CN103969954B - Colored photosensitive resin composition suitable for columnar spacers and black matrixes - Google Patents
Colored photosensitive resin composition suitable for columnar spacers and black matrixes Download PDFInfo
- Publication number
- CN103969954B CN103969954B CN201410113761.8A CN201410113761A CN103969954B CN 103969954 B CN103969954 B CN 103969954B CN 201410113761 A CN201410113761 A CN 201410113761A CN 103969954 B CN103969954 B CN 103969954B
- Authority
- CN
- China
- Prior art keywords
- photosensitive resin
- black
- resin composition
- colored photosensitive
- meth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 61
- 125000006850 spacer group Chemical group 0.000 title claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 64
- 229920001577 copolymer Polymers 0.000 claims abstract description 38
- 239000003086 colorant Substances 0.000 claims abstract description 37
- 239000011159 matrix material Substances 0.000 claims abstract description 26
- 238000002834 transmittance Methods 0.000 claims abstract description 21
- 239000003822 epoxy resin Substances 0.000 claims abstract description 16
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 16
- 230000003287 optical effect Effects 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 239000000038 blue colorant Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 31
- 239000007787 solid Substances 0.000 claims description 13
- 125000001834 xanthenyl group Chemical group C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 5
- 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 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 19
- 238000011084 recovery Methods 0.000 abstract description 17
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 63
- -1 2-phenoxyethyl Chemical group 0.000 description 52
- 239000010410 layer Substances 0.000 description 36
- 239000002904 solvent Substances 0.000 description 22
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 19
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 16
- 239000000758 substrate Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- 239000004094 surface-active agent Substances 0.000 description 13
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 238000011161 development Methods 0.000 description 9
- 239000002270 dispersing agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000011417 postcuring Methods 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 150000003951 lactams Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 150000002923 oximes Chemical class 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 2
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 2
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-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
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-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
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- SEEVRZDUPHZSOX-WPWMEQJKSA-N [(e)-1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino] acetate Chemical compound C=1C=C2N(CC)C3=CC=C(C(\C)=N\OC(C)=O)C=C3C2=CC=1C(=O)C1=CC=CC=C1C SEEVRZDUPHZSOX-WPWMEQJKSA-N 0.000 description 2
- 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 2
- 150000007513 acids Chemical class 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000005529 alkyleneoxy group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 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
- 239000006229 carbon black Substances 0.000 description 2
- 229930016911 cinnamic acid Natural products 0.000 description 2
- 235000013985 cinnamic acid Nutrition 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 125000002993 cycloalkylene group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 150000003949 imides Chemical class 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
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 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
- LDWBQADKOUWRIR-UHFFFAOYSA-N n-trimethoxysilylaniline Chemical compound CO[Si](OC)(OC)NC1=CC=CC=C1 LDWBQADKOUWRIR-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- ZTQUBBFVYUHQRC-UHFFFAOYSA-N spiro[fluorene-9,9'-xanthene]-3',6'-diol Chemical compound C12=CC=CC=C2C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 ZTQUBBFVYUHQRC-UHFFFAOYSA-N 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 229940014800 succinic anhydride Drugs 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- CQKAPARXKPTKBK-UHFFFAOYSA-N tert-butylazanium;bromide Chemical compound Br.CC(C)(C)N CQKAPARXKPTKBK-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZCCAOOJIWMTVGN-UHFFFAOYSA-N 1,6-diisocyanatohexane;[2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound O=C=NCCCCCCN=C=O.C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C ZCCAOOJIWMTVGN-UHFFFAOYSA-N 0.000 description 1
- FPZQYYXSOJSITC-UHFFFAOYSA-N 1-(4-chlorophenyl)pyrrole-2,5-dione Chemical compound C1=CC(Cl)=CC=C1N1C(=O)C=CC1=O FPZQYYXSOJSITC-UHFFFAOYSA-N 0.000 description 1
- BLLFPKZTBLMEFG-UHFFFAOYSA-N 1-(4-hydroxyphenyl)pyrrole-2,5-dione Chemical compound C1=CC(O)=CC=C1N1C(=O)C=CC1=O BLLFPKZTBLMEFG-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical group CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- VTRZMLZNHGCYLK-UHFFFAOYSA-N 1-ethenyl-2-(methoxymethyl)benzene Chemical compound COCC1=CC=CC=C1C=C VTRZMLZNHGCYLK-UHFFFAOYSA-N 0.000 description 1
- HDEWQSUXJCDXIX-UHFFFAOYSA-N 1-ethenyl-3-(methoxymethyl)benzene Chemical compound COCC1=CC=CC(C=C)=C1 HDEWQSUXJCDXIX-UHFFFAOYSA-N 0.000 description 1
- XVXKXOPCFWAOLN-UHFFFAOYSA-N 1-ethenyl-4-(methoxymethyl)benzene Chemical compound COCC1=CC=C(C=C)C=C1 XVXKXOPCFWAOLN-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical group CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- DMFAHCVITRDZQB-UHFFFAOYSA-N 1-propoxypropan-2-yl acetate Chemical compound CCCOCC(C)OC(C)=O DMFAHCVITRDZQB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- HLIQLHSBZXDKLV-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol Chemical compound OCCOCC(O)OC1=CC=CC=C1 HLIQLHSBZXDKLV-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- AQKDMKKMCVJJTC-UHFFFAOYSA-N 2-(2-methylpropoxymethyl)oxirane Chemical compound CC(C)COCC1CO1 AQKDMKKMCVJJTC-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 description 1
- NWLUZGJDEZBBRH-UHFFFAOYSA-N 2-(propan-2-yloxymethyl)oxirane Chemical compound CC(C)OCC1CO1 NWLUZGJDEZBBRH-UHFFFAOYSA-N 0.000 description 1
- CWNOEVURTVLUNV-UHFFFAOYSA-N 2-(propoxymethyl)oxirane Chemical compound CCCOCC1CO1 CWNOEVURTVLUNV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- JFWFAUHHNYTWOO-UHFFFAOYSA-N 2-[(2-ethenylphenyl)methoxymethyl]oxirane Chemical compound C=CC1=CC=CC=C1COCC1OC1 JFWFAUHHNYTWOO-UHFFFAOYSA-N 0.000 description 1
- OCKQMFDZQUFKRD-UHFFFAOYSA-N 2-[(3-ethenylphenyl)methoxymethyl]oxirane Chemical compound C=CC1=CC=CC(COCC2OC2)=C1 OCKQMFDZQUFKRD-UHFFFAOYSA-N 0.000 description 1
- ZADXFVHUPXKZBJ-UHFFFAOYSA-N 2-[(4-ethenylphenyl)methoxymethyl]oxirane Chemical compound C1=CC(C=C)=CC=C1COCC1OC1 ZADXFVHUPXKZBJ-UHFFFAOYSA-N 0.000 description 1
- SZTBMYHIYNGYIA-UHFFFAOYSA-N 2-chloroacrylic acid Chemical compound OC(=O)C(Cl)=C SZTBMYHIYNGYIA-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- FZHNODDFDJBMAS-UHFFFAOYSA-N 2-ethoxyethenylbenzene Chemical group CCOC=CC1=CC=CC=C1 FZHNODDFDJBMAS-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- DDBYLRWHHCWVID-UHFFFAOYSA-N 2-ethylbut-1-enylbenzene Chemical group CCC(CC)=CC1=CC=CC=C1 DDBYLRWHHCWVID-UHFFFAOYSA-N 0.000 description 1
- KBKNKFIRGXQLDB-UHFFFAOYSA-N 2-fluoroethenylbenzene Chemical compound FC=CC1=CC=CC=C1 KBKNKFIRGXQLDB-UHFFFAOYSA-N 0.000 description 1
- OZPOYKXYJOHGCW-UHFFFAOYSA-N 2-iodoethenylbenzene Chemical compound IC=CC1=CC=CC=C1 OZPOYKXYJOHGCW-UHFFFAOYSA-N 0.000 description 1
- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical group COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical group CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ILYSKJPEZAABAA-UHFFFAOYSA-N 2-propoxyethenylbenzene Chemical group CCCOC=CC1=CC=CC=C1 ILYSKJPEZAABAA-UHFFFAOYSA-N 0.000 description 1
- WYYQKWASBLTRIW-UHFFFAOYSA-N 2-trimethoxysilylbenzoic acid Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1C(O)=O WYYQKWASBLTRIW-UHFFFAOYSA-N 0.000 description 1
- ZTHJQCDAHYOPIK-UHFFFAOYSA-N 3-methylbut-2-en-2-ylbenzene Chemical group CC(C)=C(C)C1=CC=CC=C1 ZTHJQCDAHYOPIK-UHFFFAOYSA-N 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
- 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 1
- CYCBPQPFMHUATH-UHFFFAOYSA-N 4-(oxiran-2-ylmethoxy)butan-1-ol Chemical compound OCCCCOCC1CO1 CYCBPQPFMHUATH-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical group CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- CFZDMXAOSDDDRT-UHFFFAOYSA-N 4-ethenylmorpholine Chemical compound C=CN1CCOCC1 CFZDMXAOSDDDRT-UHFFFAOYSA-N 0.000 description 1
- YAXPDWVRLUOOBJ-UHFFFAOYSA-N 4-ethylhex-3-en-3-ylbenzene Chemical group CCC(CC)=C(CC)C1=CC=CC=C1 YAXPDWVRLUOOBJ-UHFFFAOYSA-N 0.000 description 1
- RTANHMOFHGSZQO-UHFFFAOYSA-N 4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)C#N RTANHMOFHGSZQO-UHFFFAOYSA-N 0.000 description 1
- JAGRUUPXPPLSRX-UHFFFAOYSA-N 4-prop-1-en-2-ylphenol Chemical compound CC(=C)C1=CC=C(O)C=C1 JAGRUUPXPPLSRX-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000551547 Dione <red algae> Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- PSBPNWBGNOWCCU-UHFFFAOYSA-N OB(O)O.S.S.S Chemical class OB(O)O.S.S.S PSBPNWBGNOWCCU-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical group 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 125000005571 adamantylene group Chemical group 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- DKNWSYNQZKUICI-UHFFFAOYSA-N amantadine Chemical compound C1C(C2)CC3CC2CC1(N)C3 DKNWSYNQZKUICI-UHFFFAOYSA-N 0.000 description 1
- 229960003805 amantadine Drugs 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- BWHOZHOGCMHOBV-UHFFFAOYSA-N benzylideneacetone Chemical compound CC(=O)C=CC1=CC=CC=C1 BWHOZHOGCMHOBV-UHFFFAOYSA-N 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical group CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 150000001716 carbazoles Chemical class 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 125000004976 cyclobutylene group Chemical group 0.000 description 1
- 125000004977 cycloheptylene group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- MAWOHFOSAIXURX-UHFFFAOYSA-N cyclopentylcyclopentane Chemical group C1CCCC1C1CCCC1 MAWOHFOSAIXURX-UHFFFAOYSA-N 0.000 description 1
- 125000004979 cyclopentylene group Chemical group 0.000 description 1
- 125000004980 cyclopropylene group Chemical group 0.000 description 1
- RTVSUIOGXLXKNM-UHFFFAOYSA-N dec-1-enylbenzene Chemical group CCCCCCCCC=CC1=CC=CC=C1 RTVSUIOGXLXKNM-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 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
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 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
- KETWBQOXTBGBBN-UHFFFAOYSA-N hex-1-enylbenzene Chemical group CCCCC=CC1=CC=CC=C1 KETWBQOXTBGBBN-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 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
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 235000019239 indanthrene blue RS Nutrition 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 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 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920001427 mPEG Polymers 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 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
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 125000005699 methyleneoxy group Chemical group [H]C([H])([*:1])O[*:2] 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- KXAFIXYQEIQJBN-UHFFFAOYSA-N n-[3-[3,5-dimethyl-4-(oxiran-2-ylmethoxy)phenyl]propyl]prop-2-enamide Chemical compound CC1=CC(CCCNC(=O)C=C)=CC(C)=C1OCC1OC1 KXAFIXYQEIQJBN-UHFFFAOYSA-N 0.000 description 1
- OHBCEHHJPNBVME-UHFFFAOYSA-N n-[[3,5-dimethyl-4-(oxiran-2-ylmethoxy)phenyl]methyl]prop-2-enamide Chemical compound CC1=CC(CNC(=O)C=C)=CC(C)=C1OCC1OC1 OHBCEHHJPNBVME-UHFFFAOYSA-N 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- KNZIIQMSCLCSGZ-UHFFFAOYSA-N non-1-enylbenzene Chemical group CCCCCCCC=CC1=CC=CC=C1 KNZIIQMSCLCSGZ-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RCALDWJXTVCBAZ-UHFFFAOYSA-N oct-1-enylbenzene Chemical group CCCCCCC=CC1=CC=CC=C1 RCALDWJXTVCBAZ-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-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
- 239000012044 organic layer Substances 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- KHMYONNPZWOTKW-UHFFFAOYSA-N pent-1-enylbenzene Chemical group CCCC=CC1=CC=CC=C1 KHMYONNPZWOTKW-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 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
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- ADXGNEYLLLSOAR-UHFFFAOYSA-N tasosartan Chemical compound C12=NC(C)=NC(C)=C2CCC(=O)N1CC(C=C1)=CC=C1C1=CC=CC=C1C=1N=NNN=1 ADXGNEYLLLSOAR-UHFFFAOYSA-N 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- GSECCTDWEGTEBD-UHFFFAOYSA-N tert-butylperoxycyclohexane Chemical compound CC(C)(C)OOC1CCCCC1 GSECCTDWEGTEBD-UHFFFAOYSA-N 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
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- MCZDHTKJGDCTAE-UHFFFAOYSA-M tetrabutylazanium;acetate Chemical compound CC([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC MCZDHTKJGDCTAE-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-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
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- 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
-
- 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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
-
- 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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
- G03F7/2014—Contact or film exposure of light sensitive plates such as lithographic plates or circuit boards, e.g. in a vacuum frame
- G03F7/2016—Contact mask being integral part of the photosensitive element and subject to destructive removal during post-exposure processing
- G03F7/202—Masking pattern being obtained by thermal means, e.g. laser ablation
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Optics & Photonics (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
- Liquid Crystal (AREA)
- Electroluminescent Light Sources (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention provides a colored photosensitive resin composition comprising a copolymer, an epoxy resin compound or a compound derived therefrom, a polymerizable compound, a photopolymerization initiator, and a colorant including a black colorant and a blue colorant. When the colored photosensitive resin composition forms a cured layer, good light transmittance and optical density, as well as good elastic recovery, resolution, chemical resistance, and thickness can be obtained. Thus, the colored photosensitive resin composition can form a columnar spacer, a black matrix, or a black columnar spacer, and can be used in various electronic parts such as a panel of an organic light emitting diode display and a liquid crystal display device.
Description
Technical Field
The present invention relates to a colored photosensitive resin composition suitable for forming a passivation layer, an interlayer dielectric, a spacer, a light shielding portion used in an Organic Light Emitting Diode (OLED) display or a Liquid Crystal Display (LCD) panel, and a cured layer formed of the composition, particularly a columnar spacer (BCS), in which the columnar spacer and a black matrix are in one body.
Background
Recently, spacers formed of a photosensitive composition are employed in order to maintain a distance between top and bottom transparent substrates in LCD liquid crystal cells. Accordingly, LCDs are electro-optical devices driven by a liquid crystal material injected into a constant gap between two transparent substrates by applying a voltage thereto, and thus it is very important to maintain a constant gap between the two substrates. If the gap between the transparent substrates is not constant, the voltage thereon and the light transmittance through the portion may be changed, resulting in defects in uneven brightness. According to the latest choice of the size of large LCD panels, it has become more critical to maintain a constant gap between two transparent substrates.
The spacers may be formed by coating a photosensitive resin composition on a substrate, and exposing the coated substrate to ultraviolet rays or the like thereon using a mask, followed by developing it. Recently, efforts have been made to use a light shielding material for spacers, and thus, colored photosensitive resins are also being actively developed.
Korean laid-open patent No. 2006-125993 discloses a method of simultaneously forming a color filter passivation layer and a column spacer for an LCD, and a negative photoresist composition used in the method, and more particularly, a method of simultaneously forming a color filter passivation layer (i.e., an insulating layer) and a column spacer from a composition having a phosphine oxide-based photopolymerization initiator and an acrylic adhesive.
In addition, recently, the method has been simplified by developing a BCS in which a column spacer and a black matrix are integrated into one module. However, BCS must have properties such as elastic recovery and chemical resistance required for the columnar spacers to meet the properties such as light shielding properties for black matrix. Therefore, further research and development of colored photosensitive resin compositions suitable for these purposes are required.
Disclosure of Invention
Accordingly, an object of the present invention is to provide a colored photosensitive resin composition that satisfies both the columnar spacer and black matrix properties.
According to one aspect of the present invention, there is provided a colored photosensitive resin composition comprising (a) a copolymer, (b) an epoxy resin compound or a compound derived therefrom, (c) a polymerizable compound, (d) a photopolymerization initiator, and (e) a colorant comprising 0 to 5% by weight of an inorganic black colorant, 10 to 40% by weight of an organic black colorant, and 1 to 15% by weight of a blue colorant, based on the total weight of the solid content of the colored photosensitive resin composition.
According to another aspect of the present invention, there is provided a columnar spacer, a black matrix or a Black Columnar Spacer (BCS) formed of the colored photosensitive resin composition.
According to still another aspect of the present invention, there is provided an electronic component comprising the columnar spacer, black matrix, or BCS.
The colored photosensitive resin composition of the present invention has good exposure margin and development margin, and provides properties such as light transmittance and optical density for a black matrix, and those for a columnar spacer such as elastic recovery, resolution, chemical resistance and coating thickness at the time of forming a cured layer, which are also satisfied. Thus, the composition is useful for forming color spacers, black matrixes, BCS, and the like, which can be used in various electronic components such as OLED displays and panels of LCDs.
Drawings
The above and other objects and features of the present invention will become apparent from the following description of the present invention when taken in conjunction with the accompanying drawings, in which:
fig. 1: schematic diagram of a cross-sectional example of a black pillar spacer (BCS) (a: thickness of pillar spacer, B: thickness of black matrix portion, and C: critical Dimension (CD) of pillar spacer feature).
Detailed Description
Hereinafter, the present invention will be described in more detail.
Colored photosensitive resin composition
According to an embodiment of the present invention, a colored photosensitive resin composition comprises (a) a copolymer, (b) an epoxy resin compound or a derivative thereof, (c) a polymerizable compound, (d) a photopolymerization initiator, and (e) a colorant including a black colorant and a blue colorant, and optionally (f) a solvent, (g) a surfactant, and/or (h) a silane coupling agent.
In the present specification, "(meth) acrylic" means "acrylic" and/or "methacrylic", and "(meth) acrylate" means "acrylate" and/or "methacrylate".
Hereinafter, each component for coloring the photosensitive resin composition will be described in detail.
(a) Copolymer
The copolymer used in the present invention may contain (a-1) units derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic anhydride, or a mixture thereof, (a-2) units derived from an aromatic ring-containing ethylenically unsaturated compound, and may also contain (a-3) units derived from an ethylenically unsaturated compound other than (a-1) and (a-2).
The copolymer is an alkali-soluble resin that can provide a developing function in a developing step, and at the same time, can serve as a substrate for forming a coating layer and a structure for forming a final pattern.
(a-1) units derived from ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic acid anhydrides, or mixtures thereof
In the present invention, the (a-1) units are derived from ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic anhydrides, or mixtures thereof. Ethylenically unsaturated carboxylic acids and ethylenically unsaturated carboxylic anhydrides are polymerizable unsaturated monomers having at least one carboxylic acid group in the molecule. Examples thereof include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α -chloroacrylic acid, cinnamic acid and the like; unsaturated dicarboxylic acids and anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, and the like; and trivalent or more unsaturated polycarboxylic acids and anhydrides thereof; mono [ (meth) acryloxyalkyl ] esters of divalent or higher polycarboxylic acids, such as mono [2- (meth) acryloxyethyl ] succinate, mono [2- (meth) acryloxyethyl ] phthalate, and the like. Units derived from the above exemplary compounds may be included in the copolymer as a single compound or in a combination of two or more.
The content of the unit (a-1) may be 5 to 65mol%, preferably 10 to 50mol%, based on the total molar amount of the units constituting the copolymer. Within this content range, the developing performance can be easily maintained.
(a-2) units derived from an aromatic ring-containing ethylenically unsaturated compound
The (a-2) unit is derived from an aromatic ring-containing ethylenically unsaturated compound. Examples thereof may include phenyl (meth) acrylate, benzyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, (p-nonylphenoxy polyethylene glycol) acrylate, (p-nonylphenoxy polypropylene glycol) acrylate, tribromophenyl (meth) acrylate; styrene; styrene having an alkyl substituent such as methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene and the like; styrene having halogen such as fluoro-styrene, chloro-styrene, bromo-styrene, iodo-styrene; styrene having an alkoxy substituent such as methoxystyrene, ethoxystyrene, propoxystyrene and the like; 4-hydroxystyrene, p-hydroxy-alpha-methylstyrene, acetylstyrene; vinyl toluene, divinylbenzene, vinylphenol, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like.
Units derived from the above exemplary compounds may be included in the copolymer as a single compound or in a combination of two or more.
Among these compounds, styrene-based compounds are preferable in view of their polymerizability.
The content of the unit (a-2) may be 2 to 70mol%, preferably 5 to 60mol%, based on the total mole number of the units constituting the copolymer. Within this content range, the resin composition may have favorable chemical resistance.
(a-3) units derived from olefinically unsaturated compounds other than (a-1) and (a-2)
In addition to (a-1) and (a-2), the copolymers used in the present invention may further comprise units derived from olefinically unsaturated compounds other than (a-1) and (a-2). Examples thereof may include unsaturated carboxylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, ethylhexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, methyl alpha-methylolacrylate, ethyl alpha-methylolacrylate, propyl alpha-methylolacrylate, butyl alpha-methylolacrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxydiglycol (meth) acrylate, methoxytriglycol (meth) acrylate, methoxypropyl (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1, 3-fluoropentyl (meth) acrylate, octafluoropentyl (meth) acrylate, propylisobornyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and the like; tertiary amines having an N-vinyl group such as N-vinylpyrrolidone, N-vinylcarbazole, N-vinylmorpholine and the like; unsaturated ethers such as vinyl methyl ether, and vinyl ethyl ether; ethylenically unsaturated compounds having an epoxy group such as glycidyl (meth) acrylate, 3, 4-epoxybutyl (meth) acrylate, 4, 5-epoxypentyl (meth) acrylate, 5, 6-epoxyhexyl (meth) acrylate, 6, 7-epoxyheptyl (meth) acrylate, 2, 3-epoxycyclopentyl (meth) acrylate, 3, 4-epoxycyclohexyl (meth) acrylic acid, α -glycidyl ethacrylate, α -N-propyl glycidyl acrylate, α -N-butyl glycidyl acrylate, N- (4- (2, 3-epoxypropoxy) -3, 5-dimethylbenzyl) acrylamide, N- (4- (2, 3-epoxypropoxy) -3, 5-dimethylphenylpropyl) acrylamide, 4-hydroxybutyl (meth) acrylate glycidyl ether, allyl glycidyl ether, 2-methallyl glycidyl ether and the like; unsaturated imides such as N-phenylmaleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N-cyclohexylmaleimide and the like.
Units derived from the above exemplary compounds may be included in the copolymer as a single compound or in a combination of two or more.
In view of their copolymerization properties and for improving the strength of the insulating layer, it is preferable to use a unit derived from an ethylenically unsaturated compound having an epoxy group and/or an unsaturated imide, and it is more preferable to use a unit derived from glycidyl (meth) acrylate, 4-hydroxybutyl glycidyl ether of (meth) acrylate and/or N-substituted maleimide.
The content of the unit (a-3) may be 10 to 80mol%, preferably 20 to 75mol%, based on the total molar amount of the units constituting the copolymer. Within this content range, the stability of the adhesive can be maintained and the residual rate of the coating can be improved.
Copolymers having the above-mentioned (a-1) and (a-3) units may include (meth) acrylic acid/styrene copolymers, (meth) acrylic acid/benzyl (meth) acrylate copolymers, (meth) acrylic acid/styrene/(meth) acrylic acid methyl ester/(meth) acrylic acid glycidyl ester copolymers, (meth) acrylic acid/styrene/(meth) acrylic acid glycidyl ester/N-phenylmaleimide copolymers, (meth) acrylic acid/styrene/(meth) acrylic acid methyl ester/(meth) acrylic acid glycidyl ester/N-cyclohexylmaleimide copolymers, (meth) acrylic acid/styrene/(meth) acrylic acid N-butyl ester/(meth) acrylic acid glycidyl ester/N-phenylmaleimide copolymers, and the like.
One or more of the copolymers may be contained in the colored photosensitive resin composition.
The weight average molecular weight (Mw) of the polystyrene-equivalent copolymer as measured by gel permeation chromatography (eluent: tetrahydrofuran, etc.) may be 3000 to 50000, preferably 5000 to 40000. Within this range, adhesion to a substrate, physical/chemical properties, and viscosity may be satisfied.
The content of the copolymer in the colored photosensitive resin composition may be 0.5 to 60wt%, preferably 5 to 50wt%, based on the total weight of the colored photosensitive resin composition containing no solvent (i.e., based on the solid content). Within the above range, a pattern having a good shape can be obtained after development, and properties such as chemical resistance can be improved.
The copolymer was prepared by adding the molecular weight modifier, the radical polymerization initiator, the solvent, and the units (a-1) to (a-3) to the reactor, injecting nitrogen gas, and slowly stirring the mixture to perform polymerization.
The molecular weight regulator is not particularly limited, and may include mercaptans such as butanethiol, octanethiol, etc., or α -methylstyrene dimer.
The radical polymerization initiator is not particularly limited and may include azo compounds such as 2,2' -azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), 2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile), etc., benzoyl peroxide, lauryl peroxide, t-butyl peroxypivalate, 1-bis (t-butyl peroxy) cyclohexane, etc. The radical polymerization initiator may be used singly or in combination of two or more.
In addition, a solvent for preparing the copolymer may be used, which may include, for example, propylene Glycol Monomethyl Ether Acetate (PGMEA).
(b) Epoxy resin compound or compound derived therefrom
The colored photosensitive resin composition of the present invention contains an epoxy resin compound or a compound derived therefrom, preferably an epoxy resin compound having a xanthene skeleton structure or a compound derived therefrom. A compound having a weight average molecular weight (Mw) of 400 to 10,000 in terms of polystyrene as measured by gel permeation chromatography may be used as the epoxy resin compound, and the compound may be an epoxy resin compound having a xanthene skeleton structure represented by the following formula 1:
[ chemical formula 1]
Wherein each carbon atom marked by is independently marked by and contained in
L 1 each independently is C 1-10 Alkylene group, C 3-20 Cycloalkylene or C 1-10 An alkyleneoxy group;
R 1 to R 7 Each independently H, C 1-10 Alkyl, C 1-10 Alkoxy, C 2-10 Alkenyl, or C 6-14 An aryl group;
R 8 is H, methyl, ethyl, CH 3 CHCl-、CH 3 CHOH-、CH 2 ＝CHCH 2 -or phenyl; and
n is an integer from 0 to 10.
C 1-10 Specific examples of the alkylene group may include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, sec-butylene, tert-butylene, pentylene, isopentylene, tert-pentylene, hexylene, heptylene, octylene, isooctylene, tert-octylene, 2-ethylhexyl, nonylene, isononyl, decylene, isodecylene and the like. C (C) 3-20 Specific examples of the cycloalkylene group may include cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cycloheptylene group, naphthylene group (decalinalyene), adamantylene group (amantadine), and the like. C (C) 1-10 Specific examples of the alkyleneoxy group may include a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, a butyleneoxy group, a sec-butyleneoxy group, a t-butyleneoxy group, a pentyleneoxy group, a hexyleneoxy group, a heptyleneoxy group, an octyleneoxy group, a 2-ethyl-hexyleneoxy group and the like. C (C) 1-10 Specific examples of the alkyl group may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl and the like. C (C) 1-10 Specific examples of the alkoxy group may include methoxy, ethoxy, propoxy, butoxy, sec-butoxy, tert-butoxy, pentoxy, hexoxy, heptoxy, octoxy, 2-ethylhexoxy and the like. C (C) 2-10 Specific examples of alkenyl groups may include vinyl, allyl, butenyl, propenyl, and the like. C (C) 6-14 Specific examples of the aryl group may include phenyl, tolyl, xylyl, naphthyl, and the like.
The epoxy resin compound derived from the xanthene skeleton structure having formula 1 may be obtained by reacting an epoxy resin having the xanthene skeleton structure having formula 1 with an unsaturated alkali acid to obtain an epoxy adduct, and reacting the epoxy adduct with a polybasic acid anhydride, or alternatively by reacting the thus obtained compound with a monofunctional or polyfunctional epoxy compound. Any unsaturated acid known in the art may be used in the present invention, such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, and the like. Any of the polybasic anhydrides known in the art such as succinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like may be used in the present invention. Any mono-or polyfunctional epoxy compound known in the art may be used in the present invention, such as glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, bisphenol Z glycidyl ether, and the like.
When a compound derived from an epoxy resin having a xanthene skeleton structure of formula 1 is used, the xanthene skeleton structure can improve adhesion of a cured product to a substrate, alkali resistance, processability, strength, and the like, and once uncured portions are removed at the time of near development, an image with fine resolution can be formed in a pattern.
The content of the epoxy resin compound or the compound derived therefrom may be 1 to 70wt%, preferably 5 to 50wt%, based on the total amount of the colored photosensitive resin composition free of solvent (i.e., based on the solid content). Within this range, resolution and chemical resistance can be improved, the shape of the image can be kept good, and a constant step difference between patterns having a desired side width (i.e., allowable width) can be advantageously obtained.
(c) Polymerizable compounds
The polymerizable compound used in the present invention may be any compound polymerized by a polymerization initiator, and may be a monofunctional monomer, oligomer or polymer conventionally used in coloring photosensitive resin compositions.
More specifically, the polymerizable compound may include a polyfunctional ester compound of acrylic acid or methacrylic acid having at least one ethylenically unsaturated double bond, and it may be a polyfunctional compound having at least two functional groups for the desired chemical resistance.
The polymerizable compound may be selected from the group consisting of ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate and succinic acid monoester, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and succinic acid monoester, caprolactone-modified dipentaerythritol hexa (meth) acrylate, pentaerythritol triacrylate hexamethylene diisocyanate (reactant of pentaerythritol triacrylate and hexamethylene diisocyanate), tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, bisphenol a epoxy acrylate, ethylene glycol monomethyl ether, and mixtures thereof.
The content of the polymerizable compound may be 1 to 60wt%, preferably 5 to 45wt%, based on the total amount of the solvent-free colored photosensitive resin composition (i.e., based on the solid content). Within this range, the pattern can be easily formed, and defects such as scum in the bottom portion image shape during development can be suppressed.
(d) Photopolymerization initiator
Any known polymerization initiator may be used as the photopolymerization initiator in the present invention.
The photopolymerization initiator is selected from acetophenones, non-imidazoles, triazines, onium salts, benzoins, benzophenones, diones, alpha-diones, polycyclic quinones, thioxanthones, diazonium compounds, imide sulfonates, oximes, carbazoles, sulfonium borates, and mixtures thereof.
Among the above compounds, preferred are oximes disclosed in korean laid-open patent nos. 2004-7700, 2005-84149, 2008-83650, 2008-80208, 2007-44052, 2007-91110, 2007-44753, 2009-9991, 2009-93933, 2010-97658, or 2011-5925, or PCT publication No. WO2010/102502 or WO 2010/133077. In addition, for high sensitivity and resolution, commercially available materials such as OXE-01 and OXE-02 (Ciba corporation), N-1919 (ADEKA corporation) are preferably used.
The content of the polymerization initiator may be 0.1 to 10wt%, preferably 0.5 to 5wt%, based on the total amount of the colored photosensitive resin composition free of solvent (i.e., based on the solid content). Within this range, the curing by exposure can be sufficiently performed, whereby the pattern for the spacer can be easily formed, and the spacer thus formed can be sufficiently adhered to the substrate in development.
(e) Coloring agent
In order to impart light-shielding properties, the colored photosensitive resin composition of the present invention contains a colorant.
The colorant used in the present invention may be a mixture of two or more inorganic or organic colorants, preferably a colorant having high color development and heat resistance. In particular, the use of a mixture of two or more organic colorants is advantageous for suppressing light leakage through the black matrix and obtaining light transmittance for mask calibration.
Further, the colorant includes a black colorant and a blue colorant. The black colorant may be a black inorganic colorant and/or a black organic colorant.
Any black inorganic colorant, black organic colorant, and blue colorant known in the art may be used, such as a compound classified as a pigment in Color Index (published by The Society of Dyers and Colourists), and any known dye may be used.
Specific examples of the black inorganic colorant include carbon black, titanium black, metal oxides such as cu—fe—mn oxide, synthetic iron black, and the like. Among them, carbon black is preferable for desired pattern properties and chemical resistance.
Further, specific examples of the black organic colorant may include aniline black, lactam black, perylene black, and the like. Among them, lactam Black (e.g., black582 of FASF corporation) is preferable for the desired optical density, permeability, light transmittance, etc.
Specific examples of blue colorants include c.i. pigment blue 15:6. c.i. pigment blue 15: 4. c.i. pigment blue 60, c.i. pigment blue 16, etc. Among them, preferred is c.i. pigment blue 15 for suppressing light leakage: 6.
the contents of the black inorganic colorant, the black organic colorant and the blue colorant are respectively 0 to 5wt%, 10 to 40wt% and 1 to 15wt%, based on the total amount of the solvent-free colored photosensitive resin composition (i.e., based on the solid content). Within this range, the optical density is high enough to suppress light leakage, and the light transmittance required for mask alignment may also be desirable, for example, less than 15% at 730nm and at least 15% at 900 nm.
Meanwhile, a dispersant for dispersing the colorant may be used in the colored photosensitive resin composition of the present invention. Examples of dispersants may include any known dispersants for colorants. Specific examples may include cationic surfactants, anionic surfactants, nonionic surfactants, zwitterionic surfactants, silicon-based surfactants, fluorine-based surfactants, and the like. Commercially available dispersants may be Disperbyk-182, -183, -184, -185, -2000, -2150, -2155, -2163 or-2164 from BYK company. These compounds may be used singly or in combination of two or more. The dispersant may be added to the colorant by surface-treating the colorant with the dispersant, or may be added together with the colorant during the preparation of the colored photosensitive resin composition.
Alternatively, a colorant may be mixed with the binder and used to prepare the colored photosensitive resin composition. In this case, the binder may be the copolymer (a) described in the present invention, a known copolymer, or a mixture thereof.
Therefore, the colorant used in the present invention can be added to the colored photosensitive resin composition in the form of a colored dispersion (colored slurry) obtained by mixing the colorant with a dispersant, a binder, a solvent, or the like.
(f) Solvent(s)
The colored photosensitive resin composition of the present invention can be preferably prepared as a liquid composition by mixing the above components and a solvent. Any solvent known in the art may be used in the colored photosensitive resin composition that is compatible with but non-reactive with the components in the colored photosensitive resin composition.
Examples of the solvent include glycol ethers such as ethylene glycol monoethyl ether and the like; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate and the like; esters such as ethyl 2-hydroxypropionate and the like; diethylene glycols such as diethylene glycol monomethyl ether and the like; and propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, and the like. These solvents may be used singly or in combination of two or more.
The amount of the solvent used is not particularly limited, but may be determined so that the total concentration of each component in the composition (i.e., based on the solid content) except the solvent is usually 5 to 70% by weight, preferably 10 to 55% by weight, for the dispersibility and stability of the finally obtained colored photosensitive resin composition.
(g) Surface active agent
In order to improve coating properties and prevent occurrence of defects, the colored photosensitive resin composition of the present invention may further comprise a surfactant, if necessary.
The kind of the surfactant is not particularly limited, and for example, a fluorine-based surfactant or a silicon-based surfactant can be used.
Commercially available silicon-based surfactants are DC3PA, DC7PA, SH11PA, SH21PA and SH8400 from Kang Ningdong silicone company (Dow Corning Toray Silicone Co.,), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460 and TSF-4452 from GE Toshiba silicon Co., ltd (GE Toshiba Silicones Co.,), BYK333 from BYK company, and the like. These compounds may be used singly or in combination of two or more. Commercially available fluorine-based surfactants are Megafac F-470, F-471, F-475, F-482, F-489, etc. of Dahon ink chemical industry Co., ltd (Dainippon Ink Kagaku Kogyo Co.). Among them, BYK333 of BYK corporation is preferred for dispersibility.
The amount of the surfactant may be 0.01 to 10wt%, preferably 0.05 to 5wt%, based on the total amount (i.e., solid content) of the solvent-free colored photosensitive resin composition. Within this range, the colored photosensitive resin composition can be easily applied.
(h) Silane coupling agent
In order to improve the adhesion with the substrate, the colored photosensitive resin composition of the present invention may further comprise a silane coupling agent having a reactive substituent selected from the group consisting of a carboxyl group, (meth) acryl group, isocyanate group, amino group, mercapto group, vinyl group, epoxy group, and a combination thereof, if necessary.
The type of the silane coupling agent is not particularly limited, but may be preferably selected from trimethoxysilylbenzoic acid, γ -methacryloxypropyl trimethoxysilane, vinyltriacetoxy silane, vinyltrimethoxysilane, γ -isocyanatopropyl triethoxysilane, γ -glycidoxypropyl trimethoxysilane, γ -glycidoxypropyl triethoxysilane, β - (3, 4-epoxycyclohexyl) ethyl trimethoxysilane, phenylamino trimethoxysilane and mixtures thereof. Among them, gamma-isocyanatopropyl triethoxysilane having an isocyanate group (such as KBE-9007 of Shin-Etsu Co.) or phenylamino trimethoxysilane may be preferable because of its good chemical resistance and good adhesion to a substrate.
The amount of the silane coupling agent may be 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the total amount of the solvent-free colored photosensitive resin composition (i.e., based on the solid content). Within this range, the adhesiveness of the colored photosensitive resin composition can be improved.
In addition, other additives such as antioxidants, stabilizers, and the like may be contained as long as the physical properties of the colored photosensitive resin composition are not impaired.
When the cured layer is formed from the colored photosensitive resin composition of the present invention, properties of the black matrix such as light transmittance and optical density and properties of the columnar spacers such as elastic recovery, resolution, chemical resistance and property thickness of the coating layer can be equally satisfactory. Therefore, the limits of exposure and development of both are satisfactory. In particular, when a cured layer having a thickness of 1 μm is formed from the colored photosensitive resin composition of the present invention, an optical density of 0.6 to 1.5, more precisely an optical density of 0.6 to 1.4, can be achieved. In addition, when a cured layer having a thickness of 1.5 to 2.5 μm is formed, light transmittance of less than 15% can be achieved at a wavelength of 730nm, and when a cured layer having a thickness of 3.5 to 4.5 μm is formed, light transmittance of at least 15% can be achieved at a wavelength of 900 nm. Accordingly, the colored photosensitive resin composition of the present invention can form the columnar spacers and the black matrix at the same time, thereby reducing the required processing time.
Method for preparing colored photosensitive resin composition
The colored photosensitive resin composition of the present invention comprising the above-mentioned components can be prepared by a conventional method, and an embodiment will be described below.
First, the colorant is premixed with a solvent and dispersed in a sand mill or the like until the average diameter of the colorant becomes a desired size. At this stage, if desired, a surfactant may be added, and a portion or all of the copolymer may be added. The remainder of the copolymer, the epoxy resin compound or derivative thereof, the polymerizable compound, and the photopolymerization initiator are added to the dispersion. Additives such as silane coupling agents or additional solvents may be added to adjust the concentration of the mixture if desired. Then, the mixture is sufficiently stirred to obtain a desired colored photosensitive resin composition.
Columnar spacer, black matrix, and BCS
According to the present invention, there are provided a columnar spacer and a black matrix formed of a photosensitive resin composition. In particular, an integrated BCS formed from the colored photosensitive resin composition is provided in the present invention. Fig. 1 shows an embodiment of a BCS pattern.
The columnar spacers, black matrix, or BCS may be formed by coating to form a layer, exposing, developing, and heat treating steps.
In the coating layer forming step, the colored photosensitive resin composition of the present invention is coated on a pretreated substrate by a spin or slot coating method, a roll coating method, a screen printing method, an application method, or the like to obtain a desired thickness, for example, 2 to 25 μm, and then is pre-cured at 70 to 100 ℃ for 1 to 10 minutes to remove the solvent and the formed coating layer.
In order to form the pattern of the coating thus obtained, a mask having a certain shape is provided thereon, and then irradiated with active light of 200 to 500 nm. At this stage, in order to obtain an integrated BCS, a mask having different light transmittance in a certain shape may be used to simultaneously form the column spacers and the black matrix. As a light source for exposure, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon laser, or the like can be used; and X-rays, electron rays, etc. may also be used if necessary. The dosage may vary depending on the kind and mixing ratio of the components of the composition and the thickness of the dried layer. When a high pressure mercury lamp is used, the dose may be 500mJ/cm 2 Or smaller (at a wavelength of 365 nm).
After the exposure step, a development step using an alkaline aqueous solution such as sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide step, etc. is performed, and unnecessary portions are removed by dissolving them, thereby patterning the remaining exposed portions. The image pattern obtained by the development is cooled to room temperature and then baked in a hot air circulation type drying oven at 180 to 250 c for 10 to 60 minutes, thereby obtaining a final pattern.
The thus manufactured column spacer, black matrix or BCS can be effectively used for electronic parts such as OLED displays, liquid crystals, etc. due to good physical properties. Accordingly, an electronic component including a column spacer, a black matrix, or a BCS may be provided in the present invention.
In addition to the spacers, the OLED display, the liquid crystal display, etc. of the present invention may include elements known to those skilled in the art. That is, an OLED display, a liquid crystal display, etc. may also be included in the present invention, in which the column spacers, the black matrix, or the BCS thereof of the present invention may be used.
Hereinafter, the present invention is more specifically described by the following examples, but these are provided for illustrative purposes only, and the present invention is not limited thereto.
Preparation example 1: preparation of the copolymer
In a 500 ml round bottom flask equipped with a reflux condenser and a stirrer, 100 g of the monomer mixture showing the quantitative ratio of Table 1, 300 g of PGMEA as a solvent, and 2 g of 2,2' -azobis (2, 4-dimethylvaleronitrile) as a radical polymerization initiator were charged. The temperature was raised to 70℃and the mixture was stirred for 5 hours for polymerization to produce a copolymer. The copolymer thus obtained had an acid value of 80 mgKOH/g and a weight average molecular weight (Mw) in terms of polystyrene (polystyrene-reference) as measured by gel permeation chromatography of 11,000.
Table 1 shows the amount and weight average molecular weight of each constituent unit of the copolymer.
TABLE 1
Preparation example 2: derived from epoxy resin compounds having xanthene skeleton structure
125.4 g of spiro [ fluorene-9, 9' -xanthene ] -3',6' -diol and 0.1386 g of t-butyl ammonium bromide were placed in a 3000 ml round bottom flask and mixed. To this was further added 78.6 g of epichlorohydrin, and the mixture was heated to 90 ℃ to effect a reaction. After complete consumption of spiro [ fluorene-9, 9' -xanthene ] -3',6' -diol was determined by liquid chromatography analysis, the reaction was cooled to 30 ℃ and an aqueous solution (3 eq.) containing 50% naoh was slowly added. After the complete consumption of epichlorohydrin was determined by liquid chromatography analysis, the reaction was extracted with dichloromethane and washed three times. The organic layer was dried using magnesium sulfate, and methylene chloride was removed by distillation under the reduced pressure. The crude product was recrystallized from a methylene chloride/methanol (50:50, V/V) mixture solvent.
To 1 equivalent of the thus obtained epoxy compound, 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2, 6-diisobutylphenol, and 2.2 equivalent of acrylic acid were added. Next, 8.29 g PGMEA solvent was added thereto, followed by mixing the solution. Air was blown into the thus prepared solution at a rate of 25 ml/min, and the solution was heated to 90 to 100 ℃ to dissolve the reactants. When the solution was white turbid, the temperature was raised to 120 ℃ to completely dissolve the reactants. When it became clear and the viscosity increased, the acid value of the solution was measured, and the solution was stirred until the acid value reached less than 1.0mgKOH/g. Until the acid value reached the target value (0.8), stirring was continued for 11 hours. After the reaction was completed, the temperature of the reactor was lowered to room temperature to obtain a colorless transparent solid.
43 g of the solid product thus obtained, 33.6 g of acrylic acid, 0.04 g of 2, 6-di-t-butyl-p-cresol, 0.21 g of tetrabutylammonium acetate, and 18g of PGMEA were placed in a reaction flask, and the mixture was stirred at 120℃for 13 hours. After this time, the reaction was cooled to room temperature, and 24 g PGMEA and 10 g succinic anhydride were added to each, followed by stirring the mixture at 100 ℃ for 3 hours. 8g of bisphenol Z glycidyl ether was added to the mixture and the mixture was stirred at 120℃for 4 hours, at 90℃for 3 hours, at 60℃for 2 hours, and at 40℃for 5 hours. Reprecipitation is carried out in water and alcohol to obtain the final resin in powder form. PGMEA was then added so that the solids content was 48%. The acid value of the resin thus obtained was 105mgKOH/g, and the weight average molecular weight (Mw) with reference to polystyrene as measured by gel permeation chromatography was 5500.
Preparation example 3: preparation of the colored Dispersion
The components were mixed in the amounts shown in table 2 below. In this case, the copolymer obtained in preparation example 1 was used as a copolymer of BASF corporation, lactam Black (Black 582) was used as an organic Black, a polymer dispersant (DISPERBYK-2000) was used as a dispersant and PGMEA was used as a solvent. The mixture thus obtained is dispersed in a paint shaker at 25-60 ℃. The dispersion step was performed using 0.3mm zircon beads. After the dispersion step is completed, the beads are separated from the dispersion, thereby producing colored dispersions a-C, respectively.
TABLE 2
Examples 1 to 6 and comparative examples 1 to 3: preparation of colored photosensitive resin composition
The copolymer a having 31% of solid content obtained in production example 1, the epoxy resin compound having xanthene grip obtained in production example 2, dipentaerythritol hexaacrylate (DPHA, japan chemical company (Nippon kayaku.co.)) as a polymerizable compound, and the colored dispersions a to C obtained in production example 3 were mixed according to the amounts described in table 3 below. In addition, 0.04 g of an oxime-based photoinitiator (OXE-02, baba corporation (Ciba co.)), 0.0082 g of a surfactant (BYK-333, BYK corporation), and 7.5176 g of PGMEA as a solvent were mixed as photopolymerization initiators by a conventional method, and stirred for 5 hours to prepare respective colored photosensitive resin compositions (examples 1 to 6 and comparative examples 1 to 3).
Table 3 below shows the amounts of the components of the compositions prepared in the examples and comparative examples.
TABLE 3
Experimental example 1: determination of physical Properties of cured layer formed from colored photosensitive resin composition
Each of the colored photosensitive resin compositions prepared in examples and comparative examples was coated on a glass substrate using a spin coater and pre-cured at 100 ℃ for 150 seconds to form a coating layer. A mask pattern having a 100% full-tone Columnar Spacer (CS) pattern and a 30% halftone black matrix pattern was disposed on the obtained coating layer, and then exposed to a light of 40mJ/cm 2 Is 365 nm. However, the method is thatAfter that, the time for the lower critical point (BP) was checked at 23℃with a 1wt% potassium hydroxide diluted aqueous solution and developed for 15 seconds. After washing with pure water for 1 minute, the formed pattern was post-cured by heating in an oven at 230 ℃ for 30 minutes, thereby obtaining a cured layer.
(1) Measuring elastic recovery
According to the method of forming a cured layer as described above, a cured layer of 4.0 (±0.2) μm total thickness and 35 (±1) μm pattern width was formed after post-curing, and the cured layer was set as a reference shape for measuring physical properties, i.e., compression displacement and elastic recovery. The compression displacement and elastic recovery were measured using an elastic measuring device (DUH-W201S, simadzu co., japan) according to the following measurement conditions.
As a platen for pressing the pattern, a flat platen having a diameter of 50 μm was used in a weight-mounting/dismounting manner. Elastic recovery was measured at 300MN load of the test delivery to obtain results that were distinguishable between the control groups. The loading rate of 3 grams force (gf)/second and the holding time of 3 seconds were maintained. Regarding the elastic recovery, the flat platen was continuously loaded for 3 seconds, and then the true elastic recovery of the pattern before and after loading was determined by using a three-dimensional thickness measuring device. The elastic recovery rate refers to a ratio of a recovery distance to a compression distance (compression displacement) after a recovery time of 10 minutes when a constant force is applied, and is represented by the following formula 1.
[ formula 1]
Elastic recovery (%) = [ (recovery distance/compression displacement) ×100]
(2) Measurement resolution
According to the method of forming the cured layer, a cured layer having a thickness of 3.5 (±0.2) μm was formed, and then exposed and developed using a photomask (a pattern having a size of 8, 10, 12, 14 μm, etc.) under the same conditions as those used for developing the cured layer. The critical dimension of the cured layer pattern was measured and the resolution (μm) was evaluated.
(3) Measurement of chemical resistance
By a method of forming a cured layer without a mask, a cured layer having a thickness of 3.0 (±0.2) μm after post-curing was prepared, and the initial thickness of the cured layer thus prepared was measured. Then, the sample was immersed in 1g of 100% N-methylpyrrolidone (NMP), boiled at 100℃for 5 minutes in a thermostat, and baked at 100℃for 2 minutes in a furnace, and the second thickness was measured. The samples were finally baked in an oven at 230 ℃ for 20 minutes and the final thickness was measured. Based on the values thus measured, chemical resistance is calculated by the following equation 2. The lower the chemical resistance (%), the better the properties of the cured layer.
[ formula 2]
Chemical resistance (%) = [ (final thickness)/(initial thickness) ×100] -100
(4) Measurement of BCS thickness
Similar to the measurement method of elastic recovery, a BCS pattern (see fig. 1) in which the black matrix and the spacers are integrated was prepared. The total thickness of BCS (a+b), the thickness of columnar spacer portion (a), and the thickness of black bottom portion (B) were measured by a height measuring device (SIS-2000, university of first-aid (Seoul National University)). When the thickness of the black matrix portion (a) is in the range of 2.0±0.5 μm, the light shielding property will be desirable.
(5) Measuring transmittance with respect to wavelength
By a method of forming a cured layer without a mask, cured layers having post-curing thicknesses of 2.0 μm and 4.0 μm were prepared, and light transmittance at a wavelength of 730nm and light transmittance at a wavelength of 900nm were measured for each thickness of the cured layer using a spectrometer (Cary 100, agilent). When the light transmittance at 730nm is less than 15% at a thickness of 2.0 (±0.5) μm, light leakage can be prevented, which will not generate any in-line defects, and the minimum light transmittance at 900nm wavelength is at least 15% at a thickness of 4.0 (±0.5) μm.
(6) Measuring optical density
A cured layer having a thickness of 3.0 μm after post-curing was prepared by a method of forming a cured layer without a mask. The light transmittance of the cured layer at 550nm was measured by using an optical density system (361T, X-lite Co.)) and an optical density of 1 μm was obtained.
The measurement results obtained above are shown in tables 4 and 5.
TABLE 4
TABLE 5
As shown in tables 4 and 5, the cured layers, such as the columnar spacers, black matrixes, and BCSs, prepared from the colored photosensitive resin compositions according to examples 1 to 6 exhibited equally good elastic recovery, resolution, chemical resistance, thickness, light transmittance, and optical density. In contrast, at least one of the above properties of the cured layers prepared from the colored photosensitive resin compositions according to comparative examples 1 to 3 showed unsatisfactory results. In particular, the transmittance measured at a wavelength of 730nm at a thickness of 2 μm was higher than that of the cured layers of comparative examples 1 and 3, which was not applicable to BCS. Meanwhile, the transmittance measured at a wavelength of 900nm at a thickness of 4 μm was lower than that of the cured layer of comparative example 2, which was not suitable for BCS. Accordingly, the colored photosensitive resin composition according to the present invention can be used for spacers and/or black matrixes of various electronic parts including LCDs.
Claims (4)
1. A columnar spacer, black matrix, or black columnar spacer formed of a colored photosensitive resin composition comprising:
(a) A copolymer;
(b) An epoxy resin compound or a compound derived therefrom;
(c) A polymerizable compound;
(d) Photopolymerization initiator
(e) A colorant comprising 0 to 5% by weight of an inorganic black colorant, 10 to 40% by weight of an organic black colorant, and 1 to 15% by weight of a blue colorant, based on the total weight of the solid content in the colored photosensitive resin composition,
when a cured layer having a thickness of 1 μm is formed, the colored photosensitive resin composition has an optical density of 0.6 to 1.4,
the light transmittance at 730nm is less than 15% when the cured layer is formed in a thickness of 1.5 to 2.5 μm, and the light transmittance at 900nm is at least 15% when the cured layer is formed in a thickness of 3.5 to 4.5 μm.
2. The columnar spacer, black matrix, or black columnar spacer of claim 1, wherein the copolymer comprises:
(a-1) units derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or mixtures thereof;
(a-2) units derived from an aromatic ring-containing ethylenically unsaturated compound, and
(a-3) units derived from olefinically unsaturated compounds different from (a-1) and (a-2).
3. The columnar spacer, black matrix, or black columnar spacer of claim 1, wherein the epoxy compound comprises a xanthene backbone structure.
4. The columnar spacer, black matrix, or black columnar spacer of claim 1 wherein the blue colorant is CI pigment blue 15:6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110097238.0A CN112904672B (en) | 2013-01-25 | 2014-01-26 | Colored photosensitive resin composition suitable for columnar spacers and black matrixes |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2013-0008530 | 2013-01-25 | ||
| KR1020130008530A KR101658374B1 (en) | 2013-01-25 | 2013-01-25 | Colored photosensitive resin composition with dual property for column spacer and black matrix |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110097238.0A Division CN112904672B (en) | 2013-01-25 | 2014-01-26 | Colored photosensitive resin composition suitable for columnar spacers and black matrixes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103969954A CN103969954A (en) | 2014-08-06 |
| CN103969954B true CN103969954B (en) | 2023-04-28 |
Family
ID=51239621
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110097238.0A Active CN112904672B (en) | 2013-01-25 | 2014-01-26 | Colored photosensitive resin composition suitable for columnar spacers and black matrixes |
| CN201410113761.8A Active CN103969954B (en) | 2013-01-25 | 2014-01-26 | Colored photosensitive resin composition suitable for columnar spacers and black matrixes |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110097238.0A Active CN112904672B (en) | 2013-01-25 | 2014-01-26 | Colored photosensitive resin composition suitable for columnar spacers and black matrixes |
Country Status (4)
| Country | Link |
|---|---|
| JP (2) | JP2014146029A (en) |
| KR (1) | KR101658374B1 (en) |
| CN (2) | CN112904672B (en) |
| TW (1) | TWI667336B (en) |
Families Citing this family (41)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101658374B1 (en) * | 2013-01-25 | 2016-09-22 | 롬엔드하스전자재료코리아유한회사 | Colored photosensitive resin composition with dual property for column spacer and black matrix |
| TWI484295B (en) * | 2013-03-19 | 2015-05-11 | Chi Mei Corp | Photosensitive resin composition, black matrix, color filter and liquid crystal display element |
| JP5890375B2 (en) * | 2013-11-19 | 2016-03-22 | 東京応化工業株式会社 | Line pattern forming method |
| KR101784049B1 (en) * | 2014-11-14 | 2017-10-10 | 롬엔드하스전자재료코리아유한회사 | Colored photosensitive resin composition and light shielding spacer prepared therefrom |
| JP7131907B2 (en) | 2015-03-11 | 2022-09-06 | 三菱ケミカル株式会社 | Photosensitive coloring composition, cured product, colored spacer, image display device |
| KR102437844B1 (en) * | 2015-04-02 | 2022-08-31 | 롬엔드하스전자재료코리아유한회사 | Colored photosensitive resin composition and black column spacer prepared therefrom |
| KR102450387B1 (en) * | 2015-05-13 | 2022-10-04 | 롬엔드하스전자재료코리아유한회사 | Negative-type photosensitive resin composition and insulating film using same |
| JP6713746B2 (en) * | 2015-10-08 | 2020-06-24 | 日鉄ケミカル＆マテリアル株式会社 | Photosensitive resin composition for light-shielding film having spacer function, light-shielding film, liquid crystal display device, method for producing photosensitive resin composition for light-shielding film having spacer function, method for producing light-shielding film, and production of liquid crystal display device Method |
| KR101829998B1 (en) * | 2015-11-04 | 2018-02-19 | 롬엔드하스전자재료코리아유한회사 | Colored photosensitive resin composition and light shielding spacer using same |
| KR101755318B1 (en) | 2015-11-19 | 2017-07-10 | 롬엔드하스전자재료코리아유한회사 | Method for preparing column spacer |
| WO2017086590A1 (en) * | 2015-11-19 | 2017-05-26 | Rohm And Haas Electronic Materials Korea Ltd. | Method for preparing column spacer |
| KR102674718B1 (en) | 2016-01-18 | 2024-06-14 | 듀폰스페셜티머터리얼스코리아 유한회사 | Black photosensitive resin composition and black column spacer prepared therefrom |
| WO2017126795A1 (en) * | 2016-01-18 | 2017-07-27 | Rohm And Haas Electronic Materials Korea Ltd. | Black photosensitive resin composition and black column spacer prepared therefrom |
| WO2017138605A1 (en) * | 2016-02-12 | 2017-08-17 | 三菱化学株式会社 | Photosensitive coloring composition for forming colored spacer, cured material, colored spacer, and image display device |
| JPWO2017204079A1 (en) | 2016-05-27 | 2019-03-22 | 昭和電工株式会社 | Photosensitive resin composition for forming black column spacer, black column spacer and image display device |
| KR102590768B1 (en) * | 2016-05-31 | 2023-10-19 | 주식회사 이엔에프테크놀로지 | Photosensitive colorant composition for black column spacer or black matrix |
| WO2018043262A1 (en) * | 2016-08-31 | 2018-03-08 | 富士フイルム株式会社 | Pattern forming method, method for producing laminate and method for producing electronic device |
| KR101991699B1 (en) * | 2016-09-26 | 2019-06-21 | 삼성에스디아이 주식회사 | Photosensitive resin composition, black pixel defining layer using the same and display device |
| KR101832097B1 (en) * | 2016-10-31 | 2018-02-23 | 롬엔드하스전자재료코리아유한회사 | Colored photosensitive resin composition and light shielding spacer prepared therefrom |
| JP6380723B1 (en) * | 2017-02-15 | 2018-08-29 | 三菱ケミカル株式会社 | Photosensitive coloring composition, cured product, colored spacer, image display device |
| JP7040089B2 (en) * | 2017-02-17 | 2022-03-23 | 三菱ケミカル株式会社 | Photosensitive resin composition for partition wall formation, partition wall, organic electroluminescent element, image display device and lighting |
| WO2018159265A1 (en) | 2017-03-01 | 2018-09-07 | 株式会社Adeka | Polymerizable composition and photosensitive composition for black column spacer |
| KR102216990B1 (en) * | 2017-03-29 | 2021-02-22 | 도레이 카부시키가이샤 | Photosensitive composition, cured film, and organic EL display device |
| KR102565582B1 (en) * | 2017-06-12 | 2023-08-11 | 롬엔드하스전자재료코리아유한회사 | Colored photosensitive resin composition and light shielding spacer prepared therefrom |
| KR20180135375A (en) * | 2017-06-12 | 2018-12-20 | 롬엔드하스전자재료코리아유한회사 | Colored photosensitive resin composition and light shielding spacer prepared therefrom |
| WO2018235664A1 (en) | 2017-06-20 | 2018-12-27 | 株式会社Adeka | Polymerizable composition, photosensitive composition for black matrixes, and photosensitive composition for black column spacers |
| TWI690751B (en) | 2017-07-27 | 2020-04-11 | 南韓商Ｌｇ化學股份有限公司 | Substrate, method of producing the same and optical device |
| JP6374595B1 (en) * | 2017-09-26 | 2018-08-15 | 東京応化工業株式会社 | Photosensitive resin composition, cured film, display device, and pattern forming method |
| KR101869205B1 (en) | 2017-10-13 | 2018-07-19 | 동우 화인켐 주식회사 | Photosensitive resin composition, and pattern formed therefrom, color filter comprising thereof and liquid crystal display device comprigin the color filter |
| TWI741223B (en) | 2017-10-20 | 2021-10-01 | 南韓商東友精細化工有限公司 | A pigment dispersion, a photo sensitive resin composition comprising the pigment dispersion, a pattern layer prepared by using the composition, a color filter comprising the pattern layer, and a display device comprising the color filter |
| KR102157142B1 (en) | 2017-10-20 | 2020-09-17 | 동우 화인켐 주식회사 | A black photo sensitive resin composition, a color filter comprising a black metrics and/or a column spacer prepared by using the composition, and a display comprising the color filter |
| KR20190048321A (en) | 2017-10-31 | 2019-05-09 | 동우 화인켐 주식회사 | Photosensitive resin composition, and pattern formed therefrom, color filter comprising thereof and liquid crystal display device comprigin the color filter |
| KR101897925B1 (en) | 2017-11-02 | 2018-09-12 | 동우 화인켐 주식회사 | A photo sensitive resin composition, a color filter comprising a black metrics, a column spacer or black column spacer prepared by using the composition, and a display device comprising the color filter |
| KR102371728B1 (en) | 2017-11-09 | 2022-03-07 | 동우 화인켐 주식회사 | Colored photosensitive resin composition, color filter prepared by using the same, and display device comprising the color filter |
| KR101931449B1 (en) * | 2017-11-09 | 2018-12-20 | 동우 화인켐 주식회사 | Colored photosensitive resin composition, color filter prepared by using the same, and display device comprising the color filter |
| KR101923832B1 (en) | 2017-11-20 | 2019-02-27 | 동우 화인켐 주식회사 | Photosensitive resin composition, and pattern formed therefrom, color filter comprising thereof and liquid crystal display device comprigin the color filter |
| JP7006358B2 (en) * | 2018-02-21 | 2022-01-24 | 三菱ケミカル株式会社 | Photosensitive coloring composition, cured product, coloring spacer, and image display device |
| KR102528890B1 (en) | 2018-10-11 | 2023-05-04 | 동우 화인켐 주식회사 | A black photo sensitive resin composition, a color filter comprising a black metrics and/or a column spacer prepared by using the composition, and a display comprising the color filter |
| US20200201180A1 (en) * | 2018-12-21 | 2020-06-25 | Rohm And Haas Electronic Materials Korea Ltd. | Colored photosensitive resin composition and black matrix prepared therefrom |
| KR102560228B1 (en) | 2018-12-24 | 2023-07-27 | 동우 화인켐 주식회사 | Photosensitive resin composition, and color filter and liquid crystal display device formed therefrom |
| TWI795064B (en) | 2020-11-09 | 2023-03-01 | 南韓商Ｌｇ化學股份有限公司 | Photosensitive resin composition, photosensitive material including the same, black matrix including the same and electronic device including the same |
Family Cites Families (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6250434A (en) * | 1985-08-30 | 1987-03-05 | Sumitomo Metal Mining Co Ltd | Cobalt base dispersion strengthened alloy and its manufacture |
| JP2552391B2 (en) * | 1990-11-26 | 1996-11-13 | 出光興産株式会社 | Light-shielding film and method for manufacturing the same |
| JP4330096B2 (en) * | 1999-12-16 | 2009-09-09 | 日本化薬株式会社 | Resin composition, film thereof and cured product thereof |
| JP2003295433A (en) * | 2002-03-28 | 2003-10-15 | Tamura Kaken Co Ltd | Photosensitive resin composition |
| JP4269596B2 (en) * | 2002-08-26 | 2009-05-27 | 住友化学株式会社 | Colored photosensitive resin composition |
| CN100356204C (en) * | 2003-03-12 | 2007-12-19 | 三菱化学株式会社 | Photosensitive composition, photosensitive color composition, color filter, and liquid crystal display equipemnt |
| KR100791022B1 (en) | 2005-06-03 | 2008-01-03 | 세끼스이화인켐 주식회사 | Method of taking shape simultaneously both column spacer and overcoat on color filter of LCD and negative photoresist composition usable thereto |
| JP2007071994A (en) * | 2005-09-05 | 2007-03-22 | Tokyo Ohka Kogyo Co Ltd | Black photosensitive resin composition |
| JP4788485B2 (en) * | 2006-06-13 | 2011-10-05 | 住友化学株式会社 | Colored photosensitive resin composition |
| JP4994923B2 (en) * | 2007-04-06 | 2012-08-08 | 太陽ホールディングス株式会社 | Black solder resist composition and cured product thereof |
| JP5270113B2 (en) * | 2007-06-06 | 2013-08-21 | 新日鉄住金化学株式会社 | Photosensitive resin composition for black resist, light shielding film and color filter using the same |
| JP2009069822A (en) * | 2007-08-22 | 2009-04-02 | Mitsubishi Chemicals Corp | Resin black matrix, light blocking photosensitive resin composition, tft element substrate and liquid crystal display device |
| JP2009251480A (en) * | 2008-04-10 | 2009-10-29 | Kyocera Chemical Corp | Photosensitive heat-curable resin composition and flexible printed wiring board |
| US20100163811A1 (en) * | 2008-12-31 | 2010-07-01 | Cheil Industries Inc. | Organic Layer Photosensitive Resin Composition and Organic Layer Fabricated Using Same |
| KR101859710B1 (en) * | 2010-06-08 | 2018-05-21 | 토요잉크Sc홀딩스주식회사 | Coloring composition for color filter and color filter |
| JP5007453B2 (en) | 2010-06-11 | 2012-08-22 | 株式会社タムラ製作所 | Black curable resin composition |
| JP5732762B2 (en) * | 2010-07-16 | 2015-06-10 | 大日本印刷株式会社 | Resin composition for color filter |
| KR20120010622A (en) * | 2010-07-21 | 2012-02-06 | 엘지디스플레이 주식회사 | Resin black matrix material and liquid crystal display device |
| JP5641412B2 (en) * | 2010-09-24 | 2014-12-17 | 大日本印刷株式会社 | RESIN COMPOSITION FOR COLORED LAYER AND METHOD FOR PRODUCING COLOR FILTER USING THE SAME |
| KR20120088026A (en) * | 2010-10-14 | 2012-08-08 | 동우 화인켐 주식회사 | A colored photosensitive resin composition, color filter and liquid crystal display device having the same |
| KR101323562B1 (en) * | 2011-03-10 | 2013-10-29 | 롬엔드하스전자재료코리아유한회사 | Photosensitive resin composition, low dielectric constant light shielding layer and liquid crystal display apparatus using the same |
| TW201302921A (en) * | 2011-05-30 | 2013-01-16 | Nippon Kayaku Kk | Pigment for color filter, colored resin composition using the same and color filter comprising the resin composition |
| JP2013011845A (en) * | 2011-05-31 | 2013-01-17 | Mitsubishi Chemicals Corp | Photosensitive colored resin composition for color filter, color filter, liquid crystal display device, and organic electroluminescent display |
| JP2013134263A (en) * | 2011-12-22 | 2013-07-08 | Tokyo Ohka Kogyo Co Ltd | Photosensitive resin composition for black column spacer, black column spacer, display device, and method for forming black column spacer |
| JP2013207124A (en) * | 2012-03-29 | 2013-10-07 | Toyo Ink Sc Holdings Co Ltd | Photosensitive black composition, black matrix and organic el light-emitting display device |
| WO2013179237A1 (en) * | 2012-06-01 | 2013-12-05 | Basf Se | Black colorant mixture |
| KR101658374B1 (en) * | 2013-01-25 | 2016-09-22 | 롬엔드하스전자재료코리아유한회사 | Colored photosensitive resin composition with dual property for column spacer and black matrix |
-
2013
- 2013-01-25 KR KR1020130008530A patent/KR101658374B1/en active IP Right Grant
-
2014
- 2014-01-24 JP JP2014011303A patent/JP2014146029A/en active Pending
- 2014-01-24 TW TW103102604A patent/TWI667336B/en active
- 2014-01-26 CN CN202110097238.0A patent/CN112904672B/en active Active
- 2014-01-26 CN CN201410113761.8A patent/CN103969954B/en active Active
-
2020
- 2020-05-27 JP JP2020092618A patent/JP2020144396A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| TWI667336B (en) | 2019-08-01 |
| CN112904672B (en) | 2024-08-20 |
| TW201439293A (en) | 2014-10-16 |
| KR101658374B1 (en) | 2016-09-22 |
| CN112904672A (en) | 2021-06-04 |
| CN103969954A (en) | 2014-08-06 |
| JP2014146029A (en) | 2014-08-14 |
| JP2020144396A (en) | 2020-09-10 |
| KR20140096423A (en) | 2014-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103969954B (en) | Colored photosensitive resin composition suitable for columnar spacers and black matrixes | |
| JP4680867B2 (en) | Photosensitive resin composition | |
| CN108008601B (en) | Color photosensitive resin composition and light shielding spacer prepared from same | |
| CN108475013B (en) | Black photosensitive resin composition and black columnar spacer prepared therefrom | |
| CN108073037B (en) | Color sensitive resin composition and light shielding spacer prepared therefrom | |
| JP2022028693A (en) | Method of preparing column spacer | |
| KR102066281B1 (en) | Colored photosensitive resin composition and light shielding spacer prepared therefrom | |
| KR20150134989A (en) | Colored photosensitive resin composition with dual property for column spacer and black matrix | |
| TW201437242A (en) | Active energy beam-curable resin composition, colored spacer for display device and black matrix using the same | |
| KR102437844B1 (en) | Colored photosensitive resin composition and black column spacer prepared therefrom | |
| CN108351589B (en) | Colored photosensitive resin composition and light-shielding spacer prepared therefrom | |
| TWI751966B (en) | Colored photosensitive resin composition and light shielding spacer prepared therefrom | |
| TWI801387B (en) | Colored photosensitive resin composition and light shielding spacer prepared therefrom | |
| JP2007264467A (en) | Photosensitive resin composition for color filter substrate protection layer | |
| KR20140143951A (en) | Photosensitive resin composition and spacer prepared therefrom | |
| KR101394676B1 (en) | Photosensitive resin compositions and light shielding spacer prepared therefrom | |
| TWI666230B (en) | Blue photosensitive resin composition and color filter and image display device manufactured using the same | |
| KR102066283B1 (en) | Colored photosensitive resin composition | |
| KR101779215B1 (en) | Colored photosensitive resin composition and light shielding spacer prepared therefrom | |
| KR20140098462A (en) | White photosensitive resin composition | |
| KR20150075815A (en) | Cover member of display device | |
| KR20130139611A (en) | Colored photosensitive resin composition and light shielding spacer prepared therefrom |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |