly or via a carbonyl group to the 3-position of the indole skeleton, and the indole skeleton 5 It is preferred that the position is substituted with a nitro group.
-C (R 11 ) = NOC (R 12 ) = O (1)
(However, R 11 and R 12 each represent a saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms which may have a substituent. R 11 and R 12 represent a branched structure or a ring structure. And a hetero atom may be present at any position, R 11 may be bonded to a substituent on the indole skeleton, and R 11 may be a hydrogen atom. )
－Ｃ（Ｒ１１）＝Ｎ－Ｏ－Ｃ（Ｒ１２）＝Ｏ （１）
（ただし、Ｒ１１及びＲ１２は置換基を有していてもよい炭素原子数１～２０の飽和又は不飽和の一価の有機基を表す。Ｒ１１及びＲ１２は分岐構造や環構造を形成していてもよく、任意の位置にヘテロ原子が存在していてもよい。また、Ｒ１１はインドール骨格上の置換基と結合していてもよい。更に、Ｒ１１は水素原子でもよい。） Here, in the photopolymerization initiator of the present invention, a group having an oxime ester bond represented by the following general formula (1) is bonded directly or via a carbonyl group to the 3-position of the indole skeleton, and the indole skeleton 5 It is preferred that the position is substituted with a nitro group.
-C (R 11 ) = NOC (R 12 ) = O (1)
(However, R 11 and R 12 each represent a saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms which may have a substituent. R 11 and R 12 represent a branched structure or a ring structure. And a hetero atom may be present at any position, R 11 may be bonded to a substituent on the indole skeleton, and R 11 may be a hydrogen atom. )
また、本発明は、オレフィン結合を有する重合性化合物及び上記光重合開始剤を含有する感光性組成物、並びに当該感光性組成物を硬化した硬化物である。ここで、上記感光性組成物について、好適には溶剤としてプロピレングリコールモノメチルエーテルアセテートを含有するものであるのがよい。
Further, the present invention is a photosensitive composition containing a polymerizable compound having an olefin bond and the photopolymerization initiator, and a cured product obtained by curing the photosensitive composition. Here, the photosensitive composition preferably contains propylene glycol monomethyl ether acetate as a solvent.
以下、本発明を詳細に説明する。
本発明の光重合開始剤は、置換基を有していてもよいインドール骨格にオキシムエステル結合を有する基が結合してなる。ここで、インドール骨格は少なくとも１つのニトロ基で置換されていることが必要であり、その置換位置は５位であることが好ましい。また、オキシムエステル結合を有する基としては下記一般式（１）で表される基が有利であり、このオキシムエステル結合を有する基がインドール骨格の３位に直接又はカルボニル基を介して結合していることが好ましい。
－Ｃ（Ｒ１１）＝Ｎ－Ｏ－Ｃ（Ｒ１２）＝Ｏ （１）
（ただし、Ｒ１１及びＲ１２は置換基を有していてもよい炭素原子数１～２０の飽和又は不飽和の一価の有機基を表す。Ｒ１１及びＲ１２は分岐構造や環構造を形成していてもよく、任意の位置にヘテロ原子が存在していてもよい。また、Ｒ１１はインドール骨格上の置換基と結合していてもよい。更に、Ｒ１１は水素原子でもよい。） Hereinafter, the present invention will be described in detail.
The photopolymerization initiator of the present invention is formed by bonding a group having an oxime ester bond to an indole skeleton which may have a substituent. Here, the indole skeleton needs to be substituted with at least one nitro group, and the substitution position is preferably the 5-position. Further, as the group having an oxime ester bond, a group represented by the following general formula (1) is advantageous, and the group having the oxime ester bond is bonded directly to the 3-position of the indole skeleton or via a carbonyl group. Preferably it is.
-C (R 11 ) = NOC (R 12 ) = O (1)
(However, R 11 and R 12 each represent a saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms which may have a substituent. R 11 and R 12 represent a branched structure or a ring structure. And a hetero atom may be present at any position, R 11 may be bonded to a substituent on the indole skeleton, and R 11 may be a hydrogen atom. )
本発明の光重合開始剤は、置換基を有していてもよいインドール骨格にオキシムエステル結合を有する基が結合してなる。ここで、インドール骨格は少なくとも１つのニトロ基で置換されていることが必要であり、その置換位置は５位であることが好ましい。また、オキシムエステル結合を有する基としては下記一般式（１）で表される基が有利であり、このオキシムエステル結合を有する基がインドール骨格の３位に直接又はカルボニル基を介して結合していることが好ましい。
－Ｃ（Ｒ１１）＝Ｎ－Ｏ－Ｃ（Ｒ１２）＝Ｏ （１）
（ただし、Ｒ１１及びＲ１２は置換基を有していてもよい炭素原子数１～２０の飽和又は不飽和の一価の有機基を表す。Ｒ１１及びＲ１２は分岐構造や環構造を形成していてもよく、任意の位置にヘテロ原子が存在していてもよい。また、Ｒ１１はインドール骨格上の置換基と結合していてもよい。更に、Ｒ１１は水素原子でもよい。） Hereinafter, the present invention will be described in detail.
The photopolymerization initiator of the present invention is formed by bonding a group having an oxime ester bond to an indole skeleton which may have a substituent. Here, the indole skeleton needs to be substituted with at least one nitro group, and the substitution position is preferably the 5-position. Further, as the group having an oxime ester bond, a group represented by the following general formula (1) is advantageous, and the group having the oxime ester bond is bonded directly to the 3-position of the indole skeleton or via a carbonyl group. Preferably it is.
-C (R 11 ) = NOC (R 12 ) = O (1)
(However, R 11 and R 12 each represent a saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms which may have a substituent. R 11 and R 12 represent a branched structure or a ring structure. And a hetero atom may be present at any position, R 11 may be bonded to a substituent on the indole skeleton, and R 11 may be a hydrogen atom. )
ここで、オキシム部位のＣ＝Ｎ二重結合にはＥ体及びＺ体の幾何異性体が存在し得るが、本発明ではこれらを特に区別することなく扱う。したがって、一般式（１）及び後述の式で示される構造のオキシム部位は、これら幾何異性体の混合物又はそのうちのいずれか一つを表すものである。
Here, although there may exist E isomers and Z isomers in the C = N double bond of the oxime moiety, these are handled without distinction in the present invention. Therefore, the oxime moiety of the structure represented by the general formula (1) and the formula described later represents a mixture of these geometric isomers or any one of them.
本発明の光重合開始剤において、好ましい構造は下記一般式（２）、
で表される。ここで、Ｒ１、Ｒ２、Ｒ４、Ｒ６及びＲ７は任意の置換基であってよいが、置換基を有していてもよい炭素原子数１～２０の飽和又は不飽和の一価の有機基であるか、水素原子、ハロゲン原子又はニトロ基であることが好ましい。かかる一価の有機基の場合、Ｒ１、Ｒ２、Ｒ４、Ｒ６及びＲ７は分岐構造や環構造を形成していてもよく、任意の位置にヘテロ原子が存在していてもよく、また相互に結合していてもよい。なお、Ｒ１１及びＲ１２は一般式（１）と同様である。 In the photopolymerization initiator of the present invention, a preferable structure is the following general formula (2),
It is represented by Here, R 1 , R 2 , R 4 , R 6 and R 7 may be any substituent, but may be a saturated or unsaturated group having 1 to 20 carbon atoms which may have a substituent. It is preferably a valent organic group, or a hydrogen atom, a halogen atom or a nitro group. In the case of such a monovalent organic group, R 1 , R 2 , R 4 , R 6 and R 7 may form a branched structure or a ring structure, and a hetero atom may exist at an arbitrary position. Or may be bonded to each other. R 11 and R 12 are the same as those in the general formula (1).
で表される。ここで、Ｒ１、Ｒ２、Ｒ４、Ｒ６及びＲ７は任意の置換基であってよいが、置換基を有していてもよい炭素原子数１～２０の飽和又は不飽和の一価の有機基であるか、水素原子、ハロゲン原子又はニトロ基であることが好ましい。かかる一価の有機基の場合、Ｒ１、Ｒ２、Ｒ４、Ｒ６及びＲ７は分岐構造や環構造を形成していてもよく、任意の位置にヘテロ原子が存在していてもよく、また相互に結合していてもよい。なお、Ｒ１１及びＲ１２は一般式（１）と同様である。 In the photopolymerization initiator of the present invention, a preferable structure is the following general formula (2),
It is represented by Here, R 1 , R 2 , R 4 , R 6 and R 7 may be any substituent, but may be a saturated or unsaturated group having 1 to 20 carbon atoms which may have a substituent. It is preferably a valent organic group, or a hydrogen atom, a halogen atom or a nitro group. In the case of such a monovalent organic group, R 1 , R 2 , R 4 , R 6 and R 7 may form a branched structure or a ring structure, and a hetero atom may exist at an arbitrary position. Or may be bonded to each other. R 11 and R 12 are the same as those in the general formula (1).
一般式（１）及び（２）における、置換基を有していてもよい炭素原子数１～２０の飽和又は不飽和の一価の有機基の具体的な例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ－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、ｔｅｒｔ－ペンチル基、ヘキシル基、ヘプチル基、オクチル基、２－エチルヘキシル基、ノニル基、デシル基、ドデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、イコシル基、シクロプロピル基、シクロペンチル基、シクロペンチルエチル基、シクロヘキシル基、シクロヘキシルメチル基、４－メチルシクロヘキシル基、アダマンチル基、ビニル基、アリル基、エチニル基、フェニル基、トリル基、メシチル基、ナフチル基、アントリル基、フェナントリル基、ベンジル基、２－フェニルエチル基、２－フェニルビニル基等の飽和又は不飽和の一価の炭化水素基や、ピリジル基、ピペリジル基、ピペリジノ基、ピロリル基、ピロリジニル基、イミダゾリル基、イミダゾリジニル基、フリル基、テトラヒドロフリル基、チエニル基、テトラヒドロチエニル基、モルホリニル基、モルホリノ基、キノリル基等の飽和又は不飽和の一価の複素環基等を挙げることができる。更に、上記の炭化水素基及び複素環基等の任意の位置に、ハロゲン原子、ヒドロキシ基、スルファニル基、カルボニル基、チオカルボニル基、カルボキシ基、チオカルボキシ基、ジチオカルボキシ基、ホルミル基、シアノ基、ニトロ基、ニトロソ基、スルホ基、アミノ基、イミノ基、シリル基、エーテル基、チオエーテル基、エステル基、チオエステル基、ジチオエステル基、アミド基、チオアミド基、ウレタン基、チオウレタン基、ウレイド基、チオウレイド基等を置換基として導入した構造も挙げることができる。ここで、一価の有機基としては、メチル基のような炭素原子上の一価の有機基だけでなく、メトキシ基、メチルスルファニル基、ジメチルアミノ基のようなヘテロ原子上の一価の有機基も含まれる。あるいは、一価の有機基としては、カルボキシ基、チオカルボキシ基、ジチオカルボキシ基、ホルミル基、シアノ基、第一級アミド基、第一級チオアミド基、ウレイド基、チオウレイド基等の炭素原子数１の官能基が直接結合したものであってもよい。
Specific examples of the saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms which may have a substituent in the general formulas (1) and (2) include a methyl group and an ethyl group. Propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group , Nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, icosyl group, cyclopropyl group, cyclopentyl group, cyclopentylethyl group, cyclohexyl group, cyclohexylmethyl group, 4-methylcyclohexyl group, adamantyl group, vinyl Group, allyl group, ethynyl group, phenyl group, tolyl group, mesityl group, Saturated or unsaturated monovalent hydrocarbon group such as butyl group, anthryl group, phenanthryl group, benzyl group, 2-phenylethyl group, 2-phenylvinyl group, pyridyl group, piperidyl group, piperidino group, pyrrolyl group, Examples include saturated or unsaturated monovalent heterocyclic groups such as pyrrolidinyl group, imidazolyl group, imidazolidinyl group, furyl group, tetrahydrofuryl group, thienyl group, tetrahydrothienyl group, morpholinyl group, morpholino group, and quinolyl group. . Furthermore, at any position such as the above hydrocarbon group and heterocyclic group, a halogen atom, a hydroxy group, a sulfanyl group, a carbonyl group, a thiocarbonyl group, a carboxy group, a thiocarboxy group, a dithiocarboxy group, a formyl group, a cyano group , Nitro group, nitroso group, sulfo group, amino group, imino group, silyl group, ether group, thioether group, ester group, thioester group, dithioester group, amide group, thioamide group, urethane group, thiourethane group, ureido group Moreover, the structure which introduce | transduced the thioureido group etc. as a substituent can also be mentioned. Here, the monovalent organic group includes not only a monovalent organic group on a carbon atom such as a methyl group, but also a monovalent organic group on a heteroatom such as a methoxy group, a methylsulfanyl group, or a dimethylamino group. Groups are also included. Alternatively, as the monovalent organic group, carboxy group, thiocarboxy group, dithiocarboxy group, formyl group, cyano group, primary amide group, primary thioamide group, ureido group, thioureido group, etc. The functional group may be directly bonded.
かかる一価の有機基は、目的とする光重合開始剤の分子量、感度、溶解性等に応じて適宜選定されればよいが、性能及び経済性の点から炭素原子数１～２０の飽和又は不飽和の一価の炭化水素基であることが好ましく、炭素原子数１～１２の飽和又は不飽和の一価の炭化水素基であることがより好ましく、更には炭素原子数１～４の飽和又は不飽和の一価の炭化水素基であることが最も好ましい。炭素原子数が２０を超える場合は、光重合開始剤の溶解性が低下する懸念がある。なお後述の実施例には、一価の炭化水素基について、飽和又は不飽和、分岐構造や環構造の有無を問わず実施可能であることが具体的に示されている。
The monovalent organic group may be appropriately selected according to the molecular weight, sensitivity, solubility, etc. of the target photopolymerization initiator, but is saturated or saturated with 1 to 20 carbon atoms from the viewpoint of performance and economy. An unsaturated monovalent hydrocarbon group is preferable, a saturated or unsaturated monovalent hydrocarbon group having 1 to 12 carbon atoms is more preferable, and further, a saturated one having 1 to 4 carbon atoms. Or, it is most preferably an unsaturated monovalent hydrocarbon group. When the number of carbon atoms exceeds 20, there is a concern that the solubility of the photopolymerization initiator is lowered. In the examples described later, it is specifically shown that the monovalent hydrocarbon group can be used regardless of the presence or absence of a saturated or unsaturated, branched structure or ring structure.
以下に、本発明の光重合開始剤の具体例を示す。ただし、本発明はこれらに限定されない。
Specific examples of the photopolymerization initiator of the present invention are shown below. However, the present invention is not limited to these.
置換基が相互に結合する例としては、次の構造が挙げられる。
Examples of the substituents bonded to each other include the following structures.
本発明の光重合開始剤は、下記一般式（１９）及び（２０）で表される構造のように、適当な置換基を介して多量化させたものであってもよい。
（ただし、Ｒ１ａ及びＲ１１ａは置換基を有していてもよい炭素原子数１～２０の飽和又は不飽和の二価の有機基を表す。Ｒ１、Ｒ２、Ｒ４、Ｒ６、Ｒ７、Ｒ１１及びＲ１２は一般式（１）及び（２）と同様である。） The photopolymerization initiator of the present invention may be obtained by multiplying it through an appropriate substituent as in the structures represented by the following general formulas (19) and (20).
(However, R 1a and R 11a represent a saturated or unsaturated divalent organic group having 1 to 20 carbon atoms which may have a substituent. R 1 , R 2 , R 4 , R 6 , R 7 , R 11 and R 12 are the same as those in the general formulas (1) and (2).
（ただし、Ｒ１ａ及びＲ１１ａは置換基を有していてもよい炭素原子数１～２０の飽和又は不飽和の二価の有機基を表す。Ｒ１、Ｒ２、Ｒ４、Ｒ６、Ｒ７、Ｒ１１及びＲ１２は一般式（１）及び（２）と同様である。） The photopolymerization initiator of the present invention may be obtained by multiplying it through an appropriate substituent as in the structures represented by the following general formulas (19) and (20).
(However, R 1a and R 11a represent a saturated or unsaturated divalent organic group having 1 to 20 carbon atoms which may have a substituent. R 1 , R 2 , R 4 , R 6 , R 7 , R 11 and R 12 are the same as those in the general formulas (1) and (2).
また、本発明の光重合開始剤は、下記一般式（２１）、（２２）及び（２３）で表される構造であってもよい。
（ただし、Ｒ１、Ｒ２、Ｒ４、Ｒ６、Ｒ７、Ｒ１１及びＲ１２は一般式（１）及び（２）と同様であり、Ｒ１ａ及びＲ１１ａは一般式（１９）及び（２０）と同様である。） The photopolymerization initiator of the present invention may have a structure represented by the following general formulas (21), (22), and (23).
(However, R 1 , R 2 , R 4 , R 6 , R 7 , R 11 and R 12 are the same as those in the general formulas (1) and (2), and R 1a and R 11a are the same as those in the general formula (19) and (Same as (20).)
（ただし、Ｒ１、Ｒ２、Ｒ４、Ｒ６、Ｒ７、Ｒ１１及びＲ１２は一般式（１）及び（２）と同様であり、Ｒ１ａ及びＲ１１ａは一般式（１９）及び（２０）と同様である。） The photopolymerization initiator of the present invention may have a structure represented by the following general formulas (21), (22), and (23).
(However, R 1 , R 2 , R 4 , R 6 , R 7 , R 11 and R 12 are the same as those in the general formulas (1) and (2), and R 1a and R 11a are the same as those in the general formula (19) and (Same as (20).)
本発明の光重合開始剤の製造方法は特に制限されないが、例えば一般式（２）の光重合開始剤を得るには、工業的に入手可能な５－ニトロインドールを原料として以下の手順を適用することが経済的に有利である。５－ニトロインドールの１位に求核置換反応等でＲ１を導入した後、フリーデルクラフツアシル化反応で３位にＲ１１ＣＯを導入し、ケトン体を得る。これをヒドロキシルアミンでオキシムに変換し、更にＲ１２ＣＯＯＨの酸ハロゲン化物又は酸無水物でオキシムのエステル化を行って、目的の光重合開始剤に導く。また一般式（２１）の光重合開始剤を得るには、上記ケトン体に亜硝酸エステルを作用させてα－オキソオキシムとし、同様にオキシムのエステル化を行えばよい。なお、５－ニトロインドールを出発物質とせず、インドールにＲ１やＲ１１ＣＯを先に導入し、その後ニトロ化を行ってもよい。
The production method of the photopolymerization initiator of the present invention is not particularly limited. For example, in order to obtain the photopolymerization initiator of the general formula (2), the following procedure is applied using commercially available 5-nitroindole as a raw material. It is economically advantageous to do. After introducing R 1 into the 1-position of 5-nitroindole by a nucleophilic substitution reaction or the like, R 11 CO is introduced into the 3-position by Friedel-Crafts acylation reaction to obtain a ketone body. This is converted into an oxime with hydroxylamine, and further esterified with an acid halide or acid anhydride of R 12 COOH to lead to a target photopolymerization initiator. In order to obtain the photopolymerization initiator of the general formula (21), a nitrite is allowed to act on the ketone body to form an α-oxooxime, and the oxime is esterified in the same manner. Note that 5-nitroindole may not be used as a starting material, and R 1 or R 11 CO may be first introduced into the indole, followed by nitration.
本発明の光重合開始剤はインドール骨格を有するが、これはカルバゾール骨格と比較して縮合環の数が１つ少なく、平面の広がりの小さい骨格である。そのため、本発明の光重合開始剤は溶解性に優れており、感光性組成物の設計自由度を向上させる効果を有している。例えば、カラーフィルターのブラックマトリクスの製造に用いられる遮光性のフォトレジストのように光硬化が困難な用途においても、感光性組成物中に高濃度で存在させることで良好な感度を得ることができるようになる。一方、光重合開始剤がその機能を発現するためには光吸収を起こして励起状態になる必要があるが、縮合環の数が少ないとπ共役系が小さくなるため一般に光吸収には不利となる。しかし、本発明の光重合開始剤ではインドール骨格を少なくとも１つのニトロ基で置換することでかかる課題を克服し、紫外光から可視光にわたる広い波長範囲において光吸収を起こすことができる。
The photopolymerization initiator of the present invention has an indole skeleton, which is a skeleton having a smaller number of condensed rings and a smaller plane spread than the carbazole skeleton. Therefore, the photopolymerization initiator of the present invention is excellent in solubility and has an effect of improving the degree of freedom in designing the photosensitive composition. For example, even in applications where photocuring is difficult, such as a light-shielding photoresist used in the production of a black matrix for a color filter, good sensitivity can be obtained by being present at a high concentration in the photosensitive composition. It becomes like this. On the other hand, in order for the photopolymerization initiator to exhibit its function, it needs to absorb light and be in an excited state. However, if the number of condensed rings is small, the π-conjugated system becomes small, which is generally disadvantageous for light absorption. Become. However, the photopolymerization initiator of the present invention can overcome this problem by substituting the indole skeleton with at least one nitro group, and can cause light absorption in a wide wavelength range from ultraviolet light to visible light.
本発明の感光性組成物は、上記の光重合開始剤に加えて、オレフィン結合を有する重合性化合物を含有する。オレフィン結合を有する重合性化合物としては、従来感光性組成物に用いられている公知の化合物を特に制限なく使用することができるが、アクリル酸及びメタクリル酸（以下、両者をあわせて「（メタ）アクリル酸」等という）の誘導体が有利であり、例えば、ジエチレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等の（メタ）アクリル酸エステル誘導体や、ビスフェノールＡ型エポキシジ（メタ）アクリレート、ビスフェノールＦ型エポキシジ（メタ）アクリレート、ビスフェノールフルオレン型エポキシジ（メタ）アクリレート、フェノールノボラック型エポキシポリ（メタ）アクリレート、クレゾールノボラック型エポキシポリ（メタ）アクリレート等の（メタ）アクリル酸エポキシエステル誘導体等を好ましく用いることができる。また、上記（メタ）アクリル酸誘導体と、構造中に（好ましくは複数の）イソシアネート基や酸無水物基等を有する化合物との反応生成物等も適している。更に、公知の樹脂類であるビニル樹脂（アクリル酸（共）重合体、メタクリル酸（共）重合体、マレイン酸（共）重合体、スチレン（共）重合体等）、ポリエステル樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリウレタン樹脂、ポリエーテル樹脂等の主鎖又は側鎖に、エステル結合、アミド結合、ウレタン結合等により（メタ）アクリロイル基を導入した樹脂類等も用いることができる。なお、（メタ）アクリル酸誘導体以外にも、マレイン酸誘導体、マレイミド誘導体、クロトン酸誘導体、イタコン酸誘導体、ケイヒ酸誘導体、ビニル誘導体、ビニルアルコール誘導体、ビニルケトン誘導体、ビニル芳香族誘導体等も挙げることができる。これらのオレフィン結合を有する重合性化合物は、更にエポキシ基等の熱反応性の官能基やカルボキシ基等のアルカリ溶解性の官能基等を有して、複合機能化されたものであってもよい。これらのオレフィン結合を有する重合性化合物は、単独で用いてもよく、複数を組み合わせて用いてもよい。
The photosensitive composition of the present invention contains a polymerizable compound having an olefin bond in addition to the above photopolymerization initiator. As the polymerizable compound having an olefin bond, known compounds conventionally used in photosensitive compositions can be used without particular limitation, but acrylic acid and methacrylic acid (hereinafter referred to as “(meth)” Acrylic acid "etc.) derivatives are advantageous, for example, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipenta (Meth) acrylic acid ester derivatives such as erythritol hexa (meth) acrylate, bisphenol A type epoxy di (meth) acrylate, bisphenol F type epoxy di (meth) acrylate, bisphenol fluorene type epoxy di (meth) acrylate Over DOO, phenol novolak type epoxy poly (meth) acrylate, can be preferably used cresol novolac epoxy poly (meth) (meth) acrylic acid epoxy ester derivatives of acrylate and the like. In addition, a reaction product of the (meth) acrylic acid derivative and a compound having an (preferably plural) isocyanate group or an acid anhydride group in the structure is also suitable. Furthermore, vinyl resins (acrylic acid (co) polymer, methacrylic acid (co) polymer, maleic acid (co) polymer, styrene (co) polymer, etc.), which are known resins, polyester resins, polyamide resins, Resins in which a (meth) acryloyl group is introduced into the main chain or side chain of a polyimide resin, polyurethane resin, polyether resin or the like by an ester bond, an amide bond, a urethane bond, or the like can also be used. In addition to (meth) acrylic acid derivatives, maleic acid derivatives, maleimide derivatives, crotonic acid derivatives, itaconic acid derivatives, cinnamic acid derivatives, vinyl derivatives, vinyl alcohol derivatives, vinyl ketone derivatives, vinyl aromatic derivatives, etc. it can. These polymerizable compounds having an olefinic bond may further have a heat-functional functional group such as an epoxy group, an alkali-soluble functional group such as a carboxy group, etc., and a composite function. . These polymerizable compounds having an olefinic bond may be used alone or in combination.
本発明の感光性組成物における光重合開始剤の配合割合は特に制限されないが、オレフィン結合を有する重合性化合物１００重量部に対して光重合開始剤が０．０１～５０重量部であることが好ましく、０．１～２０重量部であることがより好ましい。
The mixing ratio of the photopolymerization initiator in the photosensitive composition of the present invention is not particularly limited, but the photopolymerization initiator is 0.01 to 50 parts by weight with respect to 100 parts by weight of the polymerizable compound having an olefin bond. The amount is preferably 0.1 to 20 parts by weight.
本発明の感光性組成物は溶剤を含んだものであってもよく、特にプロピレングリコールモノメチルエーテルアセテートを好ましく使用できる。プロピレングリコールモノメチルエーテルアセテートは適度な溶解性と乾燥性を有する安全溶剤であり、カラーフィルターの製造に用いられるフォトレジスト等で広く使用されているが、本発明の光重合開始剤は当該溶剤系において溶解不良等の問題を生じにくく、感光性組成物を有利に作製することができる。また、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以外の公知の化合物も利用でき、例えばエステル系溶剤、ケトン系溶剤、エーテル系溶剤、アルコール系溶剤、芳香族系溶剤、脂肪族系溶剤、アミン系溶剤、アミド系溶剤等を特に制限なく使用することができる。
The photosensitive composition of the present invention may contain a solvent, and in particular, propylene glycol monomethyl ether acetate can be preferably used. Propylene glycol monomethyl ether acetate is a safe solvent having moderate solubility and drying properties, and is widely used in photoresists and the like used in the production of color filters, but the photopolymerization initiator of the present invention is used in the solvent system. It is difficult to cause problems such as poor dissolution, and a photosensitive composition can be advantageously produced. Further, as the solvent, known compounds other than propylene glycol monomethyl ether acetate can also be used, for example, ester solvents, ketone solvents, ether solvents, alcohol solvents, aromatic solvents, aliphatic solvents, amine solvents, An amide solvent or the like can be used without any particular limitation.
本発明の感光性組成物は、必要に応じてその他の任意の成分を含んだものであってもよく、例えば着色材、フィラー、樹脂、添加剤等を配合させることができる。ここで、着色材としては染料、有機顔料、無機顔料、カーボンブラック顔料等を、フィラーとしてはシリカ、タルク等を、樹脂としてはビニル樹脂（アクリル酸（共）重合体、メタクリル酸（共）重合体、マレイン酸（共）重合体、スチレン（共）重合体等）、ポリエステル樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリウレタン樹脂、ポリエーテル樹脂、エポキシ樹脂、メラミン樹脂等を、添加剤としては硬化剤、架橋剤、分散剤、界面活性剤、シランカップリング剤、粘度調整剤、湿潤剤、消泡剤、酸化防止剤等を挙げることができる。これら任意の成分としては、公知の化合物を特に制限なく使用することができる。
The photosensitive composition of the present invention may contain other optional components as necessary. For example, a coloring material, a filler, a resin, an additive and the like can be blended. Here, as coloring materials, dyes, organic pigments, inorganic pigments, carbon black pigments, etc., as fillers, silica, talc, etc., as resins, vinyl resins (acrylic acid (co) polymer, methacrylic acid (co) heavy) Coalesce, maleic acid (co) polymer, styrene (co) polymer, etc.), polyester resin, polyamide resin, polyimide resin, polyurethane resin, polyether resin, epoxy resin, melamine resin, etc. Crosslinking agents, dispersants, surfactants, silane coupling agents, viscosity modifiers, wetting agents, antifoaming agents, antioxidants and the like can be mentioned. As these optional components, known compounds can be used without particular limitation.
また、本発明の感光性組成物には、本発明の光重合開始剤に加えて、公知の光重合開始剤や色素増感剤等を併用することもできる。例えば、アセトフェノン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、ベンジルジメチルケタール等のアセトフェノン化合物、ベンゾフェノン、２，４，６－トリメチルベンゾフェノン、４，４′－ビス（Ｎ，Ｎ－ジエチルアミノ）ベンゾフェノン等のベンゾフェノン化合物、ベンゾインエチルエーテル、ベンゾイン－ｔｅｒｔ－ブチルエーテル等のベンゾインエーテル化合物、２－メチル－１－［４－（メチルスルファニル）フェニル］－２－モルホリノプロパン－１－オン、２－ベンジル－２－（Ｎ，Ｎ－ジメチルアミノ）－１－（４－モルホリノフェニル）ブタン－１－オン等のα－アミノアルキルフェノン化合物、チオキサントン、２，４－ジエチルチオキサントン等のチオキサントン化合物、３，３′，４，４′－テトラキス（ｔｅｒｔ－ブチルペルオキシカルボニル）ベンゾフェノン等の有機過酸化物、２，２′－ビス（２－クロロフェニル）－４，４′，５，５′－テトラフェニル－１，２－ビイミダゾール等のビイミダゾール化合物、ビス（η５－シクロペンタジエニル）ビス［２，６－ジフルオロ－３－（１－ピロリル）フェニル］チタン等のチタノセン化合物、２，４，６－トリス（トリクロロメチル）－１，３，５－トリアジン、２－［３，４－（メチレンジオキシ）フェニル］－４，６－ビス（トリクロロメチル）－１，３，５－トリアジン等のトリアジン化合物、（２，４，６－トリメチルベンゾイル）ジフェニルホスフィンオキシド、ビス（２，４，６－トリメチルベンゾイル）フェニルホスフィンオキシド等のアシルホスフィンオキシド化合物、カンファーキノン等のキノン化合物、１－［４－（フェニルスルファニル）フェニル］オクタン－１，２－ジオン＝２－Ｏ－ベンゾイルオキシム、１－［９－エチル－６－（２－メチルベンゾイル）カルバゾール－３－イル］エタノン＝Ｏ－アセチルオキシム等のオキシムエステル化合物等を特に制限なく使用することができる。
Moreover, in addition to the photoinitiator of this invention, a well-known photoinitiator, a dye sensitizer, etc. can also be used together for the photosensitive composition of this invention. For example, acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, benzophenone, 2,4,6-trimethylbenzophenone, 4,4′-bis (N, N Benzophenone compounds such as -diethylamino) benzophenone, benzoin ether compounds such as benzoin ethyl ether and benzoin-tert-butyl ether, 2-methyl-1- [4- (methylsulfanyl) phenyl] -2-morpholinopropan-1-one, Α-aminoalkylphenone compounds such as benzyl-2- (N, N-dimethylamino) -1- (4-morpholinophenyl) butan-1-one, thioxanthone compounds such as thioxanthone and 2,4-diethylthioxanthone, 3 , 3 ', 4, Organic peroxides such as '-tetrakis (tert-butylperoxycarbonyl) benzophenone, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2-biimidazole, etc. Biimidazole compounds, titanocene compounds such as bis (η 5 -cyclopentadienyl) bis [2,6-difluoro-3- (1-pyrrolyl) phenyl] titanium, 2,4,6-tris (trichloromethyl)- Triazine compounds such as 1,3,5-triazine, 2- [3,4- (methylenedioxy) phenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, (2,4, Acyl phosphines such as 6-trimethylbenzoyl) diphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide Oxide compounds, quinone compounds such as camphorquinone, 1- [4- (phenylsulfanyl) phenyl] octane-1,2-dione = 2-O-benzoyloxime, 1- [9-ethyl-6- (2-methylbenzoyl) An oxime ester compound such as) carbazol-3-yl] ethanone = O-acetyloxime can be used without particular limitation.
本発明の感光性組成物の硬化物を作製する方法としては公知の方法が利用でき、目的や用途に合わせた適切な基材や型へ感光性組成物を塗布又は注入した後、露光により硬化が行われればよい。ここで、フォトマスク等を使用して選択的な露光を行い、更に現像を実施することで、画像形成や造形等の加工を行うこともできる。本発明の光重合開始剤は現像液への溶解性にも優れているため、感光性組成物の現像に要する時間を短縮させる効果があり、生産の効率が向上する点で好ましい。露光や現像を行った後、必要に応じて更に焼成等の処理を行ってもよい。
As a method for producing a cured product of the photosensitive composition of the present invention, a known method can be used. After the photosensitive composition is applied or injected onto an appropriate substrate or mold suitable for the purpose or application, it is cured by exposure. Should just be done. Here, by performing selective exposure using a photomask or the like, and further performing development, processing such as image formation or modeling can be performed. Since the photopolymerization initiator of the present invention is excellent in solubility in a developer, it has an effect of shortening the time required for developing the photosensitive composition, and is preferable in terms of improving production efficiency. After performing exposure and development, a treatment such as baking may be further performed as necessary.
本発明の光重合開始剤は感度に優れ、少ない露光量で効率よく硬化できる高感度な感光性組成物を提供することができることから、きわめて有用である。本発明の光重合開始剤は、紫外光及び可視光を吸収して励起状態になると、オキシムエステル結合を速やかに開裂させて活性の高いラジカル種を生成し、感光性組成物に含まれるオレフィン結合を有する重合性化合物を高速に重合反応させるものと考えられる。また、本発明の光重合開始剤は溶解性に優れ、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溶剤系で好適に使用することができる。
The photopolymerization initiator of the present invention is extremely useful because it is excellent in sensitivity and can provide a highly sensitive photosensitive composition that can be cured efficiently with a small amount of exposure. When the photopolymerization initiator of the present invention absorbs ultraviolet light and visible light and enters an excited state, the oxime ester bond is rapidly cleaved to generate a highly active radical species, and the olefin bond contained in the photosensitive composition It is considered that a polymerizable compound having a high molecular weight undergoes a polymerization reaction at high speed. Further, the photopolymerization initiator of the present invention is excellent in solubility and can be suitably used in a solvent system such as propylene glycol monomethyl ether acetate.
以下、実施例により本発明を更に詳細に説明するが、本発明はこれらに限定されない。
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
［実施例１］
（光重合開始剤の合成）
以下４ステップの反応により、１－（１－エチル－５－ニトロインドール－３－イル）エタノン＝Ｏ－アセチルオキシム（式（３）の化合物）を合成した。反応はガラス製反応器を用いて常圧下実施した。 [Example 1]
(Synthesis of photopolymerization initiator)
1- (1-Ethyl-5-nitroindol-3-yl) ethanone = O-acetyloxime (compound of formula (3)) was synthesized by the following four-step reaction. The reaction was carried out under normal pressure using a glass reactor.
（光重合開始剤の合成）
以下４ステップの反応により、１－（１－エチル－５－ニトロインドール－３－イル）エタノン＝Ｏ－アセチルオキシム（式（３）の化合物）を合成した。反応はガラス製反応器を用いて常圧下実施した。 [Example 1]
(Synthesis of photopolymerization initiator)
1- (1-Ethyl-5-nitroindol-3-yl) ethanone = O-acetyloxime (compound of formula (3)) was synthesized by the following four-step reaction. The reaction was carried out under normal pressure using a glass reactor.
ステップ１： Ｎ，Ｎ－ジメチルホルムアミドを溶媒として、５－ニトロインドール０．１００モル、ブロモエタン０．１１０モル及び水酸化カリウム０．１１０モルを３５℃で２時間反応させた。冷却後、反応液を水に滴下して析出した固体を回収し、十分に洗浄及び乾燥を行って、１－エチル－５－ニトロインドール０．０９９モルを得た。
Step 1: Using N, N-dimethylformamide as a solvent, 0.100 mol of 5-nitroindole, 0.110 mol of bromoethane and 0.110 mol of potassium hydroxide were reacted at 35 ° C. for 2 hours. After cooling, the reaction solution was dropped into water, and the precipitated solid was collected, washed thoroughly and dried to obtain 0.099 mol of 1-ethyl-5-nitroindole.
ステップ２： ニトロメタンを溶媒として、ステップ１の生成物全量、塩化アセチル０．１２０モル及び塩化アルミニウム０．１２０モルを室温で２時間反応させた。反応液を氷水に滴下して析出した固体を回収し、十分に洗浄及び乾燥を行って、１－（１－エチル－５－ニトロインドール－３－イル）エタノン０．０９５モルを得た。
Step 2: Using nitromethane as a solvent, the total amount of the product of Step 1, 0.120 mol of acetyl chloride and 0.120 mol of aluminum chloride were reacted at room temperature for 2 hours. The reaction solution was dropped into ice water, and the precipitated solid was collected, washed thoroughly and dried to obtain 0.095 mol of 1- (1-ethyl-5-nitroindol-3-yl) ethanone.
ステップ３： Ｎ，Ｎ－ジメチルホルムアミドを溶媒として、ステップ２の生成物全量及び塩酸ヒドロキシルアミン０．１５０モルを８０℃で４時間反応させた。冷却後、反応液を水に滴下して析出した固体を回収し、十分に洗浄及び乾燥を行って、１－（１－エチル－５－ニトロインドール－３－イル）エタノン＝オキシム０．０９２モルを得た。
Step 3: Using N, N-dimethylformamide as a solvent, the total amount of the product of Step 2 and 0.150 mol of hydroxylamine hydrochloride were reacted at 80 ° C. for 4 hours. After cooling, the reaction solution is dropped into water, and the precipitated solid is recovered, washed thoroughly and dried to give 1- (1-ethyl-5-nitroindol-3-yl) ethanone = oxime 0.092 mol. Got.
ステップ４： Ｎ，Ｎ－ジメチルホルムアミドを溶媒として、ステップ３の生成物全量及び無水酢酸０．１５０モルを８０℃で２時間反応させた。冷却後、反応液を水に滴下して析出した固体を回収し、十分に洗浄及び乾燥を行って、目的化合物である１－（１－エチル－５－ニトロインドール－３－イル）エタノン＝Ｏ－アセチルオキシム０．０８８モルを得た。更に、酢酸イソプロピルで再結晶を行って、黄色の針状結晶である目的化合物の純品０．０７０モルを得た。得られた純品を重クロロホルム中４００ＭＨｚの１Ｈ－ＮＭＲで同定したところ、次の結果を示した。δ＝９．２７（ｄ，１Ｈ，Ｒ４）、８．１９（ｄｄ，１Ｈ，Ｒ６）、７．６０（ｓ，１Ｈ，Ｒ２）、７．３９（ｄ，１Ｈ，Ｒ７）、４．２５（ｑ，２Ｈ，Ｒ１）、２．４２（ｓ，３Ｈ，Ｒ１１）、２．３８（ｓ，３Ｈ，Ｒ１２）、１．５４（ｔ，３Ｈ，Ｒ１）。また、示差走査熱量測定による融点は１９４℃、分解開始点は２１０℃であった。
Step 4: Using N, N-dimethylformamide as a solvent, the total amount of the product of Step 3 and 0.150 mol of acetic anhydride were reacted at 80 ° C. for 2 hours. After cooling, the reaction solution is added dropwise to water, and the precipitated solid is recovered, washed thoroughly and dried, and the target compound 1- (1-ethyl-5-nitroindol-3-yl) ethanone = O -0.088 mol of acetyloxime was obtained. Furthermore, recrystallization was performed with isopropyl acetate to obtain 0.070 mol of a pure product of the target compound as yellow needle crystals. When the obtained pure product was identified by 1 H-NMR at 400 MHz in deuterated chloroform, the following results were shown. δ = 9.27 (d, 1H, R 4 ), 8.19 (dd, 1H, R 6 ), 7.60 (s, 1H, R 2 ), 7.39 (d, 1H, R 7 ), 4.25 (q, 2H, R 1 ), 2.42 (s, 3H, R 11 ), 2.38 (s, 3H, R 12 ), 1.54 (t, 3H, R 1 ). Further, the melting point by differential scanning calorimetry was 194 ° C., and the decomposition start point was 210 ° C.
［実施例２］
実施例１と同様にして、１－（１－アリル－５－ニトロインドール－３－イル）エタノン＝Ｏ－アセチルオキシム（式（４）の化合物）を合成した。ただしステップ１ではブロモエタンの代わりに３－ブロモプロペンを用い、油状の生成物を溶媒抽出により回収した。得られた純品を重クロロホルム中４００ＭＨｚの１Ｈ－ＮＭＲで同定したところ、次の結果を示した。δ＝９．２９（ｄ，１Ｈ，Ｒ４）、８．１９（ｄｄ，１Ｈ，Ｒ６）、７．５７（ｓ，１Ｈ，Ｒ２）、７．３７（ｄ，１Ｈ，Ｒ７）、６．０１（ｄｄｔ，１Ｈ，Ｒ１）、５．３３（ｄｄｔ，１Ｈ，Ｒ１）、５．１５（ｄｄｔ，１Ｈ，Ｒ１）、４．８１（ｄｄｄ，２Ｈ，Ｒ１）、２．４２（ｓ，３Ｈ，Ｒ１１）、２．３９（ｓ，３Ｈ，Ｒ１２）。なお、ステップ１の生成物は１－アリル－５－ニトロインドール、ステップ２の生成物は１－（１－アリル－５－ニトロインドール－３－イル）エタノン、ステップ３の生成物は１－（１－アリル－５－ニトロインドール－３－イル）エタノン＝オキシムであった。 [Example 2]
In the same manner as in Example 1, 1- (1-allyl-5-nitroindol-3-yl) ethanone = O-acetyloxime (compound of formula (4)) was synthesized. However, in Step 1, 3-bromopropene was used instead of bromoethane, and the oily product was recovered by solvent extraction. When the obtained pure product was identified by 1 H-NMR at 400 MHz in deuterated chloroform, the following results were shown. δ = 9.29 (d, 1H, R 4 ), 8.19 (dd, 1H, R 6 ), 7.57 (s, 1H, R 2 ), 7.37 (d, 1H, R 7 ), 6.01 (ddt, 1H, R 1 ), 5.33 (ddt, 1H, R 1 ), 5.15 (ddt, 1H, R 1 ), 4.81 (ddd, 2H, R 1 ), 2. 42 (s, 3H, R 11 ), 2.39 (s, 3H, R 12 ). The product of Step 1 is 1-allyl-5-nitroindole, the product of Step 2 is 1- (1-allyl-5-nitroindol-3-yl) ethanone, and the product of Step 3 is 1- ( 1-allyl-5-nitroindol-3-yl) ethanone oxime.
実施例１と同様にして、１－（１－アリル－５－ニトロインドール－３－イル）エタノン＝Ｏ－アセチルオキシム（式（４）の化合物）を合成した。ただしステップ１ではブロモエタンの代わりに３－ブロモプロペンを用い、油状の生成物を溶媒抽出により回収した。得られた純品を重クロロホルム中４００ＭＨｚの１Ｈ－ＮＭＲで同定したところ、次の結果を示した。δ＝９．２９（ｄ，１Ｈ，Ｒ４）、８．１９（ｄｄ，１Ｈ，Ｒ６）、７．５７（ｓ，１Ｈ，Ｒ２）、７．３７（ｄ，１Ｈ，Ｒ７）、６．０１（ｄｄｔ，１Ｈ，Ｒ１）、５．３３（ｄｄｔ，１Ｈ，Ｒ１）、５．１５（ｄｄｔ，１Ｈ，Ｒ１）、４．８１（ｄｄｄ，２Ｈ，Ｒ１）、２．４２（ｓ，３Ｈ，Ｒ１１）、２．３９（ｓ，３Ｈ，Ｒ１２）。なお、ステップ１の生成物は１－アリル－５－ニトロインドール、ステップ２の生成物は１－（１－アリル－５－ニトロインドール－３－イル）エタノン、ステップ３の生成物は１－（１－アリル－５－ニトロインドール－３－イル）エタノン＝オキシムであった。 [Example 2]
In the same manner as in Example 1, 1- (1-allyl-5-nitroindol-3-yl) ethanone = O-acetyloxime (compound of formula (4)) was synthesized. However, in Step 1, 3-bromopropene was used instead of bromoethane, and the oily product was recovered by solvent extraction. When the obtained pure product was identified by 1 H-NMR at 400 MHz in deuterated chloroform, the following results were shown. δ = 9.29 (d, 1H, R 4 ), 8.19 (dd, 1H, R 6 ), 7.57 (s, 1H, R 2 ), 7.37 (d, 1H, R 7 ), 6.01 (ddt, 1H, R 1 ), 5.33 (ddt, 1H, R 1 ), 5.15 (ddt, 1H, R 1 ), 4.81 (ddd, 2H, R 1 ), 2. 42 (s, 3H, R 11 ), 2.39 (s, 3H, R 12 ). The product of Step 1 is 1-allyl-5-nitroindole, the product of Step 2 is 1- (1-allyl-5-nitroindol-3-yl) ethanone, and the product of Step 3 is 1- ( 1-allyl-5-nitroindol-3-yl) ethanone oxime.
［実施例３］
実施例１と同様にして、１－（１－ブチル－５－ニトロインドール－３－イル）エタノン＝Ｏ－アセチルオキシム（式（５）の化合物）を合成した。ただしステップ１ではブロモエタンの代わりに１－ブロモブタンを用い、油状の生成物を溶媒抽出により回収した。得られた純品を重クロロホルム中４００ＭＨｚの１Ｈ－ＮＭＲで同定したところ、次の結果を示した。δ＝９．２７（ｄ，１Ｈ，Ｒ４）、８．１９（ｄｄ，１Ｈ，Ｒ６）、７．５６（ｓ，１Ｈ，Ｒ２）、７．３８（ｄ，１Ｈ，Ｒ７）、４．１９（ｔ，２Ｈ，Ｒ１）、２．４２（ｓ，３Ｈ，Ｒ１１）、２．３９（ｓ，３Ｈ，Ｒ１２）、１．８７（ｔｔ，２Ｈ，Ｒ１）、１．３７（ｔｑ，２Ｈ，Ｒ１）、０．９７（ｔ，３Ｈ，Ｒ１）。なお、ステップ１の生成物は１－ブチル－５－ニトロインドール、ステップ２の生成物は１－（１－ブチル－５－ニトロインドール－３－イル）エタノン、ステップ３の生成物は１－（１－ブチル－５－ニトロインドール－３－イル）エタノン＝オキシムであった。 [Example 3]
In the same manner as in Example 1, 1- (1-butyl-5-nitroindol-3-yl) ethanone = O-acetyloxime (compound of formula (5)) was synthesized. However, in Step 1, 1-bromobutane was used instead of bromoethane, and the oily product was recovered by solvent extraction. When the obtained pure product was identified by 1 H-NMR at 400 MHz in deuterated chloroform, the following results were shown. δ = 9.27 (d, 1H, R 4 ), 8.19 (dd, 1H, R 6 ), 7.56 (s, 1H, R 2 ), 7.38 (d, 1H, R 7 ), 4.19 (t, 2H, R 1 ), 2.42 (s, 3H, R 11 ), 2.39 (s, 3H, R 12 ), 1.87 (tt, 2H, R 1 ), 1. 37 (tq, 2H, R 1 ), 0.97 (t, 3H, R 1 ). The product of Step 1 is 1-butyl-5-nitroindole, the product of Step 2 is 1- (1-butyl-5-nitroindol-3-yl) ethanone, and the product of Step 3 is 1- ( 1-butyl-5-nitroindol-3-yl) ethanone oxime.
実施例１と同様にして、１－（１－ブチル－５－ニトロインドール－３－イル）エタノン＝Ｏ－アセチルオキシム（式（５）の化合物）を合成した。ただしステップ１ではブロモエタンの代わりに１－ブロモブタンを用い、油状の生成物を溶媒抽出により回収した。得られた純品を重クロロホルム中４００ＭＨｚの１Ｈ－ＮＭＲで同定したところ、次の結果を示した。δ＝９．２７（ｄ，１Ｈ，Ｒ４）、８．１９（ｄｄ，１Ｈ，Ｒ６）、７．５６（ｓ，１Ｈ，Ｒ２）、７．３８（ｄ，１Ｈ，Ｒ７）、４．１９（ｔ，２Ｈ，Ｒ１）、２．４２（ｓ，３Ｈ，Ｒ１１）、２．３９（ｓ，３Ｈ，Ｒ１２）、１．８７（ｔｔ，２Ｈ，Ｒ１）、１．３７（ｔｑ，２Ｈ，Ｒ１）、０．９７（ｔ，３Ｈ，Ｒ１）。なお、ステップ１の生成物は１－ブチル－５－ニトロインドール、ステップ２の生成物は１－（１－ブチル－５－ニトロインドール－３－イル）エタノン、ステップ３の生成物は１－（１－ブチル－５－ニトロインドール－３－イル）エタノン＝オキシムであった。 [Example 3]
In the same manner as in Example 1, 1- (1-butyl-5-nitroindol-3-yl) ethanone = O-acetyloxime (compound of formula (5)) was synthesized. However, in Step 1, 1-bromobutane was used instead of bromoethane, and the oily product was recovered by solvent extraction. When the obtained pure product was identified by 1 H-NMR at 400 MHz in deuterated chloroform, the following results were shown. δ = 9.27 (d, 1H, R 4 ), 8.19 (dd, 1H, R 6 ), 7.56 (s, 1H, R 2 ), 7.38 (d, 1H, R 7 ), 4.19 (t, 2H, R 1 ), 2.42 (s, 3H, R 11 ), 2.39 (s, 3H, R 12 ), 1.87 (tt, 2H, R 1 ), 1. 37 (tq, 2H, R 1 ), 0.97 (t, 3H, R 1 ). The product of Step 1 is 1-butyl-5-nitroindole, the product of Step 2 is 1- (1-butyl-5-nitroindol-3-yl) ethanone, and the product of Step 3 is 1- ( 1-butyl-5-nitroindol-3-yl) ethanone oxime.
［実施例４］
実施例１と同様にして、１－（１－エチル－５－ニトロインドール－３－イル）プロパン－１－オン＝Ｏ－アセチルオキシム（式（６）の化合物）を合成した。ただしステップ２では塩化アセチルの代わりに塩化プロピオニルを用いた。得られた純品を重クロロホルム中４００ＭＨｚの１Ｈ－ＮＭＲで同定したところ、次の結果を示した。δ＝９．２７（ｄ，１Ｈ，Ｒ４）、８．１９（ｄｄ，１Ｈ，Ｒ６）、７．６０（ｓ，１Ｈ，Ｒ２）、７．３９（ｄ，１Ｈ，Ｒ７）、４．２６（ｑ，２Ｈ，Ｒ１）、２．８４（ｑ，２Ｈ，Ｒ１１）、２．３９（ｓ，３Ｈ，Ｒ１２）、１．５５（ｔ，３Ｈ，Ｒ１）、１．２９（ｔ，３Ｈ，Ｒ１１）。なお、ステップ２の生成物は１－（１－エチル－５－ニトロインドール－３－イル）プロパン－１－オン、ステップ３の生成物は１－（１－エチル－５－ニトロインドール－３－イル）プロパン－１－オン＝オキシムであった。 [Example 4]
In the same manner as in Example 1, 1- (1-ethyl-5-nitroindol-3-yl) propan-1-one = O-acetyloxime (compound of formula (6)) was synthesized. However, in Step 2, propionyl chloride was used instead of acetyl chloride. When the obtained pure product was identified by 1 H-NMR at 400 MHz in deuterated chloroform, the following results were shown. δ = 9.27 (d, 1H, R 4 ), 8.19 (dd, 1H, R 6 ), 7.60 (s, 1H, R 2 ), 7.39 (d, 1H, R 7 ), 4.26 (q, 2H, R 1 ), 2.84 (q, 2H, R 11 ), 2.39 (s, 3H, R 12 ), 1.55 (t, 3H, R 1 ), 1. 29 (t, 3H, R 11 ). The product of Step 2 is 1- (1-ethyl-5-nitroindol-3-yl) propan-1-one, and the product of Step 3 is 1- (1-ethyl-5-nitroindole-3- Yl) propan-1-one oxime.
実施例１と同様にして、１－（１－エチル－５－ニトロインドール－３－イル）プロパン－１－オン＝Ｏ－アセチルオキシム（式（６）の化合物）を合成した。ただしステップ２では塩化アセチルの代わりに塩化プロピオニルを用いた。得られた純品を重クロロホルム中４００ＭＨｚの１Ｈ－ＮＭＲで同定したところ、次の結果を示した。δ＝９．２７（ｄ，１Ｈ，Ｒ４）、８．１９（ｄｄ，１Ｈ，Ｒ６）、７．６０（ｓ，１Ｈ，Ｒ２）、７．３９（ｄ，１Ｈ，Ｒ７）、４．２６（ｑ，２Ｈ，Ｒ１）、２．８４（ｑ，２Ｈ，Ｒ１１）、２．３９（ｓ，３Ｈ，Ｒ１２）、１．５５（ｔ，３Ｈ，Ｒ１）、１．２９（ｔ，３Ｈ，Ｒ１１）。なお、ステップ２の生成物は１－（１－エチル－５－ニトロインドール－３－イル）プロパン－１－オン、ステップ３の生成物は１－（１－エチル－５－ニトロインドール－３－イル）プロパン－１－オン＝オキシムであった。 [Example 4]
In the same manner as in Example 1, 1- (1-ethyl-5-nitroindol-3-yl) propan-1-one = O-acetyloxime (compound of formula (6)) was synthesized. However, in Step 2, propionyl chloride was used instead of acetyl chloride. When the obtained pure product was identified by 1 H-NMR at 400 MHz in deuterated chloroform, the following results were shown. δ = 9.27 (d, 1H, R 4 ), 8.19 (dd, 1H, R 6 ), 7.60 (s, 1H, R 2 ), 7.39 (d, 1H, R 7 ), 4.26 (q, 2H, R 1 ), 2.84 (q, 2H, R 11 ), 2.39 (s, 3H, R 12 ), 1.55 (t, 3H, R 1 ), 1. 29 (t, 3H, R 11 ). The product of Step 2 is 1- (1-ethyl-5-nitroindol-3-yl) propan-1-one, and the product of Step 3 is 1- (1-ethyl-5-nitroindole-3- Yl) propan-1-one oxime.
［実施例５］
実施例１と同様にして、１－（１－エチル－５－ニトロインドール－３－イル）エタノン＝Ｏ－プロピオニルオキシム（式（７）の化合物）を合成した。ただしステップ４では無水酢酸の代わりに無水プロピオン酸を用いた。得られた純品を重クロロホルム中４００ＭＨｚの１Ｈ－ＮＭＲで同定したところ、次の結果を示した。δ＝９．２８（ｄ，１Ｈ，Ｒ４）、８．１９（ｄｄ，１Ｈ，Ｒ６）、７．５９（ｓ，１Ｈ，Ｒ２）、７．３８（ｄ，１Ｈ，Ｒ７）、４．２５（ｑ，２Ｈ，Ｒ１）、２．６８（ｑ，２Ｈ，Ｒ１２）、２．４１（ｓ，３Ｈ，Ｒ１１）、１．５４（ｔ，３Ｈ，Ｒ１）、１．３１（ｔ，３Ｈ，Ｒ１２）。 [Example 5]
In the same manner as in Example 1, 1- (1-ethyl-5-nitroindol-3-yl) ethanone = O-propionyloxime (compound of formula (7)) was synthesized. However, in Step 4, propionic anhydride was used instead of acetic anhydride. When the obtained pure product was identified by 1 H-NMR at 400 MHz in deuterated chloroform, the following results were shown. δ = 9.28 (d, 1H, R 4 ), 8.19 (dd, 1H, R 6 ), 7.59 (s, 1H, R 2 ), 7.38 (d, 1H, R 7 ), 4.25 (q, 2H, R 1 ), 2.68 (q, 2H, R 12 ), 2.41 (s, 3H, R 11 ), 1.54 (t, 3H, R 1 ), 1. 31 (t, 3H, R 12 ).
実施例１と同様にして、１－（１－エチル－５－ニトロインドール－３－イル）エタノン＝Ｏ－プロピオニルオキシム（式（７）の化合物）を合成した。ただしステップ４では無水酢酸の代わりに無水プロピオン酸を用いた。得られた純品を重クロロホルム中４００ＭＨｚの１Ｈ－ＮＭＲで同定したところ、次の結果を示した。δ＝９．２８（ｄ，１Ｈ，Ｒ４）、８．１９（ｄｄ，１Ｈ，Ｒ６）、７．５９（ｓ，１Ｈ，Ｒ２）、７．３８（ｄ，１Ｈ，Ｒ７）、４．２５（ｑ，２Ｈ，Ｒ１）、２．６８（ｑ，２Ｈ，Ｒ１２）、２．４１（ｓ，３Ｈ，Ｒ１１）、１．５４（ｔ，３Ｈ，Ｒ１）、１．３１（ｔ，３Ｈ，Ｒ１２）。 [Example 5]
In the same manner as in Example 1, 1- (1-ethyl-5-nitroindol-3-yl) ethanone = O-propionyloxime (compound of formula (7)) was synthesized. However, in Step 4, propionic anhydride was used instead of acetic anhydride. When the obtained pure product was identified by 1 H-NMR at 400 MHz in deuterated chloroform, the following results were shown. δ = 9.28 (d, 1H, R 4 ), 8.19 (dd, 1H, R 6 ), 7.59 (s, 1H, R 2 ), 7.38 (d, 1H, R 7 ), 4.25 (q, 2H, R 1 ), 2.68 (q, 2H, R 12 ), 2.41 (s, 3H, R 11 ), 1.54 (t, 3H, R 1 ), 1. 31 (t, 3H, R 12 ).
［実施例６］
実施例１と同様にして、１－（１－エチル－５－ニトロインドール－３－イル）エタノン＝Ｏ－シクロプロパンカルボニルオキシム（式（８）の化合物）を合成した。ただしステップ４では無水酢酸の代わりに塩化シクロプロパンカルボニルを用い、ピリジンを溶媒として室温で４時間反応させた。得られた純品を重クロロホルム中４００ＭＨｚの１Ｈ－ＮＭＲで同定したところ、次の結果を示した。δ＝９．３０（ｄ，１Ｈ，Ｒ４）、８．１８（ｄｄ，１Ｈ，Ｒ６）、７．５９（ｓ，１Ｈ，Ｒ２）、７．３７（ｄ，１Ｈ，Ｒ７）、４．２５（ｑ，２Ｈ，Ｒ１）、２．４４（ｓ，３Ｈ，Ｒ１１）、１．９６（ｔｔ，１Ｈ，Ｒ１２）、１．５４（ｔ，３Ｈ，Ｒ１）、１．２１（ｄｔ，２Ｈ，Ｒ１２）、１．０３（ｄｔ，２Ｈ，Ｒ１２）。 [Example 6]
In the same manner as in Example 1, 1- (1-ethyl-5-nitroindol-3-yl) ethanone = O-cyclopropanecarbonyloxime (compound of formula (8)) was synthesized. However, in Step 4, cyclopropanecarbonyl chloride was used in place of acetic anhydride, and the reaction was performed at room temperature for 4 hours using pyridine as a solvent. When the obtained pure product was identified by 1 H-NMR at 400 MHz in deuterated chloroform, the following results were shown. δ = 9.30 (d, 1H, R 4 ), 8.18 (dd, 1H, R 6 ), 7.59 (s, 1H, R 2 ), 7.37 (d, 1H, R 7 ), 4.25 (q, 2H, R 1 ), 2.44 (s, 3H, R 11 ), 1.96 (tt, 1H, R 12 ), 1.54 (t, 3H, R 1 ), 1. 21 (dt, 2H, R 12 ), 1.03 (dt, 2H, R 12 ).
実施例１と同様にして、１－（１－エチル－５－ニトロインドール－３－イル）エタノン＝Ｏ－シクロプロパンカルボニルオキシム（式（８）の化合物）を合成した。ただしステップ４では無水酢酸の代わりに塩化シクロプロパンカルボニルを用い、ピリジンを溶媒として室温で４時間反応させた。得られた純品を重クロロホルム中４００ＭＨｚの１Ｈ－ＮＭＲで同定したところ、次の結果を示した。δ＝９．３０（ｄ，１Ｈ，Ｒ４）、８．１８（ｄｄ，１Ｈ，Ｒ６）、７．５９（ｓ，１Ｈ，Ｒ２）、７．３７（ｄ，１Ｈ，Ｒ７）、４．２５（ｑ，２Ｈ，Ｒ１）、２．４４（ｓ，３Ｈ，Ｒ１１）、１．９６（ｔｔ，１Ｈ，Ｒ１２）、１．５４（ｔ，３Ｈ，Ｒ１）、１．２１（ｄｔ，２Ｈ，Ｒ１２）、１．０３（ｄｔ，２Ｈ，Ｒ１２）。 [Example 6]
In the same manner as in Example 1, 1- (1-ethyl-5-nitroindol-3-yl) ethanone = O-cyclopropanecarbonyloxime (compound of formula (8)) was synthesized. However, in Step 4, cyclopropanecarbonyl chloride was used in place of acetic anhydride, and the reaction was performed at room temperature for 4 hours using pyridine as a solvent. When the obtained pure product was identified by 1 H-NMR at 400 MHz in deuterated chloroform, the following results were shown. δ = 9.30 (d, 1H, R 4 ), 8.18 (dd, 1H, R 6 ), 7.59 (s, 1H, R 2 ), 7.37 (d, 1H, R 7 ), 4.25 (q, 2H, R 1 ), 2.44 (s, 3H, R 11 ), 1.96 (tt, 1H, R 12 ), 1.54 (t, 3H, R 1 ), 1. 21 (dt, 2H, R 12 ), 1.03 (dt, 2H, R 12 ).
［実施例７］
実施例１と同様にして、１－（１－エチル－５－ニトロインドール－３－イル）エタノン＝Ｏ－ピバロイルオキシム（式（９）の化合物）を合成した。ただしステップ４では無水酢酸の代わりに塩化ピバロイルを用い、ピリジンを溶媒として室温で４時間反応させた。得られた純品を重クロロホルム中４００ＭＨｚの１Ｈ－ＮＭＲで同定したところ、次の結果を示した。δ＝９．３２（ｄ，１Ｈ，Ｒ４）、８．１８（ｄｄ，１Ｈ，Ｒ６）、７．５９（ｓ，１Ｈ，Ｒ２）、７．３７（ｄ，１Ｈ，Ｒ７）、４．２４（ｑ，２Ｈ，Ｒ１）、２．４１（ｓ，３Ｈ，Ｒ１１）、１．５４（ｔ，３Ｈ，Ｒ１）、１．３７（ｓ，９Ｈ，Ｒ１２）。 [Example 7]
In the same manner as in Example 1, 1- (1-ethyl-5-nitroindol-3-yl) ethanone = O-pivaloyl oxime (compound of formula (9)) was synthesized. However, in Step 4, pivaloyl chloride was used instead of acetic anhydride, and the reaction was performed at room temperature for 4 hours using pyridine as a solvent. When the obtained pure product was identified by 1 H-NMR at 400 MHz in deuterated chloroform, the following results were shown. δ = 9.32 (d, 1H, R 4 ), 8.18 (dd, 1H, R 6 ), 7.59 (s, 1H, R 2 ), 7.37 (d, 1H, R 7 ), 4.24 (q, 2H, R 1 ), 2.41 (s, 3H, R 11 ), 1.54 (t, 3H, R 1 ), 1.37 (s, 9H, R 12 ).
実施例１と同様にして、１－（１－エチル－５－ニトロインドール－３－イル）エタノン＝Ｏ－ピバロイルオキシム（式（９）の化合物）を合成した。ただしステップ４では無水酢酸の代わりに塩化ピバロイルを用い、ピリジンを溶媒として室温で４時間反応させた。得られた純品を重クロロホルム中４００ＭＨｚの１Ｈ－ＮＭＲで同定したところ、次の結果を示した。δ＝９．３２（ｄ，１Ｈ，Ｒ４）、８．１８（ｄｄ，１Ｈ，Ｒ６）、７．５９（ｓ，１Ｈ，Ｒ２）、７．３７（ｄ，１Ｈ，Ｒ７）、４．２４（ｑ，２Ｈ，Ｒ１）、２．４１（ｓ，３Ｈ，Ｒ１１）、１．５４（ｔ，３Ｈ，Ｒ１）、１．３７（ｓ，９Ｈ，Ｒ１２）。 [Example 7]
In the same manner as in Example 1, 1- (1-ethyl-5-nitroindol-3-yl) ethanone = O-pivaloyl oxime (compound of formula (9)) was synthesized. However, in Step 4, pivaloyl chloride was used instead of acetic anhydride, and the reaction was performed at room temperature for 4 hours using pyridine as a solvent. When the obtained pure product was identified by 1 H-NMR at 400 MHz in deuterated chloroform, the following results were shown. δ = 9.32 (d, 1H, R 4 ), 8.18 (dd, 1H, R 6 ), 7.59 (s, 1H, R 2 ), 7.37 (d, 1H, R 7 ), 4.24 (q, 2H, R 1 ), 2.41 (s, 3H, R 11 ), 1.54 (t, 3H, R 1 ), 1.37 (s, 9H, R 12 ).
［実施例８］
実施例１と同様にして、１－（１－エチル－５－ニトロインドール－３－イル）プロパン－１－オン＝Ｏ－アクリロイルオキシム（式（１０）の化合物）を合成した。ただしステップ２では塩化アセチルの代わりに塩化プロピオニルを用い、ステップ４では無水酢酸の代わりに無水アクリル酸を用いた。得られた純品を重クロロホルム中４００ＭＨｚの１Ｈ－ＮＭＲで同定したところ、次の結果を示した。δ＝９．３２（ｄ，１Ｈ，Ｒ４）、８．１９（ｄｄ，１Ｈ，Ｒ６）、７．６０（ｓ，１Ｈ，Ｒ２）、７．３８（ｄ，１Ｈ，Ｒ７）、６．６１（ｄｄ，１Ｈ，Ｒ１２）、６．４０（ｄｄ，１Ｈ，Ｒ１２）、５．９８（ｄｄ，１Ｈ，Ｒ１２）、４．２６（ｑ，２Ｈ，Ｒ１）、２．８６（ｑ，２Ｈ，Ｒ１１）、１．５５（ｔ，３Ｈ，Ｒ１）、１．３１（ｔ，３Ｈ，Ｒ１１）。なお、ステップ２の生成物は１－（１－エチル－５－ニトロインドール－３－イル）プロパン－１－オン、ステップ３の生成物は１－（１－エチル－５－ニトロインドール－３－イル）プロパン－１－オン＝オキシムであった。 [Example 8]
In the same manner as in Example 1, 1- (1-ethyl-5-nitroindol-3-yl) propan-1-one = O-acryloyloxime (compound of formula (10)) was synthesized. However, in Step 2, propionyl chloride was used instead of acetyl chloride, and in Step 4, acrylic acid anhydride was used instead of acetic anhydride. When the obtained pure product was identified by 1 H-NMR at 400 MHz in deuterated chloroform, the following results were shown. δ = 9.32 (d, 1H, R 4 ), 8.19 (dd, 1H, R 6 ), 7.60 (s, 1H, R 2 ), 7.38 (d, 1H, R 7 ), 6.61 (dd, 1H, R 12 ), 6.40 (dd, 1 H, R 12 ), 5.98 (dd, 1 H, R 12 ), 4.26 (q, 2H, R 1 ), 2. 86 (q, 2H, R 11 ), 1.55 (t, 3H, R 1 ), 1.31 (t, 3H, R 11 ). The product of Step 2 is 1- (1-ethyl-5-nitroindol-3-yl) propan-1-one, and the product of Step 3 is 1- (1-ethyl-5-nitroindole-3- Yl) propan-1-one oxime.
実施例１と同様にして、１－（１－エチル－５－ニトロインドール－３－イル）プロパン－１－オン＝Ｏ－アクリロイルオキシム（式（１０）の化合物）を合成した。ただしステップ２では塩化アセチルの代わりに塩化プロピオニルを用い、ステップ４では無水酢酸の代わりに無水アクリル酸を用いた。得られた純品を重クロロホルム中４００ＭＨｚの１Ｈ－ＮＭＲで同定したところ、次の結果を示した。δ＝９．３２（ｄ，１Ｈ，Ｒ４）、８．１９（ｄｄ，１Ｈ，Ｒ６）、７．６０（ｓ，１Ｈ，Ｒ２）、７．３８（ｄ，１Ｈ，Ｒ７）、６．６１（ｄｄ，１Ｈ，Ｒ１２）、６．４０（ｄｄ，１Ｈ，Ｒ１２）、５．９８（ｄｄ，１Ｈ，Ｒ１２）、４．２６（ｑ，２Ｈ，Ｒ１）、２．８６（ｑ，２Ｈ，Ｒ１１）、１．５５（ｔ，３Ｈ，Ｒ１）、１．３１（ｔ，３Ｈ，Ｒ１１）。なお、ステップ２の生成物は１－（１－エチル－５－ニトロインドール－３－イル）プロパン－１－オン、ステップ３の生成物は１－（１－エチル－５－ニトロインドール－３－イル）プロパン－１－オン＝オキシムであった。 [Example 8]
In the same manner as in Example 1, 1- (1-ethyl-5-nitroindol-3-yl) propan-1-one = O-acryloyloxime (compound of formula (10)) was synthesized. However, in Step 2, propionyl chloride was used instead of acetyl chloride, and in Step 4, acrylic acid anhydride was used instead of acetic anhydride. When the obtained pure product was identified by 1 H-NMR at 400 MHz in deuterated chloroform, the following results were shown. δ = 9.32 (d, 1H, R 4 ), 8.19 (dd, 1H, R 6 ), 7.60 (s, 1H, R 2 ), 7.38 (d, 1H, R 7 ), 6.61 (dd, 1H, R 12 ), 6.40 (dd, 1 H, R 12 ), 5.98 (dd, 1 H, R 12 ), 4.26 (q, 2H, R 1 ), 2. 86 (q, 2H, R 11 ), 1.55 (t, 3H, R 1 ), 1.31 (t, 3H, R 11 ). The product of Step 2 is 1- (1-ethyl-5-nitroindol-3-yl) propan-1-one, and the product of Step 3 is 1- (1-ethyl-5-nitroindole-3- Yl) propan-1-one oxime.
［実施例１１］
（感光性組成物の作製）
実施例１で合成した光重合開始剤０．１０重量％、ビスフェノールフルオレン型エポキシジアクリレート構造を有するアルカリ現像型感光性樹脂（オレフィン結合を有する重合性化合物）の５６．５重量％プロピレングリコールモノメチルエーテルアセテート溶液（新日鐵化学社製「Ｖ－２５９ＭＥ」）２６．２０重量％、ペンタエリスリトールテトラアクリレート（オレフィン結合を有する重合性化合物）５．００重量％、シリコーン系界面活性剤（東レ・ダウコーニング社製「ＦＺ－２１２２」）０．０５重量％、３－（グリシジルオキシ）プロピルトリメトキシシラン（シランカップリング剤）０．０５重量％及びプロピレングリコールモノメチルエーテルアセテート（溶剤）６８．６０重量％の割合で配合を行い、室温で３時間攪拌混合して感光性組成物を作製した。かかる感光性組成物は、固形分濃度２０．０重量％のアルカリ現像可能なネガ型の透明フォトレジストである。なお、ここで固形分とは溶剤以外の成分をいう。 [Example 11]
(Preparation of photosensitive composition)
56.5% by weight of propylene glycol monomethyl ether of 0.10% by weight of the photopolymerization initiator synthesized in Example 1 and 56.5% by weight of an alkali-developable photosensitive resin (polymerizable compound having an olefin bond) having a bisphenolfluorene type epoxy diacrylate structure Acetate solution (“V-259ME” manufactured by Nippon Steel Chemical Co., Ltd.) 26.20% by weight, pentaerythritol tetraacrylate (polymerizable compound having an olefin bond) 5.00% by weight, silicone surfactant (Toray Dow Corning) "FZ-2122" manufactured by the company) 0.05 wt%, 3- (glycidyloxy) propyltrimethoxysilane (silane coupling agent) 0.05 wt% and propylene glycol monomethyl ether acetate (solvent) 68.60 wt% Mix in proportion and stir at room temperature for 3 hours Combined was produced a photosensitive composition. Such a photosensitive composition is a negative-type transparent photoresist having a solid content concentration of 20.0% by weight and capable of alkali development. In addition, solid content means components other than a solvent here.
（感光性組成物の作製）
実施例１で合成した光重合開始剤０．１０重量％、ビスフェノールフルオレン型エポキシジアクリレート構造を有するアルカリ現像型感光性樹脂（オレフィン結合を有する重合性化合物）の５６．５重量％プロピレングリコールモノメチルエーテルアセテート溶液（新日鐵化学社製「Ｖ－２５９ＭＥ」）２６．２０重量％、ペンタエリスリトールテトラアクリレート（オレフィン結合を有する重合性化合物）５．００重量％、シリコーン系界面活性剤（東レ・ダウコーニング社製「ＦＺ－２１２２」）０．０５重量％、３－（グリシジルオキシ）プロピルトリメトキシシラン（シランカップリング剤）０．０５重量％及びプロピレングリコールモノメチルエーテルアセテート（溶剤）６８．６０重量％の割合で配合を行い、室温で３時間攪拌混合して感光性組成物を作製した。かかる感光性組成物は、固形分濃度２０．０重量％のアルカリ現像可能なネガ型の透明フォトレジストである。なお、ここで固形分とは溶剤以外の成分をいう。 [Example 11]
(Preparation of photosensitive composition)
56.5% by weight of propylene glycol monomethyl ether of 0.10% by weight of the photopolymerization initiator synthesized in Example 1 and 56.5% by weight of an alkali-developable photosensitive resin (polymerizable compound having an olefin bond) having a bisphenolfluorene type epoxy diacrylate structure Acetate solution (“V-259ME” manufactured by Nippon Steel Chemical Co., Ltd.) 26.20% by weight, pentaerythritol tetraacrylate (polymerizable compound having an olefin bond) 5.00% by weight, silicone surfactant (Toray Dow Corning) "FZ-2122" manufactured by the company) 0.05 wt%, 3- (glycidyloxy) propyltrimethoxysilane (silane coupling agent) 0.05 wt% and propylene glycol monomethyl ether acetate (solvent) 68.60 wt% Mix in proportion and stir at room temperature for 3 hours Combined was produced a photosensitive composition. Such a photosensitive composition is a negative-type transparent photoresist having a solid content concentration of 20.0% by weight and capable of alkali development. In addition, solid content means components other than a solvent here.
（感光性組成物の評価）
上記感光性組成物を無アルカリガラス基板にスピンコーターを用いて塗布し、８０℃のホットプレートで１分間乾燥させて試験片を作成した。このとき、膜厚１．０μｍの硬化膜が得られるように塗布条件（スピン回転数）を調節した。次に、透過率を０～１００％の間で段階的に変化させたフォトマスク及び３５０ｎｍ以下の光を吸収するカットフィルターを介して、照度３０ｍＷ／ｃｍ２（ｉ線基準）の超高圧水銀ランプで１００ｍＪ／ｃｍ２（ｉ線基準）の紫外線を照射して試験片に画像露光を行った。その後、試験片を２３℃のアルカリ現像液（新日鐵化学社製「Ｖ－２４０１ＩＤ」の１０倍希釈液）で１分間処理し、更に水洗を行って画像を現像した。この画像は、光硬化に必要な露光量を読み取ることができるものである。最後に試験片を２３０℃の熱風オーブンで３０分間焼成し、感光性組成物の硬化膜を得た。画像から判定された光硬化に必要な露光量は２３ｍＪ／ｃｍ２（ｉ線基準）であった。 (Evaluation of photosensitive composition)
The photosensitive composition was applied to an alkali-free glass substrate using a spin coater, and dried on an 80 ° C. hot plate for 1 minute to prepare a test piece. At this time, the coating conditions (spin rotation speed) were adjusted so that a cured film having a thickness of 1.0 μm was obtained. Next, an ultra-high pressure mercury lamp with an illuminance of 30 mW / cm 2 (based on i-line) through a photomask whose transmittance is changed stepwise between 0 and 100% and a cut filter that absorbs light of 350 nm or less And 100 mJ / cm 2 (i-line basis) was irradiated with ultraviolet rays to perform image exposure on the test piece. Thereafter, the test piece was treated with an alkaline developer at 23 ° C. (10-fold diluted solution of “V-2401ID” manufactured by Nippon Steel Chemical Co., Ltd.) for 1 minute, and further washed with water to develop the image. This image can read the exposure amount required for photocuring. Finally, the test piece was baked in a hot air oven at 230 ° C. for 30 minutes to obtain a cured film of the photosensitive composition. The exposure necessary for photocuring determined from the image was 23 mJ / cm 2 (i-line reference).
上記感光性組成物を無アルカリガラス基板にスピンコーターを用いて塗布し、８０℃のホットプレートで１分間乾燥させて試験片を作成した。このとき、膜厚１．０μｍの硬化膜が得られるように塗布条件（スピン回転数）を調節した。次に、透過率を０～１００％の間で段階的に変化させたフォトマスク及び３５０ｎｍ以下の光を吸収するカットフィルターを介して、照度３０ｍＷ／ｃｍ２（ｉ線基準）の超高圧水銀ランプで１００ｍＪ／ｃｍ２（ｉ線基準）の紫外線を照射して試験片に画像露光を行った。その後、試験片を２３℃のアルカリ現像液（新日鐵化学社製「Ｖ－２４０１ＩＤ」の１０倍希釈液）で１分間処理し、更に水洗を行って画像を現像した。この画像は、光硬化に必要な露光量を読み取ることができるものである。最後に試験片を２３０℃の熱風オーブンで３０分間焼成し、感光性組成物の硬化膜を得た。画像から判定された光硬化に必要な露光量は２３ｍＪ／ｃｍ２（ｉ線基準）であった。 (Evaluation of photosensitive composition)
The photosensitive composition was applied to an alkali-free glass substrate using a spin coater, and dried on an 80 ° C. hot plate for 1 minute to prepare a test piece. At this time, the coating conditions (spin rotation speed) were adjusted so that a cured film having a thickness of 1.0 μm was obtained. Next, an ultra-high pressure mercury lamp with an illuminance of 30 mW / cm 2 (based on i-line) through a photomask whose transmittance is changed stepwise between 0 and 100% and a cut filter that absorbs light of 350 nm or less And 100 mJ / cm 2 (i-line basis) was irradiated with ultraviolet rays to perform image exposure on the test piece. Thereafter, the test piece was treated with an alkaline developer at 23 ° C. (10-fold diluted solution of “V-2401ID” manufactured by Nippon Steel Chemical Co., Ltd.) for 1 minute, and further washed with water to develop the image. This image can read the exposure amount required for photocuring. Finally, the test piece was baked in a hot air oven at 230 ° C. for 30 minutes to obtain a cured film of the photosensitive composition. The exposure necessary for photocuring determined from the image was 23 mJ / cm 2 (i-line reference).
［実施例１２］
実施例１１における光重合開始剤を実施例２で合成した光重合開始剤に変更し、その他は実施例１１と同様にして感光性組成物を作製し評価を行った。画像から判定された光硬化に必要な露光量は２３ｍＪ／ｃｍ２（ｉ線基準）であった。 [Example 12]
The photopolymerization initiator in Example 11 was changed to the photopolymerization initiator synthesized in Example 2, and the others were prepared and evaluated in the same manner as in Example 11. The exposure necessary for photocuring determined from the image was 23 mJ / cm 2 (i-line reference).
実施例１１における光重合開始剤を実施例２で合成した光重合開始剤に変更し、その他は実施例１１と同様にして感光性組成物を作製し評価を行った。画像から判定された光硬化に必要な露光量は２３ｍＪ／ｃｍ２（ｉ線基準）であった。 [Example 12]
The photopolymerization initiator in Example 11 was changed to the photopolymerization initiator synthesized in Example 2, and the others were prepared and evaluated in the same manner as in Example 11. The exposure necessary for photocuring determined from the image was 23 mJ / cm 2 (i-line reference).
［実施例１３］
実施例１１における光重合開始剤を実施例３で合成した光重合開始剤に変更し、その他は実施例１１と同様にして感光性組成物を作製し評価を行った。画像から判定された光硬化に必要な露光量は２６ｍＪ／ｃｍ２（ｉ線基準）であった。 [Example 13]
The photopolymerization initiator in Example 11 was changed to the photopolymerization initiator synthesized in Example 3, and the others were prepared and evaluated in the same manner as in Example 11. The exposure amount required for photocuring determined from the image was 26 mJ / cm 2 (i-line reference).
実施例１１における光重合開始剤を実施例３で合成した光重合開始剤に変更し、その他は実施例１１と同様にして感光性組成物を作製し評価を行った。画像から判定された光硬化に必要な露光量は２６ｍＪ／ｃｍ２（ｉ線基準）であった。 [Example 13]
The photopolymerization initiator in Example 11 was changed to the photopolymerization initiator synthesized in Example 3, and the others were prepared and evaluated in the same manner as in Example 11. The exposure amount required for photocuring determined from the image was 26 mJ / cm 2 (i-line reference).
［実施例１４］
実施例１１における光重合開始剤を実施例４で合成した光重合開始剤に変更し、その他は実施例１１と同様にして感光性組成物を作製し評価を行った。画像から判定された光硬化に必要な露光量は２３ｍＪ／ｃｍ２（ｉ線基準）であった。 [Example 14]
The photopolymerization initiator in Example 11 was changed to the photopolymerization initiator synthesized in Example 4, and the others were prepared and evaluated in the same manner as in Example 11. The exposure necessary for photocuring determined from the image was 23 mJ / cm 2 (i-line reference).
実施例１１における光重合開始剤を実施例４で合成した光重合開始剤に変更し、その他は実施例１１と同様にして感光性組成物を作製し評価を行った。画像から判定された光硬化に必要な露光量は２３ｍＪ／ｃｍ２（ｉ線基準）であった。 [Example 14]
The photopolymerization initiator in Example 11 was changed to the photopolymerization initiator synthesized in Example 4, and the others were prepared and evaluated in the same manner as in Example 11. The exposure necessary for photocuring determined from the image was 23 mJ / cm 2 (i-line reference).
［比較例１］
実施例１１における光重合開始剤を１－［９－エチル－６－（２－メチルベンゾイル）カルバゾール－３－イル］エタノン＝Ｏ－アセチルオキシム（下記式（２４）で示される化合物、ＢＡＳＦ社製「イルガキュアＯＸＥ０２」）に変更し、その他は実施例１１と同様にして感光性組成物を作製し評価を行った。画像から判定された光硬化に必要な露光量は３７ｍＪ／ｃｍ２（ｉ線基準）であって、実施例１１～１４と比較して感度が低いことが示された（硬化に必要な露光量が少ないほど高感度である）。
[Comparative Example 1]
The photopolymerization initiator in Example 11 was 1- [9-ethyl-6- (2-methylbenzoyl) carbazol-3-yl] ethanone = O-acetyloxime (a compound represented by the following formula (24), manufactured by BASF) The composition was changed to “Irgacure OXE02”), and the others were prepared and evaluated in the same manner as in Example 11. The exposure amount required for photocuring determined from the image was 37 mJ / cm 2 (i-line basis), and it was shown that the sensitivity was lower than in Examples 11 to 14 (exposure amount necessary for curing). The smaller the number, the higher the sensitivity.)
実施例１１における光重合開始剤を１－［９－エチル－６－（２－メチルベンゾイル）カルバゾール－３－イル］エタノン＝Ｏ－アセチルオキシム（下記式（２４）で示される化合物、ＢＡＳＦ社製「イルガキュアＯＸＥ０２」）に変更し、その他は実施例１１と同様にして感光性組成物を作製し評価を行った。画像から判定された光硬化に必要な露光量は３７ｍＪ／ｃｍ２（ｉ線基準）であって、実施例１１～１４と比較して感度が低いことが示された（硬化に必要な露光量が少ないほど高感度である）。
The photopolymerization initiator in Example 11 was 1- [9-ethyl-6- (2-methylbenzoyl) carbazol-3-yl] ethanone = O-acetyloxime (a compound represented by the following formula (24), manufactured by BASF) The composition was changed to “Irgacure OXE02”), and the others were prepared and evaluated in the same manner as in Example 11. The exposure amount required for photocuring determined from the image was 37 mJ / cm 2 (i-line basis), and it was shown that the sensitivity was lower than in Examples 11 to 14 (exposure amount necessary for curing). The smaller the number, the higher the sensitivity.)
［比較例２］
実施例１１における光重合開始剤を１－（１－エチルインドール－３－イル）エタノン＝Ｏ－アセチルオキシム（下記式（２５）で示される化合物）に変更し、その他は実施例１１と同様にして感光性組成物を作製し評価を行った。その結果、感光性組成物は光硬化せずにアルカリ現像液にすべて溶解してしまい、実施例１１～１４と比較して感度が低いことが示された。
[Comparative Example 2]
The photopolymerization initiator in Example 11 was changed to 1- (1-ethylindol-3-yl) ethanone = O-acetyloxime (a compound represented by the following formula (25)), and the others were the same as in Example 11. A photosensitive composition was prepared and evaluated. As a result, the photosensitive composition was completely undissolved in the alkali developer without being photocured, indicating that the sensitivity was lower than in Examples 11-14.
実施例１１における光重合開始剤を１－（１－エチルインドール－３－イル）エタノン＝Ｏ－アセチルオキシム（下記式（２５）で示される化合物）に変更し、その他は実施例１１と同様にして感光性組成物を作製し評価を行った。その結果、感光性組成物は光硬化せずにアルカリ現像液にすべて溶解してしまい、実施例１１～１４と比較して感度が低いことが示された。
The photopolymerization initiator in Example 11 was changed to 1- (1-ethylindol-3-yl) ethanone = O-acetyloxime (a compound represented by the following formula (25)), and the others were the same as in Example 11. A photosensitive composition was prepared and evaluated. As a result, the photosensitive composition was completely undissolved in the alkali developer without being photocured, indicating that the sensitivity was lower than in Examples 11-14.
［比較例３］
実施例１１における光重合開始剤を１－［１－エチル－５－（２－メチルベンゾイル）インドール－３－イル］エタノン＝Ｏ－アセチルオキシム（下記式（２６）で示される化合物）に変更し、その他は実施例１１と同様にして感光性組成物を作製し評価を行った。画像から判定された光硬化に必要な露光量は８３ｍＪ／ｃｍ２（ｉ線基準）であって、実施例１１～１４と比較して感度が低いことが示された。
[Comparative Example 3]
The photopolymerization initiator in Example 11 was changed to 1- [1-ethyl-5- (2-methylbenzoyl) indol-3-yl] ethanone = O-acetyloxime (compound represented by the following formula (26)). Other than that, a photosensitive composition was prepared and evaluated in the same manner as in Example 11. The exposure amount required for photocuring determined from the image was 83 mJ / cm 2 (i-line basis), indicating that the sensitivity was lower than in Examples 11-14.
実施例１１における光重合開始剤を１－［１－エチル－５－（２－メチルベンゾイル）インドール－３－イル］エタノン＝Ｏ－アセチルオキシム（下記式（２６）で示される化合物）に変更し、その他は実施例１１と同様にして感光性組成物を作製し評価を行った。画像から判定された光硬化に必要な露光量は８３ｍＪ／ｃｍ２（ｉ線基準）であって、実施例１１～１４と比較して感度が低いことが示された。
The photopolymerization initiator in Example 11 was changed to 1- [1-ethyl-5- (2-methylbenzoyl) indol-3-yl] ethanone = O-acetyloxime (compound represented by the following formula (26)). Other than that, a photosensitive composition was prepared and evaluated in the same manner as in Example 11. The exposure amount required for photocuring determined from the image was 83 mJ / cm 2 (i-line basis), indicating that the sensitivity was lower than in Examples 11-14.
［実施例２１］
（感光性組成物の作製）
実施例１で合成した光重合開始剤０．６０重量％、ビスフェノールフルオレン型エポキシジアクリレート構造を有するアルカリ現像型感光性樹脂（オレフィン結合を有する重合性化合物）の５６．５重量％プロピレングリコールモノメチルエーテルアセテート溶液（新日鐵化学社製「Ｖ－２５９ＭＥ」）８．２３重量％、ペンタエリスリトールテトラアクリレート（オレフィン結合を有する重合性化合物）１．３５重量％、カーボンブラック顔料（着色材）をカチオン性高分子分散剤でプロピレングリコールモノメチルエーテルアセテートに分散した分散液（カーボンブラック顔料濃度３０．０重量％、固形分濃度３４．５重量％）２６．６９重量％、フッ素系界面活性剤（ＤＩＣ社製「メガファックＦ－５５６」）０．０５重量％、３－（グリシジルオキシ）プロピルトリメトキシシラン（シランカップリング剤）０．１５重量％、プロピレングリコールモノメチルエーテルアセテート（溶剤）２９．３３重量％及びシクロヘキサノン（溶剤）３３．６０重量％の割合で配合を行い、室温で３時間攪拌混合して感光性組成物を作製した。かかる感光性組成物は、固形分濃度１６．０重量％のアルカリ現像可能なネガ型の遮光性フォトレジストである。 [Example 21]
(Preparation of photosensitive composition)
0.60% by weight of the photopolymerization initiator synthesized in Example 1, 56.5% by weight of propylene glycol monomethyl ether of an alkali development type photosensitive resin (polymerizable compound having an olefin bond) having a bisphenolfluorene type epoxy diacrylate structure Acetate solution (“V-259ME” manufactured by Nippon Steel Chemical Co., Ltd.) 8.23 wt%, pentaerythritol tetraacrylate (polymerizable compound having an olefin bond) 1.35 wt%, carbon black pigment (colorant) cationic 26.69 wt% dispersion (carbon black pigment concentration 30.0 wt%, solid content concentration 34.5 wt%) dispersed in propylene glycol monomethyl ether acetate with a polymer dispersant, fluorosurfactant (manufactured by DIC) “Megafuck F-556”) 0.05% by weight, 3- ( Lysidyloxy) propyltrimethoxysilane (silane coupling agent) 0.15% by weight, propylene glycol monomethyl ether acetate (solvent) 29.33% by weight and cyclohexanone (solvent) 33.60% by weight. A photosensitive composition was prepared by stirring and mixing for 3 hours. Such a photosensitive composition is a negative-type light-shielding photoresist having a solid content concentration of 16.0% by weight and capable of alkali development.
（感光性組成物の作製）
実施例１で合成した光重合開始剤０．６０重量％、ビスフェノールフルオレン型エポキシジアクリレート構造を有するアルカリ現像型感光性樹脂（オレフィン結合を有する重合性化合物）の５６．５重量％プロピレングリコールモノメチルエーテルアセテート溶液（新日鐵化学社製「Ｖ－２５９ＭＥ」）８．２３重量％、ペンタエリスリトールテトラアクリレート（オレフィン結合を有する重合性化合物）１．３５重量％、カーボンブラック顔料（着色材）をカチオン性高分子分散剤でプロピレングリコールモノメチルエーテルアセテートに分散した分散液（カーボンブラック顔料濃度３０．０重量％、固形分濃度３４．５重量％）２６．６９重量％、フッ素系界面活性剤（ＤＩＣ社製「メガファックＦ－５５６」）０．０５重量％、３－（グリシジルオキシ）プロピルトリメトキシシラン（シランカップリング剤）０．１５重量％、プロピレングリコールモノメチルエーテルアセテート（溶剤）２９．３３重量％及びシクロヘキサノン（溶剤）３３．６０重量％の割合で配合を行い、室温で３時間攪拌混合して感光性組成物を作製した。かかる感光性組成物は、固形分濃度１６．０重量％のアルカリ現像可能なネガ型の遮光性フォトレジストである。 [Example 21]
(Preparation of photosensitive composition)
0.60% by weight of the photopolymerization initiator synthesized in Example 1, 56.5% by weight of propylene glycol monomethyl ether of an alkali development type photosensitive resin (polymerizable compound having an olefin bond) having a bisphenolfluorene type epoxy diacrylate structure Acetate solution (“V-259ME” manufactured by Nippon Steel Chemical Co., Ltd.) 8.23 wt%, pentaerythritol tetraacrylate (polymerizable compound having an olefin bond) 1.35 wt%, carbon black pigment (colorant) cationic 26.69 wt% dispersion (carbon black pigment concentration 30.0 wt%, solid content concentration 34.5 wt%) dispersed in propylene glycol monomethyl ether acetate with a polymer dispersant, fluorosurfactant (manufactured by DIC) “Megafuck F-556”) 0.05% by weight, 3- ( Lysidyloxy) propyltrimethoxysilane (silane coupling agent) 0.15% by weight, propylene glycol monomethyl ether acetate (solvent) 29.33% by weight and cyclohexanone (solvent) 33.60% by weight. A photosensitive composition was prepared by stirring and mixing for 3 hours. Such a photosensitive composition is a negative-type light-shielding photoresist having a solid content concentration of 16.0% by weight and capable of alkali development.
（感光性組成物の評価）
上記感光性組成物を無アルカリガラス基板にスピンコーターを用いて塗布し、９０℃のホットプレートで１分間乾燥させて試験片を作成した。このとき、膜厚１．０μｍの硬化膜が得られるように塗布条件（スピン回転数）を調節した。次に、線幅５μｍのマトリクス状のパターンを有するフォトマスクを介して、照度３０ｍＷ／ｃｍ２（ｉ線基準）の超高圧水銀ランプで１００ｍＪ／ｃｍ２（ｉ線基準）の紫外線を照射して試験片に画像露光を行った。その後、試験片を２３℃のアルカリ現像液（新日鐵化学社製「Ｖ－２４０１ＩＤ」の１０倍希釈液）で１分間処理し、更に水洗を行って画像を現像した。最後に試験片を２３０℃の熱風オーブンで３０分間焼成し、感光性組成物の硬化膜を得た。試験片には直線性良好で現像残渣のない線幅５μｍの高品位なブラックマトリクスが形成された。ブラックマトリクスの光学濃度は４．４／μｍであり、高い遮光性を有していた。 (Evaluation of photosensitive composition)
The said photosensitive composition was apply | coated to the alkali-free glass substrate using the spin coater, and it was made to dry for 1 minute with a 90 degreeC hotplate, and the test piece was created. At this time, the coating conditions (spin rotation speed) were adjusted so that a cured film having a thickness of 1.0 μm was obtained. Next, an ultraviolet ray of 100 mJ / cm 2 (i-line reference) is irradiated through an ultrahigh pressure mercury lamp with an illuminance of 30 mW / cm 2 (i-line reference) through a photomask having a matrix pattern with a line width of 5 μm. Image exposure was performed to the test piece. Thereafter, the test piece was treated with an alkaline developer at 23 ° C. (10-fold diluted solution of “V-2401ID” manufactured by Nippon Steel Chemical Co., Ltd.) for 1 minute, and further washed with water to develop the image. Finally, the test piece was baked in a hot air oven at 230 ° C. for 30 minutes to obtain a cured film of the photosensitive composition. A high-quality black matrix having a line width of 5 μm with good linearity and no development residue was formed on the test piece. The optical density of the black matrix was 4.4 / μm and had high light shielding properties.
上記感光性組成物を無アルカリガラス基板にスピンコーターを用いて塗布し、９０℃のホットプレートで１分間乾燥させて試験片を作成した。このとき、膜厚１．０μｍの硬化膜が得られるように塗布条件（スピン回転数）を調節した。次に、線幅５μｍのマトリクス状のパターンを有するフォトマスクを介して、照度３０ｍＷ／ｃｍ２（ｉ線基準）の超高圧水銀ランプで１００ｍＪ／ｃｍ２（ｉ線基準）の紫外線を照射して試験片に画像露光を行った。その後、試験片を２３℃のアルカリ現像液（新日鐵化学社製「Ｖ－２４０１ＩＤ」の１０倍希釈液）で１分間処理し、更に水洗を行って画像を現像した。最後に試験片を２３０℃の熱風オーブンで３０分間焼成し、感光性組成物の硬化膜を得た。試験片には直線性良好で現像残渣のない線幅５μｍの高品位なブラックマトリクスが形成された。ブラックマトリクスの光学濃度は４．４／μｍであり、高い遮光性を有していた。 (Evaluation of photosensitive composition)
The said photosensitive composition was apply | coated to the alkali-free glass substrate using the spin coater, and it was made to dry for 1 minute with a 90 degreeC hotplate, and the test piece was created. At this time, the coating conditions (spin rotation speed) were adjusted so that a cured film having a thickness of 1.0 μm was obtained. Next, an ultraviolet ray of 100 mJ / cm 2 (i-line reference) is irradiated through an ultrahigh pressure mercury lamp with an illuminance of 30 mW / cm 2 (i-line reference) through a photomask having a matrix pattern with a line width of 5 μm. Image exposure was performed to the test piece. Thereafter, the test piece was treated with an alkaline developer at 23 ° C. (10-fold diluted solution of “V-2401ID” manufactured by Nippon Steel Chemical Co., Ltd.) for 1 minute, and further washed with water to develop the image. Finally, the test piece was baked in a hot air oven at 230 ° C. for 30 minutes to obtain a cured film of the photosensitive composition. A high-quality black matrix having a line width of 5 μm with good linearity and no development residue was formed on the test piece. The optical density of the black matrix was 4.4 / μm and had high light shielding properties.
［実施例２２］
実施例２１における光重合開始剤を実施例２で合成した光重合開始剤に変更し、その他は実施例２１と同様にして感光性組成物を作製し評価を行った。試験片には直線性良好で現像残渣のない線幅５μｍの高品位なブラックマトリクスが形成された。ブラックマトリクスの光学濃度は４．４／μｍであり、高い遮光性を有していた。 [Example 22]
The photopolymerization initiator in Example 21 was changed to the photopolymerization initiator synthesized in Example 2, and the others were prepared and evaluated in the same manner as in Example 21. A high-quality black matrix having a line width of 5 μm with good linearity and no development residue was formed on the test piece. The optical density of the black matrix was 4.4 / μm and had high light shielding properties.
実施例２１における光重合開始剤を実施例２で合成した光重合開始剤に変更し、その他は実施例２１と同様にして感光性組成物を作製し評価を行った。試験片には直線性良好で現像残渣のない線幅５μｍの高品位なブラックマトリクスが形成された。ブラックマトリクスの光学濃度は４．４／μｍであり、高い遮光性を有していた。 [Example 22]
The photopolymerization initiator in Example 21 was changed to the photopolymerization initiator synthesized in Example 2, and the others were prepared and evaluated in the same manner as in Example 21. A high-quality black matrix having a line width of 5 μm with good linearity and no development residue was formed on the test piece. The optical density of the black matrix was 4.4 / μm and had high light shielding properties.
［実施例２３］
実施例２１における光重合開始剤を実施例３で合成した光重合開始剤に変更し、その他は実施例２１と同様にして感光性組成物を作製し評価を行った。試験片には直線性良好で現像残渣のない線幅５μｍの高品位なブラックマトリクスが形成された。ブラックマトリクスの光学濃度は４．４／μｍであり、高い遮光性を有していた。 [Example 23]
The photopolymerization initiator in Example 21 was changed to the photopolymerization initiator synthesized in Example 3, and the others were prepared and evaluated in the same manner as in Example 21. A high-quality black matrix having a line width of 5 μm with good linearity and no development residue was formed on the test piece. The optical density of the black matrix was 4.4 / μm and had high light shielding properties.
実施例２１における光重合開始剤を実施例３で合成した光重合開始剤に変更し、その他は実施例２１と同様にして感光性組成物を作製し評価を行った。試験片には直線性良好で現像残渣のない線幅５μｍの高品位なブラックマトリクスが形成された。ブラックマトリクスの光学濃度は４．４／μｍであり、高い遮光性を有していた。 [Example 23]
The photopolymerization initiator in Example 21 was changed to the photopolymerization initiator synthesized in Example 3, and the others were prepared and evaluated in the same manner as in Example 21. A high-quality black matrix having a line width of 5 μm with good linearity and no development residue was formed on the test piece. The optical density of the black matrix was 4.4 / μm and had high light shielding properties.
［実施例２４］
実施例２１における光重合開始剤を実施例４で合成した光重合開始剤に変更し、その他は実施例２１と同様にして感光性組成物を作製し評価を行った。試験片には直線性良好で現像残渣のない線幅５μｍの高品位なブラックマトリクスが形成された。ブラックマトリクスの光学濃度は４．４／μｍであり、高い遮光性を有していた。 [Example 24]
The photopolymerization initiator in Example 21 was changed to the photopolymerization initiator synthesized in Example 4, and the others were prepared and evaluated in the same manner as in Example 21. A high-quality black matrix having a line width of 5 μm with good linearity and no development residue was formed on the test piece. The optical density of the black matrix was 4.4 / μm and had high light shielding properties.
実施例２１における光重合開始剤を実施例４で合成した光重合開始剤に変更し、その他は実施例２１と同様にして感光性組成物を作製し評価を行った。試験片には直線性良好で現像残渣のない線幅５μｍの高品位なブラックマトリクスが形成された。ブラックマトリクスの光学濃度は４．４／μｍであり、高い遮光性を有していた。 [Example 24]
The photopolymerization initiator in Example 21 was changed to the photopolymerization initiator synthesized in Example 4, and the others were prepared and evaluated in the same manner as in Example 21. A high-quality black matrix having a line width of 5 μm with good linearity and no development residue was formed on the test piece. The optical density of the black matrix was 4.4 / μm and had high light shielding properties.
［比較例４］
実施例２１における光重合開始剤を１－［９－エチル－６－（２－メチルベンゾイル）カルバゾール－３－イル］エタノン＝Ｏ－アセチルオキシム（式（２４）で示される化合物、ＢＡＳＦ社製「イルガキュアＯＸＥ０２」）に変更し、その他は実施例２１と同様にして感光性組成物を作製し評価を行った。その結果、現像で除去されるべき未露光部が現像後も基板上に残存してブラックマトリクスを得ることはできず、感光性組成物の現像液への溶解性が不足していることが示された。 [Comparative Example 4]
The photopolymerization initiator in Example 21 was 1- [9-ethyl-6- (2-methylbenzoyl) carbazol-3-yl] ethanone = O-acetyloxime (a compound represented by the formula (24), manufactured by BASF “ The photosensitive composition was prepared and evaluated in the same manner as in Example 21 except that it was changed to “Irgacure OXE02”). As a result, the unexposed area to be removed by development remains on the substrate even after development, and a black matrix cannot be obtained, indicating that the solubility of the photosensitive composition in the developer is insufficient. It was done.
実施例２１における光重合開始剤を１－［９－エチル－６－（２－メチルベンゾイル）カルバゾール－３－イル］エタノン＝Ｏ－アセチルオキシム（式（２４）で示される化合物、ＢＡＳＦ社製「イルガキュアＯＸＥ０２」）に変更し、その他は実施例２１と同様にして感光性組成物を作製し評価を行った。その結果、現像で除去されるべき未露光部が現像後も基板上に残存してブラックマトリクスを得ることはできず、感光性組成物の現像液への溶解性が不足していることが示された。 [Comparative Example 4]
The photopolymerization initiator in Example 21 was 1- [9-ethyl-6- (2-methylbenzoyl) carbazol-3-yl] ethanone = O-acetyloxime (a compound represented by the formula (24), manufactured by BASF “ The photosensitive composition was prepared and evaluated in the same manner as in Example 21 except that it was changed to “Irgacure OXE02”). As a result, the unexposed area to be removed by development remains on the substrate even after development, and a black matrix cannot be obtained, indicating that the solubility of the photosensitive composition in the developer is insufficient. It was done.
［比較例５］
実施例２１における光重合開始剤を１－（９－エチル－６－ニトロカルバゾール－３－イル）エタノン＝Ｏ－アセチルオキシム（下記式（２７）で示される化合物）に変更し、その他は実施例２１と同様にして感光性組成物を作製し評価を行った。その結果、感光性組成物を塗布した試験片の塗布面に大量の異物が確認され、画像露光以降の工程を実施することができなかった。異物は未溶解の光重合開始剤であった。
[Comparative Example 5]
The photopolymerization initiator in Example 21 was changed to 1- (9-ethyl-6-nitrocarbazol-3-yl) ethanone = O-acetyloxime (a compound represented by the following formula (27)), and others were as in Example. In the same manner as in No. 21, a photosensitive composition was prepared and evaluated. As a result, a large amount of foreign matter was confirmed on the coated surface of the test piece coated with the photosensitive composition, and the steps after image exposure could not be performed. The foreign matter was an undissolved photopolymerization initiator.
実施例２１における光重合開始剤を１－（９－エチル－６－ニトロカルバゾール－３－イル）エタノン＝Ｏ－アセチルオキシム（下記式（２７）で示される化合物）に変更し、その他は実施例２１と同様にして感光性組成物を作製し評価を行った。その結果、感光性組成物を塗布した試験片の塗布面に大量の異物が確認され、画像露光以降の工程を実施することができなかった。異物は未溶解の光重合開始剤であった。
The photopolymerization initiator in Example 21 was changed to 1- (9-ethyl-6-nitrocarbazol-3-yl) ethanone = O-acetyloxime (a compound represented by the following formula (27)), and others were as in Example. In the same manner as in No. 21, a photosensitive composition was prepared and evaluated. As a result, a large amount of foreign matter was confirmed on the coated surface of the test piece coated with the photosensitive composition, and the steps after image exposure could not be performed. The foreign matter was an undissolved photopolymerization initiator.
本発明の光重合開始剤は、高感度かつ溶解性に優れることから、フォトレジスト、光硬化型インキ、光硬化型塗料、光硬化型接着剤、光造形用感光性樹脂、感光性印刷版、記録材料等に適して用いることができる。特に、カラーフィルターの製造に用いられるフォトレジストのように、高性能を要求される用途に最適である。
Since the photopolymerization initiator of the present invention is highly sensitive and excellent in solubility, a photoresist, a photocurable ink, a photocurable paint, a photocurable adhesive, a photopolymerization photosensitive resin, a photosensitive printing plate, It can be used suitably for recording materials and the like. In particular, it is optimal for applications that require high performance, such as photoresists used in the manufacture of color filters.
Claims (5)
- 置換基を有していてもよいインドール骨格にオキシムエステル結合を有する基が結合しており、かつインドール骨格が少なくとも１つのニトロ基で置換されていることを特徴とする光重合開始剤。 A photopolymerization initiator characterized in that a group having an oxime ester bond is bonded to an indole skeleton which may have a substituent, and the indole skeleton is substituted with at least one nitro group.
- インドール骨格の３位に下記一般式（１）で表されるオキシムエステル結合を有する基が直接又はカルボニル基を介して結合し、かつインドール骨格の５位がニトロ基で置換されている請求項１に記載の光重合開始剤。
－Ｃ（Ｒ１１）＝Ｎ－Ｏ－Ｃ（Ｒ１２）＝Ｏ （１）
（ただし、Ｒ１１及びＲ１２は置換基を有していてもよい炭素原子数１～２０の飽和又は不飽和の一価の有機基を表す。Ｒ１１及びＲ１２は分岐構造や環構造を形成していてもよく、任意の位置にヘテロ原子が存在していてもよい。また、Ｒ１１はインドール骨格上の置換基と結合していてもよい。更に、Ｒ１１は水素原子でもよい。） A group having an oxime ester bond represented by the following general formula (1) is bonded to the 3-position of the indole skeleton directly or via a carbonyl group, and the 5-position of the indole skeleton is substituted with a nitro group. The photoinitiator described in 1.
-C (R 11 ) = NOC (R 12 ) = O (1)
(However, R 11 and R 12 each represent a saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms which may have a substituent. R 11 and R 12 represent a branched structure or a ring structure. And a hetero atom may be present at any position, R 11 may be bonded to a substituent on the indole skeleton, and R 11 may be a hydrogen atom. ) - オレフィン結合を有する重合性化合物及び請求項１又は２に記載の光重合開始剤を含有する感光性組成物。 The photosensitive composition containing the polymeric compound which has an olefin bond, and the photoinitiator of Claim 1 or 2.
- 溶剤としてプロピレングリコールモノメチルエーテルアセテートを含有する請求項３に記載の感光性組成物。 The photosensitive composition according to claim 3 containing propylene glycol monomethyl ether acetate as a solvent.
- 請求項３又は４に記載の感光性組成物を硬化した硬化物。 Hardened | cured material which hardened | cured the photosensitive composition of Claim 3 or 4.
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| JP2013523889A JP5944898B2 (en) | 2011-07-08 | 2012-06-29 | Photopolymerization initiator, photosensitive composition and cured product |
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| WO2015120097A2 (en) | 2014-02-04 | 2015-08-13 | Contrafect Corporation | Antibodies useful in passive influenza immunization, and compositions, combinations and methods for use thereof |
| WO2015152153A1 (en) * | 2014-04-04 | 2015-10-08 | 株式会社Adeka | Oxime ester compound and photopolymerization initiator containing said compound |
| WO2017051680A1 (en) * | 2015-09-25 | 2017-03-30 | 株式会社Adeka | Oxime ester compound and polymerization initiator containing said compound |
| KR20180041622A (en) * | 2015-08-17 | 2018-04-24 | 가부시키가이샤 아데카 | Composition |
| WO2018191237A1 (en) * | 2017-04-12 | 2018-10-18 | Sun Chemical Corporation | Stable photoresist compositions comprising organosulphur compounds |
| WO2021049489A1 (en) * | 2019-09-10 | 2021-03-18 | 株式会社Adeka | Compound, acid-generating agent, composition, cured product, pattern, and methods for producing cured product and pattern |
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- 2012-06-29 JP JP2013523889A patent/JP5944898B2/en not_active Expired - Fee Related
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| JP2005128483A (en) * | 2003-06-10 | 2005-05-19 | Mitsubishi Chemicals Corp | Photopolymerizable composition, color filter and liquid crystal display device |
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| WO2015120097A2 (en) | 2014-02-04 | 2015-08-13 | Contrafect Corporation | Antibodies useful in passive influenza immunization, and compositions, combinations and methods for use thereof |
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| KR102369426B1 (en) * | 2014-04-04 | 2022-03-03 | 가부시키가이샤 아데카 | Oxime ester compound and photopolymerization initiator containing said compound |
| KR102555632B1 (en) * | 2015-08-17 | 2023-07-14 | 가부시키가이샤 아데카 | composition |
| KR20180041622A (en) * | 2015-08-17 | 2018-04-24 | 가부시키가이샤 아데카 | Composition |
| EP3339331A4 (en) * | 2015-08-17 | 2019-05-01 | Adeka Corporation | Composition |
| JPWO2017051680A1 (en) * | 2015-09-25 | 2018-07-12 | 株式会社Adeka | Oxime ester compound and polymerization initiator containing the compound |
| KR20180058657A (en) | 2015-09-25 | 2018-06-01 | 가부시키가이샤 아데카 | Oxime ester compound and polymerization initiator containing the compound |
| CN107635960B (en) * | 2015-09-25 | 2022-02-01 | 株式会社艾迪科 | Oxime ester compound and polymerization initiator containing the same |
| CN107635960A (en) * | 2015-09-25 | 2018-01-26 | 株式会社艾迪科 | Oxime ester compound and the polymerization initiator containing the compound |
| WO2017051680A1 (en) * | 2015-09-25 | 2017-03-30 | 株式会社Adeka | Oxime ester compound and polymerization initiator containing said compound |
| KR102604868B1 (en) | 2015-09-25 | 2023-11-22 | 가부시키가이샤 아데카 | Oxime ester compounds and polymerization initiators containing the compounds |
| WO2018191237A1 (en) * | 2017-04-12 | 2018-10-18 | Sun Chemical Corporation | Stable photoresist compositions comprising organosulphur compounds |
| WO2021049489A1 (en) * | 2019-09-10 | 2021-03-18 | 株式会社Adeka | Compound, acid-generating agent, composition, cured product, pattern, and methods for producing cured product and pattern |
| CN113727971A (en) * | 2019-09-10 | 2021-11-30 | 株式会社艾迪科 | Compound, acid generator, composition, cured product, pattern, and method for producing cured product and pattern |
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| Publication number | Publication date |
|---|---|
| JP5944898B2 (en) | 2016-07-05 |
| JPWO2013008652A1 (en) | 2015-02-23 |
| TW201315716A (en) | 2013-04-16 |
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