KR20210076490A - Colored photosensitive resin composition and colored spacer prepared therefrom - Google Patents
Colored photosensitive resin composition and colored spacer prepared therefrom Download PDFInfo
- Publication number
- KR20210076490A KR20210076490A KR1020190167764A KR20190167764A KR20210076490A KR 20210076490 A KR20210076490 A KR 20210076490A KR 1020190167764 A KR1020190167764 A KR 1020190167764A KR 20190167764 A KR20190167764 A KR 20190167764A KR 20210076490 A KR20210076490 A KR 20210076490A
- Authority
- KR
- South Korea
- Prior art keywords
- meth
- acrylate
- colorant
- resin composition
- photosensitive resin
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 59
- 125000006850 spacer group Chemical group 0.000 title abstract description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 143
- 150000001875 compounds Chemical class 0.000 claims description 91
- 239000003086 colorant Substances 0.000 claims description 61
- 229920001577 copolymer Polymers 0.000 claims description 46
- -1 4-methylcyclohexylmethyl Chemical group 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 17
- 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 12
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 4
- 238000004040 coloring Methods 0.000 claims description 3
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- 239000000038 blue colorant Substances 0.000 claims description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 16
- 230000035945 sensitivity Effects 0.000 abstract description 7
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 description 29
- 239000002904 solvent Substances 0.000 description 28
- 238000000576 coating method Methods 0.000 description 17
- 239000002253 acid Substances 0.000 description 16
- 230000018109 developmental process Effects 0.000 description 16
- 239000004094 surface-active agent Substances 0.000 description 16
- 239000011230 binding agent Substances 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 13
- 239000002270 dispersing agent Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 12
- 239000003999 initiator Substances 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000049 pigment Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- 150000002923 oximes Chemical class 0.000 description 9
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 8
- 239000000470 constituent Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 7
- 239000002096 quantum dot Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 5
- 150000002576 ketones Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 4
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013065 commercial product Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 230000007775 late Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-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
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 2
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 2
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 2
- UVHHADIQQIICAV-UHFFFAOYSA-N 4-amino-3-[[4-[4-[(1-amino-4-sulfonaphthalen-2-yl)diazenyl]-2-methylphenyl]-3-methylphenyl]diazenyl]naphthalene-1-sulfonic acid Chemical compound C1=CC=CC2=C(N)C(N=NC=3C=C(C(=CC=3)C=3C(=CC(=CC=3)N=NC=3C(=C4C=CC=CC4=C(C=3)S(O)(=O)=O)N)C)C)=CC(S(O)(=O)=O)=C21 UVHHADIQQIICAV-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical group CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 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
- 239000012965 benzophenone Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 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 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 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
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- HOSJNFCDDCLEBM-UHFFFAOYSA-N (2-phenyloxetan-3-yl)methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1COC1C1=CC=CC=C1 HOSJNFCDDCLEBM-UHFFFAOYSA-N 0.000 description 1
- RSHKWPIEJYAPCL-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1(CC)COC1 RSHKWPIEJYAPCL-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- ZCCAOOJIWMTVGN-UHFFFAOYSA-N 1,6-diisocyanatohexane;[2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound O=C=NCCCCCCN=C=O.C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C ZCCAOOJIWMTVGN-UHFFFAOYSA-N 0.000 description 1
- FPZQYYXSOJSITC-UHFFFAOYSA-N 1-(4-chlorophenyl)pyrrole-2,5-dione Chemical compound C1=CC(Cl)=CC=C1N1C(=O)C=CC1=O FPZQYYXSOJSITC-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
본 발명은 단차 추종성이 우수한 경화막을 제공할 수 있는 착색 감광성 수지 조성물, 및 이로부터 제조되며 액정표시장치 및 유기EL표시장치 등에 사용되는 착색 스페이서에 관한 것이다.The present invention relates to a colored photosensitive resin composition capable of providing a cured film having excellent step tracking property, and a colored spacer prepared therefrom and used for a liquid crystal display device, an organic EL display device, and the like.
최근 OLED나 QD(퀀텀닷) 기반의 디스플레이가 대형화되는 추세에 따라 대형 디스플레이의 무게에 의한 휨 불량을 방지하기 위하여, 감광성 수지 조성물을 사용하여 형성한 스페이서가 적용되고 있다. 또한, 액정디스플레이(LCD)의 액정셀에 있어서 상하 투명 기판 간의 간격을 일정하게 유지하기 위하여 스페이서를 사용하고 있다. 만약, 상기 투명 기판 간의 간격이 일정하지 않으면 인가되는 전압과 빛의 투과도가 달라져 불균일한 밝기를 나타내는 등의 불량이 야기된다. 또한, LCD도 대형화되는 추세이므로 투명 기판 간의 간격을 일정하게 유지시키는 것이 더욱 중요해지고 있다. Recently, as OLED or QD (quantum dot)-based displays are becoming larger, a spacer formed using a photosensitive resin composition is applied to prevent bending defects due to the weight of the large display. In addition, in the liquid crystal cell of a liquid crystal display (LCD), a spacer is used to maintain a constant distance between the upper and lower transparent substrates. If the distance between the transparent substrates is not constant, the applied voltage and the transmittance of light are different, thereby causing defects such as non-uniform brightness. In addition, since LCDs are also becoming larger, it is becoming more important to maintain a constant distance between transparent substrates.
최근에는 착색 감광성 수지 조성물을 사용하여 컬럼 스페이서와 블랙 매트릭스를 하나의 모듈로 일체화한 블랙 컬럼 스페이서 또는 착색 스페이서를 제조함으로써 공정 절차의 간소화를 도모하고 있다. Recently, a process procedure is simplified by manufacturing a black column spacer or a colored spacer in which a column spacer and a black matrix are integrated into one module using a colored photosensitive resin composition.
이러한 컬럼 스페이서를 제조하기 위해서는 단차 구현 및 고해상도의 패턴을 형성할 수 있는 착색 감광성 수지 조성물이 요구된다. In order to manufacture such a column spacer, a colored photosensitive resin composition capable of forming a step difference and high-resolution pattern is required.
그러나, 디스플레이의 구조가 복잡해짐에 따라 단차가 구현되지 않거나 해상도가 떨어지는 문제가 발생하고 있다. 특히, 단차 구조를 갖는 기판 상에 조성물을 도포하는 경우에는 단차에 따른 높이 차이가 발생하게 된다. 이러한 특성을 단차 추종성이라 하는데, 단차 추종성이 불량일 경우 기판 상에 평탄한(레벨링 특성이 우수한) 경화막 형성이 용이하지 않을 뿐만 아니라, 경화막에 패턴이 뚜렷히 구현되지 않고, 감도, 해상도 등이 저하될 수 있다. 이러한 문제를 해결하기 위해 종래 기술에서는 레벨링제와 같은 첨가제를 도입하고 있지만(대한민국 등록특허 제1247621호), 조성물 구성 성분 자체를 조절하여 레벨링성을 향상시키고자 한 시도는 알려지지 않았다.However, as the structure of the display becomes more complex, there is a problem that the step is not implemented or the resolution is lowered. In particular, when the composition is applied on a substrate having a step structure, a height difference occurs according to the step difference. This characteristic is called step followability. If the step followability is poor, it is not easy to form a flat cured film (with excellent leveling properties) on the substrate, the pattern is not clearly implemented on the cured film, and the sensitivity and resolution are lowered. can be In order to solve this problem, additives such as leveling agents are introduced in the prior art (Korean Patent Registration No. 1247621), but attempts to improve leveling properties by controlling the composition components themselves are not known.
따라서, 본 발명은 별도의 레벨링제 없이 착색 감광성 수지 조성물의 구성 성분 중 특정 종류의 바인더를 사용함으로써, 단차가 있는 기판에 경화막 형성시 단차에 따른 높이 차이가 발생하지 않으면서 패턴이 뚜렷이 형성되고, 나아가 감도 및 해상도가 우수한 경화막 및 착색 스페이서를 형성할 수 있는 착색 감광성 수지 조성물을 제공하고자 한다.Therefore, the present invention uses a specific type of binder among the components of the colored photosensitive resin composition without a separate leveling agent, so that when a cured film is formed on a stepped substrate, a pattern is clearly formed without a height difference according to the step, and Furthermore, it is an object to provide a colored photosensitive resin composition capable of forming a cured film and a colored spacer having excellent sensitivity and resolution.
상기 목적을 달성하기 위해, 본 발명은 (A) (a1) 에틸렌성 불포화 카복실산, 에틸렌성 불포화 카복실산 무수물, 또는 이들의 조합으로부터 유도되는 구성단위, (a2) C3-20의 지방족 고리형 에틸렌성 불포화 화합물로부터 유도되는 구성단위, (a3) C3-20의 지방족 선형 에틸렌성 불포화 화합물로부터 유도되는 구성단위, 및 (a4) 상기 (a1), (a2) 및 (a3)과 상이한 에틸렌성 불포화 화합물로부터 유도되는 구성단위를 포함하는 공중합체; (B) 광중합성 화합물; (C) 광중합 개시제; 및 (D) 착색제;를 포함하고, 상기 공중합체(A)의 중량평균분자량이 3,000 내지 9,000 Da이고, 상기 구성단위(a2)의 함량이 상기 공중합체(A) 구성단위 총 몰수를 기준으로 12 내지 28 몰%인, 착색 감광성 수지 조성물을 제공한다.In order to achieve the above object, the present invention provides (A) a structural unit derived from (a1) ethylenically unsaturated carboxylic acid, ethylenically unsaturated carboxylic acid anhydride, or a combination thereof, (a2) C 3-20 aliphatic cyclic ethylenic A structural unit derived from an unsaturated compound, (a3) a structural unit derived from a C 3-20 aliphatic linear ethylenically unsaturated compound, and (a4) an ethylenically unsaturated compound different from the above (a1), (a2) and (a3) a copolymer comprising a constituent unit derived from; (B) a photopolymerizable compound; (C) a photoinitiator; and (D) a colorant; wherein the copolymer (A) has a weight average molecular weight of 3,000 to 9,000 Da, and the content of the structural unit (a2) is 12 based on the total number of moles of the copolymer (A) structural units to 28 mol%, to provide a colored photosensitive resin composition.
본 발명의 착색 감광성 수지 조성물은 단차가 있는 기판 상에 도포되어도 단차 추종성이 우수하여(단차에 따른 높이 차이가 발생하지 않아) 평탄한 경화막을 형성할 수 있다. 나아가, 경화막은 패턴이 뚜렷히 구현될 뿐만 아니라 감도 및 해상도도 우수하여 액정표시장치 및 유기 EL표시장치의 착색 스페이서로 유용하게 사용될 수 있다.Even if the coloring photosensitive resin composition of this invention is apply|coated on the board|substrate with a level|step difference, it is excellent in step|step difference followability|trackability (a height difference does not generate|occur|produce according to a step difference), and can form a flat cured film. Furthermore, the cured film not only has a clear pattern, but also has excellent sensitivity and resolution, so that it can be usefully used as a colored spacer for a liquid crystal display device and an organic EL display device.
도 1은 실시예 및 비교예의 경화막에 풀-톤(full-tone) 마스크 적용시 경화막에 형성된 패턴을 나타낸 사진이다.
도 2는 실시예 및 비교예의 경화막에 하프-톤(half-tone) 마스크 적용시 경화막에 형성된 패턴을 나타낸 사진이다.1 is a photograph showing a pattern formed on a cured film when a full-tone mask is applied to the cured films of Examples and Comparative Examples.
2 is a photograph showing a pattern formed on a cured film when a half-tone mask is applied to the cured films of Examples and Comparative Examples.
본 발명은 이하에 개시된 내용에 한정되는 것이 아니라, 발명의 요지가 변경되지 않는 한 다양한 형태로 변형될 수 있다. The present invention is not limited to the contents disclosed below, and may be modified in various forms as long as the gist of the present invention is not changed.
본 명세서에서 "포함"한다는 것은 특별한 기재가 없는 한 다른 구성요소를 더 포함할 수 있음을 의미한다. 또한, 본 명세서에 기재된 구성성분의 양, 반응 조건 등을 나타내는 모든 숫자 및 표현은 특별한 기재가 없는 한 모든 경우에 "약"이라는 용어로써 수식되는 것으로 이해하여야 한다.In the present specification, "comprising" means that other components may be further included unless otherwise specified. In addition, it should be understood that all numbers and expressions indicating amounts of components, reaction conditions, etc. described herein are modified by the term "about" in all cases unless otherwise specified.
본 발명은 (A) 공중합체, (B) 광중합성 화합물; (C) 광중합 개시제; 및 (D) 착색제를 포함하는 착색 감광성 수지 조성물을 제공한다. 상기 조성물은 선택적으로, (E) 계면활성제, 및/또는 (F) 용매를 더 포함할 수 있다.The present invention relates to (A) a copolymer, (B) a photopolymerizable compound; (C) a photoinitiator; And (D) provides a colored photosensitive resin composition comprising a colorant. The composition may optionally further comprise (E) a surfactant, and/or (F) a solvent.
본 명세서에서, "(메트)아크릴"은 "아크릴" 및/또는 "메타크릴"을 의미하고, "(메트)아크릴레이트"는 "아크릴레이트" 및/또는 "메타크릴레이트"를 의미한다As used herein, "(meth)acryl" means "acryl" and/or "methacrylic", and "(meth)acrylate" means "acrylate" and/or "methacrylate"
하기 각 구성들에 대한 중량평균분자량은 겔 투과 크로마토그래피(gel permeation chromatography; GPC, 테트라히드로퓨란을 용출용매로 함)로 측정한 폴리스티렌 환산의 중량평균분자량(g/mol 또는 Da)을 말한다. The weight average molecular weight for each of the following components refers to the weight average molecular weight (g/mol or Da) in terms of polystyrene measured by gel permeation chromatography (GPC, using tetrahydrofuran as the elution solvent).
(A) 공중합체(A) copolymer
본 발명에 따른 착색 감광성 수지 조성물은 바인더로서 다음과 같은 구성단위들을 포함하는 공중합체를 포함한다. The colored photosensitive resin composition according to the present invention includes a copolymer including the following structural units as a binder.
구체적으로, 상기 공중합체는 (a1) 에틸렌성 불포화 카복실산, 에틸렌성 불포화 카복실산 무수물, 또는 이들의 조합으로부터 유도되는 구성단위, (a2) C3-20의 지방족 고리형 에틸렌성 불포화 화합물로부터 유도되는 구성단위, (a3) C3-20의 지방족 선형 에틸렌성 불포화 화합물로부터 유도되는 구성단위, 및 (a4) 상기 (a1), (a2) 및 (a3)과 상이한 에틸렌성 불포화 화합물로부터 유도되는 구성단위를 포함할 수 있다. 나아가, (a5) 에폭시기를 포함하는 에틸렌성 불포화 화합물을 포함하는 화합물로부터 유도되는 구성단위를 추가로 포함할 수 있다. Specifically, the copolymer (a1) a structural unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a combination thereof, (a2) a structural unit derived from a C 3-20 aliphatic cyclic ethylenically unsaturated compound, (a3) C 3 It may include a structural unit derived from an aliphatic linear ethylenically unsaturated compound of -20, and (a4) a structural unit derived from an ethylenically unsaturated compound different from the above (a1), (a2) and (a3). Furthermore, (a5) may further include a structural unit derived from a compound containing an ethylenically unsaturated compound containing an epoxy group.
하기 각각의 구성단위에 대해 자세히 설명한다. Each constituent unit will be described in detail below.
(a1) 에틸렌성 불포화 카복실산, 에틸렌성 불포화 카복실산 무수물, 또는 이들의 조합으로부터 유도되는 구성단위(a1) a structural unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a combination thereof
상기 구성단위 (a1)은 에틸렌성 불포화 카복실산, 에틸렌성 불포화 카복실산 무수물, 또는 이들의 조합으로부터 유도된다. 상기 에틸렌성 불포화 카복실산 및 에틸렌성 불포화 카복실산 무수물은, 분자에 하나 이상의 카복실기가 있는 중합가능한 불포화 단량체로서, 구체적인 예로서, (메트)아크릴산, 크로톤산, α-클로로아크릴산, 신남산 등의 불포화 모노카복실산; 말레인산, 말레인산 무수물, 푸마르산, 이타콘산, 이타콘산 무수물, 시트라콘산, 시트라콘산 무수물, 메사콘산 등의 불포화 디카복실산 및 이의 무수물; 3가 이상의 불포화 폴리카복실산 및 이의 무수물; 모노[2-(메트)아크릴로일옥시에틸]숙시네이트, 모노[2-(메트)아크릴로일옥시에틸]프탈레이트 등의 2가 이상의 폴리카복실산의 모노[(메트)아크릴로일옥시알킬]에스테르 등을 들 수 있다. 상기 예시된 화합물로부터 유도되는 구성단위는 단독으로 또는 2종 이상 조합되어 공중합체에 포함될 수 있다.The structural unit (a1) is derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a combination thereof. The ethylenically unsaturated carboxylic acid and ethylenically unsaturated carboxylic acid anhydride are polymerizable unsaturated monomers having one or more carboxyl groups in the molecule, and specific examples thereof include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. ; unsaturated dicarboxylic acids and anhydrides thereof, such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; trivalent or higher unsaturated polycarboxylic acids and anhydrides thereof; Mono[(meth)acryloyloxyalkyl]esters of polycarboxylic acids having divalence or higher, such as mono[2-(meth)acryloyloxyethyl]succinate and mono[2-(meth)acryloyloxyethyl]phthalate and the like. The constituent units derived from the compounds exemplified above may be included in the copolymer alone or in combination of two or more.
상기 구성단위 (a1)의 함량은, 상기 공중합체(A)를 구성하는 구성단위의 총 몰수를 기준으로 5 내지 65 몰%, 5 내지 50 몰%, 10 내지 50 몰%, 5 내지 40 몰%, 5 내지 30 몰% 또는 5 내지 20 몰%일 수 있다. 상기 범위 내일 때 양호한 현상성을 가질 수 있다.The content of the structural unit (a1) is 5 to 65 mol%, 5 to 50 mol%, 10 to 50 mol%, 5 to 40 mol%, based on the total number of moles of the structural units constituting the copolymer (A) , 5 to 30 mol% or 5 to 20 mol%. When it is within the above range, it may have good developability.
(a2) C(a2) C 3-203-20 의 지방족 고리형 에틸렌성 불포화 화합물로부터 유도되는 구성단위A structural unit derived from an aliphatic cyclic ethylenically unsaturated compound of
상기 구성단위 (a2)는 C3-20의 지방족 고리형 에틸렌성 불포화 화합물로부터 유도된다. 상기 구성단위 (a2)는 시클로알킬기를 함유한 단량체로부터 유도될 수 있다. 예를 들어, 상기 구성단위 (a2)는 시클로헥실(메트)아크릴레이트, 시클로헥실메틸(메트)아크릴레이트, 시클로헥실에틸(메트)아크릴레이트, 시클로헥실프로필(메트)아크릴레이트, 시클로헥실부틸(메트)아크릴레이트, 4-메틸시클로헥실메틸(메트)아크릴레이트, 4-에틸시클로헥실메틸(메트)아크릴레이트, 시클로펜틸(메트)아크릴레이트 및 4-하이드록시메틸시클로헥실메틸(메트)아크릴레이트로 이루어진 군으로부터 선택되는 1종 이상의 화합물로부터 유도될 수 있다.The structural unit (a2) is derived from a C 3-20 aliphatic cyclic ethylenically unsaturated compound. The structural unit (a2) may be derived from a monomer containing a cycloalkyl group. For example, the structural unit (a2) is cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, cyclohexylethyl (meth) acrylate, cyclohexylpropyl (meth) acrylate, cyclohexylbutyl ( Meth)acrylate, 4-methylcyclohexylmethyl(meth)acrylate, 4-ethylcyclohexylmethyl(meth)acrylate, cyclopentyl(meth)acrylate and 4-hydroxymethylcyclohexylmethyl(meth)acrylate It may be derived from one or more compounds selected from the group consisting of.
구체적으로, 시클로헥실(메트)아크릴레이트, 시클로헥실메틸(메트)아크릴레이트 및 4-메틸시클로헥실메틸(메트)아크릴레이트로 이루어진 군에서 선택되는 1종 이상의 화합물로부터 유도될 수 있다. Specifically, it may be derived from at least one compound selected from the group consisting of cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate and 4-methylcyclohexylmethyl (meth) acrylate.
상기 구성단위 (a2)의 함량은, 상기 공중합체(A)를 구성하는 구성단위의 총 몰수를 기준으로 10 내지 30 몰%, 10 내지 28 몰%, 12 내지 30 몰%, 12 내지 29 몰%, 12 내지 28 몰% 또는 12 내지 25 몰%일 수 있다. 상기 범위 내일 때, 양호한 레벨링성을 가질 수 있다.The content of the structural unit (a2) is 10 to 30 mol%, 10 to 28 mol%, 12 to 30 mol%, 12 to 29 mol%, based on the total number of moles of the structural units constituting the copolymer (A). , 12 to 28 mol% or 12 to 25 mol%. When it is within the above range, good leveling properties may be obtained.
(a3) C(a3) C 3-203-20 의 지방족 선형 에틸렌성 불포화 화합물로부터 유도되는 구성단위A structural unit derived from an aliphatic linear ethylenically unsaturated compound of
상기 구성단위 (a3)은 C3-20의 지방족 선형 에틸렌성 불포화 화합물로부터 유도된다. 구체적으로, 상기 구성단위 (a3)은 프로필(메트)아크릴레이트, 부틸(메트)아크릴레이트, 펜틸(메트)아크릴레이트, 헥실(메트)아크릴레이트, 헵틸(메트)아크릴레이트, 옥틸(메트)아크릴레이트, 노닐(메트)아크릴레이트, 데실(메트)아크릴레이트, 라우릴(메트)아크릴레이트 및 도데실(메트)아크릴레이트로 이루어진 군으로부터 선택되는 1종 이상의 화합물로부터 유도될 수 있다.The structural unit (a3) is derived from a C 3-20 aliphatic linear ethylenically unsaturated compound. Specifically, the structural unit (a3) is propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylic It may be derived from at least one compound selected from the group consisting of late, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate and dodecyl (meth) acrylate.
상기 구성단위 (a3)의 함량은, 상기 공중합체(A)를 구성하는 구성단위 총 몰수를 기준으로 20 내지 50 몰%, 20 내지 40 몰%, 30 내지 40 몰% 또는 32 내지 40 몰%일 수 있다. 상기 범위 내일 때, 양호한 레벨링성을 가질 수 있다. The content of the structural unit (a3) is 20 to 50 mol%, 20 to 40 mol%, 30 to 40 mol%, or 32 to 40 mol% based on the total number of moles of the structural units constituting the copolymer (A). can When it is within the above range, good leveling properties may be obtained.
(a4) 상기 (a1), (a2) 및 (a3)과 상이한 에틸렌성 불포화 화합물로부터 유도되는 구성단위를 포함하는 공중합체(a4) a copolymer comprising a structural unit derived from an ethylenically unsaturated compound different from the above (a1), (a2) and (a3)
본 발명에서 사용되는 공중합체(A)는, 상기 (a1), (a2) 및 (a3) 외에도, (a1), (a2) 및 (a3)과는 상이한 에틸렌성 불포화 화합물로부터 유도되는 구성단위를 추가로 포함할 수 있다. The copolymer (A) used in the present invention contains, in addition to the above (a1), (a2) and (a3), a structural unit derived from an ethylenically unsaturated compound different from (a1), (a2) and (a3). may additionally include.
상기 (a1), (a2) 및 (a3)과는 상이한 에틸렌성 불포화 화합물의 구체적인 예로는, 메틸(메트)아크릴레이트, 에틸(메트)아크릴레이트, 디메틸아미노에틸(메트)아크릴레이트, 이소부틸(메트)아크릴레이트, t-부틸(메트)아크릴레이트, 에틸헥실(메트)아크릴레이트, 테트라히드로퍼프릴(메트)아크릴레이트, 히드록시에틸(메트)아크릴레이트, 2-히드록시프로필(메트)아크릴레이트, 2-히드록시-3-클로로프로필(메트)아크릴레이트, 4-히드록시부틸(메트)아크릴레이트, 글리세롤(메트)아크릴레이트, 메틸 α-히드록시메틸아크릴레이트, 에틸 α-히드록시메틸아크릴레이트, 프로필 α-히드록시메틸아크릴레이트, 부틸 α-히드록시메틸아크릴레이트, 2-메톡시에틸(메트)아크릴레이트, 3-메톡시부틸(메트)아크릴레이트, 에톡시디에틸렌글리콜(메트)아크릴레이트, 메톡시트리에틸렌글리콜(메트)아크릴레이트, 메톡시트리프로필렌글리콜(메트)아크릴레이트, 폴리(에틸렌글리콜)메틸에테르(메트)아크릴레이트, 테트라플루오로프로필(메트)아크릴레이트, 1,1,1,3,3,3-헥사플루오로이소프로필(메트)아크릴레이트, 옥타플루오로펜틸(메트)아크릴레이트, 헵타데카플루오로데실(메트)아크릴레이트, 이소보닐(메트)아크릴레이트, 디시클로펜타닐(메트)아크릴레이트, 디시클로펜테닐(메트)아크릴레이트, 디시클로펜타닐옥시에틸(메트)아크릴레이트, 디시클로펜테닐옥시에틸(메트)아크릴레이트 등의 불포화 카복실산 에스테르류; N-비닐피롤리돈, N-비닐카바졸, N-비닐모폴린 등의 N-비닐을 포함하는 삼차아민류; 비닐메틸에테르, 비닐에틸에테르 등의 불포화 에테르류; N-페닐말레이미드, N-(4-클로로페닐)말레이미드, N-(4-히드록시페닐)말레이미드, N-시클로헥실말레이미드 등의 불포화 이미드류 등을 들 수 있다. 상기 예시된 화합물로부터 유도되는 구성단위는 단독으로 또는 2종 이상 조합되어 공중합체에 포함될 수 있다. 이들 중에서 불포화 카복실산 에스테르류로부터 유도되는 구성단위가 공중합성 및 레벨링성 향상 측면에서 보다 유리하다.Specific examples of the ethylenically unsaturated compound different from the above (a1), (a2) and (a3) include methyl (meth) acrylate, ethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl ( Meth) acrylate, t-butyl (meth) acrylate, ethylhexyl (meth) acrylate, tetrahydro puffril (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylic rate, 2-hydroxy-3-chloropropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, methyl α-hydroxymethylacrylate, ethyl α-hydroxymethyl Acrylate, propyl α-hydroxymethyl acrylate, butyl α-hydroxymethyl acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxydiethylene glycol (meth) Acrylate, methoxytriethylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1, 1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, isobornyl (meth) acrylate, unsaturated carboxylic acid esters such as dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate; tertiary amines containing N-vinyl such as N-vinylpyrrolidone, N-vinylcarbazole and N-vinylmorpholine; unsaturated ethers such as vinyl methyl ether and vinyl ethyl ether; Unsaturated imides, such as N-phenyl maleimide, N-(4-chlorophenyl) maleimide, N-(4-hydroxyphenyl) maleimide, and N-cyclohexyl maleimide, etc. are mentioned. The constituent units derived from the compounds exemplified above may be included in the copolymer alone or in combination of two or more. Among them, a structural unit derived from unsaturated carboxylic acid esters is more advantageous in terms of improving copolymerizability and leveling properties.
상기 구성단위 (a4)의 함량은, 상기 공중합체(A)를 구성하는 구성단위의 총 몰수를 기준으로 10 내지 50 몰%, 10 내지 40 몰%, 10 내지 30 몰%, 10 내지 25 몰%, 15 내지 30 몰% 또는 15 내지 25 몰%일 수 있다. 상기 범위 내일 때 상기 착색 감광성 수지 조성물의 저장 안정성을 유지시키고 잔막율을 향상시키는데 보다 유리할 수 있다.The content of the structural unit (a4) is 10 to 50 mol%, 10 to 40 mol%, 10 to 30 mol%, 10 to 25 mol%, based on the total number of moles of the structural units constituting the copolymer (A) , 15 to 30 mol% or 15 to 25 mol%. When within the above range, it may be more advantageous to maintain the storage stability of the colored photosensitive resin composition and to improve the remaining film rate.
(a5) 에폭시기를 포함하는 에틸렌성 불포화 화합물을 포함하는 화합물로부터 유도되는 구성단위(a5) a structural unit derived from a compound containing an ethylenically unsaturated compound containing an epoxy group
상기 공중합체(A)는 상술한 바와 같은 구성단위 외에도, (a5) 에폭시기를 포함하는 에틸렌성 불포화 화합물을 포함하는 화합물로부터 유도되는 구성단위를 추가로 포함할 수 있다. The copolymer (A) may further include, in addition to the structural units as described above, (a5) a structural unit derived from a compound containing an ethylenically unsaturated compound containing an epoxy group.
상기 구성단위 (a5)는 에폭시기를 포함하는 에틸렌성 불포화 화합물로부터 유도된다. 상기 에폭시기를 포함하는 에틸렌성 불포화 화합물의 구체적인 예로는, 글리시딜(메트)아크릴레이트, 3,4-에폭시부틸(메트)아크릴레이트, 4,5-에폭시펜틸(메트)아크릴레이트, 5,6-에폭시헥실(메트)아크릴레이트, 6,7-에폭시헵틸(메트)아크릴레이트, 2,3-에폭시시클로펜틸(메트)아크릴레이트, 3,4-에폭시시클로헥실(메트)아크릴레이트, α-에틸글리시딜아크릴레이트, α-n-프로필글리시딜아크릴레이트, α-n-부틸글리시딜아크릴레이트, N-(4-(2,3-에폭시프로폭시)-3,5-디메틸벤질)아크릴아미드, N-(4-(2,3-에폭시프로폭시)-3,5-디메틸페닐프로필)아크릴아미드, 4-히드록시부틸(메트)아크릴레이트글리시딜에테르, 4-히드록시부틸아크릴레이트글리시딜에테르, 알릴글리시딜에테르, 2-메틸알릴글리시딜에테르 등을 들 수 있다. 상기 예시된 화합물로부터 유도되는 구성단위는 단독으로 또는 2종 이상 조합되어 공중합체에 포함될 수 있다. 이들 중 글리시딜(메트)아크릴레이트, 3,4-에폭시시클로헥실(메트)아크릴레이트 및/또는 4-히드록시부틸(메트)아크릴레이트글리시딜에테르로부터 유도되는 구성단위가 공중합성 및 절연막의 강도 향상 측면에서 보다 유리하다.The structural unit (a5) is derived from an ethylenically unsaturated compound containing an epoxy group. Specific examples of the ethylenically unsaturated compound containing the epoxy group include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 4,5-epoxypentyl (meth) acrylate, 5,6 -Epoxyhexyl (meth) acrylate, 6,7-epoxy heptyl (meth) acrylate, 2,3-epoxy cyclopentyl (meth) acrylate, 3,4-epoxy cyclohexyl (meth) acrylate, α-ethyl Glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butylglycidyl acrylate, N-(4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl) Acrylamide, N-(4-(2,3-epoxypropoxy)-3,5-dimethylphenylpropyl)acrylamide, 4-hydroxybutyl (meth)acrylate glycidyl ether, 4-hydroxybutylacrylic Late glycidyl ether, allyl glycidyl ether, 2-methylallyl glycidyl ether, etc. are mentioned. The constituent units derived from the compounds exemplified above may be included in the copolymer alone or in combination of two or more. Among these, structural units derived from glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate and/or 4-hydroxybutyl (meth) acrylate glycidyl ether are copolymerizable and insulating film more advantageous in terms of improving the strength of
상기 구성단위 (a5)의 함량은, 상기 공중합체(A)를 구성하는 구성단위의 총 몰수를 기준으로 1 내지 40 몰%, 또는 5 내지 20 몰%일 수 있다. 상기 범위 내일 때, 공정중 잔사 및 예비경화시 마진(margin) 측면에서 보다 유리할 수 있다.The content of the structural unit (a5) may be 1 to 40 mol%, or 5 to 20 mol%, based on the total number of moles of the structural units constituting the copolymer (A). When it is within the above range, it may be more advantageous in terms of residual in-process and margin during pre-curing.
이상의 구성단위 (a1) 내지 (a4) 및/또는 (a1) 내지 (a5)를 갖는 공중합체의 예로는, (메트)아크릴산/시클로헥실(메트)아크릴레이트/부틸(메트)아크릴레이트/메틸(메트)아크릴레이트, (메트)아크릴산/시클로헥실(메트)아크릴레이트/부틸(메트)아크릴레이트/메틸(메트)아크릴레이트/글리시딜(메트)아크릴레이트, (메트)아크릴산/시클로헥실(메트)아크릴레이트/부틸(메트)아크릴레이트/메틸(메트)아크릴레이트/4-히드록시부틸(메트)아크릴레이트글리시딜에테르, (메트)아크릴산/시클로헥실(메트)아크릴레이트/부틸(메트)아크릴레이트/메틸(메트)아크릴레이트/3,4-에폭시시클로헥실(메트)아크릴레이트, (메트)아크릴산/시클로헥실(메트)아크릴레이트/펜틸(메트)아크릴레이트/메틸(메트)아크릴레이트/글리시딜(메트)아크릴레이트, (메트)아크릴산/시클로헥실(메트)아크릴레이트/펜틸(메트)아크릴레이트/메틸(메트)아크릴레이트/3,4-에폭시시클로헥실(메트)아크릴레이트, (메트)아크릴산/시클로헥실(메트)아크릴레이트/헥실(메트)아크릴레이트/메틸(메트)아크릴레이트/글리시딜(메트)아크릴레이트, (메트)아크릴산/시클로헥실(메트)아크릴레이트/헥실(메트)아크릴레이트/메틸(메트)아크릴레이트/3,4-에폭시시클로헥실(메트)아크릴레이트 등을 들 수 있다. Examples of the copolymer having the above structural units (a1) to (a4) and/or (a1) to (a5) include (meth)acrylic acid / cyclohexyl (meth) acrylate / butyl (meth) acrylate / methyl ( Meth) acrylate, (meth) acrylic acid / cyclohexyl (meth) acrylate / butyl (meth) acrylate / methyl (meth) acrylate / glycidyl (meth) acrylate, (meth) acrylic acid / cyclohexyl (meth) ) acrylate / butyl (meth) acrylate / methyl (meth) acrylate / 4-hydroxybutyl (meth) acrylate glycidyl ether, (meth) acrylic acid / cyclohexyl (meth) acrylate / butyl (meth) Acrylate / methyl (meth) acrylate / 3,4-epoxycyclohexyl (meth) acrylate, (meth) acrylic acid / cyclohexyl (meth) acrylate / pentyl (meth) acrylate / methyl (meth) acrylate / Glycidyl (meth) acrylate, (meth) acrylic acid / cyclohexyl (meth) acrylate / pentyl (meth) acrylate / methyl (meth) acrylate / 3,4-epoxycyclohexyl (meth) acrylate, ( Meth) acrylic acid / cyclohexyl (meth) acrylate / hexyl (meth) acrylate / methyl (meth) acrylate / glycidyl (meth) acrylate, (meth) acrylic acid / cyclohexyl (meth) acrylate / hexyl ( and meth)acrylate/methyl (meth)acrylate/3,4-epoxycyclohexyl (meth)acrylate.
상기 공중합체는 착색 감광성 수지 조성물에 1종 또는 2종 이상 함유될 수 있다. The copolymer may be contained in one type or two or more types in the colored photosensitive resin composition.
상기 공중합체(A)의 중량평균분자량(Mw)은 3,000 내지 10,000 Da, 3,000 내지 9,500 Da, 3,000 내지 9,000 Da, 4,000 내지 9,000 Da, 5,000 내지 8,000 Da 또는 5,000 내지 7,000 Da 일 수 있다. 공중합체의 중량평균분자량이 상기 범위 내일 때, 하부 패턴에 의한 단차 개선이 유리하고 레벨링성 및 현상 후 패턴 현상이 양호하다. The weight average molecular weight (Mw) of the copolymer (A) may be 3,000 to 10,000 Da, 3,000 to 9,500 Da, 3,000 to 9,000 Da, 4,000 to 9,000 Da, 5,000 to 8,000 Da, or 5,000 to 7,000 Da. When the weight average molecular weight of the copolymer is within the above range, the improvement of the step by the lower pattern is advantageous, and the leveling property and the pattern development after development are good.
전체 착색 감광성 수지 조성물 중의 공중합체(A)의 함량은, 착색 감광성 수지 조성물에서 용매를 제외한 고형분의 총 중량을 기준으로 대하여 5 내지 40 중량%, 5 내지 30 중량%, 10 내지 40 중량% 또는 10 내지 30 중량%일 수 있다. 상기 범위 내일 때, 레벨링성이 우수하고, 현상 후의 패턴 현상이 양호하며 잔막율 및 내화학성 등의 특성이 향상될 수 있다.The content of the copolymer (A) in the entire colored photosensitive resin composition is 5 to 40 wt%, 5 to 30 wt%, 10 to 40 wt%, or 10 based on the total weight of solids excluding the solvent in the colored photosensitive resin composition to 30% by weight. When within the above range, the leveling property is excellent, the pattern development after development is good, and properties such as a residual film rate and chemical resistance may be improved.
상기 공중합체(A)는 라디칼 중합 개시제, 용매 및 상기 구성단위들을 넣고 질소를 투입한 후 서서히 교반하면서 중합시켜 제조될 수 있다.The copolymer (A) may be prepared by adding a radical polymerization initiator, a solvent, and the constituent units, adding nitrogen, and then polymerizing while slowly stirring.
상기 라디칼 중합 개시제는 특별히 한정되지 않으나, 2,2'-아조비스이소부티로니트릴, 2,2'-아조비스(2,4-디메틸발레로니트릴), 2,2'-아조비스(4-메톡시-2,4-디메틸발레로니트릴) 등의 아조 화합물, 벤조일퍼옥사이드, 라우릴퍼옥사이드, t-부틸퍼옥시피발레이트, 1,1-비스(t-부틸퍼옥시)시클로헥산 등일 수 있다. 이들 라디칼 중합 개시제는 단독으로 또는 2종 이상을 혼합하여 사용할 수 있다.The radical polymerization initiator is not particularly limited, but 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4- Azo compounds such as methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, lauryl peroxide, t-butylperoxypivalate, 1,1-bis(t-butylperoxy)cyclohexane, etc. have. These radical polymerization initiators can be used individually or in mixture of 2 or more types.
상기 용매는 공중합체의 제조에 사용되는 것이면 어느 것이나 사용 가능하며, 예를 들어 프로필렌글리콜모노메틸에테르아세테이트(PGMEA)일 수 있다.Any solvent may be used as long as the solvent is used for preparing the copolymer, and for example, propylene glycol monomethyl ether acetate (PGMEA) may be used.
(B) 광중합성 화합물(B) photopolymerizable compound
본 발명에서 사용하는 광중합성 화합물은 광중합 개시제의 작용으로 중합할 수 있는 화합물이다. 구체적으로, 상기 광중합성 화합물은 이중결합을 갖는 단관능 또는 다관능성 화합물일 수 있다. 구체적으로, 1개 이상의 에틸렌성 불포화 이중결합을 갖는 단관능, 또는 다관능 에스테르 화합물을 포함할 수 있으며, 내화학성 측면에서 2관능 이상의 다관능성 화합물일 수 있다.The photopolymerizable compound used in the present invention is a compound capable of polymerization by the action of a photoinitiator. Specifically, the photopolymerizable compound may be a monofunctional or polyfunctional compound having a double bond. Specifically, it may include a monofunctional or polyfunctional ester compound having one or more ethylenically unsaturated double bonds, and may be a bifunctional or more polyfunctional compound in terms of chemical resistance.
상기 광중합성 화합물은 에틸렌글리콜디(메트)아크릴레이트, 프로필렌글리콜디(메트)아크릴레이트, 디에틸렌글리콜디(메트)아크릴레이트, 트리에틸렌글리콜디(메트)아크릴레이트, 1,6-헥산디올디(메트)아크릴레이트, 폴리에틸렌글리콜디(메트)아크릴레이트, 폴리프로필렌글리콜디(메트)아크릴레이트, 글리세린트리(메트)아크릴레이트, 트리메틸올프로판트리(메트)아크릴레이트, 펜타에리트리톨트리(메트)아크릴레이트, 펜타에리트리톨트리(메트)아크릴레이트와 숙신산의 모노에스테르화물, 펜타에리트리톨테트라(메트)아크릴레이트, 디펜타에리트리톨펜타(메트)아크릴레이트, 디펜타에리트리톨헥사(메트)아크릴레이트, 디펜타에리트리톨펜타(메트)아크릴레이트와 숙신산의 모노에스테르화물, 펜타에리트리톨트리아크릴레이트헥사메틸렌디이소시아네이트(펜타에리트리톨트리아크릴레이트와 헥사메틸렌디이소시아네이트의 반응물), 트리펜타에리트리톨헵타(메트)아크릴레이트, 트리펜타에리트리톨옥타(메트)아크릴레이트, 비스페놀 A 에폭시아크릴레이트, 에틸렌글리콜모노메틸에테르아크릴레이트 및 이들의 혼합물로 이루어진 군에서 선택될 수 있으나, 이에 제한되는 것은 아니다.The photopolymerizable compound is ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth) Acrylate, monoester product of pentaerythritol tri(meth)acrylate and succinic acid, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate , monoester product of dipentaerythritol penta (meth) acrylate and succinic acid, pentaerythritol triacrylate hexamethylene diisocyanate (a reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate), tripentaerythritol hepta ( It may be selected from the group consisting of meth) acrylate, tripentaerythritol octa (meth) acrylate, bisphenol A epoxy acrylate, ethylene glycol monomethyl ether acrylate, and mixtures thereof, but is not limited thereto.
보다 구체적으로, 상기 광중합성 화합물은 3관능 이상의 우레탄아크릴레이트계 화합물일 수 있다. 예를 들어, 디펜타에리트리톨 헥사아크릴레이트, 펜타에리트리톨트리(메트)아크릴레이트 및 이들의 혼합물로 이루어진 군으로부터 선택되는 1종 이상일 수 있다.More specifically, the photopolymerizable compound may be a trifunctional or higher urethane acrylate compound. For example, it may be at least one selected from the group consisting of dipentaerythritol hexaacrylate, pentaerythritol tri(meth)acrylate, and mixtures thereof.
상업적으로 구매 가능한 광중합성 화합물은, (i) 단관능 (메트)아크릴레이트의 시판품으로서, 도아고세이사의 아로닉스 M-101, M-111 및 M-114, 닛본가야꾸사의 KAYARAD T4-110S 및 T4-120S, 오사카유끼 가가꾸고교사의 V-158 및 V-2311 등이 있고; (ii) 2관능 (메트)아크릴레이트의 시판품으로서, 도아고세이사의 아로닉스 M-210, M-240 및 M-6200, 닛본가야꾸사의 KAYARAD HDDA, HX-220 및 R-604, 오사카유끼 가가꾸고교사의 V-260, V-312 및 V-335 HP 등이 있으며; (iii) 3관능 이상의 (메트)아크릴레이트의 시판품으로서, 도아고세이사의 아로닉스 M-309, M-400, M-403, M-405, M-450, M-7100, M-8030, M-8060 및 TO-1382, 닛본가야꾸사의 KAYARAD PET-30, KAYARAD TMPTA, DPHA, 오사카유끼 가가꾸고교사의 V-295, V-300, V-360, V-GPT, V-3PA, V-400 및 V-802 등을 수 있고, iv) 3관능 이상의 우레탄아크릴레이트의 시판품으로서, 다이셀사의 Ebecryl 254, Ebecryl 264, Ebecryl 265, Ebecryl 8210, Ebecryl 1290k, Ebecryl 5129 및 Ebecryl 220, 닛본가야꾸사의 KAYARAD DPHA-40H 등을 들 수 있다.Commercially available photopolymerizable compounds are (i) commercially available monofunctional (meth)acrylates, Aronix M-101, M-111 and M-114 by Toagosei, KAYARAD T4-110S by Nippon Kayaku, and T4-120S, Osaka Yuki Chemical High School's V-158 and V-2311; (ii) Aronix M-210, M-240 and M-6200 by Toagosei Corporation, KAYARAD HDDA, HX-220 and R-604 by Nippon Kayaku, as a commercial product of bifunctional (meth)acrylate, Osaka Yuki There are the V-260, V-312, and V-335 HP of Gyogyo High School; (iii) Aronix M-309, M-400, M-403, M-405, M-450, M-7100, M-8030, M of Toagosei Corporation as a commercial product of trifunctional or higher (meth)acrylate -8060 and TO-1382, KAYARAD PET-30, KAYARAD TMPTA, DPHA from Nippon Kayaku, V-295, V-300, V-360, V-GPT, V-3PA, V-400 from Osaka Yuki Chemical High School and V-802, and iv) as a commercial product of trifunctional or higher functional urethane acrylate, Ebecryl 254, Ebecryl 264, Ebecryl 265, Ebecryl 8210, Ebecryl 1290k, Ebecryl 5129 and Ebecryl 220 by Daicel Corporation, KAYARAD by Nippon Kayaku DPHA-40H etc. are mentioned.
상기 광중합성 화합물의 함량은 용매를 제외한 고형분을 기준으로 상기 공중합체(A) 100 중량부에 대하여 300 내지 600 중량부, 300 내지 500 중량부, 400 내지 600 중량부 또는 400 내지 500 중량부일 수 있다. 광중합성 화합물의 함량이 상기 범위 내일 경우, 현상 시간이 길어져 공정 및 잔사의 영향을 주는 문제가 방지되어 패턴 현상이 용이하고, 내화학성 및 탄성 복원력 등의 특성이 향상되며, 패턴 해상도가 커지는 문제 및 표면 주름 발생이 유발되는 문제가 방지될 수 있다.The content of the photopolymerizable compound may be 300 to 600 parts by weight, 300 to 500 parts by weight, 400 to 600 parts by weight, or 400 to 500 parts by weight based on 100 parts by weight of the copolymer (A) based on the solid content excluding the solvent. . When the content of the photopolymerizable compound is within the above range, the problem of influencing the process and residue due to the prolonged development time is prevented, so that the pattern development is easy, the properties such as chemical resistance and elastic restoring force are improved, the pattern resolution is increased, and A problem in which surface wrinkling is caused can be prevented.
(C) 광중합 개시제(C) photoinitiator
본 발명에서 사용하는 광중합 개시제는 공지의 광중합 개시제이면 어느 것이나 사용가능하다.As the photopolymerization initiator used in the present invention, any known photopolymerization initiator may be used.
상기 광중합 개시제는 아세토페논계 화합물, 비이미다졸계 화합물, 트리아진계 화합물, 오늄염계 화합물, 벤조인계 화합물, 벤조페논계 화합물, 다핵 퀴논계 화합물, 티오크산톤계 화합물, 디아조계 화합물, 아조계 화합물, 이미드설포네이트계 화합물, 옥심계 화합물, 카바졸계 화합물, 설포늄 보레이트계 화합물, 케톤계 화합물 및 이들의 혼합물로 이루어진 군에서 선택될 수 있다. 구체적으로, 상기 광중합 개시제는 옥심계 화합물, 트리아진계 화합물 및 케톤계 화합물로 이루어진 군으로부터 선택된 1종 이상일 수 있다. 보다 구체적으로, 상기 광중합 개시제는 옥심계 및 트리아진계 화합물의 조합 또는 옥심계, 트리아진계 및 케톤계 화합물의 조합을 사용할 수 있다. The photopolymerization initiator is an acetophenone-based compound, a biimidazole-based compound, a triazine-based compound, an onium salt-based compound, a benzoin-based compound, a benzophenone-based compound, a polynuclear quinone-based compound, a thioxanthone-based compound, a diazo-based compound, an azo-based compound , an imide sulfonate-based compound, an oxime-based compound, a carbazole-based compound, a sulfonium borate-based compound, a ketone-based compound, and mixtures thereof. Specifically, the photopolymerization initiator may be at least one selected from the group consisting of an oxime-based compound, a triazine-based compound, and a ketone-based compound. More specifically, the photopolymerization initiator may use a combination of an oxime-based compound and a triazine-based compound or a combination of an oxime-based compound, a triazine-based compound, and a ketone-based compound.
상기 광중합 개시제의 구체적인 예로는, 2,2'-아조비스(2,4-디메틸발레로니트릴), 2,2'-아조비스(4-메톡시-2,4-디메틸발레로니트릴), 벤조일퍼옥사이드, 라우릴퍼옥사이드, t-부틸퍼옥시피발레이트, 1,1-비스(t-부틸퍼옥시)시클로헥산, p-디메틸아미노아세토페논, 2-벤질-2-(디메틸아미노)-1-[4-(4-모포리닐)페닐]-1-부탄온, 2-히드록시-2-메틸-1-페닐-프로판-1-온, 벤질디메틸케탈, 벤조페논, 벤조인프로필에테르, 디에틸티옥산톤, 2,4-비스(트리클로로메틸)-6-p-메톡시페닐-s-트리아진, 2-트리클로로메틸-5-스티릴-1,3,4-옥소디아졸, 9-페닐아크리딘, 3-메틸-5-아미노-((s-트리아진-2-일)아미노)-3-페닐쿠마린, 2-(o-클로로페닐)-4,5-디페닐이미다졸릴 이량체, 1-페닐-1,2-프로판디온-2-(o-에톡시카르보닐)옥심, 1-[4-(페닐티오)페닐]-옥탄-1,2-디온-2-(o-벤조일옥심), o-벤조일-4'-(벤즈머캅토)벤조일-헥실-케톡심, 2,4,6-트리메틸페닐카르보닐-디페닐포스포닐옥사이드, 헥사플루오로포스포로-트리알킬페닐술포늄염, 2-머캅토벤즈이미다졸, 2,2'-벤조티아조릴디설파이드, (E)-2-(4-스티릴페닐)-4,6-비스(트리클로로메틸)-1,3,5-트리아진, 2-디메틸아미노-2-(4-메틸벤질)-1-(4-모르포린-4-일-페닐)-부탄-1-온 및 이들의 혼합물을 들 수 있으나, 이에 한정되는 것은 아니다.Specific examples of the photopolymerization initiator include 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), benzoyl Peroxide, lauryl peroxide, t-butylperoxypivalate, 1,1-bis(t-butylperoxy)cyclohexane, p-dimethylaminoacetophenone, 2-benzyl-2-(dimethylamino)-1 -[4-(4-morpholinyl)phenyl]-1-butanone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzyldimethylketal, benzophenone, benzoinpropyl ether, di Ethylthioxanthone, 2,4-bis(trichloromethyl)-6-p-methoxyphenyl-s-triazine, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 9-phenylacridine, 3-methyl-5-amino-((s-triazin-2-yl)amino)-3-phenylcoumarin, 2-(o-chlorophenyl)-4,5-diphenyl Midazolyl dimer, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-[4-(phenylthio)phenyl]-octane-1,2-dione-2- (o-benzoyloxime), o-benzoyl-4'-(benzmercapto)benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenylcarbonyl-diphenylphosphonyloxide, hexafluorophosphoro-tri Alkylphenylsulfonium salt, 2-mercaptobenzimidazole, 2,2'-benzothiazolyldisulfide, (E)-2-(4-styrylphenyl)-4,6-bis(trichloromethyl)-1, 3,5-triazine, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one and mixtures thereof; The present invention is not limited thereto.
참고로, 시판되는 옥심계 광중합 개시제의 예로는 SPI-03(삼양사), OXE-01(BASF), OXE-02(BASF), OXE-03(BASF), N-1919(ADEKA), NCI-930(ADEKA), NCI-831(ADEKA) 등을 들 수 있다. 또한, 시판되는 트리아진계 광중합 개시제의 예로는 Triazine-Y(Tronly) 등을 들 수 있다. For reference, examples of commercially available oxime-based photopolymerization initiators include SPI-03 (Samyang Corporation), OXE-01 (BASF), OXE-02 (BASF), OXE-03 (BASF), N-1919 (ADEKA), NCI-930 (ADEKA), NCI-831 (ADEKA), etc. are mentioned. In addition, examples of the commercially available triazine-based photopolymerization initiator include Triazine-Y (Tronly).
상기 광중합 개시제의 함량은, 용매를 제외한 고형분을 기준으로 상기 공중합체(A) 100 중량부에 대하여 1 내지 10 중량부, 2 내지 10 중량부, 4 내지 10 중량부 또는 5 내지 10 중량부일 수 있다.The content of the photopolymerization initiator may be 1 to 10 parts by weight, 2 to 10 parts by weight, 4 to 10 parts by weight, or 5 to 10 parts by weight based on 100 parts by weight of the copolymer (A) based on the solid content excluding the solvent. .
구체적으로, 상기 광중합 개시제로서 용매를 제외한 고형분을 기준으로 상기 공중합체(A) 100 중량부에 대하여 0.4 내지 4 중량부의 옥심계 화합물, 0.5 내지 5 중량부의 트리아진계 화합물 및/또는 0.1 내지 3 중량부의 케톤계 화합물을 사용할 수 있다. 보다 구체적으로, 0.5 내지 5 중량부의 옥심계 화합물 및 0.5 내지 5 중량부의 트리아진계 화합물을 사용할 수 있다. Specifically, based on the solid content excluding the solvent as the photopolymerization initiator, 0.4 to 4 parts by weight of the oxime-based compound, 0.5 to 5 parts by weight of the triazine-based compound, and/or 0.1 to 3 parts by weight based on 100 parts by weight of the copolymer (A) A ketone-based compound may be used. More specifically, 0.5 to 5 parts by weight of the oxime-based compound and 0.5 to 5 parts by weight of the triazine-based compound may be used.
상기 범위 내의 옥심계 화합물을 사용할 경우, 고감도이면서 현상 및 도막 특성이 향상될 수 있다. 또한, 상기 범위 내의 트리아진계 화합물을 사용할 경우, 고감도이면서 내화학성 및 패턴이 뚜렷히 형성된 도막을 얻을 수 있다. 나아가, 상기 범위 내의 케톤계 화합물을 사용할 경우, 심부 경화를 통해 내화학성이 우수한 도막 특성을 갖는 착색 감광성 수지 조성물을 제조할 수 있다.When an oxime-based compound within the above range is used, the development and coating film characteristics may be improved while being highly sensitive. In addition, when a triazine-based compound within the above range is used, it is possible to obtain a highly sensitive, chemically resistant and patterned coating film. Furthermore, when using the ketone-based compound within the above range, it is possible to prepare a colored photosensitive resin composition having excellent chemical resistance coating film properties through deep curing.
(D) 착색제(D) colorant
본 발명의 착색 감광성 수지 조성물은 차광성을 부여하기 위해 착색제를 포함한다. 본 발명에서 사용되는 착색제는 무기 또는 유기의 2종 이상의 혼합 착색제일 수 있으며, 발색성이 높고 내열성이 높은 착색제인 것이 바람직하다.The coloring photosensitive resin composition of this invention contains a coloring agent in order to provide light-shielding property. The colorant used in the present invention may be a mixed colorant of two or more types of inorganic or organic colorants, and is preferably a colorant having high color development and high heat resistance.
상기 착색제는 흑색 착색제를 포함할 수 있다. 상기 흑색 착색제는 흑색 유기 착색제, 흑색 무기 착색제 또는 이들의 혼합일 수 있다. The colorant may include a black colorant. The black colorant may be a black organic colorant, a black inorganic colorant, or a mixture thereof.
또한, 상기 착색제는 흑색 이외의 착색제를 추가로 포함할 수 있다. In addition, the colorant may further include a colorant other than black.
상기 흑색 무기 착색제, 흑색 유기 착색제 및 흑색 이외의 착색제로는 공지의 것이라면 어느 것이라도 사용가능하며, 예를 들어 컬러 인덱스(The Society of Dyers and Colourists 출판)에서 안료(pigment)로 분류되어 있는 화합물을 포함할 수 있고, 공지의 염료를 포함할 수도 있다.As the black inorganic colorant, black organic colorant, and colorant other than black, any known colorant can be used, for example, a compound classified as a pigment in the Color Index (published by The Society of Dyers and Colorists) It may contain, and may contain a well-known dye.
상기 흑색 무기 착색제의 구체예로는 카본 블랙, 티타늄 블랙, Cu-Fe-Mn-기저의 산화물 및 합성 철 블랙과 같은 금속 산화물 등을 들 수 있고, 그 중에서도 카본 블랙을 사용하는 것이 패턴 특성 및 내화학성의 면에서 바람직하다.Specific examples of the black inorganic colorant include carbon black, titanium black, Cu-Fe-Mn-based oxides, and metal oxides such as synthetic iron black. It is preferable in terms of chemical properties.
상기 흑색 유기 착색제의 구체예로는 아닐린 블랙, 락탐 블랙, 페릴렌 블랙 등을 들 수 있고, 그 중에서도 락탐 블랙(예: 바스프사의 Black 582)을 사용하는 것이 광학 밀도, 유전율 등의 측면에서 바람직하다.Specific examples of the black organic colorant include aniline black, lactam black, and perylene black. Among them, lactam black (eg, Black 582 manufactured by BASF) is preferably used in terms of optical density, permittivity, etc. .
상기 흑색 이외의 착색제는 청색 착색제 및 보라색 착색제로 이루어진 군으로부터 선택되는 1종 이상일 수 있다.The colorant other than black may be at least one selected from the group consisting of a blue colorant and a purple colorant.
상기 흑색 이외의 착색제의 구체예로는 피그먼트 오렌지 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 및 71; C.I. 피그먼트 레드 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 215, 216, 224, 242, 254, 255 및 264; C.I. 피그먼트 바이올렛 13, 14, 19, 23, 25, 27, 29, 32, 33, 36, 37 및 38; C.I. 피그먼트 블루 15(15:3, 15:4, 15:6등), 16, 21, 28, 60, 64 및 76; C.I. 피그먼트 그린 7, 10, 15, 25, 36, 47 및 58; 및 C.I 피그먼트 브라운 28 등을 들 수 있다. 구체적으로, C.I 피그먼트 블루 15:6 및 60, 또는 C.I. 피그먼트 바이올렛 23을 사용하는 것이 착색 분산 조성물의 분산성 및 내화학성 측면에서 바람직하다.Specific examples of the colorant other than the black include pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71; C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 215, 216, 224, 242, 254, 255 and 264; C.I. Pigment Violet 13, 14, 19, 23, 25, 27, 29, 32, 33, 36, 37 and 38; C.I. Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 16, 21, 28, 60, 64 and 76; C.I. Pigment Green 7, 10, 15, 25, 36, 47 and 58; and C.I Pigment Brown 28. Specifically, C.I Pigment Blue 15:6 and 60, or C.I. It is preferable to use Pigment Violet 23 in terms of dispersibility and chemical resistance of the colored dispersion composition.
상기 착색제의 함량은, 용매를 제외한 고형분을 기준으로 상기 공중합체(A) 100 중량부에 대하여 50 내지 200 중량부, 50 내지 150 중량부, 50 내지 100 중량부, 70 내지 150 중량부 또는 80 내지 100 중량부일 수 있다.The content of the colorant may be 50 to 200 parts by weight, 50 to 150 parts by weight, 50 to 100 parts by weight, 70 to 150 parts by weight or 80 to 100 parts by weight of the copolymer (A) based on the solid content excluding the solvent. It may be 100 parts by weight.
상기 착색제는 용매를 제외한 고형분을 기준으로 착색 감광성 수지 조성물 총 중량에 대하여 0.01 내지 50 중량%의 흑색 착색제 및 0.01 내지 20 중량%의 흑색 이외의 착색제를 포함할 수 있다. The colorant may include 0.01 to 50% by weight of a black colorant and 0.01 to 20% by weight of a colorant other than black based on the total weight of the colored photosensitive resin composition based on the solid content excluding the solvent.
구체적으로, 상기 착색제는 흑색 무기 착색제 또는 흑색 유기 착색제를 포함하고, 용매를 제외한 고형분을 기준으로 착색 감광성 수지 조성물 총 중량에 대하여 0.01 내지 15 중량%의 흑색 무기 착색제, 0.01 내지 40 중량%의 흑색 유기 착색제 및 0.01 내지 20 중량%의 흑색 이외의 착색제를 포함할 수 있다. Specifically, the colorant includes a black inorganic colorant or a black organic colorant, and based on the solid content excluding the solvent, 0.01 to 15% by weight of the black inorganic colorant, 0.01 to 40% by weight of the black organic colorant based on the total weight of the colored photosensitive resin composition a colorant and 0.01 to 20% by weight of a colorant other than black.
보다 구체적으로, 착색 감광성 수지 조성물의 고형분 총 중량에 대하여 0.01 내지 8.2 중량%의 흑색 무기 착색제, 0.01 내지 45 중량%의 흑색 유기 착색제 및 0.01 내지 15 중량%의 흑색 이외의 착색제를 포함할 수 있다. More specifically, it may include 0.01 to 8.2% by weight of a black inorganic colorant, 0.01 to 45% by weight of a black organic colorant, and 0.01 to 15% by weight of a colorant other than black, based on the total solids weight of the colored photosensitive resin composition.
착색제의 함량이 상기 범위 내일 때, 현상 후 패턴 현상이 양호하고, 내화학성 및 탄성 복원력 등의 특성이 향상될 수 있으며, 목적하는 광학 밀도 및 광투과도를 얻을 수 있다.When the content of the colorant is within the above range, pattern development after development is good, properties such as chemical resistance and elastic restoring force may be improved, and desired optical density and light transmittance may be obtained.
착색제의 함량이 상기 범위 내일 때, 현상 후 패턴 현상이 양호하고, 내화학성 및 탄성 복원력 등의 특성이 향상될 수 있으며, 목적하는 광학 밀도 및 광투과도를 얻을 수 있다.When the content of the colorant is within the above range, pattern development after development is good, properties such as chemical resistance and elastic restoring force may be improved, and desired optical density and light transmittance may be obtained.
한편, 본 발명에서 사용되는 착색제는 분산 수지, 용매 등과 혼합된 착색 분산액(mill base)의 형태로 착색 감광성 수지 조성물에 첨가될 수 있다. Meanwhile, the colorant used in the present invention may be added to the colored photosensitive resin composition in the form of a colored dispersion (mill base) mixed with a dispersion resin, a solvent, and the like.
상기 분산 수지는 안료를 용매 중에 균일하게 분산시키는 역할을 하며, 구체적으로, 분산제 및 분산 바인더로 이루어진 군으로부터 선택된 1종 이상일 수 있다.The dispersion resin serves to uniformly disperse the pigment in a solvent, and specifically, may be at least one selected from the group consisting of a dispersant and a dispersion binder.
상기 분산제의 예로는 착색제의 분산제로 공지된 것이면 어느 것이라도 사용할 수 있으며, 구체적인 예로는 양이온계 계면활성제, 음이온계 계면활성제, 비이온계 계면활성제, 양쪽성 계면활성제, 실리콘계 계면활성제, 불소계 계면활성제, 폴리에스테르계 화합물, 폴리카르본산에스테르계 화합물, 불포화 폴리아미드계 화합물, 폴리카르본산계 화합물, 폴리카르본산알킬염 화합물, 폴리아크릴계 화합물, 폴리에틸렌이민계 화합물, 폴리우레탄계 화합물, 폴리우레탄, 폴리아크릴레이트로 대표되는 폴리카르복실산 에스테르, 불포화 폴리아미드, 폴리카르복실산, 폴리카르복실산의 아민염, 폴리카르복실산의 암모늄염, 폴리카르복실산의 알킬아민염, 폴리실록산, 장쇄 폴리아미노아미드 포스페이트염, 히드록실기가 치환된 폴리카르복실산의 에스테르 및 이들의 개질 생성물, 프리(free) 카르복실기를 갖는 폴리에스테르와 폴리(저급 알킬렌이민)의 반응에 의해 형성된 아미드 또는 이들의 염, (메트)아크릴산-스티렌 코폴리머, (메트)아크릴산-(메트)아크릴레이트 에스테르 코폴리머, 스티렌-말레산 코폴리머, 폴리비닐 알코올, 폴리비닐 피롤리돈과 같은 수용성 수지 또는 수용성 폴리머 화합물, 개질된 폴리아크릴레이트, 에틸렌 옥사이드/프로필렌 옥사이드의 부가생성물, 포스페이트 에스테르 등을 들 수 있다. 시판되는 분산제로는 BYK사의 디스퍼빅(Disperbyk)-182, -183, -184, -185, -2000, -2150, -2155, -2163, -2164 등을 들 수 있다. 이들은 단독으로 또는 2종 이상을 조합하여 사용할 수 있다. 상기 분산제는 안료 친화 그룹으로 아민기 및/또는 산기를 가질 수 있으며, 경우에 따라 암모늄염 타입일 수도 있다.Examples of the dispersant include any known dispersant for colorants, and specific examples include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, silicone surfactants, and fluorine surfactants. , polyester compound, polycarboxylic acid ester compound, unsaturated polyamide compound, polycarboxylic acid compound, polycarboxylic acid alkyl salt compound, polyacrylic compound, polyethyleneimine compound, polyurethane compound, polyurethane, polyacrylic Polycarboxylic acid ester, unsaturated polyamide, polycarboxylic acid, amine salt of polycarboxylic acid, ammonium salt of polycarboxylic acid, alkylamine salt of polycarboxylic acid, polysiloxane, long-chain polyaminoamide phosphate Salts, esters of polycarboxylic acids substituted with hydroxyl groups and modified products thereof, amides or salts thereof formed by the reaction of polyesters having free carboxyl groups with poly(lower alkyleneimines), (meth ) acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, water-soluble resin or water-soluble polymer compound such as polyvinyl pyrrolidone, modified polyacrylic lates, adducts of ethylene oxide/propylene oxide, phosphate esters, and the like. Commercially available dispersants include BYK's Disperbyk-182, -183, -184, -185, -2000, -2150, -2155, -2163, and -2164. These can be used individually or in combination of 2 or more types. The dispersant may have an amine group and/or an acid group as a pigment affinity group, and may be an ammonium salt type in some cases.
상기 분산제는 미리 착색제에 표면 처리하는 방식으로 착색제에 내부 첨가시켜 사용하거나, 착색제와 함께 착색 감광성 수지 조성물 제조시에 첨가하여 사용할 수도 있다.The dispersing agent may be used by being internally added to the colorant in a manner of surface-treating the colorant in advance, or may be added and used together with the colorant when preparing the colored photosensitive resin composition.
상기 분산제의 아민가는 10 내지 200 mgKOH/g, 40 내지 200 mgKOH/g, 또는 50 내지 150 mgKOH/g일 수 있다. 분산제의 아민가가 상기 범위 내일 경우, 착색제의 분산성 및 저장 안정성이 우수하고, 상기 수지 조성물로부터 제조된 경화막의 표면의 러프니스(roughness)가 개선된다.The amine value of the dispersant may be 10 to 200 mgKOH/g, 40 to 200 mgKOH/g, or 50 to 150 mgKOH/g. When the amine number of the dispersant is within the above range, the dispersibility and storage stability of the colorant are excellent, and the roughness of the surface of the cured film prepared from the resin composition is improved.
상기 분산제는 착색 분산액 총 중량에 대하여 1 내지 20 중량%, 또는 2 내지 15 중량%로 포함될 수 있다. 분산제의 함량이 상기 범위 내일 경우, 착색제의 효과적인 분산이 이루어져 분산 안정성이 개선되며, 적절한 점도를 유지하여 제품 적용시 광학적, 물리적 및 화학적 품질이 향상됨에 따라, 분산 안정성 및 점도의 우수한 밸런스 면에서 바람직하다.The dispersant may be included in an amount of 1 to 20% by weight, or 2 to 15% by weight based on the total weight of the colored dispersion. When the content of the dispersant is within the above range, effective dispersion of the colorant is achieved to improve dispersion stability, and as the optical, physical and chemical quality is improved when the product is applied by maintaining an appropriate viscosity, it is preferable in terms of dispersion stability and excellent balance of viscosity Do.
또한, 상기 착색제는 분산 수지를 포함하고, 상기 분산 수지는 3 mgKOH/g 이하의 아민가를 포함하고, 구성단위의 총 몰수 기준으로 30 몰% 이하의 말레이미드 단량체를 포함할 수 있다. 이때, 상기 분산 수지는 분산 바인더일 수 있다.In addition, the colorant may include a dispersion resin, and the dispersion resin may include an amine value of 3 mgKOH/g or less, and 30 mol% or less of maleimide monomer based on the total number of moles of constituent units. In this case, the dispersion resin may be a dispersion binder.
상기 분산 바인더의 산가가 있는 경우, 카르복실기와 불포화 결합을 갖는 단량체를 포함할 수 있다. 상기 카르복실산기와 불포화 결합을 갖는 단량체의 구체적인 예로는 아크릴산, 메타크릴산, 크로톤산 등의 모노카르복실산류; 푸마르산, 메사콘산, 이타콘산 등의 디카르복실산류; 및 이들 디카르복실산의 무수물; ω-카르복시폴리카프로락톤모노(메트)아크릴레이트 등의 양 말단에 카르복실기와 수산기를 갖는 폴리머의 모노(메트)아크릴레이트류 등을 들 수 있으며, 아크릴산, 메타크릴산이 바람직하다.When the dispersion binder has an acid value, it may include a monomer having a carboxyl group and an unsaturated bond. Specific examples of the monomer having the carboxylic acid group and an unsaturated bond include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; and anhydrides of these dicarboxylic acids; Polymer mono(meth)acrylates having a carboxyl group and a hydroxyl group at both terminals, such as ω-carboxypolycaprolactone mono(meth)acrylate, etc. are mentioned, and acrylic acid and methacrylic acid are preferable.
또한, 상기 분산 바인더는 상기 카르복실기와 불포화 결합을 갖는 단량체는 이와 공중합 가능한 불포화 결합을 갖는 단량체를 포함할 수 있다. 상기 공중합 가능한 불포화 결합을 갖는 단량체는, 예를 들어, 스티렌, 비닐톨루엔, α-메틸스티렌, p-클로로스티렌, o-메톡시스티렌, m-메톡시스티렌, p-메톡시스티렌, o-비닐벤질메틸에테르, m-비닐벤질메틸에테르, p-비닐벤질메틸에테르, o-비닐벤질글리시딜에테르, m-비닐벤질글리시딜에테르 또는 p-비닐벤질글리시딜에테르 등의 방향족 비닐 화합물; 메틸(메트)아크릴레이트, 에틸(메트)아크릴레이트, n-프로필(메트)아크릴레이트, i-프로필(메트)아크릴레이트, n-부틸(메트)아크릴레이트, i-부틸(메트)아크릴레이트, sec-부틸(메트)아크릴레이트 또는 t-부틸(메트)아크릴레이트 등의 알킬(메타)아크릴레이트류; 시클로펜틸(메트)아크릴레이트, 시클로헥실(메트)아크릴레이트, 2-메틸시클로헥실(메트)아크릴레이트, 트리시클로[5.2.1.0 2,6 ]데칸-8-일(메트)아크릴레이트, 2-디시클로펜타닐옥시에틸(메트)아크릴레이트 또는 이소보르닐(메트)아크릴레이트 등의 지환족(메트)아크릴레이트류; 페닐(메트)아크릴레이트 또는 벤질(메트)아크릴레이트 등의 아릴(메트)아크릴레이트류; 2-히드록시에틸(메트)아크릴레이트 또는 2-히드록시프로필(메트)아크릴레이트 등의 히드록시알킬(메트)아크릴레이트류; N-시클로헥실말레이미드, N-벤질말레이미드, N-페닐말레이미드, N-o-히드록시페닐말레이미드, N-m-히드록시페닐말레이미드, N-p-히드록시페닐말레이미드, N-o-메틸페닐말레이미드, N-m-메틸페닐말레이미드, N-p-메틸페닐말레이미드, N-o-메톡시페닐말레이미드, N-m-메톡시페닐말레이미드, N-p-메톡시 페닐말레이미드 등의 N-치환 말레이미드계 화합물; (메트)아크릴아미드, N,N-디메틸(메트)아크릴아미드 등의 불포화 아미드 화합물; 3-(메타크릴로일옥시메틸)옥세탄, 3-(메타크릴로일옥시메틸)-3-에틸옥세탄, 3-(메타크릴로일옥시메틸)-2-트리플루오로메틸옥세탄, 3-(메타크릴로일옥시메틸)-2-페닐옥세탄, 2-(메타크릴로일옥시메틸)옥세탄 또는 2-(메타크릴로일옥시메틸)-4-트리플루오로메틸옥세탄 등의 불포화 옥세탄 화합물 등을 들 수 있으며, 이들은 각각 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.In addition, the dispersion binder may include a monomer having an unsaturated bond copolymerizable with the monomer having the carboxyl group and an unsaturated bond. The monomer having a copolymerizable unsaturated bond is, for example, styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinyl aromatic vinyl compounds such as benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, or p-vinyl benzyl glycidyl ether; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth)acrylates such as sec-butyl (meth)acrylate or t-butyl (meth)acrylate; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6 ] decan-8-yl (meth) acrylate, 2- alicyclic (meth)acrylates such as dicyclopentanyloxyethyl (meth)acrylate or isobornyl (meth)acrylate; aryl (meth) acrylates such as phenyl (meth) acrylate or benzyl (meth) acrylate; hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm -N-substituted maleimide compounds, such as methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide; unsaturated amide compounds such as (meth)acrylamide and N,N-dimethyl (meth)acrylamide; 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane; 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane or 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, etc. of unsaturated oxetane compounds, and these may be used alone or in combination of two or more.
상기 분산 바인더는 구성단위의 총 몰수 기준으로 30 몰% 이하의 말레이미드 단량체를 포함할 수 있다.The dispersion binder may contain 30 mol% or less of maleimide monomer based on the total number of moles of the constituent units.
상기 분산 바인더는 30 내지 200 mgKOH/g의 산가를 가질 수 있다. 구체적으로, 상기 분산 바인더는 50 내지 150 mgKOH/g의 산가를 가질 수 있다. 분산 바인더의 산가가 상기 범위 내일 경우, 안료를 감싸고 있는 분산제의 아민가에 미치는 영향이 적어져 착색 분산액의 안정성이 우수하고 균일한 입도 크기를 갖는 효과가 있다.The dispersion binder may have an acid value of 30 to 200 mgKOH/g. Specifically, the dispersion binder may have an acid value of 50 to 150 mgKOH/g. When the acid value of the dispersion binder is within the above range, the effect on the amine value of the dispersant surrounding the pigment is reduced, so that the colored dispersion has excellent stability and has a uniform particle size.
또한, 분산 바인더의 아민가가 3 mgKOH/g을 초과할 경우, 안료를 감싸고 있는 분산제의 안정성에 영향을 미쳐 수지 조성물 전체의 저장 안정성에 악영향을 미칠 수 있으므로 분산 바인더의 아민가는 3 mgKOH/g 이하가 바람직하다. 분산 바인더의 아민가가 상기 범위 내일 경우, 현상 공정에서 비노광 부분의 현상을 용이하게 하고 잔사 발생과 같은 문제점을 개선할 수 있다.In addition, when the amine value of the dispersion binder exceeds 3 mgKOH/g, it may affect the stability of the dispersant surrounding the pigment and adversely affect the storage stability of the entire resin composition, so the amine value of the dispersion binder is 3 mgKOH/g or less desirable. When the amine value of the dispersion binder is within the above range, it is possible to facilitate the development of the unexposed portion in the developing process and improve problems such as residue generation.
상기 분산 바인더는 착색 분산액 총량에 대하여 1 내지 20 중량%, 또는 2 내지 15 중량%로 포함될 수 있다. 분산 바인더가 상기 범위로 포함되는 경우, 수지 조성물이 적절한 점도를 유지할 수 있으며, 분산 안정성과 현상성 측면에서 바람직하다. The dispersion binder may be included in an amount of 1 to 20% by weight, or 2 to 15% by weight based on the total amount of the colored dispersion. When the dispersion binder is included in the above range, the resin composition can maintain an appropriate viscosity, which is preferable in terms of dispersion stability and developability.
상기 착색 분산액은 본 발명의 착색 감광성 수지 조성물에서 용매를 제외한 고형분 총 중량을 기준으로 10 내지 80 중량%, 또는 20 내지 60 중량%로 포함될 수 있다.The colored dispersion may be included in an amount of 10 to 80 wt%, or 20 to 60 wt%, based on the total weight of the solids excluding the solvent in the colored photosensitive resin composition of the present invention.
(E) 계면활성제(E) surfactant
본 발명의 착색 감광성 수지 조성물은 코팅성 향상 및 결점 생성 방지 효과를 위해 계면활성제를 추가로 포함할 수 있다.The colored photosensitive resin composition of the present invention may further include a surfactant to improve coating properties and prevent defect formation.
상기 계면활성제의 종류는 특별히 한정되지 않으나, 예를 들어 불소계 계면활성제 또는 실리콘계 계면활성제일 수 있다.The type of the surfactant is not particularly limited, but may be, for example, a fluorine-based surfactant or a silicone-based surfactant.
상기 실리콘계 계면활성제의 시판품으로는 다우코닝 도레이 실리콘사의 DC3PA, DC7PA, SH11PA, SH21PA, SH8400, GE 도시바 실리콘사의 TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452, BYK사의 BYK-333, BYK-307, BYK-3560, BYK UV-3535, BYK-361N, BYK-354, BYK-399 등을 들 수 있다. 이들은 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.Commercial products of the silicone-based surfactant include DC3PA, DC7PA, SH11PA, SH21PA, SH8400, TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 of Dow Corning Toray Silicone Co., Ltd. , BYK's BYK-333, BYK-307, BYK-3560, BYK UV-3535, BYK-361N, BYK-354, BYK-399, and the like. These can be used individually or in combination of 2 or more types.
상기 불소계 계면활성제의 시판품으로는 다이닛본 잉크 가가꾸 고교(DIC)사의 메가피스(Megaface) F-470, F-471, F-475, F-482, F-489, F-563, 산요화인텍사의 F-563 등을 들 수 있다. 상기 계면활성제 중, 산요화인텍사의 F-563, BYK사의 BYK-333, BYK-307, DIC사의 F-563 등이 수지 조성물의 코팅성 측면에서 바람직하다.Commercial products of the fluorine-based surfactant include Megaface F-470, F-471, F-475, F-482, F-489, F-563 manufactured by Dai Nippon Ink Chemical Co., Ltd. (DIC), and Sanyo Finetec Corporation. F-563 etc. are mentioned. Among the surfactants, Sanyo Finetec's F-563, BYK's BYK-333, BYK-307, DIC's F-563, etc. are preferable in terms of coating properties of the resin composition.
상기 계면활성제의 함량은, 용매를 제외한 고형분을 기준으로 상기 공중합체(A) 100 중량부에 대하여 0.01 내지 3 중량부, 0.01 내지 2 중량부, 0.1 내지 3 중량부, 0.1 내지 2 중량부 또는 0.1 내지 1 중량부일 수 있다. 계면활성제의 함량이 상기 범위 내일 때, 착색 감광성 수지 조성물의 코팅이 원활할 수 있다.The content of the surfactant is 0.01 to 3 parts by weight, 0.01 to 2 parts by weight, 0.1 to 3 parts by weight, 0.1 to 2 parts by weight, or 0.1 based on 100 parts by weight of the copolymer (A) based on the solid content excluding the solvent. to 1 part by weight. When the content of the surfactant is within the above range, the coating of the colored photosensitive resin composition may be smooth.
(F) 용매(F) solvent
본 발명의 착색 감광성 수지 조성물은 바람직하게는 상술한 성분들을 용매와 혼합한 액상 조성물로 제조될 수 있다. 상기 용매로는 전술한 착색 감광성 수지 조성물 성분들과 상용성을 가지되 이들과 반응하지 않는 것으로서, 착색 감광성 수지 조성물에 사용되는 공지의 용매이면 어느 것이나 사용 가능하다.The colored photosensitive resin composition of the present invention may be preferably prepared as a liquid composition in which the above-mentioned components are mixed with a solvent. As the solvent, any known solvent used for the colored photosensitive resin composition may be used as long as it has compatibility with the above-described colored photosensitive resin composition components but does not react with them.
이러한 용매의 예로는 에틸렌글리콜모노에틸에테르 등의 글리콜에테르류; 에틸셀로솔브 아세테이트 등의 에틸렌글리콜알킬에테르아세테이트류; 2-히드록시프로피온산 에틸 등의 에스테르류; 디에틸렌글리콜모노메틸에테르 등의 디에틸렌글리콜류; 프로필렌글리콜모노메틸에테르아세테이트, 프로필렌글리콜프로필에테르아세테이트 등의 프로필렌글리콜알킬에테르아세테이트류; 3-메톡시부틸아세테이트 등의 알콕시알킬아세테이트류를 들 수 있다. 상기 용매는 단독 또는 2종 이상을 배합하여 사용할 수 있다.Examples of such a solvent include glycol ethers such as ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; esters such as ethyl 2-hydroxypropionate; diethylene glycols such as diethylene glycol monomethyl ether; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; Alkoxyalkyl acetates, such as 3-methoxybutyl acetate, are mentioned. The solvent may be used alone or in combination of two or more.
상기 용매의 함유량은 특별히 한정되지 않지만, 최종 착색 감광성 수지 조성물의 도포성, 안정성 등의 관점에서, 착색 감광성 수지 조성물 총 중량에 대하여 50 내지 90 중량％, 또는 70 내지 85 중량%일 수 있다. 용매 함유량이 상기의 범위 내이면, 수지 조성물의 코팅이 원활하고 작업 공정에서 발생할 수 있는 지연 손실(delay margin)이 적은 효과를 얻을 수 있다.The content of the solvent is not particularly limited, but may be 50 to 90 wt%, or 70 to 85 wt%, based on the total weight of the colored photosensitive resin composition from the viewpoint of applicability and stability of the final colored photosensitive resin composition. When the solvent content is within the above range, it is possible to obtain the effect that the coating of the resin composition is smooth and the delay margin that may occur in the working process is small.
이 외에도, 본 발명의 착색 감광성 수지 조성물은 물성을 저하시키지 않는 범위 내에서 산화방지제, 안정제 등의 기타의 첨가제를 포함할 수 있다.In addition to this, the colored photosensitive resin composition of the present invention may include other additives such as antioxidants and stabilizers within a range that does not reduce physical properties.
상기 착색 감광성 수지 조성물로 형성된 경화막은 두께 1 ㎛에 대한 경화막의 광학 밀도가 0.1/㎛ 내지 3.0/㎛, 0.1/㎛ 내지 2.5/㎛일 수 있다. 광학 밀도가 상기 범위 내일 경우, 디스플레이 화면의 해상도를 높이는 효과가 있다.The cured film formed of the colored photosensitive resin composition may have an optical density of 0.1/μm to 3.0/μm, 0.1/μm to 2.5/μm, with respect to a thickness of 1 μm. When the optical density is within the above range, there is an effect of increasing the resolution of the display screen.
이상의 성분들을 포함하는 본 발명의 착색 감광성 수지 조성물은 통상적인 방법에 의해 제조될 수 있으며, 일례로 다음과 같은 방법에 의해 제조할 수 있다. The colored photosensitive resin composition of the present invention comprising the above components may be prepared by a conventional method, for example, may be prepared by the following method.
먼저, 착색제를 미리 용매와 혼합하여 착색제의 평균 입경이 원하는 수준으로 될 때까지 비드밀 등을 이용하여 분산시킨다. 이때, 계면활성제 및/또는 분산제가 사용될 수 있고, 또한 공중합체의 일부 또는 전부가 배합될 수도 있다. 이 분산액에 공중합체 및 계면활성제의 나머지, 광중합성 화합물 및 광중합 개시제를 첨가하고, 필요에 따라 첨가제 또는 추가의 용매를 소정의 농도가 되도록 더 배합한 뒤, 충분히 교반하여 목적하는 착색 감광성 수지 조성물을 얻을 수 있다.First, the colorant is mixed with a solvent in advance and dispersed using a bead mill or the like until the average particle diameter of the colorant becomes a desired level. In this case, a surfactant and/or a dispersant may be used, and some or all of the copolymer may be blended. To this dispersion, the remainder of the copolymer and surfactant, a photopolymerizable compound and a photoinitiator are added, and if necessary, an additive or additional solvent is further blended to a predetermined concentration, followed by sufficient stirring to obtain the desired colored photosensitive resin composition. can be obtained
본 발명은 상기 착색 감광성 수지 조성물로부터 제조된 착색 스페이서를 제공한다.The present invention provides a colored spacer prepared from the colored photosensitive resin composition.
구체적으로, 본 발명은 상기 착색 감광성 수지 조성물을 이용하여 제조되며 컬럼 스페이서와 블랙 매트릭스가 일체로 형성된 블랙 컬럼 스페이서(black column spacer; BCS)를 제공한다.Specifically, the present invention provides a black column spacer (BCS) prepared by using the colored photosensitive resin composition and in which a column spacer and a black matrix are integrally formed.
상기 착색 스페이서는 도막 형성 단계, 노광 단계, 현상 단계, 및 가열 처리 단계를 거쳐 제조될 수 있다.The colored spacer may be manufactured through a coating film forming step, an exposure step, a developing step, and a heat treatment step.
상기 도막 형성 단계에서는, 본 발명에 따른 착색 감광성 수지 조성물을 소정의 전처리를 한 기판 상에 스핀 또는 슬릿 코팅법, 롤 코팅법, 스크린 인쇄법, 어플리케이터법 등의 방법을 사용하여 원하는 두께, 예를 들어 1 내지 25 ㎛의 두께로 도포한 후, 70 내지 100℃의 온도에서 1분 내지 10분 동안 예비경화하여 용매를 제거함으로써 도막을 형성할 수 있다. In the coating film forming step, a desired thickness, e.g., by using a method such as spin or slit coating method, roll coating method, screen printing method, applicator method, etc., on a substrate that has been pre-treated with the colored photosensitive resin composition according to the present invention For example, after coating to a thickness of 1 to 25 μm, a coating film can be formed by pre-curing at a temperature of 70 to 100° C. for 1 to 10 minutes to remove the solvent.
상기 수득한 도막에 패턴을 형성하기 위해 소정 형태의 마스크를 개재한 뒤, 200 내지 500 nm의 활성선을 조사한다. 이때 일체형의 블랙 컬럼 스페이서의 제조를 위해서는 컬럼 스페이서와 블랙 매트릭스가 동시에 구현 가능하도록 투과율이 상이한 패턴을 갖는 마스크를 사용할 수 있다. 조사에 사용되는 광원으로는 저압 수은등, 고압 수은등, 초고압 수은등, 금속 할로겐화물 램프, 아르곤 가스 레이저 등을 사용할 수 있으며, 경우에 따라 X선, 전자선 등도 이용할 수 있다. 노광량은 조성물 각 성분의 종류, 배합량 및 건조 막 두께에 따라 다르지만, 고압 수은등을 사용하는 경우에는 100 mJ/㎠ 이하, 또는 30 내지 80 mJ/㎠ (365 nm 파장에서)일 수 있다.In order to form a pattern on the obtained coating film, a mask having a predetermined shape is interposed and then irradiated with actinic rays of 200 to 500 nm. In this case, in order to manufacture the integrated black column spacer, a mask having different transmittance patterns may be used so that the column spacer and the black matrix can be simultaneously implemented. As a light source used for irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an argon gas laser, etc. may be used, and in some cases, an X-ray, an electron beam, etc. may be used. The exposure amount varies depending on the type of each component of the composition, compounding amount, and dry film thickness, but may be 100 mJ/cm 2 or less, or 30 to 80 mJ/cm 2 (at a wavelength of 365 nm) when a high-pressure mercury lamp is used.
상기 노광 단계에 이어, 탄산나트륨, 수산화나트륨, 수산화칼륨, 테트라메틸암모늄히드록시드 등의 알칼리성 수용액을 현상액으로 이용하여 불필요한 부분을 용해 및 제거함으로써 노광 부분만을 잔존시켜 패턴을 형성시킬 수 있다. 현상에 의해 수득된 화상 패턴을 상온까지 식힌 후에, 열풍순환식 건조로에서 180 내지 250℃에서 10 내지 60분간 후경화(post-bake)하여 원하는 최종 패턴을 얻을 수 있다.Following the exposure step, an alkaline aqueous solution such as sodium carbonate, sodium hydroxide, potassium hydroxide, or tetramethylammonium hydroxide is used as a developer to dissolve and remove unnecessary portions, thereby leaving only the exposed portion to form a pattern. After the image pattern obtained by development is cooled to room temperature, a desired final pattern can be obtained by post-bake at 180 to 250° C. for 10 to 60 minutes in a hot air circulation drying furnace.
이와 같이 제조된 착색 스페이서는 우수한 물성에 기인하여 LCD, OLED, 퀀텀닷(QD) 디스플레이 등의 전자부품에 유용하게 사용될 수 있다. 따라서, 본 발명은 상기 착색 스페이서를 포함하는 전자부품을 제공한다.The colored spacer manufactured as described above may be usefully used in electronic components such as LCD, OLED, and quantum dot (QD) displays due to excellent physical properties. Accordingly, the present invention provides an electronic component including the colored spacer.
상기 LCD, OLED, 퀀텀(QD) 디스플레이 등은 본 발명의 착색 스페이서를 구비한 것을 제외하고는 본 발명의 기술분야에서 당업자에게 알려진 구성을 포함할 수 있다. 즉, 본 발명의 착색 스페이서를 적용할 수 있는 LCD, OLED, 퀀텀닷(QD) 디스플레이 등은 모두 본 발명에 포함될 수 있다.The LCD, OLED, quantum (QD) display, etc. may include a configuration known to those skilled in the art, except for having the colored spacer of the present invention. That is, LCD, OLED, quantum dot (QD) display, etc. to which the colored spacer of the present invention can be applied may all be included in the present invention.
이하, 하기 실시예에 의하여 본 발명을 좀더 상세하게 설명하고자 한다. 단, 하기 실시예는 본 발명을 예시하기 위한 것일 뿐 본 발명의 범위가 이들만으로 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail by way of Examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.
하기 제조예에 기재된 중량평균분자량은 겔 투과 크로마토그래피(GPC)에 의해 측정한 폴리스티렌 환산값이다.The weight average molecular weight described in Preparation Examples below is a polystyrene conversion value measured by gel permeation chromatography (GPC).
[실시예][Example]
제조예 1. 공중합체의 제조Preparation Example 1. Preparation of copolymer
교반기가 장착된 500 ml 둥근 플라스크에 시클로헥실메타크릴레이트(CHMA) 15 몰%, 글리시딜메타크릴레이트(GMA) 10 몰%, 부틸메타크릴레이트(BMA) 40 몰%, 메타크릴산(MAA) 13 몰% 및 메틸메타크릴레이트(MMA) 22 몰%의 몰비를 갖는 단량체 혼합물 100 g, 용매로서 프로필렌글리콜모노메틸에테르아세테이트(PGMEA) 300 g과 라디칼 중합 개시제로서 azo initiator V-65(Wako) 5 g을 첨가한 다음, 60℃에서 5시간 동안 교반하여 고형분 함량이 30 중량%인 공중합체를 제조하였다. 생성된 공중합체의 중량평균분자량(Mw)은 6,000 Da 이었다. In a 500 ml round flask equipped with a stirrer, 15 mol% of cyclohexyl methacrylate (CHMA), 10 mol% of glycidyl methacrylate (GMA), 40 mol% of butyl methacrylate (BMA), methacrylic acid (MAA) ) 100 g of a monomer mixture having a molar ratio of 13 mol% and 22 mol% of methyl methacrylate (MMA), 300 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, and azo initiator V-65 (Wako) as a radical polymerization initiator After adding 5 g, the mixture was stirred at 60° C. for 5 hours to prepare a copolymer having a solid content of 30% by weight. The weight average molecular weight (Mw) of the resulting copolymer was 6,000 Da.
제조예 2 내지 8.Preparation Examples 2 to 8.
하기 표 1에 기재된 바와 같이, 종류 및/또는 함량을 다르게 한 것을 제외하고는 제조예 1과 동일한 방법으로 공중합체를 제조하였다. As shown in Table 1 below, a copolymer was prepared in the same manner as in Preparation Example 1, except that the type and/or content was different.
실시예 및 비교예: 감광성 수지 조성물의 제조Examples and Comparative Examples: Preparation of photosensitive resin composition
상기 제조예에서 제조된 화합물들을 이용하여 하기 실시예 및 비교예의 감광성 수지 조성물을 제조하였다. The photosensitive resin compositions of the following Examples and Comparative Examples were prepared using the compounds prepared in Preparation Examples.
이하의 실시예 및 비교예에서 사용한 성분들에 대한 정보는 다음과 같다. Information on the components used in the following Examples and Comparative Examples is as follows.
실시예 1.Example 1.
공중합체로서 제조예 3에서 제조한 공중합체(A-3) 100 중량부(고형분 함량), 광중합성 화합물로서 디펜타에리트리톨 헥사아크릴레이트(B-1) 252 중량부 및 펜타에리톨 트리아크릴레이트(PET-30) 180 중량부, 광중합 개시제로서 SPI-03(C-1) 2 중량부 및 Triazine-Y(C-2) 6 중량부, 착색제(D)로서 Black-DNC-23 93 중량부 및 계면활성제(E) F-563 1 중량부를 혼합하고, 여기에 고형분 함량이 21.5 중량%가 되도록 용매(F) PGMEA를 투입한 후 쉐이커를 이용하여 2시간 동안 혼합하여 액상의 착색 감광성 수지 조성물을 제조하였다.100 parts by weight (solid content) of the copolymer (A-3) prepared in Preparation Example 3 as a copolymer, 252 parts by weight of dipentaerythritol hexaacrylate (B-1) as a photopolymerizable compound, and pentaerythritol triacrylate (PET-30) 180 parts by weight, 2 parts by weight of SPI-03(C-1) and 6 parts by weight of Triazine-Y(C-2) as a photopolymerization initiator, 93 parts by weight of Black-DNC-23 as a colorant (D) and 1 part by weight of surfactant (E) F-563 was mixed, and solvent (F) PGMEA was added thereto so that the solid content was 21.5 wt%, and then mixed for 2 hours using a shaker to prepare a liquid colored photosensitive resin composition did.
실시예 2 내지 6 및 비교예 1 내지 3.Examples 2 to 6 and Comparative Examples 1 to 3.
하기 표 3에 기재된 바와 같이, 종류 및/또는 함량을 다르게 한 것을 제외하고는 실시예 1과 동일한 방법으로 착색 감광성 수지 조성물을 제조하였다. As shown in Table 3 below, a colored photosensitive resin composition was prepared in the same manner as in Example 1, except that the type and/or content was changed.
[평가예][Evaluation example]
상기 실시예 1 내지 6 및 비교예 1 내지 3에서 제조된 감광성 수지 조성물로부터 경화막(착색 스페이서)을 제조하여 다음과 같은 평가를 수행하고 그 결과를 하기 표 4, 도 1 및 2에 나타내었다. A cured film (colored spacer) was prepared from the photosensitive resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 3, and the following evaluation was performed, and the results are shown in Table 4 and FIGS. 1 and 2 below.
[경화막(착색 스페이서)의 제조][Production of cured film (colored spacer)]
유리 기판 상에 스핀 코터를 이용하여 상기 실시예 및 비교예에서 제조된 착색 감광성 수지 조성물을 각각 도포한 후, 100℃에서 1.5분간 예비경화하여 도막을 형성하였다. 이렇게 얻어진 도막에 풀-톤(full-tone) 및 하프-톤(half-tone) 패턴 마스크를 25 ㎛ 간격으로 적용하고, 365 nm 파장의 빛을 30 내지 80 mJ/cm2의 노광량이 되도록 조사하였다. 이후, 0.04 중량% 수산화칼륨 수용액(현상액)으로 23℃에서 100초간 현상한뒤, 순수한 물로 1분간 세정하여 불필요한 부분을 제거하고 스페이서 패턴만을 남겼다. 상기 패턴이 형성된 도막을 230℃오븐에서 30분간 후경화하여 패턴이 형성된 3.5 ㎛(±0.2 ㎛)의 두께를 갖는 경화막을 얻었다.The colored photosensitive resin compositions prepared in Examples and Comparative Examples were respectively coated on a glass substrate using a spin coater, and then pre-cured at 100° C. for 1.5 minutes to form a coating film. A full-tone and half-tone pattern mask was applied to the thus obtained coating film at intervals of 25 μm, and light of a wavelength of 365 nm was irradiated to an exposure amount of 30 to 80 mJ/cm 2 . . Thereafter, development was carried out at 23° C. for 100 seconds with 0.04 wt% aqueous potassium hydroxide solution (developing solution), followed by washing with pure water for 1 minute to remove unnecessary portions and leaving only spacer patterns. The patterned coating film was post-cured in an oven at 230° C. for 30 minutes to obtain a cured film having a thickness of 3.5 μm (±0.2 μm) on which the pattern was formed.
평가예 1. 감도 평가Evaluation Example 1. Sensitivity Evaluation
상기 방법으로 경화막 제조시 패턴이 형성되는 시점까지의 노광량(mJ/cm2)을 측정하고, 상기 노광량이 작을수록 감도가 우수한 것으로 평가하였다. The exposure amount (mJ/cm 2 ) up to the time when the pattern is formed during the production of the cured film by the above method was measured, and the smaller the exposure amount, the better the sensitivity was evaluated.
평가예 2. 광학 밀도 평가Evaluation Example 2. Evaluation of Optical Density
상기 경화막에 대하여 광학 밀도계(361T, X-lite)를 이용하여 550 nm에서의 투과율을 측정하여 1 ㎛ 두께에 대한 광학 밀도(optical density;OD, 단위:/㎛)를 구하였다.For the cured film, transmittance at 550 nm was measured using an optical density meter (361T, X-lite) to obtain an optical density (OD, unit:/㎛) for a thickness of 1 μm.
평가예 3. 박리성 평가Evaluation Example 3. Peelability Evaluation
상기 방법으로 경화막 제조시 현상 공정후 패턴을 관찰하여 패턴이 아닌 부분이 깨끗이 씻겨져 나갔는지를 관찰하였다. 패턴이 아닌 부분이 깨끗이 씻겨져 나갔으면 박리성 없음, 패턴이 아닌 부분이 씻겨져 나가지 않은 경우, 남아있는 정도에 따라 강약으로 평가하였다.When the cured film was manufactured by the above method, the pattern was observed after the developing process, and it was observed whether the non-pattern part was washed out cleanly. If the non-pattern part was washed out cleanly, there was no peelability, and if the non-pattern part was not washed out, it was evaluated as strong or weak depending on the degree of remaining.
평가예 4. 패턴 유무 평가Evaluation Example 4. Pattern Presence Evaluation
광학 현미경(OLYMPUS)으로 상기 경화막의 패턴을 관찰하고, 이를 도 1 및 2에 사진으로 나타내었다. The pattern of the cured film was observed with an optical microscope (OLYMPUS), and it is shown as a photograph in FIGS. 1 and 2 .
평가예 5. 단차 평가Evaluation example 5. Step evaluation
유리 기판상에 스핀코터를 이용하여 일반적인 투명한 네거티브 타입의 감광성 수지 조성물로 두께 4 ㎛ 및 넓이 100 ㎛의 하부막을 형성한 기판을 준비하였다. 그 다음, 상기 기판 상에 상술한 바와 같은 방법으로 경화막을 형성하고, 형성된 경화막에 대하여 기판과의 높이 차이(단차, ΔH)를 측정하였다. 단차가 작을수록 레벨링 특성이 우수한 것으로 평가하였다. A substrate in which a lower layer having a thickness of 4 μm and a width of 100 μm was formed with a general transparent negative-type photosensitive resin composition on a glass substrate using a spin coater was prepared. Then, a cured film was formed on the substrate in the same manner as described above, and the height difference (step difference, ΔH) of the formed cured film with the substrate was measured. The smaller the step, the better the leveling characteristics were evaluated.
상기 표 4와 도 1 및 2의 결과를 보면, 본 발명의 범위에 속하는 실시예의 조성물로부터 얻은 경화막은 현상성이 우수하여 패턴이 뚜렷히 형성되었고, 광학 밀도도 우수하였다. 또한, 기판과의 단차도 적어 레벨링 특성도 우수하였다. 반면, 비교예의 조성물로부터 얻은 경화막은 감도나 광학 밀도 측면에서 실시예의 경화막과 유사한 결과를 보였으나, 현상시 패턴이 모두 떨어져 나가거나(비교예 1) 깨끗히 씻겨져 나가지 않아(비교예 2 및 3) 목적하는 패턴 형성이 불가능하였고, 기판과의 단차도 커서 레벨링 특성이 매우 저조한 것을 알 수 있다. Referring to the results of Table 4 and FIGS. 1 and 2, the cured film obtained from the composition of Examples within the scope of the present invention had excellent developability, so a pattern was clearly formed, and the optical density was also excellent. In addition, the leveling characteristics were excellent as the level difference with the substrate was small. On the other hand, the cured film obtained from the composition of Comparative Example showed similar results to the cured film of Examples in terms of sensitivity and optical density, but all of the patterns fell off during development (Comparative Example 1) or did not wash off (Comparative Examples 2 and 3) It can be seen that the desired pattern formation was not possible, and the leveling characteristic was very poor due to the large step difference with the substrate.
Claims (8)
(B) 광중합성 화합물
(C) 광중합 개시제; 및
(D) 착색제;를 포함하고,
상기 공중합체(A)의 중량평균분자량이 3,000 내지 9,000 Da이고, 상기 구성단위(a2)의 함량이 상기 공중합체(A) 구성단위 총 몰수를 기준으로 12 내지 28 몰%인, 착색 감광성 수지 조성물.(A) (a1) a structural unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a combination thereof, (a2) a structural unit derived from an aliphatic cyclic ethylenically unsaturated compound of C 3-20, (a3) ) A copolymer comprising a structural unit derived from a C 3-20 aliphatic linear ethylenically unsaturated compound, and (a4) a structural unit derived from an ethylenically unsaturated compound different from the above (a1), (a2) and (a3). ;
(B) photopolymerizable compound
(C) a photoinitiator; and
(D) a colorant;
The copolymer (A) has a weight average molecular weight of 3,000 to 9,000 Da, and the content of the structural unit (a2) is 12 to 28 mol% based on the total number of moles of the copolymer (A) structural units, the colored photosensitive resin composition .
상기 구성단위(a2)가 시클로헥실(메트)아크릴레이트, 시클로헥실메틸(메트)아크릴레이트 및 4-메틸시클로헥실메틸(메트)아크릴레이트로 이루어진 군으로부터 선택되는 1종 이상의 화합물로부터 유도되는 것인, 착색 감광성 수지 조성물.According to claim 1,
The structural unit (a2) is derived from at least one compound selected from the group consisting of cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate and 4-methylcyclohexylmethyl (meth) acrylate , colored photosensitive resin composition.
상기 감광성 수지 조성물이 상기 공중합체(A) 구성단위 총 몰수를 기준으로상기 구성단위(a3)를 20 내지 50 몰%의 양으로 포함하는, 착색 감광성 수지 조성물.According to claim 1,
Wherein the photosensitive resin composition comprises the structural unit (a3) in an amount of 20 to 50 mol% based on the total number of moles of the copolymer (A) structural units, the colored photosensitive resin composition.
상기 구성단위(a3)이 프로필(메트)아크릴레이트, 부틸(메트)아크릴레이트, 펜틸(메트)아크릴레이트, 헥실(메트)아크릴레이트, 헵틸(메트)아크릴레이트, 옥틸(메트)아크릴레이트, 노닐(메트)아크릴레이트, 데실(메트)아크릴레이트, 라우릴(메트)아크릴레이트 및 도데실(메트)아크릴레이트로 이루어진 군으로부터 선택되는 1종 이상의 화합물로부터 유도되는 것인, 착색 감광성 수지 조성물.According to claim 1,
The structural unit (a3) is propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (Meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate and dodecyl (meth) acrylate derived from at least one compound selected from the group consisting of, the colored photosensitive resin composition.
상기 공중합체(A)가 (a5) 에폭시기를 포함하는 에틸렌성 불포화 화합물을 포함하는 화합물로부터 유도되는 구성단위를 추가로 포함하는, 착색 감광성 수지 조성물. According to claim 1,
The said copolymer (A) further comprises the structural unit derived from the compound containing the ethylenically unsaturated compound containing the (a5) epoxy group, The colored photosensitive resin composition.
상기 광중합성 화합물(B)이 3관능 이상의 우레탄아크릴레이트계 화합물을 포함하는, 착색 감광성 수지 조성물.According to claim 1,
The colored photosensitive resin composition in which the said photopolymerizable compound (B) contains a trifunctional or more than trifunctional urethane acrylate type compound.
상기 착색제(D)가 흑색 착색제를 포함하고,
상기 흑색 착색제가 흑색 유기 착색제, 흑색 무기 착색제 또는 이들의 혼합인, 착색 감광성 수지 조성물.According to claim 1,
The colorant (D) includes a black colorant,
The colored photosensitive resin composition, wherein the black colorant is a black organic colorant, a black inorganic colorant, or a mixture thereof.
상기 착색제(D)가 흑색 이외의 착색제를 추가로 포함하고,
상기 흑색 이외의 착색제가, 청색 착색제 및 보라색 착색제로 이루어진 군으로부터 선택되는 1종 이상인, 착색 감광성 수지 조성물.According to claim 1,
The colorant (D) further comprises a colorant other than black,
The coloring photosensitive resin composition whose colorant other than the said black is 1 or more types chosen from the group which consists of a blue colorant and a purple colorant.
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