TWI743412B - Photo-curable and thermo-curable copolymer, and photosensitive resin composition using the same, photosensitive resin film and method for preparing thereof, and color filter - Google Patents
Photo-curable and thermo-curable copolymer, and photosensitive resin composition using the same, photosensitive resin film and method for preparing thereof, and color filter Download PDFInfo
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- TWI743412B TWI743412B TW107139936A TW107139936A TWI743412B TW I743412 B TWI743412 B TW I743412B TW 107139936 A TW107139936 A TW 107139936A TW 107139936 A TW107139936 A TW 107139936A TW I743412 B TWI743412 B TW I743412B
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- curable
- photosensitive resin
- meth
- chemical formula
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 81
- 239000011342 resin composition Substances 0.000 title claims abstract description 80
- 229920005989 resin Polymers 0.000 title claims abstract description 63
- 239000011347 resin Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000000126 substance Substances 0.000 claims abstract description 90
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 82
- 125000000524 functional group Chemical group 0.000 claims description 79
- -1 acrylic compound Chemical class 0.000 claims description 49
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 39
- 239000000049 pigment Substances 0.000 claims description 34
- 239000000178 monomer Substances 0.000 claims description 33
- 125000003367 polycyclic group Chemical group 0.000 claims description 29
- 125000003342 alkenyl group Chemical group 0.000 claims description 28
- 238000000576 coating method Methods 0.000 claims description 24
- 239000011248 coating agent Substances 0.000 claims description 23
- 125000002947 alkylene group Chemical group 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 125000003700 epoxy group Chemical group 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 14
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 125000005907 alkyl ester group Chemical group 0.000 claims description 12
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 12
- 238000000016 photochemical curing Methods 0.000 claims description 12
- 238000001723 curing Methods 0.000 claims description 11
- 125000004185 ester group Chemical group 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 7
- 230000001678 irradiating effect Effects 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 125000002950 monocyclic group Chemical group 0.000 claims description 6
- 125000005429 oxyalkyl group Chemical group 0.000 claims description 6
- 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 4
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 2
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 2
- 229910052805 deuterium Inorganic materials 0.000 claims description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims 4
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims 1
- 125000001475 halogen functional group Chemical group 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 description 39
- 238000003786 synthesis reaction Methods 0.000 description 39
- 230000000052 comparative effect Effects 0.000 description 25
- 239000002904 solvent Substances 0.000 description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 14
- 150000001252 acrylic acid derivatives Chemical group 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 238000002360 preparation method Methods 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 229920001187 thermosetting polymer Polymers 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 7
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 7
- 230000001965 increasing effect Effects 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
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 150000001924 cycloalkanes Chemical class 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 150000002431 hydrogen Chemical group 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000001029 thermal curing Methods 0.000 description 5
- 239000004793 Polystyrene Substances 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
- 239000011230 binding agent Substances 0.000 description 4
- 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 4
- 230000008859 change Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 229920000642 polymer Polymers 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
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 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 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229920006026 co-polymeric resin Polymers 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- 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 2
- YMUQRDRWZCHZGC-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO.CCC(CO)(CO)CO YMUQRDRWZCHZGC-UHFFFAOYSA-N 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
- 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 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- 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
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- UMLWXYJZDNNBTD-UHFFFAOYSA-N alpha-dimethylaminoacetophenone Natural products CN(C)CC(=O)C1=CC=CC=C1 UMLWXYJZDNNBTD-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical group 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
- 239000001055 blue pigment Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 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 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000012847 fine chemical Substances 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
- 125000005843 halogen group Chemical group 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000003112 inhibitor Substances 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
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000728 polyester Polymers 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
- 238000007086 side reaction Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 239000001052 yellow pigment Substances 0.000 description 2
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 description 1
- 125000006586 (C3-C10) cycloalkylene 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
- HGCMSCWGVAYWHR-UHFFFAOYSA-N 1,3,5-trimethyl-2-[[phenyl-[(2,4,6-trimethylphenyl)methyl]phosphoryl]methyl]benzene Chemical compound CC1=CC(C)=CC(C)=C1CP(=O)(C=1C=CC=CC=1)CC1=C(C)C=C(C)C=C1C HGCMSCWGVAYWHR-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
- LMGYOBQJBQAZKC-UHFFFAOYSA-N 1-(2-ethylphenyl)-2-hydroxy-2-phenylethanone Chemical compound CCC1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 LMGYOBQJBQAZKC-UHFFFAOYSA-N 0.000 description 1
- JKVSAZTYCZKNDX-UHFFFAOYSA-N 1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C1=CC(C(=O)CCC)=CC=C1N1CCOCC1 JKVSAZTYCZKNDX-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
- XBHHVVHQVJQMSL-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1.O=C1C=CC(=O)N1C1=CC=CC=C1 XBHHVVHQVJQMSL-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- DZCGZGSJEWBGRY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)CO.OCC(CO)(CO)CO.OCC(CO)(CO)CO DZCGZGSJEWBGRY-UHFFFAOYSA-N 0.000 description 1
- CERJZAHSUZVMCH-UHFFFAOYSA-N 2,2-dichloro-1-phenylethanone Chemical compound ClC(Cl)C(=O)C1=CC=CC=C1 CERJZAHSUZVMCH-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
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- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
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- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical class 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
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- 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
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
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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
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- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
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- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
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- 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
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- 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
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Abstract
Description
[相關申請案的交叉參考] [Cross reference of related applications]
本申請案主張在韓國智慧財產局於2017年11月10日申請的韓國專利申請案第10-2017-0149676號及於2018年11月8日申請的韓國專利申請案第10-2018-0136598號之權益,所述申請案的揭露內容以全文引用的方式併入本文中。 This application claims the Korean Patent Application No. 10-2017-0149676 filed by the Korean Intellectual Property Office on November 10, 2017 and the Korean Patent Application No. 10-2018-0136598 filed on November 8, 2018 The rights and interests of the application, the disclosed content of the application is incorporated herein by reference in its entirety.
本發明關於一種光可固化及熱可固化的共聚物、使用所述共聚物的感光性樹脂組成物、感光性樹脂膜以及彩色濾光片。更具體言之,本發明關於一種光可固化及熱可固化的共聚物以及使用所述共聚物的感光性樹脂組成物、感光性樹脂膜以及彩色濾光片,所述共聚物即使處於相對較低的溫度下亦具有極佳熱可固化性,可藉由光照射進行光固化,且經由充分固化而具有極佳耐久性、耐化學性以及儲存穩定性。 The present invention relates to a photocurable and thermally curable copolymer, a photosensitive resin composition using the copolymer, a photosensitive resin film, and a color filter. More specifically, the present invention relates to a photo-curable and heat-curable copolymer, and a photosensitive resin composition, photosensitive resin film, and color filter using the copolymer. It also has excellent thermal curability at low temperatures, can be photocured by light irradiation, and has excellent durability, chemical resistance and storage stability through sufficient curing.
在彩色濾光片製造製程期間,在RGB圖案的情況下,感光性樹脂組成物主要使用旋轉塗佈機或狹縫塗佈機(slit coater)來塗佈,經預烘烤(pre-baking),且接著使其暴露並顯影。 During the color filter manufacturing process, in the case of RGB patterns, the photosensitive resin composition is mainly coated with a spin coater or a slit coater, and is pre-baked. , And then expose and develop it.
在顯影之後,最後進行施加220℃或大於220℃的熱量的後烘烤(post-baking)製程,且雖然常用的玻璃在此溫度下不變形,但在可撓性(flexible)顯示器中使用的塑膠在超過220℃的溫度下會嚴重變形。 After development, a post-baking process of applying heat at 220°C or more is finally performed. Although commonly used glass does not deform at this temperature, it is used in flexible displays. Plastics will be severely deformed at temperatures exceeding 220°C.
為了減少基板的此等變形,使用降低後烘烤(post-baking)製程的溫度的方法,但當後烘烤(post-baking)製程的溫度降低時,感光性樹脂組成物可能無法完全固化,且因此所產生的氣體量可能增加,殘影(afterimages)可能出現,且耐化學性及耐熱性可能降低。 In order to reduce such deformation of the substrate, a method of lowering the temperature of the post-baking process is used. However, when the temperature of the post-baking process is lowered, the photosensitive resin composition may not be completely cured. And therefore, the amount of gas generated may increase, afterimages may appear, and chemical resistance and heat resistance may decrease.
因此,需要研發即使處於低溫下亦可固化至高水平且因此可形成具有極佳耐熱性及耐化學性的固化膜的材料及感光性樹脂組成物。 Therefore, it is necessary to develop a material and a photosensitive resin composition that can be cured to a high level even at a low temperature and therefore can form a cured film with excellent heat resistance and chemical resistance.
本發明的目的是提供一種光可固化及熱可固化的共聚物,所述共聚物即使處於相對較低的溫度下亦具有極佳熱可固化性,可藉由光照射進行光固化,且經由充分固化而具有極佳耐久性、耐化學性以及儲存穩定性。 The object of the present invention is to provide a photocurable and thermally curable copolymer, which has excellent thermal curability even at a relatively low temperature, can be photocured by light irradiation, and can be cured by light Fully cured with excellent durability, chemical resistance and storage stability.
本發明的另一目的是提供一種使用光可固化及熱可固化的共聚物的感光性樹脂組成物、感光性樹脂膜以及彩色濾光片。 Another object of the present invention is to provide a photosensitive resin composition, a photosensitive resin film, and a color filter using a photo-curable and heat-curable copolymer.
提供一種光可固化及熱可固化共聚物包含:第一(甲基)丙烯酸酯重複單元,其中包含環氧基的有機官能基鍵結至分支鏈的末端;以及第二(甲基)丙烯酸酯重複單元,其中包含烯基的有機官能基鍵結至分支鏈的末端,其中在第二(甲基)丙烯酸酯重複單元中,分支鏈包含:經羥基取代的C1-20烷酯基、經羥基取代的C1-20氧烷基酯基、經羥基所取代的C3-30環烷基取代的烷酯基、經羥基取代的C7-30多環烷酯基或經羥基所取代的C7-30多環烷氧基取代的烷酯基。 Provided is a photo-curable and heat-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 branched chain; and a second (meth)acrylate A repeating unit, wherein the organic functional group containing an alkenyl group is bonded to the end of the branched chain, wherein in the second (meth)acrylate repeating unit, the branched chain includes: a C1-20 alkyl ester group substituted by a hydroxyl group, a hydroxyl group Substituted C1-20 oxyalkyl ester group, C3-30 cycloalkyl substituted alkyl ester group substituted by hydroxy group, C7-30 polycyclic alkyl ester group substituted by hydroxy group or C7-30 polycyclic alkyl ester group substituted by hydroxy group Cycloalkoxy substituted alkyl ester group.
亦提供一種感光性樹脂組成物,包含:光可固化及熱可固化的共聚物;具有兩個或大於兩個光可固化的不飽和官能基的光可聚合單體;以及光起始劑。 A photosensitive resin composition is also provided, comprising: a photo-curable and thermally curable copolymer; a photo-polymerizable monomer having two or more than two photo-curable unsaturated functional groups; and a photoinitiator.
亦提供一種用於製備感光性樹脂膜的方法,包含以下步驟:1)在基板上塗覆感光性樹脂組成物以形成塗層;2)對塗層進行乾燥;3)使光照射至經乾燥的塗層以進行光固化;以及4)在50℃至250℃下對經光固化的膜進行熱固化。 A method for preparing a photosensitive resin film is also provided, which includes the following steps: 1) coating a photosensitive resin composition on a substrate to form a coating; 2) drying the coating; 3) irradiating light to the dried The coating is photocured; and 4) the photocured film is thermally cured at 50°C to 250°C.
亦提供一種感光性樹脂膜,包含:光可固化及熱可固化的共聚物;以及具有兩個或大於兩個光可固化的不飽和官能基的光可聚合單體的固化產物。 A photosensitive resin film is also provided, comprising: a photocurable and thermally curable copolymer; and a cured product of a photopolymerizable monomer having two or more photocurable unsaturated functional groups.
亦提供一種包含感光性樹脂膜的彩色濾光片。 A color filter including a photosensitive resin film is also provided.
在整個說明書中,當部件「包括(comprises)」構造元件時,除非具體地進行相反地描述,否則其不排除其他構造元件,而是其可更包含其他構造元件。 Throughout the specification, when a component "comprises" construction elements, unless specifically described to the contrary, it does not exclude other construction elements, but it may further include other construction elements.
術語「經取代(substituted)」意指鍵結另一官能基代替 化合物中的氫原子,且經取代的氫原子的位置不受限制,只要其是可經取代基取代的位置即可,且當經兩個或大於兩個取代基取代時,此兩個或大於兩個取代基可彼此相同或不同。 The term "substituted" means bonding to another functional group instead of The hydrogen atom in the compound, and the position of the substituted hydrogen atom is not limited, as long as it is a position that can be substituted by a substituent, and when it is substituted by two or more than two substituents, these two or more The two substituents may be the same or different from each other.
標記或意指連接至另一取代基的鍵,且直接鍵意 指在由L指示的部分處不存在單獨原子的情況。 mark or It means a bond to another substituent, and a direct bond means a case where a separate atom does not exist at the portion indicated by L.
術語「(甲基)丙烯基((meth)acryl)」意指丙烯基或甲基丙烯基。 The term "(meth)acryl" means acrylic or methacryl.
重量平均分子量意指藉由GPC方法量測的相對於聚苯乙烯標準轉化的重量平均分子量。在藉由GPC方法量測相對於聚苯乙烯標準轉化的重量平均分子量的製程期間,可使用通常已知的分析器、諸如折射率偵測器的偵測器(Refractive Index Detector)以及分析柱,且可應用通常應用的溫度條件、溶劑以及流動速率(flow rate)。舉例言之,在160℃的評估溫度下將1,2,4-三氯苯用作溶劑,使用具有聚合物實驗室(Polymer Laboratories)PLgel MIX-B 300毫米(mm)長度柱的沃特世(Waters)PL-GPC220設備在1毫升/分鐘的流動速率下製備濃度為10毫克(mg)/10毫升(mL)的樣品,且接著使所述樣品以200微升(μL)的量進料,且可使用校準曲線(使用聚苯乙烯標準形成的)得到分子量(Mw)。作為聚苯乙烯標準產物,使用具有2000/10,000/30,000/70,000/200,000/700,000/2,000,000/4,000,000/10,000,000的分子量的9種類型。 The weight average molecular weight means the weight average molecular weight measured by the GPC method relative to the polystyrene standard conversion. During the process of measuring the weight average molecular weight converted to the polystyrene standard by the GPC method, commonly known analyzers, such as Refractive Index Detector (Refractive Index Detector), and analytical columns can be used. In addition, commonly used temperature conditions, solvents, and flow rates can be applied. For example, using 1,2,4-trichlorobenzene as the solvent at an evaluation temperature of 160°C, Waters with a 300 millimeter (mm) length column of Polymer Laboratories PLgel MIX-B (Waters) PL-GPC220 equipment prepares a sample with a concentration of 10 milligrams (mg)/10 milliliters (mL) at a flow rate of 1 ml/min, and then feeds the sample in an amount of 200 microliters (μL) , And a calibration curve (formed using polystyrene standards) can be used to obtain the molecular weight (Mw). As polystyrene standard products, 9 types having molecular weights of 2000/10,000/30,000/70,000/200,000/700,000/2,000,000/4,000,000/10,000,000 are used.
在整個說明書中,烷基是衍生自烷(alkane)的直鏈單價官能基、分支鏈單價官能基或環狀單價官能基,且其可為例如甲基、乙基、丙基、異丙基、第二丁基、第三丁基、戊基,己基等。 包含於烷基中的一或多個氫原子可經其他取代基取代,且取代基的實例可包含C1-10烷基、C2-10烯基、C2-10炔基、C6-12芳基、C2-12雜芳基、C6-12芳烷基、鹵素原子、氰基、胺基、甲脒基、硝基、醯胺基、羰基、羥基、磺醯基、胺基甲酸酯基,C1-10烷氧基等。 Throughout the specification, an alkyl group is a linear monovalent functional group, a branched chain monovalent functional group, or a cyclic monovalent functional group derived from an alkane, and it may be, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group , Second butyl, tertiary butyl, pentyl, hexyl, etc. One or more hydrogen atoms contained in the alkyl group may be substituted with other substituents, and examples of the substituents may include C1-10 alkyl, C2-10 alkenyl, C2-10 alkynyl, C6-12 aryl, C2-12 heteroaryl group, C6-12 aralkyl group, halogen atom, cyano group, amino group, formamidino group, nitro group, amide group, carbonyl group, hydroxyl group, sulfonyl group, carbamate group, C1 -10 Alkoxy and so on.
在整個說明書中,環烷基(雖然不受具體限制)是衍生自單環環烷(cycloalkane)的單價官能基,且其實例不受具體限制,但其具有3至60的碳數的環烷基是較佳的,且根據一個實施例,環烷基的碳數為3至30。根據另一實施例,環烷基的碳數為3至20。根據又一實施例,環烷基的碳數為3至6。具體言之,環烷基可包含環丙基、環丁基、環戊基、3-甲基環戊基、2,3-二甲基環戊基、環己基、3-甲基環己基、4-甲基環己基、2,3-二甲基環己基、3,4,5-三甲基環己基、4-第三丁基環己基、環庚基,環辛基等,但不限於此。 Throughout the specification, a cycloalkyl group (although not specifically limited) is a monovalent functional group derived from a monocyclic cycloalkane (cycloalkane), and its examples are not specifically limited, but it has a cycloalkane having a carbon number of 3 to 60 The group is preferred, and according to one embodiment, the carbon number of the cycloalkyl group is 3-30. According to another embodiment, the carbon number of the cycloalkyl group is 3-20. According to another embodiment, the carbon number of the cycloalkyl group is 3-6. 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-tertiarybutylcyclohexyl, cycloheptyl, cyclooctyl, etc., but not limited to this.
在整個說明書中,多環烷基(雖然不受具體限制)是衍生自多環環烷(cycloalkane)的單價官能基,且其實例不受具體限制,但具有3至60的碳數的彼等多環烷基是較佳的,且根據一個實施例,環烷基的碳數為3至30。具體言之,其可包含降莰烯(norbonane),2,3-三亞甲基降茨烯(2,3-trimethylenenorbonane)等,但不限於此。 Throughout the specification, a polycyclic alkyl group (although not specifically limited) is a monovalent functional group derived from a polycyclic cycloalkane (cycloalkane), and examples thereof are not specifically limited, but those having a carbon number of 3 to 60 Polycyclic alkyl groups are preferred, and according to one embodiment, the carbon number of cycloalkyl groups is 3-30. Specifically, it may include norbonane, 2,3-trimethylenenorbonane, etc., but is not limited thereto.
在整個說明書中,芳基是衍生自芳烴(arene)的單價官能基,且其可為單環或多環。具體言之,單環芳基可包含苯基、聯苯基、聯三苯基,芪基(stilbenyl group)等,但不限於此。多環芳基可包含萘基、蒽基、菲基、芘基、苝基、基,茀基等, 但不限於此。芳基的一或多個氫原子可分別經取代基取代,就如同在烷基中那樣。 Throughout the specification, the aryl group is a monovalent functional group derived from arenes, and it may be monocyclic or polycyclic. Specifically, the monocyclic aryl group may include a phenyl group, a biphenyl group, a triphenyl group, a stilbenyl group, etc., but is not limited thereto. Polycyclic aryl groups may include naphthyl, anthracenyl, phenanthryl, pyrenyl, perylene, Ji, Chi Ji, etc., but not limited to this. One or more hydrogen atoms of an aryl group may be substituted with a substituent, respectively, as in an alkyl group.
在整個說明書中,烯基可為直鏈或分支鏈,且碳數不受具體限制,但較佳地為2至40。根據一個實施例,烯基的碳數為2至20。根據一個實施例,烯基的碳數為2至10。根據一個實施例,烯基的碳數為2至6。其具體實例可包含:1-丙烯基、異丙烯基、1-丁烯基、2-丁烯基、3-丁烯基、1-戊烯基、2-戊烯基、3-戊烯基、3-甲基-1-丁烯基、1,3-丁二烯基、烯丙基、1-苯基乙烯基-1-基、2-苯基乙烯基-1-基、2,2-二苯基乙烯基-1-基、2-苯基-2-(萘基-1-基)乙烯基-1-基、2,2-雙(二苯基-1-基)乙烯基-1-基、芪基(stibenyl),苯乙烯基等,但不限於此。 Throughout the specification, the alkenyl group may be linear or branched, and the carbon number is not specifically limited, but is preferably 2-40. According to one embodiment, the carbon number of the alkenyl group is 2-20. According to one embodiment, the carbon number of the alkenyl group is 2-10. According to one embodiment, the carbon number of the alkenyl group is 2-6. Specific examples thereof may include: 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl , 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2 -Diphenylvinyl-1-yl, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl- 1-base, stibenyl, styryl, etc., but not limited thereto.
在整個說明書中,伸烷基是衍生自烷(alkane)的二價官能基,且碳數為1至20、1至10或1至5。其可為直鏈、分支鏈或環狀,且其實例可包含亞甲基、伸乙基、伸丙基、伸異丁基、伸第二丁基、伸第三丁基、伸戊基,伸己基等。包含於伸烷基中的一或多個氫原子可分別經取代基取代,就如同在烷基中那樣。 Throughout the specification, an alkylene group is a divalent functional group derived from an alkane and has a carbon number of 1-20, 1-10, or 1-5. It may be linear, branched or cyclic, and examples thereof may include methylene, ethylene, propylene, isobutyl, ethylene, tertiary, and pentylene, Shen Heji and so on. One or more hydrogen atoms contained in the alkylene group may be substituted with a substituent, respectively, as in an alkyl group.
在整個說明書中,氧伸烷基是衍生自伸烷基的官能基,其中醚基(-O-)鍵結至伸烷基的一個末端,且碳數為1至20、1至10或1至5。其可為直鏈、分支鏈或環狀,且其實例可包含氧亞甲基、氧伸乙基、氧伸丙基、氧基伸正丁基、氧伸異丁基、氧基伸第二丁基、氧基伸第三丁基、氧伸戊基,氧伸己基等。包含於氧伸烷基中的一或多個氫原子可分別經取代基取代,就如同在烷基中那樣。 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, oxyethylene, oxyn-butyl, oxyisobutyl, and oxyethylene , Oxybutylene, oxypentyl, oxyhexylene, etc. One or more hydrogen atoms contained in the oxyalkylene group may be substituted with a substituent, respectively, as in an alkyl group.
在整個說明書中,伸環烷基是衍生自環烷(cycloalkane) 的二價官能基,且碳數為3至30、3至20或3至10。其實例可包含伸環丙基、伸環丁基、伸環戊基、2,3-二甲基伸環戊基、伸環己基、3-甲基伸環己基、4-甲基伸環己基、2,3-二甲基伸環己基、3,4,5-三甲基伸環己基、4-第三丁基伸環己基、伸環庚基,伸環辛基等,但不受其限制。 Throughout the specification, cycloalkylene is derived from cycloalkane (cycloalkane) The divalent functional group of and the carbon number is 3 to 30, 3 to 20, or 3 to 10. Examples thereof may include cyclopropylidene, cyclobutylene, cyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl , 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc., but not limited .
在整個說明書中,多環伸烷基是衍生自多環烷(cycloalkane)的二價官能基,其中多環烷基的一個氫原子經官能基取代。 Throughout the specification, a polycyclic alkylene is a divalent functional group derived from a cycloalkane, in which one hydrogen atom of the polycyclic alkyl group is substituted with a functional group.
在整個說明書中,羰基的碳數不受具體限制,但其可較佳地為1至30。具體言之,其可為以下結構的化合物,但不限於此。 Throughout the specification, the carbon number of the carbonyl group is not specifically limited, but it may preferably be 1-30. Specifically, it may be a compound of the following structure, but is not limited thereto.
在整個說明書中,在酯基中,酯基的氧可經C1-25直鏈烷基、分支鏈烷基或環烷基或多環烷基取代。可將經烷基取代的酯基稱為「烷酯基」,且可將經多環烷基取代的酯基稱為「多環烷酯基」。 Throughout the specification, in the ester group, the oxygen of the ester group may be substituted with a C1-25 linear alkyl group, a branched chain alkyl group, or a cycloalkyl group or a polycyclic alkyl group. An ester group substituted with an alkyl group may be referred to as an "alkyl ester group", and an ester group substituted with a polycyclic alkyl group may be referred to as a "polycyclic alkyl ester group".
在下文中,將詳細闡述根據具體實施例的光可固化及熱可固化的共聚物、使用所述共聚物的感光性樹脂組成物、感光性樹脂膜以及彩色濾光片。 Hereinafter, the photo-curable and heat-curable copolymer, the photosensitive resin composition using the copolymer, the photosensitive resin film, and the color filter according to specific embodiments will be explained in detail.
I.光可固化及熱可固化的共聚物I. Light-curable and thermally curable copolymers
本發明的一個實施例提供一種光可固化及熱可固化的共 聚物,包含:第一(甲基)丙烯酸酯重複單元,其中包含環氧基的有機官能基鍵結至分支鏈的末端;以及第二(甲基)丙烯酸酯重複單元,其中包含烯基的有機官能基鍵結至分支鏈的末端,其中在第二(甲基)丙烯酸酯重複單元中,分支鏈包含:經羥基取代的C1-20烷酯基、經羥基取代的C1-20氧烷基酯基、經羥基所取代的C3-30環烷基取代的烷酯基、經羥基取代的C7-30多環烷酯基或經羥基所取代的C7-30多環烷氧基取代的烷酯基。 One embodiment of the present invention provides a photo-curable and thermally curable co A polymer comprising: a first (meth)acrylate repeating unit, in which an organic functional group containing an epoxy group is bonded to the end of a branched chain; and a second (meth)acrylate repeating unit, in which an alkenyl group is contained The organic functional group is bonded to the end of the branched chain, where in the second (meth)acrylate repeating unit, the branched chain includes: a C1-20 alkyl ester group substituted by a hydroxyl group, and a C1-20 oxyalkyl group substituted by a hydroxyl group Ester group, C3-30 cycloalkyl substituted alkyl ester group substituted by hydroxy group, C7-30 polycyclic alkyl ester group substituted by hydroxy group or C7-30 polycyclic alkoxy substituted alkyl ester group substituted by hydroxy group base.
本發明人確認就如上文所闡述的包含兩種或大於兩種類型的重複單元的光可固化及熱可固化的共聚物而言,包含於第二(甲基)丙烯酸酯重複單元中的含有烯基的有機官能基可藉由光照射進行光固化以形成一級固化結構,且即使在低於200℃的低溫下,包含於第一(甲基)丙烯酸酯重複單元中的含有環氧基的有機官能基亦可經由熱固化而形成二級固化結構,且因此,即使處於低溫下亦可藉由熱固化及光固化進行充分固化。亦經由實驗確認由此最終固化的膜可具有極佳耐久性及耐化學性,且在進行固化之前的感光性樹脂組成物亦可具有極佳儲存穩定性,且本發明得以完成。 The present inventors confirmed that for the photo-curable and heat-curable copolymers containing two or more types of repeating units as described above, the second (meth)acrylate repeating unit contains The organic functional group of the alkenyl group can be photocured by light irradiation to form a primary curing structure, and even at a low temperature of less than 200°C, the epoxy-containing group contained in the first (meth)acrylate repeating unit The organic functional group can also form a secondary curing structure through thermal curing, and therefore, it can be sufficiently cured by thermal curing and photocuring even at a low temperature. It is also confirmed through experiments that the finally cured film can have excellent durability and chemical resistance, and the photosensitive resin composition before curing can also have excellent storage stability, and the present invention has been completed.
具體言之,光可固化及熱可固化的共聚物可包含第一(甲基)丙烯酸酯重複單元,其中包含環氧基的有機官能基鍵結至分支鏈的末端。藉由包含第一(甲基)丙烯酸酯重複單元,即使在低於200℃的低溫下,緻密固化結構亦可由包含於第一(甲基)丙烯酸酯重複單元中的環氧基經由熱固化而形成。 Specifically, the photo-curable and thermally curable copolymer may include a first (meth)acrylate repeating unit in which an epoxy-containing organic functional group is bonded to the end of the branched chain. By including the first (meth)acrylate repeating unit, even at a low temperature of less than 200°C, the dense curing structure can be cured by the epoxy group contained in the first (meth)acrylate repeating unit through thermal curing. form.
在第一(甲基)丙烯酸酯重複單元中,將經由包含於(甲基)丙烯酸酯中的雙鍵的聚合反應形成的鏈稱為主鏈(main chain), 且將以分支形式自主鏈長出的鏈稱為分支鏈或側鏈(side chain)。 In the first (meth)acrylate repeating unit, the chain formed by the polymerization reaction of the double bond contained in the (meth)acrylate is called the main chain, And the chain that grows from the autonomous chain in a branched form is called a branched chain or a side chain.
(甲基)丙烯酸酯重複單元是包含於(甲基)丙烯酸酯單體的均聚物中的重複單元,且(甲基)丙烯酸酯重複單元可包含藉由包含於(甲基)丙烯酸酯單體中的乙烯基的聚合而形成的聚乙烯鏈作為主鏈以及包含於(甲基)丙烯酸酯單體中的酯官能基作為分支鏈。亦即,在第一(甲基)丙烯酸酯重複單元中,含有環氧基的有機官能基所鍵結至的分支鏈的末端意指包含於(甲基)丙烯酸酯重複單元中的酯官能基的末端。 The (meth)acrylate repeating unit is a repeating unit included in the homopolymer of the (meth)acrylate monomer, and the (meth)acrylate repeating unit can be included by being included in the (meth)acrylate monomer The polyethylene chain formed by the polymerization of the vinyl group in the body serves as the main chain and the ester functional group contained in the (meth)acrylate monomer serves as the branched chain. That is, in the first (meth)acrylate repeating unit, the end of the branched chain to which the epoxy-containing organic functional group is bonded means the ester functional group contained in the (meth)acrylate repeating unit The end.
在第一(甲基)丙烯酸酯重複單元中,分支鏈可包含以下中的任一者:羰基(-CO-);C1-20烷酯基(R'COO-:R'是C1-20烷基);或C1-20氧烷基酯基,且含有環氧基的有機官能基可鍵結至羰基或包含於C1-20烷酯基中的C1-20烷基的末端。 In the first (meth)acrylate repeating unit, the branched chain may contain any of the following: carbonyl (-CO-); C1-20 alkyl ester group (R'COO-: R'is C1-20 alkane Group); or a C1-20 oxyalkyl ester group, and the organic functional group containing an epoxy group may be bonded to the carbonyl group or the end of the C1-20 alkyl group contained in the C1-20 alkyl ester group.
包含環氧基的有機官能基可包含僅由環氧基組成的官能基或環氧基與其他官能基鍵結的官能基,且具體言之,其可為由以下化學式1表示的官能基;由以下化學式2表示的官能基;以及由以下化學式3表示的官能基中的任一者。 The organic functional group including an epoxy group may include a functional group composed only of an epoxy group or a functional group in which an epoxy group is bonded to other functional groups, and specifically, it may be a functional group represented by the following Chemical Formula 1; Any one of the functional groups represented by the following Chemical Formula 2; and the functional groups represented by the following Chemical Formula 3.
在化學式1中,R1、R2以及R3中的每一者可獨立地為直接鍵、氫或C1-5烷基,且較佳地,所有R1、R2以及R3可為氫。 In Chemical Formula 1, each of R 1 , R 2 and R 3 may independently be a direct bond, hydrogen or a C1-5 alkyl group, and preferably, all of R 1 , R 2 and R 3 may be hydrogen .
[化學式2]
在化學式2中,R4及R5中的每一者可獨立地為直接鍵或C1-5伸烷基,且較佳地,R4可為亞甲基,且R5可為伸乙基。 In Chemical Formula 2, each of R 4 and R 5 may independently be a direct bond or a C1-5 alkylene group, and preferably, R 4 may be a methylene group, and R 5 may be an ethylene group .
在化學式3中,R6及R7中的每一者獨立地為直接鍵、氫或C1-5烷基,且X為直接鍵、-O-或-S-。 In Chemical Formula 3, each of R 6 and R 7 is independently a direct bond, hydrogen or a C1-5 alkyl group, and X is a direct bond, -O- or -S-.
具體言之,第一(甲基)丙烯酸酯重複單元可由以下化學式4表示。 Specifically, the first (meth)acrylate repeating unit may be represented by Chemical Formula 4 below.
在化學式4中,R8至R10中的每一者獨立地為氫或C1-10烷基;L1為直接鍵、C1-20伸烷基或C1-20氧伸烷基;且R11為包含環氧基的有機官能基。 In Chemical Formula 4, each of R 8 to R 10 is independently hydrogen or a C1-10 alkyl group; L 1 is a direct bond, a C1-20 alkylene group or a C1-20 oxyalkylene group; and R 11 It is an organic functional group containing an epoxy group.
較佳地,在化學式4中,R8及R10中的每一者獨立地為 氫,R9為C1-3烷基,L1為直接鍵或C1-3伸烷基,且R11為由化學式1表示的官能基、由化學式2表示的官能基或由化學式3表示的官能基。 Preferably, in Chemical Formula 4, each of R 8 and R 10 is independently hydrogen, R 9 is a C1-3 alkyl group, L 1 is a direct bond or a C1-3 alkylene group, and R 11 is The functional group represented by Chemical formula 1, the functional group represented by Chemical formula 2, or the functional group represented by Chemical formula 3.
更佳地,在化學式4中,L1可為直接鍵,且R11可為由化學式3表示的官能基。另外,在化學式4中,L1可為C1-3伸烷基,且R11可為由化學式1表示的官能基、由化學式2表示的官能基或由化學式3表示的官能基。 More preferably, in Chemical Formula 4, L 1 may be a direct bond, and R 11 may be a functional group represented by Chemical Formula 3. In addition, in Chemical Formula 4, L 1 may be a C1-3 alkylene group, and R 11 may 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.
具體言之,由化學式4表示的第一(甲基)丙烯酸酯重複單元的實例可包含衍生自甲基丙烯酸縮水甘油酯的以下化學式4-1、衍生自3,4-環氧環己基甲基丙烯酸甲酯(3,4-epoxycyclohexyl methylmethacrylate)的以下化學式4-2、衍生自以下合成實例3的化學式A的以下化學式4-3以及衍生自以下合成實例4的化學式B的以下化學式4-4。 Specifically, an example of the first (meth)acrylate repeating unit represented by Chemical Formula 4 may include the following Chemical Formula 4-1 derived from glycidyl methacrylate, derived from 3,4-epoxycyclohexylmethyl The following chemical formula 4-2 of methyl acrylate (3,4-epoxycyclohexyl methylmethacrylate), 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.
[化學式4-2]
光可固化及熱可固化的共聚物可包含第二(甲基)丙烯酸酯重複單元,其中包含烯基的有機官能基鍵結至分支鏈的末端。 藉由包含第二(甲基)丙烯酸酯重複單元,可由包含於第二(甲基)丙烯酸酯重複單元中的烯基藉由光照射進行光固化,以形成緻密固化結構。 The photo-curable and heat-curable copolymer may include a second (meth)acrylate repeating unit in which an alkenyl-containing organic functional group is bonded to the end of the branched chain. By including the second (meth)acrylate repeating unit, the alkenyl group included in the second (meth)acrylate repeating unit can be photocured by light irradiation to form a dense cured structure.
在第二(甲基)丙烯酸酯重複單元中,將經由包含於(甲基)丙烯酸酯中的雙鍵的聚合反應形成的鏈稱為主鏈(main chain),且將以分支形式自主鏈長出的鏈稱為分支鏈或側鏈(side chain)。 In the second (meth)acrylate repeating unit, the chain formed by the polymerization reaction of the double bond contained in the (meth)acrylate is referred to as the main chain, and will be branched as the main chain. The resulting chain is called a branched chain or a side chain.
(甲基)丙烯酸酯重複單元是包含於(甲基)丙烯酸酯單體的均聚物中的重複單元,且(甲基)丙烯酸酯重複單元可包含藉由包含於(甲基)丙烯酸酯單體中的乙烯基的聚合而形成的聚乙烯鏈作為主鏈以及包含於(甲基)丙烯酸酯單體中的酯官能基作為分支鏈。亦即,在第二(甲基)丙烯酸酯重複單元中,含有烯基的有機官能基所鍵結至的分支鏈的末端意指包含於(甲基)丙烯酸酯重複單元中的酯官能基的末端。 The (meth)acrylate repeating unit is a repeating unit included in the homopolymer of the (meth)acrylate monomer, and the (meth)acrylate repeating unit can be included by being included in the (meth)acrylate monomer The polyethylene chain formed by the polymerization of the vinyl group in the body serves as the main chain and the ester functional group contained in the (meth)acrylate monomer serves as the branched chain. That is, in the second (meth)acrylate repeating unit, the end of the branched chain to which the alkenyl-containing organic functional group is bonded means the end of the ester functional group contained in the (meth)acrylate repeating unit End.
在第二(甲基)丙烯酸酯重複單元中,分支鏈可包含經羥基取代的C1-20烷酯基或C1-10烷酯基(R'COO-:R'是C1-10烷基)、經羥基取代的C1-20氧烷基酯基、經羥基所取代的C3-30環烷基或C3-10環烷基取代的烷酯基、經羥基取代的C7-30多環烷酯基或C8-15多環烷酯基,或經羥基所取代的C7-30多環烷氧基或C8-15多環烷氧基取代的烷酯基。 In the second (meth)acrylate repeating unit, the branched chain may include a C1-20 alkyl ester group or a C1-10 alkyl ester group substituted by a hydroxyl group (R'COO-: R'is a C1-10 alkyl group), A C1-20 oxyalkyl ester group substituted by a hydroxy group, a C3-30 cycloalkyl group or a C3-10 cycloalkyl group substituted by a hydroxy group, a C7-30 polycyclic alkyl ester group substituted by a hydroxy group, or C8-15 polycyclic alkyl ester group, or C7-30 polycyclic alkoxy group substituted by hydroxy group or C8-15 polycyclic alkoxy group substituted alkyl ester group.
具體言之,在包含於經羥基取代的C1-20烷酯基中的C1-20烷基或包含於經羥基所取代的C3-30環烷基取代的烷酯基中的C3-30環烷基的末端處,含有烯基的有機官能基可經取代。 Specifically, the C1-20 alkyl group contained in the C1-20 alkyl ester group substituted with a hydroxyl group or the C3-30 cycloalkane group contained in the C3-30 cycloalkyl substituted alkyl ester group substituted with the hydroxyl group At the end of the group, the organic functional group containing an alkenyl group may be substituted.
另外,在經羥基取代的C7-30多環烷酯基中,在包含於C7-30多環烷酯基中的C7-30多環烷基的末端處,含有烯基的有機 官能基可經取代。 In addition, in the C7-30 polycyclic alkyl ester group substituted with a hydroxy group, at the end of the C7-30 polycyclic alkyl group contained in the C7-30 polycyclic alkyl ester group, the organic The functional group may be substituted.
此外,在經羥基所取代的C7-30多環烷氧基取代的烷酯基中,在包含於C7-30多環烷氧基中的C7-30多環烷基的末端處,含有烯基的有機官能基可經取代。 In addition, in the alkyl ester group substituted with a C7-30 polycyclic alkoxy group substituted with a hydroxyl group, an alkenyl group is contained at the end of the C7-30 polycyclic alkyl group contained in the C7-30 polycyclic alkoxy group The organic functional group can be substituted.
同時,羥基可作為分支鏈在包含於C1-20烷酯基中的C1-20烷基處經取代、在C3-30環烷基處經取代、在包含於C10-30多環烷酯基中的C10-30多環烷基處經取代或在包含於C10-30多環烷氧基中的C10-30多環烷基處經取代。 At the same time, the hydroxyl group can be substituted at the C1-20 alkyl group contained in the C1-20 alkyl ester group, substituted at the C3-30 cycloalkyl group, or substituted at the C10-30 polycyclic alkyl ester group as a branched chain. The C10-30 polycyclic alkyl group of is substituted or the C10-30 polycyclic alkyl group contained in the C10-30 polycyclic alkoxy group is substituted.
羥基可經由包含於第一(甲基)丙烯酸酯重複單元中的環氧基的開環反應來誘導,且更具體言之,羥基可經由包含於第一(甲基)丙烯酸酯重複單元中的環氧基與包含含有烯基的有機官能基的化合物之間的反應來誘導。 The hydroxyl group can be induced via the ring-opening reaction of the epoxy group contained in the first (meth)acrylate repeating unit, and more specifically, the hydroxyl group can be induced via the ring-opening reaction of the epoxy group contained in the first (meth)acrylate repeating unit. It is induced by the reaction between the epoxy group and the compound containing the alkenyl group-containing organic functional group.
包含烯基的有機官能基可包含僅由烯基構成的官能基及烯基與其他有機官能基鍵結的官能基,且具體言之,可使用(甲基)丙烯醯基,(甲基)丙烯醯氧基等,且較佳地,可使用甲基丙烯醯氧基。 The organic functional group including an alkenyl group may include a functional group composed only of an alkenyl group and a functional group in which the alkenyl group is bonded to other organic functional groups, and specifically, a (meth)acrylic group, (methyl) An acryloxy group and the like, and preferably, a methacryloxy group may be used.
具體言之,第二(甲基)丙烯酸酯重複單元可由以下化學式5表示。 Specifically, the second (meth)acrylate repeating unit may be represented by the following Chemical Formula 5.
在化學式5中,R12至R14中的每一者獨立地為氫或C1-10烷基;L2為直接鍵、C1-20伸烷基或C1-20氧伸烷基;L3為經羥基取代的C1-20伸烷基、經羥基取代的C1-20氧伸烷基、經羥基取代的C3-30伸環烷基或經羥基取代的C7-30多環伸烷基;且R15為包含烯基的有機官能基。 In Chemical Formula 5, each of R 12 to R 14 is independently hydrogen or a C1-10 alkyl group; L 2 is a direct bond, a C1-20 alkylene group or a C1-20 oxyalkylene group; L 3 is C1-20 alkylene substituted by hydroxy, C1-20 oxyalkylene substituted by hydroxy, C3-30 cycloalkylene substituted by hydroxy or C7-30 polycyclic alkylene substituted by hydroxy; and R 15 is an organic functional group containing an alkenyl group.
較佳地,在化學式5中,R12及R14中的每一者獨立地為氫;R13獨立地為C1-3烷基;L2為直接鍵、C1-10伸烷基或C1-10氧伸烷基;且L3為經羥基取代的C1-5伸烷基、經羥基取代的C3-10伸環烷基或經羥基取代的C8-15多環伸烷基。 Preferably, in the chemical formula 5, each of R 12 and R 14 is independently hydrogen; R 13 is independently a C1-3 alkyl group; L 2 is a direct bond, a C1-10 alkylene group or a C1- 10 oxyalkylene; and L 3 is a C1-5 alkylene substituted with a hydroxy group, a C3-10 cycloalkylene substituted with a hydroxy group, or a C8-15 polycyclic alkylene substituted with a hydroxy group.
更具體言之,在化學式5中,L2可為直接鍵,且L3可為經羥基取代的C10-20多環伸烷基。另外,在化學式5中,L2可為C1-10伸烷基或C1-10氧伸烷基,且L3可為經羥基取代的C1-5伸烷基、經羥基取代的C3-10伸環烷基或經羥基取代的C8-15多環伸烷基。 More specifically, in Chemical Formula 5, L 2 may be a direct bond, and L 3 may be a C10-20 polycyclic alkylene group substituted with a hydroxyl group. In addition, in the chemical formula 5, L 2 may be a C1-10 alkylene group or a C1-10 oxyalkylene group, and L 3 may be a C1-5 alkylene group substituted with a hydroxy group, or a C3-10 alkylene group substituted with a hydroxy group. Cycloalkyl or C8-15 polycyclic alkylene substituted by hydroxy.
具體言之,由化學式5表示的第二(甲基)丙烯酸酯重複單元的實例可包含以下化學式5-1至化學式5-4,所述化學式5-1至化學式5-4可藉由在上文所闡述的化學式4-1至化學式4-4的末端處環氧基與(甲基)丙烯酸的反應來製備。 Specifically, examples of the second (meth)acrylate repeating unit represented by Chemical Formula 5 may include the following Chemical Formula 5-1 to Chemical Formula 5-4, which may be described by It is prepared by the reaction of epoxy group and (meth)acrylic acid at the ends of Chemical Formula 4-1 to Chemical Formula 4-4 described in the text.
[化學式5-1]
第一(甲基)丙烯酸酯重複單元與第二(甲基)丙烯酸酯重複單元的莫耳比可為99:1至1:99。按此,由於光可固化及熱可固化的共聚物包含第一(甲基)丙烯酸酯重複單元及第二(甲基)丙烯酸酯重複單元二者,因此光可固化及熱可固化的共聚物可同步實現光可固化性及低溫熱可固化性。 The molar ratio of the first (meth)acrylate repeating unit to the second (meth)acrylate repeating unit may be 99:1 to 1:99. According to this, since the photo-curable and thermally curable copolymer includes both the first (meth)acrylate repeating unit and the second (meth)acrylate repeating unit, the photo-curable and thermally curable copolymer It can simultaneously realize light curability and low temperature thermal curability.
較佳地,以100莫耳的第一(甲基)丙烯酸酯重複單元計,可以10莫耳至90莫耳、20莫耳至70莫耳或30莫耳至50莫耳的比率包含第二(甲基)丙烯酸酯重複單元。若以100莫耳的第一(甲基)丙烯酸酯重複單元計的第二(甲基)丙烯酸酯重複單元的含量過度減少,則可能在合成共聚物中產生殘基問題。 Preferably, based on 100 mol of the first (meth)acrylate repeating unit, the second may be included in a ratio of 10 mol to 90 mol, 20 mol to 70 mol, or 30 mol to 50 mol. (Meth)acrylate repeating unit. If the content of the second (meth)acrylate repeating unit based on 100 mol of the first (meth)acrylate repeating unit is excessively reduced, a residue problem may occur in the synthetic copolymer.
相反,若以100莫耳的第一(甲基)丙烯酸酯重複單元計的第二(甲基)丙烯酸酯重複單元的含量增至大於90莫耳,則合成共聚物的染色特性及耐化學性可能降低。 On the contrary, if the content of the second (meth)acrylate repeating unit based on 100 mol of the first (meth)acrylate repeating unit is increased to more than 90 mol, the dyeing properties and chemical resistance of the synthetic copolymer May be reduced.
同時,光可固化及熱可固化的共聚物可更包含由下述者所組成的族群中選出的一或多個重複單元:由以下化學式6表示的第三(甲基)丙烯酸酯重複單元;由以下化學式7表示的順丁烯二醯亞胺重複單元;以及由以下化學式8表示的乙烯基重複單元。由此,可提高光可固化及熱可固化的共聚物的耐熱性及耐化學性。 At the same time, the photocurable and thermally curable copolymer may further include one or more repeating units selected from the group consisting of: the third (meth)acrylate repeating unit represented by the following chemical formula 6; The maleimide repeating unit represented by the following Chemical Formula 7; and the vinyl repeating unit represented by the following Chemical Formula 8. Thereby, the heat resistance and chemical resistance of the photocurable and thermally curable copolymer can be improved.
在化學式6至化學式8中, R16至R26中的每一者獨立地為氫;氘;鹵基;C1-20烷基;C1-20烷氧基;C6-30單環或多環芳基;C2-20烯基;或C3-30單環或多環環烷基,以及 L4是直接鍵、C1-20伸烷基或C1-20氧伸烷基。 In Chemical Formula 6 to Chemical Formula 8, each of R 16 to R 26 is independently hydrogen; deuterium; halo; C1-20 alkyl; C1-20 alkoxy; C6-30 monocyclic or polycyclic aromatic Group; C2-20 alkenyl group; or C3-30 monocyclic or polycyclic cycloalkyl group, and L 4 is a direct bond, C1-20 alkylene group or C1-20 oxyalkylene group.
更具體言之,在由化學式6表示的第三(甲基)丙烯酸酯重 複單元中,R16及R18可為氫,R17可為甲基,L4可為亞甲基,且R19可為苯基。亦即,第三(甲基)丙烯酸酯重複單元可為衍生自甲基丙烯酸苯甲酯的重複單元。 More specifically, in the third (meth)acrylate repeating unit represented by Chemical Formula 6, R 16 and R 18 may be hydrogen, R 17 may be a methyl group, L 4 may be a methylene group, and R 19 Can be phenyl. That is, the third (meth)acrylate repeating unit may be a repeating unit derived from benzyl methacrylate.
此外,在由化學式7表示的順丁烯二醯亞胺重複單元中,R20及R21可為氫,且R22可為苯基。在由化學式8表示的乙烯基重複單元中,R23、R24以及R25可為氫,且R26可為苯基。亦即,由化學式7表示的順丁烯二醯亞胺重複單元可為衍生自N-苯基順丁烯二醯亞胺(N-phenylmaleimide)的重複單元,且由化學式8表示的乙烯基重複單元可為衍生自苯乙烯的重複單元。 In addition, in the maleimide repeating unit represented by Chemical Formula 7, R 20 and R 21 may be hydrogen, and R 22 may be a phenyl group. In the vinyl repeating unit represented by Chemical Formula 8, R 23 , R 24, and R 25 may be hydrogen, and R 26 may be a phenyl group. That is, the maleimide repeating unit represented by Chemical Formula 7 may be a repeating unit derived from N-phenylmaleimide (N-phenylmaleimide), and the vinyl repeating unit represented by Chemical Formula 8 The unit may be a repeating unit derived from styrene.
第三(甲基)丙烯酸酯重複單元與第一(甲基)丙烯酸酯重複單元的莫耳比可為1:99至99:1,且第三(甲基)丙烯酸酯重複單元與第二(甲基)丙烯酸酯重複單元的莫耳比可為1:99至99:1。按此,藉由以組合形式使用第一(甲基)丙烯酸酯重複單元、第二(甲基)丙烯酸酯重複單元以及第三(甲基)丙烯酸酯重複單元,可提高耐熱性及耐化學性。 The molar ratio of the third (meth)acrylate repeating unit to the first (meth)acrylate repeating unit can be 1:99 to 99:1, and the third (meth)acrylate repeating unit and the second ( The molar ratio of the meth)acrylate repeating unit may be 1:99 to 99:1. According to this, 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 .
光可固化及熱可固化的共聚物的重量平均分子量(藉由GPC來量測)可為1000公克/莫耳(g/mol)至100,000公克/莫耳。 The weight average molecular weight of the light-curable and heat-curable copolymer (measured by GPC) can range from 1000 grams/mole (g/mol) to 100,000 grams/mole.
同時,光可固化及熱可固化的共聚物可由下述者組成:第一(甲基)丙烯酸酯重複單元,其中包含環氧基的有機官能基鍵結至分支鏈的末端;第二(甲基)丙烯酸酯重複單元,其中包含烯基的有機官能基鍵結至分支鏈的末端;由化學式6表示的第三(甲基)丙烯酸酯重複單元;由化學式7表示的順丁烯二醯亞胺重複單元;以及由化學式8表示的乙烯基重複單元。 At the same time, the photo-curable and heat-curable copolymer may be composed of the following: the first (meth)acrylate repeating unit, in which an organic functional group containing an epoxy group is bonded to the end of the branched chain; the second (a Group) acrylate repeating unit, in which an organic functional group containing an alkenyl group is bonded to the end of the branched chain; the third (meth)acrylate repeating unit represented by Chemical Formula 6; Maleic acid represented by Chemical Formula 7 Amine repeating unit; and a vinyl repeating unit represented by Chemical Formula 8.
亦即,光可固化及熱可固化的共聚物可能未更包含除上 文所闡述的五種類型的重複單元外的額外重複單元。因此,可在光可固化及熱可固化的共聚物進行固化之前抑制分子中的自發性副反應,從而確保較高的可靠性。 That is, the photo-curable and thermally curable copolymers may not contain more The five types of repeating units described in this article are extra repeating units. Therefore, the spontaneous side reaction in the molecule can be suppressed before the photocurable and thermally curable copolymer is cured, thereby ensuring high reliability.
舉例言之,假使光可固化及熱可固化的共聚物包含藉由第二(甲基)丙烯酸酯重複單元與酸酐的反應而得到的重複單元作為除上文所闡述的五種類型的重複單元外的額外重複單元,則與(甲基)丙烯基官能基或環氧基的副反應可能藉由末端羧基(所述末端羧基藉由酸酐的開環反應形成)進行,且因此難以充分實現光可固化及熱可固化的共聚物的特性。 For example, suppose that the photo-curable and thermally curable copolymer includes a repeating unit obtained by the reaction of the second (meth)acrylate repeating unit with an acid anhydride as the repeating unit in addition to the five types described above The side reaction with the (meth)propenyl functional group or epoxy group may be carried out by the terminal carboxyl group (the terminal carboxyl group is formed by the ring-opening reaction of acid anhydride), and therefore it is difficult to fully realize the light Properties of curable and thermally curable copolymers.
合成光可固化及熱可固化的共聚物的方法不受特定限制,但例如,所述共聚物可藉由使包含在末端處經含有環氧基的有機官能基取代的(甲基)丙烯酸酯單體的單體混合物聚合,接著使其與包含含有烯基的有機官能基的化合物反應來製備。在末端處經含有環氧基的有機官能基取代的(甲基)丙烯酸酯單體的實例可包含甲基丙烯酸縮水甘油酯、3,4-環氧環己基甲基丙烯酸甲酯、衍生自以下合成實例3的化學式A的以下化學式4-3,衍生自以下合成實例4的化學式B的以下化學式4-4等,且包含含有烯基的有機官能基的化合物的實例可包含甲基丙烯酸。另外,在單體混合物中,可添加甲基丙烯酸苯甲酯、N-苯基順丁烯二醯亞胺或苯乙烯作為在共聚物的合成中使用的其他單體。 The method of synthesizing the photocurable and thermally curable copolymer is not particularly limited, but for example, the copolymer may be formed by including (meth)acrylate substituted with an epoxy-containing organic functional group at the end. The monomer mixture of monomers is polymerized and then reacted with a compound containing an alkenyl group-containing organic functional group to prepare it. Examples of the (meth)acrylate monomer substituted with an epoxy-containing organic functional group at the end may include glycidyl methacrylate, 3,4-epoxycyclohexyl methyl methacrylate, derived from The following Chemical Formula 4-3 of Chemical Formula A of Synthesis Example 3, the following Chemical Formula 4-4 of Chemical Formula B of Synthesis Example 4 below, etc., and examples of the compound including an alkenyl-containing organic functional group may include methacrylic acid. In addition, in the monomer mixture, benzyl methacrylate, N-phenyl maleimide, or styrene may be added as other monomers used in the synthesis of the copolymer.
II.感光性樹脂組成物II. Photosensitive resin composition
本發明的另一實施例提供一種感光性樹脂組成物,包含:一個實施例的光可固化及熱可固化的共聚物;具有兩個或大於兩個光可固化的不飽和官能基的光可聚合單體;以及光起始劑。 Another embodiment of the present invention provides a photosensitive resin composition comprising: the photocurable and thermally curable copolymer of one embodiment; a photocurable resin having two or more photocurable unsaturated functional groups; Polymerized monomer; and photoinitiator.
光可固化及熱可固化的共聚物的細節如上文在一個實施例中所闡述。 The details of the photo-curable and thermally curable copolymer are as described above in one embodiment.
光可聚合單體可為具有兩個或大於兩個光可固化的不飽和官能基(諸如多官能乙烯基等)的化合物,且光可聚合單體可與上文所闡述的光可固化及熱可固化的共聚物的不飽和官能基形成交聯,由此在暴露於光下時藉由光固化而形成交聯結構。因此,在形成下述圖案膜時,處於暴露區域的感光性樹脂組成物可不經鹼性顯影,但可繼續存在於基板上。 The photopolymerizable monomer may be a compound having two or more than two photocurable unsaturated functional groups (such as a polyfunctional vinyl group, etc.), and the photopolymerizable monomer may be the same as the photocurable and The unsaturated functional groups of the thermally curable copolymer form crosslinks, thereby forming a crosslinked structure by photocuring when exposed to light. Therefore, when the pattern film described below is formed, the photosensitive resin composition in the exposed area may not undergo alkaline development, but may continue to exist on the substrate.
作為此光可聚合單體,可使用在室溫下為液體的彼等光可聚合單體,且從而可根據塗佈方法控制感光性樹脂組成物的黏度,或可進一步提高非暴露區域的可鹼性顯影性。 As the photopolymerizable monomer, those photopolymerizable monomers that are liquid at room temperature can be used, and thus the viscosity of the photosensitive resin composition can be controlled according to the coating method, or the non-exposed area can be further increased. Alkaline developability.
作為光可聚合單體,可使用具有兩個或大於兩個光可固化的不飽和官能基的丙烯酸酯類化合物,且更具體言之,可單獨或以組合形式使用由下述者所組成的族群中選出的一或多種化合物:含有羥基的丙烯酸酯類化合物,諸如2-丙烯酸羥乙酯(2-hydroxyethylacrylate)、2-丙烯酸羥丙酯(2-hydroxypropylacrylate)、季戊四醇三丙烯酸酯,二季戊四醇五丙烯酸酯等;水溶性丙烯酸酯類化合物,諸如聚乙二醇二丙烯酸酯,聚丙二醇二丙烯酸酯等;基於多元醇的多官能聚酯丙烯酸酯(polyester acrylate)的化合物,諸如三羥甲基丙烷三丙烯酸酯(trimethylol propane triacrylate)、季戊四醇四丙烯酸酯,二季戊四醇六丙烯酸酯等;多官能醇的環氧乙烷加成物及/或環氧丙烷加成物的丙烯酸酯類化合物,諸如三羥甲基丙烷,氫化雙酚A等,或多元酚,諸如雙酚A,聯苯酚等;多官能或單官能聚胺酯丙烯酸 酯類化合物,其為含有異氰酸酯改性的羥基的丙烯酸酯;環氧丙烯酸酯類化合物,其為雙酚A二縮水甘油醚(bisphenol A diglycidyl ether)、氫化雙酚A二縮水甘油醚(hydrogenated bisphenol A diglycidyl ether)或苯酚酚醛環氧樹脂的(甲基)丙烯酸加成物;己內酯改性的丙烯酸酯類化合物,諸如己內酯改性的二(三羥甲基丙烷)四丙烯酸酯(caprolactone-modified ditrimethylolpropane tetraacrylate)、ε-己內酯改性的二季戊四醇丙烯酸酯,己內酯改性的羥基三甲基乙酸新戊二醇酯二丙烯酸酯(caprolactone-modified hydroxy pivalic acid neopentyl glycol ester diacrylate)等;以及感光性(甲基)丙烯酸酯化合物,諸如對應於上述丙烯酸酯類化合物的甲基丙烯酸酯類化合物。 As the photopolymerizable monomer, an acrylic compound having two or more than two photocurable unsaturated functional groups can be used, and more specifically, a compound composed of the following can be used alone or in combination One or more compounds selected from the group: acrylate compounds containing hydroxyl groups, such as 2-hydroxyethylacrylate, 2-hydroxypropylacrylate, pentaerythritol triacrylate, dipentaerythritol five Acrylate, etc.; water-soluble acrylate compounds, such as polyethylene glycol diacrylate, polypropylene glycol diacrylate, etc.; polyol-based polyfunctional polyester acrylate (polyester acrylate) compounds, such as trimethylolpropane Trimethylol propane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, etc.; polyfunctional alcohol ethylene oxide adduct and/or propylene oxide adduct acrylic compound, such as trihydroxy Methyl propane, hydrogenated bisphenol A, etc., or polyphenols, such as bisphenol A, biphenol, etc.; polyfunctional or monofunctional polyurethane acrylic Ester compounds, which are acrylates containing isocyanate-modified hydroxyl groups; epoxy acrylate compounds, which are bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether and hydrogenated bisphenol A diglycidyl ether; A diglycidyl ether) or (meth)acrylic acid adduct of phenol novolac epoxy resin; caprolactone-modified acrylate compounds, such as caprolactone-modified bis(trimethylolpropane) tetraacrylate ( caprolactone-modified ditrimethylolpropane tetraacrylate, ε-caprolactone-modified dipentaerythritol acrylate, caprolactone-modified hydroxy pivalic acid neopentyl glycol ester diacrylate (caprolactone-modified hydroxy pivalic acid neopentyl glycol ester diacrylate) ) Etc.; and photosensitive (meth)acrylate compounds, such as methacrylate compounds corresponding to the above-mentioned acrylate compounds.
其中,作為光可聚合單體,可較佳地使用在一個分子中具有兩個或大於兩個(甲基)丙烯醯基的多官能(甲基)丙烯酸酯類化合物,且特定言之,可適當地使用季戊四醇三丙烯酸酯、三羥甲基丙烷三丙烯酸酯、二季戊四醇六丙烯酸酯,己內酯改性的二(三羥甲基丙烷)四丙烯酸酯等。市售的光可聚合單體的實例可包含卡亞拉德(Kayarad)的DPEA-12等。 Among them, as the photopolymerizable monomer, a polyfunctional (meth)acrylate compound having two or more (meth)acrylic groups in one molecule can be preferably used, and in particular, Pentaerythritol triacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, caprolactone-modified di(trimethylolpropane) tetraacrylate, etc. are suitably used. Examples of commercially available photopolymerizable monomers may include Kayarad's DPEA-12 and the like.
以感光性樹脂組成物的總重量計,上文所闡述的光可聚合單體的含量可為0.1重量%(wt%)至30重量%或1重量%至20重量%。若光可聚合單體的含量過度減少,則光固化可能不充分,且若含量過度增加,則固化膜的乾燥度可能降低,且特性可能降低。 Based on the total weight of the photosensitive resin composition, the content of the photopolymerizable monomer described above may be 0.1% by weight (wt%) to 30% by weight or 1% to 20% by weight. If the content of the photopolymerizable monomer is excessively reduced, the photocuring may be insufficient, and if the content is excessively increased, the dryness of the cured film may decrease, and the characteristics may decrease.
同時,例如,光起始劑用以引發光可固化及熱可固化的共聚物與感光性樹脂組成物的暴露區域中的光可聚合單體之間的 自由基光固化。 At the same time, for example, the photoinitiator is used to initiate the interaction between the photocurable and thermally curable copolymer and the photopolymerizable monomer in the exposed area of the photosensitive resin composition. Free radical light curing.
可使用通常已知的光起始劑,且具體言之,可使用安息香及其烷基醚,諸如安息香、安息香甲醚,安息香乙醚等;苯乙酮,諸如苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、1,1-二氯苯乙酮,4-(1-第三丁基二氧基-1-甲基乙基)苯乙酮等;蒽醌,諸如2-甲基蒽醌、2-戊基蒽醌、2-第三丁基蒽醌,1-氯蒽醌等;噻噸酮,諸如2,4-二甲基噻噸酮、2,4-二異丙基噻噸酮,2-氯噻噸酮(2-chlorothioxanthone)等;縮酮,諸如苯乙酮二甲基縮酮,苯甲基二甲基縮酮等;二苯甲酮,諸如二苯甲酮、4-(1-第三丁基二氧基-1-甲基乙基)二苯甲酮,3,3',4,4'-肆(第三丁基二氧羰基)二苯甲酮等。 Generally known photoinitiators can be used, and specifically, benzoin and its alkyl ethers, such as benzoin, methyl benzoin, ethyl benzoin, etc.; acetophenone, such as acetophenone, 2,2-dibenzoin Methoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4-(1-tertiary butyldioxy-1-methylethyl)acetophenone, etc.; anthraquinone, Such as 2-methylanthraquinone, 2-pentylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, etc.; thioxanthones, such as 2,4-dimethylthioxanthone, 2,4 -Diisopropylthioxanthone, 2-chlorothioxanthone, etc.; ketals, such as acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.; benzophenone, Such as benzophenone, 4-(1-tertiary butyldioxy-1-methylethyl) benzophenone, 3,3',4,4'-four (tertiary butyl dioxycarbonyl) ) Benzophenone and so on.
作為較佳光起始劑,可提及2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基丙酮-1,2-苯甲基-2-二甲胺基-1-(4-嗎啉基苯基)丁烷-1-酮(2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-one);2-(二甲胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基)苯基]-1-丁酮;α-胺基苯乙酮(aminoacetophenones),諸如N,N-二甲胺基苯乙酮(作為商用產品,汽巴精化(Ciba Specialty Chemicals)(現為汽巴日本公司)的豔佳固(Irgacure)(註冊商標)907、豔佳固369,豔佳固379等);醯基氧化膦,諸如2,4,6-三甲基苯甲醯基二苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦、雙(2,6-二甲氧基苯甲醯基)2,4,4-三甲基-戊基氧化膦(商用產品,巴斯夫(BASF)公司的魯思林(Lucirin)(註冊商標)TPO,以及汽巴精化的豔佳固819等)。 As a preferred photoinitiator, mention may be made of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoacetone-1,2-benzyl-2-dimethylamine 1-(4-morpholinophenyl)butan-1-one (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl)-butane-1-one); 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino) Phenyl]-1-butanone; α-aminoacetophenones, such as N,N-dimethylaminoacetophenone (as a commercial product, Ciba Specialty Chemicals) (now steam Irgacure (registered trademark) 907, Irgacure 369, Irgacure 379, etc. from Pakistan Japan Company); phosphine oxides such as 2,4,6-trimethylbenzyl diphenyl Phosphine oxide, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzyl)2,4,4-trimethyl -Pentyl phosphine oxide (commercial products, Lucirin (registered trademark) TPO from BASF, and Yanjiagu 819 from Ciba Fine Chemicals, etc.).
另外,較佳光起始劑可包含肟酯。肟酯的具體實例可包含2-(乙醯基氧亞胺甲基)噻噸-9-酮、(1,2-辛二酮,1-[4-(苯硫基)苯基]-,2-(O-苯甲醯基肟))、(乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯肟))等。作為商用產品,可提及汽巴精化的GGI-325、豔佳固OXE01、豔佳固OXE02;艾迪科(ADEKA)公司的N-1919;汽巴精化的達若可(Darocur)TPO等。 In addition, preferred photoinitiators may include oxime esters. Specific examples of oxime esters may include 2-(acetoxyiminomethyl)thioxanthene-9-one, (1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzyl oxime)), (ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1 -(O-acetoxime)) and so on. As commercial products, we can mention Ciba's GGI-325, Yanjiagu OXE01, Yanjiagu OXE02; ADEKA's N-1919; Ciba's Darocur TPO Wait.
以樹脂組成物的總重量計,光起始劑的含量可為0.1重量%至20重量%或1重量%至10重量%。若光起始劑的含量過低,則可能無法恰當地實現光固化,且相反,若含量過高,則感光性樹脂組成物的解析度可能降低,或圖案膜的可靠性可能不足。 Based on the total weight of the resin composition, the content of the photoinitiator may be 0.1% to 20% by weight or 1% to 10% by weight. If the content of the photoinitiator is too low, photocuring may not be properly achieved, and on the contrary, if the content is too high, the resolution of the photosensitive resin composition may decrease, or the reliability of the pattern film may be insufficient.
感光性樹脂組成物可更包含由下述者所組成的族群中選出的一或多種:溶劑、填充劑、顏料(pigment)以及添加劑。 The photosensitive resin composition may further include one or more selected from the group consisting of solvents, fillers, pigments, and additives.
添加的填充劑起到提高樹脂的耐熱性及穩定性、針對熱的尺寸穩定性以及黏著性的作用。另外,其藉由強化顏色而充當增效劑顏料。作為填充劑,可使用無機填充劑或有機填充劑,且可使用例如硫酸鋇、鈦酸鋇、非晶矽石、結晶矽石、熔融矽石、球面矽石、滑石、黏土、碳酸鎂、碳酸鈣、氧化鋁(alumina)、氫氧化鋁,雲母等。 The added filler plays a role in improving the heat resistance and stability of the resin, dimensional stability against heat, and adhesion. In addition, it acts as a synergist pigment by enhancing the color. As fillers, inorganic fillers or organic fillers can be used, and for example, barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, carbonic acid can be used Calcium, aluminum oxide (alumina), aluminum hydroxide, mica, etc.
顏料展現可視性及遮蓋力,且作為顏料,可使用紅色顏料、藍色顏料、綠色顏料、黃色顏料以及黑色顏料等。作為藍色顏料,可使用酞菁藍(Phthalocyanine Blue)、顏料藍15:1(Pigment Blue 15:1)、顏料藍15:2、顏料藍15:3、顏料藍15:4、顏料藍15:6,顏料藍60等。作為綠色顏料,可使用顏料綠7、顏料綠36、溶劑綠3、溶劑綠5、溶劑綠20,溶劑綠28等。作為黃色顏料,可使 用蒽醌類、異吲哚啉酮類、稠合偶氮類,苯并咪唑酮類等,且可使用例如顏料黃108、顏料黃147、顏料黃151、顏料黃166、顏料黃181,顏料黃193等。作為紅色顏料,可使用顏料紅254等。 Pigments exhibit visibility and hiding power, and as pigments, red pigments, blue pigments, green pigments, yellow pigments, black pigments, etc. 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 so on. 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 a yellow pigment, it can be Anthraquinones, isoindolinones, condensed azos, benzimidazolones, etc. can be used. For example, Pigment Yellow 108, Pigment Yellow 147, Pigment Yellow 151, Pigment Yellow 166, Pigment Yellow 181, and pigments can be used. Huang 193 and so on. As the red pigment, Pigment Red 254 or the like can be used.
以樹脂組成物的總重量計,顏料的含量可較佳地為0.1重量%至10重量%或0.5重量%至5重量%。 Based on the total weight of the resin composition, the content of the pigment may preferably be 0.1% to 10% by weight or 0.5% to 5% by weight.
可添加添加劑以去除樹脂組成物的氣泡、在塗膜期間去除表面上的凸起或凹坑、提供阻燃性、控制黏度、充當觸媒等。 Additives can be added to remove bubbles of the resin composition, remove bumps or pits on the surface during film coating, provide flame retardancy, control viscosity, act as a catalyst, and the like.
具體言之,可使用常用的已知添加劑,諸如:增稠劑,諸如微粉化矽石、有機膨潤土,蒙脫石等;消泡劑及/或調平劑,諸如聚矽氧類、氟類,聚合物類等的彼等消泡劑及/或調平劑;矽烷偶合劑,諸如咪唑類、噻唑類,三唑類等的彼等矽烷偶合劑;以及阻燃劑,諸如含磷阻燃劑,銻類阻燃劑等。 Specifically, commonly used known additives can be used, such as: thickeners, such as micronized silica, organic bentonite, montmorillonite, etc.; defoamers and/or leveling agents, such as silicones, fluorine , Polymers and other defoamers and/or leveling agents; silane coupling agents, such as imidazoles, thiazoles, triazoles, etc.; and flame retardants, such as phosphorus-containing flame retardants Agent, antimony flame retardant, etc.
其中,調平劑執行在塗膜期間去除表面上的的凸起或凹坑的功能,且可使用例如BYK化學公司(BYK-Chemie GmbH)的BYK-380N、BYK-307、BYK-378以及BYK-350。 Among them, the leveling agent performs the function of removing bumps or pits on the surface during coating, and can be used, for example, BYK-380N, BYK-307, BYK-378, and BYK of BYK-Chemie GmbH. -350.
以樹脂組成物的總重量計,添加劑的含量可較佳地為0.01重量%至10重量%。 Based on the total weight of the resin composition, the content of the additive may preferably be 0.01% to 10% by weight.
溶劑可以一或多種溶劑的組合使用,以溶解樹脂組成物或提供適合的黏度。 The solvent can be used in combination of one or more solvents to dissolve the resin composition or provide suitable viscosity.
作為溶劑,可提及酮,諸如甲基乙基酮,環己酮等;芳烴,諸如甲苯、二甲苯,四甲基苯等;二醇醚(賽珞蘇),諸如乙二醇單乙醚、乙二醇單甲醚、乙二醇單丁醚、二乙二醇單乙醚、二甘醇單甲基醚、二甘醇單丁醚、丙二醇單甲基醚、丙二醇單乙醚、二丙二醇二乙醚,三甘醇單乙醚等;乙酸酯,諸如乙酸乙酯、 乙酸丁酯、乙二醇單乙醚乙酸酯、乙二醇單丁醚乙酸酯、二乙二醇單乙醚乙酸酯、二甘醇單丁醚乙酸酯、丙二醇單甲醚乙酸酯,二丙二醇單甲醚乙酸酯等;醇,諸如乙醇、丙醇、乙二醇、丙二醇,卡比醇等;脂族烴,諸如辛烷,癸烷等;石油類溶劑,諸如石油醚、石腦油、氫化石腦油,溶劑石腦油等;以及醯胺,諸如二甲基乙醯胺,二甲基甲醯胺(dimethyl formamide;DMF)等。 此等溶劑可單獨使用或以兩種或大於兩種類型的所述溶劑的組合形式使用。 As the solvent, mention may be made of ketones such as methyl ethyl ketone, cyclohexanone, etc.; aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, etc.; glycol ethers (Serosol) 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, etc.; acetate, 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, etc.; alcohols, such as ethanol, propanol, ethylene glycol, propylene glycol, carbitol, etc.; aliphatic hydrocarbons, such as octane, decane, etc.; petroleum solvents, such as petroleum ether, Naphtha, hydrogenated naphtha, solvent naphtha, etc.; and amides, such as dimethyl acetamide, dimethyl formamide (DMF) and the like. These solvents can be used alone or in a combination of two or more types of the solvents.
以樹脂組成物的總重量計,溶劑的含量可為5重量%至50重量%。若含量低於5重量%,則由於較高黏度而可能降低可塗佈性,且若含量大於50重量%,則可能無法對樹脂組成物進行良好地乾燥,從而增加黏性。 Based on the total weight of the resin composition, the content of the solvent may be 5% to 50% by weight. If the content is less than 5% by weight, coatability may be reduced due to higher viscosity, and if the content is more than 50% by weight, the resin composition may not be dried well, thereby increasing the viscosity.
感光性樹脂組成物可視需要更包含酸改性的寡聚物或熱固型黏結劑,且作為酸改性的寡聚物及熱固型黏結劑,可使用(但不限於)在感光性樹脂組成物的領域中已為人所熟知的各種化合物、寡聚物或聚合物。 The photosensitive resin composition may further include acid-modified oligomers or thermosetting binders as needed, and as acid-modified oligomers and thermosetting binders, it can be used (but not limited to) in photosensitive resins. Various compounds, oligomers or polymers are well known in the field of composition.
III.感光性樹脂膜III. Photosensitive resin film
本發明的又一實施例提供一種感光性樹脂膜,包含:一個實施例的光可固化及熱可固化的共聚物;以及具有兩個或大於兩個光可固化的不飽和官能基的光可聚合單體的固化產物。 Another embodiment of the present invention provides a photosensitive resin film comprising: the photocurable and thermally curable copolymer of one embodiment; and a photocurable resin having two or more than two photocurable unsaturated functional groups. The cured product of polymerized monomers.
感光性樹脂膜可為不包含圖案的單個膜,或可包含圖案膜,所述圖案膜包含藉由暴露而形成的圖案。 The photosensitive resin film may be a single film that does not include a pattern, or may include a patterned film including a pattern formed by exposure.
感光性樹脂膜可藉由製備感光性樹脂膜的方法來製備,所述方法包含以下步驟:1)在基板上塗覆另一實施例的感光性樹 脂組成物以形成塗層;2)對所述塗層進行乾燥;3)使光照射至經乾燥的塗層以進行光固化;以及4)在50℃至250℃下對經光固化的塗層進行熱固化。 The photosensitive resin film can be prepared by a method of preparing a photosensitive resin film, and the method includes the following steps: 1) Coating another embodiment of the photosensitive resin on the substrate Grease composition to form a coating; 2) drying the coating; 3) irradiating light to the dried coating for photocuring; and 4) applying light to the photocured coating at 50°C to 250°C The layer is thermally cured.
在所述在基板上塗覆另一實施例的感光性樹脂組成物以形成塗層的步驟(步驟1)中,感光性樹脂組成物如上文在另一實施例中所闡述。 In the step of coating the photosensitive resin composition of another embodiment on the substrate to form a coating layer (step 1), the photosensitive resin composition is as described above in another embodiment.
在基板上塗佈感光性樹脂組成物的方法不受具體限制,且可使用例如網版印刷、平版印刷、柔版打印,噴墨印刷等。 The method of coating the photosensitive resin composition on the substrate is not specifically limited, and, for example, screen printing, offset printing, flexographic printing, inkjet printing, etc. can be used.
另外,感光性樹脂組成物可藉由以下步驟形成:在有機溶劑中溶解或分散一個實施例的光可固化及熱可固化的共聚物、具有兩個或大於兩個光可固化的不飽和官能基的光可聚合單體以及光起始劑。 In addition, the photosensitive resin composition can be formed by the following steps: dissolving or dispersing the photo-curable and thermally curable copolymer of one embodiment in an organic solvent, having two or more than two photo-curable unsaturated functions -Based photopolymerizable monomers and photoinitiators.
對塗層進行乾燥的步驟(步驟2)是為了去除在感光性樹脂組成物中使用的溶劑等,且可使用例如對塗層進行加熱或真空蒸發的方法。較佳地可在50℃至130℃下進行乾燥,更佳地在70℃至120℃下進行乾燥。 The step of drying the coating layer (step 2) is to remove the solvent and the like used in the photosensitive resin composition, and a method such as heating or vacuum evaporation of the coating layer can be used. Preferably, drying can be performed at 50°C to 130°C, more preferably at 70°C to 120°C.
使光照射至經乾燥的塗層以進行光固化的步驟(步驟3)是使光照射至步驟2中經乾燥的塗層以對其進行固化的步驟。如上文所闡述,包含於一個實施例的光可固化及熱可固化的共聚物中的第二(甲基)丙烯酸酯重複單元中的含有烯基的有機官能基可藉由光照射進行光固化,由此形成固化結構。 The step of irradiating light to the dried coating to perform photocuring (step 3) is a step of irradiating light to the dried coating in step 2 to cure it. As explained above, the alkenyl-containing organic functional group in the second (meth)acrylate repeating unit included in the photocurable and thermally curable copolymer of one embodiment can be photocured by light irradiation , Thereby forming a cured structure.
在照射光以進行光固化的步驟中,藉由在具體波長範圍中的光(UV等)射線來進行暴露(exposure)。暴露可藉由利用光掩模的選擇性暴露或利用雷射直接步進電動機(laser direct stepper)的直接圖案暴露來進行。暴露量根據塗層厚度而變化,但較佳地為0.1毫焦/平方公分(mJ/cm2)至1000毫焦/平方公分。 In the step of irradiating light to perform photocuring, exposure is performed by light (UV, etc.) rays in a specific wavelength range. The exposure can be performed by selective exposure using a photomask or direct pattern exposure using a laser direct stepper. The amount of exposure varies according to the thickness of the coating, but is preferably 0.1 millijoules/cm² (mJ/cm 2 ) to 1000 millijoules/cm².
在使光照射至經乾燥的塗層以進行光固化的步驟(步驟3)之後,可視需要進行使用鹼性溶劑等來顯影(development)的步驟。作為鹼性溶劑,可使用氫氧化鉀、氫氧化鈉、碳酸鈉、碳酸鉀、磷酸鈉、矽酸鈉、氨,胺等的鹼性水溶劑。藉由顯影,僅暴露區域的膜可繼續存在。 After the step of irradiating light to the dried coating to perform photocuring (step 3), a step of development using an alkaline solvent or the like may be performed as necessary. As the alkaline solvent, alkaline aqueous solvents such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, and amines can be used. By developing, only the film in the exposed area can continue to exist.
亦即,若進行暴露,則例如在暴露區域處發生光固化以在光可固化及熱可固化的共聚物與包含於光可聚合單體中的不飽和官能基之間形成交聯,且因此,可能無法藉由後續顯影將其去除。 That is, if exposure is performed, for example, photocuring occurs at the exposed area to form a crosslink between the photocurable and thermally curable copolymer and the unsaturated functional group contained in the photopolymerizable monomer, and therefore , It may not be removed by subsequent development.
在50℃至250℃下對經光固化的塗層進行熱固化的步驟(步驟4)是對步驟3中經光固化的塗層進行低溫熱處理的步驟。 低溫熱處理的溫度較佳地為200℃或小於200℃。較佳地,低溫熱處理的溫度為50℃至250℃,更佳地為70℃至150℃或80℃至120℃。此處,用於熱處理的構件不受具體限制,且熱處理可藉由諸如加熱板、熱空氣循環反應器(hot air circulating reactor),紅外爐等的加熱構件來進行。 The step of thermally curing the photocured coating at 50°C to 250°C (step 4) is a step of performing low-temperature heat treatment on the photocured coating in step 3. The temperature of the low-temperature heat treatment is preferably 200°C or less. Preferably, the temperature of the low temperature heat treatment is 50°C to 250°C, more preferably 70°C to 150°C or 80°C to 120°C. Here, the member used for the heat treatment is not specifically limited, and the heat treatment can be performed by heating members such as a heating plate, a hot air circulating reactor, an infrared furnace, and the like.
如上文所闡述,包含於一個實施例的光可固化及熱可固化的共聚物中的第一(甲基)丙烯酸酯重複單元中的含有環氧基的有機官能基可藉由熱處理進行熱固化以形成固化結構。 As explained above, the epoxy-containing organic functional group in the first (meth)acrylate repeating unit included in the photocurable and thermally curable copolymer of one embodiment can be thermally cured by heat treatment To form a cured structure.
在感光性樹脂膜經由上文所闡述的方法而經歷光固化及熱固化時,其可包含一個實施例的光可固化及熱可固化的共聚物,以及具有兩個或大於兩個光可固化的不飽和官能基的光可聚 合單體的固化產物。更具體言之,固化產物可包含:交聯結構,其中光可固化及熱可固化的共聚物的環氧基與熱可固化的官能基藉由熱固化而交聯;以及交聯結構,其中第一(甲基)丙烯酸酯重複單元的烯基與光可聚合單體的不飽和官能基藉由光固化而彼此交聯。 When the photosensitive resin film undergoes photo-curing and thermal curing via the method described above, it may include the photo-curable and thermal-curable copolymer of one embodiment, and having two or more photo-curables. Photopolymerization of unsaturated functional groups The cured product of the combined monomer. More specifically, the cured product may include: a cross-linked structure in which the epoxy group of the photo-curable and thermally curable copolymer and the thermally curable functional group are cross-linked by thermal curing; and a cross-linked structure in which The alkenyl group of the first (meth)acrylate repeating unit and the unsaturated functional group of the photopolymerizable monomer are crosslinked with each other by photocuring.
此外,感光性樹脂膜可更包含在接受光固化之後繼續存在的少量光引發劑,或視需要添加的分散於固化產物中的顏料或添加劑。 In addition, the photosensitive resin film may further contain a small amount of photoinitiator that continues to exist after receiving light curing, or optionally added pigments or additives dispersed in the cured product.
感光性樹脂膜的厚度不受具體限制,但例如可將其自由地控制在0.01微米(μm)至1000微米的範圍內。若感光性樹脂膜的厚度增加或減少了具體數值,則感光性樹脂膜中所量測到的特性可發生多達具體數值的變化。 The thickness of the photosensitive resin film is not specifically limited, but it can be freely controlled within a range of 0.01 micrometers (μm) to 1000 micrometers, for example. If the thickness of the photosensitive resin film is increased or decreased by a specific value, the characteristics measured in the photosensitive resin film may change as much as the specific value.
IV.彩色濾光片IV. Color filter
本發明的又一實施例提供一種包含另一實施例的感光性樹脂膜的彩色濾光片。 Another embodiment of the present invention provides a color filter including the photosensitive resin film of another embodiment.
感光性樹脂膜的細節如上文在另一實施例中所闡述。在彩色濾光片中使用的感光性樹脂膜可包含分散於固化產物中的顏料。 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.
對於彩色濾光片的細節,可應用(但不限於)彩色濾光片的領域中已為人所熟知的各種技術構造。 For the details of the color filter, various technical configurations that are well-known in the field of color filters can be applied (but not limited to).
根據本發明,提供一種光可固化及熱可固化的共聚物以及使用所述共聚物的感光性樹脂組成物、感光性樹脂膜以及彩色濾光片,所述共聚物即使處於相對較低的溫度下亦具有極佳熱可固化 性,可藉由光照射進行光固化,且經由充分固化而具有極佳耐久性、耐化學性以及儲存穩定性。 According to the present invention, there is provided a photo-curable and heat-curable copolymer, and a photosensitive resin composition, a photosensitive resin film, and a color filter using the copolymer, even if the copolymer is at a relatively low temperature It also has excellent thermal curability It can be cured by light irradiation, and has excellent durability, chemical resistance and storage stability through sufficient curing.
在下文中,將在以下實例中詳細地闡述本發明。然而,此等實例僅呈現為本發明的說明,且本發明的範圍不受其限制。 Hereinafter, the present invention will be explained in detail in the following examples. However, these examples are only presented as illustrations of the present invention, and the scope of the present invention is not limited thereto.
<合成實例:光可固化及熱可固化的共聚物的合成><Synthesis example: Synthesis of photocurable and thermally curable copolymers>
合成實例1 Synthesis Example 1
在反應容器中,將5.1重量%的甲基丙烯酸苯甲酯、0.8重量%的N-苯基順丁烯二醯亞胺、0.6重量%的苯乙烯以及13.2重量%的甲基丙烯酸縮水甘油酯與78.9重量%的丙二醇甲醚乙酸酯(propylene glycol methyl ether acetate;PGMEA)溶劑放置在一起以使其溶解,且接著在氮氣氛圍下將溶液的溫度升高至75℃。當反應物的溫度達到75℃時,添加1.2重量%的熱起始劑V-65,且接著使反應物反應12小時。向得到的樹脂溶液添加熱聚合抑制劑及觸媒,且接著在空氣氛圍下引入0.1重量%的甲基丙烯酸,且在使溫度保持在120℃的同時使反應物反應16小時。製備的光可固化及熱可固化的共聚物的重量平均分子量為4500公克/莫耳,在分支鏈的末端處經環氧基取代的(甲基)丙烯酸酯重複單元的含量為49莫耳%,且在分支鏈的末端處經烯基取代的(甲基)丙烯酸酯重複單元的含量為21莫耳%。 In the reaction vessel, 5.1% by weight of benzyl methacrylate, 0.8% by weight of N-phenylmaleimide, 0.6% by weight of styrene, and 13.2% by weight of glycidyl methacrylate It was placed together with 78.9% by weight of propylene glycol methyl ether acetate (PGMEA) solvent to dissolve it, and then the temperature of the solution was increased to 75°C under a nitrogen atmosphere. When the temperature of the reactant reached 75°C, 1.2% by weight of the thermal initiator V-65 was added, and then the reactant was allowed to react for 12 hours. A thermal polymerization inhibitor and a catalyst were added to the obtained resin solution, and then 0.1% by weight of methacrylic acid was introduced in an air atmosphere, and the reactants were allowed to react for 16 hours while maintaining the temperature at 120°C. The prepared light-curable and heat-curable copolymer has a weight average molecular weight of 4500 g/mol, and the content of (meth)acrylate repeating units substituted by epoxy groups at the end of the branched chain is 49 mol% , And the content of the (meth)acrylate repeating unit substituted with an alkenyl group at the end of the branched chain is 21 mol%.
合成實例2 Synthesis example 2
除使用3,4-環氧環己基甲基丙烯酸甲酯替代甲基丙烯酸縮水甘油酯之外,藉由與合成實例1相同的方法來合成光可固化及熱可固化的共聚物。製備的光可固化及熱可固化的共聚物的重量平均分子量為4700公克/莫耳,在分支鏈的末端處經環氧基取代的(甲基)丙烯酸酯重複單元的含量為49莫耳%,且在分支鏈的末端處經烯基取代的(甲基)丙烯酸酯重複單元的含量為21莫耳%。 Except that 3,4-epoxycyclohexyl methyl methacrylate was used instead of glycidyl methacrylate, the photo-curable and heat-curable copolymers were synthesized by the same method as in Synthesis Example 1. The weight-average molecular weight of the prepared photo-curable and heat-curable copolymer is 4700 g/mol, and the content of (meth)acrylate repeating units substituted by epoxy groups at the end of the branched chain is 49 mol% , And the content of the (meth)acrylate repeating unit substituted with an alkenyl group at the end of the branched chain is 21 mol%.
合成實例3 Synthesis Example 3
除使用由以下化學式A表示的化合物替代甲基丙烯酸縮水甘油酯之外,藉由與合成實例1相同的方法來合成光可固化及熱可固化的共聚物。 The photo-curable and heat-curable copolymers were synthesized by the same method as Synthesis Example 1, except that the compound represented by the following chemical formula A was used instead of glycidyl methacrylate.
合成實例4 Synthesis Example 4
除使用由以下化學式B表示的化合物替代甲基丙烯酸縮水甘油酯之外,藉由與合成實例1相同的方法來合成光可固化及熱可固化的共聚物。 The photo-curable and heat-curable copolymers were synthesized by the same method as Synthesis Example 1, except that the compound represented by the following Chemical Formula B was used instead of glycidyl methacrylate.
[化學式B]
<比較合成實例><Comparative synthesis example>
比較合成實例1 Comparative Synthesis Example 1
在反應容器中,將9.3重量%的甲基丙烯酸苯甲酯、1.5重量%的N-苯基順丁烯二醯亞胺、1.1重量%的苯乙烯以及6.8重量%的甲基丙烯酸縮水甘油酯與74.6重量%的丙二醇甲醚乙酸酯(PGMEA)溶劑放置在一起以使其溶解,且接著在氮氣氛圍下將溶液的溫度升高至65℃。當反應物的溫度達到65℃時,添加0.7重量%的熱起始劑V-65。向得到的樹脂溶液添加熱聚合抑制劑及觸媒,且接著在空氣氛圍下引入4.3重量%的甲基丙烯酸,且在使溫度保持在120℃的同時使反應物反應16小時。將製備的樹脂溶劑的溫度降至90℃,且在空氣氛圍下引入5.5重量%的1,2,5,6-四氫鄰苯二甲酸酐,且使反應物反應24小時。製備的光可固化及熱可固化的共聚物的重量平均分子量為8100公克/莫耳,酸值為83KOH毫克/公克(mg/g),在分支鏈的末端處經環氧基取代的(甲基)丙烯酸酯重複單元的含量為0莫耳%,且在分支鏈的末端處經烯基取代的(甲基)丙烯酸酯重複單元的含量為40莫耳%。 In the reaction vessel, 9.3% by weight of benzyl methacrylate, 1.5% by weight of N-phenylmaleimide, 1.1% by weight of styrene, and 6.8% by weight of glycidyl methacrylate It was placed together with 74.6% by weight of propylene glycol methyl ether acetate (PGMEA) solvent to dissolve it, and then the temperature of the solution was increased to 65° C. under a nitrogen atmosphere. When the temperature of the reactant reaches 65°C, 0.7% by weight of the thermal initiator V-65 is added. A thermal polymerization inhibitor and a catalyst were added to the obtained resin solution, and then 4.3% by weight of methacrylic acid was introduced in an air atmosphere, and the reactants were allowed to react for 16 hours while maintaining the temperature at 120°C. The temperature of the prepared resin solvent was lowered to 90° C., and 5.5% by weight of 1,2,5,6-tetrahydrophthalic anhydride was introduced in an air atmosphere, and the reactants were allowed to react for 24 hours. The prepared light-curable and heat-curable copolymer has a weight average molecular weight of 8100 g/mol, an acid value of 83KOH mg/g (mg/g), and an epoxy group substituted at the end of the branched chain (former The content of the (meth)acrylate repeating unit is 0 mol%, and the content of the (meth)acrylate repeating unit substituted with an alkenyl group at the end of the branched chain is 40 mol%.
<實例及比較例:感光性樹脂組成物及感光性樹脂圖案膜的製備><Examples and Comparative Examples: Preparation of photosensitive resin composition and photosensitive resin pattern film>
實例1 Example 1
(1)感光性樹脂組成物 (1) Photosensitive resin composition
在35公克的丙二醇甲醚乙酸酯(PGMEA)溶劑中,在室溫下攪拌並溶解1公克的光起始劑豔佳固369(Irgacure 369)(由汽巴精化製造)30分鐘,且接著引入7.5公克的合成實例1中所得到的光可固化及熱可固化的共聚物及5公克的作為具有烯系不飽和雙鍵的可交聯單體的二季戊四醇五/六丙烯酸酯(dipentaerythritol penta/hexaacrylate;DPHA,由日本化藥(Nippon Kayaku)製造),且在室溫下攪拌反應混合物1小時,且接著,引入50公克的作為顏料的C.I.顏料紅254的15%分散液及0.2公克的添加劑,且在室溫下攪拌反應混合物1小時。將藉由以上反應得到的組成物過濾兩次或大於兩次以去除雜質,由此製備感光性樹脂組成物。 In 35 grams of propylene glycol methyl ether acetate (PGMEA) solvent, stir and dissolve 1 gram of the photoinitiator Irgacure 369 (manufactured by Ciba Fine Chemicals) at room temperature for 30 minutes, and Then introduce 7.5 grams of the photocurable and thermally curable copolymer obtained in Synthesis Example 1 and 5 grams of dipentaerythritol pentaerythritol pentaerythritol pentaerythritol penta/hexaacrylate; DPHA, manufactured by Nippon Kayaku (Nippon Kayaku), and the reaction mixture was stirred at room temperature for 1 hour, and then, 50 grams of 15% dispersion of CI Pigment Red 254 as a pigment and 0.2 grams were introduced , And the reaction mixture was stirred at room temperature for 1 hour. The composition obtained by the above reaction is filtered twice or more to remove impurities, thereby preparing a photosensitive resin composition.
(2)感光性樹脂圖案膜 (2) Photosensitive resin pattern film
以230轉/分鐘的速率在5公分x 5公分(cm)的玻璃基板上塗佈感光性樹脂組成物,且在100℃下進行預烘烤100秒。其後,藉由40毫焦/平方公分的能量暴露所述感光性樹脂組成物並使其顯影,且接著在100℃下進行後烘烤30分鐘,由此製備感光性樹脂圖案膜。 The photosensitive resin composition was coated on a 5 cm x 5 cm (cm) glass substrate at a rate of 230 revolutions per minute, and prebaked at 100°C for 100 seconds. Thereafter, the photosensitive resin composition was exposed and developed with an energy of 40 mJ/cm², and then post-baked at 100°C for 30 minutes, thereby preparing a photosensitive resin patterned film.
實例2 Example 2
除在製備感光性樹脂組成物時使用C.I.顏料綠7替代C.I.顏料紅254之外,藉由與實例1相同的方法來製備感光性樹脂組 成物及感光性樹脂圖案膜。 The photosensitive resin composition was 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 preparing the photosensitive resin composition Finished product and photosensitive resin pattern film.
實例3 Example 3
除在製備感光性樹脂組成物時使用C.I.顏料藍15:6替代C.I.顏料紅254之外,藉由與實例1相同的方法來製備感光性樹脂組成物及感光性樹脂圖案膜。 Except that C.I. Pigment Blue 15:6 was used instead of C.I. Pigment Red 254 when preparing the photosensitive resin composition, the photosensitive resin composition and the photosensitive resin pattern film were prepared by the same method as in Example 1.
實例4 Example 4
除在製備感光性樹脂組成物時使用合成實例2中所得到的光可固化及熱可固化的共聚物替代合成實例1中所得到的光可固化及熱可固化的共聚物之外,藉由與實例1相同的方法來製備感光性樹脂組成物及感光性樹脂圖案膜。 In addition to using the photo-curable and heat-curable copolymer obtained in Synthesis Example 2 to replace the photo-curable and heat-curable copolymer obtained in Synthesis Example 1 when preparing the photosensitive resin composition, by The photosensitive resin composition and the photosensitive resin pattern film were prepared in the same manner as in Example 1.
實例5 Example 5
除在製備感光性樹脂組成物時使用合成實例2中所得到的光可固化及熱可固化的共聚物替代合成實例1中所得到的光可固化及熱可固化的共聚物之外,藉由與實例2相同的方法來製備感光性樹脂組成物及感光性樹脂圖案膜。 In addition to using the photo-curable and heat-curable copolymer obtained in Synthesis Example 2 to replace the photo-curable and heat-curable copolymer obtained in Synthesis Example 1 when preparing the photosensitive resin composition, by The photosensitive resin composition and the photosensitive resin pattern film were prepared in the same manner as in Example 2.
實例6 Example 6
除在製備感光性樹脂組成物時使用合成實例2中所得到的光可固化及熱可固化的共聚物替代合成實例1中所得到的光可固化及熱可固化的共聚物之外,藉由與實例3相同的方法來製備感光性樹脂組成物及感光性樹脂圖案膜。 In addition to using the photo-curable and heat-curable copolymer obtained in Synthesis Example 2 to replace the photo-curable and heat-curable copolymer obtained in Synthesis Example 1 when preparing the photosensitive resin composition, by The photosensitive resin composition and the photosensitive resin pattern film were prepared in the same manner as in Example 3.
實例7 Example 7
除在製備感光性樹脂組成物時使用合成實例3中所得到的光可固化及熱可固化的共聚物替代合成實例1中所得到的光可固化及熱可固化的共聚物之外,藉由與實例1相同的方法來製備 感光性樹脂組成物及感光性樹脂圖案膜。 In addition to using the photo-curable and heat-curable copolymer obtained in Synthesis Example 3 in the preparation of the photosensitive resin composition instead of the photo-curable and heat-curable copolymer obtained in Synthesis Example 1, by Prepared in the same way as in Example 1. The photosensitive resin composition and the photosensitive resin pattern film.
實例8 Example 8
除在製備感光性樹脂組成物時使用合成實例4中所得到的光可固化及熱可固化的共聚物替代合成實例1中所得到的光可固化及熱可固化的共聚物之外,藉由與實例1相同的方法來製備感光性樹脂組成物及感光性樹脂圖案膜。 In addition to using the photo-curable and heat-curable copolymer obtained in Synthesis Example 4 in the preparation of the photosensitive resin composition instead of the photo-curable and heat-curable copolymer obtained in Synthesis Example 1, by The photosensitive resin composition and the photosensitive resin pattern film were prepared in the same manner as in Example 1.
比較例1 Comparative example 1
除在製備感光性樹脂組成物時使用由以下化學式C表示的熱固型樹脂(酚醛環氧樹脂的雙酚類型:由國都化工(Kukdo Chemicals)製造的KBPN-110)替代合成實例1中所得到的光可固化及熱可固化的共聚物之外,藉由與實例1相同的方法來製備感光性樹脂組成物及感光性樹脂圖案膜。 Except that the thermosetting resin represented by the following chemical formula C (bisphenol type of novolac epoxy resin: KBPN-110 manufactured by Kukdo Chemicals) was used in the preparation of the photosensitive resin composition instead of the synthesis example 1 Except for the obtained photo-curable and thermally curable copolymer, a photosensitive resin composition and a photosensitive resin pattern film were prepared by the same method as in Example 1.
比較例2 Comparative example 2
除在製備感光性樹脂組成物時使用在比較例1中所使用的熱固型樹脂替代合成實例1中所得到的光可固化及熱可固化的共聚物之外,藉由與實例2相同的方法來製備感光性樹脂組成物 及感光性樹脂圖案膜。 Except that the thermosetting resin used in Comparative Example 1 was used in the preparation of the photosensitive resin composition instead of the photo-curable and thermally curable copolymer obtained in Synthesis Example 1, the same as in Example 2 Method to prepare photosensitive resin composition And photosensitive resin pattern film.
比較例3 Comparative example 3
除在製備感光性樹脂組成物時使用在比較例1中所使用的熱固型樹脂替代合成實例1中所得到的光可固化及熱可固化的共聚物之外,藉由與實例3相同的方法來製備感光性樹脂組成物及感光性樹脂圖案膜。 Except that the thermosetting resin used in Comparative Example 1 was used in the preparation of the photosensitive resin composition instead of the photocurable and thermally curable copolymer obtained in Synthesis Example 1, the same as in Example 3 The method prepares the photosensitive resin composition and the photosensitive resin pattern film.
比較例4 Comparative example 4
除在製備感光性樹脂組成物時使用藉由比較合成實例1得到的共聚物樹脂替代藉由合成實例1得到的光可固化及熱可固化的共聚物之外,藉由與實例1相同的方法來製備感光性樹脂組成物及感光性樹脂圖案膜。 Except that the copolymer resin obtained by Comparative Synthesis Example 1 was used in the preparation of the photosensitive resin composition instead of the photocurable and thermally curable copolymer obtained by Synthesis Example 1, by the same method as Example 1 To prepare a photosensitive resin composition and a photosensitive resin pattern film.
比較例5 Comparative example 5
除在製備感光性樹脂組成物時使用比較合成實例1中所得到的共聚物樹脂替代合成實例1中所得到的光可固化及熱可固化的共聚物之外,藉由與實例2相同的方法來製備感光性樹脂組成物及感光性樹脂圖案膜。 Except that the copolymer resin obtained in Comparative Synthesis Example 1 was used in the preparation of the photosensitive resin composition instead of the photo-curable and thermally curable copolymer obtained in Synthesis Example 1, the same method as in Example 2 was used. To prepare a photosensitive resin composition and a photosensitive resin pattern film.
比較例6 Comparative example 6
除在製備感光性樹脂組成物時使用藉由比較合成實例1得到的共聚物樹脂替代藉由合成實例1得到的光可固化及熱可固化的共聚物之外,藉由與實例3相同的方法來製備感光性樹脂組成物及感光性樹脂圖案膜。 Except that the copolymer resin obtained by Comparative Synthesis Example 1 was used in the preparation of the photosensitive resin composition instead of the photocurable and thermally curable copolymer obtained by Synthesis Example 1, by the same method as Example 3 To prepare a photosensitive resin composition and a photosensitive resin pattern film.
<實驗實例:在實例及比較例中所得到的感光性樹脂組成物及感光性樹脂圖案膜的特性的量測><Experimental example: Measurement of the characteristics of the photosensitive resin composition and photosensitive resin pattern film obtained in the examples and comparative examples>
如下量測在實例及比較例中所得到的感光性樹脂組成物 及感光性樹脂圖案膜的特性,且結果示於下表中。 Measure the photosensitive resin composition obtained in the examples and comparative examples as follows And the characteristics of the photosensitive resin pattern film, and the results are shown in the following table.
1.實驗實例1:染色特性 1. Experimental example 1: Dyeing characteristics
在實例及比較例中所得到的感光性樹脂圖案膜上,塗佈包含顏料(所述顏料具有與感光性樹脂圖案膜中包含的顏料不同的顏色)的感光性樹脂組成物/使所述感光性樹脂組成物顯影,且接著,針對感光性樹脂圖案膜,將顏色變化量測為最小可辨色差(Minimum Perceptible Color Difference;MPCD),使用光學裝置觀測圖案運動及膨脹(swelling),且根據以下標準來判定顏料是否溶解,且結果繪示於下表1中。 The photosensitive resin pattern film obtained in the examples and comparative examples was coated with a photosensitive resin composition containing a pigment (the pigment has a color different from the pigment contained in the photosensitive resin pattern film)/the photosensitive resin composition The photosensitive resin composition is developed, and then, for the photosensitive resin patterned film, the color change is measured as the minimum perceptible color difference (MPCD), and the pattern movement and swelling are observed using an optical device, and according to the following Standards are used to determine whether the pigment is dissolved, and the results are shown in Table 1 below.
○:顏料完全未溶解 ○: The pigment is not dissolved at all
△:觀測到顏料微量溶解。 △: A slight amount of dissolution of the pigment is observed.
X:膜在與顏料溶解的同時剝離。 X: The film peeled off while dissolving with the pigment.
2.實驗實例2:耐化學性 2. Experimental example 2: Chemical resistance
在實例及比較例中所得到的感光性圖案膜上,塗佈保護層(over coat)光阻/使所述保護層光阻暴露/使所述保護層光阻顯影,且接著,針對感光性樹脂圖案膜,將顏色變化量測為最小可辨色差(Minimum Perceptible Color Difference;MPCD),使用光學裝置觀測圖案運動及膨脹(swelling),根據以下標準來判定顏料是否溶解,且結果繪示於下表1中。 On the photosensitive pattern films obtained in the Examples and Comparative Examples, a protective layer (over coat) photoresist was coated/exposed the protective layer photoresist/the protective layer photoresist was developed, and then, the photoresist For the resin pattern film, the color change is measured as the Minimum Perceptible Color Difference (MPCD), the pattern movement and swelling are observed using an optical device, and whether the pigment is dissolved is determined according to the following criteria, and the results are shown below in FIG. 1.
○:顏料完全未溶解 ○: The pigment is not dissolved at all
△:觀測到顏料微量溶解。 △: A slight amount of dissolution of the pigment is observed.
X:膜在與顏料溶解的同時剝離。 X: The film peeled off while dissolving with the pigment.
3.實驗實例3:儲存穩定性 3. Experimental example 3: Storage stability
使在實例及比較例中所得到的感光性樹脂組成物於製造 日期及之後2週在室溫下靜置,且接著量測顯影時間(秒)。結果繪示於下表1中。可看出,在製造日期與之後2週的時間中,顯影時間的變化愈小,儲存穩定性愈佳。 The photosensitive resin composition obtained in the examples and comparative examples was used to manufacture On the date and 2 weeks thereafter, let it stand at room temperature, and then measure the development time (seconds). The results are shown in Table 1 below. It can be seen that between the manufacturing date and the next 2 weeks, the smaller the change in the development time, the better the storage stability.
如表1所示,確認與使用普通熱固型樹脂的比較例1至比較例3相比,使用在合成實例中所得到的光可固化及熱可固化的共聚物作為黏結劑樹脂的實例的感光性樹脂組成物即使在100℃的溫度下進行後烘烤,亦藉由後續製程而具有極佳耐化學性及染色特性。 As shown in Table 1, it was confirmed that compared with Comparative Examples 1 to 3 using ordinary thermosetting resins, the photo-curable and thermally curable copolymers obtained in the synthesis examples were used as examples of binder resins. Even if the photosensitive resin composition is post-baked at a temperature of 100°C, it has excellent chemical resistance and dyeing properties through subsequent processes.
亦確認即使與使用比較合成實例中所得到的不包含第一(甲基)丙烯酸酯重複單元(其中含有環氧基的有機官能基鍵結至分支鏈的末端)的樹脂的比較例4至比較例6相比,所述感光性樹脂組成物亦藉由後續製程而具有極佳耐化學性及染色特性。 It was also confirmed that the resin obtained in the comparative synthesis example does not contain the first (meth)acrylate repeating unit (in which the organic functional group containing an epoxy group is bonded to the end of the branched chain) of the comparative example 4 to the comparative example. Compared with Example 6, the photosensitive resin composition also has excellent chemical resistance and dyeing properties through subsequent processes.
因此,可確認與現有熱固型黏結劑樹脂相比,在合成實 例中所得到的光可固化及熱可固化的共聚物即使處於低溫下亦展現極佳可固化性,且因此,可形成具有極佳耐熱性及耐化學性的固化膜。 Therefore, it can be confirmed that compared with the existing thermosetting adhesive resin, the The photo-curable and heat-curable copolymer obtained in the example exhibits excellent curability even at low temperatures, and therefore, a cured film having excellent heat resistance and chemical resistance can be formed.
另外,確認實例的感光性樹脂組成物可具有等效於比較例的感光性樹脂組成物或比比較例的感光性樹脂組成物好得多的儲存穩定性。因此,可確認即使與現有熱固型黏結劑樹脂相比,在合成實例中所得到的光可固化及熱可固化的共聚物亦可在固化時形成充分鍵結,由此實現極佳儲存穩定性。 In addition, it was confirmed that the photosensitive resin composition of the example may have storage stability equivalent to the photosensitive resin composition of the comparative example or much better than the photosensitive resin composition of the comparative example. Therefore, it can be confirmed that the photo-curable and heat-curable copolymer obtained in the synthesis example can form sufficient bonding during curing, thereby achieving excellent storage stability, even when compared with existing thermosetting binder resins. sex.
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