KR101051399B1 - Photosensitive resin composition and color filter using the same - Google Patents
Photosensitive resin composition and color filter using the same Download PDFInfo
- Publication number
- KR101051399B1 KR101051399B1 KR1020050026367A KR20050026367A KR101051399B1 KR 101051399 B1 KR101051399 B1 KR 101051399B1 KR 1020050026367 A KR1020050026367 A KR 1020050026367A KR 20050026367 A KR20050026367 A KR 20050026367A KR 101051399 B1 KR101051399 B1 KR 101051399B1
- Authority
- KR
- South Korea
- Prior art keywords
- group
- component
- acid
- carbon atoms
- resin composition
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 52
- 150000001875 compounds Chemical class 0.000 claims abstract description 53
- 229920005989 resin Polymers 0.000 claims abstract description 43
- 239000011347 resin Substances 0.000 claims abstract description 43
- 239000004593 Epoxy Substances 0.000 claims abstract description 28
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 18
- 239000003086 colorant Substances 0.000 claims abstract description 17
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 16
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 9
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 6
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 5
- 239000012860 organic pigment Substances 0.000 claims abstract description 5
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 27
- 239000011248 coating agent Substances 0.000 claims description 27
- 238000000576 coating method Methods 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 25
- 150000008065 acid anhydrides Chemical class 0.000 claims description 23
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 18
- 125000005843 halogen group Chemical group 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 7
- 125000002252 acyl group Chemical group 0.000 claims description 6
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000006678 phenoxycarbonyl group Chemical group 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims 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 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 13
- 230000035945 sensitivity Effects 0.000 abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- -1 oxime ester Chemical class 0.000 description 40
- 239000000203 mixture Substances 0.000 description 26
- 239000000049 pigment Substances 0.000 description 25
- 238000011161 development Methods 0.000 description 22
- 230000018109 developmental process Effects 0.000 description 22
- 239000002253 acid Substances 0.000 description 18
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
- 239000001052 yellow pigment Substances 0.000 description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 239000003513 alkali Substances 0.000 description 10
- 239000003822 epoxy resin Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000004973 liquid crystal related substance Substances 0.000 description 10
- 229920000647 polyepoxide Polymers 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000001055 blue pigment Substances 0.000 description 8
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 8
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 8
- 239000001054 red pigment Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000001056 green pigment Substances 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000001057 purple pigment Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 150000001991 dicarboxylic acids Chemical class 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000000059 patterning Methods 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 230000007261 regionalization Effects 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- KMOUUZVZFBCRAM-UHFFFAOYSA-N 1,2,3,6-tetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21 KMOUUZVZFBCRAM-UHFFFAOYSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- RBGUKBSLNOTVCD-UHFFFAOYSA-N 1-methylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C RBGUKBSLNOTVCD-UHFFFAOYSA-N 0.000 description 2
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 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
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 2
- CGLVZFOCZLHKOH-UHFFFAOYSA-N 8,18-dichloro-5,15-diethyl-5,15-dihydrodiindolo(3,2-b:3',2'-m)triphenodioxazine Chemical compound CCN1C2=CC=CC=C2C2=C1C=C1OC3=C(Cl)C4=NC(C=C5C6=CC=CC=C6N(C5=C5)CC)=C5OC4=C(Cl)C3=NC1=C2 CGLVZFOCZLHKOH-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 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 2
- 229930003836 cresol Natural products 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920001296 polysiloxane 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
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
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Classifications
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/08—Bridged systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D498/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- G—PHYSICS
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- G—PHYSICS
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials For Photolithography (AREA)
Abstract
고농도의 착색제를 함유하는 영역에 있어서, 내열황 변성이 적고, 고색순도이며, 고감도인 컬러필터용 감광성 수지 조성물을 제공한다.In the area | region containing a coloring agent of a high concentration, it provides the photosensitive resin composition for color filters with little heat-sulfur resistance, high color purity, and high sensitivity.
필수성분으로서, (A)성분; 비스페놀류로부터 유도되는 2개의 글리시딜에테르기를 갖는 에폭시 화합물과 (메타)아크릴산의 반응물을 또한 다염기 카르복실산 또는 그 무수물과 반응시켜서 얻어진 불포화기 함유 알칼리 가용성 수지, (B)성분; 1이상의 에틸렌성 불포화 결합을 갖는 광중합성 모노머, (C)성분; 1개 이상의 에폭시기를 갖는 화합물, (D)성분; 일반식(Ⅰ)으로 나타내는 화합물을 함유하는 광중합 개시제류, 및 (E)성분; 1개 이상의 유기안료를 함유하는 착색제를 필수성분으로 하고, 수지성분의 총중량(R)에 대한 (E)의 비율(E)/(R)이 0.5∼2.5인 컬리필터용 감광성 수지 조성물.As an essential component, (A) component; Unsaturated group-containing alkali-soluble resins obtained by reacting a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols with (meth) acrylic acid with a polybasic carboxylic acid or anhydride thereof, (B) component; Photopolymerizable monomer which has one or more ethylenically unsaturated bond, (C) component; A compound having one or more epoxy groups, (D) component; Photoinitiators containing the compound represented by general formula (I), and (E) component; The photosensitive resin composition for curling filters whose ratio (E) / (R) of (E) with respect to the gross weight (R) of a resin component is 0.5-2.5 as a coloring agent containing one or more organic pigments as an essential component.
[화 1][Tue 1]
Description
본 발명은 광경화성 조성물 및 그것을 이용한 컬러필터에 관한 것이고, 자세하게는, 컬러필터용의 레지스트에 적합한 감광성 수지 조성물에 관한 것이다.The present invention relates to a photocurable composition and a color filter using the same, and more particularly, to a photosensitive resin composition suitable for a resist for color filters.
컬러액정 표시장치는 광의 투과량 혹은 반사량을 제어하는 액정부와 컬러필터를 구성요소로 하지만, 그 컬러필터의 제조 방법은, 통상, 유리, 플라스틱 시트 등의 투명기판의 표면에 흑색의 매트릭스를 형성하고, 이어서, 적, 녹, 청의 다른색상을 순차, 스트라이프상 혹은 모자이크상 등의 색패턴으로 형성하는 방법이 사용되고 있다. 최근 몇년, 액정 텔레비전, 액정 모니터, 컬러액정 휴대전화 등 모든 분야에서 컬러액정 표시장치가 이용되고 있고, 컬러필터는 이들 컬러액정 표시장치의 시인성(視認性)을 좌우하는 중요한 부재 중 하나이다. 패턴 사이즈는 컬러필터의 용도 및 각각의 색에 따라 다르지만 적, 녹, 청의 화소는 200∼300㎛에서 세선화되고, 이에 따라 감광성 수지재료(감광성 수지 조성물 또는 광경화성 조성물이라고도 한다)에는 높은 치수정밀도가 요구되고 있다.The color liquid crystal display device includes a liquid crystal unit for controlling the amount of light transmission or reflection and a color filter, but the manufacturing method of the color filter generally forms a black matrix on the surface of a transparent substrate such as glass or plastic sheet. Subsequently, a method of forming different colors of red, green, and blue into color patterns such as sequential, striped, or mosaic forms is used. In recent years, color liquid crystal display devices have been used in all fields such as liquid crystal televisions, liquid crystal monitors, and color liquid crystal cell phones, and color filters are one of the important members that influence the visibility of these color liquid crystal display devices. The pattern size is different depending on the use of the color filter and the respective colors, but the red, green, and blue pixels are thinned at 200 to 300 µm, so that the dimensional accuracy is high for the photosensitive resin material (also called photosensitive resin composition or photocurable composition). Is required.
또, 최근의 컬러액정 디스플레이에 있어서, 고색순도이며 밝은 디스플레이가 요구되고 있지만, 거기에 따라 광경화성 조성물 중의 착색제의 함유비율이 증가하는 경향에 있다. 그러나, 착색제의 함유량이 증가하면, 컬러필터 형성시, 자외선 영역의 광이 도막심부까지 도달하기 어려워져, 광경화성 조성물 중의 경화불량에 의해 패턴의 밀착불량이나 현상시의 패턴 박리, 에지 형상의 샤프성 손실이 생기는 문제가 발생한다. 그 경화 불량을 개선하기 위해서, 표면거칠기가 없이 심부경화가 충분히 진행할때 까지 광중합 개시제나 증감제를 첨가하면, 광개시제의 착색이나 열처리후의 변색에 의한 컬러필터의 명도저하, 특히, 청색 컬러필터의 투과율을 저하시키는 원인도 된다.Moreover, in recent color liquid crystal displays, although high color purity and a bright display are calculated | required, there exists a tendency for the content rate of the coloring agent in a photocurable composition to increase accordingly. However, when the content of the colorant increases, light in the ultraviolet region is hard to reach the coating film core portion during the formation of the color filter, resulting in poor adhesion of the pattern or pattern peeling at the time of development due to poor curing in the photocurable composition, and sharp edge shape. The problem of sex loss occurs. In order to improve the curing failure, the addition of the photopolymerization initiator or the sensitizer until the deep curing is sufficiently progressed without surface roughness results in a decrease in the brightness of the color filter due to coloration of the photoinitiator or discoloration after heat treatment, in particular, the transmittance of the blue color filter. It also causes a decrease.
그래서, 광경화성 조성물 중의 경화 불량이 생기지 않도록 광중합 개시제를 다량으로 첨가했을 경우라도, 그 착색이나 열처리에 의한 변색이 적은 광중합 개시제의 종류 및 처방의 선택이 필요하게 된다. 또한 동시에, 저노광량에서의 패턴 치수안정성, 패턴 밀착성, 패턴 에지형상의 샤프성이 양호한 패턴을 넓은 현상 마진으로 얻는 것이 요구되고 있고, 그것을 위해서는 감광성 수지 조성물의 고감도화가 불가결하다.Therefore, even when a large amount of photoinitiator is added so that a curing failure in a photocurable composition does not arise, the kind of photoinitiator with little discoloration by the coloring and heat processing, and selection of a prescription are needed. At the same time, it is required to obtain a pattern having good pattern dimensional stability, pattern adhesion, and sharpness of a pattern edge shape at a low exposure amount with a wide development margin. For this purpose, high sensitivity of the photosensitive resin composition is indispensable.
[특허문헌 1] 일본 특허공개 평1-152449호 공보[Patent Document 1] Japanese Patent Application Laid-Open No. Hei1-152449
[특허문헌 2] 일본 특허공개 평7-278214호 공보[Patent Document 2] Japanese Patent Application Laid-Open No. 7-278214
[특허문헌 3] 일본 특허공개 2001-264530호 공보[Patent Document 3] Japanese Patent Application Laid-Open No. 2001-264530
[특허문헌 4] 일본 특허공개 2002-323762호 공보[Patent Document 4] Japanese Patent Application Laid-Open No. 2002-323762
[특허문헌 5] 일본 특허공개 2003-96118호 공보 [Patent Document 5] Japanese Patent Publication No. 2003-96118
[특허문헌 6] 일본 특허공개 2004-10838호 공보[Patent Document 6] Japanese Patent Application Laid-Open No. 2004-10838
[특허문헌 7] 일본 특허공개 2003-270785호 공보 [Patent Document 7] Japanese Patent Laid-Open No. 2003-270785
[특허문헌 8] 일본 특허공개 평10-301276호 공보[Patent Document 8] Japanese Patent Application Laid-Open No. 10-301276
[특허문헌 9] 일본 특허공개 평9-197663호 공보[Patent Document 9] Japanese Patent Application Laid-Open No. 9-197663
[특허문헌 10] 일본 특허공개 평9-95638호 공보 [Patent Document 10] Japanese Patent Application Laid-Open No. 9-95638
[특허문헌 11] 일본 특허공개 평7-3122호 공보 [Patent Document 11] Japanese Patent Application Laid-Open No. 7-3122
특허문헌 1에는 안료농도를 높여서 양호한 색재현성을 꾀하면서 감도저하를 방지하기 위해서, 고감도 광중합 개시제로서 할로메틸옥사디아졸계 화합물, 할로메틸-S-트리아진계 화합물의 사용예가 개시되어 있다. 그러나, 이들의 화합물은 산소에 의한 반응저해에 의해 표면 평탄성 저하는 개선되지만, 패턴치수 정밀도의 점에서는 여전히 만족할 만한 수준에는 달하지 않고 있다. 또한, 특허문헌 2∼5 등에는 고감도 광중합 개시제로서 감광성 수지 조성물에 옥심 에스테르계의 광중합 개시제를 사용한 예가 개시되어 있지만, 병용되어 있는 알칼리 가용성 수지의 감도 및 현상 특성이 충분하지 않기 때문에, 고농도의 착색제를 함유하는 감광성 수지 조성물에서는 양호한 패턴형성을 행하는 것이 곤란하다.Patent Literature 1 discloses examples of use of halomethyloxadiazole-based compounds and halomethyl-S-triazine-based compounds as high-sensitivity photopolymerization initiators in order to increase the pigment concentration and prevent deterioration of sensitivity while achieving good color reproducibility. However, these compounds have a reduction in surface flatness due to the inhibition of reaction with oxygen, but are still not satisfactory in terms of pattern dimension accuracy. Moreover, although patent documents 2-5 etc. disclose the example which used the oxime ester type photoinitiator for the photosensitive resin composition as a high-sensitivity photoinitiator, since the sensitivity and image development property of alkali-soluble resin used together are not enough, a high concentration coloring agent is disclosed. In the photosensitive resin composition containing, it is difficult to perform favorable pattern formation.
또, 상기 특허문헌 6∼11에는, 비스페놀 플루오렌 구조를 갖는 컬러필터용 감광성 수지 조성물의 실시예가 나타나 있지만, 비교적 통상의 광중합 개시제가 사용되어 있기 때문에, 특히 고농도의 착색제를 함유하는 감광성 수지 조성물에서는, 광중합 개시제의 첨가량이 많아지고, 거기에 따른 광개시제의 흡수나 열처리 후의 변색이 발생하고, 특히 청색 컬러필터의 투과성이나 색재현성을 충분히 얻을 수 없 다.Moreover, although the Example of the photosensitive resin composition for color filters which has a bisphenol fluorene structure is shown by the said patent documents 6-11, since the comparatively usual photoinitiator is used, especially in the photosensitive resin composition containing a high concentration coloring agent, The amount of addition of the photopolymerization initiator increases, resulting in absorption of the photoinitiator and discoloration after heat treatment, and in particular, the transparency and color reproducibility of the blue color filter cannot be sufficiently obtained.
따라서, 본 발명의 목적은 상기의 문제를 해결하고, 고농도의 착색제를 함유하는 영역에 있어서, 내열황 변성이 적고 고색순도이며, 또한 고감도의 컬러필터용 감광성 수지 조성물을 제공하는데 있다. 또한, 다른 목적은, 이 알칼리 현상형 감광성 수지 조성물을 사용해서 형성한 도막 및 컬러필터를 제공하는 것이다.It is therefore an object of the present invention to solve the above problems and to provide a photosensitive resin composition for color filters having low heat sulfur denaturation, high color purity, and high sensitivity in a region containing a high concentration of colorant. Moreover, another object is to provide the coating film and color filter formed using this alkali image development type photosensitive resin composition.
본 발명자들은 상기의 과제를 해결하기 위해 검토를 행한 결과, 비스페놀류로부터 유도되는 방향족 에폭시 화합물과 (메타)아크릴산의 반응물을 또한, 다염기산 카르복실산 또는 그 무수물과 반응시켜서 얻어진 불포화기 함유 화합물을 함유하는감광성 수지 조성물에, 광중합 개시제로서 특정한 화학구조를 갖는 옥심에스테르계의 광중합 개시제를 배합함으로써, 상기의 문제점이 해결되는 것을 찾아내고, 본 발명을 완성시켰다.MEANS TO SOLVE THE PROBLEM The present inventors conducted the examination in order to solve the said subject, and, as a result, it contains the unsaturated group containing compound obtained by making the reaction material of the aromatic epoxy compound and (meth) acrylic acid derived from bisphenols react with polybasic carboxylic acid or its anhydride. By mix | blending the oxime ester type photoinitiator which has a specific chemical structure as a photoinitiator to the said photosensitive resin composition, it discovered that the said problem was solved and completed this invention.
본 발명은 필수성분으로서 하기 (A)∼(E)성분The present invention provides the following components (A) to (E) as essential components.
(A)성분; 비스페놀류로부터 유도되는 2개의 글리시딜에테르기를 갖는 에폭시 화합물과 (메타)아크릴산과 반응물을 또한 다염기 카르복실산 또는 그 무수물과 반응시켜서 얻어진 불포화기 함유 알칼리 가용성 수지, (A) component; Unsaturated group-containing alkali-soluble resins obtained by reacting an epoxy compound having two glycidyl ether groups derived from bisphenols, a (meth) acrylic acid, and a reactant with a polybasic carboxylic acid or an anhydride thereof,
(B)성분; 적어도 1종류 이상의 에틸렌성 불포화 결합을 갖는 광중합성 모노머, (B) component; Photopolymerizable monomers having at least one or more ethylenically unsaturated bonds,
(C)성분; 적어도 1종류 이상의 에폭시기를 갖는 화합물, (C) component; A compound having at least one or more epoxy groups,
(D)성분; 일반식(Ⅰ)으로 나타내어지는 화합물을 필수로 하는 광중합 개시제, 및(D) component; Photoinitiator which makes a compound represented by general formula (I) essential, and
(E)성분; 적어도 1종류 이상의 유기안료를 함유하는 착색제를 함유하고, (E) component; It contains a coloring agent containing at least one organic pigment,
(A)성분과 (B)성분의 중량비율(A)/(B)이, 20/80∼90/10이며, 또한, 수지 및 중합성 성분의 합계로 이루어진 수지성분의 총중량(R)에 대한 (E)의 비율(E)/(R)이 0.5∼2.5가 되는 농도영역에서, (A)성분과 (B)성분의 합계 100중량부에 대하여, (D)성분을 2∼30중량부 함유하는 것을 특징으로 하는 컬러필터용 감광성 수지 조성물이다.The weight ratio (A) / (B) of (A) component and (B) component is 20/80-90/10, and with respect to the total weight (R) of the resin component which consists of the sum total of resin and a polymerizable component. 2-30 weight part of (D) component is contained with respect to a total of 100 weight part of (A) component and (B) component in the density | concentration area whose ratio (E) / (R) of (E) becomes 0.5-2.5. It is a photosensitive resin composition for color filters characterized by the above-mentioned.
[화 1][Tue 1]
단, R1은 페닐기(탄소수 1∼6의 알킬기, 페닐기 혹은 할로겐 원자로 치환되어 있어도 좋다), 탄소수 1∼20의 알킬기(1개 이상의 수산기로 치환되어 있어도 좋고, 알킬쇄의 중간에 l개 이상의 산소원자를 갖고 있어도 좋다), 탄소수 5∼8의 시클로알킬기, 탄소수 2∼20의 알카노일기 또는 벤조일기(탄소수가 1∼6의 알킬기 혹은 페닐기로 치환되어도 좋다)를 나타내고;However, R 1 may be substituted with a phenyl group (may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (may be substituted with one or more hydroxyl groups, and at least 1 oxygen in the middle of the alkyl chain). An atom), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group);
R2는 탄소수2∼12의 알카노일기(1개 이상의 할로겐 원자 혹은 시아노기에서 치환되어 있어도 좋다), 그 이중결합이 카르보닐기와 공역하지 않고 있는 탄소수 4∼6의 알케노일기, 벤조일기(탄소수 1∼6의 알킬기, 할로겐 원자 혹은 시아노기로 치환되어 있어도 좋다), 탄소수 2∼6의 알콕시 카르보닐기 또는 페녹시카르보닐기(1개 이상의 탄소수 1∼6의 알킬기 혹은 할로겐 원자로 치환되어 있어도 좋다)를 나타내고;R 2 is an alkanoyl group having 2 to 12 carbon atoms (may be substituted with one or more halogen atoms or a cyano group), an alkenoyl group having 4 to 6 carbon atoms in which the double bond is not conjugated with a carbonyl group, and a benzoyl group (with 1 carbon atom). Or an alkyl group, a halogen atom or a cyano group of 6 to 6), an alkoxycarbonyl group or phenoxycarbonyl group of 2 to 6 carbon atoms (which may be substituted with one or more alkyl groups or halogen atoms of 1 to 6 carbon atoms);
R3, R4 , R5, R6 및 R7은 서로 독립하고, 수소원자, 할로겐 원자, 탄소수 1∼12의 알킬기, 시클로펜틸기, 시클로헥실기, 페닐기, 벤질기, 벤조일기, 탄소수 2∼l2의 알카노일기, 탄소수2∼12의 알콕시 카르보닐기(알콕실기를 구성하는 알킬기의 탄소수가 2 이상의 경우, 알킬기는 1개 이상의 수산기로 치환되어 있어도 좋고, 알킬쇄의 중간에 1개 이상의 산소원자를 갖고 있어도 좋다), 페닐티오기(탄소수 1∼6의 알킬기로 치환되어 있어도 좋다) 또는 페녹시카르보닐기를 나타낸다.R 3 , R 4 , R 5 , R 6 and R 7 are independent of each other and represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group and 2 carbon atoms. An alkanoyl group of -l2 and an alkoxycarbonyl group having 2 to 12 carbon atoms (when the carbon number of the alkyl group constituting the alkoxyl group is 2 or more, the alkyl group may be substituted with one or more hydroxyl groups, and one or more oxygen atoms in the middle of the alkyl chain) Or a phenylthio group (may be substituted with an alkyl group having 1 to 6 carbon atoms) or a phenoxycarbonyl group.
또, 본 발명은 상기의 컬러필터용 감광성 수지 조성물을 경화시켜서 형성한 도막이다. 또한, 본 발명은 상기의 컬러필터용 감광성 수지 조성물을 도포, 경화시켜서 얻어진 도막에 의해 형성되어 있는 컬러필터이다.Moreover, this invention is the coating film which hardened | cured and formed said photosensitive resin composition for color filters. Moreover, this invention is a color filter formed with the coating film obtained by apply | coating and hardening said photosensitive resin composition for color filters.
본 발명의 컬러필터용 감광성 수지 조성물에 있어서, (A)성분이 비스페놀류로부터 유도되는 2개의 글리시딜에테르기를 갖는 에폭시 화합물과 (메타)아크릴산의 반응물과, a)포화 디카르복실산 또는 그 산무수물 및 b)포화 테트라카르복실산 또는 그 산2무수물을 그 몰비a/b가 O.1∼1O이 되는 범위에서 반응시켜서 얻어지고, 하기 일반식(Ⅱ)으로 나타내는 수지를 주성분으로서 함유하는 것이 바람직하다.In the photosensitive resin composition for color filters of this invention, (A) component is the reaction product of the epoxy compound which has two glycidyl ether groups derived from bisphenol, and (meth) acrylic acid, a) saturated dicarboxylic acid, or its It is obtained by making an acid anhydride and b) saturated tetracarboxylic acid or its acid anhydride react in the range whose molar ratio a / b becomes 0.1-10, and contains resin represented by following General formula (II) as a main component. It is preferable.
[화 2][Tue 2]
여기서 R1, R2, R3, R4는 독립적으로 수소원자, 탄소수 1∼5의 알킬기, 할로겐 원자 또는 페닐기를 나타내고, R5는 수소원자 또는 메틸기를 나타낸다. 또한, A는 -CO-, -S02-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -0-, 9,9-플루오레닐기 또는 직결합을 나타내고, X는 4가의 카르복실산 잔기를 나타내고, Y1, Y2는 독립적으로 수소원자 또는 -0C-Z-C00H를 나타내고(Z는 2가의 카르복실산 잔기를 나타낸다), n은 1∼20의 수를 나타낸다.R 1 , R 2 , R 3 and R 4 independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R 5 represents a hydrogen atom or a methyl group. In addition, A is -CO-, -S0 2- , -C (CF 3 ) 2- , -Si (CH 3 ) 2- , -CH 2- , -C (CH 3 ) 2- , -0-, 9 , A 9-fluorenyl group or a direct bond, X represents a tetravalent carboxylic acid residue, Y 1 , Y 2 independently represent a hydrogen atom or -0C-Z-C00H (Z is a divalent carboxylic acid N represents a number from 1 to 20.
본 발명의 컬러필터용 감광성 수지 조성물에 있어서, (D)성분이, 하기식(Ⅲ)으로 나타내는 화합물을 필수로 하는 광중합 개시제류인 것이 바람직하다. In the photosensitive resin composition for color filters of this invention, it is preferable that (D) component is a photoinitiator which makes the compound represented by following formula (III) essential.
[화 3][Tue 3]
이하, 본 발명의 감광성 수지 조성물에 대해서 상세하게 설명한다.Hereinafter, the photosensitive resin composition of this invention is demonstrated in detail.
본 발명의 감광성 수지 조성물은, 상기 (A)∼(E)성분을 필수성분으로서 함유하는 알칼리 현상 특성을 갖는 수지 조성물이다.The photosensitive resin composition of this invention is a resin composition which has alkali image development characteristic containing the said (A)-(E) component as an essential component.
(A)성분은 비스페놀류로부터 유도되는 2개의 글리시딜에테르기를 갖는 에폭시 화합물에 (메탈)아크릴산을 반응시켜, 얻어진 히드록시기를 갖는 화합물에, 다염기산인 디카르복실산류와 테트라카르복실산류 중 적어도 각 1종류와 반응시켜서 얻어진 에폭시(메타)아크릴레이트 산부가물이다. (A)성분은 에틸렌성 불포화 이중 결합과 카르복실기를 함께 갖기 때문에, 알칼리 현상형 감광성 수지 조성물이 뛰어난 광경화성, 양현상성, 패터닝 특성을 주고, 적, 녹, 청 각 화소의 물성향상을 초래한다.At least each of dicarboxylic acids and tetracarboxylic acids which are polybasic acids to the compound which has a hydroxyl group obtained by making (metal) acrylic acid react with the epoxy compound which has two glycidyl ether groups derived from bisphenols (A) component (A) It is an epoxy (meth) acrylate acid addition product obtained by making it react with one type. Since the component (A) has an ethylenically unsaturated double bond and a carboxyl group together, the alkali-developing photosensitive resin composition gives excellent photocurability, positive developability, and patterning characteristics, resulting in improvement of physical properties of red, green, and auditory pixels.
즉, (A)성분은 (메타)아크릴산에 유래하는 불포화기를 갖기 위해서 중합성을 갖는 것 외에, a)디카르복실산 또는 그 산무수물(이하, 디카르복실산류라고 약칭하는 경우가 있다) 및 b)테트라카르복실산 또는 그 산2무수물(이하, 테트라카르복실산류로 약칭하는 경우가 있다) 등의 다염기 카르복실산류에 유래하는 산성기를 갖기 위해서 알칼리 가용성을 갖는다.That is, in addition to having polymerizability in order to have an unsaturated group derived from (meth) acrylic acid, (A) component is a) dicarboxylic acid or its acid anhydride (henceforth abbreviated as dicarboxylic acids), and b) It has alkali solubility in order to have acidic groups derived from polybasic carboxylic acids, such as tetracarboxylic acid or its acid dianhydride (henceforth abbreviated to tetracarboxylic acids).
또한, 본 명세서에 있어서, 다염기 카르복실산류라고 할 때는, 상기 디카르복실산류, 테트라카르복실산류 등의 다염기 카르복실산 또는 이들의 산무수물을 의미하고, (메타)아크릴산은 아크릴산, 메타크릴산 또는 양쪽을 의미한다.In addition, in this specification, when it is polybasic carboxylic acid, it means polybasic carboxylic acid, such as the said dicarboxylic acid, tetracarboxylic acids, or these acid anhydrides, and (meth) acrylic acid is acrylic acid, meta Krylic acid or both.
(A)성분으로서는, 상기 특허문헌 6∼11 등에서 공지의 알칼리 가용성 수지를사용할 수 있지만, 이것에 한정되지 않는다. 바람직하게는, 일반식(Ⅱ)으로 나타내어지는 알칼리 가용성 수지이다. 이 알칼리 가용성 수지는, 하기 일반식(Ⅶ)으로 나타내어지는 아크릴레이트 화합물로부터 유도되어, 이 아크릴레이트 화합물은 대응하는 일반식(Ⅳ)또는 (Ⅵ)로 나타내어지는 에폭시 화합물로부터 유도되어, 이 에폭시 화합물은 대응하는 비스페놀류로부터 유도된다. 따라서, 비스페놀류를 예시하는 것에 의해, (A)성분이 이해된다.As (A) component, although well-known alkali-soluble resin can be used by the said patent documents 6-11, etc., it is not limited to this. Preferably, it is alkali-soluble resin represented by general formula (II). This alkali-soluble resin is derived from the acrylate compound represented by the following general formula (VII), and this acrylate compound is derived from the epoxy compound represented by the corresponding general formula (IV) or (VI), and this epoxy compound Is derived from the corresponding bisphenols. Therefore, (A) component is understood by illustrating bisphenols.
또한, 에폭시 화합물은 통상은 일반식(Ⅳ)으로 나타내지만, 주성분은 일반식(Ⅵ)으로 나타내는 화합물이므로, 이해를 쉽게 하기 위해서 일반식(Ⅵ)으로 나타낼 경우가 있다. 마찬가지로 아크릴레이트 화합물에 대해서도, 일반식(Ⅵ)으로 나타내어지는 에폭시 화합물에 대응하는 일반식(Ⅶ)으로 나타내어지는 아크릴레이트 화합물로 나타낼 경우가 있다.In addition, although an epoxy compound is normally represented by general formula (IV), since a main component is a compound represented by general formula (VI), it may be represented by general formula (VI) for easy understanding. Similarly, an acrylate compound may be represented by the acrylate compound represented by general formula (i) corresponding to the epoxy compound represented by general formula (VI).
[화 4][Tue 4]
[화 5][Tue 5]
일반식(Ⅱ), (Ⅳ), (Ⅵ), (Ⅶ)에 있어서, R1, R2, R3, R4는 독립적으로 수소원자, 탄소수1∼5의 알킬기, 할로겐 원자 또는 페닐기를 나타내지만, 바람직하게는 수소원자이며, A는 -CO-, -SO2-, -C(CF3)2-, Si(CH3)2-, -CH2-, -(CH3)2-, -O-, 9,9- 플루오레닐기 또는 부존재를 나타내지만, 바람직하게는 9,9-플루오레닐기이다. 1은 0∼10의 정수이지만, 바람직하게는 0 또는 평균값으로써 0∼2의 범위이다. 여기서, 9,9-플루오레닐기는 하기식 일반식(Ⅴ)으로 나타내는 기를 의미한다.In formulas (II), (IV), (VI) and ( iii ), R 1 , R 2 , R 3 and R 4 independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group. But preferably hydrogen atom, and A is -CO-, -SO 2- , -C (CF 3 ) 2- , Si (CH 3 ) 2- , -CH 2 -,-(CH 3 ) 2- , Although -O-, 9,9- fluorenyl group or absence is shown, Preferably it is 9,9- fluorenyl group. Although 1 is an integer of 0-10, Preferably it is the range of 0-2 as 0 or an average value. Here, 9, 9- fluorenyl group means group represented by following General formula (V).
[화 6][Tue 6]
또한, 일반식(Ⅱ)에 있어서는, X는 4가의 카르복실산 잔기를 나타내고, Y1, Y2는 독립적으로 수소원자, -OC-Z-(COOH)m으로 나타내어지는 카르복실산 잔기(m은 1∼3의 수를 나타낸다)를 나타내고, n은 1∼20의 수를 나타내지만, 평균의 반복수로서는 1∼10의 범위에 있는 것이 바람직하다.In General Formula (II), X represents a tetravalent carboxylic acid residue, and Y 1 and Y 2 independently represent a hydrogen atom and a carboxylic acid residue represented by -OC-Z- (COOH) m (m). Represents a number of 1 to 3), and n represents a number of 1 to 20, but the average repeating number is preferably in the range of 1 to 10.
바람직한 (A)성분의 알칼리 가용성 수지를 주는 비스페놀류로서는, 다음과 같은 것을 들 수 있다. 비스(4-히드록시페닐)케톤, 비스(4-히드록시-3,5-디메틸페닐)케톤, 비스(4-히드록시-3,5-디클로로페닐)케톤, 비스(4-히드록시페닐)술폰, 비스(4-히드록시-3,5-디메틸페닐)술폰, 비스(4-히드록시-3,5-디클로로페닐)술폰, 비스(4-히드록시페닐)헥사플루오로프로판, 비스(4-히드록시-3,5-디메틸페닐)헥사플루오로프로판, 비스(4-히드록시-3,5-디클로로페닐)헥사플루오로프로판, 비스(4-히드록시페닐)디메틸실란, 비스(4-히드록시-3,5-디메틸페닐)디메틸실란, 비스(4-히드록시-3,5-디클로로페닐)디메틸실란, 비스(4-히드록시페닐)메탄, 비스(4-히드록시- 3,5-디클로로페닐)메탄, 비스(4-히드록시-3,5-디브로모페닐)메탄, 2,2-비스(4-히드록시페닐)프로판, 2,2-비스(4-히드록시-3,5-디메틸페닐)프로판, 2,2-비스(4-히드록시-3,5-디클로로페닐)프로판, 2,2-비스(4-히드록시-3-메틸페닐)프로판, 2,2-비스(4-히드록시-3-클로로페닐)프로판, 비스(4-히드록시페닐)에테르, 비스(4-히드록시-3,5-디메틸페닐)에테르, 비스(4-히드록시-3,5-디클로로페닐)에테르 등. 또는 A가 9,9-플루오레닐기인 9,9-비스(4-히드록시페닐)플루오렌, 9,9-비스(4-히드록시-3-메틸페닐)플루오렌, 9,9-비스(4-히드록시-3-클로로페닐)플루오렌, 9,9-비스(4-히드록시-3-브로모페닐)플루오렌, 9,9-비스(4-히드록시-3-플루오로페닐)플루오렌, 9,9-비스(4-히드록시-3,5-디메틸페닐)플루오렌, 9,9-비스(4-히드록시-3,5-디클로로페닐)플루오렌, 9,9-비스(4-히드록시-3,5-디브로모페닐)플루오렌 등도 바람직하게 들 수 있다. 또한, 4,4'-비페놀, 3,3'-비페놀 등도 바람직하게 들 수 있다.As bisphenol which gives alkali-soluble resin of a preferable (A) component, the following are mentioned. Bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, bis (4-hydroxy-3,5-dichlorophenyl) ketone, bis (4-hydroxyphenyl) Sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) sulfone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4 -Hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4- Hydroxy-3,5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5 -Dichlorophenyl) methane, bis (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3 , 5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy -3,5-dichlorophenyl) ether and the like. Or 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (A is a 9,9-fluorenyl group) 4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) Fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene etc. are mentioned preferably. Moreover, 4,4'-biphenol, 3,3'-biphenol etc. are mentioned preferably.
(A)성분은 상기와 같은, 비스페놀류로부터 유도되는 에폭시 화합물로부터 얻을 수 있지만, 그 에폭시 화합물 외에 페놀 노볼락형 에폭시 화합물이나, 크레졸 노볼락형 에폭시 화합물 등도 2개의 글리시딜에테르기를 갖는 화합물을 유용하게 함유한 것이면 사용할 수 있다. 또한, 비스페놀류를 글리시딜 에테르화할 때, 올리고머 단위가 혼입되게 되지만, 식(Ⅳ)에 있어서의 1의 평균값이 0∼10, 바람직하게는 0∼2의 범위이면, 본 수지 조성물의 성능에는 문제는 없다.The component (A) can be obtained from the above-described epoxy compounds derived from bisphenols, but in addition to the epoxy compound, a phenol novolak-type epoxy compound, a cresol novolak-type epoxy compound, and the like have a compound having two glycidyl ether groups. If it contains usefully, it can be used. In addition, when glycidyl etherification of bisphenols, an oligomer unit will mix, but if the average value of 1 in Formula (IV) is 0-10, Preferably it is the range of 0-2, the performance of this resin composition will There is no problem.
이러한 에폭시 화합물과 (메타)아크릴산의 반응은, 에폭시 화합물 1몰에 대하여, 약 2몰의 (메타)아크릴산을 사용하여 행하지만, 그 반응은 상기 특허문헌 6∼11 등에서 공지한 것이다. 이 반응방법이나 반응물은, 상기 특허문헌 등에 기재 되어 있다. Although reaction of such an epoxy compound and (meth) acrylic acid is performed using about 2 mol of (meth) acrylic acid with respect to 1 mol of epoxy compounds, the reaction is well-known in the said patent documents 6-11. This reaction method and a reactant are described in the said patent document.
에폭시 화합물과 (메타)아크릴산의 반응으로 얻어진 반응물과, 다가 카르복실산류를 반응시켜서 (A)성분의 알칼리 가용성 수지를 얻는다. 다가 카르복실산류로서는, 에폭시(메타)아크릴레이트 화합물 분자 중의 히드록시기와 반응하여 얻는 a)디카르복실산류와 b)테트라카르복실산류의 병용이 바람직하다.The reactant obtained by reaction of an epoxy compound and (meth) acrylic acid, and polyhydric carboxylic acid are made to react, and alkali-soluble resin of (A) component is obtained. As polyhydric carboxylic acid, the combination of a) dicarboxylic acid and b) tetracarboxylic acid obtained by reacting with the hydroxyl group in an epoxy (meth) acrylate compound molecule is preferable.
여기서, 디카르복실산류로서는, 쇄식 탄화수소 디카르복실산 또는 그 산무수물이나 지환식 디카르복실산 또는 그 산무수물, 방향족 디카르복실산이나 그 산무수물이 사용된다. Here, as dicarboxylic acid, chain hydrocarbon dicarboxylic acid or its acid anhydride, alicyclic dicarboxylic acid or its acid anhydride, aromatic dicarboxylic acid or its acid anhydride is used.
쇄식 탄화수소 디카르복실산 또는 그 산무수물로서는, 예를 들면, 숙신산, 아세틸숙신산, 마레인산, 아디핀산, 이타콘산, 아제라인산, 시트라말릭산(Citramalic acid), 말론산, 글루타르산, 구연산, 주석산, 옥소글루타르산, 피메린산(pimelic acid), 세바신산, 스베린산(suberic acid), 디글리콜산 등의 화합물이 있고, 또한, 임의인 치환기의 도입된 디카르복실산류 또는 그 산무수물이어도 좋다.Examples of the chain hydrocarbon dicarboxylic acid or its acid anhydride include succinic acid, acetyl succinic acid, maleic acid, adipic acid, itaconic acid, azaline acid, citramalic acid, malonic acid, glutaric acid and citric acid. , Tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, and the like, and dicarboxylic acids introduced with an optional substituent, or It may be an acid anhydride.
또, 지환식 디카르복실산 또는 그 산무수물로서는, 예를 들면, 헥사 히드로 프탈산, 시클로부탄 디카르복실산, 시클로펜탄 디카르복실산, 노르보르난 디카르복실산 등의 화합물이 있고, 또한, 임의의 치환기의 도입된 디카르복실산류 또는 그 산무수물이어도 좋다.Moreover, as alicyclic dicarboxylic acid or its acid anhydride, there exist compounds, such as hexa hydrophthalic acid, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, norbornane dicarboxylic acid, for example, Or dicarboxylic acids introduced with arbitrary substituents or acid anhydrides thereof.
또한, 방향족 디카르복실산이나 그 산무수물로서는, 예를 들면 프탈산, 이소프탈산 등의 화합물이 있고, 또한 임의의 치환기의 도입된 디카르복실산류 또는 그 산무수물이어도 좋다.Moreover, as aromatic dicarboxylic acid and its acid anhydride, there exist compounds, such as a phthalic acid and an isophthalic acid, for example, and the dicarboxylic acid in which arbitrary substituents were introduced, or its acid anhydride may be sufficient.
또, b)테트라카르복실산류로서는, 쇄식 탄화수소 테트라카르복실산 또는 그 산2무수물이나 지환식 테트라카르복실산 또는 그 산2무수물, 혹은, 방향족다가 카르복실산 혹은 그 산 2무수물이 사용된다.B) As tetracarboxylic acids, a linear hydrocarbon tetracarboxylic acid or an acid dianhydride thereof, an alicyclic tetracarboxylic acid or an acid dianhydride thereof, or an aromatic polyvalent carboxylic acid or an acid dianhydride is used.
여기서, 쇄상 테트라카르복실산 또는 그 산무수물로서는, 예를 들면, 부탄테트라카르복실산, 펜탄 테트라카르복실산, 헥산 테트라카르복실산 등이 있고, 또한 치환기의 도입된 테트라카르복실산류 또는 그 산무수물이어도 좋다. 또한, 지환식 테트라카르복실산 또는 그 산무수물로서는, 예를 들면, 시클로부탄 테트라카르복실산, 시클로펜탄 테트라카르복실산, 시클로헥산 테트라카르복실산, 시클로헵탄 테트라카르복실산 노르보르난 테트라카르복실산 등이 있고, 또한 치환기의 도입된 테트라카르복실산류 또는 그 산무수물이어도 좋다.Here, as chain | strand tetracarboxylic acid or its acid anhydride, butane tetracarboxylic acid, a pentane tetracarboxylic acid, hexane tetracarboxylic acid, etc. are mentioned, for example, the tetracarboxylic acids or its acid which were introduce | transduced by a substituent. Anhydrides may be used. Moreover, as alicyclic tetracarboxylic acid or its acid anhydride, For example, cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid norbornane tetracarbox Acid and the like, or tetracarboxylic acids introduced with a substituent or an acid anhydride thereof may be used.
또한, 방향족 테트라카르복실산이나 그 산무수물로서는, 예를 들면, 피로멜리틱산(Pyromellitic acid), 벤조페논 테트라카르복실산, 비페닐 테트라카르복실산, 비페닐에테르 테트라카르복실산 또는 그 산무수물을 들 수 있고, 또한 치환기의 도입된 테트라카르복실산류 또는 그 산무수물이어도 좋다.Moreover, as aromatic tetracarboxylic acid or its acid anhydride, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, or its acid anhydride, for example These may be mentioned, and tetracarboxylic acids of the substituent or the acid anhydride thereof may be used.
a)디카르복실산류와 b)테트라카르복실산류는 각각 1종 이상을 사용할 수 있고, a)디카르복실산류와 b)테트라카르복실산류의 사용비율은, 양자의 몰비a/b로서 0.1∼10이 되는 범위, 바람직하게는 0.2∼1이 되는 범위이다. 이 사용비율은 최적분자량, 알칼리 현상성, 광투과성, 내열성, 대용제성, 패턴형상의 효과에 적합한 비율을 선택할 수 있지만, 테트라카르복실산류의 사용비율이 클수록 알칼리 용해성 이 커지고, 분자량이 커지는 경향이 된다.The a) dicarboxylic acid and b) tetracarboxylic acid can be used 1 or more types, respectively, and the usage ratio of a) dicarboxylic acid and b) tetracarboxylic acid is 0.1-0.1 as molar ratio a / b of both. It is a range used as 10, Preferably it is a range used as 0.2-1. Although the ratio is suitable for the optimum molecular weight, alkali developability, light transmittance, heat resistance, solvent resistance, and pattern shape effect, the ratio of tetracarboxylic acids used increases alkali solubility and tends to increase molecular weight. do.
또, a)디카르복실산류로서, 포화 디카르복실산이나 그 산무수물, 또한, b)테트라카르복실산류로서 포화 테트라카르복실산이나 그 산무수물을 사용한 경우, 패턴 치수안정성이나 패턴 밀착성 및 패턴 에지 형상의 샤프성이 보다 양호하게 되고, 넓은 현상 마진에서의 패터닝이 가능해 지는 경우가 있다.Moreover, when a) saturated dicarboxylic acid and its acid anhydride are used as a) dicarboxylic acids, and b) tetracarboxylic acid and its acid anhydride are used as tetracarboxylic acids, pattern dimensional stability, pattern adhesiveness, and pattern Sharpness of the edge shape may be better, and patterning at a wider development margin may be possible.
에폭시 화합물과 (메타)아크릴산의 반응으로 얻어진 반응물과, 산성분을 반응시켜 (A)성분을 제조하는 방법에 대해서는, 특별히 한정되는 것이 아닌, 상기 특허문헌 6∼11에 기재된 바와 같은 공지의 방법을 채용할 수 있다.The method for producing the component (A) by reacting the reactant obtained by the reaction of the epoxy compound with (meth) acrylic acid and the acid component is not particularly limited, and the known methods as described in the Patent Documents 6 to 11 are used. It can be adopted.
유리하게는, 에폭시(메타)아크릴레이트 화합물 분자 중의 히드록시기 1몰당 산성분이 1/2몰이 되도록 정량적으로 반응시키는 것이 바람직하다. 또한, 반응온도로서는, 90∼130℃, 바람직하게는 95∼125℃이다.Advantageously, it is preferred to react quantitatively so that the acid component per mole of hydroxy group in the epoxy (meth) acrylate compound molecule is 1/2 mole. Moreover, as reaction temperature, it is 90-130 degreeC, Preferably it is 95-125 degreeC.
(A)성분을 제조하는 방법의 일례를 9,9-비스(4-히드록시페닐)플루오렌을 출발원료로 하는 경우에 대해서 나타내면, 다음과 같다.When an example of the method of manufacturing (A) component is shown about the case where 9, 9-bis (4-hydroxyphenyl) fluorene is used as a starting raw material, it is as follows.
우선, 9,9-비스(4-히드록시페닐)플루오렌과 에피클로로히드린을 반응시켜서 일반식(Ⅵ)으로 나타내는 바와 같은 비스페놀 플루오렌형 에폭시 화합물을 합성하고, 이 비스페놀 플루오렌형 에폭시 화합물과 CH2=CR5-COOH로 나타내어지는 (메타)아크릴산을 반응시켜서 일반식(Ⅶ)으로 나타내어지는 것 같은 비스페놀 플루오렌형 에폭시 아크릴레이트 수지를 합성하고, 다음으로 프로필렌 글리콜 모노메틸 용제중에서 비스페놀 플루오렌형 에폭시 아크릴레이트 수지와 상기 산성분을 가열하에 반 응시켜, (A)성분인 상기 일반식(Ⅱ)으로 나타내는 플루오렌형의 알칼리 가용성 수지를 얻는다.First, 9,9-bis (4-hydroxyphenyl) fluorene and epichlorohydrin are reacted to synthesize a bisphenol fluorene type epoxy compound represented by the general formula (VI), and the bisphenol fluorene type epoxy compound Reacting (meth) acrylic acid represented by CH 2 = CR 5 -COOH to synthesize a bisphenol fluorene type epoxy acrylate resin represented by the general formula (VIII), and then in a propylene glycol monomethyl solvent, a bisphenol flu Orene type epoxy acrylate resin and the said acid component are reacted under heating, and alkali-soluble resin of fluorene type represented by the said General formula (II) which is (A) component is obtained.
본 발명의 감광성 수지 조성물은 상기 (A)성분을 수지성분의 필수성분으로서 함유한다. 여기서, 수지성분이란, 중합 또는 경화시키는 것에 의해 수지가 되는 성분을 말하고, 수지 외에, 올리고머, 모노머도 함유한다. 또한, (A)성분은 1Owt% 이상, 바람직하게는 20wt% 이상, 보다 바람직하게는 30wt% 이상 함유하는 것이 좋다.The photosensitive resin composition of this invention contains the said (A) component as an essential component of a resin component. Here, a resin component means the component which becomes a resin by superposing | polymerizing or hardening, and contains an oligomer and a monomer other than resin. The component (A) is preferably 10 wt% or more, preferably 20 wt% or more, and more preferably 30 wt% or more.
본 발명의 감광성 수지 조성물이, (A)성분 이외에 다음의 (B)∼(D)성분을 유효량 함유한다.The photosensitive resin composition of this invention contains an effective amount of following (B)-(D) component other than (A) component.
(B)성분; 적어도 1종류 이상의 에틸렌성 불포화 결합을 갖는 광중합성 모노머(B) component; Photopolymerizable monomers having at least one ethylenically unsaturated bond
(C)성분; 적어도 1종류 이상의 에폭시기를 갖는 화합물(C) component; Compound having at least one kind or more epoxy group
(D)성분; 일반식(I)으로 나타내어지는 화합물을 유효량 함유하는 광중합 개시제류 (D) component; Photoinitiators containing an effective amount of the compound represented by general formula (I)
(B)성분의 적어도 1개 이상의 에틸렌성 불포화 결합을 갖는 광중합성 모노머로서는, 예를 들면, 2-히드록시에틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트 등의 수산기를 갖는 모노머나, 에틸렌글리콜디(메타)아크릴레이트, 디에틸렌글리콜디(메타)아크릴레이트, 트리에틸렌글리콜디(메타)아크릴레이트, 테트라에틸렌글리콜디(메타)아크릴레이트, 테트라메틸렌글리콜디(메타)아크릴레이트, 트리메티롤프로판트리(메타)아크릴레이트, 트리메티롤에탄트리(메타)아크릴레이트, 펜타에리스리톨디(메타)아크릴레이트, 펜타에리스리톨트리(메타)아크릴레이트, 펜타에리스리톨테트라(메타)아크릴레이트, 디펜타에리스리톨테트라(메타)아크릴레이트, 디펜타에리스리톨헥사(메타)아크릴레이트, 글리세롤(메타)아크릴레이트 등의 (메타)아크릴산 에스테르류를 들 수 있고, 이들의 화합물은, 그 1종 또는 2종 이상을 사용할 수 있다.As a photopolymerizable monomer which has at least 1 or more ethylenically unsaturated bond of (B) component, For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl Monomers having hydroxyl groups such as (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acryl Rate, tetramethylene glycol di (meth) acrylate, trimetholpropane tri (meth) acrylate, trimetholethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylic Elate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) a (Meth) acrylic acid esters, such as a acrylate, are mentioned, These compounds can use 1 type (s) or 2 or more types.
이들 (A)성분과 (B)성분의 배합비율은, 중량비(A)/(B)로 20/80∼90/10이며, 바람직하게는 40/60∼80/20이다. (A)성분의 배합비율이 적으면, 광 경화후의 경화 물이 물러지고, 또한, 미노광부에 있어서 도막의 산가가 낮기 때문에 알칼리 현상액에 대한 용해성이 저하하고, 패턴 에지가 덜컥거려 샤프하게 되지 않는다는 문제가 발생하고, 또한 많게는 수지를 차지하는 광반응성 관능기의 비율이 적은 가교 구조의 형성이 충분하지 않고, 또한, 수지성분에 있어서의 산가도가 지나치게 높아서, 노광부에 있어서의 알칼리 현상액에 대한 용해성이 높아진다는 점으로부터, 형성된 패턴이 목표로 하는 선폭보다 가늘어지거나, 패턴의 결락이 발생되기 쉬워진다는 문제가 생길 우려가 있다.The compounding ratio of these (A) component and (B) component is 20 / 80-90 / 10 in weight ratio (A) / (B), Preferably it is 40 / 60-80 / 20. When the blending ratio of the component (A) is small, the cured product after the photocuring is receded, and since the acid value of the coating film is low in the unexposed part, the solubility in the alkaline developer is lowered, and the edge of the pattern does not become mushy and sharp. A problem arises, and formation of a crosslinked structure with a small proportion of photoreactive functional groups occupying a resin is not sufficient, and the acid value in the resin component is too high, so that the solubility in the alkaline developer in the exposed portion is high. From the high point, there exists a possibility that a problem may arise that the formed pattern becomes thinner than the target line width, or the fall of a pattern becomes easy to occur.
(C)성분의 에폭시 화합물은, 또한 밀착성 향상, 내알칼리성의 향상을 목적으로 배합한다. 에폭시기를 갖는 화합물로서는, 예를 들면 페놀 노블락형 에폭시수지, 크레졸 노블락형 에폭시수지, 비스페놀A형 에폭시수지, 비스페놀F형 에폭시수지, 비스페놀S형 에폭시수지, 비스페닐형 에폭시수지, 지환식 에폭시수지 등의 에폭시수지, 페닐글리시딜에테르, p-부틸페놀글리시딜에테르, 트리글리시딜 이소시아누레이트, 디글리시딜 이소시아누레이트, 알릴글리시딜 에테르, 글리시딜메타크릴레이트 등의 기를 적어도 1개 갖는 화합물 등을 들 수 있다.The epoxy compound of (C) component is mix | blended for the purpose of further improving adhesiveness and alkali resistance. Examples of the compound having an epoxy group include phenol noblock type epoxy resins, cresol noblock type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenyl type epoxy resins, and alicyclic epoxy resins. Epoxy resins, phenylglycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, allyl glycidyl ether, glycidyl methacrylate, and the like. The compound etc. which have at least one group are mentioned.
이 에폭시 화합물의 배합량은, 상기 (A)성분과 (B)성분의 합계 100 중량부에 대하여 10∼30중량부의 범위로 배합하는 것이 좋다.It is preferable to mix | blend the compounding quantity of this epoxy compound in the range of 10-30 weight part with respect to a total of 100 weight part of said (A) component and (B) component.
또, (D)성분의 광중합 개시제류로서는, 일반식(I)으로 나타내는 옥심 에스테르형 광중합 개시제를 사용하지만, 더욱 감도를 올리고, 감광성 수지의 경화밀도를 높이기 위해서, 다른 종류의 개시제나 증감제 등과 병용해서 사용할 수 있다. 일반식(I)에 있어서, R1∼R8은 상기한 대로의 의미를 갖지만, 바람직하게는 R6이 페닐티오기이며, R1이 탄소수2∼6의 알킬기이며, R2가 치환기를 가지고 있어도 좋은 벤조일기이며, 기타가 H이다. 보다 바람직한 옥심 에스테르형 광중합 개시제는, 일반식(Ⅲ)으로 나타내는 화합물이다. 본 발명에서 말하는 광중합 개시제류는, 광중합 개시제의 이외에 증감제를 함유하는 의미로 사용된다.Moreover, although the oxime ester type photoinitiator represented by General formula (I) is used as photoinitiator of (D) component, in order to raise a sensitivity and to raise hardening density of photosensitive resin, other types of initiators, sensitizers, etc. Can be used in combination. In general formula (I), although R <1> -R <8> has the meaning as mentioned above, Preferably R <6> is a phenylthio group, R <1> is a C2-C6 alkyl group, and R <2> has a substituent It may be a benzoyl group, and the guitar is H. More preferable oxime ester type photoinitiator is a compound represented by general formula (III). The photoinitiators mentioned in this invention are used by the meaning containing a sensitizer other than a photoinitiator.
또, 병용가능한 광중합 개시제 혹은 증감제로서는 예를 들면, 아세토페논, 2,2-디에톡시 아세토페논, p-디메틸 아세토페논, p-디메틸 아미노 프로피오페논, 디클로로 아세토페논, 트리클로로 아세토페논, p-tert-부틸 아세토페논 등의 아세토페논류, 벤조페논, 2-클로로 벤조페논, p,p'-비스디메틸 아미노 벤조페논 등의 벤조페논류, 벤질, 벤조인, 벤조인 메틸에테르, 벤조인 이소프로필 에테르, 벤조인 이소부틸 에테르 등의 벤조일 에테르류, 2-(o-클로로 페닐)-4,5-페닐비이미다졸, 2-(o-클로로페닐)-4,5-디(m-메톡시페닐)비이미다졸, 2-(o-플루오로페닐)-4,5-디페닐비이미다졸, 2-(o-메톡시페닐)-4,5-디페닐비이미다졸, 2,4,5-트리아릴비이미다졸 등의 비이미다졸계 화합물류, 2-트리클로로메틸-5-스티릴-1,3,4-옥사디아졸, 2-트리클로로메틸-5-(p-시아노스티릴)-1,3,4-옥사디아졸, 2-트리클로로메틸-5-(p-메톡시스티릴)-1,3,4-옥사디아졸 등의 할로메틸티아졸 화합물류, 2,4,6-트리스(트리클 로로메틸)-1,3,5-트리아진, 2-메틸-4,6-비스(트리클로로메틸)-1,3,5-트리아진, 2-페닐-4,6-비스(트리클로로메틸)-1,3,5-트리아진, 2-(4-클로로페닐)-4,6-비스(트리클로로메틸)-1,3,5-트리아진, 2-(4-메톡시페닐)-4,6-비스(트리클로로메틸)-1,3,5-트리아진, 2-(4-메톡시나프틸)-4,6-비스(트리클로로R메틸)-1,3,5-트리아진, 2-(4-메톡시스티릴)-4,6-비스(트리클로로메틸)-1,3,5-트리아진, 2-(3,4,5-트리메톡시스티릴)-4,6-비스(트리클로로메틸)-1,3,5-트리아진, 2-(4-메틸티오스티릴)-4,6-비스(트리클로로메틸)-1,3,5-트리아진 등의 할로메틸-S-트리아진계 화합물류, 1,2-옥탄디온, 1-[4-(페닐티오)페닐]-, 2-(O-벤조일옥심), 1-(4-페닐술파닐페닐)부탄-1,2-디온-2-옥심-0-벤조에이트, 1∼(4∼메틸술파닐페닐)부탄-1,2-디온-2-옥심-0-아세테이트, 1-(4-메틸술파닐페닐)부탄-1-온옥심-0-아세테이트 등의 O-아실 옥심계 화합물류, 벤질디메틸케탈, 티옥산톤, 2-클로로티옥산톤, 2,4-디에틸티옥산톤, 2-메틸티옥산톤, 2-이소프로필티옥산톤 등의 유황 화합물, 2-에틸안트라퀴논, 옥탄메틸안트퀴라논, 1,2-벤즈안트라퀴논, 2,3-디페닐안트퀴라논 등의 안트라퀴논류, 아조비스이소부틸니트릴, 벤조일퍼옥사이드, 쿠멘퍼옥시드 등의 유기과산화물, 2-메르캅토벤조이미다졸, 2-메르캅토벤조옥사졸, 2-메르캅토벤조티아졸 등의 티올 화합물, 트리에탄올아민, 트리에틸아민 등의 제 3급 아민 등을 들 수 있다.Moreover, as a photoinitiator or sensitizer which can be used together, for example, acetophenone, 2,2- diethoxy acetophenone, p-dimethyl acetophenone, p-dimethyl amino propiophenone, dichloro acetophenone, trichloro acetophenone, p acetophenones such as -tert-butyl acetophenone, benzophenones such as benzophenone, 2-chloro benzophenone, p, p'-bisdimethylamino benzophenone, benzyl, benzoin, benzoin methyl ether, benzoin iso Benzoyl ethers such as propyl ether, benzoin isobutyl ether, 2- (o-chloro phenyl) -4,5-phenylbiimidazole, 2- (o-chlorophenyl) -4,5-di (m-meth Methoxyphenyl) biimidazole, 2- (o-fluorophenyl) -4,5-diphenylbiimidazole, 2- (o-methoxyphenyl) -4,5-diphenylbiimidazole, 2,4 Biimidazole-based compounds such as, 5-triarylbiimidazole, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-sia Nothryl) -1,3,4-oxadi Halomethylthiazole compounds such as sol and 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole, 2,4,6-tris (trichloromethyl)- 1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1, 3,5-triazine, 2- (4-chlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl) -4,6- Bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloroRmethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis Halomethyl- such as (trichloromethyl) -1,3,5-triazine and 2- (4-methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine S-triazine compounds, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), 1- (4-phenylsulfanylphenyl) butane-1, 2-dione-2-oxime-0-benzoate, 1- (4-methylsulfate) O-acyl oxime compounds such as panylphenyl) butane-1,2-dione-2-oxime-0-acetate and 1- (4-methylsulfanylphenyl) butan-1-one oxime-0-acetate, benzyl Sulfur compounds, such as dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethyl thioxanthone, 2-methyl thioxanthone, and 2-isopropyl thioxanthone, 2-ethyl anthraquinone, and octane Anthraquinones such as methyl anthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthydranone, organic peroxides such as azobisisobutylnitrile, benzoyl peroxide, cumene peroxide, and 2-mercapto Thiol compounds such as benzoimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole, and tertiary amines such as triethanolamine and triethylamine.
(D)성분의 광중합 개시제류는, 그 1종 또는 2종 이상을 병용할 수 있다. 일반식(Ⅰ)으로 나타내는 화합물은, (D)성분의 광중합 개시제류 중에 유효량 이상, 바람직하게는 50중량% 이상, 보다 바람직하게는 80중량% 이상 함유시키는 것이 좋다.The photoinitiator of (D) component can use together 1 type (s) or 2 or more types. The compound represented by the general formula (I) is preferably contained in the photopolymerization initiators of the component (D) in an effective amount or more, preferably 50% by weight or more, and more preferably 80% by weight or more.
또한, (D)성분의 광중합 개시제류의 총사용량은, (A) 및 (B)의 각 성분의 합계 100중량부를 기준으로서 2∼50중량부이며, 바람직하게는 5∼40중량부이다. (D)성분의 배합비율이 적으면, 광중합의 속도가 늦어져서 감도가 저하되고, 한편, 너무 많으면 감도가 너무 강해져 패턴 선폭이 패턴 마스크에 대하여 두꺼운 상태가 되고, 마스크에 대하여 충실한 선폭을 재현할 수 없다. 또한, 패턴 에지가 덜컹거려 샤프하게 되지 않는다는 문제가 발생될 우려가 있다.The total amount of photopolymerization initiators of component (D) is 2 to 50 parts by weight, and preferably 5 to 40 parts by weight based on 100 parts by weight in total for each component of (A) and (B). When the blending ratio of component (D) is small, the speed of photopolymerization is slowed down, and sensitivity is lowered. On the other hand, when the amount is too large, the sensitivity is too strong. Can't. In addition, there is a fear that a problem occurs that the pattern edge is not ragged and sharp.
또한, (E)성분의 착색제는, 색조가 특별히 한정된 것은 아니고, 얻어진 컬러필터의 용도에 따라서 적정 선택되며, 안료, 염료 혹은 천연색소 어느 것이라도 좋다. 컬러필터에는 고정밀 세밀한 발색과 내열성이 요구되고 있다는 점에서, 유기안료를 함유하는 것, 바람직하게는 50∼100중량% 함유하는 것이 이용된다.In addition, the coloring agent of (E) component is not specifically limited in color tone, It selects suitably according to the use of the obtained color filter, Any of a pigment, dye, or a natural pigment may be sufficient. Since the color filter requires high color development and heat resistance, the thing containing an organic pigment, Preferably what contains 50-100 weight% is used.
상기 유기안료로서는, 적색용도에는 단일의 적색안료계를 이용해도 좋고, 황색안료계를 적색안료계에 혼합해서 색조를 행해도 좋다. 적색안료계로서는, 예를 들면 안트라퀴논계 안료, 퀴나크리돈계 안료, 티케토피로로계 안료, 페릴렌계 안료 등, 특히 바람직하게는 디케토피로로피롤 레드(C.I 피그멘트 레드 254)나 디안트라퀴논 레드(C.I 피그멘트 레드 177) 등을 들 수 있다.As said organic pigment, a single red pigment system may be used for red use, and a yellow pigment system may be mixed with a red pigment system, and color tone may be performed. As the red pigment system, for example, anthraquinone pigments, quinacridone pigments, tiketopyrroro pigments, and perylene pigments, particularly preferably diketopyrrolopyrrole red (CI pigment red 254) or dianthra Quinone red (CI pigment red 177), and the like.
황색안료계로서는, 예를 들면, 이소인돌린 옐로(C.I 피그멘트 옐로 139), 니켈아조 옐로(C.I 피그멘트 옐로 150), 디아리리드 옐로(C.I 피그멘트 옐로 83) 등을 들 수 있다. 이들 적색안료계 및 황색안료계는 각각 2종 이상을 혼합해서 이용할 수도 있다. 또한, 적색안료계와 황색안료계를 혼합해서 이용하는 경우에는, 적색안료계와 황색안료계의 총량 100중량부에 대하여 황색안료계를 90중량부 이하로 이용하는 것이 바람직하다.As a yellow pigment type | system | group, isoindolin yellow (C.I pigment yellow 139), nickel azo yellow (C.I pigment yellow 150), a diary lead yellow (C.I pigment yellow 83), etc. are mentioned, for example. These red pigment type and yellow pigment type can also mix and use 2 or more types, respectively. In addition, when mixing and using a red pigment system and a yellow pigment system, it is preferable to use a yellow pigment system at 90 weight part or less with respect to 100 weight part of total amounts of a red pigment system and a yellow pigment system.
녹색의 안료에는 단일의 녹색안료계를 이용해도 좋고, 황색안료계를 녹색안료계에 혼합해서 조색을 행해도 좋다. 적색안료계로서는, 염소화 프탈로시아닌 그린(C.I 피그멘트 그린 7), 브롬 염소화 프탈로시아닌 그린(C.I 피그멘트 그린 36) 등을 들 수 있다. 또한, 황색안료로서는 예를 들면, 이소인돌린 옐로(C.I 피그멘트 옐로 139), 니켈아조 옐로(C.I 피그멘트 옐로 150), 디아리리드 옐로(C.I 피그멘트 옐로 83) 등을 들 수 있다. 이들의 녹색안료계 및 황색안료계는 각각 2종 이상 혼합해서 이용하는 것도 가능하다. 또한, 녹색안료계와 황색안료계를 혼합해서 이용하는 경우에는 녹색안료계와 황색안료계의 총량 100중량부에 대하여 황색안료계를 90중량부 이하로 이용하는 것이 바람직하다.A single green pigment system may be used for the green pigment, or a yellow pigment system may be mixed with the green pigment system to colorize. Examples of the red pigment system include chlorinated phthalocyanine green (C.I pigment green 7), brominated chlorinated phthalocyanine green (C.I pigment green 36), and the like. Examples of the yellow pigment include isoindolin yellow (C.I pigment yellow 139), nickel azo yellow (C.I pigment yellow 150), diaryrid yellow (C.I pigment yellow 83), and the like. These green pigments and yellow pigments may be used in combination of two or more kinds, respectively. In addition, when using a mixture of a green pigment system and a yellow pigment system, it is preferable to use a yellow pigment system at 90 weight part or less with respect to 100 weight part of total amounts of a green pigment system and a yellow pigment system.
청색의 안료에는, 단일의 청색안료계를 이용해도 좋고, 자색안료계를 청색안료계에 혼합해서 조색을 행해도 좋다. 청색안료계로서는, 프탈로시아닌계 안료, 스렌계 안료 등, 특히 바람직하게는 ε-프탈로시아닌 블루(C.I 피그멘트 블루 15:6) 등을 들 수 있다. 또한, 자색안료계로서는, 예를 들면, 디옥사진 바이올렛(C.I 피그멘트 바이올렛 23) 등을 들 수 있다. 이들의 청색안료계 및 자색안료계는 각각 2종 이상 혼합해서 이용할 수도 있다. 또한, 청색안료계와 자색안료계를 혼합해서 이용하는 경우에는, 청색안료계와 자색안료계의 총량 100중량부에 대하여 자색안료계를 90중량부 이하로 이용하는 것이 바람직하다.As a blue pigment, a single blue pigment system may be used, and a purple pigment system may be mixed with a blue pigment system, and coloration may be performed. Examples of the blue pigments include phthalocyanine-based pigments and srenne-based pigments, and particularly preferably ε-phthalocyanine blue (C.I pigment blue 15: 6). Moreover, as a purple pigment type, dioxazine violet (C.I pigment violet 23) etc. are mentioned, for example. These blue pigments and purple pigments may be used in combination of two or more kinds, respectively. In addition, when mixing and using a blue pigment system and a purple pigment system, it is preferable to use a purple pigment system at 90 weight part or less with respect to 100 weight part of total amounts of a blue pigment system and a purple pigment system.
또한, (E)성분의 착색제의 첨가량은, 수지성분의 총중량(R)에 대한 (E)성분의 (E)/(R)이 0.5∼2.5, 바람직하게는 1.0∼2.0, 보다 바람직하게는 1.5∼1.8이 되 도록 배합한다. 여기서 수지성분의 총중량(R)은 조성물 중의 수지 및 중합성 성분(모노머, 올리고머 등으로 중합 또는 경화해서 수지가 되는 성분을 말한다)의 합계를 말한다.Moreover, the addition amount of the coloring agent of (E) component is 0.5-2.5, Preferably it is 1.0-2.0, More preferably, 1.5 (E) / (R) of (E) component with respect to gross weight (R) of a resin component. Mix it so that it may become -1.8. Here, the total weight (R) of the resin component refers to the sum of the resin in the composition and the polymerizable component (the component that is polymerized or cured with a monomer, oligomer, etc. to be a resin).
이 (E)/(R)비가 낮으면, 색순도가 충분하지 않게 되고, 바람직한 콘트래스트를 얻기 위해서는, 막두께를 두껍게 하지 않으면 안되고, 컬러필터의 면평활성을 얻기 어렵다. 반대로 너무 높으면, (E)성분을 함유하는 컬러필터용 감광성 수지 조성물의 분산 안정성이 저하되고, 또한, 본래의 바인더가 되는 감광성 수지의 함유량도 감소하기 때문에, 현상특성을 손상함과 아울러 막형성능이 손상된다는 바람직하지 않은 문제가 발생될 우려가 있다.If this (E) / (R) ratio is low, color purity will become inadequate, and in order to obtain favorable contrast, a film thickness must be made thick and the surface smoothness of a color filter is hard to be obtained. On the contrary, when too high, dispersion stability of the photosensitive resin composition for color filters containing (E) component will fall, and content of the photosensitive resin used as an original binder will also fall, and it will impair development characteristics and a film forming ability. There is a fear that undesirable problems of damage occur.
또한, 착색제의 분산 안정화 용도에 분산제를 이용하는 경우가 있다. 분산제는 착색제와 함꼐 사용할 수 있고, 이러한 분산제로서는, 예를 들면, 양이온계, 음이온계, 비이온계, 양성, 실리콘계, 불소계 등의 계면 활성제를 들 수 있다. 상기 계면활성제의 구체예로서는, 폴리옥시에틸렌라우릴에테르, 폴리옥시에틸렌스테아릴에테르 등의 폴리옥시에틸렌알킬에테르류 등을 들 수 있다.Moreover, a dispersing agent may be used for the dispersion stabilization use of a coloring agent. The dispersant may be used together with a colorant, and examples of such dispersants include surfactants such as cationic, anionic, nonionic, amphoteric, silicone, and fluorine based. Specific examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether.
본 발명의 감광성 수지 조성물을 컬러필터용에 사용하는 경우, 상기 (A)∼(E)성분 외에 용제를 사용하는 것이 바람직하다. 용제로서는 예를 들면, 메탄올, 에탄올, n-프로판올, 이소프로판올, 에틸렌글리콜, 프로필렌글리콜 등의 알콜류, α- 혹은 β-텔피네올 등의 텔펜류 등, 아세톤, 메틸에틸케톤, 시클로헥사논, N-메틸-2-피롤리돈 등의 케톤류, 톨루엔, 크실렌, 테트라메틸벤젠 등의 방향족 탄화수소류, 셀로솔브, 메틸셀로솔브, 에틸셀로솔브, 카르비톨, 메틸카르비톨, 에틸카르 비톨, 부틸카르비톨, 프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노에틸에테르, 디프로필렌글리콜모노메틸에테르, 디프로필렌글리콜모노에틸에테르, 트리에틸렌글리콜모노메틸에테르, 트리에틸렌글리콜모노에틸에테르 등의 글리콜에테르류, 초산에틸, 초산부틸, 셀로솔브아세테이트, 에틸셀로솔브아세테이트, 부틸셀로솔브아세테이트, 카르비톨아세테이트, 에틸카르비톨아세테이트, 부틸카르비톨아세테이트, 프리필렌글리콜모노메틸에테르아세테이트, 프로필렌글리콜모노에틸에테르아세테이트 등의 초산에세테르류 등을 들 수 있고, 이들을 이용하여, 용해, 혼합시킴으로써, 균일한 용액상의 조성물로 할 수 있다.When using the photosensitive resin composition of this invention for color filters, it is preferable to use a solvent other than said (A)-(E) component. As a solvent, For example, alcohols, such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, telpens, such as (alpha)-or (beta)-tepineol, acetone, methyl ethyl ketone, cyclohexanone, N- Ketones such as methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methylcarbitol, ethylcarbitol, butylcarb Glycol ethers such as bitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, Butyl Acetate, Cellosolve Acetate, Ethyl Cellosolve Acetate, Butyl Cellosolve Acetate, Carbitol Acetate, Ethyl Carbitol Acetate, Butyl Acetate acetates, such as carbitol acetate, a propylene glycol monomethyl ether acetate, and a propylene glycol monoethyl ether acetate, etc. are mentioned, It can be set as a uniform solution composition by melt | dissolving and mixing using these.
또한, 본 발명의 감광성 수지 조성물에는 필요에 따라서 경화 촉진제, 열중합 금지제, 가소제, 충전재, 용제, 레벨링제, 소포제 등의 첨가제를 배합할 수 있다. 열중합 금지제로서는 하이드로퀴논, 하이드로퀴논모노메틸에테르, 피로갈롤, tert-부틸카테콜, 페노티아진 등을 들 수 있고, 가소제로서는, 디부틸프탈레이트, 디옥틸프탈레이트, 트리크레딜 등을 들 수 있고, 충전재로서는 유리섬유, 실리카, 마이카, 산화 알루미늄 등을 들 수 있고, 또한, 소포제나 레벨링제로서는, 예를 들면, 실리콘계, 불소계, 아크릴계의 화합물을 들 수 있다.Moreover, additives, such as a hardening accelerator, a thermal polymerization inhibitor, a plasticizer, a filler, a solvent, a leveling agent, an antifoamer, can be mix | blended with the photosensitive resin composition of this invention as needed. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butyl catechol, phenothiazine, and the like. As the plasticizer, dibutyl phthalate, dioctyl phthalate, and tricredyl may be mentioned. Examples of the filler include glass fiber, silica, mica, aluminum oxide, and the like, and examples of the antifoaming agent and the leveling agent include silicone, fluorine, and acrylic compounds.
본 발명의 감광성 수지 조성물은 상기 (A)∼(B)성분, 또는 이들과 용제를 주성분으로서 함유한다. 용제를 제외한 고형분(고형분에는 경화후에 고형분이 되는 모노머를 함유한다) 중에 (A)∼(E)성분이 합계로 70wt% 이상, 바람직하게는 80wt%이상, 보다 바람직하게는 90wt% 이상 함유하는 것이 바람직하다. 용제의 양은, 목표로 하는 점도에 의해 변화하지만, 20∼80wt%의 범위가 바람직하다.The photosensitive resin composition of this invention contains the said (A)-(B) component or these and a solvent as a main component. Solid content excluding a solvent (solid content contains a monomer which becomes a solid content after curing) includes (A) to (E) components in total of 70 wt% or more, preferably 80 wt% or more, and more preferably 90 wt% or more. desirable. The amount of the solvent varies depending on the target viscosity, but is preferably in the range of 20 to 80 wt%.
본 발명의 도막은, 예를 들면, 상기 감광성 수지 조성물의 용액을, 기판 등에 도포하고, 건조하고, 광(자외선, 방사선 등을 포함하는)을 조사하고, 이것을 경화시킴으로써 얻을 수 있다. 광이 닿는 부분과 닿지 않는 부분을 형성해서, 광이 닿는 부분만을 경화시켜, 다른 부분을 알칼리 용액으로 용해시키면, 소망의 패턴의 도막을 얻을 수 있다.The coating film of this invention can be obtained by apply | coating the solution of the said photosensitive resin composition to a board | substrate etc., for example, irradiating light (including ultraviolet rays, a radiation, etc.), and hardening this. If the part which does not touch the part which light contacts, is hardened | cured, and only the part which light hits is hardened and another part is melt | dissolved in alkaline solution, the coating film of a desired pattern can be obtained.
다음으로, 감광성 수지 조성물을 사용한 컬러필터의 제조법에 대해서 설명한다. 우선, 기판의 표면상에, 필요에 따라서, 화소를 형성하는 부분을 구획하도록 차광층을 형성하고, 이 기판 상에 예를 들면, 적색의 안료가 분산된 감광성 수지 조성물의 액상 조성물을 도포한 후, 프리 베이킹를 행하여 용제를 증발시키고, 도막을 형성한다. 그 다음에, 이 도막에 포토 마스크를 개재해서 노광한 뒤, 알카리성현상액을 사용해서 현상하고, 도막의 미노광부를 용해 제거하고, 그 후 포스트 베이킹함으로써, 적색의 화소 패턴이 소정의 배열로 배치된 화소 어레이를 형성한다. 그 후, 녹색 또는 청색의 안료가 분산되어진 감광성 수지 조성물의 액상 조성물을 사용하고, 상기와 마찬가지로 하여, 각 액상 조성물의 도포, 프리 베이킹, 노광, 현상 및 포스트 베이킹을 행하고, 녹색의 화소 어레이 및 청색의 화소 어레이를 동일 기판 상에 순차 형성함으로써, 적색, 녹색 및 청색의 3원색의 화소 어레이가 기판 상에 배치되고, 또한, 이 위에 보호막으로서, 감광성 수지 조성물의 액상 조성물을 상기와 마찬가지로 하여, 각 액상 조성물의 도포, 프리 베이킹, 노광, 현상 및 포스트 베이킹을 행하고, 보호막이 형성된 컬러필터를 얻는다.Next, the manufacturing method of the color filter using the photosensitive resin composition is demonstrated. First, on the surface of a board | substrate, a light shielding layer is formed so that the part which forms a pixel may be divided as needed, and for example, after apply | coating the liquid composition of the photosensitive resin composition in which the red pigment was disperse | distributed on this board | substrate, The solvent is evaporated by prebaking to form a coating film. Next, after exposing through a photomask to this coating film, it develops using alkaline developing solution, dissolves and removes the unexposed part of a coating film, and post-bakes, and the red pixel pattern was arrange | positioned in predetermined | prescribed arrangement. A pixel array is formed. Then, using the liquid composition of the photosensitive resin composition in which the green or blue pigment was disperse | distributed, apply | coating, prebaking, exposing, developing, and postbaking each liquid composition similarly to the above, and green pixel array and blue By sequentially forming pixel arrays on the same substrate, a pixel array of three primary colors of red, green, and blue is disposed on the substrate, and as a protective film thereon, the liquid composition of the photosensitive resin composition is prepared in the same manner as above. Application | coating, prebaking, exposure, image development, and postbaking of a liquid composition are performed, and the color filter in which the protective film was formed is obtained.
감광성 수지 조성물의 액상 조성물을 기판에 도포할 시에는, 공지의 용액침 지법, 스프레이법 외에, 롤러 코터기, 랜드 코터기나 스피너기를 사용하는 방법 등의 어떤 방법도 채용할 수 있다. 이들의 방법에 의해, 소망의 두께에 도포한 후, 용제를 제거하는(프리 베이킹) 것에 의해, 피막이 형성된다. 프리 베이킹은 오븐, 핫플레이트 등에 의한 가열, 진공건조 또는 이들의 조합에 의해 행하여진다. 프리 베이킹에 있어서의 가열온도 및 가열시간은 사용하는 용제에 따라서 적절하게 선택되고, 예를 들면, 80∼120℃의 온도로 1∼10분간 행하여진다.When apply | coating the liquid composition of the photosensitive resin composition to a board | substrate, in addition to a well-known solution immersion method and a spray method, any method, such as the method of using a roller coater, a land coater, or a spinner group, can be employ | adopted. By these methods, after apply | coating to desired thickness, a film is formed by removing a solvent (prebaking). Prebaking is performed by heating with an oven, a hot plate or the like, vacuum drying or a combination thereof. The heating temperature and the heating time in the prebaking are appropriately selected according to the solvent to be used, for example, performed at a temperature of 80 to 120 ° C. for 1 to 10 minutes.
컬러필터를 제작할 때에 사용되는 방사선으로서는, 예를 들면, 가시광선, 자외선, 원자외선, 전자선, X선 등을 사용할 수 있지만, 파장이 250∼450㎚의 범위에 있는 방사선이 바람직하다. 또한, 이 알칼리 현상에 적합한 현상액으로서는, 예를 들면, 알칼리 금속이나 알칼리 토류금속의 탄산염의 수용액, 알칼리 금속의 수산화물의 수용액 등을 들 수 있지만, 특히, 탄산 나트륨, 탄산 칼륨, 탄산 리튬 등의 탄산염을 0.05∼10중량% 함유하는 약알칼리성 수용액을 사용해서 20∼30℃의 온도로 현상하는 것이 좋고, 시판의 현상기나 초음파 세정기 등을 사용해서 미세한 화상을 정밀하게 형성할 수 있다. 또한, 알칼리 현상후는 통상, 수세한다. 현상 처리법으로서는, 샤워 현상법, 스프레이 현상법, 딥(침지)현상법, 패들(액분량)현상법 등을 적용할 수 있다. 현상 조건은 상온에서 10∼120초가 바람직하다.As the radiation used when producing the color filter, for example, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X rays and the like can be used, but radiation having a wavelength in the range of 250 to 450 nm is preferable. Moreover, as a developer suitable for this alkali image development, although the aqueous solution of the carbonate of an alkali metal or alkaline-earth metal, the aqueous solution of the hydroxide of an alkali metal, etc. are mentioned, Especially, carbonates, such as sodium carbonate, potassium carbonate, lithium carbonate, etc., are mentioned, for example. It is good to develop at the temperature of 20-30 degreeC using the weakly alkaline aqueous solution containing 0.05-10 weight%, and a fine image can be formed precisely using a commercially available developer, an ultrasonic cleaner, and the like. In addition, after alkali image development, water washing is normally performed. As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid amount) developing method, or the like can be applied. As for image development conditions, 10 to 120 second is preferable at normal temperature.
이렇게 하여 현상한 후, 180∼250℃의 온도 및 20∼100분의 조건으로 열처리(포스트 베이킹)가 행하여진다. 이 포스트 베이킹은 패터닝된 도막과 기판의 밀착성을 향상시키기 위해서 등의 목적으로 행하여진다. 이것은 프리 베이킹과 마찬가지로, 오븐, 핫플레이트 등에 의해 가열함으로써 행하여진다. 본 발명의 패터닝된 도막은, 이상의 포토리소 그래피법에 의한 각 공정을 거쳐 형성된다.After developing in this way, heat processing (post-baking) is performed on the temperature of 180-250 degreeC, and the conditions of 20-100 minutes. This post-baking is performed for the purpose of improving the adhesiveness of a patterned coating film and a board | substrate. This is done by heating with an oven, a hot plate or the like, like prebaking. The patterned coating film of this invention is formed through each process by the above photolithographic method.
화소 및/또는 블랙 매트릭스를 구비한 컬러필터를 형성할 때에 사용되는 기판으로서 예를 들면, 유리, 투명 필름(예를 들면, 폴리카보네이트, 폴리에틸렌텔레프탈레이트, 폴리에테르술폰 등) 상에 ITO, 금 등의 투명전극이 증착 혹은 패터닝된 것 등이 이용된다. 또한, 이들의 기판에는, 소망에 의해, 실란 커플링제 등에 의한 약품처리, 플라즈마 처리, 이온 플레이팅, 스패터링, 기상반응법, 진공증착 등의 적당한 전처리를 실시해 둘 수도 있다.As a substrate used when forming a color filter having a pixel and / or a black matrix, for example, ITO, gold, etc., on glass, transparent film (for example, polycarbonate, polyethylene terephthalate, polyether sulfone, etc.) A transparent electrode deposited or patterned is used. Further, these substrates may be subjected to a suitable pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, vapor phase reaction, vacuum deposition, or the like as desired.
이하, 합성예, 실시예, 비교예에 의해, 본 발명을 더욱 상세하게 설명한다. 또한, 이하의 합성예에 있어서의 수지의 평가는, 사전 언급이 없는 한 이하와 같다.Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples. In addition, evaluation of resin in the following synthesis examples is as follows unless there is a prior notice.
고형분 농도: 수지용액을 160℃에서 2hr 가열해서 구했다.Solid content concentration: The resin solution was calculated | required by heating at 160 degreeC for 2 hours.
산가: 1/1ON-KOH에탄올(50%) 수용액으로 적정(滴定)해서 구했다.Acid value: titrated with 1 / 1ON-KOH ethanol (50%) aqueous solution, and calculated | required.
분자량: GPC에 의해 구했다. 이 분자량은 미반응 원료를 제외한 (A)성분의 폴리스티렌 환산의 중량평균 분자량(Mw)이다.Molecular weight: It calculated | required by GPC. This molecular weight is the weight average molecular weight (Mw) of polystyrene conversion of (A) component except an unreacted raw material.
또, 합성예로 사용하는 약호는 다음과 같다.In addition, the symbol used by a synthesis example is as follows.
FHPA: 플루오렌 비스페놀형 에폭시수지와 아크릴산의 등당량 반응물(신니테츠 카가쿠사 제품, ASF-400의 용액: 고형분 농도50wt%, 고형분 환산의 산가1.28mgKOH/g, 에폭시 당량 21300)FHPA: Equivalent reactant of fluorene bisphenol-type epoxy resin and acrylic acid (Shin-Nitetsu Kagaku Co., ASF-400 solution: solid content concentration 50wt%, solid content equivalent 1.28mgKOH / g, epoxy equivalent 21300)
CHDA: 시클로헥산 카르복실산 2무수물CHDA: cyclohexane carboxylic dianhydride
SA: 무수숙신산SA: succinic anhydride
TPP: 트리페닐포스핀TPP: Triphenylphosphine
PGMEA: 프로필렌 글리콜 모노메틸에테르 아세테이트PGMEA: Propylene Glycol Monomethyl Ether Acetate
합성예 1Synthesis Example 1
환류 냉각기 당 50Oml 4개의 플라스코 속에 FHPA의 50% PGMEA용액 238.0g과 CHDA 33.0g, SA 9.81g, PGMEA 46g 및 TPP0 46g을 주입하고, 120∼125℃의 가열하에서 1hr 교반하고, 또한, 75∼80℃에서 6hr의 가열 교반을 행해서, 알칼리 가용성 수지용액을 합성했다. 얻어진 수지용액의 고형분은 53.5wt%, 산가(고형분 환산)는 150mgKOH/g, GPC분석에 의한 수지 용액중의 알칼리 가용성수지(A)-2의 면적%는 91%, Mw는 10000이었다.238.0 g of 50% PGMEA solution of FHPA, 33.0 g of CHDA, 9.81 g of PGMEA, 46 g of PGMEA and 46 g of TPP0 were charged into four 50 mL flasks of reflux, and stirred for 1 hr under heating at 120 to 125 ° C. 6 hours of heating and stirring were performed at 80 degreeC, and the alkali-soluble resin solution was synthesize | combined. Solid content of the obtained resin solution was 53.5 wt%, acid value (solid content conversion) was 150 mgKOH / g, the area% of alkali-soluble resin (A) -2 in the resin solution by GPC analysis was 91%, and Mw was 10000.
[실시예][Example]
(A)-1: 상기 합성예 1에 있어서, CHDA의 변화에 벤조페논 테트라카르복실산 2무수물(BTDA)을, SA의 변화에 1,2,3,6-테트라 히드로 프탈산 무수물(THPA)을 사용한 것 이외는, 마찬가지로 합성해서 얻어진 알칼리 가용성 수지. 산가(고형분 환산)100mgK0H/g, Mw 4000.(A) -1: In the above Synthesis Example 1, benzophenone tetracarboxylic dianhydride (BTDA) is used to change CHDA, and 1,2,3,6-tetrahydrophthalic anhydride (THPA) is used to change SA. Alkali-soluble resin obtained by synthesizing similarly except using. Acid value (solid content conversion) 100 mgK0H / g, Mw 4000.
(A)-2: 상기 합성예 1로 얻어진 알칼리 가용성수지(A) -2: alkali-soluble resin obtained in Synthesis Example 1
(A)-3: Mw8800, 산가 130의 N-페닐 말레이미드/메타크릴산/벤질메타크릴레이트 공중합체의 프로필렌글리콜 모노메틸에테르아세테이트 용액(수지 고형분 농도=37.9 중량%)(N-페닐 말레이미드: 메타크릴산: 벤질메타크릴레이트=26:34:40mol%)(A) -3: Propylene glycol monomethyl ether acetate solution of Mw8800, N-phenyl maleimide / methacrylic acid / benzyl methacrylate copolymer of acid value 130 (resin solid content concentration: 37.9 wt%) (N-phenyl maleimide Methacrylic acid: benzyl methacrylate = 26: 34: 40 mol%)
(B): 디펜타에리스리톨 헥사 아크릴레이트와 디펜타에리스리톨 펜타 아크릴레이트의 혼합물(니혼카야쿠(주) 제품 상품명 DPHA)(B): A mixture of dipentaerythritol hexa acrylate and dipentaerythritol penta acrylate (Nihon Kayaku Co., Ltd. product name DPHA)
(C): 플루오렌형 에폭시 수지(신니테츠 카가쿠사 제품, 상품명 ESF-300)(C): fluorene-type epoxy resin (Shin-Nitetsu Kagaku Corporation make, brand name ESF-300)
(D)-1: 1,2-옥탄디온, 1-[4-(페닐티오)페닐]-, 2-(0-벤조일옥심); 식(Ⅲ)으로 나타내어지는 화합물, (치바 스페셜리티 제품, CGI124)(D) -1: 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (0-benzoyloxime); Compound represented by formula (III), (Chiba Specialty Product, CGI124)
(D)-2: 2-메틸-1-[4-(메틸티오)페닐]-2-모르포리노-1-온(치바 가이기 제품, 일가큐어 907)(D) -2: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-one (available from Chiba-Geigi, Monocure 907)
(D)-3 : 하기 화학식(Ⅷ)으로 나타내는 화합물(D) -3: the compound represented by chemical formula (i)
[화 7][Tue 7]
(E)-1: ε-프탈로시아닌 블루(C.I. 피그멘트 블루 15:6)(E) -1: ε-phthalocyanine blue (C.I. Pigment Blue 15: 6)
(E)-2: 브롬 염소화 프탈로시아닌 그린(C.I. 피그멘트 그린 36)(E) -2: brominated chlorinated phthalocyanine green (C.I. pigment green 36)
(E)-3: 디케토피로로피롤 레드(C.I. 피그멘트 레드 254)(E) -3: diketopyrrolopyrrole red (C.I. Pigment Red 254)
(E)-4: 니켈아조 옐로(C.I. 피그멘트 옐로 150)(E) -4: nickel azo yellow (C.I. pigment yellow 150)
(E)-5: 이소인도린 옐로(C.I. 피그멘트 옐로 139)(E) -5: Isoindorin Yellow (C.I. Pigment Yellow 139)
(E)-6: 디옥사진 바이올렛(C.I. 피그멘트 바이올렛 23) (E) -6: Dioxazine Violet (C.I. Pigment Violet 23)
용제-1: 프로필렌글리콜 모노메틸에테르 아세테이트 Solvent-1: Propylene Glycol Monomethyl Ether Acetate
용제-2: 유산 에틸Solvent-2: ethyl lactate
첨가제-1: 실란 커플링제Additive-1: Silane Coupling Agent
첨가제-2: 계면 활성제Additive-2: Surfactant
실시예 1∼12 및 비교예 1∼15Examples 1-12 and Comparative Examples 1-15
상기 배합성분을 표 1∼3에 기재된 비율로 배합하고, 실시예 1∼12 및 비교예 1∼15의 수지 조성물을 조제했다. 표 1∼3에 있어서, 기재가 없는 성분 및 -로 나타낸 성분의 배합량은 0인 것을 의미한다.The said compounding component was mix | blended in the ratio of Tables 1-3, and the resin composition of Examples 1-12 and Comparative Examples 1-15 was prepared. In Tables 1-3, the compounding quantity of the component without description and the component shown by-means that it is zero.
상기 실시예 1∼12 및 비교예 1∼15의 감광성 수지 조성물을 균일하게 혼합해서 얻은 감광성 수지 조성물을 스핀코터를 사용해서 125㎜×125㎜의 유리 기판 상에포스트 베이킹 후의 막두께가 2.O㎛가 되도록 도포하고, 90℃에서 2분간 프리 베이킹 후, I선 조도30mW/cm2의 초고압 수은램프로 20Omj/cm2의 자외선을 조사해 감광 부분의 광경화 반응을 행했다. 그 다음에, 이 노광종료 도판을 0.04% 수산화 칼륨수용액 중, 23℃에서 60초의 0.1MPa압 샤워 현상 및 0.5MPa압의 스프레이 수세를 행하고, 도막의 미노광부를 제거하고, 현상성의 평가를 행했다. 그 후, 열풍건조기를 사용해서 23O℃에서 30분간 열포스트 베이킹해서 컬러필터용 도막을 작성하고, 현상성 평가 및 패턴형상 평가, 또는 투과율 평가를 행했다.The photosensitive resin composition obtained by uniformly mixing the photosensitive resin compositions of Examples 1 to 12 and Comparative Examples 1 to 15 using a spin coater on a glass substrate of 125 mm x 125 mm has a post-baked film thickness of 2.O. After apply | coating so that it might become micrometer, and prebaking for 2 minutes at 90 degreeC, the ultraviolet-ray of 20Omj / cm <2> was irradiated with the ultrahigh pressure mercury lamp of I-line roughness 30mW / cm <2> , and the photocuring reaction of the photosensitive part was performed. Subsequently, the exposure finish plate was subjected to 0.1 MPa pressure shower development and spray washing at 0.5 MPa pressure for 60 seconds at 23 ° C. in 0.04% potassium hydroxide aqueous solution, and the unexposed part of the coating film was removed to evaluate developability. Thereafter, hot post-baking was carried out at 23O < 0 > C for 30 minutes using a hot air dryer to create a coating film for color filters, and evaluation of developability, pattern shape, or transmittance was performed.
또한, 포스트 베이킹 실시종료의 컬러필터 작성기판을 열풍건조기를 사용해서 250℃/60분 열처리를 행하고 내열 변색성 평가했다.In addition, the color filter preparation substrate at the end of post-baking was heat-treated at 250 ° C./60 minutes using a hot air dryer to evaluate heat discoloration resistance.
실시예, 비교예에 있어서의 광투과성 등의 평가결과를 표4∼6에 나타낸다. 이들의 평가방법은 이하와 같다.Tables 4 to 6 show evaluation results such as light transmittance in Examples and Comparative Examples. These evaluation methods are as follows.
현상: 알칼리 현상에 의한 1OO㎛의 패터닝의 현상이 ○<가능>인가 ×<불가능>인가를 평가했다.Development: It evaluated whether the phenomenon of 100 micrometers patterning by alkali image development is (circle) <orable> or << impossible>.
막두께: 촉침식 단차형상 측정장치(케이엘에이 텐콜(주)제품 상품명P-10)를 이용해서 측정했다.Film thickness: It measured using the stylus type | mold step shape measuring apparatus (KLA Tencol Co., Ltd. brand name P-10).
투과율: 분광 광도계를 이용하여, 평균 투과율의 비교평가를 했다. 수치가 가장 높은 것을 ◎<보다 양호>, 다음으로 높은 것을 ○<양호>, 가장 낮은 값의 것을 ×<불량>으로 판정했다.Transmittance: The comparative evaluation of average transmittance was performed using the spectrophotometer. The one with the highest numerical value was determined to be " better than ", the next higher one was " good ", and the one with the lowest value was × <defect>.
내열 변색성: 분광 광도계를 이용한 평균 투과율을 측정했을 때, 열처리후의 투과율의 저하율이 1% 미만일 때를 ○<양호>, 1% 이상일 때를 ×<불량>로 판정했다.Heat discoloration resistance: When measuring the average transmittance | permeability using a spectrophotometer, when the fall rate of the transmittance | permeability after heat processing was less than 1%, it determined as << good> and when it is 1% or more as x <defect>.
패턴형상: 측장 현미경을 사용하고, 현상후의 화소패턴을 관찰하고, 기판에 대한 박리나 패턴 에지 부분의 홈이 확인되지 않는 것을 ○<양호>, 확인되는 것을 ×<불량>으로 판정했다.Pattern shape: Using the side microscope, the pixel pattern after image development was observed, and it was determined that (<good>) and (x) <(bad)> that the peeling with respect to a board | substrate and the groove | channel of a pattern edge part were not recognized.
감도: 100㎛ 패턴 마스크를 이용하여 노광하고, 알칼리 현상을 행했을 시의 남아있는 패턴의 선폭을 측장 현미경((주)니콘제 상품명XD-20)을 이용하여, 평가했다.(선폭이 굵을수록 감도가 높다고 생각된다.)Sensitivity: The line width of the remaining pattern at the time of exposing using a 100-micrometer pattern mask and performing alkali image development was evaluated using the measurement microscope (brand name XD-20 by Nikon Corporation). (Line width is thick It is thought that the higher the sensitivity.)
100㎛ 이하일 때를 ×<불량>, 100∼105㎛일 때를 ○<양호>, 105 이상일 때를 ◎<보다 양호>라고 판정했다.When <100 micrometers or less, when it is 100 micrometers or less, when it is (<good>) and when 105 or more, the time when it is 100-105 micrometers, it determined as (better than).
표4는 3종류의 다른 알칼리 가용성 수지인 (A)-1, (A)-2, (A)-3을 사용해서 실시예 1∼4 및 비교예 1∼5의 적색 컬러필터용 감광성 수지 조성물을 조제하고, 물성비교를 행한 예를 나타낸다. 그 결과 (A)-3을 이용한 경우, (E)/(R)이 2.6에서는 현상에 의한 패턴형성을 할 수 없었다.Table 4 shows the photosensitive resin composition for red color filters of Examples 1-4 and Comparative Examples 1-5 using (A) -1, (A) -2, and (A) -3 which are three different alkali-soluble resin. The example which prepared and carried out the physical property comparison is shown. As a result, when (A) -3 was used, pattern formation by development was not possible in (E) / (R) of 2.6.
표5는 3종류의 다른 알칼리 가용성 수지인 (A)-1, (A)-2, (A)-3을 사용해서 실시예 5∼8 및 비교예 6∼10의 청색 컬러필터용 감광성 수지 조성물을 조제하고, 물성비교를 행한 예를 나타낸다. (A)-3을 사용했을 경우, (E)/(R)이 2.6에서는 현상에 의한 패턴형성을 할 수 없고, 현상이 불가했다Table 5 shows the photosensitive resin compositions for blue color filters of Examples 5 to 8 and Comparative Examples 6 to 10 using (A) -1, (A) -2 and (A) -3 which are three different alkali-soluble resins. The example which prepared and carried out the physical property comparison is shown. When (A) -3 was used, pattern formation by development was not possible and development was impossible at (E) / (R) of 2.6.
표6은 3종류의 다른 알칼리 가용성 수지인 (A)-1, (A)-2, (A)-3을 사용해서 실시예 9∼12 및 비교예 11∼15의 녹색 컬러필터용 감광성 수지 조성물을 조제하고, 물성비교를 행한 예를 나타낸다. (A)-3을 사용했을 경우, (E)/(R)이 1,5에서 노광부, 미노광부 전부 모두 박리하고, 현상이 불가했다. 또한, (A)-1과 (A)-2에 대해서, (A)-2쪽 현상성이 보다 양호했다.Table 6 shows the photosensitive resin compositions for green color filters of Examples 9 to 12 and Comparative Examples 11 to 15 using (A) -1, (A) -2 and (A) -3 which are three different alkali-soluble resins. The example which prepared and carried out the physical property comparison is shown. When (A) -3 was used, (E) / (R) peeled all the exposure part and the unexposed part at 1, 5, and image development was not possible. Moreover, the developability of (A) -2 was more favorable about (A) -1 and (A) -2.
표 4∼6에서, (-)는, 현상 불가였기 때문에 평가를 할 수 없었던 것을 의미한다.In Tables 4-6, (-) means that evaluation was not possible because it was impossible to develop.
실시예 13, 14 및 비교예 16, 17 Examples 13 and 14 and Comparative Examples 16 and 17
광중합 개시제(D)성분을 표7에 기재된 비율로 배합해서 균일하게 혼합하고, 실시예 13, 14 및 비교예 16, 17의 감광성 수지 조성물을 조제했다. 이들의 감광성 수지 조성물에 대해서, (E)/(R)은 1.5로, 고형분 농도는 22%로 통일했다.The photoinitiator (D) component was mix | blended in the ratio of Table 7, it was mixed uniformly, and the photosensitive resin composition of Example 13, 14 and comparative examples 16 and 17 was prepared. About these photosensitive resin compositions, (E) / (R) was 1.5 and solid content concentration was 22%.
이 수지 조성물을 스핀코터를 사용해서 125㎜×125㎜의 유리 기판 상에 포스트 베이킹 후의 막두께가 2.0㎛가 되도록 도포하고, 90℃에서 2분간 프리 베이킹후, I선 조도 30mW/cm2의 초고압 수은램프로 200mj/cm2의 자외선을 조사해 감광 부분의 광경화 반응을 행했다. 그 다음에, 이 노광종료 도판을 0.04% 수산기화 칼륨 수용액 중, 23℃에서 60초의 0.1MPa압 샤워현상 및 0.5MPa압의 스프레이 수세를 행하고, 도막의 미노광부를 제거하고, 현상성의 평가를 행했다. 그 후, 열풍건조기를 사용해서 230℃에서 30분간 열포스트 베이킹해서 컬러필터용 도막을 작성하고, 막의 투과율, 감도(10O㎛ 패턴) 및 명도(Y값) 평가를 행했다. 배합조성 및 평가결과를 표7에 나타낸다.This resin composition was applied onto a glass substrate of 125 mm x 125 mm using a spin coater so that the film thickness after post-baking was 2.0 µm, and after pre-baking at 90 ° C. for 2 minutes, an ultra-high pressure of 30 mW / cm 2 of I-ray roughness was applied. Ultraviolet rays of 200mj / cm 2 were irradiated with a mercury lamp and the photocuring reaction of the photosensitive part was performed. Subsequently, this exposure finish plate was subjected to 60 MPa of 0.1 MPa pressure showering and 0.5 MPa pressure spray washing at 23 ° C. in 0.04% potassium hydroxide aqueous solution, to remove unexposed portions of the coating film, and to evaluate developability. . Thereafter, hot post-baking was performed at 230 ° C. for 30 minutes using a hot air dryer to prepare a color filter coating film, and evaluation of the transmittance, sensitivity (100 μm pattern) and brightness (Y value) of the film was performed. Table 7 shows the composition and evaluation results.
광중합 개시제(D)-1를 이용한 실시예 13에서는, 제 물성의 균형을 취한 것이며, 첨가량이 조금 많아도 명도(Y값)의 저하는 거의 볼 수 없었지만, (D)-2를 이용한 비교예 16의 경우는 실시예 13과 같은 첨가량의 경우, 명도(Y값) 저하가 보여졌다. 또한, (D)-3을 이용한 경우, 감도가 낮고, (E)/(R)=1.5의 농도 영역에서는 박리해 버렸다. 한편, (D)-1과 (D)-3을 병용한 실시예 14에서는, 거의 명도(Y값)의 저하도 볼 수 없고, 또한, 패턴형상 등도 가장 양호한 결과를 얻을 수 있었다.In Example 13 using the photoinitiator (D) -1, the physical properties were balanced, and even if the amount of addition was a little, the decrease in brightness (Y value) was hardly seen, but in Comparative Example 16 using (D) -2 In the case of addition amount similar to Example 13, the fall of brightness (Y value) was seen. Moreover, when (D) -3 was used, sensitivity was low and it peeled in the density | concentration area of (E) / (R) = 1.5. On the other hand, in Example 14 which used (D) -1 and (D) -3 together, the fall of the brightness (Y value) was hardly seen, and also the pattern shape etc. could obtain the best result.
비스페놀류로 유도되는 2개의 글리시딜에테르기를 갖는 에폭시 화합물과 (메타)아크릴산의 반응물을 또한 다염기 카르복실산 또는 그 무수물과 반응시켜서 얻어진 불포화기 함유 알칼리 가용성 수지와 다량의 착색제를 함유하는 감광성 수지 조성물을 특정의 화학구조를 가지는 옥심 에스테르계의 광중합 개시제로 광경화시킴으로써, 개시제를 다량으로 함유하고 있는 경우에도 내열황 변성이 적고 양호한 현상특성을 갖는 컬러필터용 수지 조성물을 얻을 수 있다. 또한, 옥심에스테르계 이외의 1종류 내지 그 이상의 광중합 개시제를 병용함으로써, 패턴 형상의 컨트롤도 가능해졌다. 또한, 그 컬러필터용 수지 조성물을 성막함으로써, 고색 순도이며 고신뢰성을 갖는 컬러필터를 작성하는 것이 가능해 지고, 컬러액정 표시장치, 컬러 팩시밀리, 이미지 센서 등의 각종의 다색표시체나, 광학기기 등에 사용되는 컬러필터용의 착색 잉크, 및, 이들에 의해 형성된 블랙 매트릭스를 갖는 컬러필터나, 텔레비전, 비디오 모니터, 혹은, 컴퓨터의 디스플레이 등에 적절하게 사용할 수 있다. 또한, 이렇게 하여 얻어진 컬러필터는 예를 들면, 투과형 혹은 반사형의 컬러액정 표시장치, 컬러 촬상관 소자, 컬러 센서 등에 극히 유용하다.Photosensitive composition containing unsaturated group containing alkali-soluble resin obtained by reacting the reaction compound of the epoxy compound which has two glycidyl ether groups derived from bisphenol, and (meth) acrylic acid with polybasic carboxylic acid or its anhydride, and a large amount of coloring agent. By photocuring a resin composition with the oxime ester type photoinitiator which has a specific chemical structure, even if it contains a large amount of initiator, the resin composition for color filters which has little heat-sulfur resistance and good image development characteristics can be obtained. Moreover, control of a pattern shape was also possible by using together 1 type or more photoinitiators other than an oxime ester system. In addition, by forming the resin composition for color filters, it is possible to create a color filter having high color purity and high reliability, and used for various multicolor displays such as color liquid crystal display devices, color facsimile machines, image sensors, optical devices, and the like. It can be used suitably for the color filter which has the coloring ink for color filters used, and the black matrix formed by these, a television, a video monitor, or a display of a computer. In addition, the color filter thus obtained is extremely useful, for example, in a transmissive or reflective color liquid crystal display device, a color imaging tube element, a color sensor, and the like.
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