TW201837065A - 藍色感光性樹脂組成物以及利用其製造之彩色濾光片與影像顯示裝置 - Google Patents
藍色感光性樹脂組成物以及利用其製造之彩色濾光片與影像顯示裝置 Download PDFInfo
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- TW201837065A TW201837065A TW106141185A TW106141185A TW201837065A TW 201837065 A TW201837065 A TW 201837065A TW 106141185 A TW106141185 A TW 106141185A TW 106141185 A TW106141185 A TW 106141185A TW 201837065 A TW201837065 A TW 201837065A
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- Prior art keywords
- blue
- group
- photosensitive resin
- resin composition
- alkyl
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- 239000011342 resin composition Substances 0.000 title claims abstract description 58
- 150000001875 compounds Chemical class 0.000 claims abstract description 76
- 229920005989 resin Polymers 0.000 claims abstract description 59
- 239000011347 resin Substances 0.000 claims abstract description 59
- 239000011230 binding agent Substances 0.000 claims abstract description 37
- 239000003999 initiator Substances 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 30
- 239000000038 blue colorant Substances 0.000 claims abstract description 15
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 9
- -1 3-cinnamyl-4-hydroxyphenyl Chemical group 0.000 claims description 74
- 239000000126 substance Substances 0.000 claims description 57
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 39
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- 239000002096 quantum dot Substances 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- 239000012965 benzophenone Substances 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 125000001797 benzyl group Chemical class [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 13
- 125000005843 halogen group Chemical group 0.000 claims description 13
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 12
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 claims description 12
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 12
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 12
- 239000012964 benzotriazole Substances 0.000 claims description 12
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 claims description 12
- 235000021286 stilbenes Nutrition 0.000 claims description 12
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000003086 colorant Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 6
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 5
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 239000001045 blue dye Substances 0.000 claims description 4
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 4
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical group C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- 239000001055 blue pigment Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 2
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 2
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 abstract description 8
- GPHBRIXCGCGLBG-UHFFFAOYSA-N diphenylmethanone;triazine Chemical compound C1=CN=NN=C1.C=1C=CC=CC=1C(=O)C1=CC=CC=C1 GPHBRIXCGCGLBG-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 52
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 36
- 239000010410 layer Substances 0.000 description 35
- 239000000203 mixture Substances 0.000 description 29
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 25
- 239000000243 solution Substances 0.000 description 23
- 238000002360 preparation method Methods 0.000 description 22
- 239000000178 monomer Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- VRVDFJOCCWSFLI-UHFFFAOYSA-K trisodium 3-[[4-[(6-anilino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]-5-methoxy-2-methylphenyl]diazenyl]naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].[Na+].COc1cc(N=Nc2cc(c3cccc(c3c2)S([O-])(=O)=O)S([O-])(=O)=O)c(C)cc1N=Nc1c(O)c2ccc(Nc3ccccc3)cc2cc1S([O-])(=O)=O VRVDFJOCCWSFLI-UHFFFAOYSA-K 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000000049 pigment Substances 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 12
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 12
- 239000010408 film Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000011161 development Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000000758 substrate Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 9
- 230000035945 sensitivity Effects 0.000 description 9
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 8
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 150000008064 anhydrides Chemical class 0.000 description 8
- 238000004811 liquid chromatography Methods 0.000 description 8
- 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 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 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 7
- 238000000034 method Methods 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 6
- 239000002671 adjuvant Substances 0.000 description 6
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 6
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 6
- AXMCIYLNKNGNOT-UHFFFAOYSA-N sodium;3-[[4-[(4-dimethylazaniumylidenecyclohexa-2,5-dien-1-ylidene)-[4-[ethyl-[(3-sulfophenyl)methyl]amino]phenyl]methyl]-n-ethylanilino]methyl]benzenesulfonate Chemical compound [Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](C)C)C=2C=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S(O)(=O)=O)=C1 AXMCIYLNKNGNOT-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000004383 yellowing Methods 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- 239000002250 absorbent Substances 0.000 description 5
- 230000002745 absorbent Effects 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 125000000623 heterocyclic group Chemical group 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KMOUUZVZFBCRAM-UHFFFAOYSA-N 1,2,3,6-tetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21 KMOUUZVZFBCRAM-UHFFFAOYSA-N 0.000 description 4
- JRPBSTGRRSTANR-UHFFFAOYSA-N 2,6-bis(2-methylpropyl)phenol Chemical compound CC(C)CC1=CC=CC(CC(C)C)=C1O JRPBSTGRRSTANR-UHFFFAOYSA-N 0.000 description 4
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 4
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 4
- 125000004018 acid anhydride group Chemical group 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 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 4
- 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 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- CQKAPARXKPTKBK-UHFFFAOYSA-N tert-butylazanium;bromide Chemical compound Br.CC(C)(C)N CQKAPARXKPTKBK-UHFFFAOYSA-N 0.000 description 4
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 4
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 3
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 3
- 244000028419 Styrax benzoin Species 0.000 description 3
- 235000000126 Styrax benzoin Nutrition 0.000 description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229960002130 benzoin Drugs 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- SXGBREZGMJVYRL-UHFFFAOYSA-N butan-1-amine;hydrobromide Chemical compound [Br-].CCCC[NH3+] SXGBREZGMJVYRL-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 125000002541 furyl group Chemical group 0.000 description 3
- WTIFIAZWCCBCGE-UUOKFMHZSA-N guanosine 2'-monophosphate Chemical compound C1=2NC(N)=NC(=O)C=2N=CN1[C@@H]1O[C@H](CO)[C@@H](O)[C@H]1OP(O)(O)=O WTIFIAZWCCBCGE-UUOKFMHZSA-N 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 3
- 125000000160 oxazolidinyl group Chemical group 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 125000003386 piperidinyl group Chemical group 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 125000004076 pyridyl group Chemical group 0.000 description 3
- 125000000714 pyrimidinyl group Chemical group 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
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- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
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- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
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- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
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- UWMZZSRDUVJJDP-UHFFFAOYSA-N sodium 4-[[9-(2-carboxyphenyl)-6-(2-methylanilino)xanthen-10-ium-3-yl]amino]-3-methylbenzenesulfonate Chemical compound [Na+].Cc1ccccc1Nc1ccc2c(-c3ccccc3C(O)=O)c3ccc(Nc4ccc(cc4C)S([O-])(=O)=O)cc3[o+]c2c1 UWMZZSRDUVJJDP-UHFFFAOYSA-N 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- DJDYMAHXZBQZKH-UHFFFAOYSA-M sodium;1-amino-4-(cyclohexylamino)-9,10-dioxoanthracene-2-sulfonate Chemical compound [Na+].C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(N)=C(S([O-])(=O)=O)C=C1NC1CCCCC1 DJDYMAHXZBQZKH-UHFFFAOYSA-M 0.000 description 1
- RRETZLLHOMHNNB-UHFFFAOYSA-M sodium;1-amino-9,10-dioxo-4-(2,4,6-trimethylanilino)anthracene-2-sulfonate Chemical compound [Na+].CC1=CC(C)=CC(C)=C1NC1=CC(S([O-])(=O)=O)=C(N)C2=C1C(=O)C1=CC=CC=C1C2=O RRETZLLHOMHNNB-UHFFFAOYSA-M 0.000 description 1
- IXNUVCLIRYUKFB-UHFFFAOYSA-M sodium;3-[[4-[[4-(diethylamino)-2-methylphenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]cyclohexa-2,5-dien-1-ylidene]methyl]-n-ethylanilino]methyl]benzenesulfonate Chemical compound [Na+].CC1=CC(N(CC)CC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC=1C=C(C=CC=1)S([O-])(=O)=O)=C(C=C1)C=CC1=[N+](CC)CC1=CC=CC(S([O-])(=O)=O)=C1 IXNUVCLIRYUKFB-UHFFFAOYSA-M 0.000 description 1
- FJBHGWADYLMEJG-UHFFFAOYSA-M sodium;3-[[4-[[4-(diethylamino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]cyclohexa-2,5-dien-1-ylidene]methyl]-n-ethylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC=1C=C(C=CC=1)S([O-])(=O)=O)=C(C=C1)C=CC1=[N+](CC)CC1=CC=CC(S([O-])(=O)=O)=C1 FJBHGWADYLMEJG-UHFFFAOYSA-M 0.000 description 1
- MIBVDSFVCOIWCC-UHFFFAOYSA-M sodium;4-(3-acetamidoanilino)-1-amino-9,10-dioxoanthracene-2-sulfonate Chemical compound [Na+].CC(=O)NC1=CC=CC(NC=2C=3C(=O)C4=CC=CC=C4C(=O)C=3C(N)=C(C=2)S([O-])(=O)=O)=C1 MIBVDSFVCOIWCC-UHFFFAOYSA-M 0.000 description 1
- NTOOJLUHUFUGQI-UHFFFAOYSA-M sodium;4-(4-acetamidoanilino)-1-amino-9,10-dioxoanthracene-2-sulfonate Chemical compound [Na+].C1=CC(NC(=O)C)=CC=C1NC1=CC(S([O-])(=O)=O)=C(N)C2=C1C(=O)C1=CC=CC=C1C2=O NTOOJLUHUFUGQI-UHFFFAOYSA-M 0.000 description 1
- KQRZWHVIXVADGL-UHFFFAOYSA-M sodium;4-[[4-(dibenzylamino)phenyl]-(4-dibenzylazaniumylidenecyclohexa-2,5-dien-1-ylidene)methyl]benzene-1,3-disulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC(S(=O)(=O)[O-])=CC=C1C(C=1C=CC(=CC=1)N(CC=1C=CC=CC=1)CC=1C=CC=CC=1)=C(C=C1)C=CC1=[N+](CC=1C=CC=CC=1)CC1=CC=CC=C1 KQRZWHVIXVADGL-UHFFFAOYSA-M 0.000 description 1
- FTUYQIPAPWPHNC-UHFFFAOYSA-M sodium;4-[[4-[benzyl(ethyl)amino]phenyl]-[4-[benzyl(ethyl)azaniumylidene]cyclohexa-2,5-dien-1-ylidene]methyl]benzene-1,3-disulfonate Chemical compound [Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=CC=CC=2)C=2C(=CC(=CC=2)S([O-])(=O)=O)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC=C1 FTUYQIPAPWPHNC-UHFFFAOYSA-M 0.000 description 1
- RIJLWEYDGZAVGC-UHFFFAOYSA-M sodium;5-methyl-2-[[4-(methylamino)-9,10-dioxoanthracen-1-yl]amino]benzenesulfonate Chemical compound [Na+].C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(NC)=CC=C1NC1=CC=C(C)C=C1S([O-])(=O)=O RIJLWEYDGZAVGC-UHFFFAOYSA-M 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
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- G—PHYSICS
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
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- 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
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- 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
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- 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
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- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
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Abstract
本發明係關於一種藍色感光性樹脂組成物及關於一種利用該藍色感光性樹脂組成物製造的彩色濾光片與影像顯示裝置,該藍色感光性樹脂組成物包括散射粒子、藍色著色劑、作為黏結劑樹脂的軸節(cardo)系黏結劑樹脂、光聚合起始劑、可光聚合的化合物、紫外線吸收劑、及溶劑,且該紫外線吸收劑包括苯并三唑系紫外線吸收劑、三嗪系紫外線吸收劑及二苯甲酮系紫外線吸收劑中之至少一者。
Description
本發明係關於一種藍色感光性樹脂組成物以及一種利用該藍色感光性樹脂組成物製造的彩色濾光片與影像顯示裝置。
彩色濾光片為一種薄膜型光學部件,其中從白光中提取三種顏色,即紅色、綠色及藍色,從而能夠逐一畫素地使用該三種顏色,並且單個畫素之尺寸近似數十至數百微米。此種彩色濾光片被配置為包括依次堆疊的黑色矩陣層與畫素部分,該黑色矩陣層以預定圖案形成於透明基板上,旨在遮蔽各個畫素之間的邊界,該等畫素部分由以預定順序排列以形成各個畫素的三種顏色(即,紅色(R)、綠色(G)及藍色(B))構成。
近來,藉由使用顏料分散型感光性樹脂的顏料分散製程來製造彩色濾光片。然而,在從光源發出的光通過彩色濾光片的過程中,一部分光被彩色濾光片吸收,從而降低了光效率,並且由於彩色濾光片中所含顏料之性質,顏色再現之準確性可能下降。
為瞭解決該等問題,已經提出了使用包括量子點的自發光感光性樹脂組成物製造彩色濾光片的方法。
具體而言,韓國專利申請公開案第2007-0094679號揭示了由量子點形成的旨在增加顏色再現性的彩色濾光片層,且韓國專利申請公開案第2009-0036373號揭示了藉由通過用包含量子點磷光體的發光層代替現有的彩色濾光片來提高光效率而達成顯示品質之改善。
但是,到目前為止開發的用於製造彩色濾光片的感光性樹脂組成物不能充分滿足例如優異的圖案特性、耐熱性等的要求。
[引文列表]
[專利文獻]
(專利文獻1)韓國專利申請公開案第2007-0094679號
(專利文獻2)韓國專利申請公開案第2009-0036373號
因此,本發明旨在提供一種藍色感光性樹脂組成物及一種利用該藍色感光性樹脂組成物製造的彩色濾光片與影像顯示裝置,該藍色感光性樹脂組成物能夠實現彩色濾光片,特別是自發光彩色濾光片,該彩色濾光片具有優異的顯影速率並且因此具有高加工性能,在形成固化膜時由於耐熱性高而能夠防止在高溫下發生黃變,從而可呈現均勻的光強度,並且由於藉由以預定的值形成精細的圖案而具有良好的圖案特性,從而可以減輕精細 畫素缺陷的問題。
因此,本發明提供一種藍色感光性樹脂組成物,該藍色感光性樹脂組成物包含散射粒子、藍色著色劑、作為黏結劑樹脂的軸節(cardo)系黏結劑樹脂、可光聚合的化合物、光聚合起始劑、紫外線吸收劑及溶劑,該紫外線吸收劑包括苯并三唑系紫外線吸收劑、三嗪系紫外線吸收劑及二苯甲酮系紫外線吸收劑中之至少一者。
另外,本發明提供了一種彩色濾光片,該彩色濾光片包含一由上述藍色感光性樹脂組成物形成的藍色圖案層。
另外,本發明提供一種影像顯示裝置,該影像顯示裝置包含上述彩色濾光片及用於發出藍色光的光源。
根據本發明,藍色感光性樹脂組成物包括含有苯并三唑系紫外線吸收劑、三嗪系紫外線吸收劑及二苯甲酮系紫外線吸收劑中之至少一者的紫外線吸收劑,並且因此可實現彩色濾光片,特別是自發光彩色濾光片,該彩色濾光片由於高耐熱性防止高溫黃變而顯示均勻的光強度,並且藉由以預定值形成精細圖案,由於優異的圖案特性而減輕了精細畫素缺陷的問題。此外,可提供具有高品質影像及優異的視角的自發光彩色濾光片。
根據本發明,藍色感光性樹脂組成物可包括散射粒 子、藍色著色劑、作為黏結劑樹脂的軸節系黏結劑樹脂、光聚合起始劑、可光聚合的化合物、熱固化劑及溶劑。具體而言,本發明之藍色感光性樹脂組成物包含苯并三唑系紫外線吸收劑、三嗪系紫外線吸收劑、二苯甲酮系紫外線吸收劑中之至少一者,從而包括由此種藍色感光性樹脂組成物形成之藍色圖案層的彩色濾光片、特別是自發光彩色濾光片,由於高耐熱性而防止在高溫下黃變,從而可表現出均勻的光強度,並且可藉由以預定值形成精細圖案來減輕精細畫素缺陷的問題。此外,可提供具有高品質影像及優異的視角的彩色濾光片,特別是自發光彩色濾光片,以及包括該彩色濾光片的影像顯示裝置。
以下,將詳細描述本發明之構造。
散射粒子
在本發明中,散射粒子可為平均粒徑為10奈米至1000奈米、且較佳30奈米至300奈米的金屬氧化物。若散射粒子之平均粒徑小於上述下限,則不能實現入射光之充分散射。另一方面,若其平均粒徑超過上述上限,則散射粒子可能在組成物中沉澱,或者無法得到品質一致的自發光層表面。
金屬氧化物可為包括選自以下群組之任一種金屬的氧化物:Li、Be、B、Na、Mg、Al、Si、K、Ca、Sc、V、Cr、Mn、Fe、Ni、Cu、Zn、Ga、Ge、Rb、Sr、Y、Mo、Cs、Ba、La、Hf、W、Tl、Pb、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Ti、Sb、Sn、Zr、Nb、Ce、Ta、In及其組合。更具體而言,金屬氧化物可為選自以下群組之至少一者:Al2O3、SiO2、ZnO、 ZrO2、BaTiO3、TiO2、Ta2O5、Ti3O5、ZnO、Nb2O3、SnO、MgO及其組合。視需要,可使用經具有不飽和鍵之化合物(例如丙烯酸酯)進行表面處理之材料。
散射粒子之平均粒徑及其在組成物中之量可視需要進行適當調整,以充分改善彩色濾光片之光強度。
以藍色感光性樹脂之固體含量之總重量計,散射粒子之含量可為0.1重量%至50重量%,較佳為5重量%至30重量%。當散射粒子之量落入上述範圍中時,可增加光強度並且可確保組成物之穩定性。
藍色著色劑
在本發明之藍色著色劑中,藍色顏料可包括根據比色指數(Color Index)(由英國染料與色彩師協會(Society of Dyers and Colourists)出版)分類為顏料的化合物,並且可具體而言包括但不限於以下比色指數(C.I.)編號的顏料。藍色顏料之具體實例可包括C.I.顏料藍15:3、C.I.顏料藍15:4、C.I.顏料藍15:6、C.I.顏料藍16、C.I.顏料藍21、C.I.顏料藍28及C.I.顏料藍76。較佳使用選自以下群組之至少一者:C.I.顏料藍15:3、C.I.顏料藍15:6及C.I.顏料藍16。
本發明之藍色著色劑可更包括藍色染料,並且藍色染料可包括根據比色指數(由英國染料與色彩師協會出版)分類為染料的化合物或染色注意事項(Dyeing Note,由色染社株式會社(Shikisensha Co.Ltd.)出版)中揭示之習知染料。
可另外使用的染料之具體實例可包括C.I.溶劑染料、C.I.酸染料、C.I.直接染料及C.I.媒染染料。
C.I.溶劑染料之實例可包括C.I.溶劑藍5、C.I.溶劑藍35、C.I.溶劑藍36、C.I.溶劑藍37、C.I.溶劑藍44、C.I.溶劑藍45、C.I.溶劑藍59、C.I.溶劑藍67及C.I.溶劑藍70,且較佳使用C.I.溶劑藍35、C.I.溶劑藍36、C.I.溶劑藍44、C.I.溶劑藍45及C.I.溶劑藍70中之至少一者。
並且,C.I.酸染料之實例可包括C.I.酸藍1、C.I.酸藍7、C.I.酸藍9、C.I.酸藍15、C.I.酸藍18、C.I.酸藍23、C.I.酸藍25、C.I.酸藍27、C.I.酸藍29、C.I.酸藍40、C.I.酸藍42、C.I.酸藍45、C.I.酸藍51、C.I.酸藍62、C.I.酸藍70、C.I.酸藍74、C.I.酸藍80、C.I.酸藍83、C.I.酸藍86、C.I.酸藍87、C.I.酸藍90、C.I.酸藍92、C.I.酸藍96、C.I.酸藍103、C.I.酸藍112、C.I.酸藍113、C.I.酸藍120、C.I.酸藍129、C.I.酸藍138、C.I.酸藍147、C.I.酸藍150、C.I.酸藍158、C.I.酸藍171、C.I.酸藍182、C.I.酸藍192、C.I.酸藍210、C.I.酸藍242、C.I.酸藍243、C.I.酸藍256、C.I.酸藍259、C.I.酸藍267、C.I.酸藍278、C.I.酸藍280、C.I.酸藍285、C.I.酸藍290、C.I.酸藍296、C.I.酸藍315、C.I.酸藍324:1、C.I.酸藍335及C.I.酸藍340。其中,較佳使用C.I.酸藍80與C.I.酸藍90中之至少一者。
並且,C.I.直接染料之實例可包括C.I.直接藍38、C.I.直接藍44、C.I.直接藍57、C.I.直接藍70、C.I.直接藍77、C.I.直接藍80、C.I.直接藍81、C.I.直接藍84、C.I.直接藍85、C.I.直接藍86、C.I.直接藍90、C.I.直接藍93、C.I.直接藍94、C.I.直接藍95、C.I. 直接藍97、C.I.直接藍98、C.I.直接藍99、C.I.直接藍100、C.I.直接藍101、C.I.直接藍106、C.I.直接藍107、C.I.直接藍108、C.I.直接藍109、C.I.直接藍113、C.I.直接藍114、C.I.直接藍115、C.I.直接藍117、C.I.直接藍119、C.I.直接藍137、C.I.直接藍149、C.I.直接藍150、C.I.直接藍153、C.I.直接藍155、C.I.直接藍156、C.I.直接藍158、C.I.直接藍159、C.I.直接藍160、C.I.直接藍161、C.I.直接藍162、C.I.直接藍163、C.I.直接藍164、C.I.直接藍166、C.I.直接藍167、C.I.直接藍170、C.I.直接藍171、C.I.直接藍172、C.I.直接藍173、C.I.直接藍188、C.I.直接藍189、C.I.直接藍190、C.I.直接藍192、C.I.直接藍193、C.I.直接藍194、C.I.直接藍196、C.I.直接藍198、C.I.直接藍199、C.I.直接藍200、C.I.直接藍207、C.I.直接藍209、C.I.直接藍210、C.I.直接藍212、C.I.直接藍213、C.I.直接藍214、C.I.直接藍222、C.I.直接藍228、C.I.直接藍229、C.I.直接藍237、C.I.直接藍238、C.I.直接藍242、C.I.直接藍243、C.I.直接藍244、C.I.直接藍245、C.I.直接藍247、C.I.直接藍248、C.I.直接藍250、C.I.直接藍251、C.I.直接藍252、C.I.直接藍256、C.I.直接藍257、C.I.直接藍259、C.I.直接藍260、C.I.直接藍268、C.I.直接藍274、C.I.直接藍275及C.I.直接藍293。
並且,C.I.媒染染料之實例可包括C.I.媒染藍1、C.I.媒染藍2、C.I.媒染藍3、C.I.媒染藍7、C.I.媒染藍8、C.I.媒染藍9、C.I.媒染藍12、C.I.媒染藍13、C.I.媒染藍15、C.I.媒染藍16、C.I.媒染藍19、C.I.媒染藍20、C.I.媒染藍21、C.I.媒染藍22、C.I.媒染藍23、C.I.媒染藍24、C.I.媒染藍26、C.I.媒染藍30、C.I.媒染藍31、C.I.媒染藍32、C.I.媒染藍39、C.I.媒染藍40、C.I.媒染藍41、C.I. 媒染藍43、C.I.媒染藍44、C.I.媒染藍48、C.I.媒染藍49、C.I.媒染藍53、C.I.媒染藍61、C.I.媒染藍74、C.I.媒染藍77、C.I.媒染藍83及C.I.媒染藍84。
該等藍色染料可單獨使用或以二或更多者之組合使用。
本發明之藍色著色劑可更包括其他著色劑,例如紫色著色劑。紫色著色劑可包括紫色顏料與紫色染料中之至少一者,並且紫色顏料之具體實例可以包括C.I.顏料紫1、C.I.顏料紫14、C.I.顏料紫19、C.I.顏料紫23、C.I.顏料紫29、C.I.顏料紫32、C.I.顏料紫33、C.I.顏料紫36、C.I.顏料紫37及C.I.顏料紫38。其中,較佳使用C.I.顏料紫23。
紫色染料之具體實例可包括但不限於C.I.溶劑紫、C.I.酸紫、C.I.直接紫及C.I.媒染紫。
具體而言,C.I.溶劑紫之實例可包括C.I.溶劑紫8、C.I.溶劑紫9、C.I.溶劑紫13、C.I.溶劑紫14、C.I.溶劑紫36、C.I.溶劑紫37、C.I.溶劑紫47及C.I.溶劑紫49,且較佳為C.I.溶劑紫13。C.I.酸紫之實例可包括C.I.酸紫6B、C.I.酸紫7、C.I.酸紫9、C.I.酸紫17、C.I.酸紫19及C.I.酸紫66,且較佳為C.I.酸紫66。C.I.直接紫之實例可包括C.I.直接紫47、C.I.直接紫52、C.I.直接紫54、C.I.直接紫59、C.I.直接紫60、C.I.直接紫65、C.I.直接紫66、C.I.直接紫79、C.I.直接紫80、C.I.直接紫81、C.I.直接紫82、C.I.直接紫84、C.I.直接紫89、C.I.直接紫90、C.I.直接紫93、C.I.直接紫95、C.I.直接紫96、C.I.直接紫103及C.I.直接紫104。
並且,可包括C.I.媒染紫1、C.I.媒染紫2、C.I.媒染紫4、C.I.媒染紫5、C.I.媒染紫7、C.I.媒染紫14、C.I.媒染紫22、C.I.媒染紫24、C.I.媒染紫30、C.I.媒染紫31、C.I.媒染紫32、C.I.媒染紫37、C.I.媒染紫40、C.I.媒染紫41、C.I.媒染紫44、C.I.媒染紫45、C.I.媒染紫47、C.I.媒染紫48、C.I.媒染紫53及C.I.媒染紫58。
以藍色感光性樹脂之固體含量之總重量計,藍色著色劑可以0.1重量%至50重量%、較佳0.5重量%至30重量%之量使用。當藍色著色劑之量落入上述範圍內時,可實現抑制外部光反射的理想效果,可有效地顯示具有良好光強度的顏色,並且可確保組成物之黏度穩定性。
在包括量子點的自發光感光性樹脂的情形下,量子效率可能降低並且不能獲得期望的性能。特別地,藍色量子點昂貴,因此導致製造成本高,並且由於潛在破壞性的高溫處理,其製程應用受到限制。然而,在本發明中,不包括藍色量子點,而是包括藍色著色劑及散射粒子,藉此防止彩色濾光片、特別是自發光彩色濾光片之藍色畫素效率降低。
黏結劑樹脂
本發明之黏結劑樹脂包括軸節系黏結劑樹脂。軸節系黏結劑樹脂在光或熱之作用下具有鹼溶性及反應性,並用作著色材料之分散介質。本發明之藍色感光性樹脂組成物中含有的軸節系黏結劑樹脂作為散射粒子的黏結劑樹脂而發揮作用,且其並無限制,只要能夠在製造彩色濾光片期間溶解於顯影製程中使用的鹼性顯影液中的樹脂即可。
本發明之軸節系黏結劑樹脂可包括由以下化學式1-1及化學式1-2表示的化合物中之至少一者。
在化學式1-1或化學式1-2中,R1、R2、R3及R4分別獨立地為,其中X為氫原子、C1-C5烷基、或羥基,且R5為氫原子或C1-C5烷基。
在本發明中,化學式1-1之化合物可由以下化學式2-1表示的化合物合成,並且化學式1-2之化合物可由以下化學式2-2表示的化合物合成。
[化學式2-2]
具體而言,化學式1-1之化合物可為由以下化學式1-1-1及化學式1-1-2表示的化合物中之至少一者,並且化學式1-2之化合物可為由以下化學式1-2-1及化學式1-2-2表示的化合物中之至少一者。
軸節系黏結劑樹脂可藉由使選自由9,9-雙(3-肉桂酸二酯)茀、9,9-雙(3-肉桂醯基-4-羥苯基)茀、9,9-雙(縮水甘油基甲基丙烯酸酯醚)茀、9,9-雙(3,4-二羥苯基)茀二肉桂酸酯、3,6-二縮水甘油基甲基丙烯酸酯醚螺(茀-9,9-二苯并哌喃 (xanthene))、9,9-雙(3-烯丙基-4-羥苯基)茀、9,9-雙(4-烯丙氧基苯基)茀及9,9-雙(3,4-甲基丙烯酸二酯)茀組成之群組之至少一者與選自下列的至少一者反應而製備:由馬來酸酐、琥珀酸酐、伊康酸酐、鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、甲基內亞甲基四氫鄰苯二甲酸酐、氯橋酐(chlorendic anhydride)及甲基四氫鄰苯二甲酸酐組成的酸酐群組;或由芳族多羧酸酐如焦蜜石酸二酐(pyromellitic anhydride)、二苯甲酮四羧酸二酐、聯苯四羧酸二酐及聯苯醚四羧酸二酐組成的酸二酐群組,但是本發明並不限於此。
本發明之黏結劑樹脂可更包括丙烯酸系鹼溶性樹脂。丙烯酸系鹼溶性樹脂可由含有羧基的單體與其他可與之聚合的共聚單體的共聚物舉例說明。含羧基單體可包括例如在其分子中具有至少一個羧基的不飽和羧酸,包括不飽和一元羧酸或不飽和多元羧酸,例如不飽和二元羧酸、不飽和三元羧酸等。此處,不飽和一元羧酸之實例可包括丙烯酸、甲基丙烯酸、巴豆酸、α-氯丙烯酸、肉桂酸等。不飽和二羧酸之實例可包括馬來酸、富馬酸、伊康酸、檸康酸、中康酸等。不飽和多元羧酸可為酸酐,其具體實例可包括馬來酸酐、伊康酸酐及檸康酸酐。並且,不飽和多元羧酸可為其單(2-甲基丙烯醯氧基烷基)酯,例如,單(2-丙烯醯氧基乙基)琥珀酸酯、單(2-甲基丙烯醯氧基乙基)琥珀酸酯、單(2-丙烯醯氧基乙基)鄰苯二甲酸酯、或單(2-甲基丙烯醯氧基乙基)鄰苯二甲酸酯。不飽和多元羧酸可為在其兩端具有二羧酸聚合物的單(甲基)丙烯酸酯,例如,ω-羧基聚己內酯單丙烯酸酯、ω-羧基聚己內酯單甲基丙烯酸酯等。該等含有羧基的 單體可單獨使用或以其二或更多者之組合使用。可與含羧基之單體共聚合的其他共聚單體之實例可包括芳族乙烯基化合物,例如苯乙烯、α-甲基苯乙烯、鄰乙烯基甲苯、間乙烯基甲苯、對乙烯基甲苯、對氯苯乙烯、鄰甲氧基苯乙烯、間甲氧基苯乙烯、對甲氧基苯乙烯、鄰乙烯基苄基甲醚、間乙烯基苄基甲醚、對乙烯基苄基甲醚、鄰乙烯基苄基縮水甘油醚、間乙烯基苄基縮水甘油醚、對乙烯基苄基縮水甘油醚、及茚;不飽和羧酸酯,例如丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸正丙酯、甲基丙烯酸正丙酯、丙烯酸異丙酯、甲基丙烯酸異丙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸異丁酯、甲基丙烯酸異丁酯、丙烯酸第二丁酯、甲基丙烯酸第二丁酯、丙烯酸第三丁酯、甲基丙烯酸第三丁酯、丙烯酸-2-羥乙酯、甲基丙烯酸-2-羥乙酯、丙烯酸-2-羥丙酯、甲基丙烯酸-2-羥丙酯、丙烯酸-3-羥丙酯、甲基丙烯酸-3-羥丙酯、丙烯酸-2-羥丁酯、甲基丙烯酸-2-羥丁酯、丙烯酸-3-羥丁酯、甲基丙烯酸-3-羥丁酯、丙烯酸-4-羥丁酯、甲基丙烯酸-4-羥丁酯、丙烯酸烯丙酯、甲基丙烯酸烯丙酯、丙烯酸苄酯、甲基丙烯酸苄酯、丙烯酸環己酯、甲基丙烯酸環己酯、丙烯酸苯酯、甲基丙烯酸苯酯、丙烯酸-2-甲氧基乙酯、甲基丙烯酸-2-甲氧基乙酯、丙烯酸-2-苯氧基乙酯、甲基丙烯酸-2-苯氧基乙酯、甲氧基二乙二醇丙烯酸酯、甲氧基二乙二醇甲基丙烯酸酯、甲氧基三乙二醇丙烯酸酯、甲氧基三乙二醇甲基丙烯酸酯、甲氧基丙二醇丙烯酸酯、甲氧基丙二醇甲基丙烯酸酯、甲氧基二丙二醇丙烯酸酯、甲氧基二丙二醇甲基丙烯酸酯、丙烯酸異莰酯(isobornyl acrylate)、甲基丙烯酸異莰酯、二環戊二烯基丙烯酸酯、二環戊二 烯基甲基丙烯酸酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸降莰酯(norbornyl(meth)acrylate)、丙烯酸2-羥基-3-苯氧基丙酯、甲基丙烯酸2-羥基-3-苯氧基丙酯、甘油單丙烯酸酯及甘油單甲基丙烯酸酯;不飽和羧酸胺基烷基酯,例如丙烯酸-2-胺基乙酯、甲基丙烯酸-2-胺基乙酯、丙烯酸-2-二甲基胺基乙酯、甲基丙烯酸-2-二甲基胺基乙酯、丙烯酸-2-胺基丙酯、甲基丙烯酸-2-胺基丙酯、丙烯酸-2-二甲基胺基丙酯、甲基丙烯酸-2-二甲基胺基丙酯、丙烯酸-3-胺基丙酯、甲基丙烯酸-3-胺基丙酯、丙烯酸-3-二甲基胺基丙酯及甲基丙烯酸-3-二甲基胺基丙酯;不飽和羧酸縮水甘油酯,例如丙烯酸縮水甘油酯及甲基丙烯酸縮水甘油酯;羧酸乙烯基酯,例如乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯及苯甲酸乙烯酯;不飽和醚,例如乙烯基甲醚、乙烯基乙醚及烯丙基縮水甘油醚;乙烯基氰化物,例如丙烯腈、甲基丙烯腈、α-氯丙烯腈及二氰亞乙烯;不飽和醯胺,例如丙烯醯胺、甲基丙烯醯胺、α-氯丙烯醯胺、N-2-羥乙基丙烯醯胺、及N-2-羥乙基甲基丙烯醯胺;不飽和醯亞胺,例如馬來醯亞胺、苄基馬來醯亞胺、N-苯基馬來醯亞胺、及N-環己基馬來醯亞胺;脂族共軛二烯,例如1,3-丁二烯、異戊二烯及氯丁二烯;以及在聚合物分子鏈末端具有單丙烯醯基或單甲基丙烯醯基的大分子單體,例如聚苯乙烯、聚丙烯酸甲酯、聚甲基丙烯酸甲酯、聚丙烯酸正丁酯、聚甲基丙烯酸正丁酯、及聚矽氧烷。該等單體可單獨使用或以其二或更多者之組合使用。作為可與含羧基單體聚合的其他共聚單體,特別有用者為大單體(bulky monomer),例如具有降莰基主鏈的單體、具有金剛烷主鏈的單體、具有松香主鏈的單體等,乃因此種單體會降低相對介電常數。 在本發明中,軸節系黏結劑樹脂及/或丙烯酸系鹼溶性樹脂可具有20至200(毫克KOH/克)的酸值。在上述酸值範圍內,在顯影液中之溶解性可得到改善,並且因此未曝光部分可容易地溶解並且感光度可增加,由此在顯影時曝光部分之圖案可保留,從而改善殘膜比。此處,酸值為中和1克丙烯酸系聚合物所需的氫氧化鉀之量(毫克),且通常藉由使用氫氧化鉀水溶液進行滴定過程來確定。另外,軸節系黏結劑樹脂或丙烯酸系鹼可溶性樹脂可具有2000至200000、且較佳3000至100000的通過凝膠滲透層析法(GPC,使用四氫呋喃作為洗提溶劑)針對聚苯乙烯標準物量測的重量平均分子量(以下簡稱為「重量平均分子量」)。在上述分子量範圍內,塗佈膜之硬度可能會增加,從而獲得高膜殘留率,並且未曝光部分在顯影液中之溶解度高,並且其解析度提高。
軸節系黏結劑樹脂及/或丙烯酸系鹼溶性樹脂之分子量分佈[重量平均分子量(Mw)/數量平均分子量(Mn)]較佳落入1.0至6.0的範圍內,並且更佳為1.5至6.0。當分子量分佈[重量平均分子量(Mw)/數量平均分子量(Mn)]為1.5至6.0時,可產生高顯影性。
以藍色感光性樹脂之固體含量之總重量計,本發明之黏結劑樹脂之量為5重量%至85重量%,且較佳為5重量%至60重量%。當黏結劑樹脂之量落入上述範圍內時,在顯影溶液中之溶解度變得足夠大,因此難以在基板上產生非畫素部分之顯影殘留物。此外,在顯影時難以產生曝光部分之畫素部分之膜減少,因 此非畫素部分可根據需要進行處理。
可光聚合的化合物
在本發明之藍色感光性樹脂組成物中,可光聚合的化合物為可在光及稍後描述的光聚合起始劑的作用下聚合的化合物,且可包括單官能單體、雙官能單體及其他多官能單體。單官能單體之具體實例可包括壬基苯基卡必醇丙烯酸酯、丙烯酸2-羥基-3-苯氧基丙酯、2-乙基己基卡必醇丙烯酸酯、丙烯酸-2-羥乙酯及N-乙烯基吡咯啶酮。雙官能單體之具體實例可包括1,6-己二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、雙酚A雙(丙烯醯氧基乙基)醚及3-甲基戊二醇二(甲基)丙烯酸酯。其他多官能單體之具體實例可包括三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、季戊四醇五(甲基)丙烯酸酯及二季戊四醇六(甲基)丙烯酸酯。其中,較佳使用雙官能單體或更高官能的多官能單體。以藍色感光性樹脂組成物之固體含量之總重量計,可光聚合的化合物之量為5重量%至50重量%,且較佳為5重量%至45重量%。當可光聚合的化合物之量落入上述範圍內時,感光性可能不會降低,因此可以獲得足夠的膜強度,並且在顯影時可能沒有圖案損失,由此可在精細圖案部分有效地形成圖案,並且可改善抗蝕層平滑性。
光聚合起始劑
在本發明中,光聚合起始劑可包括選自下面的化學式3至化學式5表示的化合物中之至少一者。當以此方式包括化學 式3至化學式5的化合物時,感光性樹脂組成物之自由基反應被引發,從而引起固化並提高感光度。
在化學式3中,R8可為氫原子、鹵素原子、羥基、未經取代或經C1-C12烷基取代的苯基、未經取代或經C1-C12烷基取代的苄基、未經取代或經C1-C12烷基取代的萘基、或-SRa,Ra為氫、C1-C12烷基或苄基;且R9至R12分別獨立地為氫原子、鹵素原子、羥基、未經取代或經C1-C12烷基取代的苯基、未經取代或經C1-C12烷基取代的苄基、或未經取代或經C1-C12烷基取代的萘基,R11與R12能夠一起形成環。
化學式3化合物之實例可包括2-甲基-2-胺基(4-嗎啉代苯基)乙-1-酮、2-乙基-2-胺基(4-嗎啉代苯基)乙-1-酮、2-丙基-2-胺基(4-嗎啉代苯基)乙-1-酮、2-丁基-2-胺基(4-嗎啉代苯基)乙-1-酮、2-甲基-2-胺基(4-嗎啉代苯基)丙-1-酮、2-甲基-2-胺基(4-嗎啉代苯基)丁-1-酮、2-乙基-2-胺基(4-嗎啉代苯基)丙-1-酮、2-乙基-2-胺基(4-嗎啉代苯基)丁-1-酮、2-甲基-2-甲基胺基(4-嗎啉代苯基)丙-1-酮、2-甲基-2-二甲基胺基(4-嗎啉代苯基)丙-1-酮及2-甲基-2-二乙基胺基(4-嗎啉代苯基)丙-1-酮。
[化學式4]
在化學式4中,R14為氫、C1-C20烷基、C3-C8環烷基、未經取代或經取代的苯基或,n為1至4的整數且m為1至6的整數;R15為C1-C8烷基、苯基、經取代的苯基、苄基、或經取代的苄基;且R13為二苯基硫醚基、經取代的二苯基硫醚基、咔唑基(carbazole group)、經取代的咔唑基、茀基、或經取代的茀基。
在化學式5中,R16、R17及R18分別獨立地為R、OR、COR、SR、CONRR'、ROR'或CN,其中R及R'表示C1-C20烷基、C6-C30芳基、C7-C30芳烷基或C2-C20雜環基,各自可經鹵素原子及/或C2-C20雜環基取代且其中該烷基及該芳烷基之伸烷基部分可被不飽和鍵、醚鍵、硫醚鍵或酯鍵中斷,R與R'能夠一起形成環;Y1表示氧原子、硫原子或硒原子,m為0至4的整數,且r為0至5的整數; s為0或1;R19、R20、R21及R22分別獨立地表示氫原子、鹵素原子或C1-C8烷基;X1及X2表示C1-C20烷基、C6-C30芳基、C7-C30芳烷基或C2-C20雜環基,各自可被鹵素原子及/或C2-C20雜環基取代且其中該烷基及該芳烷基之伸烷基部分可被不飽和鍵、醚鍵、硫醚鍵或酯鍵中斷;X2可與相鄰環之碳原子一起形成環,且更具體而言可形成C6-C30芳族環;且Y2及Y3分別獨立地表示氧原子、硫原子或硒原子。
由R及R'表示之烷基之較佳實例包括甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、戊基、異戊基、第三戊基、己基、庚基、辛基、異辛基、2-乙基己基、第三辛基、壬基、異壬基、癸基、異癸基、乙烯基、芳基、丁烯基、乙炔基、丙炔基、甲氧基乙基、乙氧基乙基、丙氧基乙基、甲氧基乙氧基乙基、乙氧基乙氧基乙基、丙氧基乙氧基乙基、甲氧基丙基、單氟甲基、二氟甲基、三氟甲基、三氟乙基、全氟乙基、2-(苯并唑-2'-基)乙烯基等。其中,較佳使用C1-C8烷基。
另外,由R及R'表示之芳基之實例包括苯基、甲苯基、二甲苯基、乙基苯基、氯苯基、萘基、蒽基、菲基等。其中,較佳使用C6-C12芳基。此外,由R及R'表示之芳烷基可包括例如C7-C13芳烷基,如苄基、氯苄基、α-甲基苄基、α,α-二甲基苄基、 苯乙基、苯乙烯基等。由R及R'表示之雜環基可包括例如C5-C7雜環基,如吡啶基、嘧啶基、呋喃基、噻吩基等。另外,由R及R'二者形成之環可包括例如C5-C7環,如哌啶環、嗎啉環等。此外,R及R'可被例如氟、氯、溴、碘等鹵素元素取代,或者可被例如吡啶基、嘧啶基、呋喃基、苯并唑-2-基、四氫哌喃基、吡咯啶基、咪唑啶基、吡唑啶基、四氫噻唑基、異四氫噻唑基、唑啶基、異唑啶基、哌啶基、哌嗪基或嗎啉基等C5-C7雜環基取代。
由X1及X2表示之烷基之較佳實例包括甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、戊基、異戊基、第三戊基、己基、庚基、辛基、異辛基、2-乙基己基、第三辛基、壬基、異壬基、癸基、異癸基、乙烯基、芳基、丁烯基、乙炔基、丙炔基、甲氧基乙基、乙氧基乙基、丙氧基乙基、甲氧基乙氧基乙基、乙氧基乙氧基乙基、丙氧基乙氧基乙基、甲氧基丙基、單氟甲基、二氟甲基、三氟甲基、三氟乙基、全氟乙基、2-(苯并唑-2'-基)乙烯基等。其中,較佳使用C1-C8烷基。
另外,由X1及X2表示之芳基之實例包括苯基、甲苯基、二甲苯基、乙基苯基、氯苯基、萘基、蒽基、菲基等。其中,較佳使用C6-C12芳基。此外,由X1及X2表示之芳烷基可包括例如C7-C13芳烷基,例如苄基、氯苄基、α-甲基苄基、α,α-二甲基苄基、苯乙基、苯乙烯基等。由X1及X2表示之雜環基可包括例如C5-C7雜環基,例如吡啶基、嘧啶基、呋喃基、苯并唑-2-基、四氫哌喃基、吡咯啶基、咪唑啶基、吡唑啶基、四氫噻唑基、異四氫噻唑基、唑啶基、異唑啶基、哌啶基、哌嗪基、嗎啉基、噻吩 基等。
另外,由X1及X2表示之鹵素原子之實例可包括氟、氯、溴及碘。
由X1及X2表示之烷基之實例可包括甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、戊基、異戊基、第三戊基、己基、庚基、辛基、異辛基、2-乙基己基及第三辛基,各自被鹵素原子取代。
X2可與相鄰環之碳原子一起形成環,並且具體而言可形成C6-C30芳族環或C5-C10環狀化合物。
由R19、R20、R21及R22表示之鹵素原子之實例可包括氟、氯、溴及碘。
由R19、R20、R21及R22表示之烷基之實例可包括甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、戊基、異戊基、第三戊基、己基、庚基、辛基、異辛基、2-乙基己基及第三辛基。
化學式5之化合物可包括以下化合物。
另外,光聚合起始劑較佳含有苯乙酮系化合物。苯乙酮系化合物之實例可包括寡聚物,例如二乙氧基苯乙酮、2-羥基-2-甲基-1-苯基丙-1-酮、苄基二甲基縮酮、2-羥基-1-[4-(2-羥乙氧基)苯基]-2-甲基丙-1-酮、1-羥基環己基苯酮、2-甲基-1-(4-甲硫基苯基)-2-嗎啉代丙-1-酮、2-苄基-2-二甲基胺基-1-(4-嗎啉代苯基)丁-1-酮、及2-羥基-2-甲基[4-(1-甲基乙烯基)苯基]丙-1-酮寡聚物,且較佳包括2-苄基-2-二甲基胺基-1-(4-嗎啉代苯基)丁-1-酮。
另外,化學式3至化學式5之光聚合起始劑可包括由以下化學式5-1至化學式5-8表示之結構。
[化學式5-2]
[化學式5-8]
另外,苯乙酮系化合物可與其他光聚合起始劑組合使用。
除苯乙酮系化合物之外的其他光聚合起始劑可包括用於通過光輻照產生活性自由基的活性自由基產生劑、增感劑、酸產生劑等。活性自由基產生劑之實例可包括安息香系化合物、二苯甲酮系化合物、噻噸酮系化合物及三嗪系化合物。
安息香系化合物之實例可包括安息香、安息香甲醚、安息香乙醚、安息香異丙醚、安息香異丁醚等。二苯甲酮系化合物之實例可包括二苯甲酮、鄰苯甲醯基苯甲酸甲酯、4-苯基二苯甲酮、4-苯甲醯基-4'-甲基二苯基硫醚、3,3',4,4'-四(第三丁基過氧羰基)二苯甲酮、2,4,6-三甲基二苯甲酮等。
噻噸酮系化合物之實例可包括2-異丙基噻噸酮、4-異丙基噻噸酮、2,4-二乙基噻噸酮、2,4-二氯噻噸酮、1-氯-4-丙氧基噻噸酮等。
三嗪系化合物之實例可包括2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(4-二乙基胺基-2-甲基苯基)乙 烯基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三嗪等。
活性自由基產生劑之實例可包括2,4,6-三甲基苯甲醯基二苯基氧化膦、2,2'-雙(鄰氯苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑、10-丁基-2-氯吖啶酮、2-乙基蒽醌、苄基、9,10-菲醌、樟腦醌、甲基苯基乙醛酸酯、二茂鈦化合物等。酸產生劑之實例可包括鎓鹽,例如4-羥苯基二甲基鋶對甲苯磺酸鹽、4-羥苯基二甲基鋶六氟銻酸鹽、4-乙醯氧基苯基二甲基鋶對甲苯磺酸鹽、4-乙醯氧基苯基甲基苄基鋶六氟銻酸鹽、三苯基鋶對甲苯磺酸鹽、三苯基鋶六氟銻酸鹽、二苯基碘鎓對甲苯磺酸鹽及二苯基碘鎓六氟銻酸鹽、硝基苄基甲苯磺酸鹽、安息香甲苯磺酸鹽等。
此外,活性自由基產生劑可包括能夠同時產生活性自由基與酸的化合物,並且舉例而言,三嗪系光聚合起始劑亦可用作產酸劑。
以藍色感光性樹脂之固體含量之總重量計,光聚合起始劑之量為0.1重量%至20重量%,且較佳為0.3重量%至15重量%。在上述量之範圍內,藍色感光性樹脂組成物被高度增感,且因而可改善使用上述組成物形成之畫素部分之強度或畫素部分之表面平滑性。
而且,在本發明中,可使用光聚合起始劑助劑。光聚合起始劑助劑可與光聚合起始劑組合使用,並且為用於促進可光聚合的化合物之聚合的化合物,可光聚合的化合物之聚合係藉由光聚合起始劑來起始反應。
光聚合起始劑助劑之實例可包括胺系化合物、烷氧基蒽系化合物、及噻噸酮系化合物。
胺系化合物之實例可包括三乙醇胺、甲基二乙醇胺、三異丙醇胺、4-二甲基胺基苯甲酸甲酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸異戊酯、苯甲酸-2-二甲胺基乙酯、4-二甲基胺基苯甲酸-2-乙基己酯、N,N-二甲基對甲苯胺、4,4'-雙(二甲基胺基)二苯甲酮(即米其勒酮(Michler’s ketone))、4,4'-雙(二乙基胺基)二苯甲酮、及4,4'-雙(乙基甲基胺基)二苯甲酮。特別有用者為4,4'-雙(二乙基胺基)二苯甲酮。
烷氧基蒽系化合物之實例可包括9,10-二甲氧基蒽、2-乙基-9,10-二甲氧基蒽、9,10-二乙氧基蒽及2-乙基-9,10-二乙氧基蒽。
噻噸酮系化合物之實例可包括2-異丙基噻噸酮、4-異丙基噻噸酮、2,4-二乙基噻噸酮、2,4-二氯噻噸酮、及1-氯-4-丙氧基噻噸酮。
該等光聚合起始劑可單獨使用或以其二或更多者之組合使用。另外,可使用市售的光聚合起始劑助劑,例示性市售光聚合起始劑助劑為「EAB-F」[保土谷化學工業株式會社(Hodogaya Chemical Co.Ltd.)製]。
當以此方式使用光聚合起始劑助劑時,對於1莫耳光聚合起始劑,光聚合起始劑助劑之量為10莫耳或少於10莫耳,且較佳為0.01莫耳至5莫耳。在上述量之範圍內,藍色感光性樹脂組 成物之感光度進一步提高,並且使用上述組成物形成的彩色濾光片之生產率可得到改善。
紫外線吸收劑
在本發明中證實,紫外線吸收劑在調節圖案尺寸方面是有效的,並且在防止高溫處理過程中之黃變方面亦有效,從而提高了量子效率。
通常,當由於感光性樹脂組成物之CD偏差(CD bias)增加而不能形成精細圖案時,已知紫外線吸收劑是有用的。此處,「CD」係指圖案之壓紋部分,且「CD偏差」表示所形成的圖案尺寸大於要實現的遮罩圖案的程度。當添加紫外線吸收劑時,紫外線吸收劑可吸收一部分紫外光,從而減少由繞射引起的CD偏差,由此獲得所需的圖案。
此外,具有低耐熱性的量子點之使用使得難以在製造彩色濾光片期間保持高的光強度。此處,添加紫外線吸收劑時,即使經過多次後烘烤處理,亦可保持高的光強度。
根據本發明,紫外線吸收劑基本上含有苯并三唑系紫外線吸收劑、三嗪系紫外線吸收劑及二苯甲酮系紫外線吸收劑中之至少一者。
苯并三唑系紫外線吸收劑可包括已知的化合物,其具體實例可包括3-[3-第三丁基-4-羥基-5-(5-氯-2H-苯并三唑-2-基)苯基]丙酸辛酯、(3-第三丁基-4-羥基-5-(5-氯-2H-苯并三唑-2-基)苯基)丙酸-2-乙基己酯、[3-[3-(2H-苯并三唑-2-基)-5-(1,1- 甲基乙基)-4-羥苯基]-1-氧丙基]-w-[3-[3-(2H-苯并三唑-2-基)-5-(1,1-二甲基乙基)-4-羥苯基]-1-氧丙氧基]聚(氧-1,2-乙二基)、(3-(3-(2H-苯并三唑-2-基)-5-(1,1-二甲基乙基)-4-羥苯基)-1-氧丙基)-羥基聚(氧-1,2-乙二基)、2-(3-第三丁基-2-羥基-5-甲基苯基)-5-氯-2H-苯并三唑、2-(2H-苯并三唑-2-基)-4,6-二第三戊基苯酚、3-(2H-苯并三唑基)-5-(1,1-二甲基乙基)-4-羥基-苯丙酸辛酯、2-(2H-苯并三唑-2-基)-4,6-雙(1-甲基-1-苯基乙基)苯酚、2-(2H-苯并三唑-2-基)-6-(1-甲基-1-苯基乙基)-4-(1,1,3,3-四甲基丁基)苯酚等。
三嗪系紫外線吸收劑可包括已知的化合物,其具體實例可包括2-(4,6-二甲基-1,3,5-三嗪-2-基)-5-((己基)氧)苯酚、2-(4-(2-羥基-3-十三烷氧基丙基)氧)-2-羥苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪、2-(4-(2-羥基-3-二癸氧基丙基)氧)-2-羥苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪、2-(2-羥基-4-(3-(2-乙基己基-1-氧)-2-羥基丙氧基)苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪、2,2'-[6-(2,4-二丁氧基苯基)-1,3,5-三嗪-2,4-二基]雙(5-丁氧基苯酚)、2-{4-[4,6-二(4-聯苯基)-1,3,5-三嗪-2-基]-3-羥基苯氧基}丙酸6-甲基庚酯等。
二苯甲酮系紫外線吸收劑可包括已知化合物,其具體實例可包括2-羥基-4-正辛氧基二苯甲酮、2-羥基-4-甲氧基二苯甲酮等。
以藍色感光性樹脂之固體含量之總重量計,紫外線吸收劑之量為0.001重量%至10重量%,並且較佳為0.025重量%至7 重量%。當紫外線吸收劑之量落入上述範圍內時,可改善吸收劑之效果,並且可有效地形成圖案而不妨礙光聚合起始劑之作用。
溶劑
在根據本發明之藍色感光性樹脂組成物中,溶劑不受特別限制,並且可包括在藍色感光性樹脂組成物領域中使用的各種有機溶劑。其具體實例可包括乙二醇單烷基醚,例如乙二醇單甲醚、乙二醇單乙醚、乙二醇單丙醚及乙二醇單丁醚;二乙二醇二烷基醚,例如二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇二丙醚及二乙二醇二丁醚;乙二醇烷基醚乙酸酯,例如乙酸-2-甲氧基乙酯(methylcellosolve acetate)及乙酸-2-乙氧基乙酯(ethyl cellosolve acetate);伸烷基二醇烷基醚乙酸酯,例如丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯、乙酸甲氧基丁酯及乙酸甲氧基戊酯;芳族烴,例如苯、甲苯、二甲苯及均三甲苯;酮,例如甲基乙基酮、丙酮、甲基戊基酮、甲基異丁基酮及環己酮;醇,例如乙醇、丙醇、丁醇、己醇、環己醇、乙二醇及甘油;酯,例如3-乙氧基丙酸乙酯及3-甲氧基丙酸甲酯;以及環狀酯,例如γ-丁內酯。溶劑較佳為在塗佈及乾燥方面具有為100℃至200℃之沸點的有機溶劑,且更佳包括伸烷基二醇烷基醚乙酸酯、酮及酯,例如3-乙氧基丙酸乙酯及3-甲氧基丙酸甲酯。其具體實例包括丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、環己酮、3-乙氧基丙酸乙酯及3-甲氧基丙酸甲酯。該等溶劑可單獨使用或以其二或更多者之組合使用。
在根據本發明之藍色感光性樹脂組成物中,以藍色 感光性樹脂組成物之總重量計,溶劑之量為60質量%至90質量%,且較佳為60質量%至85質量%。當溶劑之量落入上述範圍內時,可使用輥塗機、旋塗機、狹縫旋塗機、狹縫塗佈機(或模具塗佈機)或噴墨塗佈機等塗佈裝置施用組成物,由此可改善塗佈性。
添加劑
用於形成藍色圖案層的根據本發明之藍色感光性樹脂組成物視需要可更包括添加劑,例如填充劑、其他聚合物化合物、顏料分散劑、助黏劑、抗氧化劑、紫外線吸收劑、防凝聚劑等。
其他聚合物化合物之實例可包括可固化樹脂,例如環氧樹脂或馬來醯亞胺樹脂,以及熱塑性樹脂,例如聚乙烯醇、聚丙烯酸、聚乙二醇單烷基醚、丙烯酸聚氟烷基酯、聚酯或聚胺甲酸酯。
顏料分散劑可包括市售表面活性劑,其實例包括聚矽氧系表面活性劑、氟系表面活性劑、酯系表面活性劑、陽離子表面活性劑、陰離子表面活性劑、非離子表面活性劑及兩性表面活性劑,其可單獨使用或以其二或更多者之組合使用。
表面活性劑之實例可包括聚氧乙烯烷基醚、聚氧乙烯烷基苯基醚、聚乙二醇二酯、脫水山梨糖醇脂肪酸酯、脂肪酸改質的聚酯、三級胺改質的聚胺甲酸酯、聚乙烯亞胺及市售產品如KP(信越化學工業株式會社(Shin-Etsu Chemical Industry Co.)製)、POLYFLOW(共榮社化學株式會社(Kyoeisha Chemical Co.))、EFTOP(Tochem Products有限公司製)、MEGAFAC(大日本油墨化學工業株式會社(Dainippon Ink & Chemical Industry Co.)製)、Flourad(住友3M株式會社(Sumitomo 3M Ltd.)製)、Asahi guard and Surflon(旭硝子株式會社(Asahi Glass Co.)製)、SOLSPERSE(捷利康公司(Zeneca)製))、EFKA(埃夫卡化學公司(EFKA Chemicals)製)及PB 821(味之素株式會社(Ajinomoto Co.)製)
助黏劑之實例可包括乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三(2-甲氧基乙氧基)矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷及3-巰基丙基三甲氧基矽烷。抗氧化劑之具體實例可包括2,2'-硫代雙(4-甲基-6-第三丁基苯酚)、2,6-二第三丁基-4-甲基苯酚等。
紫外線吸收劑之具體實例可包括2-(3-第三丁基-2-羥基-5-甲基苯基)-5-氯苯并三唑、烷氧基二苯甲酮等。
防凝聚劑可由聚丙烯酸鈉舉例說明。
熟習此項技術者可在不妨礙本發明效果之範圍內適當添加添加劑。例如,以總計100重量份的藍色感光性樹脂組成物計,添加劑之用量為0.05重量份至10重量份,較佳為0.1重量份至10重量份,且更佳為0.1重量份至5重量份,但並不限於此。
根據本發明之藍色感光性樹脂組成物可通過以下方法製備。具體而言,將散射粒子與溶劑預先混合,並使用珠磨機等分散至平均粒徑為30奈米至300奈米。如此,可視需要進一步使用分散劑,並且可將一些或全部的黏結劑樹脂與其混合。向得到的分散溶液(亦可稱為「研磨基料」)添加剩餘的黏結劑樹脂、可光聚合的化合物及光聚合起始劑以及視需要其他組分及額外的溶劑,使得組成物具有預定的濃度,從而得到期望的藍色感光性樹脂組成物。
<彩色濾光片及影像顯示裝置>
另外,本發明提出了一種彩色濾光片,該彩色濾光片包含一包括上述藍色感光性樹脂組成物之固化產物的藍色圖案層。
使用用於形成藍色圖案層的藍色感光性樹脂組成物代替藍色量子點來製造本發明之彩色濾光片,由此降低製造成本並確保優異的視角。
另外,本發明之藍色感光性樹脂組成物包括含有苯并三唑系紫外線吸收劑、三嗪系紫外線吸收劑及二苯甲酮系紫外線吸收劑中之至少一者的紫外線吸收劑,由此包括由本發明之藍色感光性樹脂組成物形成的藍色圖案層的彩色濾光片(尤其是自發光彩色濾光片)由於耐熱性高,因此能夠防止高溫黃變,從而能夠顯示出均勻的光強度,並且藉由以預定的值形成精細圖案而可減輕精細畫素缺陷的問題。
彩色濾光片包括一基板及形成在基板上的一藍色圖案層。
基板本身可為彩色濾光片,或可為彩色濾光片位於顯示裝置上的位置,且並不特別限定。基板可為玻璃、矽(Si)、氧化矽(SiOx)或聚合物基板,且聚合物基板可為聚醚碸(PES)或聚碳酸酯(PC)。
藍色圖案層為包括本發明之藍色感光性樹脂組成物的層,並且可係以如下方式形成:施加用於形成藍色圖案層的藍色感光性樹脂組成物,以預定圖案曝光,顯影並熱固化。圖案層可藉由實施本技術中通常已知的任何方法來形成。
在本發明的另一個實施態樣中,彩色濾光片可更包括選自由紅色圖案層及綠色圖案層組成之群組之至少一者。
在本發明的又一個實施態樣中,紅色圖案層或綠色圖案層可包括量子點及/或散射粒子。具體而言,本發明之彩色濾光片可包括含有紅色量子點的紅色圖案層或含有綠色量子點的綠色圖案層,且紅色圖案層或綠色圖案層可包括散射粒子。紅色圖案層或綠色圖案層能夠藉由用於發出藍色光的光源而發出紅色光或綠色光,稍後將對此予以描述。
在本發明的又一個實施態樣中,包含在紅色圖案層或綠色圖案層中之散射粒子可包括平均粒徑為30奈米至500奈米的金屬氧化物,並且為了描述散射粒子及金屬氧化物,將參照對根據本發明之藍色感光性樹脂組成物中所包括的散射粒子及金屬 氧化物之說明。
在本發明中,紅色圖案層或綠色圖案層之量子點之形狀、構造及量不受限制,並且可應用本技術中通常使用的量子點。
包括基板及圖案層的彩色濾光片可更包括在圖案之間形成的障壁,並且亦可包括一黑色矩陣,但是本發明並不限於此。
在本發明中,彩色濾光片可為自發光彩色濾光片。
另外,本發明提出了一種包含上述彩色濾光片及用於發出藍色光的光源的影像顯示裝置。本發明之影像顯示裝置包括彩色濾光片及發出藍色光的光源,該彩色濾光片包括含有藍色感光性樹脂組成物之固化產物的藍色圖案層。
本發明之彩色濾光片不僅可應用於典型的液晶顯示裝置,而且還可應用於各種影像顯示裝置,例如電致發光顯示器、電漿顯示器、場致發射顯示器等。
當影像顯示裝置包括含有本發明的藍色圖案層的彩色濾光片及光源時,其可以表現出優異的光強度或優異的視角。此外,本發明之彩色濾光片中包括的藍色圖案層不包括藍色量子點,從而期望以低成本製造影像顯示裝置係可能的。
經由下面的實施例可更好地理解本發明,該等實施例是為了舉例說明,但不應被解釋為限制本發明之範圍。提供本發明之實施例是為了向本發明所屬領域中具有通常技術者更全面 地解釋本說明書。除非另外提及,否則下列實施例中表示量的「%」及「份」係以重量基準給出。
合成例:黏結劑樹脂之合成
製備例1:丙烯酸系鹼溶性樹脂
準備裝備有攪拌器、溫度計、回流冷凝器、滴液漏斗及氮氣入口管的燒瓶。添加74.8克(0.20莫耳)苄基馬來醯亞胺、43.2克(0.30莫耳)丙烯酸、118.0克(0.50莫耳)乙烯基甲苯、4克己酸第三丁基過氧化-2-乙酯及40克丙二醇單甲醚乙酸酯(PGMEA)並在攪拌下混合,以此方式製備單體滴液漏斗,並且添加6克正十二烷硫醇及24克PGMEA並在攪拌下混合,以此方式製備鏈轉移劑滴液漏斗。之後,將395克PGMEA放入燒瓶中,並用氮氣置換燒瓶中之空氣,然後在攪拌下將燒瓶溫度升至90℃。隨後,單體及鏈轉移劑從各自的滴液漏斗中滴下。分別在溫度保持在90℃之情形下滴液2小時。1小時後,將溫度升至110℃並保持3小時,然後通過氣體入口管吹入氧氣/氮氣=5/95(體積/體積)的氣體混合物。接著,在燒瓶中加入甲基丙烯酸縮水甘油酯28.4克[(0.10莫耳),(以此反應中之丙烯酸之羧基計為33莫耳%)]、0.4克的2,2'-亞甲基雙(4-甲基-6-第三丁基苯酚)及0.8克三乙胺,然後在110℃下反應8小時,由此獲得固體酸值為70毫克KOH/克的樹脂A。通過GPC針對聚苯乙烯標準量測,其重量平均分子量為16000,且其分子量分佈(Mw/Mn)為2.3。
製備例2:化學式1-1-1之化合物之合成
在3000毫升三頸圓底燒瓶中,將364.4克3',6'-二羥基螺(茀-9,9-二苯并哌喃)及0.4159克第三丁基溴化銨混合,將2359克表氯醇加入其中,並將所得混合物加熱至90℃並反應。當通過液相層析分析3',6'-二羥基螺(茀-9,9-二苯并哌喃)被完全消耗時,冷卻至30℃,並向其中緩慢加入50% NaOH水溶液(3當量)。當通過液相層析分析表氯醇被完全消耗時,用二氯甲烷萃取,然後水洗三次,之後用硫酸鎂乾燥有機層,然後減壓蒸餾掉二氯甲烷,接著用二氯甲烷與甲醇混合比例為50:50之混合物再結晶。
將1當量由此合成的環氧化合物、0.004當量的第三丁基溴化銨、0.001當量的2,6-二異丁基苯酚及2.2當量的丙烯酸混合,然後向其中加入24.89克丙二醇單甲醚乙酸酯溶劑。所得反應溶液以25毫升/分鐘吹入空氣,並加熱至90℃至100℃。將處於渾濁狀態的反應溶液加熱至120℃以完全溶解。當溶液變得透明並且其黏度增加時,量測酸值,並且攪拌直至酸值小於1.0毫克KOH/克。需要11小時才能達到所需的酸值(0.8)。反應結束後,將反應器之溫度降至室溫,由此得到下述化學式1-1-1的無色透明化合物。
製備例3:化學式1-1-2之化合物之合成
在3000毫升三頸圓底燒瓶中,將364.4克化學式2-1之3',6'-二羥基螺(茀-9,9-二苯并哌喃)及0.4159克第三丁基溴化銨混合,向其中加入2359克表氯醇,並將所得混合物加熱至90℃ 並反應。當通過液相層析分析3',6'-二羥基螺(茀-9,9-二苯并哌喃)被完全消耗時,冷卻至30℃,並向其中緩慢加入50% NaOH水溶液(3當量)。當通過液相層析分析表氯醇被完全消耗時,用二氯甲烷萃取,然後水洗三次,之後用硫酸鎂乾燥有機層,然後減壓蒸餾掉二氯甲烷,接著用二氯甲烷與甲醇混合比例為50:50的混合物再結晶。
將1當量由此合成的環氧化合物、0.004當量第三丁基溴化銨、0.001當量2,6-二異丁基苯酚及2.2當量甲基丙烯酸混合,然後向其中加入24.89克丙二醇單甲醚乙酸酯溶劑。所得反應溶液以25毫升/分鐘吹入空氣,並加熱至90℃至100℃。將處於渾濁狀態的反應溶液加熱至120℃以完全溶解。當溶液變得透明並且其黏度增加時,量測酸值,並且攪拌直至酸值小於1.0毫克KOH/克。需要11小時才能達到所需的酸值(0.8)。反應結束後,將反應器之溫度降至室溫,由此得到下述化學式1-1-2的無色透明化合物。
製備例4:化學式1-2-1之化合物之合成
在3000毫升三頸圓底燒瓶中,將364.4克4,4'-(9H-二苯并哌喃-9,9-二基)二酚及0.4159克第三丁基溴化銨混合,將2359克表氯醇加入其中,並將所得混合物加熱至90℃並反應。當通過液相層析分析4,4'-(9H-二苯并哌喃-9,9-二基)二酚被完全消耗時,冷卻至30℃,並向其中緩慢加入50% NaOH水溶液(3當量)。 當通過液相層析分析表氯醇被完全消耗時,用二氯甲烷萃取,然後水洗三次,之後用硫酸鎂乾燥有機層,然後減壓蒸餾掉二氯甲烷,接著用二氯甲烷與甲醇混合比例為50:50的混合物再結晶。將1當量由此合成的環氧化合物、0.004當量第三丁基溴化銨、0.001當量2,6-二異丁基苯酚及2.2當量丙烯酸混合,然後向其中加入24.89克丙二醇單甲醚乙酸酯溶劑。所得反應溶液以25毫升/分鐘吹入空氣,並加熱至90℃至100℃。將處於渾濁狀態的反應溶液加熱至120℃以完全溶解。當溶液變得透明並且其黏度增加時,量測酸值,並且攪拌直至酸值小於1.0毫克KOH/克。需要11小時才能達到所需的酸值(0.8)。反應結束後,將反應器之溫度降至室溫,由此得到下述化學式1-2-1的無色透明化合物。
製備例5:化學式1-2-2之化合物之合成
在3000毫升三頸圓底燒瓶中,混合364.4克4,4'-(9H-二苯并哌喃-9,9-二基)二酚及0.4159克第三丁基溴化銨,將2359克表氯醇加入其中,並將所得混合物加熱至90℃並反應。當通過液相層析分析4,4'-(9H-二苯并哌喃-9,9-二基)二酚被完全消耗時,冷卻至30℃,並向其中緩慢加入50% NaOH水溶液(3當量)。當通過液相層析分析表氯醇被完全消耗時,用二氯甲烷萃取,然後水洗三次,之後用硫酸鎂乾燥有機層,然後減壓蒸餾掉二氯甲烷,接著用二氯甲烷與甲醇混合比例為50:50的混合物再結晶。 將1當量由此合成的環氧化合物、0.004當量第三丁基溴化銨、0.001當量2,6-二異丁基苯酚及2.2當量甲基丙烯酸混合,然後向其中加入24.89克丙二醇單甲醚乙酸酯溶劑。所得反應溶液以25毫升/分鐘吹入空氣,並加熱至90℃至100℃。將處於渾濁狀態的反應溶液加熱至120℃以完全溶解。當溶液變得透明並且其黏度增加時,量測酸值,並且攪拌直至酸值小於1.0毫克KOH/克。需要11小時才能達到所需的酸值(0.8)。反應結束後,將反應器之溫度降至室溫,由此得到下述化學式1-2-2的無色透明化合物。
製備例6:軸節系黏結劑樹脂(A-1)之合成
將307.0克製備例2的化學式1-1-1之化合物添加到600克丙二醇單甲基醚乙酸酯中,溶解,並與78克聯苯四甲酸二酐及1克四乙基溴化銨混合,逐漸加熱,並在110℃至115℃下反應4小時。在確認酸酐基團之損耗後,將反應溶液與38.0克1,2,3,6-四氫鄰苯二甲酸酐混合,並在90℃下反應6小時,由此聚合成軸節系黏結劑樹脂。通過紅外光譜分析證實了酸酐之損耗。重量平均分子量:3500。
製備例7:軸節系黏結劑樹脂(A-2)之合成
將307.0克製備例3的化學式1-1-2之化合物添加到600克丙二醇單甲基醚乙酸酯中,溶解,並與78克聯苯四甲酸二酐 及1克四乙基溴化銨混合,逐漸加熱並在110℃至115℃下反應4小時。在確認酸酐基團之損耗後,將反應溶液與38.0克1,2,3,6-四氫鄰苯二甲酸酐混合,並在90℃下反應6小時,由此聚合成軸節系黏結劑樹脂。通過紅外光譜分析證實了酸酐之損耗。重量平均分子量:3800。
製備例8:軸節系黏結劑樹脂(A-3)之合成
將307.0克製備例4的化學式1-2-1之化合物加入600克丙二醇單甲基醚乙酸酯中,溶解,並與78克苯基四甲酸二酐及1克四乙基溴化銨混合,逐漸加熱,並在110℃至115℃下反應4小時。在確認酸酐基團之損耗後,將反應溶液與38.0克1,2,3,6-四氫鄰苯二甲酸酐混合,並在90℃下反應6小時,由此聚合成軸節系黏結劑樹脂。通過紅外光譜分析證實了酸酐之損耗。重量平均分子量:4500。
製備例9:軸節系黏結劑樹脂(A-4)之合成
將307.0克製備例5的化學式1-2-2之化合物加入600克丙二醇單甲基醚乙酸酯中,溶解,並與78克苯基四甲酸二酐及1克四乙基溴化銨混合,逐漸加熱,並在110℃至115℃下反應4小時。在確認酸酐基團之損耗後,將反應溶液與38.0克1,2,3,6-四氫鄰苯二甲酸酐混合,並在90℃下反應6小時,由此聚合成軸節系黏結劑樹脂。通過紅外光譜分析證實了酸酐之損耗。重量平均分子量:4900。
裝置:HLC-8120 GPC(東曹株式會社(Tosoh Corp.) 製)
管柱:TSK-GELG4000HXL+TSK-GELG2000HXL(串聯)
柱溫:40℃
流動相溶劑:四氫呋喃
流速:1.0毫升/分鐘
引入量:50微升
檢測器:RI
量測樣品濃度:0.6重量%(溶劑=四氫呋喃)
標準校正材料:TSK聚苯乙烯標準品F-40、F-4、F-1、A-2500、A-500(東曹株式會社製)
將上面得到的重量平均分子量與數量平均分子量之比定義為分子量分佈(Mw/Mn)。
實施例1至實施例9與比較實施例1至比較實施例4:藍色感光性樹脂組成物之製備
使用下表1至表3中所示量的各組分製備實施例1至實施例9與比較實施例1至比較實施例4的相應藍色感光性樹脂組成物。(表1示出了散射粒子,表2示出了各實施例之組成物之組分與量,且表3示出了各比較實施例之組成物之組分與量)。
0)藍色著色劑:C.I.顏料藍15:6
1)黏結劑樹脂:
A-1:製備例A-1
A-2:製備例A-2
A-3:製備例A-3
A-4:製備例A-4
A-5:單(2-甲基丙烯醯氧基烷基)酯
2)可光聚合的化合物:二季戊四醇六丙烯酸酯(KAYARAD DPHA;日本化藥(Nippon Kayaku)製)
3)光聚合起始劑:
D-1:Irgacure-907(巴斯夫公司(BASF)製)
D-2:OXE-01(巴斯夫公司製)
D-3:OXE-02(巴斯夫公司製)
D-4:PBG-327(化學式5-3)(強力公司(Tronly)製)
4)紫外線吸收劑:
F-1:TINUVIN 109(巴斯夫公司製)-苯并三唑型
F-2:TINUVIN 328(巴斯夫公司製)-苯并三唑型
F-3:TINUVIN 1577(巴斯夫公司製)-三嗪型
F-4:TINUVIN 400(巴斯夫公司製)-三嗪型
F-5:Chimassorb 81(巴斯夫公司製)-二苯甲酮型
5)溶劑:丙二醇單甲醚乙酸酯
0)藍色著色劑:C.I.顏料藍15:6
1)黏結劑樹脂:
A-1:製備例A-1
A-2:製備例A-2
A-3:製備例A-3
A-4:製備例A-4
A-5:單(2-甲基丙烯醯氧基烷基)酯
2)可光聚合的化合物:二季戊四醇六丙烯酸酯(KAYARAD DPHA;日本化藥製)
3)光聚合起始劑:
D-1:Irgacure-907(巴斯夫公司製)
D-2:OXE-01(巴斯夫公司製)
D-3:OXE-02(巴斯夫公司製)
D-4:PBG-327(化學式5-3)(強力公司製)
4)紫外線吸收劑:
F-1:TINUVIN 109(巴斯夫公司製)-苯并三唑型
F-2:TINUVIN 328(巴斯夫公司製)-苯并三唑型
F-3:TINUVIN 1577(巴斯夫公司製)-三嗪型
F-4:TINUVIN 400(巴斯夫公司製)-三嗪型
F-5:Chimassorb 81(巴斯夫公司製)-二苯甲酮型
5)溶劑:丙二醇單甲醚乙酸酯
彩色濾光片之製造
使用實施例1至實施例9及比較實施例1至比較實施例4各自的藍色感光性樹脂組成物製造彩色濾光片。具體而言,將各感光性樹脂組成物通過旋塗塗佈在玻璃基板上,並將玻璃基板放置在加熱板上並在100℃下保持3分鐘,從而形成薄膜。
隨後,在薄膜上放置具有20毫米(寬)×20毫米(長)的尺寸及1微米至100微米的線/間隔圖案的正方形透射圖案的測試光罩,且然後用距離100微米的紫外光輻照。
此處,使用由牛尾電機株式會社(Ushio Electric Co.)製造的超高壓汞燈(USH-250D)作為紫外線光源以200毫焦/平方公分(365奈米)之曝光量在大氣氣氛中施加紫外光。沒有使用特殊的濾光片。
將施加了紫外光的薄膜浸入pH為10.5的KOH顯影水溶液中80秒,由此進行顯影。用蒸餾水洗滌薄膜塗覆的玻璃基板,用氮氣乾燥,並在150℃的烘箱中加熱10分鐘,由此製造彩色濾光片圖案。如此製造的彩色圖案之膜厚為5.0微米。
測試例1:彩色濾光片之顯影速率、感光度、圖案穩定性、耐熱性
如下表4所示評估使用實施例1至實施例9及比較實施例1至比較實施例4各自的藍色感光性樹脂組成物製造的彩色濾光片。下面介紹各個測試之評估標準。
顯影速率:顯影時首先將未曝光部分溶解在顯影溶液中所需的時間(秒)<噴霧顯影劑HPMJ方法>
感光度:感光度遮罩之精細圖案(1至60)不會起皺的薄膜形成程度(感光度被視為在數值減小時優異)
圖案穩定性:在低曝光劑量(20至100毫焦(mJ))下曝光圖案遮罩之後的圖案誤差程度。
優異:無圖案錯誤
好:一或兩個圖案錯誤
合理:三個圖案錯誤
差:四個或更多個圖案錯誤
通過使用用於三維表面形狀量測的光學顯微鏡進行觀察來進行評估。
耐熱性及亮度變化評估:將如上製造的彩色濾光片在230℃的烘箱中加熱2小時。
使用數學公式(1)確定其顏色的變化,並且量測耐熱性評估前後的亮度變化(△Y),由此評估亮度是否因熱黃變而降低。
△Y(亮度變化):
O:-0.04至0.00
X:小於-0.04
從表4可看出,實施例1至實施例9顯示出優異的加工效果,包括顯影速率為15或小於15,具有50或小於50的優異的感光度,圖案遮罩曝光之後沒有圖案錯誤,因此具有優異的圖案穩定性及高耐熱性。
然而,在僅含有丙烯酸系鹼溶性樹脂而無軸節系黏結劑樹脂的比較實施例2中,由於固化困難而容易發生剝離,因此無法量測該等值。在比較實施例3中,可光聚合的化合物之含量落在適當的範圍以外,因此難以進行固化並導致全部圖案發生剝離。另外,在不含紫外線吸收劑的比較實施例4中,由於難以控制自由基之產生,因此無法獲得期望的耐熱性。
測試例2:精細圖案之量測
在使用實施例1至實施例9及比較實施例1至比較實施例4各自的藍色感光性樹脂製造的彩色濾光片中,使用具有100微米的線/間隔圖案的遮罩形成的圖案之尺寸係使用OM裝置(ECLIPSE LV100POL,尼康(Nikon)製)量測。
當遮罩之線條/間隔圖案之設計值與所獲得的精細圖案之量測值之間的差值為20微米或更大時,難以實現精細的畫素,並且圖案線性度及平坦化可能變得成問題。而且,很難實現 所需的錐度。
從表5可看出,在實施例1至實施例9中,遮罩圖案之設計值與所獲得的精細圖案之量測值之間的差值為20微米或更小,因此使得可以形成精細畫素並表現出優異的圖案特性。
然而,在僅含有丙烯酸系樹脂的比較實施例2中,由於固化困難而出現膜起皺,並且在比較實施例3中,可光聚合的化合物之含量低於適當範圍,不利地導致固化困難及膜起皺。另外,在不含紫外線吸收劑的比較實施例4中,難以形成精細圖案。
測試例3:光強度之量測
在使用實施例1至實施例9及比較實施例1至比較實施例4各自的藍色感光性樹脂製造的彩色濾光片中,使用365奈米管型4瓦紫外燈(VL-4LC,VILBER LOURMAT)用光輻照尺寸為20毫米×20毫米的正方形圖案部分,以量測光轉換區域。在實施例1至實施例9及比較實施例1至比較實施例4中,使用分光計(海洋光學公司(Ocean Optics)製)量測450奈米下的光強度。
當所量測的光強度增加時,光效率被視為較高。
在實施例1至實施例9中,光強度高達2或更高,表明光效率高。但是,在僅含有丙烯酸系樹脂的比較實施例2中,由於固化困難而發生了膜起皺,並且在不含紫外線吸收劑的比較實施例4中,光效率下降。
測試例4:視角之量測
在使用實施例1至實施例9及比較實施例1至比較實施例4各自的藍色感光性樹脂製造的彩色濾光片中,使用測角光度計(GC-5000L,日本電色(Nippon Denshoku))量測尺寸為20毫米×20毫米的正方形圖案部分的取決於光透射條件下的視角的光強度,並且使用下面的方程式1計算擴散率。
[方程式1]擴算率=(B70+B20)/2×B5×100
(Bθ=Iθ/cosθ)
此處,I表示在每一角度處量測的光強度,且B70、B20及B5為70°、20°及5°量測的相應值。
在所量測的擴散率增加時,視角被認為是優異的。從表7可看出,實施例1至實施例9在視角方面得到了改善。但是,在不含紫外線吸收劑的比較實施例4中,擴散率降低。
儘管為了舉例說明的目的已經公開了本發明之較佳 實施態樣,但是熟習此項技術者將會理解,在不脫離如隨附申請專利範圍所揭示的本發明之範圍及精神之情形下,可進行各種修改、添加及替換。
Claims (16)
- 一種藍色感光性樹脂組成物,包含散射粒子、藍色著色劑、作為黏結劑樹脂的軸節(cardo)系黏結劑樹脂、可光聚合的化合物、光聚合起始劑、紫外線吸收劑、及溶劑,該紫外線吸收劑包括苯并三唑系紫外線吸收劑、三嗪系紫外線吸收劑及二苯甲酮系紫外線吸收劑中之至少一者。
- 如請求項1所述之藍色感光性樹脂組成物,其中該等散射粒子包括具有10奈米至1000奈米之平均粒徑的金屬氧化物。
- 如請求項1所述之藍色感光性樹脂組成物,其中該等散射粒子包括選自以下群組之至少一者:Al 2O 3、SiO 2、ZnO、ZrO 2、BaTiO 3、TiO 2、Ta 2O 5、Ti 3O 5、Nb 2O 3、SnO、及MgO。
- 如請求項1所述之藍色感光性樹脂組成物,更包含紫色著色劑。
- 如請求項1所述之藍色感光性樹脂組成物,其中該藍色著色劑包括藍色顏料與藍色染料中之至少一者。
- 如請求項1所述之藍色感光性樹脂組成物,其中該軸節系黏結劑樹脂包括由以下化學式1-1及化學式1-2表示的化合物中之至少一者:
[化學式1-2] (在化學式1-1及化學式1-2中,R 1、R 2、R 3及R 4分別獨立地為 ,其中X為氫原子、C1-C5烷基、或羥基,且R 5為氫原子或C1-C5烷基)。 - 如請求項1所述之藍色感光性樹脂組成物,其中該軸節系黏結劑樹脂包括選自以下群組之至少一者:9,9-雙(3-肉桂酸二酯)茀、9,9-雙(3-肉桂醯基-4-羥苯基)茀、9,9-雙(縮水甘油基甲基丙烯酸酯醚)茀、9,9-雙(3,4-二羥苯基)茀二肉桂酸酯、3,6-二縮水甘油基甲基丙烯酸酯醚螺(茀-9,9-二苯并哌喃(xanthene))、9,9-雙(3-烯丙基4-羥苯基)茀、9,9-雙(4-烯丙氧基苯基)茀、及9,9-雙(3,4-甲基丙烯酸二酯)茀。
- 如請求項1所述之藍色感光性樹脂組成物,其中該黏結劑樹脂更包含丙烯酸系鹼溶性樹脂。
- 如請求項1所述之藍色感光性樹脂組成物,其中該光聚合起始劑包括選自由以下化學式3至化學式5表示之化合物的至少一者:[化學式3]
(在化學式3中,R 8為氫原子、鹵素原子、羥基、未經取代或經C1-C12烷基取代的苯基、未經取代或經C1-C12烷基取代的苄基、未經取代或經C1-C12烷基取代的萘基、或-SR a,R a為氫、C1-C12烷基或苄基;且R 9至R 12分別獨立地為氫原子、鹵素原子、羥基、未經取代或經C1-C12烷基取代的苯基、未經取代或經C1-C12烷基取代的苄基、或未經取代或經C1-C12烷基取代的萘基,R 11與R 12能夠一起形成環) (在化學式4中,R 13為二苯基硫醚基、經取代的二苯基硫醚基、咔唑基(carbazole group)、經取代的咔唑基、茀基、或經取代的茀基;R 14為氫、C1-C20烷基、C3-C8環烷基、未經取代或經取代的苯基或 ,n為1至4的整數且m為1至6的整數;且R 15為C1-C8烷基、苯基、經取代的苯基、苄基、或經取代 的苄基) (在化學式5中,R 16、R 17及R 18分別獨立地為R、OR、COR、SR、CONRR'、ROR'或CN,其中R及R'表示C1-C20烷基、C6-C30芳基、C7-C30芳烷基或C2-C20雜環基,各自經鹵素原子或C2-C20雜環基取代且其中該烷基及該芳烷基之伸烷基部分被不飽和鍵、醚鍵、硫醚鍵或酯鍵中斷,R與R'能夠一起形成環;Y 1表示氧原子、硫原子或硒原子,m為0至4的整數,且r為0至5的整數;s為0或1;R 19、R 20、R 21及R 22分別獨立地表示氫原子、鹵素原子或C1-C8烷基;X 1及X 2表示C1-C20烷基、C6-C30芳基、C7-C30芳烷基或C2-C20雜環基,各自被鹵素原子或C2-C20雜環基取代且其中該烷基及該芳烷基之伸烷基部分被不飽和鍵、醚鍵、硫醚鍵或酯鍵中斷;X 2與相鄰環之碳原子一起形成環;且 Y 2及Y 3分別獨立地表示氧原子、硫原子或硒原子)。 - 如請求項1所述之藍色感光性樹脂組成物,其中該光聚合起始劑包括選自由以下化學式組成之群組之至少一者:
[化學式5-6] - 如請求項1所述之藍色感光性樹脂組成物,以該藍色感光性樹脂之固體含量之總重量計,該藍色感光性樹脂組成物包含0.1重量%至50重量%的該等散射粒子、0.1重量%至50重量%的該藍色著色劑、5重量%至85重量%的該黏結劑樹脂、5重量%至50重量%的該可光聚合的化合物、0.1重量%至20重量%的該光聚合起始劑、及0.001重量%至10重量%的包括苯并三唑系紫外線吸收劑、三嗪系紫外線吸收劑及二苯甲酮系紫外線吸收劑中之至少一者的該紫外線吸收劑,且以該藍色感光樹脂組合物之總重量計包含60重量%至90重量%的該溶劑。
- 一種彩色濾光片,包含由如請求項1至11中任一項所述之藍色感光性樹脂組成物形成的藍色圖案層。
- 如請求項12所述之彩色濾光片,更包含選自由紅色圖案層及綠色圖案層組成之群組之至少一者。
- 如請求項13所述之彩色濾光片,其中該紅色圖案層或該綠色圖案層包括量子點。
- 如請求項14所述之彩色濾光片,其中該彩色濾光片為自發光彩色濾光片。
- 一種影像顯示裝置,包含:如請求項12所述之彩色濾光片;以及用於發出藍色光的光源。
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| US12216403B2 (en) | 2019-10-11 | 2025-02-04 | Donjin Semichem Co., Ltd. | Positive photosensitive resin composition and display device using the same |
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| JP7422303B2 (ja) * | 2019-12-06 | 2024-01-26 | artience株式会社 | 感光性緑色組成物、カラーフィルタおよび表示装置 |
| WO2021172112A1 (ja) * | 2020-02-27 | 2021-09-02 | 富士フイルム株式会社 | 感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜、パターン形成方法、及び、電子デバイスの製造方法 |
| KR102835869B1 (ko) * | 2021-02-26 | 2025-07-22 | 동우 화인켐 주식회사 | 격벽 형성용 감광성 수지 조성물, 이를 이용하여 제조된 격벽 구조물 및 상기 격벽 구조물을 포함하는 표시 장치 |
| JP7503027B2 (ja) | 2021-06-29 | 2024-06-19 | 株式会社Soken | 電池測定システム |
| TW202302739A (zh) * | 2021-06-30 | 2023-01-16 | 住華科技股份有限公司 | 感光性樹脂組合物、及應用其之彩色濾光片和顯示裝置 |
| CN119325567A (zh) * | 2022-06-10 | 2025-01-17 | Dnp精细化工股份有限公司 | 蓝色固化膜的制造方法、蓝色感光性组合物、彩色滤光片及其制造方法、以及显示装置 |
| JP2024039610A (ja) * | 2022-09-09 | 2024-03-22 | 信越化学工業株式会社 | レジスト材料及びパターン形成方法 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US12216403B2 (en) | 2019-10-11 | 2025-02-04 | Donjin Semichem Co., Ltd. | Positive photosensitive resin composition and display device using the same |
| TWI896563B (zh) * | 2019-10-11 | 2025-09-11 | 南韓商東進世美肯股份有限公司 | 正型感光性樹脂組成物及使用其之顯示元件 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20220115890A (ko) | 2022-08-19 |
| JP2020514788A (ja) | 2020-05-21 |
| WO2018182136A9 (ko) | 2018-11-08 |
| JP2021107928A (ja) | 2021-07-29 |
| WO2018182136A1 (ko) | 2018-10-04 |
| KR20180111067A (ko) | 2018-10-11 |
| CN110121679A (zh) | 2019-08-13 |
| TWI791476B (zh) | 2023-02-11 |
| KR102582662B1 (ko) | 2023-09-25 |
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