KR101030486B1 - Photoresist composition for column spacer - Google Patents
Photoresist composition for column spacer Download PDFInfo
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- KR101030486B1 KR101030486B1 KR1020040063044A KR20040063044A KR101030486B1 KR 101030486 B1 KR101030486 B1 KR 101030486B1 KR 1020040063044 A KR1020040063044 A KR 1020040063044A KR 20040063044 A KR20040063044 A KR 20040063044A KR 101030486 B1 KR101030486 B1 KR 101030486B1
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- South Korea
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- weight
- photocurable composition
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- 125000006850 spacer group Chemical group 0.000 title claims abstract description 36
- 239000000203 mixture Substances 0.000 title claims abstract description 30
- 229920002120 photoresistant polymer Polymers 0.000 title 1
- 239000004593 Epoxy Substances 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 125000005529 alkyleneoxy group Chemical group 0.000 claims abstract description 15
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 10
- -1 polytetramethylene Polymers 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 229920006324 polyoxymethylene Polymers 0.000 claims description 2
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 18
- 239000002904 solvent Substances 0.000 abstract description 10
- 239000003999 initiator Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000007261 regionalization Effects 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 19
- 239000004094 surface-active agent Substances 0.000 description 14
- 230000006835 compression Effects 0.000 description 13
- 238000007906 compression Methods 0.000 description 13
- 229920001577 copolymer Polymers 0.000 description 12
- 238000006073 displacement reaction Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- 229910052731 fluorine Inorganic materials 0.000 description 8
- 239000011737 fluorine Substances 0.000 description 8
- 230000001681 protective effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 5
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 4
- 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 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 238000000411 transmission spectrum Methods 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- FUWDFGKRNIDKAE-UHFFFAOYSA-N 1-butoxypropan-2-yl acetate Chemical compound CCCCOCC(C)OC(C)=O FUWDFGKRNIDKAE-UHFFFAOYSA-N 0.000 description 2
- JMIZWXDKTUGEES-UHFFFAOYSA-N 2,2-di(cyclopenten-1-yloxy)ethyl 2-methylprop-2-enoate Chemical compound C=1CCCC=1OC(COC(=O)C(=C)C)OC1=CCCC1 JMIZWXDKTUGEES-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000005907 alkyl ester group Chemical group 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
- 238000009835 boiling Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- AQNSVANSEBPSMK-UHFFFAOYSA-N dicyclopentenyl methacrylate Chemical compound C12CC=CC2C2CC(OC(=O)C(=C)C)C1C2.C12C=CCC2C2CC(OC(=O)C(=C)C)C1C2 AQNSVANSEBPSMK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N ethyl trimethyl methane Natural products CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 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 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- HUDYANRNMZDQGA-UHFFFAOYSA-N 1-[4-(dimethylamino)phenyl]ethanone Chemical compound CN(C)C1=CC=C(C(C)=O)C=C1 HUDYANRNMZDQGA-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 description 1
- DMFAHCVITRDZQB-UHFFFAOYSA-N 1-propoxypropan-2-yl acetate Chemical compound CCCOCC(C)OC(C)=O DMFAHCVITRDZQB-UHFFFAOYSA-N 0.000 description 1
- GDOBGDUGIFUCJV-UHFFFAOYSA-N 2,2-dimethylbutane;2-methylprop-2-enoic acid Chemical class CCC(C)(C)C.CC(=C)C(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O GDOBGDUGIFUCJV-UHFFFAOYSA-N 0.000 description 1
- DXUMYHZTYVPBEZ-UHFFFAOYSA-N 2,4,6-tris(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 DXUMYHZTYVPBEZ-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- JFWFAUHHNYTWOO-UHFFFAOYSA-N 2-[(2-ethenylphenyl)methoxymethyl]oxirane Chemical compound C=CC1=CC=CC=C1COCC1OC1 JFWFAUHHNYTWOO-UHFFFAOYSA-N 0.000 description 1
- OCKQMFDZQUFKRD-UHFFFAOYSA-N 2-[(3-ethenylphenyl)methoxymethyl]oxirane Chemical compound C=CC1=CC=CC(COCC2OC2)=C1 OCKQMFDZQUFKRD-UHFFFAOYSA-N 0.000 description 1
- ZADXFVHUPXKZBJ-UHFFFAOYSA-N 2-[(4-ethenylphenyl)methoxymethyl]oxirane Chemical compound C1=CC(C=C)=CC=C1COCC1OC1 ZADXFVHUPXKZBJ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- QKTWWGYCVXCKOJ-UHFFFAOYSA-N 2-methoxy-1-(2-methoxyphenyl)-2-phenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1OC QKTWWGYCVXCKOJ-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- NMUIIYJWWOPNIP-UHFFFAOYSA-N 2-pentan-3-ylidenebutanedioic acid Chemical compound CCC(CC)=C(C(O)=O)CC(O)=O NMUIIYJWWOPNIP-UHFFFAOYSA-N 0.000 description 1
- WYYQKWASBLTRIW-UHFFFAOYSA-N 2-trimethoxysilylbenzoic acid Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1C(O)=O WYYQKWASBLTRIW-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- VXVUDUCBEZFQGY-UHFFFAOYSA-N 4,4-dimethylpentanenitrile Chemical compound CC(C)(C)CCC#N VXVUDUCBEZFQGY-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- UNDXPKDBFOOQFC-UHFFFAOYSA-N 4-[2-nitro-4-(trifluoromethyl)phenyl]morpholine Chemical compound [O-][N+](=O)C1=CC(C(F)(F)F)=CC=C1N1CCOCC1 UNDXPKDBFOOQFC-UHFFFAOYSA-N 0.000 description 1
- KSXJRXNHRYSLLC-UHFFFAOYSA-N 9H-fluorene prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.C1=CC=C2CC3=CC=CC=C3C2=C1 KSXJRXNHRYSLLC-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 206010047571 Visual impairment Diseases 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
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Images
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
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- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
- G02F1/13394—Gaskets; Spacers; Sealing of cells spacers regularly patterned on the cell subtrate, e.g. walls, pillars
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- G—PHYSICS
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- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
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- Optics & Photonics (AREA)
- Liquid Crystal (AREA)
- Materials For Photolithography (AREA)
Abstract
본 발명은 액정표시소자의 컬럼 스페이서를 제조하는데 사용되는 광경화성 조성물에 관한 것이다.The present invention relates to a photocurable composition used to manufacture a column spacer of a liquid crystal display device.
본 발명의 광경화성 조성물은 [A]알칼리 가용성 수지, [B]에틸렌 불포화 결합을 갖는 중합성 화합물, [C] 하기 화학식1로 표시되는 알킬렌옥시기를 포함하는 에폭시올리고머, [D]광중합개시제를 함유하는 것을 특징으로 한다.The photocurable composition of the present invention comprises an [A] alkali-soluble resin, [B] a polymerizable compound having an ethylenically unsaturated bond, [C] an epoxy oligomer comprising an alkyleneoxy group represented by the following formula (1), and a [D] photopolymerization initiator. It is characterized by containing.
본 발명에 따른 광경화성 조성물은 내열성이 우수할 뿐만 아니라, 액정표시소자의 컬럼 스페이서 형성시 적절한 두께로 패턴 형성이 가능하고 회복률, 평탄성, 해상성, 내용제성 및 패턴모양이 양호하다.The photocurable composition according to the present invention is not only excellent in heat resistance, but also capable of pattern formation at an appropriate thickness when forming column spacers of liquid crystal display devices, and has good recovery rate, flatness, resolution, solvent resistance, and pattern shape.
<화학식 1> <Formula 1>
컬럼스페이서, 광경화성, 에폭시 결합Column spacers, photocurable, epoxy bonds
Description
도 1은 컬럼스페이서에 힘을 가할 때의 압축변위와 회복율을 보여주기 위한 도면이다.1 is a view for showing the compression displacement and recovery rate when applying a force to the column spacer.
도 2는 컬럼스페이서의 압축변위와 회복율 관계를 나타내는 그래프이다.
2 is a graph showing the relationship between the compression displacement and the recovery rate of the column spacer.
도면의 주요부분에 대한 부호의 설명Explanation of symbols for main parts of the drawings
A : 일정 힘을 가하기 전 패턴상태A: Pattern state before applying certain force
B : 일정 힘을 가했을 때의 패턴상태B: Pattern state when a certain force is applied
C : 누른 힘을 제거했을 때의 복원된 패턴상태C: Restored pattern state when the pressed force is removed
T : 패턴높이(막두께), 3(± 0.3)㎛T: pattern height (film thickness), 3 (± 0.3) ㎛
D1 : 일정 힘을 가했을 때 압축변위(㎛)D 1 : Compression displacement (μm) when a certain force is applied
D2 : 초기 막두께와 최종 복원된 상태와의 차이
D 2 : Difference between initial film thickness and final restored state
본 발명은 액정표시소자에 사용되는 컬럼 스페이서용 광경화성 조성물에 관한 것으로서, 보다 상세하게는 액정표시소자의 컬럼 스페이서 형성시 적절한 두께로 패턴형성이 가능하고 회복률, 평탄성, 해상성, 잔막률 및 패턴안정성이 우수한 광경화성 조성물에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable composition for column spacers used in liquid crystal display devices, and more particularly, to forming a pattern with an appropriate thickness when forming a column spacer of a liquid crystal display device, and having a recovery rate, flatness, resolution, residual film rate, and pattern. It relates to a photocurable composition having excellent stability.
액정표시소자는 일정한 간격을 가지는 상부 및 하부 패널과 상기 패널 사이에 주입되는 액정에 의해 구성된다. 상기 상, 하 패널의 간격을 셀갭이라고 하며 주입되는 액정의 두께에 의해 결정된다. 액정표시소자의 셀갭은 패널 전체에 걸쳐 서 일정하게 유지될 수 있어야 한다. 왜냐하면, 셀갭이 일정하게 유지되는지 여부 즉 셀갭의 균일성 여부는 액정의 고속 응답 특성, 콘트라스트 및 광시야 각도에 영향을 미치기 때문이다.The liquid crystal display device is constituted by upper and lower panels having a constant interval and liquid crystal injected between the panels. The gap between the upper and lower panels is called a cell gap and is determined by the thickness of the injected liquid crystal. The cell gap of the liquid crystal display device should be kept constant throughout the panel. This is because whether or not the cell gap is kept constant, that is, whether the cell gap is uniform, affects the high-speed response characteristics, contrast, and wide-field angle of the liquid crystal.
종래에는 2장의 기판의 중간에 유리비드, 플라스틱비드 등의 구형 스페이서 입자를 살포하고, 이들의 크기에 의해 액정층의 두께를 조절하는 방식이 사용되어 왔다.Conventionally, the method of spraying spherical spacer particles, such as glass beads and plastic beads, in the middle of two board | substrates, and adjusting the thickness of a liquid crystal layer by these sizes has been used.
그러나 이 방법은 1) 이들 스페이서 입자는 무작위로 살포되기 때문에 유효 픽셀내부에 상기의 스페이서가 비치거나, 입사광이 산란되어 액정패널의 콘트라스트 및 개구율을 저하하거나, 2) 또한 액정주입시 구형의 유리비드나 부분적으로 가교된 폴리메틸메타아크릴레이트 비드의 구형 스페이서는 외부의 충격에 의하여 위치가 변하게 되어 화상에 영향을 주기도 하며, 3) 스페이서 입자크기가 분포를 가 지므로 갭의 불균일을 야기하는 등의 문제점을 나타낸다. 특히 패널의 크기가 커지고 고해상도화됨에 따라 이러한 문제점은 극단적으로 보이게 된다.However, in this method, 1) these spacer particles are randomly sprayed, so that the spacers are reflected inside the effective pixels, or incident light is scattered to reduce the contrast and aperture ratio of the liquid crystal panel, or 2) spherical glass beads during liquid crystal injection. The spherical spacers of partially cross-linked polymethylmethacrylate beads may change position due to external impact, which may affect the image. 3) Since the particle size of the spacer has a distribution, it may cause unevenness of the gap. Indicates. In particular, as the panel becomes larger and higher in resolution, this problem becomes extreme.
이러한 문제점을 해결하기 위하여 스페이서를 포토리소그래피방법으로 형성시키는 방법이 제안되었다. 이 방법은 광경화성 조성물을 기판에 도포한 후 소정의 마스크를 통하여 자외선을 조사한 후, 현상하여 노광한 부분만 스페이서로 남게하는 방법이며 이러한 방법으로 컬럼 스페이서를 형성할 수 있다. 이 방법의 장점은 1) 유효 픽셀 이외의 부분에만 스페이스 형성이 가능하고 2) 도포되는 막의 두께를 조절함으로써 셉갭의 조절이 가능하다는 점이다.
In order to solve this problem, a method of forming a spacer by a photolithography method has been proposed. This method is a method of applying a photocurable composition to a substrate, irradiating ultraviolet rays through a predetermined mask, and then leaving only the exposed and exposed portions as spacers. In this way, column spacers can be formed. The advantage of this method is that 1) the space can be formed only on the portions other than the effective pixels, and 2) the sep gap can be controlled by adjusting the thickness of the film to be applied.
본 발명은 포토리소그래피 법으로 액정표시소자의 컬럼스페이서를 형성하는 경우에 있어서 패턴후 두께균일도가 있으며, 고감도이며, 잔상이 없는 현상성, 내용제성, 높은 회복률을 갖는 우수한 광경화성 조성물을 제공하는 것을 목적으로 한다.
The present invention provides an excellent photocurable composition having a uniform thickness after patterning, high sensitivity, and no developable afterimage, solvent resistance, and high recovery rate when forming a column spacer of a liquid crystal display by photolithography. The purpose.
상기 기술적 과제 및 목적은,The technical problem and object,
[A] 알칼리가용성수지[A] Alkali-soluble resin
[B] 에틸렌성 불포화 결합을 갖는 중합성 화합물[B] a polymerizable compound having an ethylenically unsaturated bond
[C] 알킬렌옥시기를 포함한 에폭시올리고머 [C] epoxy oligomers containing alkyleneoxy groups
[D] 광중합개시제[D] Photopolymerization Initiator
를 함유하는 것을 특징으로 하는 광경화성 수지 조성물에 의하여 달성된다.
It is achieved by the photocurable resin composition characterized by containing.
이하에서 본 발명의 광경화성 조성물의 각 성분에 대해 상술한다.Hereinafter, each component of the photocurable composition of this invention is explained in full detail.
[A] 알칼리가용성수지[A] Alkali-soluble resin
본 발명의 광경화성 조성물에 사용되는 [A]알카리가용성수지는[A] alkali-soluble resin used in the photocurable composition of the present invention
(a1) 불포화 카르복시산 및/또는 불포화 카르복시산 무수물,(a1) unsaturated carboxylic acids and / or unsaturated carboxylic anhydrides,
(a2) 에폭시기 함유 불포화 화합물,(a2) epoxy group-containing unsaturated compounds,
(a3) 상기 (a1) 및 (a2) 이외의 올레핀계 불포화 화합물(a3) Olefinic unsaturated compounds other than said (a1) and (a2)
을 라디칼 중합하여 얻어진다.Obtained by radical polymerization.
상기 화합물 (a1)불포화 카르복시산 및/또는 불포화 카르복시산 무수물로서는 아크릴산,크로톤산, 이타콘산, 말레산, 푸마르산, 시트라콘산, 메사콘산 및 이들 디카르복시산의 무수물을 들 수 있다. 이 중, 아크릴산, 메타크릴산, 무수 말레산 등이 공중합 반응성, 내열성 및 입수가 용이한 점에서 바람직하게 사용된다. 이러한 화합물 (a1)은 단독으로 또는 조합해서 사용된다.Examples of the compound (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride include acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid and anhydrides of these dicarboxylic acids. Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used in view of copolymerization reactivity, heat resistance and easy availability. These compounds (a1) are used individually or in combination.
상기 화합물 (a2)에폭시기 함유 불포화 화합물로는 아크릴산 글리시딜, 메타크릴산 글리시딜, α-에틸 아크릴산 글리시딜, α-n-프로필 아크릴산 글리시딜, α-n-부틸 아크릴산 글리시딜, 아크릴산-3,4-에폭시 부틸, 메타크릴산-3,4-에폭시 부틸, 아크릴산-6,7-에폭시 헵틸, 메타크릴산-6,7-에폭시 헵틸, α-에틸 아크릴산-6,7-에폭시 헵틸, o-비닐 벤질 글리시딜 에테르, m-비닐 벤질 글리시딜 에테르, p- 비닐 벤질 글리시딜 에테르 등이 공중합 반응성 및 얻어지는 보호막의 내열성, 경도를 높인다는 점에서 바람직하게 사용된다. 이러한 화합물 (a2)는 단독으로 또는 조합해서 사용된다.Epoxy group-containing unsaturated compounds of the compound (a2) include glycidyl acrylate, glycidyl methacrylate, α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl , Acrylic acid-3,4-epoxy butyl, methacrylic acid-3,4-epoxy butyl, acrylic acid-6,7-epoxy heptyl, methacrylic acid-6,7-epoxy heptyl, α-ethyl acrylic acid-6,7- Epoxy heptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and the like are preferably used in view of increasing copolymerization reactivity and heat resistance and hardness of the resulting protective film. These compounds (a2) are used individually or in combination.
화합물 (a3)으로서는 메틸 메타크릴레이트, 에틸 메타크릴레이트, n-부틸 메타크릴레이트, sec-부틸 메타크릴레이트, t-부틸 메타크릴레이트 등의 메타크릴산 알킬 에스테르 메틸 아크릴레이트, 이소프로필 아크릴레이트 등의 아크릴산 알킬 에스테르 시클로헥실 메타크릴레이트, 2-메틸 시클로헥실 메타크릴레이트, 디시클로펜테닐 메타크릴레이트, 디시클로펜테닐옥시에틸 메타크릴레이트, 이소보로닐 메타크릴레이트 등의 메타크릴산 시클로알킬 에스테르 시클로헥실 아크릴레이트, 2-메틸 시클로헥실 아크릴레이트, 디시클로펜테닐 아크릴레이트, 디시클로펜테닐옥시에틸 아크릴레이트, 이소보로닐 아크릴레이트 등의 아크릴산 시클로알킬 에스테르 페틸 메타크릴레이트, 벤질 메타크릴레이트 등의 메타크릴산 아릴 에스테르 페닐 아크릴레이트, 벤질 아크릴레이트 등의 아크릴산 아릴 에스테르 말레산 디에틸, 푸마르산 디에틸, 이타콘산 디에틸 등의 디카르복시산 디에스테르 2-히드록시 에틸 메타크릴레이트, 2-히드록시 프로필 메타크릴레이트 등의 히드록시알킬 에스테르 및 스티렌, o-메틸 스티렌, m-메틸 스티렌, p-메틸 스티렌, 비닐 톨루엔, p-메톡시 스티렌, 아크릴로니트릴, 메타크릴로니트릴, 염화 비닐, 염화 비닐리덴, 아크릴 아미드, 메타크릴 아미드, 초산 비닐, 1,3-부타디엔, 이소프렌, 2,3-디메틸-1,3-부타디엔 등을 들 수 있다. 이 중 스티렌, t-부틸 메타크릴레이트, 디시클로펜테닐 메타크릴레이트, p-메톡시 스티렌, 2-메틸 시클로헥실 아크릴레이트, 1,3-부타디엔 등이 공중합 반응성 및 내열성의 관점에서 바람직하다. 이러한 화합물 (a3)는 단독으로 또는 조합하여 사용된다.Examples of the compound (a3) include methacrylic acid alkyl ester methyl acrylate and isopropyl acrylate such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate and t-butyl methacrylate. Methacrylic acid, such as acrylic acid alkyl ester cyclohexyl methacrylate, 2-methyl cyclohexyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, isoboroyl methacrylate, etc. Cycloalkyl ester cyclohexyl acrylate, 2-methyl cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, isoboroyl acrylate, such as acrylic acid cycloalkyl ester petyl methacrylate, benzyl Methacrylic acid aryl ester phenyl acrylates such as methacrylate, Hydroxyalkyl esters such as dicarboxylic acid acrylate ester diethyl maleate, diethyl fumarate, diethyl itaconic acid, etc. And styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxy styrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, Vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like. Among them, styrene, t-butyl methacrylate, dicyclopentenyl methacrylate, p-methoxy styrene, 2-methyl cyclohexyl acrylate, 1,3-butadiene, and the like are preferred from the viewpoint of copolymerization reactivity and heat resistance. These compounds (a3) are used alone or in combination.
본 발명에서 사용된 공중합체 [A]는 화합물 (a3)으로부터 유도된 구성단위를 바람직한 것은 10~70%, 특히 바람직한 것은 20~50 %를 함유하고 있다. 이 구성단위가 10 % 미만인 경우는 공중합체 [A]의 보존안전성이 저하되는 경향이 있고, 70 %를 초과하는 경우에는 공중합체 [A]의 알칼리 가용성, 내열성, 표면경도가 저하되는 경향이 있다.The copolymer [A] used in the present invention preferably contains 10 to 70%, particularly preferably 20 to 50% of the structural unit derived from the compound (a3). When this structural unit is less than 10%, the storage stability of copolymer [A] tends to fall, and when it exceeds 70%, alkali solubility, heat resistance, and surface hardness of copolymer [A] will fall. .
본 발명에서 사용된 상기와 같은 [A]공중합체는 카르복실기 및/또는 카르복시산 무수물기 및 에폭시기를 갖고 있으며, 특별한 경화제를 병용하지 않더라도 가열에 의하여 용이하게 경화시키는 것이 가능하고, 알칼리 수용액에 가용성이다.The above-mentioned [A] copolymer used in the present invention has a carboxyl group and / or a carboxylic anhydride group and an epoxy group, and can be easily cured by heating without using a special curing agent and is soluble in an aqueous alkali solution.
상기의 공중합체 [A]의 분자량 및 그 분포는 본 발명의 조성물 용액을 균일하게 도포하는 일이 가능한 한 특정한 값으로 한정되는 것은 아니다.
The molecular weight of the copolymer [A] and its distribution are not limited to specific values as far as possible to apply the composition solution of the present invention uniformly.
공중합체 [A]의 합성에 사용된 용매로는 메탄올, 에탄올 등의 알코올류 테트라하이드로퓨란, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디에틸에테르 등의 에테르류 프로필렌 글리콜 메틸 에테르 아세테이트, 프로필렌 글리콜 에틸 에테르 아세테이트, 프로펠렌 글리콜 프로필 에테르 아세테이트, 프로필렌 글리콜 부틸 에테르 아세테이트 등의 프로필렌 글리콜 알킬 에테르 아세테이트류 등이 바람직하다.
As a solvent used for the synthesis of the copolymer [A], ethers such as alcohols such as methanol and ethanol, tetrahydrofuran, diethylene glycol dimethyl ether and diethylene glycol diethyl ether, propylene glycol methyl ether acetate, and propylene glycol ethyl ether Propylene glycol alkyl ether acetates such as acetate, propylene glycol propyl ether acetate and propylene glycol butyl ether acetate are preferred.
공중합체 [A]의 합성에 사용된 중합개시제로는, 일반적으로 래디칼 중합개시제로서 알려져 있는 것을 사용할 수 있다. 예를 들면 2,2'-아조비스 이소부티로니트릴, 2,2'-아조비스-(2,4-디메틸발레로니트릴), 2,2'-아조비스-(4-메톡시-2,4-디메틸발레로니트릴) 등의 아조 화합물 벤조일 퍼옥시드, t-부틸 퍼옥시 피바레이트, 1,1'-비스-(t-부틸 퍼옥시) 시클로 헥산 등의 유기 과산화물 및 과산화수소를 들 수 있다. 래디칼 중합 개시제로서 과산화물을 이용한 경우에는 과산화물을 환원제와 함께 이용하여 레독스 개시제로 사용해도 좋다.
As a polymerization initiator used for the synthesis | combination of copolymer [A], what is generally known as a radical polymerization initiator can be used. For example, 2,2'-azobis isobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2, Azo compounds, such as 4-dimethylvaleronitrile), organic peroxides, such as benzoyl peroxide, t-butyl peroxy pibarate, and 1,1'-bis- (t-butyl peroxy) cyclohexane, and hydrogen peroxide are mentioned. When a peroxide is used as a radical polymerization initiator, you may use as a redox initiator by using a peroxide together with a reducing agent.
[B] 에틸렌성 불포화 결합을 갖는 중합성 화합물[B] a polymerizable compound having an ethylenically unsaturated bond
본 발명에서 사용된 [B] 에틸렌성 불포화 결합을 갖는 중합성 화합물로는 단관능, 2관능, 또는 3관능 이상의 (메타)아크릴레이트가 중합성이 양호하고, 얻어지는 보호막의 내열성, 표면경도가 향상된다는 관점에서 바람직하다.As the polymerizable compound having an [B] ethylenically unsaturated bond used in the present invention, mono-, bi-, or tri- or higher (meth) acrylates have good polymerizability, and the heat resistance and surface hardness of the resulting protective film are improved. It is preferable from a viewpoint of being.
단관능 (메타)아크릴레이트로는, 예를 들면 2-히드록시 에틸 (메타)아크릴레이트, 카비톨 (메타)아크릴레이트, 이소보닐 (메타)아크릴레이트, 3-메톡시 부틸 (메타)아크릴레이트, 2-(메타)아크릴로일 옥시 에틸 2-히드록시 프로필 프탈레이트 등을 들 수 있다.As monofunctional (meth) acrylate, 2-hydroxy ethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxy butyl (meth) acrylate, for example , 2- (meth) acryloyl oxyethyl 2-hydroxy propyl phthalate, and the like.
2관능 (메타)아크릴레이트로는, 예를 들면 에텔렌글리콜 (메타)아크릴레이트, 1,6-헥산디올 (메타)아크릴레이트, 1,9-노난디올 (메타)아크릴레이트, 프로필렌글리콜 (메타)아크릴레이트, 테트라에틸렌글리콜 (메타)아크릴레이트, 비스페녹시 에틸알콜 플루오렌 디아크릴레이트 등을 들 수 있다. As a bifunctional (meth) acrylate, for example, ethylene glycol (meth) acrylate, 1,6-hexanediol (meth) acrylate, 1,9-nonanediol (meth) acrylate, propylene glycol (meth) ) Acrylate, tetraethylene glycol (meth) acrylate, bisphenoxy ethyl alcohol fluorene diacrylate, etc. are mentioned.
3관능 이상의 (메타)아크릴레이트로는, 예를 들면 트리스히드록시에틸이소시아뉴레이트 트리(메타)아크릴레이트, 트리메틸프로판 트리(메타)아크릴레이트, 펜타에리스리톨 트리(메타)아크릴레이트, 펜타에리스리톨 테트라(메타)아크릴레이트, 디펜타에리스리톨 헥사(메타)아크릴레이트 등을 들 수 있다.As (meth) acrylate more than trifunctional, for example, tris hydroxyethyl isocyanurate tri (meth) acrylate, trimethyl propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.
이러한 단관능, 2관능 또는 3관능 이상의 (메타)아크릴레이트는 단독으로 또는 조합하여 사용된다.
Such mono-, bi-, or tri- or more (meth) acrylates are used alone or in combination.
[C]알킬렌옥시기를 포함한 에폭시올리고머Epoxy oligomers containing [C] alkyleneoxy groups
본 발명에서 사용된 하기 화학식1로 표시된 구조식과 같은 [C]알킬렌옥시기를 포함한 에폭시올리고머는 경화성이 양호하고, 얻어지는 보호막의 내열성, 복원률을 향상시킨다는 관점에서 바람직하며, 이는 전체 광경화성 조성물 100중량% 중 0.1 내지 20 중량%를 포함하는 것이 더욱 바람직하다. 0.1 중량% 미만으로 포함 될 경우에는 복원률 향상의 효과가 나타나지 않으며, 20 중량% 초과로 포함 될 경우에는 복원률은 어느 정도 향상되나, 내열성 및 패턴 모양에 있어서 효과가 떨어지게 된다. Epoxy oligomers containing [C] alkyleneoxy groups such as the structural formulas represented by the following general formula (1) used in the present invention are preferable from the viewpoint of good curing property and improving heat resistance and recovery rate of the resulting protective film, which is 100 wt% of the total photocurable composition. More preferably from 0.1 to 20% by weight. When included in less than 0.1% by weight does not show the effect of improving the recovery rate, when included in more than 20% by weight is restored to some extent, but the effect on heat resistance and pattern shape is less.
<화학식 1> <Formula 1>
특히, 상기 본 발명에서는 알킬렌옥시기를 포함한 에폭시올리고머로서, In particular, in the present invention, as the epoxy oligomer containing an alkyleneoxy group,
알파,오메가-비스(3-글리시도시메칠)폴리테트라메칠렌글리콜, Alpha, omega-bis (3-glycidomethyl) polytetramethylene glycol,
알파,오메가-비스(3-글리시도시메칠)폴리프로필렌글리콜, Alpha, omega-bis (3-glycidomethyl) polypropylene glycol,
알파,오메가-비스(3-글리시도시메칠)폴리에칠렌글리콜, Alpha, omega-bis (3-glycidomethyl) polyethylene glycol,
알파,오메가-비스(3-글리시도시메칠)폴리메칠렌글리콜 중 어느 하나 이상을 포함하는 것이 더욱 바람직하다.
More preferably, at least one of alpha, omega-bis (3-glycidomethyl) polymethylene glycol is included.
[D] 광중합개시제[D] Photopolymerization Initiator
본 발명에서 사용된 [D]광중합개시제로는 벤질, 디아세틸 등의 α-디케톤류 벤조인 등의 아실로인류 벤조인 메틸 에테르, 벤조인 에틸 에테르, 벤조인 이소프로필 에테르 등의 아실로인 에테르류 티옥산톤, 2,4-디에틸 티옥산톤, 티옥산톤-4-술폰산, 벤조페논, 4,4'-비스(디메틸아미노)벤조페논, 4,4'-비스(디에틸아미노)벤조페논 등의 벤조페논류 아세토페논, p-디메틸아미노아세토페논, α,α'-디메톡시 아세톡시벤조페논, 2,2'-디메톡시-2-페닐아세토페논, p-메톡시아세토페논, 2-메틸[4-(메틸티오)페닐]-2-모르폴리노-1-프로파논, 2-벤질-2-디에틸아미노-1-(4-모르폴리노페닐)-부탄-1-온 등의 아세토페논류 안트라퀴논, 1,4-나프토퀴논 등의 퀴논류 페나실 클로라이드, 트리브로모메틸페닐술폰, 트리스(트리클로로메틸)-s-트리아진 등의 할로겐 화합물 디-t-부틸 퍼옥사이드 등의 과산화물 2,4,6-트리메틸 벤조일 디페닐 포스핀 옥사이드 등의 아실 포스핀 옥사이드류 등을 들 수 있다.
[D] photopolymerization initiators used in the present invention include acyloin ethers such as acyl benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, such as a-diketones benzoin such as benzyl and diacetyl. Ryu thioxanthone, 2,4-diethyl thioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) Benzophenones such as benzophenone, acetophenone, p-dimethylaminoacetophenone, α, α'-dimethoxy acetoxybenzophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-diethylamino-1- (4-morpholinophenyl) -butan-1-one Halogen compounds, such as acetophenones anthraquinone and 1, 4- naphthoquinone, quinone phenacyl chloride, tribromomethylphenyl sulfone, and tris (trichloromethyl) -s-triazine, etc. Oksa Acyl phosphine, such as peroxide, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, such as DE may be mentioned oxides such as pins.
[E] 용매[E] solvent
본 발명의 광경화성 수지 조성물은 통상 적당한 용매에 용해시켜 용액상태로 사용된다. 이 용매는 [A]공중합체 , [B]중합성 화합물 , [C]알킬렌옥시기를 포함한 에폭시올리고머, [D]열 래디칼 중합개시제의 각 성분을 균일하게 용해할 수 있으며, 어느 한 성분과도 반응하지 않는 것이 사용된다. 구체적으로 예를 들면, 메탄올, 에탄올 등의 알코올류 테트라하이드로퓨란, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디에틸에테르 등의 에테르류 프로필렌 글리콜 메틸 에테르 아세테이트, 프로필렌 글리콜 에틸 에테르 아세테이트, 프로펠렌 글리콜 프로필 에테르 아세테이트, 프로필렌 글리콜 부틸 에테르 아세테이트 등의 프로필렌 글리콜 알킬 에테르 아세테이트류 등을 들 수 있다. 이러한 용매 가운데에서 용해성, 각 성분과의 반응성 및 도막 형성의 편리성의 관점에서 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디에틸에테르, 프로펠렌 글리콜 메틸 에테르 아세테이트가 바람직하게 사용된다. The photocurable resin composition of this invention is normally melt | dissolved in a suitable solvent, and is used in a solution state. This solvent is capable of uniformly dissolving each component of the [A] copolymer, the [B] polymerizable compound, the epoxy oligomer containing the [C] alkyleneoxy group, and the [D] thermal radical polymerization initiator. What does not react is used. Specifically, for example, alcohols, such as methanol and ethanol, ethers, such as tetrahydrofuran, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether And propylene glycol alkyl ether acetates such as acetate and propylene glycol butyl ether acetate. Among these solvents, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate are preferably used in view of solubility, reactivity with each component, and convenience of coating film formation.
또한 상기 용매와 함께 고비등점 용매를 병용한 것도 가능하다. 병용할 수 있는 고비등점 용매로서는, 예를 들면 N-메틸 포름아미드, N,N-디메틸 포름아미드, N-메틸 아세트아미드, N,N-디메틸 아세트아미드, N-메틸 피롤리돈, 디메틸 설폭시드, 벤질 에틸 에테르 등을 들 수 있다.
Moreover, it is also possible to use a high boiling point solvent together with the said solvent. As a high boiling point solvent which can be used together, it is N-methyl formamide, N, N-dimethyl formamide, N-methyl acetamide, N, N-dimethyl acetamide, N-methyl pyrrolidone, dimethyl sulfoxide, for example. And benzyl ethyl ether.
[F] 기타 계면활성제 및 접착조제[F] Other surfactants and adhesive aids
본 발명의 광경화형 조성물은, 본 발명의 목적에 손상하지 않는 범위에서, 필요에 따라서 상기 성분 이외의 다른 성분을 함유하여도 좋다.The photocurable composition of this invention may contain other components other than the said component as needed in the range which does not impair the objective of this invention.
여기에서 다른 성분으로는 도포성을 향상하기 위한 계면활성제를 들 수 있다. 계면활성제로는 불소 및 실리콘계 계면활성제를 들 수 있는데, 예를 들면 3M사의 FC-129, FC-170C, FC-430, DIC사의 F-172, F-173, F-183, F-470, F-475, 신에츠실리콘사의 KP322, KP323, KP340, KP341 등을 들 수 있다. 이러한 계면활성제는 공중합체 [A] 100 중량부에 대하여 바람직한 것은 5 중량부 이하, 보다 바람직한 것은 2 중량부 이하의 양으로 사용된다. 계면활성제의 양이 5 중량부를 초과한 경우에는 도포시 거품이 발생하기 쉬워진다.
Here, as another component, surfactant for improving applicability | paintability is mentioned. Surfactants include fluorine and silicone-based surfactants, for example, 3M's FC-129, FC-170C, FC-430, DIC's F-172, F-173, F-183, F-470, F -KP322, KP323, KP340, KP341 by Shin-Etsu Silicone, etc. are mentioned. Such surfactant is used in an amount of preferably 5 parts by weight or less, more preferably 2 parts by weight or less, based on 100 parts by weight of the copolymer [A]. When the amount of the surfactant exceeds 5 parts by weight, bubbles are likely to occur during application.
또 기체와의 밀착성을 향상시키기 위해 접착 조제를 사용하는 것도 가능하다. 이와 같은 접착 조제로는 관능성 실란 커플링제가 바람직하게 사용되는데, 예를 들면 트리메톡시실릴 안식향산, γ-메타크릴록시프로필트리메톡시실란, 비닐트리아세톡시실란, 비닐트리메톡시실란, γ-이소시아네이트프로필트리에톡시실란, γ -글리시독시프로필트리메톡시실란 등을 들 수 있다. 이러한 접착 조제는 공중합체 [A] 100 중량부에 대하여 바람직한 것은 20 중량부 이하, 보다 바람직한 것은 10 중량부 이하의 양으로 사용된다. 접착 조제의 양이 20 중량부를 초과한 경우에는 내열성이 저하되기 쉽다.
Moreover, in order to improve adhesiveness with gas, it is also possible to use an adhesion | attachment adjuvant. As such an adhesion aid, a functional silane coupling agent is preferably used. For example, trimethoxysilyl benzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ -Isocyanate propyl triethoxysilane, (gamma)-glycidoxy propyl trimethoxysilane, etc. are mentioned. Such adhesion aid is used in an amount of preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the copolymer [A]. When the amount of the adhesion assistant exceeds 20 parts by weight, the heat resistance tends to be lowered.
조성물 용액에서의 농도는 특별히 제한하지 않는다. 고형분의 농도는 바람직하게는 10~60중량%. 보다 바람직하게는 15~40중량%이다. 상기와 같이 조제된 조성물 용액은 구멍지름 0.1~5 ㎛ 정도의 필터 등을 이용하여 여과한 후 사용된다.
The concentration in the composition solution is not particularly limited. The concentration of solids is preferably 10 to 60% by weight. More preferably, it is 15-40 weight%. The composition solution prepared as described above is used after filtration using a filter having a pore diameter of about 0.1 to 5 μm.
이하의 합성예, 실시예는 본 발명을 더욱 구체적으로 설명하지만, 본 발명은 이하의 실시예로 한정하는 것이 아니다.
The following synthesis examples and examples further illustrate the present invention, but the present invention is not limited to the following examples.
<합성예 1>Synthesis Example 1
냉각관과 교반기가 구비된 반응 용기에 2,2'-아조비스 이소부티로니트릴 5 중량부를 프로필렌글리콜메틸에테르아세테이트 200 중량부에 녹였다. 계속해서 스티렌 20 중량부, 메타크릴산 30 중량부, 메타크릴산 글리시딜 40 중량부 및 디시클로펜테닐옥시에틸 메타크릴레이트 10 중량부를 투입하고 질소 치환한 후 부드럽게 교반을 시작했다. 용액의 온도를 80℃로 상승시키고 이 온도를 4시간 동안 유지하여 공중합체를 포함한 중합체 용액을 얻었다. 얻어진 중합체 용액의 고형분 농도는 33 중량%이었다. 이 중합체를 [A-1]이라고 명명한다.
5 parts by weight of 2,2'-azobis isobutyronitrile was dissolved in 200 parts by weight of propylene glycol methyl ether acetate in a reaction vessel equipped with a cooling tube and a stirrer. Subsequently, 20 parts by weight of styrene, 30 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, and 10 parts by weight of dicyclopentenyloxyethyl methacrylate were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 80 ° C. and maintained at this temperature for 4 hours to obtain a polymer solution including a copolymer. Solid content concentration of the obtained polymer solution was 33 weight%. This polymer is named [A-1].
교반기가 있는 혼합조에 아래 기재된 조성 및 함량에 따라 알칼리가용성 수지[A], 중합성 화합물[B], 알킬렌옥시기를 포함한 에폭시올리고머[C], 광개시제, 실란커플링제와 열중합방지제, 계면활성제를 순차적으로 첨가하여 컬럼스페이서용 광경화성 조성물을 제조한 후 25℃에서 교반하였다.
In the mixing tank with agitator, alkali-soluble resin [A], polymerizable compound [B], epoxy oligomer including alkyleneoxy group [C], photoinitiator, silane coupling agent and thermal polymerization inhibitor, and surfactant Sequential addition was made to prepare a photocurable composition for a column spacer, followed by stirring at 25 ° C.
<실시예 1>≪ Example 1 >
얻어진 공중합체 [A-1] 60 중량부(고형분), 중합성 화합물 [B]로서 트리메틸프로판 트리메타아크릴레이트 30중량부, [C]로서 알파,오메가-비스(3-글리시도시메칠)폴리테트라메칠렌글리콜 (n=10) 5중량부(4.95 중량%), 광중합개시제 [D]로서 이가큐어 907 5 중량부 및 불소계계면활성제 1 중량부를 혼합하여 프로필렌글리콜메틸에테르아세테이트에 용해시킨 후 고형분농도가 30 중량%가 되도록 하였다. 그 후, 구멍지름 0.45㎛의 필터로 여과하여 광경화성 수지 조성물 용액 (S-1)을 조제했다.
60 weight part (solid content) of obtained copolymer [A-1], 30 weight part of trimethyl propane trimethacrylates as a polymeric compound [B], and alpha, omega-bis (3-glycido methyl) poly as [C] 5 parts by weight of tetramethylene glycol (n = 10) (4.95% by weight), 5 parts by weight of Igacure 907 and 1 part by weight of fluorine-based surfactant as a photopolymerization initiator [D] were dissolved in propylene glycol methyl ether acetate, and then the solid concentration Was 30% by weight. Then, it filtered by the filter of 0.45 micrometers of pore diameters, and prepared the photocurable resin composition solution (S-1).
<실시예 2~4><Examples 2-4>
상기 실시예1의 조성물 및 함량에서 하기 표 1과 같이, [C] 알킬렌옥시기 포함 에폭시 올리고머의 함량 및 종류를 달리하는 외에는 동일한 방법으로 칼럼 스페이서용 광경화성 조성물을 제조하였다.The photocurable composition for the column spacer was prepared in the same manner as in Table 1, except that the content and type of the [C] alkyleneoxy group-containing epoxy oligomer were changed.
[A]Alkali-soluble resin
[A]
Example 1
60중량부
[A-1]
60 parts by weight
30중량부
DPHA
30 parts by weight
5중량부 (4.95중량%)Alpha, Omega-Bis (3-Glycidomethyl) polytetramethylene glycol (n = 10)
5 parts by weight (4.95% by weight)
907 5
중량부
Igacure
907 5
Parts by weight
1 part by weight of fluorine-based surfactant
Example 2
60중량부
[A-1]
60 parts by weight
30중량부
DPHA
30 parts by weight
10중량부 (9.43중량%)Alpha, Omega-Bis (3-Glycidomethyl) polytetramethylene glycol (n = 10)
10 parts by weight (9.43% by weight)
907 5
중량부
Igacure
907 5
Parts by weight
1 part by weight of fluorine-based surfactant
Example 3
60중량부
[A-1]
60 parts by weight
30중량부
DPHA
30 parts by weight
20중량부 (17.2 중량%)Alpha, Omega-Bis (3-Glycidomethyl) polytetramethylene glycol (n = 10)
20 parts by weight (17.2% by weight)
907 5
중량부
Igacure
907 5
Parts by weight
1 part by weight of fluorine-based surfactant
Example 4
60중량부
[A-1]
60 parts by weight
30중량부
DPHA
30 parts by weight
10중량부 (9.43 중량%)Alpha, omega-bis (3-glycidomethyl) polypropylene glycol (n = 10)
10 parts by weight (9.43% by weight)
907 5
중량부
Igacure
907 5
Parts by weight
1 part by weight of fluorine-based surfactant
< 비교실시예 1~2><Comparative Examples 1 and 2>
하기 표 1과 같이, 비교실시예 1은 [C] 알킬렌옥시기 포함 에폭시 올리고머를 포함하지 않았으며, 비교예실시예 2는 [C] 알킬렌옥시기 포함 에폭시 올리고머 함량을 20중량% 초과하는 23.8중량%를 포함하는 외에는 상기 실시예1의 조성물 및 함량과 동일한 방법으로 칼럼 스페이서용 광경화성 조성물을 제조하였다.As shown in Table 1 below, Comparative Example 1 did not include the [C] alkyleneoxy group-containing epoxy oligomer, Comparative Example Example 2 [C] alkyleneoxy group-containing epoxy oligomer content more than 20% by weight 23.8 weight A photocurable composition for a column spacer was prepared in the same manner as the composition and content of Example 1, except for including%.
[A]Alkali-soluble resin
[A]
실시예
1compare
Example
One
60중량부[A-1]
60 parts by weight
30중량부DPHA
30 parts by weight
907 5
중량부Igacure
907 5
Parts by weight
실시예
2compare
Example
2
60중량부[A-1]
60 parts by weight
30중량부DPHA
30 parts by weight
폴리테트라메칠렌글리콜(n=10)
30 중량부 (23.8중량%)Alpha, Omega-Bis (3-Glycidomethyl)
Polytetramethylene glycol (n = 10)
30 parts by weight (23.8% by weight)
907 5
중량부Igacure
907 5
Parts by weight
<컬럼스페이서의 형성><Formation of column spacer>
스핀코터를 이용하여 유리기판 위에 상기의 감광성 수지 조성물의 최종 막두께가 3㎛로 되도록 도포하였다. 80℃에서 2분간 건조시킨 후, 소정 형태의 마스크를 얻어진 도막 위에 놓은 상태에서 365nm의 자외선을 150 mJ/cm2 조사하였다. 알칼리 수용액을 현상액으로 이용하여 불필요한 부분을 용해, 제거하여 노광된 부위만을 잔존시켜 패턴을 형성시킨 후, 이를 클린 오븐에서 220℃로 30분 동안 소성하여 유리기판 위에 보호막을 형성하였다.
Using a spin coater, the glass film was coated on the glass substrate such that the final film thickness of the photosensitive resin composition was 3 μm. After drying at 80 ° C. for 2 minutes, ultraviolet rays of 365 nm were irradiated with 150 mJ / cm 2 in a state where a mask of a predetermined form was placed on the obtained coating film. The aqueous solution was used as a developer to dissolve and remove unnecessary portions, leaving only the exposed portions to form a pattern, which was then baked at 220 ° C. for 30 minutes in a clean oven to form a protective film on the glass substrate.
<평가방법><Evaluation Method>
앞에서 언급한 실시예 및 비교실시예에 대한 평가 방법은 하기와 같다.
Evaluation methods for the aforementioned examples and comparative examples are as follows.
(1) 밀착성(1) adhesion
바둑판 무늬 테이프 법에 따라 보호막에 100개의 바둑판 무늬를 커터 나이프로 형성하고 밀착성 시험을 행하여, 박리된 바둑판 무늬의 수를 측정하고 다음 기준에 의하여 보호막의 밀착성을 평가하였다.According to the checkered tape method, 100 checkers were formed on the protective film with a cutter knife, and the adhesion test was carried out to measure the number of peeled checkered patterns and to evaluate the adhesion of the protective film according to the following criteria.
양호 : 박리된 바둑판 무늬의 수 5개 이하Good: No more than 5 peeled checkerboard patterns
부족 : 박리된 바둑판 무늬의 수 6~49개Shortage: 6 ~ 49 number of checkerboard
불량 : 박리된 바둑판 무늬의 수 50개 이상
Poor: More than 50 peeled checkerboard
(2) 패턴 모양(2) pattern shape
ITO가 스파트된 유리기판에 상기의 조성물을 패턴을 형성 후 라이패턴의 수직방향으로 절단하고, 패턴의 단면방향을 전자현미경으로 관찰하여 바닥과 탑의 길이비가 85%이상이면 양호 85%이하이면 불량으로 표시
After forming the pattern on the glass substrate on which ITO was spattered, cut it in the vertical direction of the lie pattern, and observe the cross-sectional direction of the pattern with an electron microscope. Mark as
(3) 평탄도(3) flatness
ITO가 스파트된 유리기판에 상기의 조성물을 패턴을 형성 후 각각 다른 25곳의 코팅막의 표면 요철을 α스텝을 이용하여 최대 두께와 최소두께의 차를 구하였다.After the pattern of the composition was formed on the glass substrate on which the ITO was spattered, the difference between the maximum thickness and the minimum thickness was determined by using α step for the surface irregularities of the 25 coating layers, respectively.
양호 : 400Å이하Good: Below 400Å
부족 : 1000Å이하Shortage: less than 1000Å
불량 : 1000Å이상
Poor: More than 1000Å
(4) 내열성(4) heat resistance
보호막을 클린 오븐 240℃, 60분 동안 가열하고, 가열 전후에 투과 스펙트럼을 측정하고 다음 기준에 의하여 보호막의 내열성을 평가하였다.The protective film was heated in a clean oven at 240 ° C. for 60 minutes, and the transmission spectrum was measured before and after heating, and the heat resistance of the protective film was evaluated according to the following criteria.
양호 : 투과 스펙트럼의 변화가 1% 이내Good: Change in transmission spectrum is within 1%
불량 : 투과 스펙트럼의 변화가 1% 이상
Poor: Change of transmission spectrum is over 1%
(5)압축변위 및 회복율 측정방법 (5) Compression displacement and recovery rate
본 발명에서는 광경화성 조성물로부터 형성된 두께(T)가 3㎛이고 패턴의 폭(W)이 20(±2)㎛의 도트패턴을 패턴의 기계적 물성 즉, 압축변위와 탄성회복율을 측정하기 위한 기본조건의 모양으로 정하였다. 압축변위 및 탄성회복율의 측정기기는 SHIMADZU사 초미소압축경도계(모델명:DUH-W201S)를 사용하였으며 측정조건은 다음과 같다. 패턴을 누르는 압자로는 직경 50㎛ 평면압자를 사용하였으며 측정원리는 하중부가-제거(Load-unload) 방법으로 진행하였고 시험 하중부여 기준치는 5gf/㎠ 이고 부하속도는 0.45 gf/sec, 보전시간(holding time)은 2초로 일정하게 진행하였다.In the present invention, a dot pattern having a thickness (T) of 3 μm and a width (W) of 20 (± 2) μm formed from a photocurable composition is a basic condition for measuring mechanical properties of the pattern, that is, compression displacement and elastic recovery rate. It was set as the shape of. SHIMADZU's ultra-compact hardness tester (model name: DHU-W201S) was used for measuring the compression displacement and elastic recovery rate. A flat indenter with a diameter of 50㎛ was used as the indenter for pressing the pattern. The measurement principle was carried out by a load-unload method. The test loading standard was 5gf / ㎠, the load speed was 0.45 gf / sec, and the maintenance time ( holding time) was constant at 2 seconds.
이하, 도 1을 참조하여 본 발명의 감광성 수지로 형성되는 칼럼스페이서의 압축변위와 회복률을 설명하기로 한다.Hereinafter, the compression displacement and the recovery rate of the column spacer formed of the photosensitive resin of the present invention will be described with reference to FIG. 1.
패턴 공정에 의해 형성된 스페이서(20)는 일정한 두께(T)를 가지고 있다(상태 S0). 도 2에는 하나의 스페이서(20)만을 도시하고 있지만, 기판 상에 형성되는 각 스페이서(20)의 두께(T)는 일정한 범위의 편차를 가지고 있다.The
상기 스페이서에 예컨대 어레이 기판과 같은 다른 기판을 합착하면, 상기 스페이서의 두께는 압착에 의하여 감소한다(상태 S1). 이때 압축변위는 도1에 나타낸 그림에서와 같이 일정 힘을 주었을 때 패턴이 들어간 길이(D1)을 의미한다. 또한, 상기 압착력(F)를 제거하면, 상기 스페이서의 두께는 복원력에 의해 증가한다(상태 S2). 이 때 스페이서의 두께와 압착하지 않은 스페이서의 최초 두께와의 차이는 D2로 표시되어 있다. When another substrate, such as an array substrate, is bonded to the spacer, the thickness of the spacer is reduced by pressing (state S 1 ). At this time, the compression displacement refers to the length (D 1 ) in which the pattern enters when a given force is applied as shown in FIG. In addition, when the pressing force F is removed, the thickness of the spacer is increased by the restoring force (state S 2 ). At this time, the difference between the thickness of the spacer and the initial thickness of the non-compressed spacer is indicated by D 2 .
회복율은 두가지의 개념으로 나타낼 수 있다.Recovery rates can be expressed in two ways.
첫째는 도 1에 나타난 바와 같이 일정 힘을 주었을 때 들어간 길이(D1)에 대해 회복된 거리(D1-D2)의 비율을 의미(회복율A)한다.First, as shown in FIG. 1, the ratio of the recovered distance (D 1 -D 2 ) to the length (D 1 ) entered when given a constant force (recovery rate A).
둘째는 원래의 패턴의 높이(T)에 대해 최종 변형후의 패턴높이(T-D2)의 비율을 의미(회복율B)할 수 있다.Second, the ratio of the pattern height (T-D2) after the final deformation to the height (T) of the original pattern can mean (recovery rate B).
이를 정리하면 다음과 같다.This is summarized as follows.
압축변위 = D1(㎛)
Compression displacement = D 1 (㎛)
회복율 Recovery rate
본 발명의 실시예에서는 상기 회복율 A로서 비교 평가한다. In the Example of this invention, it evaluates comparatively as said recovery rate A.
상기 실시예 및 비교실시예의 평가 물성은 다음 표 3과 같다.Evaluation properties of the Examples and Comparative Examples are shown in Table 3 below.
(D1)(㎛)Compression displacement
(D 1 ) (㎛)
(㎛)D 2
(Μm)
상기 결과에서 알 수 있듯이, 본 발명의 컬럼스페이서용 광경화성 조성물은 종래의 레지스트 조성물과 비교하여 압축변위, 밀착력, 내열성, 평탄도,패턴모양이 우수함을 알 수 있다. 본 발명에서의 감광성 조성물은 두께에 대한 균일성 물성 확보 즉 압축변위의 증대 및 회복율이 개선됨에 따라 패턴의 과다 침식을 방지할 수 있으며 압축에 의한 두께를 용이하게 조절할 수 있는 장점이 있음을 알 수 있다.
As can be seen from the above results, it can be seen that the photocurable composition for a column spacer of the present invention is superior in compression displacement, adhesion, heat resistance, flatness, and pattern shape as compared with the conventional resist composition. It can be seen that the photosensitive composition of the present invention can prevent excessive erosion of the pattern as it secures uniform physical properties to the thickness, that is, increases the compression displacement and improves the recovery rate, and can easily control the thickness by compression. have.
Claims (4)
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0619134A (en) * | 1992-06-30 | 1994-01-28 | Tamura Kaken Kk | Photosensitive resin composition |
JPH10186657A (en) | 1996-12-27 | 1998-07-14 | Hitachi Chem Co Ltd | Photosensitive resin composition and photosensitive element using same |
JP2002099081A (en) | 2000-09-21 | 2002-04-05 | Tamura Kaken Co Ltd | Photosensitive resin composition and printed-wiring board |
JP2003107703A (en) | 2001-09-19 | 2003-04-09 | Qimei Industry Co Ltd | Photosensitive resin composition for spacer of liquid crystal display |
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2004
- 2004-08-11 KR KR1020040063044A patent/KR101030486B1/en not_active IP Right Cessation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0619134A (en) * | 1992-06-30 | 1994-01-28 | Tamura Kaken Kk | Photosensitive resin composition |
JPH10186657A (en) | 1996-12-27 | 1998-07-14 | Hitachi Chem Co Ltd | Photosensitive resin composition and photosensitive element using same |
JP2002099081A (en) | 2000-09-21 | 2002-04-05 | Tamura Kaken Co Ltd | Photosensitive resin composition and printed-wiring board |
JP2003107703A (en) | 2001-09-19 | 2003-04-09 | Qimei Industry Co Ltd | Photosensitive resin composition for spacer of liquid crystal display |
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