WO2022270349A1 - 感光性赤色樹脂組成物、硬化物、カラーフィルタ、表示装置 - Google Patents
感光性赤色樹脂組成物、硬化物、カラーフィルタ、表示装置 Download PDFInfo
- Publication number
- WO2022270349A1 WO2022270349A1 PCT/JP2022/023753 JP2022023753W WO2022270349A1 WO 2022270349 A1 WO2022270349 A1 WO 2022270349A1 JP 2022023753 W JP2022023753 W JP 2022023753W WO 2022270349 A1 WO2022270349 A1 WO 2022270349A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- mass
- general formula
- resin composition
- carbon atoms
- Prior art date
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 124
- 239000011347 resin Substances 0.000 claims abstract description 81
- 229920005989 resin Polymers 0.000 claims abstract description 81
- 239000002904 solvent Substances 0.000 claims abstract description 76
- 239000002270 dispersing agent Substances 0.000 claims abstract description 62
- 229920001400 block copolymer Polymers 0.000 claims abstract description 47
- 150000001875 compounds Chemical class 0.000 claims abstract description 47
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 47
- 239000000049 pigment Substances 0.000 claims abstract description 44
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000002834 transmittance Methods 0.000 claims abstract description 31
- 239000001054 red pigment Substances 0.000 claims abstract description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 79
- 150000002430 hydrocarbons Chemical class 0.000 claims description 71
- 239000000758 substrate Substances 0.000 claims description 68
- 238000004040 coloring Methods 0.000 claims description 65
- 239000000463 material Substances 0.000 claims description 62
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 60
- 125000001424 substituent group Chemical group 0.000 claims description 36
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 34
- 125000005647 linker group Chemical group 0.000 claims description 29
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 27
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 125000002947 alkylene group Chemical group 0.000 claims description 18
- 239000003963 antioxidant agent Substances 0.000 claims description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 18
- 125000005842 heteroatom Chemical group 0.000 claims description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 13
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 230000003078 antioxidant effect Effects 0.000 claims description 10
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 9
- 125000004185 ester group Chemical group 0.000 claims description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000003086 colorant Substances 0.000 abstract description 38
- 239000002250 absorbent Substances 0.000 abstract description 8
- 230000002745 absorbent Effects 0.000 abstract description 8
- 239000010410 layer Substances 0.000 description 126
- -1 oxime ester Chemical class 0.000 description 83
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 65
- 238000011161 development Methods 0.000 description 65
- 230000018109 developmental process Effects 0.000 description 65
- 238000000034 method Methods 0.000 description 55
- 239000000178 monomer Substances 0.000 description 51
- 229920000642 polymer Polymers 0.000 description 49
- 239000006185 dispersion Substances 0.000 description 42
- 239000010408 film Substances 0.000 description 38
- 239000000243 solution Substances 0.000 description 38
- 229920001577 copolymer Polymers 0.000 description 35
- 239000004973 liquid crystal related substance Substances 0.000 description 32
- 239000006096 absorbing agent Substances 0.000 description 31
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 27
- 238000000576 coating method Methods 0.000 description 25
- 125000000217 alkyl group Chemical group 0.000 description 24
- 239000011248 coating agent Substances 0.000 description 22
- 238000004519 manufacturing process Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 21
- 230000009477 glass transition Effects 0.000 description 19
- 125000001931 aliphatic group Chemical group 0.000 description 18
- 230000000694 effects Effects 0.000 description 17
- 239000002245 particle Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 125000003118 aryl group Chemical group 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 14
- 239000003960 organic solvent Substances 0.000 description 13
- 150000008282 halocarbons Chemical class 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 10
- 125000003710 aryl alkyl group Chemical group 0.000 description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 10
- 238000005227 gel permeation chromatography Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 150000003512 tertiary amines Chemical class 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 8
- 125000003342 alkenyl group Chemical group 0.000 description 8
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 8
- 239000012964 benzotriazole Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 229920006243 acrylic copolymer Polymers 0.000 description 7
- 239000011324 bead Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 description 7
- 125000004430 oxygen atom Chemical group O* 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 150000001721 carbon Chemical group 0.000 description 6
- 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 6
- 238000010586 diagram Methods 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- 230000006870 function Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 6
- 238000004904 shortening Methods 0.000 description 6
- 229920000178 Acrylic resin Polymers 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 125000003277 amino group Chemical class 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 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
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 4
- 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
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 238000002356 laser light scattering Methods 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000004434 sulfur atom Chemical group 0.000 description 4
- 230000001629 suppression Effects 0.000 description 4
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 3
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 3
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- SEEVRZDUPHZSOX-UHFFFAOYSA-N [1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino] acetate Chemical compound C=1C=C2N(CC)C3=CC=C(C(C)=NOC(C)=O)C=C3C2=CC=1C(=O)C1=CC=CC=C1C SEEVRZDUPHZSOX-UHFFFAOYSA-N 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 3
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 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
- 238000010894 electron beam technology Methods 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000004210 ether based solvent Substances 0.000 description 3
- 229940116333 ethyl lactate Drugs 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000003827 glycol group Chemical group 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 239000007788 liquid 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
- WSFSSNUMVMOOMR-BJUDXGSMSA-N methanone Chemical compound O=[11CH2] WSFSSNUMVMOOMR-BJUDXGSMSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 239000012860 organic pigment Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000000059 patterning Methods 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 2
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-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
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- 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 2
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 description 2
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical group CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 2
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- AIJULSRZWUXGPQ-UHFFFAOYSA-N Methylglyoxal Chemical compound CC(=O)C=O AIJULSRZWUXGPQ-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical group C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical group C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229930016911 cinnamic acid Natural products 0.000 description 2
- 235000013985 cinnamic acid Nutrition 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 210000002858 crystal cell Anatomy 0.000 description 2
- 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000007607 die coating method Methods 0.000 description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical group C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- UHKJHMOIRYZSTH-UHFFFAOYSA-N ethyl 2-ethoxypropanoate Chemical compound CCOC(C)C(=O)OCC UHKJHMOIRYZSTH-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- RGFNRWTWDWVHDD-UHFFFAOYSA-N isobutyl butyrate Chemical compound CCCC(=O)OCC(C)C RGFNRWTWDWVHDD-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 2
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000001053 orange pigment Substances 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 125000003386 piperidinyl group Chemical group 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000007261 regionalization Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- 239000001052 yellow pigment Substances 0.000 description 2
- JNOGVQJEBGEKMG-UHFFFAOYSA-N (1-methoxy-2-methylprop-1-enoxy)-trimethylsilane Chemical compound COC(=C(C)C)O[Si](C)(C)C JNOGVQJEBGEKMG-UHFFFAOYSA-N 0.000 description 1
- RYNQKSJRFHJZTK-UHFFFAOYSA-N (3-methoxy-3-methylbutyl) acetate Chemical compound COC(C)(C)CCOC(C)=O RYNQKSJRFHJZTK-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- BNHGVULTSGNVIX-UHFFFAOYSA-N 1-(2-ethoxyethoxy)ethanol Chemical compound CCOCCOC(C)O BNHGVULTSGNVIX-UHFFFAOYSA-N 0.000 description 1
- SXYRTDICSOVQNZ-UHFFFAOYSA-N 1-(2-methoxyethoxy)ethanol Chemical compound COCCOC(C)O SXYRTDICSOVQNZ-UHFFFAOYSA-N 0.000 description 1
- ZKCJJGOOPOIZTE-UHFFFAOYSA-N 1-(4-hydroxyphenyl)pentan-1-one Chemical compound CCCCC(=O)C1=CC=C(O)C=C1 ZKCJJGOOPOIZTE-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- NKVCQMYWYHDOOF-UHFFFAOYSA-N 1-phenoxyethane-1,2-diol Chemical compound OCC(O)OC1=CC=CC=C1 NKVCQMYWYHDOOF-UHFFFAOYSA-N 0.000 description 1
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 description 1
- BJINVQNEBGOMCR-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethyl acetate Chemical compound COCCOCCOC(C)=O BJINVQNEBGOMCR-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- SITYOOWCYAYOKL-UHFFFAOYSA-N 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(3-dodecoxy-2-hydroxypropoxy)phenol Chemical compound OC1=CC(OCC(O)COCCCCCCCCCCCC)=CC=C1C1=NC(C=2C(=CC(C)=CC=2)C)=NC(C=2C(=CC(C)=CC=2)C)=N1 SITYOOWCYAYOKL-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical group CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- XUDBVJCTLZTSDC-UHFFFAOYSA-N 2-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=C XUDBVJCTLZTSDC-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- HHCHLHOEAKKCAB-UHFFFAOYSA-N 2-oxaspiro[3.5]nonane-1,3-dione Chemical compound O=C1OC(=O)C11CCCCC1 HHCHLHOEAKKCAB-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- MPAGVACEWQNVQO-UHFFFAOYSA-N 3-acetyloxybutyl acetate Chemical compound CC(=O)OC(C)CCOC(C)=O MPAGVACEWQNVQO-UHFFFAOYSA-N 0.000 description 1
- ZSPOJBDHHFFJAP-UHFFFAOYSA-M 3-chlorobenzoate;tetrabutylazanium Chemical compound [O-]C(=O)C1=CC=CC(Cl)=C1.CCCC[N+](CCCC)(CCCC)CCCC ZSPOJBDHHFFJAP-UHFFFAOYSA-M 0.000 description 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- ZEWLHMQYEZXSBH-UHFFFAOYSA-M 4-[2-(2-methylprop-2-enoyloxy)ethoxy]-4-oxobutanoate Chemical compound CC(=C)C(=O)OCCOC(=O)CCC([O-])=O ZEWLHMQYEZXSBH-UHFFFAOYSA-M 0.000 description 1
- 125000004801 4-cyanophenyl group Chemical group [H]C1=C([H])C(C#N)=C([H])C([H])=C1* 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- VMRIVYANZGSGRV-UHFFFAOYSA-N 4-phenyl-2h-triazin-5-one Chemical compound OC1=CN=NN=C1C1=CC=CC=C1 VMRIVYANZGSGRV-UHFFFAOYSA-N 0.000 description 1
- WDMFHQNUSVLQMS-UHFFFAOYSA-N 5-(3,3-dimethyl-2-bicyclo[2.2.1]heptanylidene)pent-3-en-2-one Chemical compound C1CC2C(C)(C)C(=CC=CC(=O)C)C1C2 WDMFHQNUSVLQMS-UHFFFAOYSA-N 0.000 description 1
- WIYVVIUBKNTNKG-UHFFFAOYSA-N 6,7-dimethoxy-3,4-dihydronaphthalene-2-carboxylic acid Chemical compound C1CC(C(O)=O)=CC2=C1C=C(OC)C(OC)=C2 WIYVVIUBKNTNKG-UHFFFAOYSA-N 0.000 description 1
- NUXLDNTZFXDNBA-UHFFFAOYSA-N 6-bromo-2-methyl-4h-1,4-benzoxazin-3-one Chemical compound C1=C(Br)C=C2NC(=O)C(C)OC2=C1 NUXLDNTZFXDNBA-UHFFFAOYSA-N 0.000 description 1
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- YYLLIJHXUHJATK-UHFFFAOYSA-N Cyclohexyl acetate Chemical compound CC(=O)OC1CCCCC1 YYLLIJHXUHJATK-UHFFFAOYSA-N 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Chemical group C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- RVWADWOERKNWRY-UHFFFAOYSA-N [2-(dimethylamino)phenyl]-phenylmethanone Chemical compound CN(C)C1=CC=CC=C1C(=O)C1=CC=CC=C1 RVWADWOERKNWRY-UHFFFAOYSA-N 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical group O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- UYAAVKFHBMJOJZ-UHFFFAOYSA-N diimidazo[1,3-b:1',3'-e]pyrazine-5,10-dione Chemical compound O=C1C2=CN=CN2C(=O)C2=CN=CN12 UYAAVKFHBMJOJZ-UHFFFAOYSA-N 0.000 description 1
- 229940077445 dimethyl ether Drugs 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical group C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 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
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000012156 elution solvent Substances 0.000 description 1
- NHOGGUYTANYCGQ-UHFFFAOYSA-N ethenoxybenzene Chemical compound C=COC1=CC=CC=C1 NHOGGUYTANYCGQ-UHFFFAOYSA-N 0.000 description 1
- IAJNXBNRYMEYAZ-UHFFFAOYSA-N ethyl 2-cyano-3,3-diphenylprop-2-enoate Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC)C1=CC=CC=C1 IAJNXBNRYMEYAZ-UHFFFAOYSA-N 0.000 description 1
- WHRLOJCOIKOQGL-UHFFFAOYSA-N ethyl 2-methoxypropanoate Chemical compound CCOC(=O)C(C)OC WHRLOJCOIKOQGL-UHFFFAOYSA-N 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- MJEMIOXXNCZZFK-UHFFFAOYSA-N ethylone Chemical compound CCNC(C)C(=O)C1=CC=C2OCOC2=C1 MJEMIOXXNCZZFK-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical group C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 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
- 125000000623 heterocyclic 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
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000001257 hydrogen Chemical group 0.000 description 1
- 229910052739 hydrogen Chemical group 0.000 description 1
- ILHIHKRJJMKBEE-UHFFFAOYSA-N hydroperoxyethane Chemical compound CCOO ILHIHKRJJMKBEE-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- JSLCOZYBKYHZNL-UHFFFAOYSA-N isobutyric acid butyl ester Natural products CCCCOC(=O)C(C)C JSLCOZYBKYHZNL-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 235000010746 mayonnaise Nutrition 0.000 description 1
- 239000008268 mayonnaise Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N methyl 2-hydroxypropionate Chemical compound COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Chemical group C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- FMJSMJQBSVNSBF-UHFFFAOYSA-N octocrylene Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC(CC)CCCC)C1=CC=CC=C1 FMJSMJQBSVNSBF-UHFFFAOYSA-N 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
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- MLCHBQKMVKNBOV-UHFFFAOYSA-N phenylphosphinic acid Chemical compound OP(=O)C1=CC=CC=C1 MLCHBQKMVKNBOV-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 229940116423 propylene glycol diacetate Drugs 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000001062 red colorant Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 239000011593 sulfur Substances 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
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005011 time of flight secondary ion mass spectroscopy Methods 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-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
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/12—Polymers provided for in subclasses C08C or C08F
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—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
- G03F7/004—Photosensitive materials
-
- 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
Definitions
- the present invention relates to a photosensitive red resin composition, a cured product, a color filter, and a display device.
- an organic light emitting element emitting white light or an inorganic light emitting element emitting white light may be used.
- An organic light-emitting display device uses a color filter for color adjustment.
- the color filter is generally formed on a substrate, a colored layer formed on the substrate and composed of colored patterns of the three primary colors of red, green, and blue, and formed on the substrate so as to partition each colored pattern. and a light shielding part.
- a method for forming a colored layer in a color filter for example, a colored resin composition obtained by adding a binder resin, a photopolymerizable compound and a photoinitiator to a coloring material dispersion liquid in which a coloring material is dispersed using a dispersing agent or the like is prepared. After being coated on a glass substrate and dried, it is exposed using a photomask and developed to form a colored pattern, which is fixed by heating to form a colored layer. These steps are repeated for each color to form a color filter.
- Patent Document 1 discloses a coloring agent (A), a resin (B), a photopolymerizable monomer (C), and an acylphosphine oxide-based A photopolymerization initiator (D) containing an organic compound or an oxime ester-based organic compound, and at least one UV absorber selected from the group consisting of benzotriazole-based organic compounds, triazine-based organic compounds, and benzophenone-based organic compounds ( E), and the resin (B) comprises the following (b1), (b2) and (b3): (b1); a compound having an alicyclic skeleton and an ethylenically unsaturated bond in one molecule (b2); a compound having an epoxy group and an ethylenically unsaturated bond in one molecule (b3); A compound having an ethylenically unsaturated bond other than (a2) is copolymerized to obtain a copolymer
- a photosensitive coloring composition which is characterized by In Patent Document 1, a photosensitive coloring composition having high resolution that can correspond to high image quality and low power consumption, in particular, high resolution even in a thick film such as the COA method, and adhesion that does not cause pattern peeling The object is to obtain an excellent photosensitive coloring composition.
- Patent Document 2 discloses a colorant (A), a resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D), a benzotriazole-based monomer and other monomers.
- a coloring composition for a color filter characterized by comprising an ultraviolet absorber (E) obtained by polymerizing raw material monomers containing a monomer component, wherein a benzotriazole-based monomer is included in the raw material monomers. 10.0% by mass to 90.0% by mass of the body, and the ultraviolet absorber (E) is contained in the solid content of the entire color filter coloring composition in an amount of 0.5 to 6.0% by mass.
- Coloring compositions for filters are disclosed.
- Patent Document 2 aims at providing a coloring composition for color filters which is excellent in light resistance even when a finely divided pigment or dye is used as a coloring agent.
- the red colored layer tends to have a reverse tapered cross-sectional shape compared to the green colored layer and the blue colored layer.
- the cross-sectional shape of the colored layer pattern becomes an inversely tapered shape, various problems arise, such as that the transparent electrode such as ITO formed on the colored layer pattern is easily disconnected, and the solvent resistance of the colored layer is lowered.
- the colored layer of the photosensitive colored resin composition cures the photocurable component by irradiating light (usually ultraviolet rays with a peak wavelength of 365 nm), but since it is difficult for light to reach near the substrate interface in the colored layer, compared to the surface of the colored layer Hardening becomes weak in the vicinity of the substrate interface. Therefore, the colored layer after development basically has an inversely tapered cross-sectional shape in which the width becomes narrower near the substrate interface. However, during post-baking after development, the green colored layer and the blue colored layer tend to undergo thermal flow in the insufficiently hardened portion near the substrate interface, so that the reverse tapered shape is eliminated.
- the red colored layer has a higher transmittance at a wavelength of 365 nm used during light irradiation than the green colored layer and the blue colored layer. Curing proceeds more easily in the vicinity of the substrate interface than in the green colored layer and the blue colored layer. Therefore, in the red colored layer, heat flow is less likely to occur in the vicinity of the substrate interface during post-baking after development, and the reverse tapered shape is likely to be maintained.
- the concentration of coloring materials in the colored layer of the color filter is higher than before, so the components required for photopolymerization are relatively reduced, and patterning is becoming more difficult, resulting in the generation of development residues. In addition, adhesion to the substrate is also a problem.
- the present invention has been made in view of the above circumstances, and can form a red colored layer having a cross-sectional shape with a taper angle of less than 60 degrees and excellent adhesion to a substrate while suppressing the generation of development residues.
- An object of the present invention is to provide a photosensitive red resin composition.
- Another object of the present invention is to provide a color filter and a display device formed using the photosensitive red resin composition.
- the photosensitive red resin composition according to the present invention contains a coloring material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a solvent
- the coloring material is made of a pigment containing at least a red pigment
- the dispersant contains at least one of a block copolymer and a graft copolymer
- the UV absorber has a transmittance of 35% or less at a wavelength of 365 nm in a 0.002% by mass propylene glycol monomethyl ether acetate solution.
- the color filter according to the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a cured photosensitive red resin composition according to the present invention. It is a thing.
- a display device has the color filter according to the present invention.
- a photosensitive red resin composition capable of forming a red colored layer having a cross-sectional shape with a taper angle of less than 60 degrees and excellent adhesion to a substrate while suppressing the generation of development residues. be able to.
- the color filter and display apparatus which were formed using the said photosensitive red resin composition can be provided.
- FIG. 1 is a schematic diagram showing an example of the color filter of the present invention.
- FIG. 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention.
- FIG. 3 is a schematic diagram showing an example of the organic light-emitting display device of the present invention.
- FIG. 4 is a schematic diagram for explaining the taper angle ( ⁇ 1) of the cross-sectional shape of the colored layer of the fine line pattern.
- light includes electromagnetic waves with wavelengths in the visible and non-visible regions, and radiation
- radiation includes, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves with a wavelength of 5 ⁇ m or less and electron beams.
- (meth)acryloyl represents acryloyl and methacryloyl
- (meth)acryl represents acrylic and methacrylic
- (meth)acrylate represents acrylate and methacrylate.
- the term "to" indicating a numerical range is used to include the numerical values before and after it as lower and upper limits.
- the photosensitive red resin composition according to the present invention contains a colorant, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a solvent,
- the coloring material is made of a pigment containing at least a red pigment
- the dispersant contains at least one of a block copolymer and a graft copolymer
- the UV absorber has a transmittance of 35% or less at a wavelength of 365 nm in a 0.002% by mass propylene glycol monomethyl ether acetate solution.
- the photosensitive red resin composition according to the present invention contains a colorant, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a solvent, and the colorant is made of a pigment containing at least a red pigment, and the ultraviolet absorber has a transmittance at a wavelength of 365 nm of 35% or less in a 0.002% by mass propylene glycol monomethyl ether acetate solution.
- a red colored layer having a cross-sectional shape with a taper angle of less than 60 degrees and excellent adhesion to a substrate can be formed.
- the red colored layer has a higher transmittance at a wavelength of 365 nm used during light irradiation than the green colored layer and the blue colored layer, so the same amount of light as the green colored layer and the blue colored layer
- curing progresses more easily in the vicinity of the substrate interface than in the green colored layer or the blue colored layer, and during post-baking after development, heat flow is less likely to occur in the vicinity of the substrate interface, resulting in a reverse tapered shape. It was easy to maintain.
- a UV absorber having a transmittance of 0.002% by mass at a wavelength of 365 nm in a propylene glycol monomethyl ether acetate solution of 35% or less was selected and combined.
- the transmittance at a wavelength of 365 nm is effectively reduced, and curing near the substrate interface is suppressed like the green colored layer and the blue colored layer, and during post-baking after development, the same as the green colored layer and the blue colored layer.
- heat flow is likely to occur in the vicinity of the base material interface, and a red colored layer having a cross-sectional shape with a taper angle of less than 60 degrees can be formed.
- the red colored layer having a cross-sectional shape with a taper angle of less than 60 degrees has the advantage of improving the adhesion to the substrate compared to the colored layer having a cross-sectional shape with a taper angle of more than 60 degrees.
- the red colored layer having a cross-sectional shape with a taper angle of less than 60 degrees can prevent disconnection when forming an electrode by coating, and can prevent unnecessary gaps from being formed between the base material and the colored layer. There is an advantage that it is possible to prevent air bubbles from being generated in the liquid crystal.
- a dispersant having many pigment-adsorbing groups per molecule efficiently adsorbs to a pigment, It is possible to prevent the pigment alone from remaining on the substrate and becoming a development residue.
- an ultraviolet absorber having a transmittance at a wavelength of 365 nm of 0.002% by mass in a propylene glycol monomethyl ether acetate solution of 35% or less is selected to form a block copolymer and a graft copolymer.
- the synergistic effect improves the effect of suppressing the generation of development residues.
- the coloring material is made of a pigment containing at least a red pigment
- the red colored layer which is a cured product of the photosensitive red resin composition according to the present invention, has a chromaticity due to steps during production such as ultraviolet irradiation and post-baking. Change is suppressed.
- the photosensitive red resin composition according to the present invention contains at least a coloring material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a solvent. , may further contain other components within a range that does not impair the effects of the present invention.
- a coloring material e.g., a coloring material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a solvent.
- the ultraviolet absorber in the present invention refers to a compound that has a maximum absorption wavelength of 400 nm or less and does not absorb visible light with a wavelength exceeding 420 nm.
- the ultraviolet absorber used in the present invention may be a compound that does not absorb visible light with a wavelength exceeding 400 nm.
- an ultraviolet absorbent having a transmittance of 35% or less in a 0.002% by mass propylene glycol monomethyl ether acetate solution at a wavelength of 365 nm is selected and used.
- an ultraviolet absorber with a small transmittance at a wavelength of 365 nm in combination with a red colorant it is possible to ensure thermal fluidity near the substrate interface of the red colored layer during post-baking after development as described above.
- a red colored layer having a cross-sectional shape with a taper angle of less than 60 degrees can be formed.
- the transmittance of the UV absorber at a wavelength of 365 nm was determined by preparing a 0.002% by mass propylene glycol monomethyl ether acetate solution of the UV absorber, and measuring the transmittance of the 0.002% by mass propylene glycol monomethyl ether acetate solution by measuring the transmittance of the UV absorber at a wavelength of 365 nm. It can be measured using an external spectrophotometer (eg, JASCO Corporation V-770).
- the ultraviolet absorber used in the present invention has a transmittance at a wavelength of 365 nm in a 0.002% by mass propylene glycol monomethyl ether acetate solution, more preferably 32% or less, may be 25% or less, or 20% or less. may be
- the structure of the ultraviolet absorber used in the present invention is not particularly limited as long as the transmittance at a wavelength of 365 nm is 35% or less in a 0.002% by mass propylene glycol monomethyl ether acetate solution.
- ultraviolet absorbers include benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, benzoic acid-based ultraviolet absorbers, anthranilic acid-based ultraviolet absorbers, and salicylic acid-based ultraviolet absorbers.
- Absorbents, cinnamic acid-based UV absorbers, and the like can be mentioned.
- the transmittance at a wavelength of 365 nm satisfies 35% or less in a 0.002 mass% propylene glycol monomethyl ether acetate solution
- X 1 , X 2 and X 3 are each independently a hydrogen atom, a hydroxyl group, —OR a , or an optionally substituted hydrocarbon having 1 to 15 carbon atoms
- R a represents an optionally substituted hydrocarbon group having 1 to 15 carbon atoms
- at least one of X 1 , X 2 and X 3 is a hydroxyl group, —OR a , or an optionally substituted hydrocarbon group having 1 to 15 carbon atoms
- X 4 represents a hydrogen atom or a halogen atom.
- the hydrocarbon group having 1 to 15 carbon atoms in X 1 , X 2 and X 3 and R a is a linear or branched aliphatic hydrocarbon group, an aromatic hydrocarbon group groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, dodecyl group, phenyl group, naphthyl group and biphenyl group.
- the hydrocarbon group may have 1 to 12 carbon atoms, or 1 to 8 carbon atoms.
- the hydrocarbon group may be an aliphatic hydrocarbon group, may be a linear or branched alkyl group, a methyl group, a t-butyl group, a t-pentyl group, an n-octyl group, a t-octyl group. (1,1,3,3-tetramethylbutyl group), 2-ethylhexyl group.
- substituents include halogen atoms, hydroxyl groups, cyano groups, or groups containing carbonyl groups, ester groups, ether groups, amide groups, imide groups, etc., and acyl groups, acyloxy groups, alkoxy groups, aryloxy groups, glycidyl groups, and the like.
- the substituent of the aromatic hydrocarbon group may be an alkyl group.
- hydrocarbon groups having substituents include -C 2 H 3 (OH)-CH 2 -O-C 8 H 17 , -C 2 H 3 (OH)-CH 2 -O-C 12 H 25 , —CH(CH 3 )—CO 2 —C 8 H 17 , methacryloyloxyethyl, etc., and also 4-methylphenyl, 3-chlorophenyl, 4-benzyloxyphenyl, 4-cyanophenyl, 4-phenoxyphenyl , 4-glycidyloxyphenyl, 4-isocyanuratephenyl, and the like.
- the —C 8 H 17 , —C 12 H 25 , etc. may each be linear or branched.
- the halogen atom includes a chlorine atom, a fluorine atom, a bromine atom, and the like.
- X 1 , X 2 and X 3 , and R a having 1 to 15 carbon atoms which may have a substituent group
- the hydrocarbon group may be an unsubstituted hydrocarbon group having 1 to 15 carbon atoms, an unsubstituted aliphatic hydrocarbon group, an unsubstituted linear or It may be a branched alkyl group.
- X 2 is a hydrogen atom
- X 1 and X 3 are each independently a hydrogen atom or have 1 carbon atom without a substituent.
- 1 to 15 aliphatic hydrocarbon groups at least one of X 1 and X 3 is an unsubstituted aliphatic hydrocarbon group having 1 to 15 carbon atoms
- X 4 is a hydrogen atom or chlorine Atoms are preferred.
- the unsubstituted aliphatic hydrocarbon group having 1 to 15 carbon atoms of X 1 and X 3 may be an aliphatic hydrocarbon group having 1 to 12 carbon atoms and has 1 carbon atom. ⁇ 8 aliphatic hydrocarbon groups.
- the transmittance at a wavelength of 365 nm satisfies 35% or less in a 0.002% by mass propylene glycol monomethyl ether acetate solution, and a triazine-based ultraviolet absorber having the following general formula (B) At least one UV absorber selected from the group consisting of
- Y 1 , Y 2 , Y 3 , Y 4 , Y 5 and Y 6 each independently may have a hydrogen atom, a hydroxyl group, —OR b , or a substituent represents a hydrocarbon group having 1 to 15 carbon atoms
- R b represents a hydrocarbon group having 1 to 15 carbon atoms which may have a substituent
- Y 1 , Y 2 , Y 3 , Y 4 At least one of Y 5 and Y 6 represents a hydroxyl group, —OR b , or a hydrocarbon group having 1 to 15 carbon atoms which may have a substituent.
- the optionally substituted hydrocarbon group having 1 to 15 carbon atoms in Y 1 , Y 2 , Y 3 , Y 4 , Y 5 and Y 6 and R b is the above X 1 , X 2 , X 3 , and R a may be the same as the hydrocarbon group having 1 to 15 carbon atoms which may have a substituent.
- At least one of Y 2 , Y 4 and Y 6 may be a hydroxyl group and may be a hydroxyphenyltriazine-based UV absorber.
- Y 1 , Y 2 , Y 3 , Y 4 , Y 5 and Y 6 are each independently a hydroxyl group, —OR b , or an unsubstituted aliphatic hydrocarbon group having 1 to 15 carbon atoms, R b being an optionally substituted aliphatic hydrocarbon group having 1 to 15 carbon atoms, Y 2 , At least one of Y 4 and Y 6 is preferably a hydroxyl group, and each of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 and Y 6 is independently a hydroxyl group or -OR b .
- R b is an aliphatic hydrocarbon group having 1 to 15 carbon atoms which may have an ester group, and at least one of Y 2 , Y 4 and Y 6 is more preferably a hydroxyl group.
- Y 1 and Y 2 are each independently hydroxyl groups or —OR b
- Y 4 and Y 6 are hydroxyl groups
- Y 3 and Y 5 is —OR b and R b is an aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have an ester group such as —CH(CH 3 )—CO 2 —C 8 H 17 It's okay.
- the benzophenone-based ultraviolet absorber includes a hydroxybenzophenone-based ultraviolet absorber, which has a transmittance of 35% or less in a 0.002% by mass propylene glycol monomethyl ether acetate solution at a wavelength of 365 nm, and has the following general formula ( At least one ultraviolet absorber selected from the group consisting of hydroxybenzophenone-based ultraviolet absorbers represented by C) can be mentioned.
- Z 1 represents a hydroxyl group, —OR c , or an optionally substituted hydrocarbon group having 1 to 15 carbon atoms
- Z 2 represents a hydrogen atom, a hydroxyl group, —OR c or an optionally substituted hydrocarbon group having 1 to 15 carbon atoms
- Z 3 represents a hydrogen atom or a hydroxyl group
- R c optionally has a substituent represents a hydrocarbon group having 1 to 15 carbon atoms.
- the optionally substituted hydrocarbon group having 1 to 15 carbon atoms in Z 1 and Z 2 and R c is the above X 1 , X 2 and X 3 , and the hydrocarbon group having 1 to 15 carbon atoms which may have a substituent for R a .
- Z 1 is a hydroxyl group, —OR c , or an aliphatic hydrocarbon having 1 to 8 carbon atoms having no substituents.
- Z 2 is a hydrogen atom, a hydroxyl group, —OR c , or an unsubstituted aliphatic hydrocarbon group having 1 to 8 carbon atoms
- Z 3 is a hydrogen atom or a hydroxyl group
- R c is preferably an unsubstituted aliphatic hydrocarbon group having 1 to 8 carbon atoms
- Z 1 is a hydroxyl group, —OR c , or an unsubstituted aliphatic group having 1 to 4 carbon atoms
- it is a hydrocarbon group
- Z 2 and Z 3 are a hydrogen atom or a hydroxyl group
- R c is an unsubstituted aliphatic hydrocarbon group having 1 to 4 carbon atoms.
- the weight average molecular weight of the ultraviolet absorber used in the present invention is usually 80 or more, preferably 150 or more, more preferably 300 or more, and usually 2000 or less, preferably 1500 or less, and more preferably 1500 or less, from the viewpoint of efficiently absorbing ultraviolet rays. is 900 or less.
- the polymer of the ultraviolet absorber has a low ultraviolet absorbing ability, a non-polymeric compound having no repeating unit is preferable.
- two or more ultraviolet absorbers may be mixed and used in the present invention as long as the transmittance at a wavelength of 365 nm is 35% or less in a 0.002% by mass propylene glycol monomethyl ether acetate solution. That is, the ultraviolet absorber used in the present invention alone has a transmittance of 0.002% by mass at a wavelength of 365 nm exceeding 35% in a propylene glycol monomethyl ether acetate solution. If the transmittance at a wavelength of 365 nm is 35% or less in a 0.002% by mass propylene glycol monomethyl ether acetate solution, an ultraviolet absorber of a mixture thereof can be used.
- UV absorbers used in the present invention include 2-phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl), 5-chloro-2 -[3-(tert-butyl)-2-hydroxy-5-methylphenyl]-2H-benzotriazole, 2,2'-dihydroxy-4-methoxybenzophenone, and the like, but are not limited to these.
- Commercially available UV absorbers used in the present invention include, but are not limited to, Tinuvin329, Tinuvin326, Tinuvin477, TinuvinPS (manufactured by BASF), KEMIISORB111, and KEMISORB73 (Kemipro Kasei). is not.
- the content of the ultraviolet absorber while forming a cross-sectional shape with a taper angle of less than 60 degrees, is easy to suppress development residue, from the point that it is difficult to cause pixel chipping, the total solid content of the photosensitive red resin composition
- it may generally be in the range of 0.1% by mass to 10.0% by mass, preferably in the range of 0.1% by mass to 7.0% by mass, more preferably 0.1% by mass % to 5.0 mass %, more preferably 0.1 mass % to 4.0 mass %.
- the solid content is everything other than the solvent, and liquid photopolymerizable compounds and the like are also included.
- the ratio of the total mass of the ultraviolet absorber to the total mass of the photoinitiator and the ultraviolet absorber is preferably in the range of 5% by mass to 70% by mass, more preferably 10% by mass to 50% by mass. Within range.
- the content ratio of the ultraviolet absorber is within the above range, it is easy to form a cross-sectional shape with a taper angle of less than 60 degrees, it is easy to suppress development residues, and it is difficult to cause pixel chipping.
- the coloring material is composed of a pigment containing at least a red pigment. That is, the pigment is 100% by mass with respect to the total amount of the coloring material. Since the coloring material is composed of a pigment containing at least a red pigment, it is possible to form a red colored layer in which chromaticity change due to manufacturing processes such as ultraviolet irradiation and post-baking is suppressed.
- the term "pigment” as used herein means a solvent-insoluble dye compound.
- the amount dissolved in 100 g of propylene glycol monomethyl ether acetate at 25° C. the amount dissolved in 100 g of water at 25° C.
- Organic pigments are both preferably 0.1 g or less, and 0.1 g or less. It is more preferably 05 g or less, and even more preferably 0.01 g or less.
- Organic pigments are preferably used because of their high color developability and high heat resistance. Examples of organic pigments include compounds classified as pigments in the Color Index (C.I.; published by The Society of Dyers and Colorists). .) numbered ones can be mentioned.
- red pigment for example, C.I. I. Pigment Red 1, 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, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243
- R 61 and R 62 are each independently a 4-chlorophenyl group or a 4-bromophenyl group.
- the red pigment from the viewpoint of expanding the color gamut, it is preferable to use a diketopyrrolopyrrole pigment, and the diketopyrrolopyrrole content in the total amount of the coloring material is preferably 30% by mass or more, preferably 40% by mass or more. Containing is more preferable.
- diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, 255, 264, 272, 291, and diketopyrrolopyrrole pigments represented by the above general formula (i), among which C.I. I. Pigment Red 254, 272, 291, and at least one selected from diketopyrrolopyrrole pigments in which R 61 and R 62 in the general formula (i) are each a 4-bromophenyl group are preferred.
- the red pigment is preferably at least one selected from Pigment Red 254, Pigment Red 177, and Pigment Red 291 from the viewpoint of improving brightness.
- pigments may be used as the coloring material from the viewpoints of color adjustment, brightness improvement, and re-solubility improvement.
- yellow pigments for example, yellow pigments, orange pigments and the like are preferably used.
- yellow pigments include C.I. I.
- the total content of other pigments other than the red pigment may be 0% by mass, may be 1% by mass or more, and may be 10% by mass with respect to the total amount of the colorant. On the other hand, it is usually 50% by mass or less, preferably 30% by mass or less.
- the average primary particle diameter of the coloring material used in the present invention is not particularly limited as long as the coloring layer of the color filter can develop a desired color, and varies depending on the type of coloring material used. is preferably in the range of 10 to 100 nm, more preferably 15 to 60 nm. Since the average primary particle size of the colorant is within the above range, the display device equipped with the color filter produced using the photosensitive red resin composition according to the present invention has high contrast and high quality. be able to.
- the average dispersed particle size of the colorant in the photosensitive red resin composition varies depending on the type of colorant used, but is preferably in the range of 10 to 100 nm, more preferably in the range of 15 to 60 nm. is more preferred.
- the average dispersed particle size of the colorant in the photosensitive red resin composition is the dispersed particle size of the colorant particles dispersed in the dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. It is a thing.
- the photosensitive red resin composition is diluted with a solvent used in the photosensitive red resin composition to a concentration that can be measured with a laser light scattering particle size distribution meter (for example, 1000 times), and measured at 23° C. by a dynamic light scattering method using a laser light scattering particle size distribution analyzer (eg, Nanotrack particle size distribution analyzer UPA-EX150 manufactured by Nikkiso Co., Ltd.).
- the average distribution particle size here is the volume average particle size.
- the coloring material used in the present invention can be produced by known methods such as recrystallization and solvent salt milling. Alternatively, a commercially available coloring material may be used after undergoing fine processing.
- the content of the coloring material in the photosensitive red resin composition according to the present invention is not particularly limited.
- the content of the coloring material is usually in the range of 3% to 65% by mass, preferably 4% to 60% by mass, based on the total solid content of the photosensitive red resin composition, from the viewpoint of dispersibility and dispersion stability. % by mass, more preferably 15% to 60% by mass. If it is at least the above lower limit, the colored layer will have a sufficient color density when the photosensitive red resin composition is applied to a predetermined film thickness (usually 1.0 ⁇ m to 5.0 ⁇ m). Moreover, if it is below the said upper limit, while being excellent in storage stability, the coloring layer which has sufficient hardness and adhesiveness with a board
- the total content of the colorant is preferably 20% by mass to 65% by mass, more preferably 20% by mass to 65% by mass, based on the total solid content of the photosensitive red resin composition. It is within the range of 30% by mass to 60% by mass.
- the colorant is dispersed in a solvent with a dispersant.
- the dispersant used in the present invention contains at least one of a block copolymer and a graft copolymer from the viewpoint of being able to suitably disperse the colorant and suppress development residue.
- At least one of the block copolymer and the graft copolymer contains a tertiary amine because it can disperse the coloring material appropriately, has good dispersion stability, and can easily suppress development residue. It is preferably at least one of a block copolymer containing a repeating unit and a graft copolymer containing a repeating unit having a tertiary amine.
- a repeating unit having a tertiary amine is a site having affinity with the coloring material.
- a block copolymer containing a repeating unit having a tertiary amine, and a graft copolymer containing a repeating unit having a tertiary amine are usually block copolymers containing a repeating unit that serves as a site having affinity with a solvent. Or it may be a graft copolymer.
- the repeating unit having a tertiary amine may have a tertiary amine, and the tertiary amine may be contained in the side chain of the copolymer or may constitute the main chain. .
- the site having affinity with the coloring material is preferably a repeating unit having a tertiary amine in the side chain, and the main chain skeleton is difficult to thermally decompose and has high heat resistance. ) is more preferred.
- R 41 is a hydrogen atom or a methyl group
- a 1 is a divalent linking group
- R 42 and R 43 are each independently a hydrogen atom, or a hydrocarbon optionally containing a hetero atom. group, and R 42 and R 43 may combine with each other to form a ring structure.
- a 1 is a divalent linking group.
- the divalent linking group for example, a linear, branched or cyclic alkylene group, a linear, branched or cyclic alkylene group having a hydroxyl group, an arylene group, -CONH- group, -COO- group, -NHCOO- groups, ether groups (--O--groups), thioether groups (--S--groups), and combinations thereof.
- the bonding direction of the divalent linking group is arbitrary.
- a 1 in the general formula (I) is preferably a divalent linking group containing a -CONH- group or a -COO- group, and a -CONH- group or a -COO- group.
- an alkylene group having 1 to 10 carbon atoms are more preferable.
- Examples of the hydrocarbon group in the hydrocarbon group optionally containing a heteroatom for R 42 and R 43 include an alkyl group, an aralkyl group and an aryl group.
- Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2-ethylhexyl group, cyclopentyl group, cyclohexyl group and the like, and the number of carbon atoms in the alkyl group is 1 to 18 are preferable, and among them, a methyl group or an ethyl group is more preferable.
- the aralkyl group includes, for example, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like.
- the number of carbon atoms in the aralkyl group is preferably 7-20, more preferably 7-14.
- Aryl groups include phenyl, biphenyl, naphthyl, tolyl, and xylyl groups.
- the number of carbon atoms in the aryl group is preferably 6-24, more preferably 6-12.
- the preferable number of carbon atoms does not include the number of carbon atoms of the substituent.
- a hydrocarbon group containing a heteroatom has a structure in which a carbon atom in the hydrocarbon group is replaced with a heteroatom, or a structure in which a hydrogen atom in the hydrocarbon group is replaced by a substituent containing a heteroatom.
- the heteroatom that the hydrocarbon group may contain include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom and the like.
- hydrogen atoms in the hydrocarbon group may be substituted with halogen atoms such as fluorine, chlorine and bromine atoms.
- R 42 and R 43 are bonded to each other to form a ring structure means that R 42 and R 43 form a ring structure via a nitrogen atom.
- the ring structure formed by R42 and R43 may contain a heteroatom.
- the ring structure is not particularly limited, examples thereof include pyrrolidine ring, piperidine ring, morpholine ring and the like.
- R 42 and R 43 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, or R 42 and R 43 are bonded to form a pyrrolidine ring, It preferably forms a piperidine ring or a morpholine ring.
- Examples of monomers that derive structural units represented by the general formula (I) include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, and the like.
- Alkyl group-substituted amino group-containing (meth)acrylates, alkyl group-substituted amino group-containing (meth)acrylamides such as dimethylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, and the like can be mentioned.
- dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylaminopropyl (meth)acrylamide can be preferably used in terms of improving dispersibility and dispersion stability.
- the structural unit represented by formula (I) may consist of one type, or may contain two or more types of structural units.
- the structural unit that functions as the coloring material adsorption site includes at least a part of the nitrogen site of the structural unit represented by the general formula (I) and an organic At least one selected from the group consisting of acid compounds and halogenated hydrocarbons preferably forms a salt (hereinafter, such a copolymer may be referred to as a salt-type copolymer).
- a salt-type copolymer As the organic acid compound, among others, a compound represented by the following general formula (1) and a compound represented by the following general formula (3) are preferable. ) are preferred. That is, at least one compound selected from the group consisting of the organic acid compound and the halogenated hydrocarbon is preferably one or more compounds selected from the group consisting of the following general formulas (1) to (3). can.
- R a is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group which may have a substituent or a benzyl group, or -O- Represents R e
- R e is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group which may have a substituent or a benzyl group, or a C 1 to 4 represents a (meth)acryloyl group via an alkylene group.
- R b , R b′ , and R b′′ each independently represent a hydrogen atom, an acidic group or an ester group thereof, or a substituent.
- a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms a vinyl group which may have a substituent, a phenyl group which may have a substituent or a benzyl group, or -O- R f represents an optionally substituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group optionally having a substituent, a substituted may be a phenyl group or a benzyl group, or a (meth)acryloyl group via an alkylene group having 1 to 4 carbon atoms, and X represents a chlorine atom, a bromine atom, or an iodine atom.
- R c and R d are each independently a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl group or a benzyl group, Alternatively, —O—R e , where R e is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl group or a benzyl group, or a carbon number represents a (meth)acryloyl group via 1 to 4 alkylene groups, provided that at least one of R c and R d contains a carbon atom.
- each code of the general formulas (1) to (3) may be the same as described in WO2016/104493.
- the organic acid compound is an acidic organic phosphorus compound such as phenylphosphonic acid or phenylphosphinic acid from the viewpoint of excellent dispersibility and dispersion stability of the coloring material.
- Specific examples of the organic acid compound used in such a dispersant include, for example, organic acid compounds described in JP-A-2012-236882 and the like as suitable ones.
- the halogenated hydrocarbon is preferably at least one selected from allyl halides such as allyl bromide and benzyl chloride, and aralkyl halides, from the viewpoint of excellent dispersibility and dispersion stability of the coloring material.
- the content of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons forms a salt with the terminal nitrogen moiety of the structural unit represented by general formula (I). Therefore, the total of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons is 0 for the terminal nitrogen portion of the structural unit represented by general formula (I) It is preferably 0.01 mol or more, more preferably 0.05 mol or more, still more preferably 0.1 mol or more, and particularly preferably 0.2 mol or more. When it is at least the above lower limit, the effect of improving the dispersibility of the coloring material by salt formation is likely to be obtained.
- At least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons may be used singly or in combination of two or more. When two or more are combined, the total content is preferably within the above range.
- the salt-type copolymer As a method for preparing the salt-type copolymer, at least one selected from the group consisting of the organic acid compound and the halogenated hydrocarbon is added to the solvent in which the copolymer before salt formation is dissolved or dispersed, and the mixture is stirred. and a method of heating if necessary.
- the terminal nitrogen portion of the structural unit represented by the general formula (I) of the copolymer and at least one selected from the group consisting of the organic acid compound and the halogenated hydrocarbon form a salt. and the ratio thereof can be confirmed by a known technique such as NMR.
- the copolymer having a structural unit represented by the general formula (I) is a graft copolymer having a structural unit represented by the general formula (I), and It is more preferably at least one block copolymer having an A block and a B block containing the structural unit represented by the general formula (I).
- the graft copolymer and the block copolymer will be described in order.
- a graft copolymer having a structural unit represented by the general formula (I) As a graft copolymer having a structural unit represented by the general formula (I), a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the following general formula (II) a copolymer, and at least one selected from the group consisting of at least a portion of the nitrogen moieties possessed by the structural unit represented by the general formula (I) of the graft copolymer, an organic acid compound, and a halogenated hydrocarbon; and at least one salt-type graft copolymer in which a salt is formed.
- R 41′ is a hydrogen atom or a methyl group
- a 2 is a direct bond or a divalent linking group
- Polymer represents a polymer chain
- the constituent units of the polymer chain include (meth)acrylate (Contains structural units derived from
- A2 is a direct bond or a divalent linking group.
- the divalent linking group for A2 is not particularly limited as long as it can link the carbon atom derived from the ethylenically unsaturated bond and the polymer chain.
- Examples of the divalent linking group for A 2 include those similar to the divalent linking group for A 1 .
- a 2 in general formula (II) is preferably a divalent linking group containing a -CONH- group or a -COO- group, and a -CONH- group or a -COO- group. , and an alkylene group having 1 to 10 carbon atoms.
- Polymer represents a polymer chain, and structural units of the polymer chain include structural units derived from (meth)acrylate.
- the graft copolymer has a structural unit represented by the general formula (II) having a specific polymer chain, so that the solvent affinity is improved, and the dispersibility and dispersion stability of the coloring material are improved. and the compatibility with the photoinitiator, which will be described later, is also improved.
- Examples of structural units of the polymer chain include structural units represented by the following general formula (IV).
- R 44′′ is a hydrogen atom or a methyl group
- a 4 is a divalent linking group
- R 50 is a hydrogen atom or a hydrocarbon group which may contain a hetero atom.
- Examples of the divalent linking group for A 4 include those similar to the divalent linking group for A 1 .
- a structural unit derived from (meth)acrylate a structural unit represented by general formula (IV), in which A 4 in general formula (IV) is a divalent linking group containing a —COO— group, is , at least included.
- a 4 in general formula (IV) may contain a divalent linking group containing a -CONH- group.
- hydrocarbon groups in the hydrocarbon group optionally containing a heteroatom in R 50 include alkyl groups, alkenyl groups, aryl groups, and combinations thereof such as aralkyl groups and alkyl-substituted aryl groups.
- the hydrocarbon group in the hydrocarbon group optionally containing a heteroatom for R 50 includes, for example, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group, an aralkyl group, and an alkyl-substituted Combinations of these, such as aryl groups, are included.
- the alkyl group having 1 to 18 carbon atoms may be linear, branched, or cyclic, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, n- nonyl group, n-lauryl group, n-stearyl group, cyclopentyl group, cyclohexyl group, bornyl group, isobornyl group, dicyclopentanyl group, adamantyl group, lower alkyl group-substituted adamantyl group and the like.
- the number of carbon atoms in the alkyl group is preferably 1-12, more preferably 1-6.
- the alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. Examples of such alkenyl groups include vinyl groups, allyl groups, and propenyl groups. Although the position of the double bond of the alkenyl group is not limited, it is preferable that the alkenyl group has a double bond at the terminal from the viewpoint of the reactivity of the resulting polymer.
- the alkenyl group preferably has 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms.
- Aryl groups include phenyl, biphenyl, naphthyl, tolyl, and xylyl groups. The number of carbon atoms in the aryl group is preferably 6-24, more preferably 6-12.
- the aralkyl group includes a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like, and may further have a substituent.
- the number of carbon atoms in the aralkyl group is preferably 7-20, more preferably 7-14.
- a linear or branched alkyl group having 1 to 30 carbon atoms may be bonded as a substituent to the aromatic ring such as the aryl group or the aralkyl group.
- hydrocarbon group for R 50 from the viewpoint of dispersion stability, among them, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 12 carbon atoms which may be substituted with an alkyl group, and an alkyl group.
- aralkyl groups having 7 to 14 carbon atoms, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n It is preferably one or more selected from the group consisting of -nonyl group, n-lauryl group, n-stearyl group, phenyl group optionally substituted with alkyl group, and benzyl group.
- heteroatom examples include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom and the like.
- the hydrocarbon group which may contain a heteroatom includes, for example, -CO-, -COO-, -OCO-, -O-, -S-, -CO-S-, - S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O- , —O—NH— and other connecting groups.
- the hydrocarbon group may have a substituent as long as it does not interfere with the dispersion performance of the graft copolymer. Nitro group, cyano group, epoxy group, isocyanate group, thiol group and the like.
- the hydrocarbon group optionally containing a heteroatom for R 50 may have a structure in which a polymerizable group such as an alkenyl group is added to the end of the hydrocarbon group via a linking group containing a heteroatom.
- Examples of monomers that induce structural units represented by general formula (IV) include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) Acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate , dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, (meth) acrylic acid, 2-methacryloyloxyethyl succinate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- Hydroxybut
- the R 50 it is preferable to use one having excellent solubility in the organic solvent described later, and it may be appropriately selected according to the organic solvent used in the colorant dispersion.
- the organic solvent is an ether-alcohol acetate-based, ether-based, ester-based, or alcohol-based organic solvent generally used as an organic solvent for a colorant dispersion
- a structural unit represented by the following general formula (III) and a structural unit represented by the following general formula (III') are added to the structural unit of the polymer chain in the structural unit represented by the general formula (II).
- the inclusion of at least one structural unit selected from the group consisting of the structural units is the suppression of development residue, the shortening of the development time of the photosensitive resin composition, and the cured product of the photosensitive red resin composition It is preferable from the point that the solvent resistance of is further improved.
- the structural unit represented by the following general formula (III) and the structural unit represented by the following general formula (III') are structural units included in the structural unit represented by the general formula (IV).
- R 44 is a hydrogen atom or a methyl group
- a 3 is a divalent linking group
- R 45 is an ethylene group or a propylene group
- R 46 is a hydrogen atom or a hydrocarbon group
- m represents a number of 3 or more and 80 or less.
- R 44′ is a hydrogen atom or a methyl group
- a 3′ is a divalent linking group
- R 47 is an alkylene group having 1 to 10 carbon atoms
- R 48 has 3 to 7 carbon atoms.
- the alkylene group of R 49 is a hydrogen atom or a hydrocarbon group
- n represents a number of 1 or more and 40 or less.
- Examples of the divalent linking group for A 3 include those similar to the divalent linking group for A 1 . Among them, from the viewpoint of solubility in organic solvents used for color filters, A 3 in general formula (III) is preferably a divalent linking group containing a -CONH- or -COO- group. , -CONH- group or -COO- group is more preferred, and -COO- group is even more preferred.
- m represents the number of repeating units of an ethylene oxide chain or a propylene oxide chain, and represents a number of 3 or more. is more preferable.
- the upper limit of m is 80 or less, but preferably 50 or less from the viewpoint of solubility in organic solvents used for color filters.
- the hydrocarbon group for R 46 may be the same as the hydrocarbon group for R 50 .
- an alkyl group having 1 to 18 carbon atoms an aryl group having 6 to 12 carbon atoms which may be substituted with an alkyl group
- the alkyl group is preferably one or more selected from the group consisting of optionally substituted aralkyl groups having 7 to 14 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl. It is preferably one or more selected from the group consisting of groups, n-nonyl groups, n-lauryl groups, n-stearyl groups, phenyl groups optionally substituted with alkyl groups, and benzyl groups.
- examples of the divalent linking group for A3 ' include the same divalent linking groups as the divalent linking groups for A1.
- a 3' in general formula (III') is a divalent linking group containing a -CONH- or -COO- group. is preferred, a -CONH- group or a -COO- group is more preferred, and a -COO- group is even more preferred.
- R 47 is an alkylene group having 1 to 10 carbon atoms, and an alkylene group having 2 to 8 carbon atoms is preferable from the viewpoint of solvent resolubility.
- R 48 is an alkylene group having 3 to 7 carbon atoms. Among them, an alkylene group having 3 to 5 carbon atoms, and more preferably an alkylene group having 5 carbon atoms are preferable from the standpoint of substrate adhesion.
- R 49 is a hydrogen atom or a hydrocarbon group, and the hydrocarbon group for R 49 may be the same as the hydrocarbon group for R 46 above.
- n in the general formula (III′) represents the number of repeating units of the ester chain, and represents a number of 1 or more. There is preferably one, and more preferably 3 or more. On the other hand, the upper limit of n is 40 or less, but preferably 20 or less in terms of solubility in organic solvents used for color filters.
- At least one structural unit selected from the group consisting of structural units represented by the general formula (III) and structural units represented by the following general formula (III') may be Although it is good, 2 or more types may be mixed.
- the structural unit represented by the general formula (III) is included in the polymer chain, the effect of the solvent affinity portion due to the oxygen atom becomes more pronounced, suppressing development residue and developing the photosensitive resin composition. It is preferable from the viewpoint of shortening the time and improving the solvent resistance.
- the general formula (I) is preferably 1% by mass or more, It is more preferably 2% by mass or more, and even more preferably 4% by mass or more.
- the total proportion of at least one structural unit selected from the group consisting of structural units represented by the general formula (III) and structural units represented by the general formula (III') is the point of solvent re-solubility Therefore, it is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less when the total constituent units of the polymer chain are 100% by mass.
- the structural unit represented by the general formula (IV) including the structural unit represented by the general formula (III) and the structural unit represented by the general formula (III') is one It may be used alone or in combination of two or more.
- the total proportion of the structural units represented by the general formula (IV) is 70% by mass or more when the total structural units of the polymer chain are 100% by mass. It is preferably 90% by mass or more, more preferably 90% by mass or more.
- the total proportion of the structural units represented by the general formula (IV) is 100 of the total structural units of the polymer chain. When expressed as % by mass, it may be 100% by mass.
- the structural unit of the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer includes the structural unit represented by the general formula (III) and the structural unit represented by the general formula (III').
- Other structural units may be included in addition to the structural units represented by the general formula (IV) including the structural units represented by the formula (IV).
- Examples of other structural units include structural units derived from monomers having unsaturated bonds copolymerizable with the monomers from which the structural units represented by general formula (IV) are derived.
- monomers from which other structural units are derived include styrene, styrenes such as ⁇ -methylstyrene, vinyl ethers such as phenyl vinyl ether, and the like.
- the total proportion of other structural units is 100% of the total structural units of the polymer chain, from the viewpoint of the effect of the present invention.
- % by mass it is preferably 30% by mass or less, more preferably 10% by mass or less.
- the weight average molecular weight Mw of the polymer chain in the polymer is preferably 2000 or more, more preferably 3000 or more, and even more preferably 4000 or more, from the viewpoint of the dispersibility and dispersion stability of the colorant. , 15000 or less, and even more preferably 12000 or less. Within the above range, a sufficient steric repulsion effect as a dispersant can be maintained, and the specific surface area of the solvent affinity part of the dispersant increases, allowing the solvent to penetrate the coating film and reach the coloring material.
- the polymer chain in Polymer preferably has a solubility of 20 (g/100 g solvent) or more at 23° C. in the organic solvent used in combination.
- the solubility of the polymer chain can be determined based on the solubility of the raw material into which the polymer chain is introduced when preparing the graft copolymer. For example, when a polymerizable oligomer (macromonomer) containing a group having an ethylenically unsaturated bond at the polymer chain and its terminal is used to introduce a polymer chain into the graft copolymer, the polymerizable oligomer has the above solubility. I wish I had it.
- ethylenically unsaturated bond-containing monomer ethylenically unsaturated bond-containing monomer, hereinafter simply referred to as an ethylenically unsaturated monomer
- the polymer chain containing the reactive group should have the aforementioned solubility.
- the structural unit represented by the general formula (I) is preferably contained in a proportion of 3 to 60% by mass, more preferably 6 to 45% by mass, and 9 to 30% by mass. % is more preferred. If the structural unit represented by the general formula (I) in the graft copolymer is within the above range, the ratio of the affinity portion with the coloring material in the graft copolymer will be appropriate, and the solubility in the organic solvent will be good. Since the deterioration of the properties can be suppressed, the adsorptivity to the coloring material is improved, and excellent dispersibility and dispersion stability can be obtained.
- the structural unit represented by the general formula (II) is preferably contained at a rate of 40 to 97% by mass, more preferably 55 to 94% by mass, and 70 to 70% by mass. 91% by mass is more preferred. If the structural unit represented by the general formula (II) in the graft copolymer is within the above range, the ratio of the solvent-affinity portion in the graft copolymer will be appropriate, resulting in sufficient stericity as a dispersant.
- the repulsion effect can be maintained, and by increasing the specific surface area of the solvent affinity part of the dispersant, it is possible to suppress the penetration of the solvent into the coating film and the arrival of the coloring material, and the polyethylene oxide chain or polypropylene oxide When a chain is included, the interaction with oxygen atoms becomes remarkable, shortening the development time, improving the solvent resistance, and further improving the effect of suppressing the occurrence of water stains and the occurrence of development residues. can be done.
- the graft copolymer used in the present invention other than the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II), within a range that does not impair the effects of the present invention
- it may have other structural units.
- an ethylenically unsaturated monomer that can be copolymerized with the ethylenically unsaturated monomer or the like that induces the structural unit represented by the general formula (I) is appropriately selected and copolymerized. Building blocks can be introduced.
- Other structural units copolymerized with the structural units represented by the general formula (I) include, for example, structural units represented by the general formula (IV).
- the content ratio of the structural units is, at the time of production, the structural unit represented by the general formula (I), the structural unit represented by the general formula (II), and the structural unit represented by the general formula (II) when synthesizing the graft copolymer. It is calculated from the charged amount of the monomer that induces the structural unit represented by the general formula (IV).
- the weight average molecular weight Mw of the graft copolymer is preferably 4000 or more, more preferably 6000 or more, and even more preferably 8000 or more, from the viewpoint of dispersibility and dispersion stability. . On the other hand, it is preferably 50,000 or less, more preferably 30,000 or less, from the viewpoint of solvent resolubility.
- the mass average molecular weight Mw in the present invention is a value measured by GPC (gel permeation chromatography).
- the measurement was carried out using Tosoh's HLC-8120GPC, the elution solvent was N-methylpyrrolidone to which 0.01 mol/liter of lithium bromide was added, and the polystyrene standards for the calibration curve were Mw 377400, 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (Easi PS-2 series manufactured by Polymer Laboratories) and Mw 1090000 (manufactured by Tosoh), and the measurement column was TSK-GEL ALPHA-M ⁇ 2 (manufactured by Tosoh). is.
- graft copolymer (Method for producing graft copolymer)
- a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II) is produced. It is not particularly limited as long as it can be done.
- a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II) for example, a monomer represented by the following general formula (Ia) and a polymerizable oligomer (macromonomer) comprising a group having an ethylenically unsaturated bond at the end of the polymer chain as a copolymerization component, and copolymerizing to produce a graft copolymer.
- a monomer represented by the following general formula (Ia) and a polymerizable oligomer (macromonomer) comprising a group having an ethylenically unsaturated bond at the end of the polymer chain as a copolymerization component and copolymerizing to produce a graft copolymer.
- other monomers may also be used, and the graft copolymer can be produced using known polymerization means.
- the monomer represented by the general formula (Ia) and other ethylenically unsaturated monomers to form a copolymer using a polymer chain containing a reactive group capable of reacting with a reactive group contained in the copolymer, the polymer chain may be introduced.
- a functional group that reacts with the substituent is added.
- a polymer chain may be introduced by reacting with a polymer chain contained therein.
- a copolymer having a glycidyl group in the side chain is reacted with a polymer chain having a terminal carboxyl group, or a copolymer having an isocyanate group in the side chain is reacted with a polymer chain having a hydroxyl group at the terminal.
- additives commonly used in polymerization such as polymerization initiators, dispersion stabilizers, and chain transfer agents, may be used.
- each block in the block copolymer is not particularly limited, and examples thereof include AB block copolymers, ABA block copolymers, and BAB block copolymers. Among them, an AB block copolymer or an ABA block copolymer is preferable because of its excellent dispersibility.
- the A block is a block that functions as a coloring material adsorption site and contains at least the structural unit represented by the general formula (I). At least part of the nitrogen sites of the structural units represented by the general formula (I) of the block copolymer and at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons form a salt. It may be a salt-type block copolymer.
- the A block may have a structural unit other than the structural unit represented by general formula (I) within the scope of achieving the object of the present invention, and the structural unit represented by general formula (I) and Any structural unit that can be copolymerized can be contained. Specific examples thereof include structural units represented by the general formula (IV).
- the content ratio of the structural unit represented by general formula (I) in the A block in the block copolymer before salt formation is 50 to 100% by mass with respect to the total mass of all structural units in the A block. is preferred, 80 to 100% by mass is more preferred, and 100% by mass is most preferred. This is because the higher the ratio of the structural unit represented by the general formula (I), the better the adsorptive power to the coloring material, and the better the dispersibility and dispersion stability of the block copolymer.
- the content ratio of the structural unit is calculated from the charged mass when synthesizing the A block having the structural unit represented by the general formula (I).
- the content ratio of the structural unit represented by the general formula (I) is the total structural units of the block copolymer from the viewpoint of good dispersibility and dispersion stability. It is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, based on the total mass of. The content ratio of each structural unit in the block copolymer is calculated from the charged mass when synthesizing the block copolymer before salt formation.
- the structural unit represented by the general formula (I) only needs to have an affinity with the colorant, and may consist of one type or may contain two or more types of structural units. good.
- the B block is a block that functions as a solvent affinity site.
- the B block is appropriately selected according to the solvent so as to have solvent affinity, from among monomers having an unsaturated bond that can be copolymerized with the monomer that derives the structural unit represented by general formula (I). It is preferably used As a guideline, it is preferable to introduce the B block so that the solubility of the copolymer at 23° C. in the solvent used in combination is 20 (g/100 g solvent) or more.
- the structural unit constituting the B block part may consist of one type, or may contain two or more types of structural units. Examples of structural units contained in the B block include structural units represented by the general formula (IV).
- the structural unit represented by the general formula (IV) at least one selected from the group consisting of the structural unit represented by the general formula (III) and the structural unit represented by the general formula (III') It is preferable from the viewpoint of suppressing development residue, shortening the development time of the photosensitive resin composition, and further improving the solvent resistance of the cured product of the photosensitive red resin composition.
- the unit number m of the structural unit represented by the general formula (I) and the unit number n of other structural units constituting the solvent-affinity block portion is preferably in the range of 0.01 or more and 1 or less, and is preferably in the range of 0.05 or more and 0.7 or less from the viewpoint of dispersibility and dispersion stability of the coloring material. more preferred.
- a block copolymer containing an A block containing a structural unit represented by the general formula (I) and a B block containing a structural unit derived from a carboxy group-containing monomer a polymer, and at least one selected from the group consisting of at least part of the nitrogen sites possessed by the structural units represented by the general formula (I) of the block copolymer, an organic acid compound, and a halogenated hydrocarbon contains at least one salt-type block copolymer forming a salt, the block copolymer and at least one of the salt-type block copolymers have an acid value of 1 to 18 mgKOH/g, and a glass transition temperature of It may be 30°C or higher. In this case, it is preferable from the viewpoint of suppressing the generation of development residues.
- the B block in this case may be similar to the B block of WO2016/104493.
- the mass average molecular weight Mw of the block copolymer is not particularly limited, but is preferably 1000 or more and 20000 or less, and 2000 or more and 15000 or less, from the viewpoint of improving the colorant dispersibility and dispersion stability. is more preferably 3000 or more and 12000 or less.
- the weight average molecular weight (Mw) can be measured in the same manner as described above.
- the content ratio of the structural unit represented by the general formula (IV) is, from the viewpoint of improving the dispersibility of the coloring material, relative to the total mass of all structural units of the block copolymer. It is preferably 40 to 95% by mass, more preferably 50 to 90% by mass. In addition, the content ratio of the structural unit is calculated from the charged mass when synthesizing the block copolymer before salt formation.
- the copolymer containing the structural unit represented by the general formula (I) has an amine value of 40 mgKOH/g or more and 120 mgKOH/g or less. It is preferable from the viewpoint of improving brightness and contrast. When the amine value is within the above range, the viscosity stability over time and heat resistance are excellent, and alkali developability and solvent re-solubility are also excellent.
- the amine value of the copolymer containing the structural unit represented by the general formula (I) is preferably 80 mgKOH/g or more, more preferably 90 mgKOH/g or more. preferable.
- the amine value of the copolymer containing the structural unit represented by the general formula (I) is preferably 110 mgKOH/g or less, more preferably 105 mgKOH/g or less. more preferred.
- the amine value refers to the number of mg of potassium hydroxide equivalent to perchloric acid required to neutralize the amine component contained in 1 g of the sample, and can be measured by the method defined in JIS-K7237. When measured by this method, even if the amino group forms a salt with the organic acid compound in the dispersant, the organic acid compound is usually dissociated. Amine value can be measured.
- the content ratio (mol%) of each structural unit in the copolymer in the dispersant can be obtained from the amount of raw materials charged at the time of production, and can be measured using an analyzer such as NMR. Also, the structure of the dispersant can be measured using NMR, various mass spectrometry, and the like. In addition, if necessary, the dispersant is decomposed by thermal decomposition or the like, and the obtained decomposition product is subjected to high performance liquid chromatography, gas chromatograph mass spectrometer, NMR, elemental analysis, XPS / ESCA, TOF-SIMS, etc. can ask.
- the content of the dispersant may be appropriately selected according to the type of coloring material used, the solid content concentration in the photosensitive red resin composition described later, and the like.
- the content of the dispersant is preferably in the range of 1% by mass to 40% by mass, more preferably in the range of 2% by mass to 30% by mass, based on the total solid content of the photosensitive red resin composition. be.
- it is at least the above lower limit the dispersibility and dispersion stability of the coloring material are excellent, and the storage stability of the photosensitive red resin composition is excellent. Moreover, if it is below the said upper limit, developability will become favorable.
- the content of the dispersant is preferably 2% by mass to 45% by mass, more preferably 3% by mass, based on the total solid content of the photosensitive red resin composition. It is in the range of mass % to 40 mass %.
- the alkali-soluble resin in the present invention has an acidic group, and can be appropriately selected and used from those that act as a binder resin and are soluble in an alkali developer used for pattern formation.
- the alkali-soluble resin can be defined as having an acid value of 40 mgKOH/g or more.
- a preferable alkali-soluble resin in the present invention is a resin having an acidic group, usually a carboxy group. resins, epoxy (meth)acrylate resins having a carboxyl group, and the like. Among these, particularly preferred are those having a carboxy group in the side chain and a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain.
- acrylic copolymers acrylic resins such as styrene-acrylic copolymers, and epoxy acrylate resins may be used in combination.
- Acrylic resins such as acrylic copolymers having a structural unit having a carboxy group and styrene-acrylic copolymers having a carboxy group are, for example, a carboxy group-containing ethylenically unsaturated monomer and, if necessary, a copolymer. It is a (co)polymer obtained by (co)polymerizing other polymerizable monomers by a known method.
- Carboxy group-containing ethylenically unsaturated monomers include, for example, (meth)acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer.
- the alkali-soluble resin preferably further has a hydrocarbon ring from the viewpoint of excellent adhesion of the colored layer.
- the present inventors have found that the presence of a hydrocarbon ring, which is a bulky group, in the alkali-soluble resin suppresses the solvent resistance of the resulting colored layer, particularly swelling of the colored layer. Although the action is not clear, the presence of bulky hydrocarbon rings in the colored layer suppresses the movement of molecules in the colored layer, which increases the strength of the coating film and suppresses swelling due to solvents.
- hydrocarbon rings include cyclic aliphatic hydrocarbon rings which may have substituents, aromatic rings which may have substituents, and combinations thereof, and hydrocarbon rings may have a substituent such as a carbonyl group, a carboxy group, an oxycarbonyl group or an amide group.
- hydrocarbon rings may have a substituent such as a carbonyl group, a carboxy group, an oxycarbonyl group or an amide group.
- hydrocarbon rings include aliphatic hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, tricyclo[5.2.1.0(2,6)]decane (dicyclopentane), and adamantane.
- Aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, and fluorene; chain polycyclic rings such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, and stilbene; cardo structures represented by the following chemical formula (ii); be done.
- the alkali-soluble resin preferably has a maleimide structure represented by the following general formula (iii).
- RM is an optionally substituted hydrocarbon ring.
- the alkali-soluble resin has a maleimide structure represented by the above general formula (iii), it has a nitrogen atom in the hydrocarbon ring, so that it has very good compatibility with the dispersant of the present invention and an effect of suppressing development residue. improves.
- Specific examples of the optionally substituted hydrocarbon ring in R 1 M of the general formula (iii) are the same as the specific examples of the hydrocarbon ring described above.
- the heat resistance and adhesiveness of the colored layer are improved, and the brightness of the obtained colored layer is also preferably improved.
- the curability of the colored layer is improved, and the solvent resistance (NMP swelling suppression) is improved, which is particularly preferable.
- the alkali-soluble resin used in the present invention apart from the structural unit having a carboxy group, using an acrylic copolymer having a structural unit having the above hydrocarbon ring makes it easy to adjust the amount of each structural unit, and the above It is preferable from the viewpoint that the amount of structural units having a hydrocarbon ring can be increased to easily improve the functions of the structural units.
- the acrylic copolymer having a structural unit having a carboxy group and the above hydrocarbon ring is prepared by using an ethylenically unsaturated monomer having a hydrocarbon ring as the above-mentioned "other copolymerizable monomer". be able to.
- Examples of ethylenically unsaturated monomers having a hydrocarbon ring include cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, phenoxy Ethyl (meth) acrylate, styrene, etc., and from the point that the cross-sectional shape of the colored layer after development is maintained even in heat treatment, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (Meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate and styrene are preferred.
- the alkali-soluble resin used in the present invention also preferably has an ethylenically unsaturated bond in its side chain.
- the alkali-soluble resin and the dispersant of the present invention described above can form a crosslinked bond in the step of curing the resin composition during the production of a color filter, and
- the alkali-soluble resins can form cross-links, or the alkali-soluble resins and the photopolymerizable compound can form cross-links.
- an alkali-soluble resin having an ethylenically unsaturated bond in the side chain is used in combination with the dispersant of the present invention, the film strength of the cured film is further improved by a synergistic effect, so that the brightness of the colored layer and the ITO film are improved. Furthermore, the resistance to development is improved, and the heat shrinkage of the cured film is suppressed, resulting in excellent adhesion to the substrate.
- a method for introducing an ethylenically unsaturated bond into an alkali-soluble resin may be appropriately selected from conventionally known methods.
- a method in which a compound having both an epoxy group and an ethylenically unsaturated bond in the molecule, such as glycidyl (meth)acrylate, is added to the carboxyl group of the alkali-soluble resin to introduce an ethylenically unsaturated bond into the side chain is added to the carboxyl group of the alkali-soluble resin to introduce an ethylenically unsaturated bond into the side chain.
- a structural unit having a hydroxyl group is introduced into a copolymer, a compound having an isocyanate group and an ethylenically unsaturated bond is added to the molecule, and an ethylenically unsaturated bond is introduced into the side chain.
- the alkali-soluble resin used in the present invention may further contain other structural units such as a structural unit having an ester group such as methyl (meth)acrylate and ethyl (meth)acrylate.
- a structural unit having an ester group functions not only as a component that suppresses the alkali solubility of the photosensitive colored resin composition, but also as a component that improves the solubility in a solvent and the solvent re-solubility.
- the alkali-soluble resin used in the present invention should contain an alkali-soluble resin having a glass transition temperature (Tg) of 60° C. or less, since it is easy to form a red colored layer having a cross-sectional shape with a taper angle of less than 60 degrees. is preferable, and it is preferable to contain an alkali-soluble resin having a glass transition temperature (Tg) of 30° C. or less.
- the alkali-soluble resin having a glass transition temperature (Tg) of 60° C. or lower may have a glass transition temperature (Tg) of 0° C. or higher from the viewpoint of improving the development adhesion.
- the alkali-soluble resin used in the present invention preferably contains 30% by mass or more, preferably 35% by mass or more, of an alkali-soluble resin having a glass transition temperature (Tg) of 60° C. or less with respect to the total amount of the alkali-soluble resin. is more preferable, more preferably 40% by mass or more, and may be 100% by mass.
- Tg glass transition temperature
- the glass transition temperature (Tg) of the alkali-soluble resin is measured using differential scanning calorimetry (DSC) (for example, EXSTAR DSC 7020 manufactured by SII Nanotechnology) according to the method described in JIS K7121. be able to.
- DSC differential scanning calorimetry
- the peak area that is, the peak with the largest area of the portion protruding from the baseline of the obtained chart is taken as the representative value of the glass transition temperature.
- the glass transition temperature (Tg) of the copolymer can be calculated by the following formula and used as a guideline.
- Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer.
- Tgi homopolymer glass transition temperature value of each monomer, the value in Polymer Handbook (3rd Edition) (J. Brandrup, EHImmergut (Wiley-Interscience, 1989)) can be adopted.
- the glass transition temperature value (Tgi) of the homopolymer is derived from a monomer of 0°C or less, even if it contains —O— bonds. It preferably contains a structural unit containing a good hydrocarbon group in its side chain, and preferably contains 15% by mass or more of all structural units. Further, the glass transition temperature value (Tgi) of the monomer having a glass transition temperature value (Tgi) of 0° C. or less in the homopolymer is not particularly limited, but from the viewpoint of ensuring durability, it is ⁇ 100. °C or higher, and more preferably -60°C or higher.
- monomers having a glass transition temperature value (Tgi) of 60° C. or less in a homopolymer include n-butyl methacrylate (Tgi: 20° C.), isobutyl methacrylate (Tgi: 48° C.), 2- Ethylhexyl methacrylate (Tgi: -10°C), 2-ethoxyethyl methacrylate (Tgi: -16°C), isodecyl methacrylate (Tgi: -41°C), methoxypolyethylene glycol #400 methacrylate (Tgi: -69°C), etc. be done.
- the alkali-soluble resin used in the present invention is an acrylic resin such as an acrylic copolymer and a styrene-acrylic copolymer having a structural unit having a carboxyl group and a structural unit having a hydrocarbon ring.
- Acrylic resins such as acrylic copolymers and styrene-acrylic copolymers preferably having a structural unit having a carboxy group, a structural unit having a hydrocarbon ring, and a structural unit having an ethylenically unsaturated bond. It is more preferable to have
- the alkali-soluble resin can be made into an alkali-soluble resin with desired performance by appropriately adjusting the charging amount of each structural unit.
- the amount of the carboxyl group-containing ethylenically unsaturated monomer to be charged is preferably 5% by mass or more, more preferably 10% by mass or more, based on the total amount of the monomers in order to obtain a good pattern.
- the amount of the carboxyl group-containing ethylenically unsaturated monomer charged is preferably 50% by mass or less, and 40% by mass or less with respect to the total amount of the monomer.
- the coating film obtained has sufficient solubility in an alkaline developer, and the proportion of the carboxy group containing ethylenically unsaturated monomer is at the above upper limit. If it is below, the formed pattern tends not to come off from the substrate and the film roughening on the pattern surface tends not to occur during development with an alkaline developer.
- acrylic resins such as acrylic copolymers and styrene-acrylic copolymers having structural units having ethylenically unsaturated bonds, which are more preferably used as alkali-soluble resins, epoxy groups and ethylenically unsaturated
- the compound having a bond is preferably 10% by mass to 95% by mass, more preferably 15% by mass to 90% by mass, based on the charged amount of the carboxy group-containing ethylenically unsaturated monomer.
- a preferred weight average molecular weight (Mw) of the carboxy group-containing copolymer is in the range of 1,000 to 50,000, more preferably 3,000 to 20,000. If it is less than 1,000, the binder function after curing may be significantly deteriorated, and if it exceeds 50,000, pattern formation may become difficult during development with an alkaline developer.
- the weight average molecular weight (Mw) of the carboxy group-containing copolymer can be measured by Shodex GPC System-21H using polystyrene as a standard substance and THF as an eluent.
- the epoxy (meth)acrylate resin having a carboxy group is not particularly limited, but an epoxy (meth)acrylate obtained by reacting a reaction product of an epoxy compound and an unsaturated group-containing monocarboxylic acid with an acid anhydride.
- Acrylate compounds are suitable. Epoxy compounds, unsaturated group-containing monocarboxylic acids, and acid anhydrides can be appropriately selected from known ones and used. Epoxy (meth)acrylate resins having a carboxy group may be used alone or in combination of two or more.
- an alkali-soluble resin having an acid value of 50 mgKOH/g or more.
- the alkali-soluble resin preferably has an acid value of 60 mgKOH/g or more and 300 mgKOH/g or less from the viewpoint of developability (solubility) in an alkaline aqueous solution used as a developer and adhesion to a substrate. It is preferably 70 mgKOH/g or more and 200 mgKOH/g or less.
- the acid value of the alkali-soluble resin can be measured according to JIS K 0070:1992.
- the ethylenically unsaturated bond equivalent when the side chain of the alkali-soluble resin has an ethylenically unsaturated group improves the film strength of the cured film, improves the development resistance, and provides the effect of excellent adhesion to the substrate. From the point of view, it is preferably in the range of 100 to 2000, more preferably in the range of 140 to 1500. If the ethylenically unsaturated bond equivalent is 2000 or less, the development resistance and adhesion are excellent. Also, if it is 100 or more, the ratio of other structural units such as structural units having a carboxy group and structural units having a hydrocarbon ring can be relatively increased, so that excellent developability and heat resistance can be obtained.
- the ethylenically unsaturated bond equivalent is the weight average molecular weight per mole of the ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following formula (1).
- Ethylenically unsaturated bond equivalent (g / mol) W (g) / M (mol) (In formula (1), W represents the mass (g) of the alkali-soluble resin, and M represents the number of moles (mol) of ethylenically unsaturated bonds contained in the alkali-soluble resin W (g).)
- the ethylenically unsaturated bond equivalent is obtained, for example, by measuring the number of ethylenically unsaturated bonds contained per 1 g of the alkali-soluble resin in accordance with the iodine value test method described in JIS K 0070: 1992. can be calculated.
- the alkali-soluble resin used in the photosensitive red resin composition may be used alone or in combination of two or more, and the content is not particularly limited, but the photosensitive red resin
- the alkali-soluble resin is preferably in the range of 5% to 60% by mass, more preferably in the range of 10% to 40% by mass, based on the total solid content of the composition.
- the content of the alkali-soluble resin is at least the above lower limit, sufficient alkali developability is obtained, and when the content of the alkali-soluble resin is at most the above upper limit, film roughness and pattern chipping during development are prevented. can be suppressed.
- the photopolymerizable compound used in the photosensitive red resin composition is not particularly limited as long as it can be polymerized by the photoinitiator, and usually a compound having two or more ethylenically unsaturated bonds is suitable.
- Polyfunctional (meth)acrylates having two or more acryloyl groups or methacryloyl groups are particularly preferred.
- As such a polyfunctional (meth)acrylate it may be appropriately selected and used from conventionally known ones. Specific examples include those described in JP-A-2013-029832.
- polyfunctional (meth)acrylates may be used singly or in combination of two or more. Further, when excellent photocurability (high sensitivity) is required for the photosensitive red resin composition of the present invention, the polyfunctional (meth)acrylate has three polymerizable ethylenically unsaturated bonds (three Functionality) or more is preferable, and poly(meth)acrylates of trihydric or higher polyhydric alcohols and their dicarboxylic acid-modified products are preferable.
- trimethylolpropane tri(meth)acrylate penta Erythritol tri(meth)acrylate, succinic acid-modified pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol penta (Meth)acrylate modified with succinic acid, dipentaerythritol hexa(meth)acrylate and the like are preferred.
- the content of the photopolymerizable compound used in the photosensitive red resin composition is not particularly limited, but is preferably in the range of 5% by mass to 60% by mass with respect to the total solid content of the photosensitive red resin composition. , more preferably in the range of 10% by mass to 40% by mass.
- the content of the photopolymerizable compound is at least the above lower limit, photocuring sufficiently proceeds, the exposed portion can be suppressed from elution during development, the line width shift is suppressed, the solvent resistance is improved, and
- the content of the photopolymerizable compound is equal to or less than the above upper limit, the alkali developability is sufficient.
- the photoinitiator in the photosensitive red resin composition of the present invention is not particularly limited, and can be used alone or in combination of two or more of conventionally known various initiators.
- photoinitiators include aromatic ketones, benzoin ethers, halomethyloxadiazole compounds, ⁇ -aminoketones, biimidazoles, N,N-dimethylaminobenzophenone, halomethyl-S-triazine compounds, and thioxanthone. , oxime esters, and the like.
- a photoinitiator having an oxime ester skeleton hereinafter referred to as a photoinitiator (hereinafter referred to as It is preferable to use an oxime ester photoinitiator).
- oxime ester photoinitiators examples include 1,2-octadione-1-[4-(phenylthio)phenyl]-,2-(o-benzoyloxime), ethanone, 1-[9-ethyl-6-( 2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyloxime), JP 2000-80068, JP 2001-233842, JP 2010-527339, JP It can be appropriately selected from among the oxime ester photoinitiators described in Table 2010-527338, JP-A-2013-041153, and the like.
- the oxime ester photoinitiator preferably has a carbazole skeleton, a diphenyl sulfide skeleton or a fluorene skeleton from the viewpoint of improving sensitivity. It is also preferable from the viewpoint of improving the thermal stability and sensitivity of the oxime ester compound because of the internal electron transfer characteristics.
- oxime ester photoinitiators having a carbazole skeleton examples include ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime ) (eg, Irgacure OXE02, manufactured by BASF), methanone, [8-[[(acetyloxy)imino][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methyl]-11-(2 -ethylhexyl)-11H-benzo[a]carbazol-5-yl]-, (2,4,6-trimethylphenyl) (eg, Irgacure OXE-03, manufactured by BASF), ethanone, 1-[9-ethyl-6 -(1,3-dioxolane, 4-(2-methoxyphenoxy)-9H-carbazol-3-yl]-, 1-(o-acetylox
- the oxime ester photoinitiator having a carbazole skeleton it may be used alone or in combination of two or more.
- 9H-carbazol-3-yl]-,1-(o-acetyloxime) for example, TR-PBG-304, manufactured by Changzhou Tenryu Electric New Materials Co., Ltd.
- ethanone 1-[9-ethyl-6-( 2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (eg, Irgacure OXE02, manufactured by BASF), and methanone, (9-ethyl-6-nitro-9H- carbazol-3-yl)[4-(2-methoxy-1-methylethoxy-2-methylphenyl]-, o-acetyloxime, among others, 1-propanone ,3-cyclopentyl-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl
- Examples of the oxime ester photoinitiator having a diphenyl sulfide skeleton include an oxime ester compound represented by the following chemical formula (iv), 1,2-octadione, 1-[4-(phenylthio)phenyl]-, 2-( o-benzoyloxime] (e.g., Irgacure OXE01, manufactured by BASF), 1,2-propanedione, 3-cyclopentyl-1-[4-(phenylthio)phenyl]-,2-(o-benzoyloxime] (e.g., TR-PBG-305, manufactured by Changzhou Power Electronics New Materials Co., Ltd.), 1,2-propanedione, 3-cyclopentyl-1-[4-[(2-hydroxyethoxy)phenylthio]phenyl]-,2-(o-acetyl oxime], 1-pentanone, 1-[4-[4-(2-benzofuranylcarbonyl)phen
- an oxime ester compound represented by the general formula (1) described in WO 2018/062105 (the following general formula (v)).
- the oxime ester compound represented by the following general formula (v) may be the same as the oxime ester compound represented by general formula (1) described in WO 2018/062105.
- R a and R b are each independently a hydrogen atom or an alkyl group, and R c is a thioether bond (-S-), an ether bond (-O-) and a carbonyl bond (- CO—) is a hydrocarbon group optionally containing at least one divalent linking group selected from Z is a hydrogen atom or —(C ⁇ O)R d , where R d is an oxygen atom and a hydrocarbon group optionally containing at least one selected from a sulfur atom, or a heterocyclic group containing no nitrogen atom and containing at least one selected from an oxygen atom and a sulfur atom, and Re is a hydrocarbon group having 1 to 10 carbon atoms.
- a compound represented by the following chemical formula (v-1) is more preferable.
- Commercially available products include, for example, TR-PBG-365 (manufactured by Changzhou Tenryu Electric New Materials Co., Ltd.).
- the total content of the photoinitiator used in the photosensitive red resin composition of the present invention is not particularly limited as long as the effects of the present invention are not impaired, but with respect to the total solid content of the photosensitive red resin composition, It is preferably within the range of 0.1% by mass to 12.0% by mass, more preferably within the range of 1.0% by mass to 8.0% by mass.
- photocuring proceeds sufficiently to suppress the elution of the exposed portion during development, resulting in good solvent resistance. A decrease in luminance due to yellowing of the layer and deterioration of developability can be suppressed.
- the content ratio of the photopolymerizable compound and the photoinitiator used in the photosensitive red resin composition is such that the line width shift is suppressed, the solvent resistance is improved, and the development residue is suppressed.
- the total content of the photoinitiator is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, preferably 40 parts by mass with respect to 100 parts by mass of the photopolymerizable compound. It is not more than 30 parts by mass, more preferably not more than 30 parts by mass.
- the ratio of the total mass of the photoinitiator to the total mass of the photoinitiator and the ultraviolet absorber is preferably in the range of 30% to 95% by mass, more preferably 50% to 90% by mass. It is within the range of % by mass.
- photocuring proceeds sufficiently to suppress the elution of the exposed portion during development, while when it is at most the above upper limit, a cross-sectional shape with a taper angle of less than 60 degrees is formed. It's easy to do.
- the solvent used in the present invention is not particularly limited as long as it does not react with each component in the photosensitive red resin composition and is capable of dissolving or dispersing them.
- a solvent can be used individually or in combination of 2 or more types.
- Specific examples of solvents include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, i-propyl alcohol, methoxy alcohol and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ester solvents such
- glycol ether acetate-based solvents examples include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and one or more selected from the group consisting of 3-methoxybutyl acetate, from the viewpoint of solubility of other components and applicability.
- BCA butyl carbitol acetate
- 3-methoxy-3-methyl-1-butyl acetate ethyl ethoxypropionate
- ethyl lactate examples include one or more selected from the group consisting of 3-methoxybutyl acetate, from the viewpoint of solubility of other components and applicability.
- the content of the solvent may be appropriately set within a range in which the colored layer can be formed with high accuracy. It may generally be in the range of 55% by mass to 95% by mass, preferably in the range of 65% by mass to 88% by mass, based on the total amount of the photosensitive red resin composition containing the solvent. When the content of the solvent is within the above range, excellent applicability can be obtained.
- the photosensitive red resin composition of the present invention may optionally contain various additives.
- additives include antioxidants, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, antifoaming agents, silane coupling agents, ultraviolet absorbers, adhesion promoters, and the like.
- specific examples of surfactants and plasticizers include those described in JP-A-2013-029832.
- the photosensitive red resin composition of the present invention further contains an antioxidant from the viewpoint of suppressing the generation of development residues.
- the photosensitive red resin composition of the present invention contains an antioxidant in combination with a photoinitiator, an alkali-soluble resin, and a photopolymerizable compound, so that during drying during the formation of a coating film of the photosensitive red resin composition, , the photoinitiator, the alkali-soluble resin, and the photopolymerizable compound can be prevented from thermally reacting and deteriorating the developability, so that residues are less likely to occur during development.
- the heat resistance can be improved, and the decrease in luminance after exposure and post-baking can be suppressed, so that the luminance can be improved.
- the antioxidant used in the present invention is not particularly limited, and may be appropriately selected from those conventionally known.
- Specific examples of antioxidants include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, and the like. It is preferable to use a hindered phenol-based antioxidant from the viewpoint of improving the ability to form a fine line pattern according to the design of the line width and from the viewpoint of heat resistance. It may also be a latent antioxidant as described in WO 2014/021023.
- Hindered phenol-based antioxidants include, for example, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: trade name: IRGANOX1010, manufactured by BASF), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4,6-tris(4-hydroxy-3 ,5-di-tert-butylbenzyl)mesitylene (trade name: Irganox 1330, manufactured by BASF), 2,2′-methylenebis(6-tert-butyl-4-methylphenol) (trade name: Sumilizer MDP-S, Sumitomo Chemical), 6,6′-thiobis(2-tert-butyl-4-methylphenol) (trade name: Irganox 1081, manufactured by BASF), 3,5-di-
- pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX1010, manufactured by BASF) is preferable from the viewpoint of heat resistance and light resistance. .
- the content of the antioxidant is preferably in the range of 0.1% by mass to 10.0% by mass, more preferably 0.5% by mass to the total solid content of the photosensitive red resin composition. It is within the range of 5.0% by mass. If it is at least the above lower limit, it is excellent in that the suppression of generation of development residue is improved and heat resistance is improved. On the other hand, if it is the above upper limit or less, the colored resin composition of the present invention can be made into a highly sensitive photosensitive resin composition.
- the content of the antioxidant is preferably 2 parts by mass to 100 parts by mass, more preferably 5 parts by mass to 80 parts by mass, with respect to 100 parts by mass of the total amount of the photoinitiator. Within the above range, the effect of the above combination is excellent.
- silane coupling agents examples include KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-903, KBE-903, KBM573, KBM-403, KBE-402, KBE-403 , KBM-303, KBM-802, KBM-803, KBE-9007, X-12-967C (manufactured by Shin-Etsu Silicone Co., Ltd.) and the like.
- KBM-502, KBM-503, KBE-502, KBE-503 and KBM-5103 having a methacrylic group or an acrylic group are preferable from the viewpoint of adhesion to SiN substrates.
- the content of the silane coupling agent is preferably in the range of 0.05% by mass to 10.0% by mass, more preferably 0.1% by mass, relative to the total solid content of the photosensitive red resin composition. % to 5.0% by mass. If it is more than the said lower limit and below the said upper limit, it is excellent in board
- the method for producing a photosensitive red resin composition of the present invention comprises a coloring material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, the specific ultraviolet absorber, a solvent, and a desired It is preferable from the viewpoint of improving the contrast that it is a method that contains various additive components used by and the coloring material can be uniformly dispersed in the solvent by the dispersant. By mixing using a known mixing means, can be prepared.
- a coloring material and a dispersant are added to a solvent to prepare a coloring material dispersion, and an alkali-soluble resin and a light are added to the dispersion.
- a method of mixing a polymerizable compound, a photoinitiator, the specific ultraviolet absorber, and various additive components optionally used (2) a colorant, a dispersant, an alkali-soluble resin, and A method of simultaneously adding and mixing a photopolymerizable compound, a photoinitiator, the specific ultraviolet absorber, and various additive components that are optionally used; (3) dispersing agent and alkali-soluble resin in solvent; , a method of adding a photopolymerizable compound, a photoinitiator, the specific ultraviolet absorber, and various additive components that are optionally used, mixing, and then adding and dispersing a coloring material; (4) in a solvent A coloring material, a dispersant, and an alkali-soluble resin are added
- the above methods (1) and (4) are preferable because they can effectively prevent the aggregation of the colorant and uniformly disperse the colorant.
- the method for preparing the colorant dispersion can be appropriately selected from conventionally known dispersion methods. For example, (1) a dispersant is mixed with a solvent in advance and stirred to prepare a dispersant solution, and then an organic acid compound is mixed as necessary to form a salt between the amino group of the dispersant and the organic acid compound.
- a method of mixing this with a coloring material and, if necessary, other components and dispersing using a known stirrer or disperser (2) mixing and stirring a dispersant in a solvent to prepare a dispersant solution; , a coloring material and, if necessary, an organic acid compound, and if necessary, other components are mixed and dispersed using a known stirrer or disperser; (3) a dispersant is mixed with a solvent and stirred; , Prepare a dispersant solution, then mix the coloring material and other components as necessary, make a dispersion using a known stirrer or disperser, and then add an organic acid compound as necessary. methods and the like.
- dispersing machines for dispersing include roll mills such as two-roll and three-roll roll mills, ball mills such as ball mills and vibrating ball mills, bead mills such as paint conditioners, continuous disk-type bead mills, and continuous annular-type bead mills.
- the diameter of the beads used is preferably 0.03 mm to 2.00 mm, more preferably 0.10 mm to 1.0 mm.
- the photosensitive red resin composition according to the present invention has a cross-sectional shape with a taper angle of less than 60 degrees while suppressing the generation of development residues, and can form a red colored layer with excellent substrate adhesion. , can be suitably used for color filter applications.
- the color filter according to the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is the photosensitive red resin composition according to the present invention. It is a hardened material.
- FIG. 1 is a schematic cross-sectional view showing an example of the color filter of the present invention.
- the color filter 10 of the present invention has a substrate 1, a light shielding portion 2 and a colored layer 3. As shown in FIG.
- At least one of the colored layers used in the color filter of the present invention is a colored layer that is a cured product of the photosensitive red resin composition of the present invention.
- the colored layer is usually formed in the opening of the light shielding part on the substrate, which will be described later, and is usually composed of colored patterns of three or more colors.
- the arrangement of the colored layers is not particularly limited, and may be, for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a 4-pixel arrangement type.
- the width, area, etc. of the colored layer can be arbitrarily set.
- the thickness of the colored layer can be appropriately controlled by adjusting the coating method, solid content concentration and viscosity of the photosensitive red resin composition, and is preferably in the range of 1 to 5 ⁇ m.
- the colored layer can be formed, for example, by the following method.
- a coating method such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, or a die coating method.
- the spin coating method and the die coating method can be preferably used.
- After drying the wet coating film using a hot plate or an oven it is exposed to light through a mask of a predetermined pattern, and the alkali-soluble resin and the polyfunctional monomer are photopolymerized and cured. It is used as a coating film.
- Light sources used for exposure include, for example, ultraviolet light from low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and electron beams.
- the amount of exposure is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
- heat treatment may be performed.
- the heating conditions are appropriately selected depending on the mixing ratio of each component in the photosensitive red resin composition to be used, the thickness of the coating film, and the like.
- a coating film is formed in a desired pattern by developing with a developer to dissolve and remove the unexposed portions.
- a developer a solution obtained by dissolving an alkali in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to this alkaline solution.
- a general method can be adopted as the developing method.
- the developer After development processing, the developer is usually washed and the cured coating film of the photosensitive red resin composition is dried to form a colored layer.
- the heating conditions are not particularly limited and are appropriately selected according to the application of the coating film.
- the light-shielding portion in the color filter of the present invention is formed in a pattern on a substrate to be described later, and can be the same as those used as light-shielding portions in general color filters.
- the pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape, a matrix shape, and the like.
- the light shielding portion may be a metal thin film of chromium or the like formed by a sputtering method, a vacuum deposition method, or the like.
- the light-shielding portion may be a resin layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, or organic pigments in a resin binder.
- a method of patterning by development using a photosensitive resist a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring a photosensitive resist, and the like can be used. be.
- the film thickness of the light-shielding portion is set to about 0.2 to 0.4 ⁇ m in the case of a metal thin film, and is set to about 0.5 to 2 ⁇ m in the case of a black pigment dispersed or dissolved in a binder resin. be done.
- a transparent substrate, a silicon substrate, and a transparent substrate or a silicon substrate on which an aluminum, silver, silver/copper/palladium alloy thin film or the like is formed are used.
- Other color filter layers, resin layers, transistors such as TFTs, circuits, and the like may be formed on these substrates.
- the transparent substrate in the color filter of the present invention is not particularly limited as long as it is transparent to visible light, and transparent substrates used in general color filters can be used. Specifically, transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible materials such as transparent resin films, optical resin plates, and flexible glass. material.
- the thickness of the transparent substrate is not particularly limited, a thickness of about 100 ⁇ m to 1 mm, for example, can be used depending on the application of the color filter of the present invention.
- the color filter of the present invention may be formed with, for example, an overcoat layer, a transparent electrode layer, an alignment film, columnar spacers, etc., in addition to the above substrate, light shielding portion and colored layer.
- Display Device A display device according to the present invention includes the color filter according to the present invention.
- the configuration of the display device is not particularly limited, and can be appropriately selected from conventionally known display devices, such as liquid crystal display devices and organic light-emitting display devices.
- FIG. 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention.
- a liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer formed between the color filter 10 and the counter substrate 20.
- the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, and may have a known configuration as a liquid crystal display device generally using color filters.
- the driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for liquid crystal display devices can be adopted. Examples of such driving methods include the TN method, IPS method, OCB method, and MVA method. Any of these methods can be suitably used in the present invention. Also, the counter substrate can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention. Further, as the liquid crystal forming the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used according to the driving method of the liquid crystal display device of the present invention.
- a method for forming the liquid crystal layer a method generally used as a method for manufacturing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method. After the liquid crystal layer is formed by the above method, the liquid crystal cell is gradually cooled to room temperature, thereby aligning the enclosed liquid crystal.
- FIG. 3 is a schematic diagram showing an example of the organic light-emitting display device of the present invention.
- the organic light-emitting display device 100 of the present invention has a color filter 10 and an organic light-emitting body 80.
- An organic protective layer 50 and an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitter 80 .
- a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light emitting layer 74, an electron injection layer 75, and a cathode 76 are sequentially formed on the upper surface of the color filter.
- method, and a method of bonding the organic light-emitting body 80 formed on another substrate onto the inorganic oxide film 60, and the like are known structures can be appropriately used.
- the organic light-emitting display device 100 manufactured in this way can be applied to, for example, a passive drive type organic EL display and an active drive type organic EL display.
- the organic light-emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and may have a known configuration as an organic light-emitting display device generally using color filters.
- the mass average molecular weight (Mw) of the copolymer before salt formation was determined as a standard polystyrene equivalent value by GPC (gel permeation chromatography) according to the measurement method described in the specification of the present invention.
- the transmittance of the ultraviolet absorber at a wavelength of 365 nm was obtained by preparing a 0.002% by mass propylene glycol monomethyl ether acetate solution of each ultraviolet absorber, and measuring the transmittance of the 0.002% by mass propylene glycol monomethyl ether acetate solution by measuring the transmittance of the 0.002% by mass propylene glycol monomethyl ether acetate solution. It was measured using an infrared spectrophotometer (JASCO Corporation V-770). Table 1 shows the measurement results of the transmittance of the ultraviolet absorbent at a wavelength of 365 nm.
- UV absorber 2 Tinuvin 326
- BASF UV absorber 3 Tinuvin 477
- BASF UV absorber 4 KEMISORB111
- Chemipro Kasei comparative UV absorber C1 Tinuvin 400
- BASF comparative UV absorber C2 Tinuvin 900
- BASF comparative UV Absorbent C3 Tinuvin384-2, manufactured by BASF Comparative UV absorber C4: Kemisorb12, manufactured by Chemipro Kasei Comparative UV absorber C5: Tinuvin479, manufactured by BASF
- Preparation Example 1 Preparation of alkali-soluble resin A
- a polymerization tank was charged with 300 parts by mass of PGMEA, heated to 100° C. under a nitrogen atmosphere, and then 55.6 parts by mass of benzyl methacrylate (BzMA), 2.4 parts by mass of MMA, methoxypolyethylene glycol-methacrylate (manufactured by NOF 66 parts by mass of PME-1000), 56 parts by mass of methacrylic acid (MAA), 6 parts by mass of Perbutyl O (manufactured by NOF), and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) continuously over 1.5 hours. Dripped.
- BzMA benzyl methacrylate
- MMA methoxypolyethylene glycol-methacrylate
- MAA methoxypolyethylene glycol-methacrylate
- MAA methoxypolyethylene glycol-methacrylate
- MAA methoxypolyethylene glyco
- An addition reaction was carried out to obtain an alkali-soluble resin A solution (weight average molecular weight (Mw) of 8500, acid value of 75 mgKOH/g, Tg of 25°C, solid content of 40% by mass).
- the weight average molecular weight was measured with a Shodex GPC System-21H using polystyrene as a standard and THF as an eluent.
- the acid value was measured according to JIS K 0070.
- the glass transition temperature (Tg) was measured using differential scanning calorimetry (EXSTAR DSC 7020, manufactured by SII Nano Technology Co., Ltd.) according to the method described in JIS K7121.
- MMA methyl methacrylate
- MMA methoxypolyethylene glycol-methacrylate
- DMMA dimethylaminoethyl methacrylate
- PGMEA propylene glycol monomethyl ether acetate
- HLC-8220 manufactured by Tosoh Corporation equipped with an RI detector was used, the developing solvent was THF, the molecular weight standard polymer was standard polystyrene, and GPC was measured to obtain the molecular weight distribution and the mass average molecular weight. Moreover, the amine value was 67 mgKOH/g.
- AIBN '-azobisisobutyronitrile
- Example 1 Production of photosensitive red resin composition R-1)
- Preparation of Colorant Dispersion R (1) In a 225 mL mayonnaise bottle, 64.3 parts by mass of PGMEA, 13.5 parts by mass of the alkali-soluble resin A solution of Preparation Example 1 (solid content: 40% by mass), Synthesis Example 1 10.1 parts by mass of a PGMEA solution (solid content 40% by mass) of the block copolymer (dispersant A) and 0.17 parts by mass of phenylphosphonic acid as a salt-forming agent a of the dispersant were added and stirred. there, C. I.
- Example 2 Production of photosensitive red resin composition R-2)
- Example 1 As shown in Table 2, the type of dispersant was changed from dispersant A to the graft copolymer (dispersant B) of Synthesis Example 2 to prepare a colorant dispersion.
- a photosensitive red resin composition R-2 was obtained in the same manner as the red resin composition R-1.
- Examples 3 to 5 Production of photosensitive red resin compositions R-3 to R-5)
- photosensitive red resin compositions R-3 to R-5 were prepared in the same manner as the photosensitive red resin composition R-1, except that the type of ultraviolet absorber was changed as shown in Table 2. got
- Example 6 to 8 Production of photosensitive red resin compositions R-6 to R-8
- photosensitive red resin compositions R-6 to R-8 were obtained in the same manner as the photosensitive red resin composition R-1, except that the type of pigment was changed as shown in Table 2. rice field.
- Example 8 instead of using 12 parts by mass of PR291, 10.2 parts by mass of PR291 and C.I. I. Pigment Yellow 150 (PY150) was used in an amount of 1.8 parts by mass.
- Example 9 Production of photosensitive red resin composition R-9
- a photosensitive red resin composition R-9 was obtained in the same manner as the photosensitive red resin composition R-1 except that the antioxidant was not added as shown in Table 2 in Example 1.
- Example 10 to 12 Production of photosensitive red resin compositions R-10 to R-12
- salt-forming agent a of the dispersant as shown in Table 2
- salt-forming agent b benzyl chloride
- salt-forming agent c benzyl bromide
- Example 13 Production of photosensitive red resin composition R-13
- the amount of the ultraviolet absorber was increased three times as shown in Table 2 (30 parts by weight per 100 parts by weight of the total solid content excluding the pigment component), except for the photosensitive red resin composition
- a photosensitive red resin composition R-13 was obtained in the same manner as in product R-1.
- Comparative Examples 1 and 2 Production of photosensitive red resin compositions CR-1 and CR-2)
- Example 1 or Example 8 as shown in Table 2, the photosensitive red resin compositions of Comparative Examples 1 and 2 were prepared in the same manner as in Example 1 or Example 8, except that no ultraviolet absorber was used. Products CR-1 and CR-2 were manufactured.
- Photosensitive red resin compositions CR-3 to CR-8 were prepared in the same manner as in Example 1, except that the types of ultraviolet absorbers in Example 1 were changed as shown in Table 2. -7 was produced.
- a photosensitive red resin composition CR-8 of Comparative Example 8 was produced in the same manner as in Comparative Example 3, except that the type and amount of the ultraviolet absorbent in Comparative Example 3 were changed as shown in Table 2. .
- Example 9 Production of photosensitive red resin composition CR-9)
- the type of dispersant was changed from dispersant A to dispersant C (Solsperse 20000, manufactured by Lubrizol) to prepare a colorant dispersion.
- a photosensitive red resin composition CR-9 was obtained in the same manner as the resin composition R-1.
- the photosensitive red resin composition obtained in each example and each comparative example was coated on a glass substrate (manufactured by NH Techno Glass, "NA35") using a spin coater to form a cured coating film having a thickness of 3.0 ⁇ m. After the coating was applied so as to have a uniform thickness, it was dried at 80° C. for 3 minutes using a hot plate to form a coating film on the substrate. This coating film is exposed to ultraviolet rays of 50 mJ/cm 2 using an ultra-high pressure mercury lamp through a photomask (chromium mask) having a pattern with an opening size of 2 ⁇ m to 100 ⁇ m for forming independent thin lines, thereby exposing the glass. A post-exposure coating was formed on each substrate.
- a photomask chromium mask
- ⁇ Cross-sectional shape evaluation of fine line pattern colored layer The cross-sectional shape in the thickness direction of the resulting colored layer in the form of an independent thin line pattern was observed with a scanning electron microscope (manufactured by Shimadzu Corporation, super scan model 220, magnification of 10,000 times), and the cross-sectional shape of the colored layer was determined according to the following evaluation criteria.
- the taper angle ( ⁇ 1) (see FIG. 4) was evaluated.
- ⁇ Adhesion evaluation> The colored layer thus obtained was observed with an optical microscope to confirm the line width of the thinnest pattern as to how many ⁇ m of pattern the mask opening remained.
- D The line width of the thinnest pattern is 26 ⁇ m or more If the evaluation result is B, the substrate adhesion is good. If the evaluation result is A, the adhesion to the substrate is excellent.
- Examples 1 to 13 which are photosensitive red resin compositions according to the present invention, a coloring material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a solvent , and the coloring material is made of a pigment containing at least a red pigment, and the ultraviolet absorber has a transmittance at a wavelength of 365 nm of 35% or less in a 0.002% by mass propylene glycol monomethyl ether acetate solution. It was shown that a red colored layer having a cross-sectional shape with a taper angle of less than 60 degrees and excellent adhesion to a substrate can be formed while suppressing the generation of residues.
- the photosensitive red resin compositions of Comparative Examples 1 and 2 which differ from Examples 1 and 8 only in that they do not contain an ultraviolet absorber, have a taper angle ( ⁇ 1) exceeding 90 degrees in the cross-sectional shape. As a result, it was not possible to form a red colored layer with an excellent cross-sectional shape. Moreover, the photosensitive red resin compositions of Comparative Examples 1 and 2 were inferior to those of Examples 1 and 8 in terms of development residue.
- the taper angle ( ⁇ 1) exceeded 90 degrees, and a red colored layer with an excellent cross-sectional shape could not be formed.
- the photosensitive red resin composition of Comparative Example 8 which used a lot of ultraviolet absorbers having a transmittance of 0.002% by mass at a wavelength of 365 nm exceeding 35% in a propylene glycol monomethyl ether acetate solution, had a tapered cross-sectional shape.
- the angle ([theta]1) exceeded 90 degrees, and a red colored layer with an excellent cross-sectional shape could not be formed, and the adhesion to the substrate was also poor.
- the photosensitive red resin composition of Comparative Example 9 in which a dispersant different from at least one of the block copolymer and the graft copolymer was used as the dispersant, had poor development residue and poor dispersibility. was
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Optics & Photonics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optical Filters (AREA)
Abstract
Description
これらの液晶表示装置や有機発光表示装置には、カラーフィルタが用いられる。例えば液晶表示装置のカラー画像の形成は、カラーフィルタを通過した光がそのままカラーフィルタを構成する各画素の色に着色されて、それらの色の光が合成されてカラー画像を形成する。その際の光源としては、従来の冷陰極管のほか、白色発光の有機発光素子や白色発光の無機発光素子が利用される場合がある。有機発光表示装置では、色調整などのためにカラーフィルタを用いる。
カラーフィルタにおける着色層の形成方法としては、例えば、分散剤等により色材を分散してなる色材分散液にバインダー樹脂、光重合性化合物及び光開始剤を添加してなる着色樹脂組成物をガラス基板に塗布して乾燥後、フォトマスクを用いて露光し、現像を行うことによって着色パターンを形成し、加熱することによりパターンを固着して着色層を形成する。これらの工程を、各色ごとに繰り返してカラーフィルタを形成する。
(b1);1分子中に脂環式骨格とエチレン性不飽和結合とを有する化合物
(b2);1分子中にエポキシ基とエチレン性不飽和結合とを有する化合物
(b3);(a1)及び(a2)以外の、エチレン性不飽和結合を有する化合物、を共重合させて共重合体(b6)を得て、得られた共重合体(b6)と不飽和1塩基酸(b4)とを反応させて共重合体(b7)を得て、更に得られた共重合体(b7)と多塩基酸無水物(b5)とを反応させて得られる感光性樹脂(B-1)を含むことを特徴とする感光性着色組成物が開示されている。特許文献1においては、高画質化、低消費電力化に対応できる高解像性を有する感光性着色組成物、特に、COA方式のような厚膜でも高解像度で、パターン剥がれをおこさない密着性の優れた感光性着色組成物を得ることを目的としている。
また、特許文献2には、着色剤(A)と、樹脂(B)と、光重合性単量体(C)と、光重合開始剤(D)と、ベンゾトリアゾール系単量体とその他単量体成分を含む原料単量体を重合させてなる紫外線吸収剤(E)とを含むことを特徴とするカラーフィルタ用着色組成物であって、前記原料単量体中にベンゾトリアゾール系単量体を10.0質量%~90.0質量%含み、前記紫外線吸収剤(E)が、カラーフィルタ用着色組成物全体の固形分中に0.5~6.0重量%含有される、カラーフィルタ用着色組成物が開示されている。特許文献2においては、微細化顔料や染料を着色剤として用いても耐光性に優れたカラーフィルタ用着色組成物を提供することを目的としている。
感光性着色樹脂組成物の着色層は光(通常ピーク波長365nmの紫外線)照射により光硬化成分を硬化させるが、着色層における基材界面付近では光が届き難いため、着色層の表面に比べて基材界面付近は硬化が弱くなる。そのため、現像後の着色層は、基本的に、基材界面付近になるにつれて幅が狭くなる、逆テーパー形状の断面形状になる。しかしながら現像後のポストベーク時に、緑色着色層と青色着色層は、基材界面付近の十分に硬化していない部分の熱流動が起こりやすいことから、逆テーパー形状が解消される。それに対して赤色着色層は、緑色着色層や青色着色層に比べて、光照射時に用いられる波長365nmの透過率が高いことから、緑色着色層や青色着色層と同量の光照射を行うと、緑色着色層や青色着色層に比べて基材界面付近も硬化が進行しやすい。そのため、赤色着色層は、現像後のポストベーク時に、基材界面付近の部分の熱流動が起こり難く、逆テーパー形状が維持されやすいと考えられる。
また、前述のように、従来と比べカラーフィルタの着色層における色材濃度が高くなることで、相対的に光重合に必要な成分が少なくなり、パターニングが難しくなってきており、現像残渣の発生や、基板との密着性も問題となっている。
前記色材は、少なくとも赤色顔料を含む顔料からなり、
前記分散剤が、ブロック共重合体、及び、グラフト共重合体の少なくとも1種を含有し、
前記紫外線吸収剤は、波長365nmの透過率が0.002質量%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において35%以下である。
なお、本発明において光には、可視及び非可視領域の波長の電磁波、さらには放射線が含まれ、放射線には、例えばマイクロ波、電子線が含まれる。具体的には、波長5μm以下の電磁波、及び電子線のことをいう。
本発明において(メタ)アクリロイルとは、アクリロイル及びメタクリロイルの各々を表し、(メタ)アクリルとは、アクリル及びメタクリルの各々を表し、(メタ)アクリレートとは、アクリレート及びメタクリレートの各々を表す。
また、本明細書において数値範囲を示す「~」とは、その前後に記載された数値を下限値及び上限値として含む意味で使用される。
本発明に係る感光性赤色樹脂組成物は、色材と、分散剤と、アルカリ可溶性樹脂と、光重合性化合物と、光開始剤と、紫外線吸収剤と、溶剤とを含有し、
前記色材は、少なくとも赤色顔料を含む顔料からなり、
前記分散剤が、ブロック共重合体、及び、グラフト共重合体の少なくとも1種を含有し、
前記紫外線吸収剤は、波長365nmの透過率が0.002質量%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において35%以下である。
それに対して、前記感光性赤色樹脂組成物において、波長365nmの透過率が0.002質量%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において35%以下の紫外線吸収剤を選択して組み合わせたことから、赤色着色層における波長365nmの透過率が効果的に低減され、緑色着色層や青色着色層と同様に基材界面付近の硬化が抑制されて、現像後のポストベーク時に、緑色着色層や青色着色層と同様に基材界面付近の部分の熱流動が起こりやすくなり、テーパー角が60度未満になる断面形状を有する赤色着色層を形成可能になる。このようにテーパー角が60度未満になる断面形状を有する赤色着色層は、テーパー角が60度超過の断面形状を有する着色層に比べて、基材に対する密着性が向上するというメリットがある。また、このようなテーパー角が60度未満になる断面形状を有する赤色着色層は、塗布により電極を形成する際の断線を防止し得たり、基材と着色層間に不要な空隙が形成されて液晶内に気泡が生じることを防止し得るというメリットがある。
また、本発明においては分散剤としてブロック共重合体、及び、グラフト共重合体の少なくとも1種を用いることから、1分子当たりの顔料吸着基が多い分散剤が効率的に顔料に吸着するため、顔料単体が基板上に残って現像残渣となることを抑制できる。
さらに、前記感光性赤色樹脂組成物では、波長365nmの透過率が0.002質量%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において35%以下の紫外線吸収剤を選択して、ブロック共重合体及びグラフト共重合体の少なくとも1種の分散剤と組み合わせたことから、その相乗効果により現像残渣発生を抑制する効果が向上する。紫外線吸収剤によって回折光の影響が抑制されることでパターン部以外の硬化が抑えられ、現像残渣が発生し難くなって、現像残渣発生を抑制しながら、密着性に優れた赤色着色層を形成可能であると推定される。
さらに、色材が少なくとも赤色顔料を含む顔料からなることから、本発明に係る感光性赤色樹脂組成物の硬化物である赤色着色層は、紫外線照射やポストベーク等の製造時の工程による色度変化が抑制されたものである。
以下、このような本発明に係る感光性赤色樹脂組成物の各成分について、まず紫外線吸収剤から順に詳細に説明する。
本発明における紫外線吸収剤は、400nm以下に吸収極大波長があり、波長420nm超過の可視光に吸収を有しない化合物をいう。本発明に用いられる紫外線吸収剤は、波長400nm超過の可視光に吸収波長を有しない化合物であってよい。
置換基としては、例えば、ハロゲン原子、水酸基、シアノ基、又は、カルボニル基、エステル基、エーテル基、アミド基、イミド基等を含む基が挙げられ、アシル基、アシルオキシ基、アルコキシ基、アリールオキシ基、グリシジル基等であってよい。さらに芳香族炭化水素基の置換基としては、アルキル基であってもよい。
置換基を有する炭化水素基としては、例えば、-C2H3(OH)-CH2-O-C8H17、-C2H3(OH)-CH2-O-C12H25、-CH(CH3)-CO2-C8H17、メタクリロイルオキシエチル等であってよく、また、4-メチルフェニル、3-クロロフェニル、4-ベンジルオキシフェニル、4-シアノフェニル、4-フェノキシフェニル、4-グリシジルオキシフェニル、4-イソシアヌレートフェニル等であってよい。前記-C8H17、-C12H25等はそれぞれ直鎖又は分岐であってよい。
一般式(A)において、前記ハロゲン原子としては、塩素原子、フッ素原子、臭素原子等が挙げられる。
Y2、Y4、及びY6の少なくとも1つは、水酸基であってよく、ヒドロキシフェニルトリアジン系紫外線吸収剤であってよい。
なお、固形分とは、溶剤以外のもの全てであり、液状の光重合性化合物等も含まれる。
本発明の感光性赤色着色樹脂組成物において、色材は、少なくとも赤色顔料を含む顔料からなる。すなわち色材全量に対して顔料が100質量%である。色材が、少なくとも赤色顔料を含む顔料からなることから、紫外線照射やポストベーク等の製造時の工程による色度変化が抑制された赤色着色層を形成することが可能である。ここで本発明における顔料とは、溶剤に不溶性の色素化合物を意味する。本発明に用いられる顔料は、例えば、25℃のプロピレングリコールモノメチルエーテルアセテ-ト100gに対する溶解量、及び、25℃の水100gに対する溶解量がいずれも0.1g以下であることが好ましく、0.05g以下であることがより好ましく、0.01g以下であることが更に好ましい。
有機顔料は、発色性が高く、耐熱性も高いので、好ましく用いられる。有機顔料としては、例えばカラーインデックス(C.I.;The Society of Dyers and Colourists 社発行)においてピグメント(Pigment)に分類されている化合物、具体的には、下記のようなカラーインデックス(C.I.)番号が付されているものを挙げることができる。
ジケトピロロピロール顔料としては、例えば、C.I.ピグメントレッド254、255、264、272、291、及び前記一般式(i)で表されるジケトピロロピロール顔料が挙げられ、中でもC.I.ピグメントレッド254、272、291、及び前記一般式(i)においてR61及びR62がそれぞれ4-ブロモフェニル基であるジケトピロロピロール顔料から選ばれる少なくとも1種が好ましい。
黄色顔料としては、例えば、C.I.ピグメントイエロー1、3、12、13、14、15、16、17、20、24、31、55、60、61、65、71、73、74、81、83、93、95、97、98、100、101、104、106、108、109、110、113、114、116、117、119、120、126、127、128、129、138、139、150、151、152、153、154、155、156、166、168、175、185、及びC.I.ピグメントイエロー150の誘導体顔料等が挙げられる。
オレンジ色顔料としては、例えば、C.I.ピグメントオレンジ1、5、13、14、16、17、24、34、36、38、40、43、46、49、51、61、63、64、71、73等が挙げられる。
感光性赤色樹脂組成物中の色材の平均分散粒径は、少なくとも溶剤を含有する分散媒体中に分散している色材粒子の分散粒径であって、レーザー光散乱粒度分布計により測定されるものである。レーザー光散乱粒度分布計による粒径の測定としては、感光性赤色樹脂組成物に用いられている溶剤で、感光性赤色樹脂組成物をレーザー光散乱粒度分布計で測定可能な濃度に適宜希釈(例えば、1000倍など)し、レーザー光散乱粒度分布計(例えば、日機装社製ナノトラック粒度分布測定装置UPA-EX150)を用いて動的光散乱法により23℃にて測定することができる。ここでの平均分布粒径は、体積平均粒径である。
本発明の感光性赤色樹脂組成物において、前記色材は、分散剤により溶剤中に分散させて用いられる。色材を好適に分散でき、現像残渣を抑制可能な点から、本発明において用いられる分散剤は、ブロック共重合体、及び、グラフト共重合体の少なくとも1種を含有する。
3級アミンを有する繰り返し単位は、前記色材と親和性を有する部位である。3級アミンを有する繰り返し単位を含むブロック共重合体、及び、3級アミンを有する繰り返し単位を含むグラフト共重合体は、通常、溶剤と親和性を有する部位となる繰り返し単位を含むブロック共重合体又はグラフト共重合体であって良い。
3級アミンを有する繰り返し単位は、3級アミンを有していれば良く、該3級アミンは、共重合体の側鎖に含まれていても、主鎖を構成するものであっても良い。
中でも、前記色材と親和性を有する部位は、側鎖に3級アミンを有する繰り返し単位であることが好ましく、主鎖骨格が熱分解し難く、耐熱性が高い点から、下記一般式(I)で表される構造であることがより好ましい。
中でも、分散性の点から、一般式(I)におけるA1は、-CONH-基又は-COO-基を含む2価の連結基であることが好ましく、-CONH-基又は-COO-基と、炭素原子数1~10のアルキレン基とを含む2価の連結基であることがより好ましい。
アルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、tert-ブチル基、2-エチルヘキシル基、シクロペンチル基、シクロヘキシル基等が挙げられ、アルキル基の炭素原子数は、1~18が好ましく、中でも、メチル基又はエチル基であることがより好ましい。
アラルキル基としては、例えば、ベンジル基、フェネチル基、ナフチルメチル基、ビフェニルメチル基等が挙げられる。アラルキル基の炭素原子数は、7~20が好ましく、更に7~14が好ましい。
また、アリール基としては、フェニル基、ビフェニル基、ナフチル基、トリル基、キシリル基等が挙げられる。アリール基の炭素原子数は、6~24が好ましく、更に6~12が好ましい。なお、上記好ましい炭素原子数には、置換基の炭素原子数は含まれない。
ヘテロ原子を含む炭化水素基とは、上記炭化水素基中の炭素原子がヘテロ原子で置き換えられた構造を有するか、上記炭化水素基中の水素原子がヘテロ原子を含む置換基で置き換えられた構造を有する。炭化水素基が含んでいてもよいヘテロ原子としては、例えば、酸素原子、窒素原子、硫黄原子、ケイ素原子等が挙げられる。
また、炭化水素基中の水素原子は、フッ素原子、塩素原子、臭素原子等のハロゲン原子により置換されていてもよい。
重合体において、一般式(I)で表される構成単位は、1種類からなるものであってもよく、2種以上の構成単位を含むものであってもよい。
前記有機酸化合物としては、中でも、下記一般式(1)で表される化合物及び下記一般式(3)で表される化合物が好ましく、前記ハロゲン化炭化水素としては、中でも、下記一般式(2)で表される化合物が好ましい。すなわち、前記有機酸化合物及びハロゲン化炭化水素からなる群から選ばれる少なくとも1種としては、下記一般式(1)~(3)よりなる群から選択される1種以上の化合物を好ましく用いることができる。
前記有機酸化合物がフェニルホスホン酸やフェニルホスフィン酸等の酸性有機リン化合物であることが、色材の分散性及び分散安定性に優れる点から好ましい。このような分散剤に用いられる有機酸化合物の具体例としては、例えば、特開2012-236882号公報等に記載の有機酸化合物が好適なものとして挙げられる。
また、前記ハロゲン化炭化水素としては、臭化アリル、塩化ベンジル等のハロゲン化アリル及びハロゲン化アラルキルの少なくとも1種であることが、色材の分散性及び分散安定性に優れる点から好ましい。
なお、有機酸化合物及びハロゲン化炭化水素からなる群から選ばれる少なくとも1種は、1種単独で用いてもよく、2種以上を組み合わせてもよい。2種以上を組み合わせる場合は、その合計の含有量が上記範囲内であることが好ましい。
なお、共重合体の当該一般式(I)で表される構成単位が有する末端の窒素部位と、前記有機酸化合物及びハロゲン化炭化水素からなる群から選ばれる少なくとも1種とが塩を形成していること、及びその割合は、例えばNMR等、公知の手法により確認することができる。
以下、前記グラフト共重合体、及び、前記ブロック共重合体について、順に説明する。
中でも、分散性の点から、一般式(II)におけるA2は、-CONH-基又は-COO-基を含む2価の連結基であることが好ましく、-CONH-基又は-COO-基と、炭素原子数1~10のアルキレン基とを含む2価の連結基であることがより好ましい。
当該ポリマー鎖の構成単位としては、下記一般式(IV)で表される構成単位が挙げられる。
前記炭素数1~18のアルキル基は、直鎖状、分岐状、環状のいずれであってもよく、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、n-ノニル基、n-ラウリル基、n-ステアリル基、シクロペンチル基、シクロヘキシル基、ボルニル基、イソボルニル基、ジシクロペンタニル基、アダマンチル基、低級アルキル基置換アダマンチル基などを挙げることができる。アルキル基の炭素数は、1~12が好ましく、更に1~6が好ましい。
前記炭素数2~18のアルケニル基は、直鎖状、分岐状、環状のいずれであってもよい。このようなアルケニル基としては、例えばビニル基、アリル基、プロペニル基などを挙げることができる。アルケニル基の二重結合の位置には限定はないが、得られたポリマーの反応性の点からは、アルケニル基の末端に二重結合があることが好ましい。アルケニル基の炭素数は、2~12が好ましく、更に2~8が好ましい。
アリール基としては、フェニル基、ビフェニル基、ナフチル基、トリル基、キシリル基等が挙げられる。アリール基の炭素数は、6~24が好ましく、更に6~12が好ましい。
また、アラルキル基としては、ベンジル基、フェネチル基、ナフチルメチル基、ビフェニルメチル基等が挙げられ、更に置換基を有していてもよい。アラルキル基の炭素数は、7~20が好ましく、更に7~14が好ましい。
また、前記アリール基やアラルキル基等の芳香環には、置換基として炭素数1~30の直鎖状、分岐状のアルキル基が結合していても良い。
また、当該炭化水素基は、前記グラフト共重合体の分散性能等を妨げない範囲で、置換基を有しても良く、置換基としては、例えば、ハロゲン原子、水酸基、カルボキシ基、アルコキシ基、ニトロ基、シアノ基、エポキシ基、イソシアネート基、チオール基等が挙げられる。
下記一般式(III)で表される構成単位及び下記一般式(III’)で表される構成単位は、前記一般式(IV)で表される構成単位に包含される構成単位である。
一般式(III’)中、R44’は水素原子又はメチル基、A3’は2価の連結基、R47は炭素数が1~10のアルキレン基、R48は炭素数が3~7のアルキレン基、R49は、水素原子、又は炭化水素基であり、nは1以上40以下の数を表す。)
R46における炭化水素基としては、中でも、分散安定性や相溶性の点から、炭素数1~18のアルキル基、アルキル基が置換されていても良い炭素数6~12のアリール基、及び、アルキル基が置換されていても良い炭素数7~14のアラルキル基からなる群から選択される1種以上であることが好ましく、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、n-ノニル基、n-ラウリル基、n-ステアリル基、アルキル基が置換されていても良いフェニル基及びベンジル基からなる群から選択される1種以上であることが好ましい。
前記一般式(III’)において、R47は炭素数が1~10のアルキレン基であるが、中でも炭素数が2~8のアルキレン基であることが、溶剤再溶解性の点から好ましい。
R48は炭素数が3~7のアルキレン基であるが、中でも炭素数が3~5のアルキレン基、更に炭素数が5のアルキレン基であることが基材密着性の点から好ましい。
R49は、水素原子、又は炭化水素基であり、前記R49における炭化水素基としては、前記R46における炭化水素基と同様であって良い。
一方、nの上限値は40以下であるが、カラーフィルタ用途に使用される有機溶剤への溶解性の点から、20以下であることが好ましい。
前記ポリマー鎖において、前記一般式(III)で表される構成単位が含まれることが、酸素原子による溶剤親和性部の作用がより顕著になり、現像残渣の抑制、感光性樹脂組成物の現像時間の短縮化、及び耐溶剤性が向上する点から好ましい。
色材の分散性及び分散安定性の点から、前記一般式(IV)で表される構成単位の合計割合は、当該ポリマー鎖の全構成単位を100質量%とした時に、70質量%以上であることが好ましく、90質量%以上であることがより好ましい。一方で、分散安定性、及び優れた耐溶剤性を同時に満たす点から、前記ポリマー鎖において、前記一般式(IV)で表される構成単位の合計割合は、当該ポリマー鎖の全構成単位を100質量%とした時に、100質量%であってもよい。
その他の構成単位としては、前記一般式(IV)で表される構成単位を誘導するモノマーと共重合可能な不飽和結合を有する単量体由来の構成単位を挙げることができる。
その他の構成単位を誘導するモノマーとしては、例えば、スチレン、α-メチルスチレン等のスチレン類、フェニルビニルエーテル等のビニルエーテル類等が挙げられる。
前記範囲であることにより、分散剤としての十分な立体反発効果を保持できるとともに、分散剤の溶剤親和性部の比表面積が大きくなることにより、溶剤の塗膜への侵入や色材への到達を抑制することができると共に、ポリエチレンオキシド鎖又はポリプロピレンオキシド鎖が含まれる場合には、酸素原子による相互作用が顕著になり、現像時間の短縮化、耐溶剤性の向上の作用、更には水染み発生抑制及び現像残渣の発生抑制効果を良好にすることができる。
当該ポリマー鎖の溶解性は、グラフト共重合体を調製する際のポリマー鎖を導入する原料が前記溶解度を有することを目安にすることができる。例えば、グラフト共重合体にポリマー鎖を導入するために、ポリマー鎖及びその末端にエチレン性不飽和結合を有する基を含む重合性オリゴマー(マクロモノマー)を用いる場合、当該重合性オリゴマーが前記溶解度を有すれば良い。また、エチレン性不飽和結合を有する基を含むモノマー(エチレン性不飽和結合含有モノマー、以下単に、エチレン性不飽和モノマーということがある)により共重合体が形成された後に、共重合体中に含まれる反応性基と反応可能な反応性基を含むポリマー鎖を用いて、ポリマー鎖を導入する場合、当該反応性基を含むポリマー鎖が前記溶解度を有すれば良い。
一方、前記グラフト共重合体において、前記一般式(II)で表される構成単位は、40~97質量%の割合で含まれていることが好ましく、55~94質量%がより好ましく、70~91質量%がさらに好ましい。グラフト共重合体中の一般式(II)で表される構成単位が前記範囲内にあれば、グラフト共重合体中の溶剤親和性部の割合が適切になって、分散剤としての十分な立体反発効果を保持できるとともに、分散剤の溶剤親和性部の比表面積が大きくなることにより、溶剤の塗膜への侵入や色材への到達を抑制することができると共に、ポリエチレンオキシド鎖又はポリプロピレンオキシド鎖が含まれる場合には、酸素原子による相互作用が顕著になり、現像時間の短縮化、耐溶剤性の向上の作用、更には水染み発生抑制及び現像残渣の発生抑制効果を良好にすることができる。
前記一般式(I)で表される構成単位と共重合されている他の構成単位としては、例えば、前記一般式(IV)で表される構成単位等が挙げられる。
なお、前記構成単位の含有割合は、製造時には、グラフト共重合体を合成する際の、前記一般式(I)で表される構成単位、前記一般式(II)で表される構成単位、及び前記一般式(IV)で表される構成単位等を誘導するモノマーの仕込み量から算出される。
なお、本発明において質量平均分子量Mwは、GPC(ゲルパーミエーションクロマトグラフィー)により測定された値である。測定は、東ソー製のHLC-8120GPCを用い、溶出溶剤を0.01モル/リットルの臭化リチウムを添加したN-メチルピロリドンとし、校正曲線用ポリスチレンスタンダードをMw377400、210500、96000、50400、20650、10850、5460、2930、1300、580(以上、Polymer Laboratories製 Easi PS-2シリーズ)及びMw1090000(東ソー製)とし、測定カラムをTSK-GEL ALPHA-M×2本(東ソー製)として行われたものである。
本発明において、前記グラフト共重合体の製造方法としては、前記一般式(I)で表される構成単位と、前記一般式(II)で表される構成単位とを有するグラフト共重合体を製造することができる方法であればよく、特に限定されない。前記一般式(I)で表される構成単位と前記一般式(II)で表される構成単位とを有するグラフト共重合体を製造する場合、例えば、下記一般式(Ia)で表されるモノマーと、前記ポリマー鎖及びその末端にエチレン性不飽和結合を有する基からなる重合性オリゴマー(マクロモノマー)とを共重合成分として含有して共重合し、グラフト共重合体を製造する方法が挙げられる。
必要に応じて更にその他のモノマーも用い、公知の重合手段を用いてグラフト共重合体を製造することができる。
例えば、側鎖にグリシジル基を有する共重合体に、末端にカルボキシル基を有するポリマー鎖を反応させたり、側鎖にイソシアネート基を有する共重合体に、末端にヒドロキシ基を有するポリマー鎖を反応させたりして、ポリマー鎖を導入することができる。
なお、前記重合においては、重合に一般的に用いられる添加剤、例えば重合開始剤、分散安定剤、連鎖移動剤などを用いてもよい。
本発明においてブロック共重合体の各ブロックの配置は特に限定されず、例えば、ABブロック共重合体、ABAブロック共重合体、BABブロック共重合体等とすることができる。中でも、分散性に優れる点で、ABブロック共重合体、又はABAブロック共重合体が好ましい。
Aブロックは、本発明の目的を達成する範囲で、一般式(I)で表される構成単位以外の構成単位を有するものであってもよく、一般式(I)で表される構成単位と共重合可能な構成単位であれば含有することができる。具体的には例えば、前記一般式(IV)で表される構成単位等が挙げられる。
塩形成前のブロック共重合体におけるAブロック中、一般式(I)で表される構成単位の含有割合は、Aブロックの全構成単位の合計質量に対して、50~100質量%であることが好ましく、80~100質量%であることがより好ましく、100質量%であることが最も好ましい。一般式(I)で表される構成単位の割合が高いほど、色材への吸着力が向上し、ブロック共重合体の分散性、及び分散安定性が良好となるからである。なお、上記構成単位の含有割合は、一般式(I)で表される構成単位を有するAブロックを合成する際の仕込み質量から算出される。
なお、一般式(I)で表される構成単位は、色材との親和性を有すればよく、1種からなるものであっても良いし、2種以上の構成単位を含んでいてもよい。
Bブロックに含まれる構成単位としては、例えば、前記一般式(IV)で表される構成単位等が挙げられる。
前記一般式(IV)で表される構成単位として、前記一般式(III)で表される構成単位及び前記一般式(III’)で表される構成単位からなる群から選択される少なくとも1種の構成単位が含まれることが、現像残渣の抑制、感光性樹脂組成物の現像時間の短縮化、及び感光性赤色樹脂組成物の硬化物の耐溶剤性が更に良好になる点から好ましい。
この場合のBブロックは、国際公開第2016/104493号のBブロックと同様であってよい。
ここで、質量平均分子量は(Mw)、前記と同様に測定することができる。
アミン価が上記範囲内であることにより、粘度の経時安定性や耐熱性に優れると共に、アルカリ現像性や、溶剤再溶解性にも優れている。本発明において、前記一般式(I)で表される構成単位を含む共重合体のアミン価は、中でも、アミン価が80mgKOH/g以上であることが好ましく、90mgKOH/g以上であることがより好ましい。一方、溶剤再溶解性の点から、前記一般式(I)で表される構成単位を含む共重合体のアミン価は、110mgKOH/g以下であることが好ましく、105mgKOH/g以下であることがより好ましい。
アミン価は、試料1g中に含まれるアミン成分を中和するのに要する過塩素酸と当量の水酸化カリウムのmg数をいい、JIS-K7237に定義された方法により測定することができる。当該方法により測定した場合には、分散剤中の有機酸化合物と塩形成しているアミノ基であっても、通常、当該有機酸化合物が解離するため、分散剤として用いられる共重合体そのもののアミン価を測定することができる。
分散剤の含有量は、感光性赤色樹脂組成物の固形分全量に対して、好ましくは1質量%~40質量%の範囲内であり、より好ましくは2質量%~30質量%の範囲内である。上記下限値以上であれば、色材の分散性及び分散安定性に優れ、感光性赤色樹脂組成物の保存安定性により優れている。また、上記上限値以下であれば、現像性が良好なものとなる。特に色材濃度が高い着色層を形成する場合には、分散剤の含有量は、感光性赤色樹脂組成物の固形分全量に対して、好ましくは2質量%~45質量%、より好ましくは3質量%~40質量%の範囲内である。
本発明におけるアルカリ可溶性樹脂は酸性基を有するものであり、バインダー樹脂として作用し、かつパターン形成する際に用いられるアルカリ現像液に可溶性であるものの中から、適宜選択して使用することができる。
本発明において、アルカリ可溶性樹脂とは、酸価が40mgKOH/g以上であることを目安にすることができる。
本発明における好ましいアルカリ可溶性樹脂は、酸性基、通常カルボキシ基を有する樹脂であり、具体的には、カルボキシ基を有するアクリル系共重合体及びカルボキシ基を有するスチレン-アクリル系共重合体等のアクリル系樹脂、カルボキシ基を有するエポキシ(メタ)アクリレート樹脂等が挙げられる。これらの中で特に好ましいものは、側鎖にカルボキシ基を有するとともに、さらに側鎖にエチレン性不飽和基等の光重合性官能基を有するものである。光重合性官能基を含有することにより形成される硬化膜の膜強度が向上するからである。また、これらアクリル系共重合体及びスチレン-アクリル系共重合体等のアクリル系樹脂、並びにエポキシアクリレート樹脂は、2種以上混合して使用してもよい。
カルボキシ基含有エチレン性不飽和モノマーとしては、例えば、(メタ)アクリル酸、ビニル安息香酸、マレイン酸、マレイン酸モノアルキルエステル、フマル酸、イタコン酸、クロトン酸、桂皮酸、アクリル酸ダイマーなどが挙げられる。また、2-ヒドロキシエチル(メタ)アクリレートなどの水酸基を有する単量体と無水マレイン酸や無水フタル酸、シクロヘキサンジカルボン酸無水物のような環状無水物との付加反応物、ω-カルボキシ-ポリカプロラクトンモノ(メタ)アクリレートなども利用できる。また、カルボキシ基の前駆体として無水マレイン酸、無水イタコン酸、無水シトラコン酸などの無水物含有モノマーを用いてもよい。中でも、共重合性やコスト、溶解性、ガラス転移温度などの点から(メタ)アクリル酸が特に好ましい。
このような炭化水素環としては、置換基を有していてもよい環状の脂肪族炭化水素環、置換基を有していてもよい芳香族環、及びこれらの組み合わせが挙げられ、炭化水素環がカルボニル基、カルボキシ基、オキシカルボニル基、アミド基等の置換基を有していてもよい。中でも、脂肪族環を含む場合には、着色層の耐熱性や密着性が向上すると共に、得られた着色層の輝度が向上する。
炭化水素環の具体例としては、シクロプロパン、シクロブタン、シクロペンタン、シクロヘキサン、ノルボルナン、トリシクロ[5.2.1.0(2,6)]デカン(ジシクロペンタン)、アダマンタン等の脂肪族炭化水素環;ベンゼン、ナフタレン、アントラセン、フェナントレン、フルオレン等の芳香族環;ビフェニル、ターフェニル、ジフェニルメタン、トリフェニルメタン、スチルベン等の鎖状多環や、下記化学式(ii)に示されるカルド構造等が挙げられる。
前記一般式(iii)のRMにおける、置換されていてもよい炭化水素環の具体例としては、前記炭化水素環の具体例と同様のものが挙げられる。
また、前記化学式(ii)に示されるカルド構造を含む場合には、着色層の硬化性が向上し、耐溶剤性(NMP膨潤抑制)が向上する点から特に好ましい。
カルボキシ基を有する構成単位と、上記炭化水素環とを有するアクリル系共重合体は、前述の“共重合可能なその他のモノマー”として炭化水素環を有するエチレン性不飽和モノマーを用いることにより調製することができる。
前記炭化水素環を有するエチレン性不飽和モノマーとしては、例えば、シクロヘキシル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、アダマンチル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ベンジル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、スチレンなどが挙げられ、現像後の着色層の断面形状が加熱処理においても維持される効果が大きい点から、シクロヘキシル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、アダマンチル(メタ)アクリレート、ベンジル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、スチレンが好ましい。
アルカリ可溶性樹脂中に、エチレン性不飽和結合を導入する方法は、従来公知の方法から適宜選択すればよい。例えば、アルカリ可溶性樹脂が有するカルボキシ基に、分子内にエポキシ基とエチレン性不飽和結合とを併せ持つ化合物、例えばグリシジル(メタ)アクリレート等を付加させ、側鎖にエチレン性不飽和結合を導入する方法や、水酸基を有する構成単位を共重合体に導入しておいて、分子内にイソシアネート基とエチレン性不飽和結合とを備えた化合物を付加させ、側鎖にエチレン性不飽和結合を導入する方法などが挙げられる。
本発明で用いられるアルカリ可溶性樹脂は、アルカリ可溶性樹脂全量に対して、ガラス転移温度(Tg)が60℃以下のアルカリ可溶性樹脂を30質量%以上含有することが好ましく、35質量%以上含有することがより好ましく、40質量%以上含有することがさらに好ましく、100質量%であってもよい。
また、共重合体のガラス転移温度(Tg)は下記式で計算して目安とすることができる。
1/Tg=Σ(Xi/Tgi)
ここでは、共重合体はi=1からnまでのn個のモノマー成分が共重合しているとする。Xiはi番目のモノマーの重量分率(ΣXi=1)、Tgiはi番目のモノマーの単独重合体のガラス転移温度(絶対温度)である。ただしΣはi=1からnまでの和をとる。なお、各モノマーの単独重合体ガラス転移温度の値(Tgi)は、Polymer Handbook (3rd Edition) (J.Brandrup, E.H.Immergut著 (Wiley-Interscience、1989))の値を採用することができる。
単独重合体でのガラス転移温度の値(Tgi)が60℃以下のモノマーとしては、具体的には例えば、n-ブチルメタクリレート(Tgi:20℃)、イソブチルメタクリレート(Tgi:48℃)、2-エチルヘキシルメタクリレート(Tgi:-10℃)、2-エトキシエチルメタクリレート(Tgi:-16℃)、イソデシルメタクリレート(Tgi:-41℃)、メトキシポリエチレングリコール#400メタクリレート(Tgi:-69℃)等が挙げられる。
カルボキシ基含有エチレン性不飽和モノマーの割合が上記下限値以上であると得られる塗膜のアルカリ現像液に対する溶解性が十分であり、また、カルボキシ基含有エチレン性不飽和モノマーの割合が上記上限値以下であると、アルカリ現像液による現像時に、形成されたパターンの基板からの脱落やパターン表面の膜荒れが起こり難い傾向がある。
なお、カルボキシ基含有共重合体の上記重量平均分子量(Mw)は、ポリスチレンを標準物質とし、THFを溶離液としてショウデックスGPCシステム-21H(Shodex GPC System-21H)により測定することができる。
エポキシ化合物、不飽和基含有モノカルボン酸、及び酸無水物は、公知のものの中から適宜選択して用いることができる。カルボキシ基を有するエポキシ(メタ)アクリレート樹脂は、それぞれ1種単独で使用してもよいし、二種以上を併用してもよい。
なお、アルカリ可溶性樹脂の酸価はJIS K 0070:1992に従って測定することができる。
ここで、エチレン性不飽和結合当量とは、上記アルカリ可溶性樹脂におけるエチレン性不飽和結合1モル当りの重量平均分子量のことであり、下記数式(1)で表される。
エチレン性不飽和結合当量(g/mol)=W(g)/M(mol)
(数式(1)中、Wは、アルカリ可溶性樹脂の質量(g)を表し、Mはアルカリ可溶性樹脂W(g)中に含まれるエチレン性不飽和結合のモル数(mol)を表す。)
感光性赤色樹脂組成物において用いられる光重合性化合物は、前記光開始剤によって重合可能なものであればよく、特に限定されず、通常、エチレン性不飽和結合を2つ以上有する化合物が好適に用いられ、特にアクリロイル基又はメタクリロイル基を2つ以上有する、多官能(メタ)アクリレートであることが好ましい。
このような多官能(メタ)アクリレートとしては、従来公知のものの中から適宜選択して用いればよい。具体例としては、例えば、特開2013-029832号公報に記載のもの等が挙げられる。
本発明の感光性赤色樹脂組成物における光開始剤は、特に制限はなく、従来知られている各種開始剤の中から、1種又は2種以上を組み合わせて用いることができる。
光開始剤としては、例えば、芳香族ケトン類、ベンゾインエーテル類、ハロメチルオキサジアゾール化合物、α-アミノケトン類、ビイミダゾール類、N,N-ジメチルアミノベンゾフェノン、ハロメチル-S-トリアジン系化合物、チオキサントン、オキシムエステル類等を挙げることができる。
現像残渣発生を抑制しながら、テーパー角が60度未満になる断面形状を有し、基板密着性に優れた赤色着色層を形成する点から、中でも、オキシムエステル骨格を有する光開始剤(以下、オキシムエステル系光開始剤という)を用いることが好ましい。
オキシムエステル系光開始剤としては、感度が向上する点から、カルバゾール骨格、ジフェニルスルフィド骨格又はフルオレン骨格を有するものが好ましく、カルバゾール骨格を有するオキシムエステル系光開始剤は、大きい共役系及びより強い分子内電子移動特性となり、オキシムエステル化合物の熱安定性および感度が向上する点からも好ましい。
カルバゾール骨格を有するオキシムエステル系光開始剤としては、単独で又は2種以上組み合わせて用いても良く、中でも、1-プロパノン,3-シクロペンチル-1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(o-アセチルオキシム)(例えば、TR-PBG-304、常州強力電子新材料社製)、エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(O-アセチルオキシム)(例えば、イルガキュアOXE02、BASF社製)、及び、メタノン,(9-エチル-6-ニトロ-9H-カルバゾール-3-イル)[4-(2-メトキシ-1-メチルエトキシ-2-メチルフェニル]-,o-アセチルオキシムからなる群から選択される少なくとも1種を用いることが、中でも、1-プロパノン,3-シクロペンチル-1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(o-アセチルオキシム)(例えば、TR-PBG-304、常州強力電子新材料社製)を用いることが、感度が高い点から好ましい。
また、感光性赤色樹脂組成物において用いられる前記光重合性化合物と前記光開始剤との含有割合は、線幅シフトが抑制され、耐溶剤性が良好になる点、更には、現像残渣の抑制効果が向上する点から、前記光重合性化合物100質量部に対して、前記光開始剤の合計含有割合が好ましくは5質量部以上であり、より好ましくは10質量部以上であり、好ましくは40質量部以下であり、より好ましくは30質量部以下である。
また、前記光開始剤と前記紫外線吸収剤の合計質量に対する、前記光開始剤の合計質量の比率は、好ましくは30質量%~95質量%の範囲内であり、より好ましくは50質量%~90質量%の範囲内である。この含有量が上記下限値以上であると十分に光硬化が進み露光部分が現像時に溶出することを抑制し、一方上記上限値以下であると、テーパー角が60度未満になる断面形状を形成しやすい。
本発明に用いられる溶剤としては、感光性赤色樹脂組成物中の各成分とは反応せず、これらを溶解もしくは分散可能な有機溶剤であればよく、特に限定されない。溶剤は単独もしくは2種以上組み合わせて使用することができる。
溶剤の具体例としては、例えば、メチルアルコール、エチルアルコール、N-プロピルアルコール、i-プロピルアルコール、メトキシアルコール、エトキシアルコールなどのアルコール系溶剤;メトキシエトキシエタノール、エトキシエトキシエタノールなどのカルビトール系溶剤;酢酸エチル、酢酸ブチル、メトキシプロピオン酸メチル、メトキシプロピオン酸エチル、エトキシプロピオン酸エチル、乳酸エチル、ヒドロキシプロピオン酸メチル、ヒドロキシプロピオン酸エチル、n-ブチルアセテート、イソブチルアセテート、酪酸イソブチル、酪酸n-ブチル、乳酸エチル、シクロヘキサノールアセテートなどのエステル系溶剤;アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、2-ヘプタノンなどのケトン系溶剤;メトキシエチルアセテート、プロピレングリコールモノメチルエーテルアセテート、3-メトキシ-3-メチル-1-ブチルアセテート、3-メトキシブチルアセテート、エトキシエチルアセテートなどのグリコールエーテルアセテート系溶剤;メトキシエトキシエチルアセテート、エトキシエトキシエチルアセテート、ブチルカルビトールアセテート(BCA)などのカルビトールアセテート系溶剤;プロピレングリコールジアセテート、1,3-ブチレングリコールジアセテート等のジアセテート類;エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテル、ジプロピレングリコールジメチルエーテルなどのグリコールエーテル系溶剤;N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチルピロリドンなどの非プロトン性アミド溶剤;γ-ブチロラクトンなどのラクトン系溶剤;テトラヒドロフランなどの環状エーテル系溶剤;ベンゼン、トルエン、キシレン、ナフタレンなどの不飽和炭化水素系溶剤;N-ヘプタン、N-ヘキサン、N-オクタンなどの飽和炭化水素系溶剤;トルエン、キシレン等の芳香族炭化水素類などの有機溶剤が挙げられる。これらの溶剤の中ではグリコールエーテルアセテート系溶剤、カルビトールアセテート系溶剤、グリコールエーテル系溶剤、エステル系溶剤が他の成分の溶解性の点で好適に用いられる。中でも、本発明に用いる溶剤としては、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、ブチルカルビトールアセテート(BCA)、3-メトキシ-3-メチル-1-ブチルアセテート、エトキシプロピオン酸エチル、乳酸エチル、及び、3-メトキシブチルアセテートよりなる群から選択される1種以上であることが、他の成分の溶解性や塗布適性の点から好ましい。
本発明の感光性赤色樹脂組成物には、必要に応じて各種添加剤を含むものであってもよい。添加剤としては、例えば、酸化防止剤、重合停止剤、連鎖移動剤、レベリング剤、可塑剤、界面活性剤、消泡剤、シランカップリング剤、紫外線吸収剤、密着促進剤等などが挙げられる。
界面活性剤及び可塑剤の具体例としては、例えば、特開2013-029832号公報に記載のものが挙げられる。
本発明に用いられる酸化防止剤としては、特に限定されず、従来公知のものの中から適宜選択すればよい。酸化防止剤の具体例としては、例えば、ヒンダードフェノール系酸化防止剤、アミン系酸化防止剤、リン系酸化防止剤、硫黄系酸化防止剤、ヒドラジン系酸化防止剤等が挙げられ、線幅マスク線幅の設計通りに細線パターンを形成する能力が向上する点、及び耐熱性の点から、ヒンダードフェノール系酸化防止剤を用いることが好ましい。国際公開第2014/021023号に記載されているような潜在性酸化防止剤であっても良い。
本発明の感光性赤色樹脂組成物の製造方法は、色材と、分散剤と、アルカリ可溶性樹脂と、光重合性化合物と、光開始剤と、前記特定の紫外線吸収剤と、溶剤と、所望により用いられる各種添加成分とを含有し、色材が分散剤により溶剤中に均一に分散されうる方法であることがコントラストを向上する点から好ましく、公知の混合手段を用いて混合することにより、調製することができる。
当該樹脂組成物の調製方法としては、例えば、(1)まず溶剤中に、色材と、分散剤とを添加して色材分散液を調製し、当該分散液に、アルカリ可溶性樹脂と、光重合性化合物と、光開始剤と、前記特定の紫外線吸収剤と、所望により用いられる各種添加成分を混合する方法;(2)溶剤中に、色材と、分散剤と、アルカリ可溶性樹脂と、光重合性化合物と、光開始剤と、前記特定の紫外線吸収剤と、所望により用いられる各種添加成分とを同時に投入し混合する方法;(3)溶剤中に、分散剤と、アルカリ可溶性樹脂と、光重合性化合物と、光開始剤と、前記特定の紫外線吸収剤と、所望により用いられる各種添加成分とを添加し、混合したのち、色材を加えて分散する方法;(4)溶剤中に、色材と、分散剤と、アルカリ可溶性樹脂とを添加して色材分散液を調製し、当該分散液に、更にアルカリ可溶性樹脂と、溶剤と、光重合性化合物と、光開始剤と、前記特定の紫外線吸収剤と、所望により用いられる各種添加成分を添加し、混合する方法;などを挙げることができる。
これらの方法の中で、上記(1)及び(4)の方法が、色材の凝集を効果的に防ぎ、均一に分散させ得る点から好ましい。
本発明に係る感光性赤色樹脂組成物は、現像残渣発生を抑制しながら、テーパー角が60度未満になる断面形状を有し、基板密着性に優れた赤色着色層を形成可能であることから、カラーフィルタ用途に好適に用いることができる。
本発明に係るカラーフィルタは、基板と、当該基板上に設けられた着色層とを少なくとも備えるカラーフィルタであって、当該着色層の少なくとも1つが、前記本発明に係る感光性赤色樹脂組成物の硬化物である。
本発明のカラーフィルタに用いられる着色層は、少なくとも1つが、前記本発明に係る感光性赤色樹脂組成物の硬化物である着色層である。
着色層は、通常、後述する基板上の遮光部の開口部に形成され、通常3色以上の着色パターンから構成される。
また、当該着色層の配列としては、特に限定されず、例えば、ストライプ型、モザイク型、トライアングル型、4画素配置型等の一般的な配列とすることができる。また、着色層の幅、面積等は任意に設定することができる。
当該着色層の厚みは、塗布方法、感光性赤色樹脂組成物の固形分濃度や粘度等を調整することにより、適宜制御されるが、通常、1~5μmの範囲であることが好ましい。
まず、前述した本発明の感光性赤色樹脂組成物を、スプレーコート法、ディップコート法、バーコート法、ロールコート法、スピンコート法、ダイコート法などの塗布手段を用いて後述する基板上に塗布して、ウェット塗膜を形成させる。なかでもスピンコート法、ダイコート法を好ましく用いることができる。
次いで、ホットプレートやオーブンなどを用いて、該ウェット塗膜を乾燥させたのち、これに、所定のパターンのマスクを介して露光し、アルカリ可溶性樹脂及び多官能モノマー等を光重合反応させて硬化塗膜とする。露光に使用される光源としては、例えば低圧水銀灯、高圧水銀灯、メタルハライドランプなどの紫外線、電子線等が挙げられる。露光量は、使用する光源や塗膜の厚みなどによって適宜調整される。
また、露光後に重合反応を促進させるために、加熱処理を行ってもよい。加熱条件は、使用する感光性赤色樹脂組成物中の各成分の配合割合や、塗膜の厚み等によって適宜選択される。
本発明のカラーフィルタにおける遮光部は、後述する基板上にパターン状に形成されるものであって、一般的なカラーフィルタに遮光部として用いられるものと同様とすることができる。
当該遮光部のパターン形状としては、特に限定されず、例えば、ストライプ状、マトリクス状等の形状が挙げられる。遮光部は、スパッタリング法、真空蒸着法等によるクロム等の金属薄膜であっても良い。或いは、遮光部は、樹脂バインダー中にカーボン微粒子、金属酸化物、無機顔料、有機顔料等の遮光性粒子を含有させた樹脂層であってもよい。遮光性粒子を含有させた樹脂層の場合には、感光性レジストを用いて現像によりパターニングする方法、遮光性粒子を含有するインクジェットインクを用いてパターニングする方法、感光性レジストを熱転写する方法等がある。
基板としては、後述する透明基板、シリコン基板、及び、透明基板又はシリコン基板上にアルミニウム、銀、銀/銅/パラジウム合金薄膜などを形成したものが用いられる。これらの基板上には、別のカラーフィルタ層、樹脂層、TFT等のトランジスタ、回路等が形成されていてもよい。
本発明のカラーフィルタにおける透明基板としては、可視光に対して透明な基材であればよく、特に限定されず、一般的なカラーフィルタに用いられる透明基板を使用することができる。具体的には、石英ガラス、無アルカリガラス、合成石英板等の可撓性のない透明なリジッド材、あるいは、透明樹脂フィルム、光学用樹脂板、フレキシブルガラス等の可撓性を有する透明なフレキシブル材が挙げられる。
当該透明基板の厚みは、特に限定されるものではないが、本発明のカラーフィルタの用途に応じて、例えば100μm~1mm程度のものを使用することができる。
なお、本発明のカラーフィルタは、上記基板、遮光部及び着色層以外にも、例えば、オーバーコート層や透明電極層、さらには配向膜や柱状スペーサ等が形成されたものであってもよい。
本発明に係る表示装置は、前記本発明に係るカラーフィルタを有することを特徴とする。本発明において表示装置の構成は特に限定されず、従来公知の表示装置の中から適宜選択することができ、例えば、液晶表示装置や、有機発光表示装置などが挙げられる。
本発明の液晶表示装置としては、例えば、前述した本発明に係るカラーフィルタと、対向基板と、前記カラーフィルタと前記対向基板との間に形成された液晶層とを有する液晶表示装置が挙げられる。
このような本発明の液晶表示装置について、図を参照しながら説明する。図2は、本発明の液晶表示装置の一例を示す概略図である。図2に例示するように本発明の液晶表示装置40は、カラーフィルタ10と、TFTアレイ基板等を有する対向基板20と、上記カラーフィルタ10と上記対向基板20との間に形成された液晶層30とを有している。
なお、本発明の液晶表示装置は、この図2に示される構成に限定されるものではなく、一般的にカラーフィルタが用いられた液晶表示装置として公知の構成とすることができる。
また、対向基板としては、本発明の液晶表示装置の駆動方式等に応じて適宜選択して用いることができる。
さらに、液晶層を構成する液晶としては、本発明の液晶表示装置の駆動方式等に応じて、誘電異方性の異なる各種液晶、及びこれらの混合物を用いることができる。
本発明の有機発光表示装置としては、例えば、前述した本発明に係るカラーフィルタと、有機発光体とを有する有機発光表示装置が挙げられる。
このような本発明の有機発光表示装置について、図を参照しながら説明する。図3は、本発明の有機発光表示装置の一例を示す概略図である。図3に例示するように本発明の有機発光表示装置100は、カラーフィルタ10と、有機発光体80とを有している。カラーフィルタ10と、有機発光体80との間に、有機保護層50や無機酸化膜60を有していても良い。
なお、本発明の有機発光表示装置は、この図3に示される構成に限定されるものではなく、一般的にカラーフィルタが用いられた有機発光表示装置として公知の構成とすることができる。
塩形成前の共重合体の質量平均分子量(Mw)は、前述の本発明の明細書に記載した測定方法に従って、GPC(ゲルパーミエーションクロマトグラフィー)により標準ポリスチレン換算値として求めた。
紫外線吸収剤の波長365nmの透過率は、各紫外線吸収剤の0.002質量%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を調製し、当該0.002質量%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の透過率を紫外可視近赤外分光光度計(日本分光(株) V-770)用いて測定した。
紫外線吸収剤の波長365nmの透過率の測定結果を表1に示す。
紫外線吸収剤2:Tinuvin326、BASF製
紫外線吸収剤3:Tinuvin477、BASF製
紫外線吸収剤4:KEMISORB111、ケミプロ化成製
比較紫外線吸収剤C1:Tinuvin400、BASF製
比較紫外線吸収剤C2:Tinuvin900、BASF製
比較紫外線吸収剤C3:Tinuvin384-2、BASF製
比較紫外線吸収剤C4:Kemisorb12、ケミプロ化成製
比較紫外線吸収剤C5:Tinuvin479、BASF製
重合槽に、PGMEAを300質量部仕込み、窒素雰囲気下で100℃に昇温した後、メタクリル酸ベンジル(BzMA)55.6質量部、MMA2.4質量部、メトキシポリエチレングリコール-メタクリレート(日本油脂製 PME-1000)66質量部、メタクリル酸(MAA)56質量部及びパーブチルO(日油製)6質量部、連鎖移動剤(n-ドデシルメルカプタン)2質量部を1.5時間かけて連続的に滴下した。その後、100℃を保持して反応を続け、上記主鎖形成用混合物の滴下終了から2時間後に重合禁止剤として、p-メトキシフェノール0.1質量部を添加して重合を停止した。
次に、空気を吹き込みながら、エポキシ基含有化合物としてメタクリル酸グリシジル(GMA)20質量部を添加して、110℃に昇温した後、トリエチルアミン0.8質量部を添加して110℃で15時間付加反応させ、アルカリ可溶性樹脂A溶液(重量平均分子量(Mw)8500、酸価75mgKOH/g、Tgは25℃、固形分40質量%)を得た。
なお、上記重量平均分子量は、ポリスチレンを標準物質とし、THFを溶離液としてショウデックスGPCシステム-21H(Shodex GPC System-21H)により重量平均分子量を測定した。酸価は、JIS K 0070に基づいて測定した。また、ガラス転移温度(Tg)はJIS K7121に記載の方法に準じて示差走査熱量測定(SIIナノテクノロジー社製、EXSTAR DSC 7020)を用いて測定した。
500mL丸底4口セパラブルフラスコに冷却管、添加用ロート、窒素用インレット、攪拌機、温度計を装備し、テトラヒドロフラン(THF)250重量部及び開始剤のジメチルケテンメチルトリメチルシリルアセタール2.32重量部を添加用ロートを介して加え、窒素置換を充分に行った。触媒としてテトラブチルアンモニウムm-クロロベンゾエートの1モル/Lアセトニトリル溶液0.2重量部をシリンジで注入し、メタクリル酸メチル(以下、MMAということがある)51.7重量部とメトキシポリエチレングリコール-メタクリレート(日本油脂製 PME-1000、一般式(III)中のR44はCH3、A3はCOO、R45はエチレン基、R46はCH3、m≒23)54.4質量部を添加用ロートを用い、60分かけて滴下した。セパラブルフラスコを氷浴で冷却しながら、温度を40℃未満に保った。次いで、1時間後、メタクリル酸ジメチルアミノエチル(以下、DMMAということがある)27.2重量部を20分で滴下した。1時間反応後、メタノール0.5質量部を加え、反応を停止させた。得られた共重合体THF溶液はヘキサン中で再沈殿させ、濾過、真空乾燥して精製し、重合体を得た。このようにして得られた3級アミンを有するブロック共重合体60重量部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(以下、PGMEAということがある)40重量部を加えて均一混合し、ブロック共重合体溶液を得た。ブロック共重合体溶液はRI検出器を装備した東ソー社製、HLC-8220を用い、展開溶媒をTHFとし、分子量標準ポリマーを標準ポリスチレンとして、GPCを測定し分子量分布及び質量平均分子量を求めた。また、アミン価は67mgKOH/gだった。質量平均分子量Mw:8500、数平均分子量Mn:6050、分子量分布Mw/Mnは1.29であった(MMA/PME-1000/DMMA質量比は4/4/2)。
冷却管、添加用ロート、窒素用インレット、機械的攪拌機、デジタル温度計を備えた反応器に、プロピレングリコールメチルエーテルアセテート(PGMEA)70.0質量部を仕込み、窒素気流下攪拌しながら、温度90℃に加温した。一般式(III)で表される構成単位を誘導する、PEG鎖を有するモノマー(Evonik製、商品名:VISIOMER MPEG 1005 MA W、一般式(III)中のR44はCH3、A3はCOO、R45はエチレン基、R46はCH3、m=22)1.0質量部、メタクリル酸メチル(MMA)99.0質量部、メルカプトエタノール4.0質量部、PGMEA30質量部、α,α’-アゾビスイソブチロニトリル(AIBN)1.0質量部の混合溶液を1.5時間かけて滴下し、さらに3時間反応した。次に、窒素気流を止めて、この反応溶液を80℃に冷却し、カレンズMOI(昭和電工製)8.74質量部、ジラウリン酸ジオクチルすず0.125g、p-メトキシフェノール0.125質量部、及びPGMEA30質量部、を加えて3時間攪拌することで、マクロモノマー1の50%溶液を得た。得られたマクロモノマー1を、GPC(ゲルパーミエーションクロマトグラフィー)にて、N-メチルピロリドン、0.01モル/L臭化リチウム添加/ポリスチレン標準の条件で確認したところ、重量平均分子量(Mw)4500、分子量分布(Mw/Mn)1.6であった。
冷却管、添加用ロート、窒素用インレット、機械的攪拌機、デジタル温度計を備えた反応器に、PGMEA63.1質量部を仕込み、窒素気流下攪拌しながら、温度85℃に加温した。合成例1のマクロモノマー1溶液141質量部(有効固形分70.5質量部)、メタクリル酸2-(ジメチルアミノ)エチル(DMMA)29.5質量部、n-ドデシルメルカプタン1.24質量部、PGMEA49.4質量部、AIBN1.0質量部の混合溶液を1.5時間かけて滴下し、3時間加熱攪拌したのち、AIBN0.10質量部 、PGMEA6.0質量部の混合液を10分かけて滴下し、さらに同温で1時間熟成することで、グラフト共重合体の35.0質量%溶液を得た。得られたグラフト共重合体は、GPC測定の結果、重量平均分子量(Mw)10000であった。なおアミン価は105mgKOH/gであった。
(1)色材分散液R(1)の調製
225mLマヨネーズ瓶中に、PGMEA64.3質量部、調製例1のアルカリ可溶性樹脂A溶液(固形分40質量%)13.5質量部、合成例1のブロック共重合体(分散剤A)のPGMEA溶液(固形分40質量%)10.1質量部、分散剤の塩形成剤aとしてフェニルホスホン酸0.17質量部を入れ攪拌した。
そこへ、C.I.ピグメントレッド291(PR291)を12質量部、粒径2.0mmジルコニアビーズ100質量部を入れ、予備解砕としてペイントシェーカー(浅田鉄工社製)で1時間振とうし、次いで粒径0.1mmのジルコニアビーズ200部に変更し本解砕としてペイントシェーカーで4時間分散を行い、色材分散液R(1)を得た。
(2)感光性赤色樹脂組成物R-1の調製
製造例1で得られた色材分散液R(1)を51.9質量部、調製例1で得られたアルカリ可溶性樹脂A溶液(固形分40質量%)を2.47質量部、多官能モノマー(商品名アロニックスM-305、東亞合成製)を3.94質量部、光開始剤(1-プロパノン,3-シクロペンチル-1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(o-アセチルオキシム)、TR-PBG-304、常州強力電子新材料社製)を0.61質量部、紫外線吸収剤(紫外線吸収剤1:Tinuvin329、BASF製)を0.56質量部(顔料成分を除いた固形分全量100質量部に対して10質量部、樹脂組成物の固形分全量に対して3.2質量%)、酸化防止剤(Irganox1010、BASF製)を0.14質量部(顔料成分を除いた固形分全量100質量部に対して2.5質量部)、PGMEAを40.4質量部加え、感光性赤色樹脂組成物R-1を得た。
実施例1において、表2に示したように分散剤の種類を分散剤Aから合成例2のグラフト共重合体(分散剤B)に変更して色材分散液を調製した以外は、感光性赤色樹脂組成物R-1と同様にして、感光性赤色樹脂組成物R-2を得た。
実施例1において、表2に示したように紫外線吸収剤の種類を変更した以外は、感光性赤色樹脂組成物R-1と同様にして、感光性赤色樹脂組成物R-3~R-5を得た。
実施例1において、表2に示したように顔料の種類を変更した以外は、感光性赤色樹脂組成物R-1と同様にして、感光性赤色樹脂組成物R-6~R-8を得た。
なお、実施例8においては、色材分散液調製時に、PR291を12質量部用いる代わりに、PR291を10.2質量部とC.I.ピグメントイエロー150(PY150)を1.8質量部用いた。
実施例1において、表2に示したように酸化防止剤を添加しなかった以外は、感光性赤色樹脂組成物R-1と同様にして、感光性赤色樹脂組成物R-9を得た。
実施例1において、表2に示したように分散剤の塩形成剤aの代わりに、塩形成剤b(ベンジルクロリド)又は塩形成剤c(ベンジルブロミド)を用いるか、塩形成剤を添加せずに色材分散液を調製した以外は、感光性赤色樹脂組成物R-1と同様にして、感光性赤色樹脂組成物R-10~R-12を得た。
実施例1において、表2に示したように紫外線吸収剤の量を3倍に増やした(顔料成分を除いた固形分全量100質量部に対して30質量部)以外は、感光性赤色樹脂組成物R-1と同様にして、感光性赤色樹脂組成物R-13を得た。
実施例1又は実施例8において、表2に示したように、紫外線吸収剤を用いなかった以外は、実施例1又は実施例8と同様にして、比較例1~2の感光性赤色樹脂組成物CR-1、CR-2を製造した。
実施例1において、紫外線吸収剤の種類を、それぞれ表2に示したように変更した以外は、実施例1と同様にして、比較例3~7の感光性赤色樹脂組成物CR-3~CR-7を製造した。
比較例3において、紫外線吸収剤の種類と量を、表2に示したように変更した以外は、比較例3と同様にして、比較例8の感光性赤色樹脂組成物CR-8を製造した。
実施例1において、表2に示したように分散剤の種類を分散剤Aから、分散剤C(ソルスパース20000、ルーブリゾール製)に変更して色材分散液を調製した以外は、感光性赤色樹脂組成物R-1と同様にして、感光性赤色樹脂組成物CR-9を得た。
実施例1において、表2に示したように顔料の種類を変更した以外は、感光性赤色樹脂組成物R-1と同様にして、感光性赤色樹脂組成物G-1及びB-1を得た。
なお、参考例1においては、色材分散液調製時に、PR291を用いる代わりに、C.I.ピグメントグリーン58(PG58)を用いた。
また、参考例2においては、色材分散液調製時に、PR291を用いる代わりに、C.I.ピグメントブルー15:6(PB15:6)を用いた。
各実施例及び各比較例で得られた感光性赤色樹脂組成物を、ガラス基板(NHテクノグラス製、「NA35」)上にそれぞれ、スピンコーターを用いて硬化塗膜が厚さ3.0μmとなるように塗布した後、ホットプレートを用いて80℃で3分間乾燥し基板上に塗膜を形成した。この塗膜に、独立細線を形成するための開口寸法2μmから100μmのパターンを有するフォトマスク(クロムマスク)を介して、超高圧水銀灯を用いて50mJ/cm2の紫外線で露光することにより、ガラス基板上にそれぞれ、露光後塗膜を形成した。次いで、0.05wt%水酸化カリウム水溶液を現像液としてスピン現像し、現像液に60秒間接液させた後に純水で洗浄することで現像処理し、独立細線パターン状の塗膜を得た。その後、90℃のクリーンオーブンで30分間ポストベークすることにより、独立細線パターン状の着色層を形成した。得られた着色層について断面形状評価及び密着性評価を行った。
得られた独立細線パターン状の着色層の厚み方向断面形状を、走査型電子顕微鏡(島津製作所製、super scan model 220、倍率10000倍)により観察し、下記評価基準により、着色層の断面形状のテーパー角(θ1)(図4参照)について評価した。
(パターン状着色層の断面形状の評価基準)
A:テーパー角(θ1)が15度以上60度未満
B:テーパー角(θ1)が60度以上80度未満
C:テーパー角(θ1)が80度以上90度以下
D:テーパー角(θ1)が90度超過
評価結果がAであれば着色層の断面形状は良好である。
得られた着色層を光学顕微鏡で観察して、マスク開口が何μmのパターンまで残存しているか、最も細いパターンの線幅の確認を行った。
A:マスク開口7μm以下までパターンが残存(最も細いパターンの線幅が7μm以下)
B:最も細いパターンの線幅が8μmから15μm以下
C:最も細いパターンの線幅が16μmから25μm以下
D:最も細いパターンの線幅が26μm以上
評価結果がBであれば基板密着性は良好であり、評価結果がAであれば基板密着性に優れている。
実施例及び比較例で得られた感光性赤色樹脂組成物を、それぞれガラス基板(NHテクノグラス製、「NA35」)上に、スピンコーターを用いてポストベーク後に厚さ2.0μmの着色層を形成する膜厚で塗布した後、ホットプレートを用いて80℃で3分間乾燥し、ガラス基板上に着色層を形成した。上記着色層が形成されたガラス板を、アルカリ現像液として0.05質量%水酸化カリウム水溶液を用いて60秒間シャワー現像させた後に純水で洗浄することで現像処理した。現像後の上記着色層の形成部を、目視により観察した後、エタノールを含ませたレンズクリーナー(東レ社製、商品名トレシーMKクリーンクロス)で十分に拭き取り、そのレンズクリーナーの着色度合いを目視で観察した。
(現像残渣評価基準)
A:目視により現像残渣が確認されず、レンズクリーナーが全く着色しなかった
B:目視により現像残渣が確認されず、レンズクリーナーの着色がわずかに確認された
C:目視により現像残渣がわずかに確認され、レンズクリーナーの着色が確認された
D:目視により現像残渣が確認され、レンズクリーナーの着色が確認された
評価結果がBであれば現像残渣抑制効果は良好であり、評価結果がAであれば現像残渣抑制効果に優れている。
実施例及び比較例で得られた色材分散液についてそれぞれ、調製直後と、25℃で30日間保存後の粘度を測定し、保存前後の粘度から粘度変化率を算出し、粘度安定性を評価した。粘度測定には振動式粘度計を用いて、25.0±0.5℃における粘度を測定した。
(分散安定性評価基準)
A:保存前後の粘度の変化率が10%未満
B:保存前後の粘度の変化率が10%以上15%未満
C:保存前後の粘度の変化率が15%以上25%未満
D:保存前後の粘度の変化率が25%以上
評価結果がBであれば分散性は良好であり、評価結果がAであれば分散性に優れている。
本発明に係る感光性赤色樹脂組成物である実施例1~13では、色材と、分散剤と、アルカリ可溶性樹脂と、光重合性化合物と、光開始剤と、紫外線吸収剤と、溶剤とを含有し、前記色材は、少なくとも赤色顔料を含む顔料からなり、前記紫外線吸収剤は、波長365nmの透過率が0.002質量%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において35%以下であるため、現像残渣発生を抑制しながら、テーパー角が60度未満になる断面形状を有し、基板密着性に優れた赤色着色層を形成することができることが示された。
それに対して、実施例1及び8と比べて紫外線吸収剤を含有しない点のみが異なる比較例1及び2の感光性赤色樹脂組成物は、断面形状においてテーパー角(θ1)が90度を超えてしまい、優れた断面形状の赤色着色層を形成することはできなかった。また、比較例1及び2の感光性赤色樹脂組成物は、実施例1及び8と比較して現像残渣が劣っていた。
また、紫外線吸収剤として、波長365nmの透過率が0.002質量%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において35%を超える紫外線吸収剤を用いた比較例3~7の感光性赤色樹脂組成物も、断面形状においてテーパー角(θ1)が90度を超えてしまい、優れた断面形状の赤色着色層を形成することはできなかった。
紫外線吸収剤として、波長365nmの透過率が0.002質量%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において35%を超える紫外線吸収剤を多く用いた比較例8の感光性赤色樹脂組成物は、断面形状においてテーパー角(θ1)が90度を超えてしまい、優れた断面形状の赤色着色層を形成することはできなかった上、基板密着性も劣っていた。
分散剤として、ブロック共重合体、及び、グラフト共重合体の少なくとも1種とは異なる分散剤を用いた比較例9の感光性赤色樹脂組成物は、現像残渣が悪化し、分散性にも劣っていた。
2 遮光部
3 着色層
5 微小孔
10 カラーフィルタ
20 対向基板
30 液晶層
40 液晶表示装置
50 有機保護層
60 無機酸化膜
71 透明陽極
72 正孔注入層
73 正孔輸送層
74 発光層
75 電子注入層
76 陰極
80 有機発光体
100 有機発光表示装置
Claims (9)
- 色材と、分散剤と、アルカリ可溶性樹脂と、光重合性化合物と、光開始剤と、紫外線吸収剤と、溶剤とを含有し、
前記色材は、少なくとも赤色顔料を含む顔料からなり、
前記分散剤が、ブロック共重合体、及び、グラフト共重合体の少なくとも1種を含有し、
前記紫外線吸収剤は、波長365nmの透過率が0.002質量%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において35%以下である、感光性赤色樹脂組成物。 - 前記分散剤が、下記一般式(I)で表される構成単位を有するグラフト共重合体、及び、下記一般式(I)で表される構成単位を含むAブロックを有するブロック共重合体の少なくとも1種において、前記一般式(I)で表される構成単位が有する末端の窒素部位の少なくとも一部と下記一般式(1)~(3)で表される化合物よりなる群から選択される1種以上の化合物とが塩を形成した、塩型グラフト共重合体及び塩型ブロック共重合体の少なくとも1種を含有する、請求項1に記載の感光性赤色樹脂組成物。
一般式(1)において、Raは、炭素数1~20の直鎖、分岐鎖又は環状のアルキル基、ビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは-O-Reを表し、Reは、炭素数1~20の直鎖、分岐鎖又は環状のアルキル基、ビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは炭素数1~4のアルキレン基を介した(メタ)アクリロイル基を表す。一般式(2)において、Rb、Rb’、及びRb”はそれぞれ独立に、水素原子、酸性基又はそのエステル基、置換基を有してもよい炭素数1~20の直鎖、分岐鎖又は環状のアルキル基、置換基を有してもよいビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは-O-Rfを表し、Rfは、置換基を有してもよい炭素数1~20の直鎖、分岐鎖又は環状のアルキル基、置換基を有してもよいビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは炭素数1~4のアルキレン基を介した(メタ)アクリロイル基を表し、Xは、塩素原子、臭素原子、又はヨウ素原子を表す。一般式(3)において、Rc及びRdはそれぞれ独立に、水素原子、水酸基、炭素数1~20の直鎖、分岐鎖又は環状のアルキル基、ビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは-O-Reを表し、Reは、炭素数1~20の直鎖、分岐鎖又は環状のアルキル基、ビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは炭素数1~4のアルキレン基を介した(メタ)アクリロイル基を表す。但し、Rc及びRdの少なくとも一つは炭素原子を含む。) - さらに、酸化防止剤を含有する、請求項1又は2に記載の感光性赤色樹脂組成物。
- 前記光開始剤が、オキシムエステル骨格を有する光開始剤を含む、請求項1~3のいずれか1項に記載の感光性赤色樹脂組成物。
- 前記紫外線吸収剤の含有量は、感光性赤色樹脂組成物の固形分全量に対して、0.1質量%~10.0質量%の範囲内である、請求項1~4のいずれか1項に記載の感光性赤色樹脂組成物。
- 前記光開始剤と前記紫外線吸収剤の合計質量に対する、前記光開始剤の合計質量の比率は、30質量%~95質量%の範囲内である、請求項1~5のいずれか1項に記載の感光性赤色樹脂組成物。
- 請求項1~6のいずれか1項に記載の感光性赤色樹脂組成物の硬化物。
- 基板と、当該基板上に設けられた着色層とを少なくとも備えるカラーフィルタであって、当該着色層の少なくとも1つが請求項7に記載の感光性赤色樹脂組成物の硬化物である、カラーフィルタ。
- 前記請求項8に記載のカラーフィルタを有する、表示装置。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2023530334A JPWO2022270349A1 (ja) | 2021-06-25 | 2022-06-14 | |
CN202280041762.9A CN117460974A (zh) | 2021-06-25 | 2022-06-14 | 感光性红色树脂组合物、固化物、滤色器、显示设备 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2021-105548 | 2021-06-25 | ||
JP2021105548 | 2021-06-25 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022270349A1 true WO2022270349A1 (ja) | 2022-12-29 |
Family
ID=84543917
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2022/023753 WO2022270349A1 (ja) | 2021-06-25 | 2022-06-14 | 感光性赤色樹脂組成物、硬化物、カラーフィルタ、表示装置 |
Country Status (4)
Country | Link |
---|---|
JP (1) | JPWO2022270349A1 (ja) |
CN (1) | CN117460974A (ja) |
TW (1) | TW202307045A (ja) |
WO (1) | WO2022270349A1 (ja) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010224308A (ja) * | 2009-03-24 | 2010-10-07 | Fujifilm Corp | カラーフィルタ及びその製造方法 |
WO2018124087A1 (ja) * | 2016-12-28 | 2018-07-05 | 株式会社Dnpファインケミカル | カラーフィルタ用色材分散液、カラーフィルタ用着色樹脂組成物、カラーフィルタ、及び表示装置 |
WO2019065185A1 (ja) * | 2017-09-28 | 2019-04-04 | 株式会社Dnpファインケミカル | 着色樹脂組成物、硬化物、カラーフィルタ、及び表示装置 |
JP2019128540A (ja) * | 2018-01-26 | 2019-08-01 | 東洋インキScホールディングス株式会社 | カラーフィルタ用感光性着色組成物及びカラーフィルタ |
JP2020177038A (ja) * | 2019-04-15 | 2020-10-29 | 東洋インキScホールディングス株式会社 | カラーフィルタ用着色組成物、フィルタセグメント、およびカラーフィルタ |
WO2021039409A1 (ja) * | 2019-08-27 | 2021-03-04 | 富士フイルム株式会社 | 硬化性組成物、硬化物、カラーフィルタ、固体撮像素子及び画像表示装置 |
-
2022
- 2022-06-14 CN CN202280041762.9A patent/CN117460974A/zh active Pending
- 2022-06-14 WO PCT/JP2022/023753 patent/WO2022270349A1/ja active Application Filing
- 2022-06-14 JP JP2023530334A patent/JPWO2022270349A1/ja active Pending
- 2022-06-22 TW TW111123219A patent/TW202307045A/zh unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010224308A (ja) * | 2009-03-24 | 2010-10-07 | Fujifilm Corp | カラーフィルタ及びその製造方法 |
WO2018124087A1 (ja) * | 2016-12-28 | 2018-07-05 | 株式会社Dnpファインケミカル | カラーフィルタ用色材分散液、カラーフィルタ用着色樹脂組成物、カラーフィルタ、及び表示装置 |
WO2019065185A1 (ja) * | 2017-09-28 | 2019-04-04 | 株式会社Dnpファインケミカル | 着色樹脂組成物、硬化物、カラーフィルタ、及び表示装置 |
JP2019128540A (ja) * | 2018-01-26 | 2019-08-01 | 東洋インキScホールディングス株式会社 | カラーフィルタ用感光性着色組成物及びカラーフィルタ |
JP2020177038A (ja) * | 2019-04-15 | 2020-10-29 | 東洋インキScホールディングス株式会社 | カラーフィルタ用着色組成物、フィルタセグメント、およびカラーフィルタ |
WO2021039409A1 (ja) * | 2019-08-27 | 2021-03-04 | 富士フイルム株式会社 | 硬化性組成物、硬化物、カラーフィルタ、固体撮像素子及び画像表示装置 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2022270349A1 (ja) | 2022-12-29 |
TW202307045A (zh) | 2023-02-16 |
CN117460974A (zh) | 2024-01-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6755715B2 (ja) | カラーフィルタ用色材分散液、カラーフィルタ用感光性着色樹脂組成物、カラーフィルタ、液晶表示装置、及び有機発光表示装置 | |
JP7011644B2 (ja) | カラーフィルタ用色材分散液、分散剤、カラーフィルタ用感光性着色樹脂組成物、カラーフィルタ、表示装置 | |
JP6851518B2 (ja) | 色材分散液、カラーフィルタ用感光性着色樹脂組成物、カラーフィルタ、液晶表示装置、及び有機発光表示装置 | |
JPWO2018062105A1 (ja) | カラーフィルタ用感光性着色樹脂組成物、カラーフィルタ、及び表示装置 | |
JP2019174635A (ja) | 感光性着色樹脂組成物、硬化物、カラーフィルタ、及び表示装置 | |
JP7153651B2 (ja) | 感光性着色樹脂組成物及びその硬化物、カラーフィルタ、並びに表示装置 | |
JP5899719B2 (ja) | 顔料分散液、カラーフィルタ用ネガ型レジスト組成物及びその製造方法、カラーフィルタ、並びに、液晶表示装置及び有機発光表示装置 | |
JP7123660B2 (ja) | 感光性着色樹脂組成物及びその硬化物、カラーフィルタ、並びに表示装置 | |
KR102243364B1 (ko) | 감광성 수지 조성물, 이를 이용하여 제조된 감광성 수지막, 컬러필터 및 디스플레이 소자 | |
WO2022270349A1 (ja) | 感光性赤色樹脂組成物、硬化物、カラーフィルタ、表示装置 | |
JP2016122073A (ja) | 色材分散液、カラーフィルタ用感光性着色樹脂組成物、カラーフィルタ、液晶表示装置、及び有機発光表示装置 | |
JP6450057B1 (ja) | 感光性着色樹脂組成物及びその硬化物、カラーフィルタ、並びに表示装置 | |
JP7317605B2 (ja) | 色材分散液、分散剤、感光性着色樹脂組成物、硬化物、カラーフィルタ、表示装置 | |
WO2022176831A1 (ja) | 感光性緑色樹脂組成物、硬化物、カラーフィルタ、表示装置、及び有機発光素子と外光反射防止膜の積層体の製造方法 | |
WO2022070977A1 (ja) | 光硬化性着色樹脂組成物、硬化物、カラーフィルタ、表示装置 | |
WO2021090762A1 (ja) | 色材分散液、分散剤、感光性着色樹脂組成物、硬化物、カラーフィルタ、表示装置 | |
JP7449765B2 (ja) | 感光性着色樹脂組成物、硬化物、カラーフィルタ、表示装置 | |
WO2022138027A1 (ja) | 光硬化性赤色樹脂組成物、表示装置、及び有機発光素子と外光反射防止膜の積層体の製造方法 | |
WO2022176830A1 (ja) | 光硬化性緑色樹脂組成物、表示装置、及び有機発光素子と外光反射防止膜の積層体の製造方法 | |
WO2023140087A1 (ja) | 感光性着色樹脂組成物、硬化物、カラーフィルタ、表示装置 | |
WO2023120087A1 (ja) | 感光性着色樹脂組成物、カラーフィルタ、及び表示装置 | |
WO2021199786A1 (ja) | 色材分散液、分散剤、着色硬化性組成物、カラーフィルタ、表示装置 | |
WO2021006077A1 (ja) | 色材分散液、分散剤、感光性着色樹脂組成物、硬化物、カラーフィルタ、表示装置 | |
JP7263031B2 (ja) | 色材分散液、分散補助樹脂、感光性着色樹脂組成物及びその硬化物、カラーフィルタ、表示装置 | |
JP2021119368A (ja) | 感光性着色樹脂組成物、硬化物、カラーフィルタ、表示装置 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22828266 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2023530334 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202280041762.9 Country of ref document: CN |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 22828266 Country of ref document: EP Kind code of ref document: A1 |