JP6195645B2 - 着色感光性組成物 - Google Patents
着色感光性組成物 Download PDFInfo
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- JP6195645B2 JP6195645B2 JP2016120040A JP2016120040A JP6195645B2 JP 6195645 B2 JP6195645 B2 JP 6195645B2 JP 2016120040 A JP2016120040 A JP 2016120040A JP 2016120040 A JP2016120040 A JP 2016120040A JP 6195645 B2 JP6195645 B2 JP 6195645B2
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- 239000000203 mixture Substances 0.000 title claims description 114
- 125000001424 substituent group Chemical group 0.000 claims description 282
- 125000004432 carbon atom Chemical group C* 0.000 claims description 159
- 150000001875 compounds Chemical class 0.000 claims description 148
- 125000000217 alkyl group Chemical group 0.000 claims description 144
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 128
- 229920000642 polymer Polymers 0.000 claims description 78
- 239000000178 monomer Substances 0.000 claims description 76
- 125000000962 organic group Chemical group 0.000 claims description 72
- 229920005989 resin Polymers 0.000 claims description 62
- 239000011347 resin Substances 0.000 claims description 62
- 125000001931 aliphatic group Chemical group 0.000 claims description 54
- 239000003999 initiator Substances 0.000 claims description 41
- 239000000758 substrate Substances 0.000 claims description 41
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 37
- 239000003086 colorant Substances 0.000 claims description 23
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 23
- 125000003118 aryl group Chemical group 0.000 claims description 22
- 229920001577 copolymer Polymers 0.000 claims description 21
- 125000004122 cyclic group Chemical group 0.000 claims description 20
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 12
- 238000004040 coloring Methods 0.000 claims description 9
- 229940125810 compound 20 Drugs 0.000 claims description 6
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 5
- 125000004429 atom Chemical group 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- ITOFPJRDSCGOSA-KZLRUDJFSA-N (2s)-2-[[(4r)-4-[(3r,5r,8r,9s,10s,13r,14s,17r)-3-hydroxy-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-17-yl]pentanoyl]amino]-3-(1h-indol-3-yl)propanoic acid Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H](CC[C@]13C)[C@@H]2[C@@H]3CC[C@@H]1[C@H](C)CCC(=O)N[C@H](C(O)=O)CC1=CNC2=CC=CC=C12 ITOFPJRDSCGOSA-KZLRUDJFSA-N 0.000 claims 1
- 206010034972 Photosensitivity reaction Diseases 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
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- -1 oxime ester compounds Chemical class 0.000 description 493
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- 125000000623 heterocyclic group Chemical group 0.000 description 72
- 229910052799 carbon Inorganic materials 0.000 description 50
- 125000001624 naphthyl group Chemical group 0.000 description 45
- 239000000049 pigment Substances 0.000 description 44
- 125000003545 alkoxy group Chemical group 0.000 description 40
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 32
- 230000015572 biosynthetic process Effects 0.000 description 31
- 125000002252 acyl group Chemical group 0.000 description 30
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- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 28
- 239000002904 solvent Substances 0.000 description 26
- 238000003786 synthesis reaction Methods 0.000 description 26
- 125000000753 cycloalkyl group Chemical group 0.000 description 25
- 239000002253 acid Substances 0.000 description 24
- 125000002723 alicyclic group Chemical group 0.000 description 24
- 125000003277 amino group Chemical group 0.000 description 23
- 125000001326 naphthylalkyl group Chemical group 0.000 description 23
- 125000003884 phenylalkyl group Chemical group 0.000 description 23
- 125000004423 acyloxy group Chemical group 0.000 description 22
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 21
- 125000003700 epoxy group Chemical group 0.000 description 21
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 20
- 238000005160 1H NMR spectroscopy Methods 0.000 description 18
- 150000001721 carbon Chemical group 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
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- 125000005322 morpholin-1-yl group Chemical group 0.000 description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 16
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 125000004093 cyano group Chemical group *C#N 0.000 description 15
- 125000000000 cycloalkoxy group Chemical group 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 229910052736 halogen Inorganic materials 0.000 description 14
- 150000002367 halogens Chemical class 0.000 description 14
- 125000001038 naphthoyl group Chemical group C1(=CC=CC2=CC=CC=C12)C(=O)* 0.000 description 14
- 125000004194 piperazin-1-yl group Chemical group [H]N1C([H])([H])C([H])([H])N(*)C([H])([H])C1([H])[H] 0.000 description 14
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 13
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- 125000002947 alkylene group Chemical group 0.000 description 12
- XSCHRSMBECNVNS-UHFFFAOYSA-N benzopyrazine Natural products N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 12
- 239000000975 dye Substances 0.000 description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 12
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 11
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 11
- 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 11
- 238000011156 evaluation Methods 0.000 description 11
- 125000005843 halogen group Chemical group 0.000 description 11
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 11
- 125000005702 oxyalkylene group Chemical group 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- 230000035945 sensitivity Effects 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 0 *CC1(*)COCCC1 Chemical compound *CC1(*)COCCC1 0.000 description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 150000002220 fluorenes Chemical class 0.000 description 10
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 10
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 239000003822 epoxy resin Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 229920000647 polyepoxide Polymers 0.000 description 9
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 9
- 239000011342 resin composition Substances 0.000 description 9
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 8
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 8
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 8
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 8
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 8
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 8
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 8
- 150000008065 acid anhydrides Chemical class 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 8
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 8
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 8
- 125000006678 phenoxycarbonyl group Chemical group 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 239000003513 alkali Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 125000006517 heterocyclyl carbonyl group Chemical group 0.000 description 7
- 239000000463 material Substances 0.000 description 7
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 7
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 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 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
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- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 6
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- 125000001309 chloro group Chemical group Cl* 0.000 description 6
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 6
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- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 6
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
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- FKMIBYMTHOJWCY-UHFFFAOYSA-N 2-(2-methylphenyl)acetyl chloride Chemical compound CC1=CC=CC=C1CC(Cl)=O FKMIBYMTHOJWCY-UHFFFAOYSA-N 0.000 description 5
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- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 5
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 5
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 5
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 5
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 5
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- 125000003136 n-heptyl 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])* 0.000 description 5
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 5
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
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- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 4
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 4
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- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 4
- VHMICKWLTGFITH-UHFFFAOYSA-N 2H-isoindole Chemical compound C1=CC=CC2=CNC=C21 VHMICKWLTGFITH-UHFFFAOYSA-N 0.000 description 4
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 4
- NRCMOYWFXMNDIO-UHFFFAOYSA-N 9,9-dipropylfluorene Chemical compound C1=CC=C2C(CCC)(CCC)C3=CC=CC=C3C2=C1 NRCMOYWFXMNDIO-UHFFFAOYSA-N 0.000 description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
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- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
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- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 4
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 4
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- MPOGZNTVZCEKSW-UHFFFAOYSA-N ethenyl 2-hydroxypropanoate Chemical compound CC(O)C(=O)OC=C MPOGZNTVZCEKSW-UHFFFAOYSA-N 0.000 description 1
- AFIQVBFAKUPHOA-UHFFFAOYSA-N ethenyl 2-methoxyacetate Chemical compound COCC(=O)OC=C AFIQVBFAKUPHOA-UHFFFAOYSA-N 0.000 description 1
- WNMORWGTPVWAIB-UHFFFAOYSA-N ethenyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC=C WNMORWGTPVWAIB-UHFFFAOYSA-N 0.000 description 1
- ZEYMDLYHRCTNEE-UHFFFAOYSA-N ethenyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OC=C ZEYMDLYHRCTNEE-UHFFFAOYSA-N 0.000 description 1
- VYATZCPFHGSBPG-UHFFFAOYSA-N ethenyl 3-phenylbutanoate Chemical compound C=COC(=O)CC(C)C1=CC=CC=C1 VYATZCPFHGSBPG-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
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- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
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- IJUHLFUALMUWOM-UHFFFAOYSA-N ethyl 3-methoxypropanoate Chemical compound CCOC(=O)CCOC IJUHLFUALMUWOM-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
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- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
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- HSDFKDZBJMDHFF-UHFFFAOYSA-N methyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OC HSDFKDZBJMDHFF-UHFFFAOYSA-N 0.000 description 1
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- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
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- 239000007870 radical polymerization initiator Substances 0.000 description 1
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- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005092 sublimation method Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
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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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/50—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals
- C07C251/56—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals of hydrocarbon radicals substituted by doubly-bound oxygen atoms
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
-
- 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
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
-
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Description
しかし、有彩色の着色剤と、上記構造式(a)〜(d)で表される化合物とを含む、感光性樹脂組成物を用いる場合、着色膜形成時の加熱により着色膜の色相が所望する色相と変わってしまったり、着色膜中に微小な異物が発生しやすかったりする問題がある。
また、光重合開始剤の種類によっては着色膜が基板から剥離しやすかったりする。
(A)重合性基材成分、(B)光重合開始剤、及び(C)有彩色の着色剤を含み、
(A)重合性基材成分が、光重合性化合物、又は光重合性化合物と樹脂とを含み、
(B)光重合開始剤が、下式(1):
で表される化合物を含む、着色感光性組成物である。
本発明にかかる着色感光性組成物(以下、「感光性組成物」とも記す。)は、(A)重合性基材成分、(B)光重合開始剤、及び(C)有彩色の着色剤を少なくとも含有する。以下、本発明の感光性組成物に含有される各成分について詳細に説明する。
(A)重合性基材成分(以下、「(A)成分」とも記す。)は、感光性組成物に光重合性と膜形成能とを付与する成分である。(A)重合性基材成分は、(B)光重合開始剤により重合可能な成分を含み、且つ膜形成可能な感光性組成物を調製可能な成分であれば特に限定されない。(A)重合性基材成分は、典型的には、光重合性化合物、又は光重合性化合物と樹脂とを含む。光重合性化合物は、低分子化合物であってもよく、樹脂のような高分子化合物であってもよい。
また、(A)重合性基材成分が樹脂を含む場合、アルカリ現像性の観点から、アルカリ可溶性樹脂を含むのが好ましい。アルカリ可溶性樹脂は、エチレン性不飽和基を含んでいてもよい。エチレン性不飽和基を含む(構成単位中の置換基としてエチレン性不飽和基を含む)アルカリ可溶性樹脂は、光重合性とアルカリ現像性との双方の観点から好ましい。
エチレン性不飽和基を含む樹脂としては、(メタ)アクリル酸、フマル酸、マレイン酸、フマル酸モノメチル、フマル酸モノエチル、2−ヒドロキシエチル(メタ)アクリレート、エチレングリコールモノメチルエーテル(メタ)アクリレート、エチレングリコールモノエチルエーテル(メタ)アクリレート、グリセロール(メタ)アクリレート、(メタ)アクリルアミド、アクリロニトリル、メタクリロニトリル、メチル(メタ)アクリレート、エチル(メタ)アクリレート、イソブチル(メタ)アクリレート、2−エチルヘキシル(メタ)アクリレート、ベンジル(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、ブチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(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、テトラメチロールプロパンテトラ(メタ)アクリレート、ペンタエリスリトールトリ(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、ジペンタエリスリトールペンタ(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、1,6−ヘキサンジオールジ(メタ)アクリレート、カルドエポキシジアクリレート等が重合したオリゴマー類;多価アルコール類と一塩基酸又は多塩基酸とを縮合して得られるポリエステルプレポリマーに(メタ)アクリル酸を反応させて得られるポリエステル(メタ)アクリレート;ポリオールと2個のイソシアネート基を持つ化合物とを反応させた後、(メタ)アクリル酸を反応させて得られるポリウレタン(メタ)アクリレート;ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、フェノール又はクレゾールノボラック型エポキシ樹脂、レゾール型エポキシ樹脂、トリフェノールメタン型エポキシ樹脂、ポリカルボン酸ポリグリシジルエステル、ポリオールポリグリシジルエステル、脂肪族又は脂環式エポキシ樹脂、アミンエポキシ樹脂、ジヒドロキシベンゼン型エポキシ樹脂等のエポキシ樹脂と、(メタ)アクリル酸とを反応させて得られるエポキシ(メタ)アクリレート樹脂等が挙げられる。さらに、エポキシ(メタ)アクリレート樹脂に多塩基酸無水物を反応させた樹脂を好適に用いることができる。なお、本明細書において、「(メタ)アクリル」は、「アクリル又はメタクリル」を意味する。
エチレン性不飽和基を有する構成単位におけるエチレン性不飽和基としては、(メタ)アクリロイルオキシ基が好ましい。
エチレン性不飽和基を有する構成単位を含む樹脂は、後述のその他のモノマー(A1me)やポリマー(A3)で挙げた単量体(化合物)を他の構成単位として含んでいてもよい。
光重合性モノマーには、単官能モノマーと多官能モノマーとがある。以下、単官能モノマー、及び多官能モノマーについて順に説明する。
アルカリ可溶性樹脂は、アルカリ可溶性を示す樹脂である。本明細書において、アルカリ可溶性を示す樹脂とは、樹脂濃度20質量%の樹脂溶液(溶媒:プロピレングリコールモノメチルエーテルアセテート)により、膜厚1μmの樹脂膜を基板上に形成し、濃度0.05質量%のKOH水溶液に1分間浸漬した際に、膜厚0.01μm以上溶解するものをいう。
以下、主鎖に環構造を有する構成単位を含有するポリマーと、不飽和結合を有する単量体の重合体とについて説明する。
主鎖に環構造を有する構成単位を含有するポリマーを、所定の環構造を有するとともに所定のアルカリ可溶性を備える樹脂であれば特に限定されない。主鎖に環構造を有する構成単位を含有するポリマーの好適な例として、マレイミド由来の構成単位(以下、「構成単位(A2a)」ともいう。)を含有するポリマー(以下、「ポリマー(A2)」ともいう。)及び下記式(A−1)で表される構成単位(以下、「構成単位(A1a)」ともいう。)を含有するポリマー(以下、「ポリマー(A1)」ともいう。)を挙げることができる。
このような炭化水素基の具体例としては、メチル、エチル、シクロヘキシル、ベンジル等が挙げられ、メチル基が好ましい。
該各構成単位(A1a)間で同一又は異なる環Aが含有される場合、R1及びR2は結合する各環Aの種類に依存することなく相互に独立である。
さらに、ポリマー(A1)を構成する一の主鎖に、上記式(A−3)で表される構成単位(構成単位(A1a1))と上記式(A−4)で表される構成単位(構成単位(A1a2))とが含有される場合、各構成単位(A1a1)におけるR1及びR2と各構成単位(A1a2)におけるR1及びR2とは同一であってもよいし異なっていてもよい。
不飽和結合を有する単量体の重合体(以下、「ポリマー(A3)」ともいう。)をアルカリ可溶性樹脂として用いる場合、当該アルカリ可溶性樹脂は、従来から種々の感光性組成物に配合されている不飽和結合を有する単量体の重合体から適宜選択できる。ポリマー(A3)は、単独重合体であっても共重合体であってもよい。
なお、下記式(a2−1)〜(a2−16)で表される化合物において、異性体が存在する場合には、下記式はいずれの異性体をも表すものとし、特定の異性体に限定されるものではない。特に、(a2−2)(a2−3)においては、いずれの異性体であっても好ましい。
共重合体(A4)及び共重合体(A5)は、エチレン性不飽和基を含むアルカリ可溶性樹脂に該当する。
ポリマー(A3)が共重合体(A4)、又は共重合体(A5)を含む場合、感光性組成物の基板への密着性、感光性組成物の硬化後の破壊強度が高い傾向にある。
アルカリ可溶性樹脂が、主鎖に環構造を有する構成単位を含有するポリマーと、不飽和結合を有する単量体の重合体とを、組み合わせて含む場合、両者の混合比は特に限定されない。主鎖に環構造を有する構成単位を含有するポリマーの質量と、不飽和結合を有する単量体の重合体の質量との合計に対する、主鎖に環構造を有する構成単位を含有するポリマーの質量の比率は、1〜99質量%が好ましく、10〜90質量%がより好ましく、30〜70質量%が特に好ましい。
感光性組成物中のアルカリ可溶性樹脂として、エチレン性不飽和基を含む(構成単位中の置換基としてエチレン性不飽和基を含む)アルカリ可溶性樹脂を含む場合は、感光性組成物の固形分の質量に対して、60質量%以下が好ましく、45〜10質量%がより好ましく、50〜15質量%が特に好ましい。また、(A)重合性基材成分中の、アルカリ可溶性樹脂の含有量は、100質量%であってもよく、100〜30質量%が好ましい。
感光性組成物は、下記式(1)で表される化合物(B1)(以下、化合物(B1)とも記す。)を含む(B)光重合開始剤(以下、「(B)成分」とも記す。)を含有する。本発明の感光性組成物は、化合物(B1)を(B)光重合開始剤として含んでいるため、非常に感度に優れる。このため、本発明の感光性組成物を用いることで、低露光量で所望する形状のパターンを形成することが可能である。
また、感光性組成物が(B)光重合開始剤として化合物(B1)を含むことにより、基板への密着性が良好であり、異物をほとんど含まず、所望する色相である着色膜を形成することが出来る。
また、Rb1が水素原子であると、透明性が良好となる傾向があり好ましい。なお、Rb1が水素原子であり且つRb4が後述の式(R4−2)で表される基であると透明性はより良好となる傾向がある。
アルキル基が有してもよい置換基は、本発明の目的を阻害しない範囲で特に限定されない。置換基の好適な例としては、シアノ基、ハロゲン原子、環状有機基、及びアルコキシカルボニル基が挙げられる。ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。これらの中では、フッ素原子、塩素原子、臭素原子が好ましい。環状有機基としては、シクロアルキル基、芳香族炭化水素基、ヘテロシクリル基が挙げられる。シクロアルキル基の具体例としては、Rb1がシクロアルキル基である場合の好適な例と同様である。芳香族炭化水素基の具体例としては、フェニル基、ナフチル基、ビフェニリル基、アントリル基、及びフェナントリル基等が挙げられる。ヘテロシクリル基の具体例としては、Rb1がヘテロシクリル基である場合の好適な例と同様である。Rb1がアルコキシカルボニル基である場合、アルコキシカルボニル基に含まれるアルコキシ基は、直鎖状でも分岐鎖状でもよく、直鎖状が好ましい。アルコキシカルボニル基に含まれるアルコキシ基の炭素原子数は、1〜10が好ましく、1〜6がより好ましい。
また、(B)成分である光重合開始剤の含有量は、(A)成分と(B)成分との総和に対し、0.1〜50質量%であることが好ましく、0.5〜30質量%であることがより好ましく、1〜20質量%であることがさらに好ましい。
化合物(B1)の含有量は、例えば(B)成分全体に対して1〜100質量%の範囲であればよく、好ましくは50質量%以上であり、70〜100質量%であることがより好ましい。
(i)Rb1が水素原子である化合物とRb1がニトロ基である化合物との組み合わせ
(ii)Rb4が式(R4−1)である化合物とRb4が式(R4−2)である化合物との組み合わせ
(iii)Rb4が式(R4−1)又は式(R4−2)である化合物とRb4が炭素原子数1〜4のアルキル基である化合物
中でも、感度及び硬化物の透過率等の特性向上の点で、上記(i)の組み合わせが好ましく、上記(i)と、(ii)又は(iii)とを満たす組み合わせがより好ましい。
vが1である場合、化合物(B1)を含有する感光性組成物を用いて形成されるパターン中での異物の発生をより低減できる傾向がある。
アルキル基が炭素原子上に有してもよい好適な置換基の例としては、炭素数1〜20のアルコキシ基、炭素数3〜10のシクロアルキル基、炭素数3〜10のシクロアルコキシ基、炭素数2〜20の飽和脂肪族アシル基、炭素数2〜20のアルコキシカルボニル基、炭素数2〜20の飽和脂肪族アシルオキシ基、置換基を有してもよいフェニル基、置換基を有してもよいフェノキシ基、置換基を有してもよいフェニルチオ基、置換基を有してもよいベンゾイル基、置換基を有してもよいフェノキシカルボニル基、置換基を有してもよいベンゾイルオキシ基、置換基を有してもよい炭素数7〜20のフェニルアルキル基、置換基を有してもよいナフチル基、置換基を有してもよいナフトキシ基、置換基を有してもよいナフトイル基、置換基を有してもよいナフトキシカルボニル基、置換基を有してもよいナフトイルオキシ基、置換基を有してもよい炭素数11〜20のナフチルアルキル基、置換基を有してもよいヘテロシクリル基、置換基を有してもよいヘテロシクリルカルボニル基、アミノ基、1又は2の有機基で置換されたアミノ基、モルホリン−1−イル基、及びピペラジン−1−イル基、ハロゲン、ニトロ基、及びシアノ基等が挙げられる。
フェニル基が炭素原子上に有してもよい好適な置換基の例としては、アルキル基が炭素原子上に有してもよい好適な置換基として上記で例示した基に加えて、炭素数1〜20のアルキル基が挙げられる。
(B)光重合開始剤が化合物(B1)と開始剤(B2)からなる場合、質量比((B1):(B2))は、0.1:99.9〜99.9:0.1が好ましく、1:99〜99:1がより好ましく、10:90〜90:10が特に好ましい。
感光性組成物は、(C)有彩色の着色剤(以下、「(C)成分」とも記す。)を含む。有彩色から選択される異なる数種の色相を組み合わせてカラーフィルタを構成することにより、カラー画像を表示可能な表示素子を得ることができる。
感光性組成物が、前述の(B)光重合開始剤と、(C)有彩色の着色剤とを組み合わせて含むことにより、膜形成時の着色膜の変色が抑制され、所望する色相の着色膜を形成することができる。
なお、(C)成分は、色相調整の目的で、黒、白等の無彩色の着色剤を少量含んでいてもよい。
C.I.ピグメントオレンジ1(以下、「C.I.ピグメントオレンジ」は同様であり、番号のみを記載する。)、5、13、14、16、17、24、34、36、38、40、43、46、49、51、55、59、61、63、64、71、73;
C.I.ピグメントバイオレット1(以下、「C.I.ピグメントバイオレット」は同様であり、番号のみを記載する。)、19、23、29、30、32、36、37、38、39、40、50;
C.I.ピグメントレッド1(以下、「C.I.ピグメントレッド」は同様であり、番号のみを記載する。)、2、3、4、5、6、7、8、9、10、11、12、14、15、16、17、18、19、21、22、23、30、31、32、37、38、40、41、42、48:1、48:2、48:3、48:4、49:1、49:2、50:1、52:1、53:1、57、57:1、57:2、58:2、58:4、60:1、63:1、63:2、64:1、81:1、83、88、90:1、97、101、102、104、105、106、108、112、113、114、122、123、144、146、149、150、151、155、166、168、170、171、172、174、175、176、177、178、179、180、185、187、188、190、192、193、194、202、206、207、208、209、215、216、217、220、223、224、226、227、228、240、242、243、245、254、255、264、265;
C.I.ピグメントブルー1(以下、「C.I.ピグメントブルー」は同様であり、番号のみを記載する。)、2、15、15:3、15:4、15:6、16、22、60、64、66;
C.I.ピグメントグリーン7、C.I.ピグメントグリーン36、C.I.ピグメントグリーン37、ピグメントグリーン58、ピグメントグリーン59、ピグメントグリーン60;
C.I.ピグメントブラウン23、C.I.ピグメントブラウン25、C.I.ピグメントブラウン26、C.I.ピグメントブラウン28;
C.I.ピグメントブラック1、C.I.ピグメントブラック7。
RGBのブルー及びグリーンにおいては、C.I.ピグメントグリーン36、58又はC.I.ピグメントブルー15:3、15:4、15:6等のフタロシアニン系顔料を含むことが好ましい。フタロシアニン系顔料は、(C)成分全体の10質量%以上が好ましく、30質量%以上がより好ましく、40質量%以上がさらに好ましく、100質量%であってもよい。2種以上組み合わせる場合、フタロシアニン系顔料は、(C)成分全体の30〜99質量%がより好ましく、40〜97質量%がさらに好ましい。
フタロシアニン系顔料系顔料に組み合わせる他の(C)成分は、顔料又は染料であってよい。
ブルーの場合は、他の(C)成分として、C.I.ピグメントバイオレット23等のジオキサジン系紫顔料、又は染料(染料について好ましくはローダミンB等のブルー系のキサンテン系染料又ベーシックブルー7等のブルー系のトリアリールメタン系染料)が好適に挙げられる。他の(C)成分は複数種用いてもよい。当該組み合わせる他の(C)成分の比率は例えば1〜50質量%であり、1〜25質量%が好ましい。
グリーンの場合は、グリーン系のフタロシアニン系顔料系顔料に組み合わせる他の(C)成分として、C.I.ピグメントイエロー150等のニッケル錯体系黄色顔料、上記ブルー系のフタロシアニン系顔料又は染料(染料について好ましくは、ブリリアントグリーン等のグリーン系のトリアリールメタン系染料)等が好適に挙げられる。他の(C)成分は複数種用いてもよい。当該組み合わせる他の(C)成分の比率は例えば1〜70質量%であり、1〜50質量%が好ましい。
本発明に係る感光性組成物には、必要に応じて、各種の添加剤を加えてもよい。具体的には、溶剤、増感剤、硬化促進剤、光架橋剤、光増感剤、分散助剤、充填剤、密着促進剤、酸化防止剤、紫外線吸収剤、凝集防止剤、熱重合禁止剤、消泡剤、界面活性剤等が例示される。
本発明に係る感光性組成物は、上記の各成分を全て撹拌機で混合することにより調製される。なお、調製された感光性組成物が均一なものとなるようフィルタを用いて濾過してもよい。
各成分を混合する順番は特に限定されない。例えば、光重合性モノマーと、(C)光重合開始剤との混合物に、他の成分を配合して感光性組成物を調製してもよい。また、樹脂と(C)光重合開始剤との混合物に、他の成分を配合して感光性組成物を調製してもよい。
本発明の感光性組成物を用いてパターンを形成するには、まず、ロールコータ、リバースコータ、バーコータ等の接触転写型塗布装置やスピンナー(回転式塗布装置)、カーテンフローコータ等の非接触型塗布装置を用いて、基板上に感光性組成物を塗布する。
(9,9−ジ−n−プロピルフルオレンの合成)
フルオレン6.64g(40mmol)を27mLのTHFに溶解させた。得られた溶液に、カリウムtert−ブトキシド0.12g(1.1mmol)、1−ブロモプロパン12.30g(100mmol)、及び濃度50質量%の水酸化ナトリウム水溶液27mLを、窒素雰囲気下で徐々に添加した。得られた混合物を、80℃で3時間撹拌して反応を行った。反応後の混合物に、酢酸エチル33g及び水33gを加えた後、有機層と水層とに分液した。得られた有機層を無水硫酸ナトリウムで脱水した後、ロータリーエバポレーターを用いて有機層から溶媒を除去して、9,9−ジ−n−プロピルフルオレン8.32g(収率83%)を得た。
(化合物6の合成)
9,9−ジ−n−プロピルフルオレン4.10g(16.37mmol)と、(2−メチルフェニル)酢酸塩化物3.04g(18.00mmol)とを、塩化アルミニウム2.62gの存在下に、ジクロロメタン溶媒、50ml中で、氷冷下で1時間反応させた。反応混合物を氷水にあけ、有機層を分液した。回収した有機層を無水硫酸マグネシウムで乾燥後、エバポレートした。残渣を酢酸エチル/ヘキサン=1/2の溶離液でシリカゲルカラム精製して、2−(2−メチルフェニル)アセチル−9,9−ジ−n−プロピルフルオレン5.95g(15.55mmol)を得た。2−(2−メチルフェニル)アセチル−9,9−ジ−n−プロピルフルオレン5.95g(15.55mmol)と、濃塩酸1.60g(15.55mmol)とを、亜硝酸イソブチル2.42g(23.33mmol)の存在下に、ジメチルホルムアミド溶媒25ml中で、氷冷下で3時間反応させた。反応液をエバポレートし、残渣に酢酸エチルを加え、飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥後、エバポレートして、下記構造の2−[2−メチルフェニル(ヒドロキシイミノ)アセチル]−9,9−ジ−n−プロピルフルオレン4.80g(11.67mmol)を得た。
1H−NMR(600MHz,CDCl3,ppm):8.60(bs,1H),8.15(d,1H),8.14(s,1H),7.76−8.00(m,2H),7.26−7.53(m,7H),2.35(s,3H),1.98−2.01(m,4H),0.63−0.67(m,10H)
1H−NMR(600MHz,CDCl3,ppm):8.25(d,1H),8.22(s,1H),7.83(d,1H),7.81(dd,1H),7.33−7.40(m,3H),7.26−7.33(m,4H),2.35(s,3H),2.14(s,3H),1.95−2.07(m,4H),0.63−0.66(m,10H).
(化合物7の合成)
(2−メチルフェニル)酢酸塩化物3.04g(18.00mmol)を、3−シクロヘキシルプロピオン酸塩化物3.14g(18.00mmol)に変えることの他は、合成例2と同様にして、中間体である下記構造の2−[シクロヘキシルメチル(ヒドロキシイミノ)アセチル]−9,9−ジ−n−プロピルフルオレンと、化合物7、4.96g(10.80mmol、収率75%)とを得た。
1H−NMR(600MHz,CDCl3,ppm):8.80(bs,1H),7.90−7.98(m,2H),7.70−7.80(m,2H),7.30−7.40(m,3H),2.72(d,2H),1.88−2.02(m,4H),1.54−1.80(m,6H),0.95−1.28(m,5H),0.67−0.77(m,10H)
1H−NMR(600MHz,CDCl3,ppm):8.08−8.14(m,2H),7.70−7.79(m,2H),7.32−7.40(m,3H),2.78(d,2H),2.28(s,3H),1.88−2.10(m,4H),1.53−1.78(m,6H),1.00−1.30(m,5H),0.60−0.77(m,10H).
〔合成例4〕
(化合物9の合成)
(2−メチルフェニル)酢酸塩化物3.04g(18.00mmol)を3−シクロペンチルプロピオン酸塩化物2.89g(18.00mmol)に変えることの他は、合成例2と同様にして、化合物9、4.46g(10.02mmol、収率72%)を得た。化合物9の1H−NMRの測定結果は以下の通りであった。
1H−NMR(600MHz,CDCl3,ppm):8.06−8.12(m,2H),7.71−7.78(m,2H),7.31−7.40(m,3H),2.52(d,2H),2.27(s,3H),1.89−2.19(m,5H),1.48−1.80(m,6H),1.19−1.26(m,2H),0.61−0.77(m,10H).
(化合物10の合成)
(2−メチルフェニル)酢酸塩化物3.04g(18.00mmol)を(α−ナフチル)酢酸塩化物3.68g(18.00mmol)に変えることの他は、合成例2と同様にして、化合物10、5.29g(10.80mmol、収率78%)を得た。化合物10の1H−NMRの測定結果は以下の通りであった。
1H−NMR(600MHz,CDCl3,ppm):8.26(d,1H),8.24(s,1H),7.82(d,1H),7.82(dd,1H),7.30−7.70(m,10H),2.14(s,3H),1.94−2.05(m,4H),0.62−0.66(m,10H).
(化合物11の合成)
(2−メチルフェニル)酢酸塩化物3.04g(18.00mmol)を1,1’−ビフェニル−2−酢酸塩化物4.15g(18.00mmol)に変えることの他は、合成例2と同様にして、化合物11、5.36g(10.40mmol、収率73%)を得た。化合物11の1H−NMRの測定結果は以下の通りであった。
1H−NMR(600MHz,CDCl3,ppm):8.22(d,1H),8.19(s,1H),7.84(d,1H),7.83(dd,1H),7.20−7.45(m,12H),2.15(s,3H),1.94−2.07(m,4H),0.63−0.66(m,10H).
(化合物20の合成)
9,9−ジ−n−プロピルフルオレン4.10g(16.37mmol)と、フェニル酢酸塩化物2.78g(18.00mmol)とを、塩化アルミニウム2.62gの存在下に、ジクロロメタン溶媒、50ml中で、氷冷下で1時間反応させた。反応混合物を氷水にあけ、有機層を分液した。回収した有機層を無水硫酸マグネシウムで乾燥後、エバポレートした。残渣を酢酸エチル/ヘキサン=1/2の溶離液でシリカゲルカラム精製して、2−フェニルアセチル−9,9−ジ−n−プロピルフルオレンを得た。2−フェニルアセチル−9,9−ジ−n−プロピルフルオレン5.73g(15.55mmol)と、濃塩酸1.60g(15.55mmol)とを、亜硝酸イソブチル2.42g(23.33mmol)の存在下に、ジメチルホルムアミド溶媒25ml中で、氷冷下で3時間反応させた。反応液をエバポレートし、残渣に酢酸エチルを加え、飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥後、エバポレートして、下記構造の2−[フェニル(ヒドロキシイミノ)アセチル]−9,9−ジ−n−プロピルフルオレンを得た。
1H−NMR(600MHz,CDCl3,ppm):8.05(s,1H),7.76−7.92(m,2H),7.75(m,2H),7.61(m,2H),7.30−7.41(m,5H),1.92−2.05(m,4H),0.58−0.70(m,10H).
1H−NMR(600MHz,CDCl3,ppm):7.97(s,1H),7.87(dd,1H),7.74−7.79(m,4H),7.72−7.80(m,1H),7.35−7.52(m,5H),1.95−2.03(m,4H),1.94(s,3H),0.58−0.65(m,10H).
A1:下式のエチレン性不飽和基を含むアルカリ可溶性樹脂。
A2:下記合成例8で得られた主鎖に環構造を有する構成単位を含有するポリマー。
A3:下記合成例9で得られた主鎖に環構造を有する構成単位を含有するポリマー。
A4:上記式(a2−2)において、R11がメチル基であるモノマー/メタクリル酸/トリシクロデシルメタクリレート=72/18/10(質量比)、質量平均分子量14000)のアルカリ可溶性樹脂(ただし、上記式(a2−2)において、R11がメチル基であるモノマーは、メタクリル酸3,4−エポキシトリシクロ−[5.2.1.02,6]デカン−8(又は9)−イルの異性体混合物からなる)。
A5:ジペンタエリスリトールヘキサアクリレート(光重合性モノマー)。
反応槽として冷却管を付けたセパラブルフラスコを用いた。反応槽に、プロピレングリコールモノメチルエーテルアセテート(PGMEA)を仕込み、窒素置換した後、撹拌しながらオイルバスで加熱して反応槽の温度を90℃まで上げた。
他方、モノマー槽にジメチル−2,2’−[オキシビス(メチレン)]ビス−2−プロペノエート(MD)40質量部、メタクリル酸(MAA)32質量部、メタクリル酸メチル(MMA)68質量部、メタクリル酸シクロヘキシル(CHMA)60質量部、t−ブチルパーオキシ−2−エチルヘキサノエート(PBO)2.6質量部、PGMEA40質量部を混合した。
また、連鎖移動剤槽にn−ドデシルメルカプタン5.2質量部、PGMEA27質量部を混合した。
反応槽の温度が90℃に安定してから、モノマー槽及び連鎖移動剤槽から反応槽への滴下を開始し、重合を開始させた。温度を90℃に保ちながら、モノマー槽及び連鎖移動剤槽からの滴下をそれぞれ135分かけて行った。滴下が終了して60分後に昇温を開始して、反応槽の内温を110℃まで上げた。3時間、110℃を維持したあと、反応槽の内容物を室温まで冷却し、A2の溶液を得た。
ジメチル−2,2’−[オキシビス(メチレン)]ビス−2−プロペノエート(MD)40質量部を、N−ベンジルマレイミド40質量部に変更することの他は、合成例8と同様にして、A3の溶液を得た。
C1:C.I.ピグメントレッド254
C2:C.I.ピグメントイエロー139
C3:C.I.ピグメントブルー15:6
C4:C.I.ピグメントバイオレット23
C5:C.I.ピグメントグリーン36
C6:C.I.ピグメントイエロー150
C7:ローダミンB(染料、東京化成工業製)
C8:ベーシックブルー7(染料、東京化成工業製)
C9:ブリリアントグリーン(染料、和光純薬工業製)
表1に記載の種類及び量の(A)重合性基材成分と、表1に記載の種類の(B)光重合開始剤5質量部と、表1に記載の種類及び質量比であり総量50質量部の(C)有彩色の着色剤とを、溶剤中に固形分濃度が15質量%になるように均一に分散・溶解させて、各実施例及び比較例の感光性組成物を得た。
なお、実施例25及び26では、光重合開始剤として、1質量部の化合物6と、4質量部の比較化合物2とを組み合わせて用いた。
実施例1〜36、及び比較例1〜9の感光性組成物それぞれについて、以下の手順にて、パターン剥離の評価を行った。
まず、感光性組成物をガラス基板(10cm×10cm)にスピン塗布し、90℃にて120秒間加熱することにより、ガラス基板の表面に膜厚2.0μmの塗布膜を形成した。その後、塗布膜を、露光量50、又は200mJ/cm2で露光した。露光後の膜を、26℃の0.04質量%KOH水溶液で30〜50秒間現像後、30μm寸法・マトリックス形状のパターンを備える着色膜を得た。
得られたパターンについて、顕微鏡を用いて剥離の有無を観察した。パターンの剥離の有無を表2に記す。
実施例1〜36、及び比較例1〜9の感光性組成物それぞれについて、以下の手順にて、着色評価を行った。
まず、感光性組成物をガラス基板(10cm×10cm)にスピン塗布し、90℃にて120秒間加熱することにより、ガラス基板の表面に1.0μmの塗布膜を形成した。その後、塗布膜を、露光量200mJ/cm2で露光した。露光後の膜を、26℃の0.04質量%KOH水溶液で30〜50秒間現像後、230℃―30分間でポストベークを行った。瞬間マルチ測光システム(MCPD−3000:大塚電子株式会社製)を用いて、ポストベーク前後の塗布膜の380nm〜780nm波長域の透過率の差の絶対値ΔYを測定した。ΔYの値に基づいて、以下の基準に従って着色を評価した。着色評価の結果を表2に記す。
○:ΔYの値が0.5以下
△:ΔYの値が0.5超0.7以下
×:ΔYの値が0.7超
実施例1〜36、及び比較例1〜9の感光性組成物それぞれについて、以下の手順にて、異物評価を行った。
まず、感光性組成物をガラス基板(680mm×880mm)にスピン塗布し、90℃にて120秒間加熱することにより、ガラス基板の表面に膜厚2.0μmの塗布膜を形成した。その後、塗布膜を、露光量90mJ/cm2で露光した。露光後の膜を、26℃の0.04質量%KOH水溶液で30〜50秒間現像を行い、6μmマトリックスパターンを備える着色膜を得た。
得られた着色膜について、TAKANO社製の外観検査装置を用いて100μm径以上の異物の個数を測定した。異物の個数に基づいて、以下の基準に従って評価した。異物の評価結果を表2に記す。
◎:異物数0
○:異物数1又は2
△:異物数3〜5
×:異物数6以上
他方、比較例によれば、有彩色の着色剤を含む感光性組成物に、式(1)以外の構造の光重合開始剤を配合する場合、膜形成時の加熱により着色膜が変色しやすく、着色膜中の異物量が多く、着色膜の基板からの剥離が生じやすいことが分かる。
Claims (14)
- (A)重合性基材成分、(B)光重合開始剤、及び(C)有彩色の着色剤を含み、
前記(A)重合性基材成分が、光重合性化合物、又は光重合性化合物と樹脂とを含み、
前記(B)光重合開始剤が、下式(1):
で表される化合物(但し、下記化合物D−17を除く。)を含む、着色感光性組成物。
- (A)重合性基材成分、(B)光重合開始剤、及び(C)有彩色の着色剤を含み、
前記(A)重合性基材成分が、光重合性化合物、又は光重合性化合物と樹脂とを含み、
前記(B)光重合開始剤が、下式(1):
で表される化合物を含む、着色感光性組成物。
- (A)重合性基材成分、(B)光重合開始剤、及び(C)有彩色の着色剤を含み、
前記(A)重合性基材成分が、光重合性化合物、又は光重合性化合物と樹脂とを含み、
前記(B)光重合開始剤が、下式(1):
で表される化合物を含む、着色感光性組成物。 - 前記(A)重合性基材成分が、光重合性モノマー、及び/又はエチレン性不飽和基を含む樹脂を含むことを特徴とする請求項1〜6のいずれか1項に記載の着色感光性組成物。
- 前記(A)重合性基材成分が、エチレン性不飽和基を有していてもよいアルカリ可溶性樹脂を含む、請求項1〜7のいずれか1項に記載の着色感光性組成物。
- 前記光重合性化合物が、(a1)不飽和カルボン酸と、(a2−I)多環の脂環式エポキシ基を有する不飽和化合物とを含む共重合体を含む、請求項1〜5のいずれか1項に記載の着色感光性組成物。
- 前記(A)重合性基材成分が、光重合性モノマーを含む、請求項9又は10に記載の着色感光性組成物。
- 前記(C)有彩色の着色剤が分散剤を含む、請求項1〜11のいずれか1項に記載の着色感光性組成物。
- 請求項1〜12のいずれか1項に記載の着色感光性組成物を用いて形成されたカラーフィルタ。
- 請求項13に記載のカラーフィルタを備える表示装置。
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