CN110709435A - Photocurable and thermally curable copolymer, and photosensitive resin composition, photosensitive resin film and color filter using the same - Google Patents
Photocurable and thermally curable copolymer, and photosensitive resin composition, photosensitive resin film and color filter using the same Download PDFInfo
- Publication number
- CN110709435A CN110709435A CN201880032826.2A CN201880032826A CN110709435A CN 110709435 A CN110709435 A CN 110709435A CN 201880032826 A CN201880032826 A CN 201880032826A CN 110709435 A CN110709435 A CN 110709435A
- Authority
- CN
- China
- Prior art keywords
- group
- chemical formula
- photosensitive resin
- photocurable
- 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.)
- Granted
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 80
- 239000011342 resin composition Substances 0.000 title claims abstract description 79
- 229920005989 resin Polymers 0.000 title claims abstract description 61
- 239000011347 resin Substances 0.000 title claims abstract description 61
- 239000000126 substance Substances 0.000 claims abstract description 113
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 85
- 125000000524 functional group Chemical group 0.000 claims description 79
- 239000000049 pigment Substances 0.000 claims description 32
- 125000003342 alkenyl group Chemical group 0.000 claims description 31
- 239000000178 monomer Substances 0.000 claims description 31
- -1 acryloyloxy group Chemical group 0.000 claims description 29
- 125000003700 epoxy group Chemical group 0.000 claims description 26
- 125000002947 alkylene group Chemical group 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- 125000004185 ester group Chemical group 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 125000005592 polycycloalkyl group Polymers 0.000 claims description 15
- 238000000016 photochemical curing Methods 0.000 claims description 14
- 239000011247 coating layer Substances 0.000 claims description 13
- 125000005907 alkyl ester group Chemical group 0.000 claims description 12
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 12
- 125000003837 (C1-C20) alkyl group Chemical class 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 11
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 230000001678 irradiating effect Effects 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000002950 monocyclic group Chemical group 0.000 claims description 6
- 125000003367 polycyclic group Chemical group 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims description 5
- 125000005429 oxyalkyl group Chemical group 0.000 claims description 5
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 4
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 2
- 229910052805 deuterium Inorganic materials 0.000 claims description 2
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 description 40
- 238000003786 synthesis reaction Methods 0.000 description 40
- 238000000034 method Methods 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 23
- 229910052799 carbon Inorganic materials 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 7
- 238000001723 curing Methods 0.000 description 7
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 7
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 4
- 238000004043 dyeing Methods 0.000 description 4
- 150000002148 esters Chemical group 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 3
- FYYIUODUDSPAJQ-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 2-methylprop-2-enoate Chemical compound C1C(COC(=O)C(=C)C)CCC2OC21 FYYIUODUDSPAJQ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229920006026 co-polymeric resin Polymers 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000001029 thermal curing Methods 0.000 description 3
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 2
- 125000006586 (C3-C10) cycloalkylene group Chemical group 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- WYGWHHGCAGTUCH-ISLYRVAYSA-N V-65 Substances CC(C)CC(C)(C#N)\N=N\C(C)(C#N)CC(C)C WYGWHHGCAGTUCH-ISLYRVAYSA-N 0.000 description 2
- 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 2
- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical class C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 239000001055 blue pigment Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000001056 green pigment Substances 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000001054 red pigment Substances 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- 239000001052 yellow pigment Substances 0.000 description 2
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 description 1
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 description 1
- XKSUVRWJZCEYQQ-UHFFFAOYSA-N 1,1-dimethoxyethylbenzene Chemical compound COC(C)(OC)C1=CC=CC=C1 XKSUVRWJZCEYQQ-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- KTEFLEFPDDQMCB-UHFFFAOYSA-N 1,4-bis(4-butylanilino)-5,8-dihydroxyanthracene-9,10-dione Chemical compound C1=CC(CCCC)=CC=C1NC(C=1C(=O)C2=C(O)C=CC(O)=C2C(=O)C=11)=CC=C1NC1=CC=C(CCCC)C=C1 KTEFLEFPDDQMCB-UHFFFAOYSA-N 0.000 description 1
- OZQQAZPMNWJRDQ-UHFFFAOYSA-N 1,4-dihydroxy-5,8-bis(4-methylanilino)anthracene-9,10-dione Chemical compound C1=CC(C)=CC=C1NC(C=1C(=O)C2=C(O)C=CC(O)=C2C(=O)C=11)=CC=C1NC1=CC=C(C)C=C1 OZQQAZPMNWJRDQ-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 1
- ZIKLJUUTSQYGQI-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxypropoxy)propane Chemical compound CCOCC(C)OCC(C)OCC ZIKLJUUTSQYGQI-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- 125000006023 1-pentenyl group Chemical group 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- GELKGHVAFRCJNA-UHFFFAOYSA-N 2,2-Dimethyloxirane Chemical compound CC1(C)CO1 GELKGHVAFRCJNA-UHFFFAOYSA-N 0.000 description 1
- PASIEQDVKZQWRI-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol 3-hydroxy-2,2-dimethylpropanoic acid prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OCC(C)(C)CO.OCC(C)(C)C(O)=O PASIEQDVKZQWRI-UHFFFAOYSA-N 0.000 description 1
- BRKORVYTKKLNKX-UHFFFAOYSA-N 2,4-di(propan-2-yl)thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC(C(C)C)=C3SC2=C1 BRKORVYTKKLNKX-UHFFFAOYSA-N 0.000 description 1
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- DRLRGHZJOQGQEC-UHFFFAOYSA-N 2-(2-methoxypropoxy)propyl acetate Chemical compound COC(C)COC(C)COC(C)=O DRLRGHZJOQGQEC-UHFFFAOYSA-N 0.000 description 1
- PUBNJSZGANKUGX-UHFFFAOYSA-N 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=C(C)C=C1 PUBNJSZGANKUGX-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- HEQOJEGTZCTHCF-UHFFFAOYSA-N 2-amino-1-phenylethanone Chemical class NCC(=O)C1=CC=CC=C1 HEQOJEGTZCTHCF-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- WHNBDXQTMPYBAT-UHFFFAOYSA-N 2-butyloxirane Chemical compound CCCCC1CO1 WHNBDXQTMPYBAT-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- 125000006024 2-pentenyl group Chemical group 0.000 description 1
- UMWZLYTVXQBTTE-UHFFFAOYSA-N 2-pentylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(CCCCC)=CC=C3C(=O)C2=C1 UMWZLYTVXQBTTE-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- SYURNNNQIFDVCA-UHFFFAOYSA-N 2-propyloxirane Chemical compound CCCC1CO1 SYURNNNQIFDVCA-UHFFFAOYSA-N 0.000 description 1
- YTPSFXZMJKMUJE-UHFFFAOYSA-N 2-tert-butylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)(C)C)=CC=C3C(=O)C2=C1 YTPSFXZMJKMUJE-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- 125000006027 3-methyl-1-butenyl group Chemical group 0.000 description 1
- UHMARZNHEMRXQH-UHFFFAOYSA-N 3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1=CCCC2C(=O)OC(=O)C21 UHMARZNHEMRXQH-UHFFFAOYSA-N 0.000 description 1
- PBEHQFUSQJKBAS-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;phenol Chemical compound OC1=CC=CC=C1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 PBEHQFUSQJKBAS-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 206010047571 Visual impairment Diseases 0.000 description 1
- LFOXEOLGJPJZAA-UHFFFAOYSA-N [(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphoryl]-(2,6-dimethoxyphenyl)methanone Chemical compound COC1=CC=CC(OC)=C1C(=O)P(=O)(CC(C)CC(C)(C)C)C(=O)C1=C(OC)C=CC=C1OC LFOXEOLGJPJZAA-UHFFFAOYSA-N 0.000 description 1
- VMKBJESZDNXQHG-UHFFFAOYSA-N [(9-oxothioxanthen-2-yl)methylideneamino] acetate Chemical compound C1=CC=C2C(=O)C3=CC(C=NOC(=O)C)=CC=C3SC2=C1 VMKBJESZDNXQHG-UHFFFAOYSA-N 0.000 description 1
- SEEVRZDUPHZSOX-UHFFFAOYSA-N [1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino] acetate Chemical compound C=1C=C2N(CC)C3=CC=C(C(C)=NOC(C)=O)C=C3C2=CC=1C(=O)C1=CC=CC=C1C SEEVRZDUPHZSOX-UHFFFAOYSA-N 0.000 description 1
- INXWLSDYDXPENO-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CO)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C INXWLSDYDXPENO-UHFFFAOYSA-N 0.000 description 1
- SSOONFBDIYMPEU-UHFFFAOYSA-N [3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propyl] prop-2-enoate Chemical class OCC(CO)(CO)COCC(CO)(CO)COC(=O)C=C SSOONFBDIYMPEU-UHFFFAOYSA-N 0.000 description 1
- IETYNJBCXVFYIQ-UHFFFAOYSA-N [4-(2-tert-butylperoxypropan-2-yl)phenyl]-phenylmethanone Chemical compound C1=CC(C(C)(C)OOC(C)(C)C)=CC=C1C(=O)C1=CC=CC=C1 IETYNJBCXVFYIQ-UHFFFAOYSA-N 0.000 description 1
- LOCXTTRLSIDGPS-UHFFFAOYSA-N [[1-oxo-1-(4-phenylsulfanylphenyl)octan-2-ylidene]amino] benzoate Chemical compound C=1C=C(SC=2C=CC=CC=2)C=CC=1C(=O)C(CCCCCC)=NOC(=O)C1=CC=CC=C1 LOCXTTRLSIDGPS-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- MYONAGGJKCJOBT-UHFFFAOYSA-N benzimidazol-2-one Chemical compound C1=CC=CC2=NC(=O)N=C21 MYONAGGJKCJOBT-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- YLNJGHNUXCVDIX-UHFFFAOYSA-N bis(2-methylpropyl) perylene-3,9-dicarboxylate Chemical compound C=12C3=CC=CC2=C(C(=O)OCC(C)C)C=CC=1C1=CC=CC2=C1C3=CC=C2C(=O)OCC(C)C YLNJGHNUXCVDIX-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004976 cyclobutylene group Chemical group 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 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
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000004978 cyclooctylene group Chemical group 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004979 cyclopentylene group Chemical group 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000004980 cyclopropylene group Chemical group 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 235000019239 indanthrene blue RS Nutrition 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([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
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910002055 micronized silica Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 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
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005650 polypropylene glycol diacrylate Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000007639 printing Methods 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
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- TVRGPOFMYCMNRB-UHFFFAOYSA-N quinizarine green ss Chemical compound C1=CC(C)=CC=C1NC(C=1C(=O)C2=CC=CC=C2C(=O)C=11)=CC=C1NC1=CC=C(C)C=C1 TVRGPOFMYCMNRB-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 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
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- MVQLEZWPIWKLBY-UHFFFAOYSA-N tert-butyl 2-benzoylbenzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 MVQLEZWPIWKLBY-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LPSXSORODABQKT-UHFFFAOYSA-N tetrahydrodicyclopentadiene Chemical compound C1C2CCC1C1C2CCC1 LPSXSORODABQKT-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
- Epoxy Resins (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
The present invention relates to a photocurable and thermally curable copolymer which has excellent thermosetting properties even at a relatively low temperature, can be photocured by light irradiation, and has excellent durability, chemical resistance and storage stability by being sufficiently cured, and a photosensitive resin composition, a photosensitive resin film, and a color filter using the same.
Description
Technical Field
Cross Reference to Related Applications
This application claims the benefits of korean patent application No. 10-2017-0149676, filed on 10.11.2017 to the korean intellectual property office, and korean patent application No. 10-2018-0136598, filed on 8.11.8.2018 to the korean intellectual property office, the disclosures of which are incorporated herein by reference in their entirety.
The present invention relates to a photocurable and thermally curable copolymer, a photosensitive resin composition, a photosensitive resin film, and a color filter using the same. More particularly, the present invention relates to such a photocurable and thermally curable copolymer and a photosensitive resin composition, a photosensitive resin film and a color filter using the same: which has excellent heat-curable properties even at relatively low temperatures, can be photo-cured by light irradiation, and has excellent durability, chemical resistance and storage stability by being sufficiently cured.
Background
During the color filter manufacturing process, in the case of RGB patterns, the photosensitive resin composition is mainly coated using a spin coater or a slit coater, is pre-baked, and is then exposed and developed.
After development, a post-baking process of applying heat of 220 ℃ or more is finally performed, and although glass generally used does not deform at this temperature, plastics used in flexible displays are severely deformed at temperatures above 220 ℃.
In order to reduce such deformation of the substrate, a method of reducing the temperature of the post-baking process is used, but when the temperature of the post-baking process is reduced, the photosensitive resin composition may not be completely cured, and thus the amount of generated gas may increase, afterimages may occur, and chemical resistance and heat resistance may be deteriorated.
Therefore, there is a need to develop a material and a photosensitive resin composition that can be cured to a high level even at low temperatures and thus can form a cured film having excellent heat resistance and chemical resistance.
Disclosure of Invention
Technical problem
An object of the present invention is to provide a photocurable and thermally curable copolymer which has excellent thermosetting properties even at a relatively low temperature, can be photocured by light irradiation, and has excellent durability, chemical resistance, and storage stability by being sufficiently cured.
It is another object of the present invention to provide a photosensitive resin composition, a photosensitive resin film and a color filter using the photocurable and thermally curable copolymer.
Technical scheme
Provided is a photocurable and thermally curable copolymer comprising: a first (meth) acrylate repeating unit in which an organic functional group containing an epoxy group is bonded to the end of a branch chain; and a second (meth) acrylate repeating unit in which an organic functional group having an alkenyl group is bonded to a terminal of a branch, wherein in the second (meth) acrylate repeating unit, the branch includes: a hydroxy-substituted C1-20 alkyl ester group; a hydroxy-substituted C1-20 oxyalkyl ester group; an alkyl ester group substituted with a C3-30 cycloalkyl group substituted with a hydroxyl group; a C7-30 polycycloalkyl ester group substituted by hydroxyl; or an alkyl ester group substituted with a hydroxyl-substituted C7-30 polycyclic alkoxy group.
Also provided is a photosensitive resin composition comprising: a photocurable and thermally curable copolymer; a photopolymerizable monomer having two or more photocurable unsaturated functional groups; and a photoinitiator.
Also provided is a method for producing a photosensitive resin film, comprising the steps of: 1) applying a photosensitive resin composition on a substrate to form a coating layer; 2) drying the coating; 3) irradiating light to the dried coating layer to perform photocuring; and 4) thermally curing the photo-cured film at 50 ℃ to 250 ℃.
Also provided is a photosensitive resin film comprising: a photocurable and thermally curable copolymer and a cured product of a photopolymerizable monomer having two or more photocurable unsaturated functional groups.
A color filter including the photosensitive resin film is also provided.
Throughout the specification, when a portion "includes" one constituent element, it does not exclude another constituent element unless specifically described to the contrary, but it may also include another constituent element.
The term "substituted" means that an additional functional group is bonded instead of a hydrogen atom in a compound, and the position of the substituted hydrogen atom is not limited as long as it is a position where a substituent may be substituted, and when substituted with two or more substituents, the two or more substituents may be the same as or different from each other.
SymbolOr
Means a bond to another substituent, and a direct bond means that there is no separate atom present at the moiety represented by L.
The term "(meth) acryl" means acryl or methacryl.
The weight average molecular weight means a weight average molecular weight as measured by a GPC method in terms of polystyrene standards. During the process of measuring the weight average molecular weight converted to polystyrene standards by the GPC method, a commonly known analyzer, detector (e.g., refractive index detector) and analytical column may be used, and commonly applied temperature conditions, solvents and flow rates may be applied. For example, a sample having a concentration of 10mg/10mL is prepared at a flow rate of 1 mL/min using 1,2, 4-trichlorobenzene as a solvent at an evaluation temperature of 160 ℃ using a Waters PL-GPC220 instrument with a Polymer laboratory gel MIX-B300 mm length column, and then injected in an amount of 200. mu.L, and the molecular weight can be obtained using a calibration curve formed using polystyrene standards. As polystyrene standard products, 9 products having a molecular weight of 2000/10,000/30,000/70,000/200,000/700,000/2,000,000/4,000,000/10,000,000 were used.
Throughout the specification, an alkyl group is a linear, branched or cyclic monovalent functional group derived from an alkane, and for example, the alkyl group may be a methyl group, an ethyl group, a propyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, or the like. One or more hydrogen atoms contained in the alkyl group may be substituted with other substituent groups, and examples of the substituent groups may include C1-10 alkyl groups, C2-10 alkenyl groups, C2-10 alkynyl groups, C6-12 aryl groups, C2-12 heteroaryl groups, C6-12 arylalkyl groups, halogen atoms, cyano groups, amino groups, amidino groups, nitro groups, amido groups, carbonyl groups, hydroxyl groups, sulfonyl groups, carbamate groups, C1-10 alkoxy groups, and the like.
Throughout the specification, cycloalkyl groups (although not particularly limited) are monovalent functional groups derived from monocyclic cycloalkane, and examples thereof are not particularly limited, but those having a carbon number of 3 to 60 are preferred, and according to one embodiment, the cycloalkyl group has a carbon number of 3 to 30. According to another embodiment, the carbon number of the cycloalkyl group is from 3 to 20. According to yet another embodiment, the carbon number of the cycloalkyl group is from 3 to 6. Specifically, the cycloalkyl group may include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl and the like, but is not limited thereto.
Throughout the specification, a polycyclic alkyl group (although not particularly limited) is a monovalent functional group derived from a polycyclic cycloalkane, and examples thereof are not particularly limited, but those having a carbon number of 3 to 60 are preferred, and according to one embodiment, a cycloalkyl group has a carbon number of 3 to 30. Specifically, it may include norbornene, 2, 3-trimethylenenorbornane and the like, but is not limited thereto.
Throughout the specification, an aryl group is a monovalent functional group derived from an aromatic hydrocarbon, and it may be monocyclic or polycyclic. Specifically, the monocyclic aryl group may include phenyl, biphenyl, terphenyl, stilbene group and the like, but is not limited thereto. The polycyclic aromatic groups may include naphthyl, anthracenyl, phenanthrenyl, pyrenyl, perylenyl, perylene, and the like,
A phenyl group, a fluorenyl group, and the like, but are not limited thereto. One or more hydrogen atoms of the aryl group may be each substituted with a substituent as in the alkyl group.
Throughout the specification, the alkenyl group may be linear or branched, and the carbon number is not particularly limited, but is preferably 2 to 40. According to one embodiment, the carbon number of the alkenyl group is 2 to 20. According to one embodiment, the carbon number of the alkenyl group is 2 to 10. According to one embodiment, the carbon number of the alkenyl group is 2 to 6. Specific examples thereof may include 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 1, 3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-diphenylvinyl-1-yl, 2-phenyl-2- (naphthalen-1-yl) vinyl-1-yl, 2-bis (diphenyl-1-yl) vinyl-1-yl, stilbenyl, styryl and the like, but are not limited thereto.
Throughout the specification, alkylene is a divalent functional group derived from alkane, and the carbon number is 1 to 20, 1 to 10, or 1 to 5. It may be linear, branched or cyclic, and examples thereof may include methylene, ethylene, propylene, isobutylene, sec-butylene, tert-butylene, pentylene, hexylene and the like. One or more hydrogen atoms contained in the alkylene group may be each substituted with a substituent as in the alkyl group.
Throughout the specification, an oxyalkylene group is a functional group derived from an alkylene group in which an ether group (-O-) is bonded to one end of the alkylene group, and the carbon number is 1 to 20, 1 to 10, or 1 to 5. It may be linear, branched or cyclic, and examples thereof may include oxymethylene, oxyethylene, oxypropylene, n-butylene oxide, isobutylene oxide, sec-butylene oxide, tert-butylene oxide, pentylene oxide, hexylene oxide and the like. One or more hydrogen atoms contained in the oxyalkylene group may be respectively substituted with a substituent as in the alkyl group.
Throughout the specification, cycloalkylene is a divalent functional group derived from cycloalkane, and has a carbon number of 3 to 30, 3 to 20, or 3 to 10. Examples thereof may include, but are not limited to, cyclopropylene, cyclobutylene, cyclopentylene, 3-methylcyclopentylene, 2, 3-dimethylcyclopentylene, cyclohexylene, 3-methylcyclohexylene, 4-methylcyclohexylene, 2, 3-dimethylcyclohexylene, 3,4, 5-trimethylcyclohexylene, 4-tert-butylcyclohexylene, cycloheptylene, cyclooctylene and the like.
Throughout the specification, a polycycloalkylene group is a divalent functional group derived from a polycycloalkane in which one hydrogen atom of the polycycloalkyl group is substituted with a functional group.
Throughout the specification, the carbon number of the carbonyl group is not particularly limited, but it may be preferably 1 to 30. Specifically, it may be a compound of the following structure, but is not limited thereto.
Throughout the specification, in the ester group, the oxygen of the ester group may be substituted with a C1-25 linear, branched or cyclic alkyl group or a polycycloalkyl group. An alkyl-substituted ester group may be referred to as an "alkyl ester group", and an ester group substituted with a polycycloalkyl group may be referred to as a "polycycloalkyl ester group".
Hereinafter, the photocurable and thermally curable copolymer, the photosensitive resin composition using the same, the photosensitive resin film, and the color filter according to the embodiments will be described in detail.
Photocurable and thermally curable copolymers
One embodiment of the present invention provides a photocurable and thermally curable copolymer comprising: a first (meth) acrylate repeating unit in which an organic functional group containing an epoxy group is bonded to the end of a branch chain; and a second (meth) acrylate repeating unit in which an organic functional group having an alkenyl group is bonded to a terminal of a branch, wherein in the second (meth) acrylate repeating unit, the branch includes: a hydroxy-substituted C1-20 alkyl ester group; an alkyl ester group substituted with a C3-30 cycloalkyl group substituted with a hydroxyl group; a C7-30 polycycloalkyl ester group substituted by hydroxyl; or an alkyl ester group substituted with a hydroxyl-substituted C7-30 polycyclic alkoxy group.
The present inventors have determined that, in the case of the photocurable and thermally curable copolymer comprising two or more repeating units as described above, the organic functional group containing an alkenyl group contained in the second (meth) acrylate repeating unit can be photocured by light irradiation to form a primary cured structure, the organic functional group containing an epoxy group contained in the first (meth) acrylate repeating unit can be formed into a secondary cured structure by thermal curing even at a low temperature of less than 200 ℃, and thus, sufficient curing can be performed by thermal curing and photocuring even at a low temperature. It was also confirmed through experiments that the finally cured film thus obtained may have excellent durability and chemical resistance, and the photosensitive resin composition before curing may also have excellent storage stability, and the present invention was completed.
Specifically, the photocurable and thermally curable copolymer may include a first (meth) acrylate repeating unit in which an organic functional group containing an epoxy group is bonded to the end of a branch. By including the first (meth) acrylate repeating unit, a dense cured structure can be formed via an epoxy group included in the first (meth) acrylate repeating unit by thermal curing even at a low temperature of less than 200 ℃.
In the first (meth) acrylate repeating unit, a chain formed by polymerization of a double bond contained in the (meth) acrylate is referred to as a main chain, and a chain that grows out from the main chain in a branched form is referred to as a branch or a side chain.
The (meth) acrylate repeating unit is a repeating unit included in a homopolymer of the (meth) acrylate monomer, and it may include a polyethylene chain formed by polymerization of a vinyl group included in the (meth) acrylate monomer as a main chain, and an ester functional group included in the (meth) acrylate monomer as a branch chain. That is, in the first (meth) acrylate repeating unit, the end of the branch to which the organic functional group containing an epoxy group is bonded means the end of the ester functional group included in the (meth) acrylate repeating unit.
In the first (meth) acrylate repeating unit, the branch may include any one of: carbonyl (-CO-); c1-20 alkyl ester group (R 'COO-: R' is C1-20 alkyl); or a C1-20 oxyalkyl ester group, and an organic functional group containing an epoxy group may be bonded to a C1-20 alkyl group or a carbonyl group included in the C1-20 alkyl ester group.
The organic functional group containing an epoxy group may include a functional group composed of only an epoxy group or a functional group in which an epoxy group is bonded to other functional groups, and specifically, it may be any one of a functional group represented by the following chemical formula 1, a functional group represented by the following chemical formula 2, and a functional group represented by the following chemical formula 3.
[ chemical formula 1]
In chemical formula 1, R1、R2And R3May each independently be a direct bond, hydrogen, or C1-5 alkyl, and preferably, R is1、R2And R3All may be hydrogen.
[ chemical formula 2]
In chemical formula 2, R4And R5May each independently be a direct bond or C1-5 alkylene, and preferably, R4May be methylene, and R5May be an ethylene group.
[ chemical formula 3]
In chemical formula 3, R6And R7Each independently is a direct bond, hydrogen, or C1-5 alkylene, and X is a direct bond, -O-, or-S-.
Specifically, the first (meth) acrylate repeating unit may be represented by the following chemical formula 4.
[ chemical formula 4]
In chemical formula 4, R8To R10Each independently hydrogen or C1-10 alkyl; l is1Is a direct bond, C1-20 alkylene, or C1-20 oxyalkylene; and R11Is an organic functional group containing an epoxy group.
Preferably, in chemical formula 4, R8And R10Each independently is hydrogen, R7Is C1-3 alkyl, L1Is a direct bond or C1-3 alkylene, and R11Is a functional group represented by chemical formula 1, a functional group represented by chemical formula 2, or a functional group represented by chemical formula 3.
More preferably, in chemical formula 4, L1May be a direct bond, and R11May be a functional group represented by chemical formula 3. Further, in chemical formula 4, L1May be C1-3 alkylene, and R11May be a functional group represented by chemical formula 1, a functional group represented by chemical formula 2, or a functional group represented by chemical formula 3.
Specifically, examples of the first (meth) acrylate repeating unit represented by chemical formula 4 may include the following chemical formula 4-1 derived from glycidyl methacrylate, the following chemical formula 4-2 derived from 3, 4-epoxycyclohexylmethyl methacrylate, the following chemical formula 4-3 derived from chemical formula a of the following synthesis example 3, and the following chemical formula 4-4 derived from chemical formula B of the following synthesis example 4.
[ chemical formula 4-1]
[ chemical formula 4-2]
[ chemical formulas 4-3]
[ chemical formulas 4-4]
The photocurable and thermally curable copolymer may include a second (meth) acrylate repeating unit in which an organic functional group having an alkenyl group is bonded to the end of the branch. By including the second (meth) acrylate repeating unit, photocuring can be performed through the alkenyl group included in the second (meth) acrylate repeating unit by light irradiation, thereby forming a dense cured structure.
In the second (meth) acrylate repeating unit, a chain formed by polymerization of a double bond contained in the (meth) acrylate is referred to as a main chain, and a chain that grows out from the main chain in a branched form is referred to as a branch or a side chain.
The (meth) acrylate repeating unit is a repeating unit included in a homopolymer of the (meth) acrylate monomer, and it may include a polyethylene chain formed by polymerization of a vinyl group included in the (meth) acrylate monomer as a main chain, and an ester functional group included in the (meth) acrylate monomer as a branch chain. That is, in the second (meth) acrylate repeating unit, the end of the branch to which the organic functional group having an alkenyl group is bonded means the end of the ester functional group included in the (meth) acrylate repeating unit.
In the second (meth) acrylate repeating unit, the branched chain may include a C1-20 or C1-10 alkyl ester group substituted with a hydroxyl group (R 'COO-: R' is a C1-10 alkyl group), a C1-20 oxyalkyl ester group substituted with a hydroxyl group, an alkyl ester group substituted with a C3-30 or C3-10 cycloalkyl group substituted with a hydroxyl group, a C7-30 or C8-15 polycycloalkyl ester group substituted with a hydroxyl group, or an alkyl ester group substituted with a C7-30 or C8-15 polycycloalkoxy group substituted with a hydroxyl group.
Specifically, an organic functional group having an alkenyl group may be substituted at the end of the C1-20 alkyl group included in the C1-20 alkyl ester group substituted with a hydroxyl group, or the C3-30 cycloalkyl group included in the alkyl ester group substituted with the C3-30 cycloalkyl group substituted with a hydroxyl group.
Further, in the hydroxyl-substituted C7-30 polycycloalkyl ester group, an organic functional group containing an alkenyl group may be substituted at the terminal of the C7-30 polycycloalkyl group included in the C7-30 polycycloalkyl ester group.
Further, in the alkyl ester group substituted with the C7-30 polycycloalkoxy group substituted with a hydroxyl group, an organic functional group having an alkenyl group may be substituted at the terminal of the C7-30 polycycloalkyl group included in the C7-30 polycycloalkoxy group.
Meanwhile, the hydroxyl group may be substituted as a branch at the C1-10 alkyl group included in the C1-20 alkyl ester group, at the C3-30 cycloalkyl group, at the C10-30 polycycloalkyl group included in the C10-30 polycycloalkyl ester group, or at the C10-30 polycycloalkyl group included in the C10-30 polycycloalkoxy group.
The hydroxyl group may be generated by a ring-opening reaction of an epoxy group included in the first (meth) acrylate repeating unit, and more specifically, it may be generated by a reaction between an epoxy group included in the first (meth) acrylate repeating unit and a compound including an organic functional group including an alkenyl group.
The organic functional group containing an alkenyl group may include a functional group composed of only an alkenyl group and a functional group in which an alkenyl group is bonded to other organic functional groups, and specifically, a (meth) acryloyl group, a (meth) acryloyloxy group, or the like may be used, and preferably, a (meth) acryloyloxy group may be used.
Specifically, the second (meth) acrylate repeating unit may be represented by the following chemical formula 5.
[ chemical formula 5]
In chemical formula 5, R12To R14Each independently hydrogen or C1-10 alkyl; l is2Is a direct bond, C1-20 alkylene, or C1-20 oxyalkylene; l is3Is a hydroxy-substituted C1-20 alkylene group, a hydroxy-substituted C3-30 cycloalkylene group, or a hydroxy-substituted C7-30 polycycloalkylene group; and R15Is an organic functional group containing an alkenyl group.
Preferably, in chemical formula 5, R12And R14Each independently is hydrogen; each R is13Independently is a C1-3 alkyl group; l is2Is a direct bond, C1-10 alkylene or C1-10 oxyalkylene; and L3Is a hydroxyl-substituted C1-5 alkylene group, a hydroxyl-substituted C3-10 cycloalkylene group, or a hydroxyl-substituted C8-15 polycycloalkylene group.
More specifically, in chemical formula 5, L2May be a direct bond, and L3May be a hydroxyl-substituted C10-20 polycyclic alkylene group. Further, in chemical formula 5, L2May be C1-10 alkylene or C1-10 oxyalkylene, and L3May be a hydroxyl-substituted C1-5 alkylene group, a hydroxyl-substituted C3-10 cycloalkylene group, or a hydroxyl-substituted C8-15 polycycloalkylene group.
Specifically, examples of the second (meth) acrylate repeating unit represented by chemical formula 5 may include the following chemical formulae 5-1 to 5-4, which may be prepared by reacting an epoxy group at the terminal of the above chemical formulae 4-1 to 4-4 with (meth) acrylic acid.
[ chemical formula 5-1]
[ chemical formula 5-2]
[ chemical formulas 5-3]
[ chemical formulas 5-4]
The molar ratio of the first (meth) acrylate repeating unit to the second (meth) acrylate repeating unit may be from 99:1 to 1: 99. In this way, since the photocurable and thermally curable copolymer includes both the first (meth) acrylate repeating unit and the second (meth) acrylate repeating unit, it can achieve both photocurability and low-temperature thermosettability.
Preferably, the second (meth) acrylate repeating unit may be included in a ratio of 10 to 90 moles, 20 to 70 moles, or 30 to 50 moles, based on 100 moles of the first (meth) acrylate repeating unit. If the content of the second (meth) acrylate repeating unit is excessively reduced to less than 10 moles based on 100 moles of the first (meth) acrylate repeating unit, a residual problem may be generated in the synthesized copolymer.
In contrast, if the content of the second (meth) acrylate repeating unit is increased to more than 90 moles based on 100 moles of the first (meth) acrylate repeating unit, dyeing characteristics and chemical resistance of the synthesized copolymer may be deteriorated.
Meanwhile, the photocurable and thermally curable copolymer may further include one or more repeating units selected from the group consisting of: a third (meth) acrylate repeating unit represented by the following chemical formula 6, a maleimide repeating unit represented by the following chemical formula 7, and a vinyl repeating unit represented by the following chemical formula 8. Thus, the heat resistance and chemical resistance of the photocurable and thermally curable copolymer can be improved.
[ chemical formula 6]
[ chemical formula 7]
[ chemical formula 8]
In the chemical formulae 6 to 8,
R16to R26Each independently is hydrogen; deuterium; a halogen group; c1-20 alkyl; c1-20 alkoxy; c6-30 monocyclic or polycyclic aryl; c2-20 alkenyl; or C3-30 monocyclic or polycyclic cycloalkyl, and
L4is a direct bond, C1-20 alkylene or C1-20 oxyalkylene.
More specifically, in the third (meth) acrylate repeating unit represented by chemical formula 6, R16And R18May be hydrogen, R17May be methyl, L4May be methylene, and R19May be a phenyl group. That is, the third (meth) acrylate repeating unit may be a repeating unit derived from benzyl methacrylate.
Further, in the maleimide repeating unit represented by chemical formula 7, R20And R21May be hydrogen, and R22May be a phenyl group. In the vinyl repeating unit represented by chemical formula 8, R23、R24And R25May be hydrogen, and R26May be a phenyl group. That is, the maleimide repeating unit represented by chemical formula 7 may be a repeating unit derived from N-phenylmaleimide, and the vinyl repeating unit represented by chemical formula 8 may be a repeating unit derived from styrene.
The molar ratio of the third (meth) acrylate repeating unit to the first (meth) acrylate repeating unit may be 1:99 to 99:1, and the molar ratio of the third (meth) acrylate repeating unit to the second (meth) acrylate repeating unit may be 1:99 to 99: 1. Thus, by using the first (meth) acrylate repeating unit, the second (meth) acrylate repeating unit, and the third (meth) acrylate repeating unit in combination, heat resistance and chemical resistance can be improved.
The weight average molecular weight (measured by GPC) of the photocurable and thermally curable copolymer may be 1000g/mol to 100,000 g/mol.
Meanwhile, the photocurable and thermally curable copolymer may include: a first (meth) acrylate repeating unit in which an organic functional group containing an epoxy group is bonded to the end of a branch chain; a second (meth) acrylate repeating unit in which an organic functional group having an alkenyl group is bonded to the end of the branch chain; a third (meth) acrylate repeating unit represented by chemical formula 6; a maleimide repeating unit represented by chemical formula 7; and a vinyl repeating unit represented by chemical formula 8.
That is, the photocurable and thermally curable copolymer may not further comprise additional repeating units other than the above-mentioned five repeating units. Therefore, it is possible to suppress spontaneous side reactions in the molecule before the photocurable and thermally curable copolymer is cured, thereby ensuring high reliability,
for example, in the case where the photocurable and thermally curable copolymer includes a repeating unit obtained by the reaction of the second (meth) acrylate repeating unit with the acid anhydride as another repeating unit in addition to the above-mentioned five repeating units, a side reaction with the (meth) acryloyl functional group or epoxy group may be performed by a terminal carboxyl group formed through a ring-opening reaction of the acid anhydride, and thus it may be difficult to sufficiently achieve the characteristics of the photocurable and thermally curable copolymer.
The method of synthesizing the photocurable and thermally curable copolymer is not particularly limited, but, for example, it may be prepared by polymerizing a monomer mixture comprising a (meth) acrylate monomer substituted at the end with an epoxy-containing organic functional group, and then reacting it with a compound comprising an alkenyl-containing organic functional group. Examples of the (meth) acrylate monomer substituted at the terminal with an organic functional group containing an epoxy group may include glycidyl methacrylate, 3, 4-epoxycyclohexylmethyl methacrylate, the following chemical formulae 4 to 3 derived from chemical formula a of the following synthesis example 3, the following chemical formulae 4 to 4 derived from chemical formula B of the following synthesis example 4, and the like, and examples of the compound including an organic functional group containing an alkenyl group may include methacrylic acid. In addition, benzyl methacrylate, N-phenylmaleimide or styrene may be added as other monomers used in the synthesis of the copolymer in the monomer mixture.
Photosensitive resin composition
Another embodiment of the present invention provides a photosensitive resin composition comprising the photocurable and thermally curable copolymer of one embodiment; a photopolymerizable monomer having two or more photocurable unsaturated functional groups; and a photoinitiator.
The details of the photocurable and thermally curable copolymer are as set forth above in one embodiment.
The photopolymerizable monomers may be compounds having two or more photocurable unsaturated functional groups (e.g., polyfunctional vinyl groups, etc.), and they may form crosslinks with the unsaturated functional groups of the above photocurable and thermally curable copolymers, thereby forming a crosslinked structure by photocuring upon exposure to light. Therefore, when forming a pattern film described below, the photosensitive resin composition at the exposed region may not be developed by an alkali, but may remain on the substrate.
As such photopolymerizable monomers, those which are liquid at room temperature may be used, whereby the viscosity of the photosensitive resin composition may be controlled according to the coating method, or the alkali developability of the unexposed area may also be improved.
As the photopolymerizable monomer, an acrylate-based compound having two or more photocurable unsaturated functional groups may be used, and more specifically, one or more compounds selected from the group consisting of: hydroxyl group-containing acrylate-based compounds such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and the like; water-soluble acrylate-based compounds such as polyethylene glycol diacrylate, polypropylene glycol diacrylate, and the like; polyhydric alcohol-based polyfunctional polyester acrylate compounds such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and the like; acrylate-based compounds of ethylene oxide addition products and/or propylene oxide addition products of polyfunctional alcohols (e.g., trimethylolpropane, hydrogenated bisphenol a, etc.) or polyhydric phenols (e.g., bisphenol a, biphenol, etc.); a polyfunctional or monofunctional urethane acrylate-based compound which is an isocyanate-modified hydroxyl group-containing acrylate; an epoxy acrylate-based compound which is a (meth) acrylic acid addition product of bisphenol a diglycidyl ether, hydrogenated bisphenol a diglycidyl ether, or a phenol novolac epoxy resin; caprolactone-modified acrylate-based compounds such as caprolactone-modified ditrimethylolpropane tetraacrylate, epsilon-caprolactone-modified dipentaerythritol acrylate, caprolactone-modified neopentyl glycol hydroxypivalate diacrylate and the like; and photosensitive (meth) acrylate compounds such as methacrylate-based compounds corresponding to the above-mentioned acrylate-based compounds.
Among them, as the photopolymerizable monomer, a polyfunctional (meth) acrylate-based compound having two or more (meth) acryloyl groups in one molecule may be preferably used, and in particular, pentaerythritol triacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, caprolactone-modified ditrimethylolpropane tetraacrylate, or the like may be suitably used. Examples of commercially available photopolymerizable monomers may include DPEA-12 from Kayarad, and the like.
The photopolymerizable monomer may be contained in an amount of 0.1 to 30 wt%, or 1 to 20 wt%, based on the total weight of the photosensitive resin composition. If the content of the photopolymerizable monomer is excessively reduced, photocuring may be insufficient; and if it is excessively increased, the dryness of the cured film may be deteriorated and the characteristics may be deteriorated.
Meanwhile, for example, a photoinitiator is used to initiate radical photocuring between the photocurable and thermally curable copolymer and the photopolymerizable monomer in the exposed region of the photosensitive resin composition.
Conventionally known photoinitiators may be used, and in particular, benzoin and alkyl ethers thereof, such as benzoin, benzoin methyl ether, benzoin ethyl ether, and the like; acetophenones such as acetophenone, 2-dimethoxy-2-phenylacetophenone, 1-dichloroacetophenone, 4- (1-tert-butyldioxy-1-methylethyl) acetophenone and the like; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, and the like; thioxanthones such as 2, 4-dimethylthioxanthone, 2, 4-diisopropylthioxanthone, 2-chlorothioxanthone, etc.; ketals such as acetophenone dimethyl ketal, benzyl dimethyl ketal, and the like; benzophenones such as benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone, 3',4,4' -tetrakis (t-butyldioxycarbonyl) benzophenone and the like.
As preferred photoinitiators, mention may be made of 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinoacetone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone; α -aminoacetophenones, such as N, N-dimethylammoniophenone (e.g., commercial products, Irgacure (registered trademark) 907, Irgacure369, Irgacure379, etc. by Ciba Specialty Chemicals (now Ciba Japan Company)); acylphosphine oxides such as 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethyl-pentylphosphine oxide (commercial products, Lucirin (registered trademark) TPO from BASF corporation and Irgacure 819 from Ciba specialty chemicals, etc.).
In addition, preferred photoinitiators may include oxime esters. Specific examples of the oxime ester may include 2- (acetoxyiminomethyl) thioxanthen-9-one, (1, 2-octanedione, 1- [4- (phenylthio) phenyl ] -,2- (O-benzoyl oxime)), (ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (O-acetyloxime)), and the like. As commercial products, there may be mentioned GGI-325, Irgacure OXE01, Irgacure OXE02 from Ciba Specialty Chemicals; n-1919 from the ADEKA Company; darocur TPO from Ciba Specialty Chemicals, and the like.
The photoinitiator may be contained in an amount of 0.1 to 20 wt%, or 1 to 10 wt%, based on the total weight of the resin composition. If the content of the photoinitiator is too low, photocuring may not be properly achieved; in contrast, if the content of the photoinitiator is too high, the solubility (resolution) of the photosensitive resin composition may be deteriorated, or the reliability of the pattern film may be insufficient.
The photosensitive resin composition may further include one or more selected from the group consisting of a solvent, a filler, a pigment, and an additive.
The added filler is used to improve heat resistance and stability, dimensional stability against heat, and adhesion of the resin. In addition, it is used as an extender pigment by enhancing color. As the filler, inorganic or organic fillers may be used, and for example, barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide (alumina), aluminum hydroxide, mica, or the like may be used.
The pigment exhibits visibility and hiding power, and as the pigment, a red pigment, a blue pigment, a green pigment, a yellow pigment, a black pigment, and the like can be used. As the blue pigment, phthalocyanine blue, pigment blue 15:1, pigment blue 15:2, pigment blue 15:3, pigment blue 15:4, pigment blue 15:6, pigment blue 60, and the like can be used. As the green pigment, pigment green 7, pigment green 36, solvent green 3, solvent green 5, solvent green 20, solvent green 28, and the like can be used. As the yellow pigment, anthraquinone-based, isoindolinone-based, fused azo-based, benzimidazolone-based, and the like can be used, and for example, pigment yellow 108, pigment yellow 147, pigment yellow 151, pigment yellow 166, pigment yellow 181, pigment yellow 193, and the like can be used. As the red pigment, pigment red 254 or the like can be used.
The content of the pigment may preferably be 0.1 to 10% by weight, or 0.5 to 5% by weight, based on the total weight of the resin composition.
Additives may be added to remove air bubbles of the resin composition to remove projections or depressions on the surface during film coating to provide flame retardancy, to control viscosity, to serve as a catalyst, and the like.
Specifically, known additives commonly used, for example, thickeners such as micronized silica, organic bentonite, montmorillonite and the like; defoamers and/or leveling agents, such as those based on silicone, fluorine, polymers, and the like; silane coupling agents such as imidazole-based, thiazole-based, triazole-based, and the like; and flame retardants such as phosphorus flame retardants, antimony-based flame retardants, and the like.
Among them, the leveling agent functions to remove projections or depressions on the surface during film coating, and for example, BYK-380N, BYK-307, BYK-378, BYK-350, and the like from BYK-Chemie GmbH can be used.
The content of the additive may preferably be 0.01 to 10% by weight, based on the total weight of the resin composition.
The solvent may be used in combination with one or more solvents in order to dissolve the resin composition or to provide a suitable viscosity.
As the solvent, ketones such as methyl ethyl ketone, cyclohexanone, and the like; aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, etc.; glycol ethers (cellosolves) such as ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, and the like; acetates such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and the like; alcohols such as ethanol, propanol, ethylene glycol, propylene glycol, carbitol, and the like; aliphatic hydrocarbons such as octane, decane, etc.; petroleum-based solvents such as petroleum ether, naphtha, hydrogenated naphtha, solvent naphtha, and the like; and amides such as dimethylacetamide, Dimethylformamide (DMF), and the like. These solvents may be used alone or in a combination of two or more.
The solvent may be contained in an amount of 5 to 50 wt% based on the total weight of the resin composition. If the content is less than 5% by weight, coatability may be reduced due to high viscosity; whereas if the content is more than 50% by weight, the resin composition may not be dried well, thereby increasing tackiness.
The photosensitive resin composition may further include an acid-modified oligomer or a thermosetting binder as needed, and as the acid-modified oligomer and the thermosetting binder, various compounds, oligomers, or polymers well known in the art of photosensitive resin compositions may be used without limitation.
III. photosensitive resin film
Yet another embodiment of the present invention provides a photosensitive resin film comprising: the photocurable and thermally curable copolymer of one embodiment and the cured product of the photopolymerizable monomer having two or more photocurable unsaturated functional groups.
The photosensitive resin film may be a single film that does not include a pattern or may include a pattern film that includes a pattern formed by exposure.
The photosensitive resin film may be prepared by a method of preparing a photosensitive resin film, the method comprising the steps of: 1) applying another embodiment of the photosensitive resin composition to a substrate to form a coating layer; 2) drying the coating; 3) irradiating light to the dried coating layer to perform photocuring; and 4) thermally curing the photocured coating at 50 ℃ to 250 ℃.
In the step of applying a photosensitive resin composition of another embodiment to a substrate to form a coating layer (step 1), the photosensitive resin composition is as described above in another embodiment.
The method of coating the photosensitive resin composition on the substrate is not particularly limited, and for example, screen printing, offset printing, flexo printing, inkjet printing, and the like may be used.
In addition, the photosensitive resin composition may be formed by dissolving or dispersing the photocurable and thermally curable copolymer of one embodiment, the photopolymerizable monomer having two or more photocurable unsaturated functional groups, and the photoinitiator in an organic solvent.
The step of drying the coating layer (step 2) is to remove the solvent and the like used in the photosensitive resin composition, and for example, a method of heating the coating layer or vacuum evaporation may be used. The drying may be preferably performed at 50 ℃ to 130 ℃, more preferably 70 ℃ to 120 ℃.
The step of irradiating light to the dried coating layer for photocuring (step 3) is a step of irradiating light to the coating layer dried in step 2 for curing. As described above, the organic functional group having an alkenyl group in the second (meth) acrylate repeating unit included in the photocurable and thermally curable copolymer of one embodiment may be photocured by light irradiation to form a cured structure.
In the step of irradiating light to be photocured, exposure is performed with light (UV or the like) in a specific wavelength range. The exposure may be performed by selective exposure with a photomask or direct pattern exposure with a laser direct stepper. The exposure amount varies depending on the thickness of the coating layer, but is preferably 0.1mJ/cm2To 1000mJ/cm2。
After the step of irradiating light to the dried coating layer for photocuring (step 3), a step of developing using an alkaline solution or the like may be performed as necessary. As the alkaline solution, an alkaline aqueous solution of potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amine, or the like can be used. By development, only the film of the exposed region may remain.
That is, if exposure is performed, for example, photocuring occurs at the exposed region to form a cross-link between the photocurable and thermally curable copolymer and an unsaturated functional group contained in the photopolymerizable monomer, and thus, it may not be removed by subsequent development.
The step of thermally curing the photo-cured coating at 50 to 250 ℃ (step 4) is a step of thermally treating the photo-cured coating in step 3 at a low temperature. The temperature of the low-temperature heat treatment is preferably 200 ℃ or less. Preferably, the temperature of the low temperature heat treatment is 50 ℃ to 250 ℃, more preferably 70 ℃ to 150 ℃, or 80 ℃ to 120 ℃. Here, the means for heat treatment is not particularly limited, and it may be performed by a heating means (e.g., a hot plate, a hot air circulation reactor, an infrared furnace, etc.).
As described above, the organic functional group containing an epoxy group in the first (meth) acrylate repeating unit included in the photocurable and thermally curable copolymer of one embodiment may be thermally cured by heat treatment to form a cured structure.
When the photosensitive resin film is photocured and thermally cured by the above-described method, it may include a cured product of the photocurable and thermally curable copolymer of one embodiment and a photopolymerizable monomer having two or more photocurable unsaturated functional groups. More specifically, the cured product may include a crosslinked structure in which the epoxy group and the heat-curable functional group of the photo-curable and heat-curable copolymer are crosslinked by heat curing, and a crosslinked structure in which the alkenyl group of the first (meth) acrylate repeating unit and the unsaturated functional group of the photo-polymerizable monomer are crosslinked with each other by photo-curing.
In addition, the photosensitive resin film may further contain a small amount of a photoinitiator remaining after participating in photocuring or a pigment or an additive dispersed in the cured product added as needed.
The thickness of the photosensitive resin film is not particularly limited, but, for example, it can be freely controlled in the range of 0.01 μm to 1000 μm. The measured characteristics in the photosensitive resin film may vary up to a specific value if the thickness of the photosensitive resin film is increased or decreased by a specific value.
IV color filter
Still another embodiment of the present invention provides a color filter including the photosensitive resin film of another embodiment.
The details of the photosensitive resin film are as described above in another embodiment. The photosensitive resin film used in the color filter may contain a pigment dispersed in the cured product.
Various technical configurations known in the field of color filters can be applied without limitation to the details of the color filters.
Advantageous effects
According to the present invention, there are provided a photocurable and thermally curable copolymer which has excellent thermosetting properties even at a relatively low temperature, can be photocured by light irradiation, and has excellent durability, chemical resistance and storage stability by being sufficiently cured, and a photosensitive resin composition, a photosensitive resin film and a color filter using the same.
Detailed Description
Hereinafter, the present invention will be described in detail in the following examples. However, these examples are presented only as illustrations of the present invention, and the scope of the present invention is not limited thereto.
< synthesis example: synthesis of photocurable and thermally curable copolymer >
Synthesis example 1
To the reaction vessel were placed 5.1 wt% of benzyl methacrylate, 0.8 wt% of N-phenylmaleimide, 0.6 wt% of styrene, 13.2 wt% of glycidyl methacrylate, and 78.9 wt% of Propylene Glycol Methyl Ether Acetate (PGMEA) solvent to dissolve them, and then the temperature of the solution was raised to 75 ℃ under a nitrogen atmosphere. When the temperature of the reactants reached 75 ℃, 1.2 wt% of thermal initiator V-65 was added and then the reactants were allowed to react for 12 hours. To the obtained resin solution were added a thermal polymerization inhibitor and a catalyst, then 0.1 wt% of methacrylic acid was introduced under an air atmosphere, and the reactants were reacted for 16 hours while maintaining the temperature at 120 ℃. The weight average molecular weight of the prepared photocurable and thermally curable copolymer was 4500g/mol, the content of the (meth) acrylate repeating unit substituted with an epoxy group at the end of the branch was 49 mol%, and the content of the (meth) acrylate repeating unit substituted with an alkenyl group at the end of the branch was 21 mol%.
Synthesis example 2
A photocurable and thermally curable copolymer was synthesized by the same procedure as in Synthesis example 1, except that 3, 4-epoxycyclohexylmethyl methacrylate was used in place of glycidyl methacrylate. The weight average molecular weight of the prepared photocurable and thermally curable copolymer was 4700g/mol, the content of the (meth) acrylate repeating unit substituted with an epoxy group at the end of the branch was 49 mol%, and the content of the (meth) acrylate repeating unit substituted with an alkenyl group at the end of the branch was 21 mol%.
Synthesis example 3
A photocurable and thermally curable copolymer was synthesized by the same method as in synthesis example 1, except that a compound represented by the following chemical formula a was used instead of glycidyl methacrylate.
[ chemical formula A ]
Synthesis example 4
A photocurable and thermally curable copolymer was synthesized by the same method as in synthesis example 1, except that a compound represented by the following chemical formula B was used instead of glycidyl methacrylate.
[ chemical formula B ]
< comparative Synthesis example >
Comparative Synthesis example 1
To the reaction vessel were placed 9.3 wt% of benzyl methacrylate, 1.5 wt% of N-phenylmaleimide, 1.1 wt% of styrene, 6.8 wt% of glycidyl methacrylate, and 74.6 wt% of Propylene Glycol Methyl Ether Acetate (PGMEA) solvent to dissolve them, and then the temperature of the solution was raised to 65 ℃ under a nitrogen atmosphere. When the temperature of the reactants reached 65 ℃, 0.7% by weight of thermal initiator V-65 was added and then reacted for 12 hours. To the obtained resin solution were added a thermal polymerization inhibitor and a catalyst, then 4.3 wt% of methacrylic acid was introduced under an air atmosphere, and the reactants were reacted for 16 hours while maintaining the temperature at 120 ℃. The temperature of the prepared resin solution was lowered to 90 ℃, and 5.5 wt% of 1,2,5, 6-tetrahydrophthalic anhydride was introduced under an air atmosphere, and the reactants were allowed to react for 24 hours. The weight average molecular weight of the prepared photocurable and thermally curable copolymer was 8100g/mol, the acid value was 83KOH mg/g, the content of the (meth) acrylate repeating unit substituted with an epoxy group at the end of the branch was 0 mol%, and the content of the (meth) acrylate repeating unit substituted with an alkenyl group at the end of the branch was 40 mol%.
< examples and comparative examples: production of photosensitive resin composition and photosensitive resin Pattern film >
Example 1
(1) Photosensitive resin composition
In 35g of Propylene Glycol Methyl Ether Acetate (PGMEA) solvent, 1g of photoinitiator Irgacure369 (manufactured by ciba specialty Chemicals) was stirred and dissolved at room temperature for 30 minutes, then 7.5g of the photocurable and thermally curable copolymer obtained in synthesis example 1 and 5g of dipentaerythritol penta/hexaacrylate (DPHA, manufactured by Nippon Kayaku) as a crosslinkable monomer having an ethylenically unsaturated double bond were introduced, and the reaction mixture was stirred at room temperature for 1 hour, then 50g of a 15% dispersion of c.i. pigment red 254 and 0.2g of an additive were introduced as pigments, and the reaction mixture was stirred at room temperature for 1 hour. The composition obtained by the above reaction is filtered two or more times to remove impurities, thereby preparing a photosensitive resin composition.
(2) Photosensitive resin pattern film
The photosensitive resin composition was coated on a 5cm × 5cm glass substrate at 230rpm, and pre-baked at 100 ℃ for 100 seconds. Thereafter, it was exposed to 40mJ/cm2And developed, and then post-baked at 100 c for 30 minutes, thereby preparing a photosensitive resin pattern film.
Example 2
A photosensitive resin composition and a photosensitive resin pattern film were prepared by the same method as in example 1, except that c.i. pigment green 7 was used instead of c.i. pigment red 254 when the photosensitive resin composition was prepared.
Example 3
A photosensitive resin composition and a photosensitive resin pattern film were prepared by the same method as in example 1, except that c.i. pigment blue 15:6 was used instead of c.i. pigment red 254 when the photosensitive resin composition was prepared.
Example 4
A photosensitive resin composition and a photosensitive resin pattern film were prepared by the same method as in example 1, except that the photocurable and thermally curable copolymer obtained in synthesis example 2 was used instead of the photocurable and thermally curable copolymer obtained in synthesis example 1 when the photosensitive resin composition was prepared.
Example 5
A photosensitive resin composition and a photosensitive resin pattern film were prepared by the same method as in example 2, except that the photocurable and thermally curable copolymer obtained in synthesis example 2 was used instead of the photocurable and thermally curable copolymer obtained in synthesis example 1 when the photosensitive resin composition was prepared.
Example 6
A photosensitive resin composition and a photosensitive resin pattern film were prepared by the same method as in example 3, except that the photocurable and thermally curable copolymer obtained in synthesis example 2 was used instead of the photocurable and thermally curable copolymer obtained in synthesis example 1 when the photosensitive resin composition was prepared.
Example 7
A photosensitive resin composition and a photosensitive resin pattern film were prepared by the same method as in example 1, except that the photocurable and thermally curable copolymer obtained in synthesis example 3 was used instead of the photocurable and thermally curable copolymer obtained in synthesis example 1 when the photosensitive resin composition was prepared.
Example 8
A photosensitive resin composition and a photosensitive resin pattern film were prepared by the same method as in example 1, except that the photocurable and thermally curable copolymer obtained in synthesis example 4 was used instead of the photocurable and thermally curable copolymer obtained in synthesis example 1 when the photosensitive resin composition was prepared.
Comparative example 1
A photosensitive resin composition and a photosensitive resin pattern film were prepared by the same method as in example 1, except that when the photosensitive resin composition was prepared, a thermosetting resin represented by the following chemical formula C (bisphenol-type novolac epoxy resin: KBPN-110 manufactured by Kukdo Chemicals) was used in place of the photocurable and thermally curable copolymer obtained in Synthesis example 1.
[ chemical formula C ]
Comparative example 2
A photosensitive resin composition and a photosensitive resin pattern film were prepared by the same method as in example 2, except that the thermosetting resin used in comparative example 1 was used instead of the photocurable and thermally curable copolymer obtained in synthesis example 1 when preparing the photosensitive resin composition.
Comparative example 3
A photosensitive resin composition and a photosensitive resin pattern film were prepared by the same method as in example 3, except that the thermosetting resin used in comparative example 1 was used instead of the photocurable and thermally curable copolymer obtained in synthesis example 1 when preparing the photosensitive resin composition.
Comparative example 4
A photosensitive resin composition and a photosensitive resin pattern film were prepared by the same method as in example 1, except that the copolymer resin obtained in comparative synthesis example 1 was used instead of the photocurable and thermally curable copolymer obtained in synthesis example 1 when the photosensitive resin composition was prepared.
Comparative example 5
A photosensitive resin composition and a photosensitive resin pattern film were prepared by the same method as in example 2, except that the copolymer resin obtained in comparative synthesis example 1 was used instead of the photocurable and thermally curable copolymer obtained in synthesis example 1 when the photosensitive resin composition was prepared.
Comparative example 6
A photosensitive resin composition and a photosensitive resin pattern film were prepared by the same method as in example 3, except that the copolymer resin obtained in comparative synthesis example 1 was used instead of the photocurable and thermally curable copolymer obtained in synthesis example 1 when the photosensitive resin composition was prepared.
< experimental examples: measurement of characteristics of photosensitive resin compositions and photosensitive resin pattern films obtained in examples and comparative examples >
The characteristics of the photosensitive resin compositions and the photosensitive resin pattern films obtained in examples and comparative examples were measured as follows, and the results are shown in the following table.
1. Experimental example 1: dyeing characteristics
Photosensitive resin compositions containing pigments having a color different from that contained in the photosensitive resin pattern films were coated/developed on the photosensitive resin pattern films obtained in examples and comparative examples, and then, color change was measured as MPCD (minimum perceptual color difference) for the photosensitive resin pattern films, pattern shift and swelling were observed using an optical device, and whether the pigments were dissolved or not was judged according to the following criteria, and the results are shown in table 1 below.
○ pigment is completely insoluble
△ A small amount of dissolution of the pigment was observed.
X: the film was peeled off while the pigment was dissolved.
2. Experimental example 2: chemical resistance
On the photosensitive pattern films obtained in examples and comparative examples, overcoated photoresists were coated/exposed/developed, and then, color changes were measured as MPCD (minimum difference of perceived color) for the photosensitive resin pattern films, pattern shift and swelling were observed using an optical device, whether pigments were dissolved or not was judged according to the following criteria, and the results are shown in table 1 below.
○ pigment is completely insoluble
△ A small amount of dissolution of the pigment was observed.
X: the film was peeled off while the pigment was dissolved.
3. Experimental example 3: storage stability
The photosensitive resin compositions obtained in examples and comparative examples were allowed to stand at room temperature on the day of manufacture and after 2 weeks, and then the development time (seconds) was measured. The results are shown in table 1 below. It can be seen that the smaller the change in development time between the day of manufacture and after 2 weeks, the better the storage stability.
[ Table 1]
Results of the Experimental examples
As shown in table 1, it was confirmed that the photosensitive resin compositions of examples using the photocurable and thermally curable copolymers obtained in the synthesis examples as binder resins had excellent chemical resistance and dyeing properties through subsequent processes even when post-baking was performed at a temperature of 100 ℃, as compared to comparative examples 1 to 3 using general thermosetting resins.
It was also determined that the photosensitive resin compositions of the examples had excellent chemical resistance and dyeing characteristics through subsequent processes even compared to comparative examples 4 to 6 using the resins obtained in comparative synthesis examples that did not include the first (meth) acrylate repeating unit in which an organic functional group containing an epoxy group was bonded to the end of a branch.
Therefore, it was confirmed that the photocurable and thermally curable copolymer obtained in the synthesis example exhibited excellent curability even at low temperature, compared to the existing thermosetting binder resin, and thus, a cured film having excellent heat resistance and chemical resistance could be formed.
Further, it was confirmed that the photosensitive resin compositions of examples can have the same or much better storage stability than the photosensitive resin compositions of comparative examples. Therefore, it was confirmed that the photocurable and thermally curable copolymer obtained in the synthesis example can form sufficient bonds upon curing even compared to the existing thermosetting binder resin, thereby achieving excellent storage stability.
Claims (15)
1. A photocurable and thermally curable copolymer comprising:
a first (meth) acrylate repeating unit in which an organic functional group containing an epoxy group is bonded to the end of a branch chain; and
a second (meth) acrylate repeating unit in which an organic functional group having an alkenyl group is bonded to the end of the branch chain,
wherein in the second (meth) acrylate repeating unit, the branches comprise: a hydroxy-substituted C1-20 alkyl ester group; a hydroxy-substituted C1-20 oxyalkyl ester group; an alkyl ester group substituted with a C3-30 cycloalkyl group substituted with a hydroxyl group; a C7-30 polycycloalkyl ester group substituted by hydroxyl; or an alkyl ester group substituted with a hydroxyl-substituted C7-30 polycyclic alkoxy group.
2. The photocurable and thermally curable copolymer of claim 1, wherein the molar ratio of the first (meth) acrylate repeat unit to the second (meth) acrylate repeat unit is from 1:99 to 99: 1.
3. The photocurable and thermally curable copolymer of claim 1, wherein the photocurable and thermally curable copolymer has a weight average molecular weight (measured by GPC) of from 1000g/mol to 100,000 g/mol.
4. The photocurable and thermally curable copolymer of claim 1, wherein in the first (meth) acrylate repeat unit, the branch comprises a carbonyl group, a C1-20 alkyl ester group, or a C1-20 oxyalkyl ester group.
5. The photocurable and thermally curable copolymer according to claim 1, wherein the organic functional group containing an epoxy group comprises a functional group represented by the following chemical formula 1, a functional group represented by the following chemical formula 2, or a functional group represented by the following chemical formula 3:
[ chemical formula 1]
Wherein, in chemical formula 1, R1、R2And R3Each independently a direct bond, hydrogen, or C1-5 alkyl,
[ chemical formula 2]
Wherein, in chemical formula 2, R4And R5Each independently a direct bond or C1-5 alkylene,
[ chemical formula 3]
Wherein, in chemical formula 3, R6And R7Each independently is a direct bond, hydrogen, or C1-5 alkylene, and X is a direct bond, -O-, or-S-.
6. The photocurable and thermally curable copolymer according to claim 1, wherein the first (meth) acrylate repeating unit is represented by the following chemical formula 4:
[ chemical formula 4]
Wherein, in chemical formula 4,
R8to R10Each independently hydrogen or C1-10 alkyl,
L1is a direct bond, C1-20 alkylene, or C1-20 oxyalkylene, and
R11is an organic functional group containing an epoxy group.
7. The photocurable and thermally curable copolymer according to claim 1, wherein the alkenyl-containing organic functional group comprises a (meth) acryloyl group or a (meth) acryloyloxy group.
8. The photocurable and thermally curable copolymer according to claim 1, wherein the second (meth) acrylate repeating unit is represented by the following chemical formula 5:
[ chemical formula 5]
Wherein, in chemical formula 5,
R12to R14Each independently hydrogen or C1-10 alkyl,
L2is a direct bond, C1-20 alkylene, or C1-20 oxyalkylene,
L3is a hydroxy-substituted C1-20 alkylene group, a hydroxy-substituted C1-20 oxyalkylene group, a hydroxy-substituted C3-30 cycloalkylene group, or a hydroxy-substituted C7-30 polycycloalkylene group, and
R15is an organic functional group containing an alkenyl group.
9. The photocurable and thermally curable copolymer of claim 1, further comprising one or more repeating units selected from the group consisting of:
a third (meth) acrylate repeating unit represented by the following chemical formula 6;
a maleimide repeating unit represented by the following chemical formula 7; and
a vinyl repeating unit represented by the following chemical formula 8:
[ chemical formula 6]
[ chemical formula 7]
[ chemical formula 8]
Wherein, in chemical formulas 6 to 8,
R16to R26Each independently is hydrogen; deuterium; a halogen group; c1-20 alkyl; c1-20 alkoxy; c6-30 monocyclic or polycyclic aryl; c2-20 alkenyl; or C3-30 monocyclic or polycyclic cycloalkyl, and
L4is a direct bond, C1-20 alkylene, or C1-20 oxyalkylene.
10. A photosensitive resin composition comprising:
the photocurable and thermally curable copolymer of claim 1;
a photopolymerizable monomer having two or more photocurable unsaturated functional groups; and
a photoinitiator.
11. The photosensitive resin composition of claim 10, wherein the photopolymerizable monomer comprises an acrylate-based compound having two or more photocurable unsaturated functional groups.
12. The photosensitive resin composition according to claim 10, further comprising a pigment.
13. A method for producing a photosensitive resin film, comprising the steps of:
1) applying the photosensitive resin composition according to claim 10 on a substrate to form a coating layer;
2) drying the coating;
3) irradiating light to the dried coating layer to perform photocuring; and
4) the photocured film is thermally cured at 50 ℃ to 250 ℃.
14. A photosensitive resin film comprising: the cured product of the photo-curable and thermally curable copolymer of claim 1 and a photo-polymerizable monomer having two or more photo-curable unsaturated functional groups.
15. A color filter comprising the photosensitive resin film according to claim 14.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2017-0149676 | 2017-11-10 | ||
| KR20170149676 | 2017-11-10 | ||
| KR1020180136598A KR102118627B1 (en) | 2017-11-10 | 2018-11-08 | Photo-curable and thermo-curable copolymer, and photosensitive resin composition, photosensitive resin film, color filter using the same |
| KR10-2018-0136598 | 2018-11-08 | ||
| PCT/KR2018/013652 WO2019093827A1 (en) | 2017-11-10 | 2018-11-09 | Copolymer having photocurable and thermosetting property, and photosensitive resin composition, photosensitive resin film, and color filter using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110709435A true CN110709435A (en) | 2020-01-17 |
| CN110709435B CN110709435B (en) | 2021-08-24 |
Family
ID=66678453
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201880032826.2A Active CN110709435B (en) | 2017-11-10 | 2018-11-09 | Photocurable and thermally curable copolymer, and photosensitive resin composition, photosensitive resin film and color filter using the same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6911272B2 (en) |
| KR (1) | KR102118627B1 (en) |
| CN (1) | CN110709435B (en) |
| TW (1) | TWI743412B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102420536B1 (en) | 2019-03-27 | 2022-07-13 | 주식회사 엘지화학 | Alkali soluble, photo-curable and thermo-curable copolymer, and photosensitive resin composition, photosensitive resin film, color filter using the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090081208A (en) * | 2008-01-23 | 2009-07-28 | 주식회사 엘지화학 | binder resin and photosensitive resin composition comprising the same and column Spacer made by the photosensitive resin composition |
| KR20100016506A (en) * | 2007-05-11 | 2010-02-12 | 다이셀 가가꾸 고교 가부시끼가이샤 | Photo- and/or thermo-curable copolymer, curable resin compositions, and cured articles |
| CN105867069A (en) * | 2015-02-10 | 2016-08-17 | 东友精细化工有限公司 | Negative-type photosensitive resin composition, photocuring pattern formed by using the same and image display device |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3688949B2 (en) * | 1999-09-24 | 2005-08-31 | 昭和高分子株式会社 | Photosensitive resin |
| JP2005517793A (en) * | 2002-02-15 | 2005-06-16 | ピーピージー インダストリーズ オハイオ， インコーポレイテッド | Radiation curable composition containing copolymer of isobutylene monomer and acrylic monomer |
| JP2006113327A (en) * | 2004-10-15 | 2006-04-27 | Toray Fine Chemicals Co Ltd | Photosensitive resin composition |
| KR101255866B1 (en) * | 2004-11-30 | 2013-04-17 | 가부시끼가이샤 다이셀 | Alicyclic epoxy (meth)acrylates, process for production thereof, and copolymers |
| JP2008031248A (en) * | 2006-07-27 | 2008-02-14 | Daicel Chem Ind Ltd | Curable resin composition and method for forming cured coating film |
| JP2009108309A (en) * | 2007-10-11 | 2009-05-21 | Hitachi Chem Co Ltd | Resin composition, and optical member using cured product thereof |
| JP5367324B2 (en) * | 2008-07-25 | 2013-12-11 | 株式会社ダイセル | Curable copolymer and curable resin composition |
| JP6029506B2 (en) * | 2013-03-26 | 2016-11-24 | 富士フイルム株式会社 | Composition for forming underlayer film for imprint and pattern forming method |
| KR101435652B1 (en) * | 2014-01-17 | 2014-08-28 | 주식회사 삼양사 | NOVEL FLUORENYL β-OXIME ESTER COMPOUNDS, PHOTOPOLYMERIZATION INITIATOR AND PHOTORESIST COMPOSITION CONTAINING THE SAME |
| JP6720815B2 (en) * | 2015-10-06 | 2020-07-08 | 三菱ケミカル株式会社 | Photosensitive resin composition, optical element, spacer, insulating film and display device obtained by using the same |
-
2018
- 2018-11-08 KR KR1020180136598A patent/KR102118627B1/en active IP Right Grant
- 2018-11-09 JP JP2019553075A patent/JP6911272B2/en active Active
- 2018-11-09 TW TW107139936A patent/TWI743412B/en active
- 2018-11-09 CN CN201880032826.2A patent/CN110709435B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100016506A (en) * | 2007-05-11 | 2010-02-12 | 다이셀 가가꾸 고교 가부시끼가이샤 | Photo- and/or thermo-curable copolymer, curable resin compositions, and cured articles |
| KR20090081208A (en) * | 2008-01-23 | 2009-07-28 | 주식회사 엘지화학 | binder resin and photosensitive resin composition comprising the same and column Spacer made by the photosensitive resin composition |
| CN105867069A (en) * | 2015-02-10 | 2016-08-17 | 东友精细化工有限公司 | Negative-type photosensitive resin composition, photocuring pattern formed by using the same and image display device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2020515680A (en) | 2020-05-28 |
| KR102118627B1 (en) | 2020-06-09 |
| KR20190053801A (en) | 2019-05-20 |
| JP6911272B2 (en) | 2021-07-28 |
| TWI743412B (en) | 2021-10-21 |
| TW201922818A (en) | 2019-06-16 |
| CN110709435B (en) | 2021-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101518774B1 (en) | Novel fluorene oxime ester compounds, photopolymerization initiator and photoresist composition containing the same | |
| JP7002617B2 (en) | Oxime ester derivative compound, photopolymerization initiator and photosensitive composition containing the same. | |
| JP2018123274A (en) | Alkali-soluble resin, photosensitive resin composition and use therefor | |
| JP7263522B2 (en) | Carbazole multi-β-oxime ester derivative compound, photopolymerization initiator containing the same, and photoresist composition | |
| CN110709435B (en) | Photocurable and thermally curable copolymer, and photosensitive resin composition, photosensitive resin film and color filter using the same | |
| JP7205553B2 (en) | Alkali-soluble, photocurable and thermosetting copolymer, photosensitive resin composition, photosensitive resin film, and color filter using the same | |
| KR20180013744A (en) | Resin, curable resin composition and cured film | |
| KR101574535B1 (en) | Novel biphenyl oxime ester compounds, photoinitiator and photoresist composition containing the same | |
| JP6381192B2 (en) | Method for producing alkali-soluble resin | |
| KR101991903B1 (en) | Carbazole oxime ester derivative compounds and, photopolymerization initiator and photosensitive composition containing the same | |
| KR20160071994A (en) | Black photosensitive resin composition, black matrix and image display device comprising thereof | |
| WO2019093827A1 (en) | Copolymer having photocurable and thermosetting property, and photosensitive resin composition, photosensitive resin film, and color filter using same | |
| KR101478292B1 (en) | Novel biphenyl β-oxime ester compounds, photoinitiator and photoresist composition containing the same | |
| KR101840061B1 (en) | Alkali soluble polymer composition and method of manufacturing the same | |
| KR100367471B1 (en) | Resist Composition For Over-Coat | |
| JP7190294B2 (en) | Copolymer, curable resin composition containing the copolymer, and cured product thereof | |
| KR20180090135A (en) | Oxime ester biphenyl compounds, photopolymerization initiator, and photosensitive composition containing the same | |
| KR101991838B1 (en) | Novel 1,3-benzodiazole beta-oxime ester compound and composition comprising the same | |
| WO2023218876A1 (en) | Alkali-soluble resin, photosensitive resin composition, and cured product thereof | |
| KR102509606B1 (en) | Novel quinolinyl beta oxime ester derivative compound, photopolymerization initiator, and photoresist composition containing the same | |
| WO2024018984A1 (en) | Copolymer, curable resin composition, and cured article | |
| KR20210061011A (en) | Photosensitive resin composition and insulating layer prepared therefrom | |
| JP2008052043A (en) | Photosensitive resin composition and method for preparing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |