KR102615683B1 - Photosensitive resin composition and photo-cured pattern formed from the same - Google Patents
Photosensitive resin composition and photo-cured pattern formed from the same Download PDFInfo
- Publication number
- KR102615683B1 KR102615683B1 KR1020160152509A KR20160152509A KR102615683B1 KR 102615683 B1 KR102615683 B1 KR 102615683B1 KR 1020160152509 A KR1020160152509 A KR 1020160152509A KR 20160152509 A KR20160152509 A KR 20160152509A KR 102615683 B1 KR102615683 B1 KR 102615683B1
- Authority
- KR
- South Korea
- Prior art keywords
- photosensitive resin
- pattern
- resin composition
- photopolymerization initiator
- group
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 64
- 150000001875 compounds Chemical class 0.000 claims abstract description 60
- 239000003999 initiator Substances 0.000 claims abstract description 47
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 14
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 125000006850 spacer group Chemical group 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 238000000016 photochemical curing Methods 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 229920002120 photoresistant polymer Polymers 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 11
- 239000000758 substrate Substances 0.000 abstract description 11
- 230000035945 sensitivity Effects 0.000 abstract description 7
- 238000013035 low temperature curing Methods 0.000 abstract description 6
- 230000009257 reactivity Effects 0.000 abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 47
- -1 benzyldimethyl ketal Chemical compound 0.000 description 21
- 230000008569 process Effects 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- 239000000178 monomer Substances 0.000 description 13
- 238000011161 development Methods 0.000 description 10
- 230000018109 developmental process Effects 0.000 description 10
- 150000003254 radicals Chemical class 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 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 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000002843 carboxylic acid group Chemical group 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- FGRBYDKOBBBPOI-UHFFFAOYSA-N 10,10-dioxo-2-[4-(N-phenylanilino)phenyl]thioxanthen-9-one Chemical compound O=C1c2ccccc2S(=O)(=O)c2ccc(cc12)-c1ccc(cc1)N(c1ccccc1)c1ccccc1 FGRBYDKOBBBPOI-UHFFFAOYSA-N 0.000 description 2
- YTZSKPAYFHSKOL-UHFFFAOYSA-N 2-(2,3-dichlorophenyl)-2-[2-(2,3-dichlorophenyl)-4,5-diphenylimidazol-2-yl]-4,5-diphenylimidazole Chemical compound ClC1=CC=CC(C2(N=C(C(=N2)C=2C=CC=CC=2)C=2C=CC=CC=2)C2(N=C(C(=N2)C=2C=CC=CC=2)C=2C=CC=CC=2)C=2C(=C(Cl)C=CC=2)Cl)=C1Cl YTZSKPAYFHSKOL-UHFFFAOYSA-N 0.000 description 2
- GBOJZXLCJZDBKO-UHFFFAOYSA-N 2-(2-chlorophenyl)-2-[2-(2-chlorophenyl)-4,5-diphenylimidazol-2-yl]-4,5-diphenylimidazole Chemical compound ClC1=CC=CC=C1C1(C2(N=C(C(=N2)C=2C=CC=CC=2)C=2C=CC=CC=2)C=2C(=CC=CC=2)Cl)N=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=N1 GBOJZXLCJZDBKO-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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 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
- 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
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 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
- 238000002360 preparation method Methods 0.000 description 2
- 230000007261 regionalization Effects 0.000 description 2
- 125000006413 ring segment Chemical group 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
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 1
- QYGBYAQGBVHMDD-XQRVVYSFSA-N (z)-2-cyano-3-thiophen-2-ylprop-2-enoic acid Chemical compound OC(=O)C(\C#N)=C/C1=CC=CS1 QYGBYAQGBVHMDD-XQRVVYSFSA-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
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 1
- RKYJPYDJNQXILT-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxycarbonyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OCCOC(=O)C=C RKYJPYDJNQXILT-UHFFFAOYSA-N 0.000 description 1
- IEQWWMKDFZUMMU-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethyl)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)CCOC(=O)C=C IEQWWMKDFZUMMU-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
- AAMTXHVZOHPPQR-UHFFFAOYSA-N 2-(hydroxymethyl)prop-2-enoic acid Chemical compound OCC(=C)C(O)=O AAMTXHVZOHPPQR-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- 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
- XYXBMCIMPXOBLB-UHFFFAOYSA-N 3,4,5-tris(dimethylamino)-2-methylphenol Chemical compound CN(C)C1=CC(O)=C(C)C(N(C)C)=C1N(C)C XYXBMCIMPXOBLB-UHFFFAOYSA-N 0.000 description 1
- SKKHNUKNMQLBTJ-UHFFFAOYSA-N 3-bicyclo[2.2.1]heptanyl 2-methylprop-2-enoate Chemical compound C1CC2C(OC(=O)C(=C)C)CC1C2 SKKHNUKNMQLBTJ-UHFFFAOYSA-N 0.000 description 1
- JSGVZVOGOQILFM-UHFFFAOYSA-N 3-methoxy-1-butanol Chemical compound COC(C)CCO JSGVZVOGOQILFM-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- YHFGMFYKZBWPRW-UHFFFAOYSA-N 3-methylpentane-1,1-diol Chemical compound CCC(C)CC(O)O YHFGMFYKZBWPRW-UHFFFAOYSA-N 0.000 description 1
- HQHKCNMTLZRXIP-UHFFFAOYSA-N 4-[2-(2-methylprop-2-enoyloxy)ethoxycarbonyl]benzoic acid Chemical compound CC(=C)C(=O)OCCOC(=O)C1=CC=C(C(O)=O)C=C1 HQHKCNMTLZRXIP-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- IPTNXMGXEGQYSY-UHFFFAOYSA-N acetic acid;1-methoxybutan-1-ol Chemical compound CC(O)=O.CCCC(O)OC IPTNXMGXEGQYSY-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001334 alicyclic compounds Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- XTKDAFGWCDAMPY-UHFFFAOYSA-N azaperone Chemical compound C1=CC(F)=CC=C1C(=O)CCCN1CCN(C=2N=CC=CC=2)CC1 XTKDAFGWCDAMPY-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- HECGKCOICWUUJU-UHFFFAOYSA-N bis(diphenylphosphanylmethyl)-phenylphosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CP(C=1C=CC=CC=1)CP(C=1C=CC=CC=1)C1=CC=CC=C1 HECGKCOICWUUJU-UHFFFAOYSA-N 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000001162 cycloheptenyl group Chemical group C1(=CCCCCC1)* 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- KRZHXVYHGXXTOS-UHFFFAOYSA-N cyclohexen-1-yl prop-2-enoate Chemical compound C=CC(=O)OC1=CCCCC1 KRZHXVYHGXXTOS-UHFFFAOYSA-N 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000522 cyclooctenyl group Chemical group C1(=CCCCCCC1)* 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 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 description 1
- 239000003599 detergent Substances 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229940042596 viscoat Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
- G03F7/2012—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image using liquid photohardening compositions, e.g. for the production of reliefs such as flexographic plates or stamps
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Materials For Photolithography (AREA)
Abstract
본 발명의 실시예들은 감광성 수지 조성물에 관한 것으로, 보다 상세하게는 알칼리 가용성 수지; 중합성 화합물; 광중합 개시제; 및 용제를 포함하고, 상기 광중합 개시제는 특정 구조의 화합물을 포함하여, 저온 경화에서 우수한 반응성을 나타내고, 그로부터 제조된 패턴은 뛰어난 내화학성, 내열성 등 높은 내구성을 가지고, 우수한 기판 밀착력 및 잔막률을 가지면서도 감도가 뛰어난 감광성 수지 조성물에 관한 것이다.Embodiments of the present invention relate to photosensitive resin compositions, and more specifically, to alkali-soluble resins; polymerizable compounds; photopolymerization initiator; and a solvent, wherein the photopolymerization initiator includes a compound of a specific structure and exhibits excellent reactivity at low temperature curing, and the pattern prepared therefrom has high durability such as excellent chemical resistance and heat resistance, and has excellent substrate adhesion and residual film rate. It relates to a photosensitive resin composition that has excellent sensitivity while still being sensitive.
Description
본 발명은 감광성 수지 조성물 및 이로부터 형성된 광경화 패턴에 관한 것이다. 보다 상세하게는, 광중합 개시제를 포함하는 감광성 수지 조성물 및 이로부터 형성된 광경화 패턴에 관한 것이다.The present invention relates to a photosensitive resin composition and a photocurable pattern formed therefrom. More specifically, it relates to a photosensitive resin composition containing a photopolymerization initiator and a photocurable pattern formed therefrom.
디스플레이 분야에 있어서, 감광성 수지 조성물은 포토레지스트, 절연막, 보호막, 블랙 매트릭스, 컬럼 스페이서 등의 다양한 광경화 패턴을 형성하기 위해 사용된다. 구체적으로, 감광성 수지 조성물을 포토리소그래피 공정에 의해 선택적으로 노광 및 현상하여 원하는 광경화 패턴을 형성하는데, 이 과정에서 공정상의 수율을 향상시키고, 적용 대상의 물성을 향상시키기 위해, 고감도를 가지는 감광성 수지 조성물이 요구되고 있다.In the display field, photosensitive resin compositions are used to form various photocurable patterns such as photoresist, insulating film, protective film, black matrix, and column spacer. Specifically, the photosensitive resin composition is selectively exposed and developed through a photolithography process to form a desired photocuring pattern. In this process, in order to improve the yield of the process and improve the physical properties of the application target, a photosensitive resin with high sensitivity is used. A composition is needed.
감광성 수지 조성물의 패턴 형성은 포토리소그래피, 즉 광반응에 의해 일어나는 고분자의 극성변화 및 가교반응에 의한다. 특히, 노광 후 알칼리 수용액 등의 용매에 대한 용해성의 변화 특성을 이용한다. The pattern formation of the photosensitive resin composition is photolithography, that is, the polarity change and crosslinking reaction of the polymer that occurs through photoreaction. In particular, the change in solubility in solvents such as alkaline aqueous solutions after exposure is utilized.
감광성 수지 조성물에 의한 패턴 형성은 감광된 부분의 현상에 대한 용해도에 따라 포지티브형과 네가티브형으로 분류된다. 포지티브형 포토레지스트는 노광된 부분이 현상액에 의해 용해되며, 네가티브형 포토레지스트는 노광된 부분이 현상액에 녹지 않고 노광되지 아니한 부분이 용해되어 패턴이 형성되는 방식이고, 포지티브형과 네가티브형은 사용되는 바인더 수지, 가교제 등이 서로 상이하다. Pattern formation using photosensitive resin compositions is classified into positive and negative types depending on the solubility of the photosensitive portion to the phenomenon. In the case of positive type photoresist, the exposed part is dissolved by the developer, and in the case of negative type photoresist, the exposed part is not dissolved in the developer, but the unexposed part is dissolved to form a pattern. The positive and negative types are used. The binder resin, crosslinking agent, etc. are different.
감광성 수지 조성물에 의해 형성된 도막 또는 패턴은 기재와의 밀착성이 양호하지 않으면, 예를 들면 감광성 수지 조성물을 도포하여 형성된 레지스트 막을 패턴 노광하여 현상할 때, 형성된 레지스트 패턴의 붕괴나 박리가 일어날 수 있고, 에칭 시에도 패턴 붕괴나 박리 등의 문제가 발생하여 양산 프로세스에서의 제품 수율이 저하된다. 또한, 상기 감광성 수지 조성물이 적용되는 디스플레이 장치가 소형화됨에 따라 미세 선폭의 광경화 패턴을 형성하기 위해 노광 공정의 해상도 향상이 요구되고 있다.If the coating film or pattern formed by the photosensitive resin composition does not have good adhesion to the substrate, for example, when the resist film formed by applying the photosensitive resin composition is pattern exposed and developed, the formed resist pattern may collapse or peel off, Problems such as pattern collapse or peeling also occur during etching, which reduces product yield in the mass production process. In addition, as display devices to which the photosensitive resin composition is applied are miniaturized, there is a need to improve the resolution of the exposure process in order to form a photocuring pattern with a fine line width.
예를 들면, 한국등록특허 제10-1302508호는 사이클로헥세닐 아크릴레이트계 단량체를 사용하여 중합된 공중합체를 포함하는 네가티브 감광성 수지 조성물을 개시하고 있다.For example, Korean Patent No. 10-1302508 discloses a negative photosensitive resin composition containing a copolymer polymerized using a cyclohexenyl acrylate monomer.
본 발명의 일 과제는 우수한 기판 밀착력 및 잔막률을 가지면서도 고감도의 광경화 패턴 구현이 가능한 감광성 수지 조성물을 제공하는 것이다.One object of the present invention is to provide a photosensitive resin composition capable of implementing a highly sensitive photocuring pattern while having excellent substrate adhesion and residual film rate.
또한, 본 발명의 일 과제는 상기 감광성 수지 조성물로 제조된 광경화 패턴 및 상기 광경화 패턴을 포함하는 화상표시장치를 제공하는 것이다.Additionally, an object of the present invention is to provide a photocurable pattern made of the photosensitive resin composition and an image display device including the photocurable pattern.
1. 알칼리 가용성 수지; 중합성 화합물; 광중합 개시제; 및 용제를 포함하고, 상기 광중합 개시제는 하기 화학식 1로 표시되는 화합물을 포함하는 감광성 수지 조성물:1. Alkali soluble resin; polymerizable compounds; photopolymerization initiator; and a solvent, wherein the photopolymerization initiator is a photosensitive resin composition comprising a compound represented by the following formula (1):
[화학식 1][Formula 1]
(화학식 1 중, A는 니트로기 또는 시아노기이고, R1 또는 R2는 각각 독립적으로 탄소수 1 내지 20의 알킬기이고, R3은 탄소수 1 내지 20의 알킬기, 탄소수 6 내지 20 아릴기 또는 탄소수 3 내지 20의 사이클로알킬기, R4는 오쏘, 메타 또는 파라에 위치하는 하기 화학식 2로 표시되는 치환기임)(In Formula 1, A is a nitro group or a cyano group, R 1 or R 2 is each independently an alkyl group having 1 to 20 carbon atoms, and R 3 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl group having 3 carbon atoms. to 20 cycloalkyl groups, R 4 is a substituent represented by the following formula 2 located at ortho, meta or para)
[화학식 2][Formula 2]
(화학식 2 중, *는 결합부이며, R5, R6 또는 R7는 각각 독립적으로 탄소수 1 내지 3의 알킬기임).(In Formula 2, * is a bonding portion, and R 5 , R 6 or R 7 are each independently an alkyl group having 1 to 3 carbon atoms).
2. 위 1에 있어서, 상기 광중합 개시제는 아세토페논계 화합물 및 비이미다졸계 화합물로 이루어진 군에서 선택된 적어도 하나를 더 포함하는 감광성 수지 조성물.2. The photosensitive resin composition of 1 above, wherein the photopolymerization initiator further includes at least one selected from the group consisting of acetophenone-based compounds and biimidazole-based compounds.
3. 위 2에 있어서, 상기 광중합 개시제는 상기 아세토페논계 화합물 및 비이미다졸계 화합물을 1:9 내지 9:1의 몰비로 포함하는 감광성 수지 조성물.3. The photosensitive resin composition of 2 above, wherein the photopolymerization initiator includes the acetophenone-based compound and the biimidazole-based compound at a molar ratio of 1:9 to 9:1.
4. 위 1에 있어서, 상기 광중합 개시제는 상기 화학식 1로 표시되는 화합물을 상기 광중합 개시제 100중량부에 대하여 20 내지 90중량부로 포함하는 감광성 수지 조성물.4. The photosensitive resin composition of 1 above, wherein the photopolymerization initiator includes a compound represented by Formula 1 in an amount of 20 to 90 parts by weight based on 100 parts by weight of the photopolymerization initiator.
5. 위 1에 있어서, 상기 광중합 개시제는 상기 감광성 수지 조성물 고형분 100중량부에 대하여 0.1 내지 10중량부로 포함되는 감광성 수지 조성물.5. The photosensitive resin composition of 1 above, wherein the photopolymerization initiator is included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of solid content of the photosensitive resin composition.
6. 위 1 내지 5 중 어느 하나의 감광성 수지 조성물로 제조된 광경화 패턴.6. A photocurable pattern made from the photosensitive resin composition of any one of 1 to 5 above.
7. 위 6에 있어서, 상기 광경화 패턴은 어레이 평탄화막 패턴, 보호막 패턴, 절연막 패턴, 포토레지스트 패턴, 블랙 매트릭스 패턴 및 스페이서 패턴으로 이루어진 군에서 선택되는 광경화 패턴.7. The method of 6 above, wherein the photocuring pattern is selected from the group consisting of an array planarization film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern, and a spacer pattern.
8. 위 6의 광경화 패턴을 포함하는 화상 표시 장치.8. An image display device including the photocuring pattern of 6 above.
본 발명의 실시예들에 따른 감광성 수지 조성물을 사용하여 우수한 기판 밀착력 및 잔막률을 가지면서도 감도가 뛰어난 광경화 패턴을 구현할 수 있다.By using the photosensitive resin composition according to embodiments of the present invention, a photocurable pattern with excellent sensitivity while having excellent substrate adhesion and residual film rate can be implemented.
또한, 상기 감광성 수지 조성물은 높은 광효율 및 거동 제어 특성이 우수한 광중합 개시제를 포함하므로, 이로부터 우수한 해상도로 미세 선폭의 광경화 패턴을 형성할 수 있으며, 저온 경화 조건에서도 내구성이 우수한 광경화 패턴이 형성될 수 있다.In addition, since the photosensitive resin composition contains a photopolymerization initiator with high light efficiency and excellent behavior control properties, a photocurable pattern with a fine line width can be formed with excellent resolution, and a photocurable pattern with excellent durability even under low temperature curing conditions is formed. It can be.
따라서, 상기 감광성 수지 조성물은 스페이서 패턴, 절연막 패턴 등의 광경화 패턴, 이를 포함하는 화상 표시 장치의 제조에 유용하게 사용될 수 있다.Therefore, the photosensitive resin composition can be usefully used in the manufacture of photocurable patterns such as spacer patterns and insulating film patterns, and image display devices including the same.
도 1은 T/B 비의 정의를 개략적으로 나타낸 도면이다.Figure 1 is a diagram schematically showing the definition of the T/B ratio.
본 발명의 실시예들은 감광성 수지 조성물에 관한 것으로, 보다 상세하게는 알칼리 가용성 수지; 중합성 화합물; 광중합 개시제; 및 용제를 포함하고, 상기 광중합 개시제는 하기 화학식 1로 표시되는 화합물을 포함하여, 높은 광효율 및 거동 제어 특성이 우수한 광중합 개시제를 포함하므로, 이로부터 우수한 해상도로 미세 선폭의 광경화 패턴을 형성할 수 있으며, 저온 경화 조건에서도 내구성이 우수하며, 우수한 기판 밀착력 및 잔막률을 가지면서도 감도가 뛰어난 광경화 패턴을 형성할 수 있는 감광성 수지 조성물에 관한 것이다.Embodiments of the present invention relate to photosensitive resin compositions, and more specifically, to alkali-soluble resins; polymerizable compounds; photopolymerization initiator; and a solvent, wherein the photopolymerization initiator includes a compound represented by the following formula (1), and has high light efficiency and excellent behavior control properties, so that a photocurable pattern with a fine line width can be formed with excellent resolution. It relates to a photosensitive resin composition that has excellent durability even under low-temperature curing conditions and can form a highly sensitive photocurable pattern while having excellent substrate adhesion and residual film rate.
이하, 본 발명의 실시예들에 대해 상세히 설명한다.Hereinafter, embodiments of the present invention will be described in detail.
<감광성 수지 조성물><Photosensitive resin composition>
광중합light curing 개시제initiator
본 발명의 실시예들에 따른 감광성 수지 조성물은 광중합 개시제를 포함하며, 상기 광중합 개시제는 하기 화학식 1로 표시되는 화합물을 포함한다.The photosensitive resin composition according to embodiments of the present invention includes a photopolymerization initiator, and the photopolymerization initiator includes a compound represented by the following formula (1).
[화학식 1][Formula 1]
상기 화학식 1 중, A는 니트로기 또는 시아노기이고, R1 또는 R2는 각각 독립적으로 수소 또는 탄소수 1 내지 20의 알킬기이고, R3은 탄소수 1 내지 20의 알킬기, 탄소수 6 내지 20 아릴기 또는 탄소수 3 내지 20의 사이클로알킬기, R4는 오쏘, 메타 또는 파라에 위치하는 하기 화학식 2로 표시되는 치환기이다.In Formula 1, A is a nitro group or a cyano group, R 1 or R 2 is each independently hydrogen or an alkyl group having 1 to 20 carbon atoms, and R 3 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or A cycloalkyl group having 3 to 20 carbon atoms, R 4 is a substituent represented by the following formula (2) located at ortho, meta or para.
[화학식 2] [Formula 2]
상기 화학식 2 중, *는 결합부이며, R5, R6 또는 R7는 각각 독립적으로 탄소수 1 내지 3의 알킬기이며, 바람직하게는 각각 독립적으로 메틸기 또는 에틸기이다.In Formula 2, * is a bonding portion, and R 5 , R 6 or R 7 are each independently an alkyl group having 1 to 3 carbon atoms, and preferably each independently a methyl group or an ethyl group.
상기 광중합 개시제는 상기 화학식 1로 표시되는 화합물을 포함하여, 높은 광효율을 나타낼 수 있어 우수한 잔막률 및 기판 밀착력을 가지며, 상기 화학식 1에 포함된 페닐기 및 터트-부틸기의 입체 장애로 인해 라디칼의 거동 제어 성능이 향상될 수 있다. 예를 들면 노광 공정에서 상기 화학식 1에 포함된 페닐기 및 터트-부틸기의 입체 장애로 인해 라디칼이 비노광부로 확산되는 것을 방지할 수 있어 노광 공정에서의 감도가 향상될 수 있고, 현상 공정에서 우수한 해상도로 미세 선폭의 광경화 패턴을 형성할 수 있다. 또한, 상기 광중합 개시제는 저온 경화에서도 우수한 반응성을 나타내고, 이로부터 형성된 패턴은 우수한 내화학성, 내열성 등 높은 내구성을 나타낸다. The photopolymerization initiator includes the compound represented by Formula 1, and can exhibit high light efficiency and has excellent residual film rate and substrate adhesion, and the behavior of radicals due to steric hindrance of the phenyl group and tert-butyl group included in Formula 1. Control performance can be improved. For example, in the exposure process, radicals can be prevented from diffusing into non-exposed areas due to steric hindrance of the phenyl group and tert-butyl group included in Chemical Formula 1, thereby improving sensitivity in the exposure process and providing excellent performance in the development process. It is possible to form photocurable patterns of fine line width with high resolution. In addition, the photopolymerization initiator exhibits excellent reactivity even when cured at low temperatures, and the pattern formed therefrom exhibits high durability such as excellent chemical resistance and heat resistance.
또한, 상기 광중합 개시제를 포함하는 감광성 수지 조성물은 화상표시장치에 이용되는 각종 패턴 형성, 예를 들면, 여러 절연 패턴의 형성에 사용될 수 있다. 예를 들면 상기 광중합 개시제를 포함하는 감광성 수지 조성물로 스페이서 패턴을 형성하면 T/B 비 값이 향상된 스페이서 패턴을 얻을 수 있다.Additionally, the photosensitive resin composition containing the photopolymerization initiator can be used to form various patterns used in image display devices, for example, various insulating patterns. For example, if a spacer pattern is formed using a photosensitive resin composition containing the photopolymerization initiator, a spacer pattern with an improved T/B ratio value can be obtained.
도 1은 T/B 비의 정의를 개략적으로 나타낸 도면이다. 도 1을 참조하면 T/B비란, 스페이서 패턴에 있어서 상부의 직경을 하부의 직경으로 나눈 값이며, T/B비 값이 클수록 바람직하다. 본 명세서에 있어서, 패턴의 상부는 패턴의 전체 높이에 대해서 바닥면으로부터 전체 높이의 95%인 지점의 수평면으로 정의되고, 패턴의 하부는 패턴의 전체 높이에 대해서 바닥면으로부터 전체 높이의 5%인 지점의 수평면으로 정의된다.Figure 1 is a diagram schematically showing the definition of the T/B ratio. Referring to FIG. 1, the T/B ratio is a value obtained by dividing the upper diameter of the spacer pattern by the lower diameter, and the larger the T/B ratio value, the more preferable. In this specification, the upper part of the pattern is defined as a horizontal surface at a point that is 95% of the total height from the floor with respect to the total height of the pattern, and the lower part of the pattern is 5% of the total height from the floor with respect to the total height of the pattern. It is defined as the horizontal plane of the point.
상기 광중합 개시제를 포함하는 감광성 수지 조성물로 스페이서 패턴을 형성하면, 상기 화학식 1로 표시되는 화합물로 인해 상기 광중합 개시제의 입체 장애가 증가하므로 효과적으로 라디칼의 거동 제어가 가능하여, 라디칼의 확산을 방지하므로 실질적으로 수직한 프로파일의 패턴 형성이 가능하다. When a spacer pattern is formed with a photosensitive resin composition containing the photopolymerization initiator, steric hindrance of the photopolymerization initiator increases due to the compound represented by Formula 1, thereby effectively controlling the behavior of radicals and preventing diffusion of radicals, thereby substantially It is possible to form a vertical profile pattern.
본 명세서에서 사용되는 용어 "알킬기"는 직쇄형 또는 분지쇄형 알킬기를 포괄하며, "사이클로알킬기"는 단일 고리계뿐만 아니라 여러 고리계 탄화수소도 포괄하고, "아릴기"는 하나의 수소 제거에 의해서 방향족 탄화수소로부터 유도되며, 각 고리에 적절하게는 4 내지 7개, 바람직하게는 5 또는 6개의 고리원자를 포함하는 단일 또는 융합고리계를 포함하며, 다수개의 아릴이 단일결합으로 연결되어 있는 형태까지 포괄하는 개념이다.As used herein, the term “alkyl group” encompasses straight-chain or branched-chain alkyl groups, “cycloalkyl group” encompasses not only single ring systems but also multi-ring hydrocarbons, and “aryl group” encompasses aromatic hydrocarbons by removal of one hydrogen. It is derived from hydrocarbons and includes a single or fused ring system containing 4 to 7 ring atoms, preferably 5 or 6 ring atoms in each ring, and includes forms in which multiple aryls are connected by single bonds. It is a concept that does.
일부 실시예들에 있어서, 상기 광중합 개시제는 상기 화학식 1로 표시되는 화합물에 아세토페논계 화합물 및 비이미다졸계 화합물로 이루어진 군에서 선택된 적어도 하나를 더 포함할 수 있다. 아세토페논계 화합물 및 비이미다졸계 화합물을 추가적으로 병용할 때에 전술한 라디칼의 거동 제어 효과와 동시에 라디칼의 형성 감도를 보충 또는 향상시킬 수 있고, 우수한 내화학성, 내열성 등 높은 내구성을 가지는 광경화 패턴을 형성할 수 있어 바람직하다.In some embodiments, the photopolymerization initiator may further include at least one selected from the group consisting of an acetophenone-based compound and a biimidazole-based compound in addition to the compound represented by Formula 1. When an acetophenone-based compound and a biimidazole-based compound are additionally used in combination, the above-mentioned radical behavior control effect can be supplemented or improved at the same time as the sensitivity of radical formation, and a photocurable pattern with high durability such as excellent chemical resistance and heat resistance can be created. It is desirable because it can be formed.
상기 아세토페논계 화합물은 예를 들면, 디에톡시아세토페논, 2-히드록시-2-메틸-1-페닐프로판-1-온, 벤질디메틸케탈, 2-히드록시-1-[4-(2-히드록시에톡시)페닐]-2-메틸프로판-1-온, 1-히드록시시클로헥실페닐케톤, 2-메틸-1-(4-메틸티오페닐)-2-모르폴리노프로판-1-온, 2-벤질-2-디메틸아미노-1-(4-모르폴리노페닐)부탄-1-온, 2-히드록시-2-메틸-1-[4-(1-메틸비닐)페닐]프로판-1-온의 올리고머, 디페닐(2,4,6-트리메틸벤조일)-포스핀옥사이드 등 일 수 있다.The acetophenone-based compounds include, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1-[4-(2- Hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one , 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan- It may be a 1-one oligomer, diphenyl (2,4,6-trimethylbenzoyl)-phosphine oxide, etc.
상기 비이미다졸계 화합물은 예를 들면, 2,2'-비스(2-클로로페닐)-4,4',5,5'-테트라페닐비이미다졸, 2,2'-비스(2,3-디클로로페닐)-4,4',5,5'-테트라페닐비이미다졸, 2,2'-비스(2-클로로페닐)-4,4',5,5'-테트라(알콕시페닐)비이미다졸, 2,2'-비스(2-클로로페닐)-4,4',5,5'-테트라(트리알콕시페닐)비이미다졸, 4,4',5,5' 위치의 페닐기가 카르보알콕시기에 의해 치환되어 있는 이미다졸 화합물 등 일 수 있다. 이들 중에서 2,2'비스(2-클로로페닐)-4,4',5,5'-테트라 페닐비이미다졸, 2,2'-비스(2,3-디클로로페닐)-4,4',5,5'-테트라페닐비이미다졸, 2,2'4-트리스(2-클로로페닐)-5-(3,4-디메톡시페닐)-4',5'-디페닐-1,1'-비이미다졸이 바람직하게 사용된다.The biimidazole-based compounds include, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3 -Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)bi Imidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, the phenyl group at the 4,4',5,5' position is It may be an imidazole compound substituted with a boalkoxy group. Among these, 2,2'bis(2-chlorophenyl)-4,4',5,5'-tetra phenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4', 5,5'-tetraphenylbiimidazole, 2,2'4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1' -Biimidazole is preferably used.
일 실시예에 있어서, 상기 광중합 개시제가 상기 아세토페논계 화합물 및 상기 비이미다졸계 화합물을 모두 포함하는 경우, 상기 아세토페논계 화합물 및 상기 비이미졸계 화합물의 몰비는 특별히 제한되지 않으며, 예를 들면 1:9 내지 9:1의 몰비일 수 있다.In one embodiment, when the photopolymerization initiator includes both the acetophenone-based compound and the biimidazole-based compound, the molar ratio of the acetophenone-based compound and the biimidazole-based compound is not particularly limited, for example It may be a molar ratio of 1:9 to 9:1.
일 실시예에 있어서, 본 발명의 효과를 손상하지 않는 정도이면 당분야에서 통상 사용되고 있는 광중합 개시제를 추가로 병용할 수도 있으며, 추가로 병용할 수 있는 광중합 개시제로서는 벤조인계 화합물, 벤조페논계 화합물, 티오크산톤계 화합물, 안트라센계 화합물 등을 예로 들 수 있다. 이들은 각각 단독으로 또는 2종 이상 조합하여 사용할 수 있다.In one embodiment, photopolymerization initiators commonly used in the art may be additionally used as long as they do not impair the effect of the present invention. Examples of photopolymerization initiators that can be additionally used include benzoin-based compounds, benzophenone-based compounds, Examples include thioxanthone-based compounds and anthracene-based compounds. These can be used individually or in combination of two or more types.
일 실시예에 있어서, 상기 광중합 개시제는 감도를 향상시켜 생산성을 더욱 높인다는 측면에서 광중합 개시 보조제를 조합하여 사용할 수도 있다. 상기 광중합 개시 보조제의 예로는 아민 화합물, 카르복실산 화합물 등을 들 수 있다.In one embodiment, the photopolymerization initiator may be used in combination with a photopolymerization initiation auxiliary agent to further increase productivity by improving sensitivity. Examples of the photopolymerization initiation aid include amine compounds, carboxylic acid compounds, etc.
일 실시예에 있어서, 상기 광중합 개시제로 상기 화학식 1로 표시되는 화합물과 다른 개시제 화합물이 병용되는 경우에는 광중합 개시제 100중량부에 대하여, 상기 화학식 1으로 표시되는 화합물을 20 내지 90중량부로 포함할 수 있고, 바람직하게는 30 내지 60중량부로 포함할 수 있다. 상기 범위에 있을 때 스페이서 패턴의 형성 시 더욱 우수한 T/B비 값을 얻을 수 있다.In one embodiment, when the photopolymerization initiator is used in combination with the compound represented by Formula 1 and another initiator compound, 20 to 90 parts by weight of the compound represented by Formula 1 may be included based on 100 parts by weight of the photopolymerization initiator. and may preferably be included in 30 to 60 parts by weight. When it is within the above range, a more excellent T/B ratio value can be obtained when forming a spacer pattern.
일 실시예에 있어서, 상기 광중합 개시제는 감광성 수지 조성물 고형분 100중량부에 대하여 0.1 내지 10중량부로 포함될 수 있다. 상기 범위일 때 감광성 수지 조성물의 감도를 향상시켜, 형성된 패턴, 예를 들면 스페이서 패턴의 강도나 평활성이 양호하게 되기 때문에 바람직하다. 상기 광중합 개시제가 감광성 수지 조성물 고형분 100중량부에 대하여 0.1중량부 미만이면 라디칼 거동 제어 효과가 미미할 수 있고, 10중량부 초과이면 라디칼 확산 방지 효과가 충분히 구현되지 않을 수 있어 해상도가 저하될 수 있다.In one embodiment, the photopolymerization initiator may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of solid content of the photosensitive resin composition. The above range is preferable because it improves the sensitivity of the photosensitive resin composition and improves the strength and smoothness of the formed pattern, for example, a spacer pattern. If the photopolymerization initiator is less than 0.1 parts by weight based on 100 parts by weight of solid content of the photosensitive resin composition, the effect of controlling radical behavior may be insignificant, and if it is more than 10 parts by weight, the effect of preventing radical diffusion may not be sufficiently implemented, and resolution may be reduced.
알칼리 가용성 수지Alkali soluble resin
본 발명의 실시예들에 따른 감광성 수지 조성물은 알칼리 가용성 수지를 포함한다. 상기 알칼리 가용성 수지는 현상 공정에서 사용되는 알칼리 현상액에 대해 가용성을 부여하는 성분이며, 기재에의 밀착력을 부여하여 도막 형성을 가능케 하는 성분이다. 예를 들면, 상기 알칼리 가용성 수지는 상기 감광성 수지 조성물의 바인더 수지로서 기능할 수 있다. 상기 알칼리 가용성 수지는 광이나 열의 작용에 의한 반응성을 가지면서 알칼리 용해성을 갖는다.The photosensitive resin composition according to embodiments of the present invention includes an alkali-soluble resin. The alkali-soluble resin is a component that provides solubility to the alkaline developer used in the development process and provides adhesion to the substrate, enabling the formation of a coating film. For example, the alkali-soluble resin may function as a binder resin of the photosensitive resin composition. The alkali-soluble resin has alkali solubility while being reactive under the action of light or heat.
상기 알칼리 가용성 수지는 당분야의 감광성 수지 조성물에 사용되는 알칼리 가용성 수지라면 제한 없이 사용될 수 있으며, 전술한 광중합 개시제와 함께 사용될 때 저온 경화에서 우수한 반응성을 나타내고, 그로부터 제조된 패턴은 뛰어난 내화학성, 내열성 등 높은 내구성을 나타낸다.The alkali-soluble resin may be used without limitation as long as it is an alkali-soluble resin used in photosensitive resin compositions in the art, and when used with the above-mentioned photopolymerization initiator, it exhibits excellent reactivity at low temperature curing, and the pattern prepared therefrom has excellent chemical resistance and heat resistance. It shows high durability.
일부 실시예에 있어서, 상기 알칼리 가용성 수지는 당분야에서 공지된 단량체로 형성된 반복단위를 더 포함할 수 있다.In some embodiments, the alkali-soluble resin may further include repeating units formed of monomers known in the art.
예를 들면, 상기 알칼리 가용성 수지는 알칼리 가용성을 확보하기 위해 상기 카르복실산기를 포함하는 반복 단위를 더 포함할 수 있다. 카르복실산기를 포함하는 반복단위는 당분야에 알려진 단량체를 특별한 제한 없이 사용하여 형성될 수 있으며, 예를 들면, 카르복실산기를 포함하는 반복단위는 불포화 모노카르복실산이나, 불포화 디카르복실산 또는 불포화 트리카르복실산과 같이 분자 중에 2개 이상의 카르복실기를 갖는 다카 카르복실산으로 이루어진 군에서 선택되는 단량체에서 유래된 구조일 수 있다. For example, the alkali-soluble resin may further include a repeating unit containing the carboxylic acid group to ensure alkali solubility. The repeating unit containing a carboxylic acid group can be formed using monomers known in the art without particular limitation. For example, the repeating unit containing a carboxylic acid group is an unsaturated monocarboxylic acid or an unsaturated dicarboxylic acid. Alternatively, it may be a structure derived from a monomer selected from the group consisting of dacarboxylic acids having two or more carboxyl groups in the molecule, such as unsaturated tricarboxylic acids.
상기 불포화 모노카르복실산은 예를 들어 아크릴산, 메타크릴산, 크로톤산 등을 들 수 있다. 상기 불포화 다가 카르복실산은 예를 들어 말레산, 푸마르산, 시트라콘산, 메사콘산, 이타콘산 등을 들 수 있다. 상기 다가 카르복실산은 산 무수물일 수도 있으며, 상기 불포화 다가 카르복실산 무수물은 예를 들어 말레산 무수물, 이타콘산 무수물, 시트라콘산 무수물 등을 들 수 있다. 또한, 상기 불포화 다가 카르복실산은 그의 모노(2-메타크릴로일옥시알킬)에스테르일 수도 있으며, 예를 들면 숙신산모노(2-아크릴로일옥시에틸), 숙신산모노(2-메타크릴로일옥시에틸), 프탈산모노(2-아크릴로일옥시에틸), 프탈산모노(2-메타크릴로일옥시에틸) 등을 들 수 있다. 상기 불포화 다가 카르복실산은 그 양말단 디카르복시 중합체의 모노(메타)아크릴레이트일 수도 있으며, 예를 들면 ω-카르복시폴리카프로락톤모노아크릴레이트, ω-카르복시폴리카프로락톤모노메타크릴레이트 등을 들 수 있다. 또한 상기 불포화 다가 카르복실산은 동일 분자 중에 히드록시기 및 카르복실기를 함유하는 불포화 아크릴레이트일 수도 있으며, 예를 들면, α-(히드록시메틸)아크릴산 등을 들 수 있다. 이들 중, 아크릴산, 메타크릴산, 무수 말레산 등이 공중합 반응성이 높은 점에서 바람직하게 사용된다. Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid. Examples of the unsaturated polyhydric carboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid. The polyhydric carboxylic acid may be an acid anhydride, and examples of the unsaturated polyhydric carboxylic acid anhydride include maleic anhydride, itaconic anhydride, and citraconic anhydride. In addition, the unsaturated polyhydric carboxylic acid may be its mono(2-methacryloyloxyalkyl) ester, for example, mono(2-acryloyloxyethyl) succinic acid, mono(2-methacryloyloxy) succinic acid. ethyl), mono(2-acryloyloxyethyl) phthalate, mono(2-methacryloyloxyethyl) phthalate, etc. The unsaturated polyhydric carboxylic acid may be a mono(meth)acrylate of a dicarboxylic polymer at both ends, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, etc. there is. Additionally, the unsaturated polyhydric carboxylic acid may be an unsaturated acrylate containing a hydroxy group and a carboxyl group in the same molecule, and examples include α-(hydroxymethyl)acrylic acid. Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferably used because of their high copolymerization reactivity.
또한, 상기 알칼리 가용성 수지는 알칼리 가용성 수지에 광/열경화성을 부여하기 위해 아크릴레이트기를 포함하는 반복 단위를 더 포함할 수 있다. 상기 아크릴레이트기를 포함하는 반복 단위는 당분야에 알려진 단량체를 특별한 제한 없이 사용하여 형성할 수 있으며, 예를 들면, 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 부틸(메타)아크릴레이트, 2-히드록시에틸(메타)아크릴레이트, 2-히드록시-o-페닐페놀프로필아크릴레이트, 아미노에틸(메타)아크릴레이트 등의 불포화 카르복실산의 비치환 또는 치환 알킬에스테르 화합물, 시클로펜틸(메타)아크릴레이트, 시클로헥실(메타)아크릴레이트, 메틸시클로헥실(메타)아크릴레이트, 시클로헵틸(메타)아크릴레이트, 시클로옥틸(메타)아크릴레이트, 멘틸(메타)아크릴레이트, 시클로펜테닐(메타)아크릴레이트, 시클로헥세닐(메타)아크릴레이트, 시클로헵테닐(메타)아크릴레이트, 시클로옥테닐(메타)아크릴레이트, 멘타디에닐(메타)아크릴레이트, 이소보르닐(메타)아크릴레이트, 피나닐(메타)아크릴레이트, 아다만틸(메타)아크릴레이트, 노르보르닐(메타)아크릴레이트, 피네닐(메타)아크릴레이트, 트리시클로[5.2.1.02,6]데카닐 (메타)아크릴레이트, 3,4-에폭시 트리시클로[5.2.1.02,6]데카닐 (메타)아크릴레이트 등의 지환식 치환기를 포함하는 불포화 카르복실산 에스테르 화합물, 올리고에틸렌클리콜 모노알킬(메타)아크릴레이트 등의 글리콜류의 모노포화 카르복실산 에스테르 화합물, 벤질(메타)아크릴레이트, 페녹시(메타)아크릴레이트 등의 방향환을 갖는 치환기를 포함하는 불포화 카르복실산 에스테르 화합물, 스티렌, α-메틸스티렌, 비닐톨루엔 등의 방향족 비닐 화합물, 아세트산 비닐, 프로피온산 비닐 등의 카르복실산 비닐에스테르,(메타)아크릴로니트릴, α-클로로아크릴로 니트릴, 아조비스이소부티로니트릴 등의 시안화 비닐 화합물, N-시클로헥실말레이미드, N-페닐말레이미드 등의 말레이미드 화합물, 노르보르넨 등의 불포화 지환족 화합물로 이루어진 군에서 선택된 단량체에서 유래된 구조일 수 있으나, 이에 한정되는 것은 아니다.In addition, the alkali-soluble resin may further include a repeating unit containing an acrylate group to provide light/thermal curability to the alkali-soluble resin. The repeating unit containing the acrylate group can be formed using monomers known in the art without particular limitation, for example, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, Unsubstituted or substituted alkyl ester compounds of unsaturated carboxylic acids such as 2-hydroxyethyl (meth)acrylate, 2-hydroxy-o-phenylphenolpropyl acrylate, aminoethyl (meth)acrylate, cyclopentyl (meth)acrylate ) Acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, cyclooctyl (meth)acrylate, menthyl (meth)acrylate, cyclopentenyl (meth) Acrylate, cyclohexenyl (meth)acrylate, cycloheptenyl (meth)acrylate, cyclooctenyl (meth)acrylate, menthadienyl (meth)acrylate, isobornyl (meth)acrylate, pinanyl (meth)acrylate, adamantyl (meth)acrylate, norbornyl (meth)acrylate, pinenyl (meth)acrylate, tricyclo[5.2.1.0 2,6 ]decanyl (meth)acrylate, Unsaturated carboxylic acid ester compounds containing alicyclic substituents such as 3,4-epoxy tricyclo[5.2.1.0 2,6 ]decanyl (meth)acrylate, oligoethylene glycol monoalkyl (meth)acrylate, etc. Monosaturated carboxylic acid ester compounds of glycols, unsaturated carboxylic acid ester compounds containing a substituent having an aromatic ring such as benzyl (meth)acrylate, phenoxy (meth)acrylate, styrene, α-methylstyrene, vinyl Aromatic vinyl compounds such as toluene, carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate, vinyl cyanide compounds such as (meth)acrylonitrile, α-chloroacrylonitrile, and azobisisobutyronitrile, and N-cyclohexyl. The structure may be derived from a monomer selected from the group consisting of maleimide compounds such as maleimide and N-phenylmaleimide, and unsaturated alicyclic compounds such as norbornene, but is not limited thereto.
본 명세서에 있어서, "(메타)아크릴-"은 "메타크릴-", "아크릴-" 또는 이 둘 모두를 지칭한다.In this specification, “(meth)acryl-” refers to “methacryl-”, “acryl-”, or both.
상기 알칼리 가용성 수지의 함량은 특별하게 제한하지 않으며, 이로부터 형성되는 광경화 패턴의 해상도, 패턴 균일도를 고려하여 적절히 조절될 수 있다. 일 구현예에 있어서, 상기 알칼리 가용성 수지의 함량은 감광성 수지 조성물의 고형분을 기준으로 10 내지 65중량부 일 수 있다. 상기 범위 내로 포함될 경우 현상액에의 용해성이 충분하여 현상성이 우수해지며, 우수한 기계적 물성을 갖는 광경화 패턴을 형성할 수 있게 된다.The content of the alkali-soluble resin is not particularly limited and can be appropriately adjusted considering the resolution and pattern uniformity of the photocured pattern formed therefrom. In one embodiment, the content of the alkali-soluble resin may be 10 to 65 parts by weight based on the solid content of the photosensitive resin composition. When contained within the above range, the solubility in the developer is sufficient to improve developability, and it is possible to form a photocurable pattern with excellent mechanical properties.
상기 알칼리 가용성 수지의 중량평균분자량은 특별히 한정되지 않으나, 감광성 수지 조성물의 저온 조건의 반응성 향상 및 내화학성의 향상 측면에서 6,000 내지 40,000일 수 있으며, 바람직하게는 7,500 내지 35,000 더욱 바람직하게는 13,000 내지 32,000인 것이 좋다. 상기 범위를 만족하는 경우, 패턴의 CD-Bias가 적정 범위로 구현되어 우수한 해상도를 갖는 패턴을 형성할 수 있으며, 내화학성 및 연필경도 역시 향상시킬 수 있다. 한편, 알칼리 가용성 수지의 중량평균분자량이 20,000을 초과하는 경우, 분자량이 과도하게 커져 감광성 수지 조성물의 다른 성분과의 상용성이 저하되어 현상 단계에서 도막의 백화가 발생할 수 있으며, 패턴의 선폭도 증가하여 CD-Bias 특성이 저하될 수 있다.The weight average molecular weight of the alkali-soluble resin is not particularly limited, but may be 6,000 to 40,000 in terms of improving the reactivity and chemical resistance of the photosensitive resin composition under low temperature conditions, preferably 7,500 to 35,000, and more preferably 13,000 to 32,000. It's good to be If the above range is satisfied, the CD-Bias of the pattern can be implemented in an appropriate range to form a pattern with excellent resolution, and chemical resistance and pencil hardness can also be improved. On the other hand, if the weight average molecular weight of the alkali-soluble resin exceeds 20,000, the molecular weight becomes excessively large and compatibility with other components of the photosensitive resin composition decreases, which may cause whitening of the coating film during the development stage and also increase the line width of the pattern. As a result, CD-Bias characteristics may deteriorate.
중합성polymerizability 화합물 compound
본 발명의 실시예들에 따른 감광성 수지 조성물은 중합성 화합물을 포함하며, 상기 중합성 화합물은 제조 공정 중 가교 밀도를 증가시키며, 광경화 패턴의 기계적 특성을 강화시킬 수 있다.The photosensitive resin composition according to embodiments of the present invention includes a polymerizable compound, and the polymerizable compound can increase crosslinking density during the manufacturing process and strengthen the mechanical properties of the photocurable pattern.
상기 중합성 화합물은 당분야에 사용되는 것이 특별한 제한 없이 사용될 수 있으며, 예를 들면 단관능 단량체, 2관능 단량체 및 그 밖의 다관능 단량체로, 그 종류는 특별히 한정되지 않으나, 하기 화합물들을 그 예로 들 수 있다. The polymerizable compound may be used without particular limitation in the art, and includes, for example, monofunctional monomers, difunctional monomers, and other polyfunctional monomers. The types are not particularly limited, but examples include the following compounds: You can.
단관능 단량체의 구체예로는 노닐페닐카르비톨아크릴레이트, 2-히드록시-3-페녹시프로필아크릴레이트, 2-에틸헥실카르비톨아크릴레이트, 2-히드록시에틸아크릴레이트, N-비닐피롤리돈 등을 들 수 있다. 2관능 단량체의 구체예로는 1,6-헥산디올디(메타)아크릴레이트, 에틸렌글리콜디(메타)아크릴레이트, 네오펜틸글리콜디(메타)아크릴레이트, 트리에틸렌글리콜디(메타)아크릴레이트, 비스페놀 A의 비스(아크릴로일옥시에틸)에테르, 3-메틸펜탄디올디(메타)아크릴레이트 등을 들 수 있다. 그 밖의 다관능 단량체의 구체예로서는 트리메틸올프로판트리(메타)아크릴레이트, 에톡실레이티드트리메틸올프로판트리(메타)아크릴레이트, 프로폭실레이티드트리메틸올프로판트리(메타)아크릴레이트, 펜타에리트리톨트리(메타)아크릴레이트, 펜타에리트리톨테트라(메타)아크릴레이트, 디펜타에리트리톨펜타(메타)아크릴레이트, 에톡실레이티드디펜타에리트리톨헥사(메타)아크릴레이트, 프로폭실레이티드디펜타에리트리톨헥사(메타)아크릴레이트, 디펜타에리트리톨헥사(메타)아크릴레이트, 트리펜타에리트리톨옥타(메타)아크릴레이트 등을 들 수 있다. 이들 중에서 2관능 이상의 다관능 단량체가 바람직하게 사용된다. Specific examples of monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrroli. Examples include money, etc. Specific examples of bifunctional monomers include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, Bis(acryloyloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, etc. are mentioned. Specific examples of other polyfunctional monomers include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, and pentaerythritol tri. (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol Hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, etc. can be mentioned. Among these, polyfunctional monomers having two or more functions are preferably used.
상기 중합성 화합물의 함량은 특별히 한정되지 않으나, 예를 들면, 감광성 수지 조성물 고형분 100중량부를 기준으로 10 내지 85중량부, 바람직하게는 30 내지 80중량부의 범위에서 사용된다. 상기 중합성 화합물이 상기의 함량 범위로 포함되는 경우, 우수한 내구성을 가질 수 있고, 조성물의 현상성을 향상시킬 수 있다.The content of the polymerizable compound is not particularly limited, but for example, it is used in the range of 10 to 85 parts by weight, preferably 30 to 80 parts by weight, based on 100 parts by weight of solid content of the photosensitive resin composition. When the polymerizable compound is included in the above content range, excellent durability can be achieved and the developability of the composition can be improved.
용제solvent
본 발명의 실시예들에 따른 감광성 수지 조성물은 용제를 포함하며, 상기 용제는 당해 분야에서 통상적으로 사용되는 것이라면 어떠한 것이라도 제한 없이 사용될 수 있다.The photosensitive resin composition according to embodiments of the present invention includes a solvent, and the solvent may be any solvent commonly used in the field without limitation.
상기 용제의 구체적인 예로는 에틸렌글리콜모노알킬에테르류; 디에틸렌글리콜디알킬에테르류; 에틸렌글리콜알킬에테르아세테이트류; 알킬렌글리콜알킬에테르아세테이트류; 프로필렌글리콜모노알킬에테르류; 프로필렌글리콜디알킬에테르류; 프로필렌글리콜알킬에테르프로피오네이트류; 부틸디올모노알킬에테르류; 부탄디올모노알킬에테르아세테이트류; 부탄디올모노알킬에테르프로피오네이트류; 디프로필렌글리콜디알킬에테르류; 방향족 탄화수소류; 케톤류; 알코올류; 에스테르류; 고리형 에스테르류 등을 들 수 있다. 여기서 예시한 용매는, 각각 단독으로 또는 2종 이상을 혼합하여 사용할 수 있다. Specific examples of the solvent include ethylene glycol monoalkyl ethers; Diethylene glycol dialkyl ethers; ethylene glycol alkyl ether acetate; alkylene glycol alkyl ether acetates; propylene glycol monoalkyl ethers; propylene glycol dialkyl ethers; propylene glycol alkyl ether propionates; Butyldiol monoalkyl ethers; Butanediol monoalkyl ether acetate; Butanediol monoalkyl ether propionates; Dipropylene glycol dialkyl ethers; aromatic hydrocarbons; ketones; alcohol; esters; Cyclic esters, etc. can be mentioned. The solvents exemplified here can be used individually or in mixture of two or more types.
상기 용제는 도포성 및 건조성을 고려하였을 때 알킬렌글리콜알킬에테르아세테이트류, 케톤류, 부탄디올알킬에테르아세테이트류, 부탄디올모노알킬에테르류, 에스테르류가 바람직하게 사용될 수 있으며, 더욱 바람직하게는 프로필렌글리콜모노메틸에테르아세테이트, 프로필렌글리콜모노에틸에테르아세테이트, 시클로헥사논, 메톡시부틸아세테이트, 메톡시부탄올, 3-에톡시프로피온산에틸, 3-메톡시프로피온산메틸 등이 사용될 수 있다. When considering applicability and drying properties, the solvent may preferably be alkylene glycol alkyl ether acetate, ketone, butanediol alkyl ether acetate, butanediol monoalkyl ether, or ester, and more preferably propylene glycol monomethyl. Ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, methoxybutanol, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, etc. may be used.
실시예들에 따른 감광성 수지 조성물은 감광성 수지 조성물 전체 100중량부에 대하여 상기 용제를 40 내지 95중량부, 바람직하게는 45 내지 85 중량부로 포함할 수 있다. 상기 범위를 만족하는 경우, 스핀 코터, 슬릿 & 스핀 코터, 슬릿 코터(다이 코터, 커튼플로우 코터라고도 불리는 경우가 있다), 잉크젯 등의 도포 장치로 도포했을 때 도포성이 양호해지기 때문에 바람직하다.The photosensitive resin composition according to the embodiments may include 40 to 95 parts by weight, preferably 45 to 85 parts by weight, of the solvent based on 100 parts by weight of the total photosensitive resin composition. When the above range is satisfied, it is preferable because the coating properties improve when applied with a coating device such as a spin coater, slit & spin coater, slit coater (sometimes called a die coater, curtain flow coater), or inkjet.
첨가제additive
본 발명의 일부 실시예들에 따른 감광성 수지 조성물은 필요에 따라 충진제, 다른 고분자 화합물, 레벨링제, 밀착촉진제, 산화 방지제, 자외선 흡수제, 응집 방지제, 연쇄 이동제 등의 첨가제를 더 포함할 수 있다.The photosensitive resin composition according to some embodiments of the present invention may further include additives such as fillers, other polymer compounds, leveling agents, adhesion promoters, antioxidants, ultraviolet ray absorbers, aggregation inhibitors, and chain transfer agents, if necessary.
<< 광경화light curing 패턴 및 화상표시장치> Pattern and image display device>
본 발명의 실시예들은 전술한 감광성 수지 조성물로 형성된 광경화 패턴과 상기 광경화 패턴을 포함하는 화상 표시 장치를 제공한다.Embodiments of the present invention provide a photocurable pattern formed from the photosensitive resin composition described above and an image display device including the photocurable pattern.
전술한 감광성 수지 조성물로 형성된 광경화 패턴은 저온 경화성이 우수하며, 예를 들어 본 발명에 따른 감광성 수지 조성물의 가열 경화(프리 베이크 및/또는 포스트 베이크) 온도는 70 내지 100℃일 수 있다. 또한, 본 발명의 감광성 수지 조성물로 제조된 광경화 패턴은 저온 경화 후에도 밀착성, 내화학성 및 내열성 등이 우수하며, 경시안정성이 뛰어나다.The photocurable pattern formed from the photosensitive resin composition described above has excellent low-temperature curing properties. For example, the heat curing (pre-bake and/or post-bake) temperature of the photosensitive resin composition according to the present invention may be 70 to 100°C. In addition, the photocured pattern made from the photosensitive resin composition of the present invention has excellent adhesion, chemical resistance, and heat resistance even after low-temperature curing, and has excellent aging stability.
또한, 전술한 감광성 수지 조성물은 높은 광효율 및 거동 제어 특성이 우수한 광중합 개시제를 포함하므로, 이로부터 형성된 광경화 패턴은 우수한 해상도를 가진다.In addition, since the photosensitive resin composition described above includes a photopolymerization initiator with high light efficiency and excellent behavior control properties, the photocured pattern formed therefrom has excellent resolution.
이에 따라 화상 표시 장치에 있어서 각종 패턴, 예를 들면 접착제층, 어레이 평탄화막, 보호막, 절연막 패턴 등으로 이용될 수 있고, 포토레지스트, 블랙 매트릭스, 스페이서 패턴, 컬럼 스페이서 패턴, 블랙 컬럼 스페이서 패턴 등으로 이용될 수도 있으나, 이에 제한되는 것은 아니며, 특히, 스페이서 패턴 또는 절연막 패턴으로 매우 적합하다.Accordingly, it can be used as various patterns in image display devices, such as adhesive layers, array planarization films, protective films, insulating film patterns, etc., and can be used as photoresist, black matrix, spacer pattern, column spacer pattern, black column spacer pattern, etc. It may be used, but is not limited to this, and is particularly suitable as a spacer pattern or insulating film pattern.
이러한 광경화 패턴을 구비하거나 제조 과정 중에 상기 패턴을 사용하는 화상 표시 장치로는 터치 패널을 구비한 화상 표시 장치, 액정 표시 장치, OLED, 플렉서블 디스플레이 등이 있을 수 있으나, 이에 한정되는 것은 아니며 적용이 가능한 당분야에 알려진 모든 화상 표시 장치를 예시할 수 있다.Image display devices equipped with such a photocurable pattern or using the pattern during the manufacturing process may include, but are not limited to, an image display device with a touch panel, a liquid crystal display device, an OLED, a flexible display, etc., and the application is not limited thereto. All possible image display devices known in the art can be exemplified.
상기 광경화 패턴 형성에 있어, 상술한 감광성 수지 조성물을 기재 상에 도포하고 프리-베이킹(pre-baking) 공정을 통해 감광막을 형성할 수 있다. 이후, 노광 공정, 필요에 따라 현상 공정을 수행하여 광경화 패턴을 형성될 수 있으며. 노광 후 베이킹(post exposure baking: PEB) 공정이 더 수행될 수도 있다. In forming the photocurable pattern, the photosensitive resin composition described above may be applied on a substrate and a photosensitive film may be formed through a pre-baking process. Afterwards, a photocuring pattern can be formed by performing an exposure process and, if necessary, a development process. A post exposure baking (PEB) process may further be performed.
상기 노광 공정 시 상술한 바와 같이 향상된 산도를 갖는 광산 발생제에 의해 산이 발행하여 바인더 수지의 가교 반응이 유도될 수 있다. 또한, 상기 광산 발생제 및 중합 개시제의 작용에 의해 노광부 및 비노광부에서의 물리적, 화학적 특성 차이가 증가하여 노광 공정의 해상도가 향상될 수 있다.During the exposure process, acid may be generated by a photoacid generator having improved acidity as described above, thereby inducing a crosslinking reaction of the binder resin. In addition, the difference in physical and chemical properties between the exposed area and the non-exposed area increases due to the action of the photoacid generator and the polymerization initiator, thereby improving the resolution of the exposure process.
상기 노광 공정에 있어서, g선(파장: 436㎚), h선, i선(파장: 365㎚) 등과 같은 자외선 광원이 사용될 수 있다. 상기 현상 공정은 액첨가법, 디핑법, 스프레이법 등을 포함하며, 무기 및/또는 유기 알칼리성 화합물이 현상액으로서 사용될 수 있다.In the exposure process, an ultraviolet light source such as g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), etc. may be used. The development process includes a liquid addition method, a dipping method, a spray method, etc., and an inorganic and/or organic alkaline compound may be used as a developer.
예를 들면, 상기 무기 알칼리성 화합물은 알칼리 금속염을 포함할 수 있으며, 상기 유기 알칼리성 화합물은 유기 히드록사이드 계열 화합물을 포함할 수 있다.For example, the inorganic alkaline compound may include an alkali metal salt, and the organic alkaline compound may include an organic hydroxide-based compound.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 이들 실시예는 본 발명을 예시하는 것일 뿐 첨부된 특허청구범위를 제한하는 것이 아니며, 본 발명의 범주 및 기술사상 범위 내에서 실시예에 대한 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.Hereinafter, preferred embodiments are presented to aid understanding of the present invention, but these examples are only illustrative of the present invention and do not limit the scope of the appended claims, and are examples within the scope and technical idea of the present invention. It is obvious to those skilled in the art that various changes and modifications are possible, and it is natural that such changes and modifications fall within the scope of the appended patent claims.
<< 제조예Manufacturing example 1: 알칼리 가용성 수지(A)의 제조> 1: Preparation of alkali-soluble resin (A)>
교반기, 온도계 환류 냉각관, 적하 로트 및 질소 도입관을 구비한 플라스크에 프로필렌글리콜모노메틸에테르아세테이트 182g을 도입하여, 플라스크내 분위기를 공기에서 질소로 한 후, 100℃로 승온 후 비닐톨루엔 35.4g(0.30몰), 아크릴산 36.0g(0.50몰), 2-히드록시-o-페닐페놀프로필아크릴레이트 59.6g(0.2몰) 및 프로필렌글리콜모노메틸에테르아세테이트 136g을 포함하는 혼합물에 아조비스이소부티로니트릴 3.6g을 첨가한 용액을 적하 로트로부터 2시간에 걸쳐 플라스크에 적하하여 100℃에서 5시간 더 교반을 계속하였다. 이어서, 플라스크내 분위기를 질소에서 공기로 하고, 글리시딜메타크릴레이트 22.5g [0.15몰, (본 반응에 사용한 아크릴산에 대하여 50몰%)], 트리스디메틸아미노메틸페놀 0.9g 및 히드로퀴논 0.145g을 플라스크내에 투입하여 110℃에서 6시간 반응을 계속하고, 고형분 산가가 121.1㎎KOH/g인 불포화기 함유 알칼리 가용성 수지 A를 얻었다. GPC에 의해 측정한 폴리스티렌 환산의 중량평균분자량은 31,000이고, 분자량 분포(Mw/Mn)는 2.2이었다.182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, thermometer reflux cooling pipe, dropping funnel, and nitrogen introduction pipe, the atmosphere in the flask was changed from air to nitrogen, and then the temperature was raised to 100°C, and then 35.4 g of vinyl toluene ( 0.30 mol), 36.0 g (0.50 mol) of acrylic acid, 59.6 g (0.2 mol) of 2-hydroxy-o-phenylphenolpropylacrylate, and 136 g of propylene glycol monomethyl ether acetate (3.6 mol) of azobisisobutyronitrile. The solution to which g was added was added dropwise to the flask over 2 hours from the dropping funnel, and stirring was continued at 100°C for an additional 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 22.5 g of glycidyl methacrylate [0.15 mol, (50 mol% based on the acrylic acid used in this reaction)], 0.9 g of trisdimethylaminomethylphenol, and 0.145 g of hydroquinone were added. It was placed in a flask and reaction was continued at 110°C for 6 hours to obtain an unsaturated group-containing alkali-soluble resin A with a solid acid value of 121.1 mgKOH/g. The weight average molecular weight in terms of polystyrene measured by GPC was 31,000, and the molecular weight distribution (Mw/Mn) was 2.2.
<< 실시예Example 및 and 비교예Comparative example >>
하기 표 1의 조성 및 함량(단위: 중량부)으로 실시예 1 내지 9 및 비교예 1 내지 3의 감광성 수지 조성물을 제조하였다.The photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 3 were prepared using the composition and content (unit: parts by weight) shown in Table 1 below.
(B)polymerizable compound
(B)
(C)photopolymerization initiator
(C)
(E)solvent
(E)
B: 트리펜타에리스리톨 옥타아크릴레이트 (Viscoat#802: 오사카유기화학공업㈜)
C-1: 2,2'4-트리스(2-클로로페닐)-5-(3,4-디메톡시페닐)-4',5'-디페닐-1,1'-비이미다졸(CHEMCURE-TCDM: CHEMBRIDGE INTERNATIONAL CORP.)
C-2: 디페닐(2,4,6-트리메틸벤조일)-포스핀옥사이드(IRGACURE-819: BASF)
C-3: 1-(9,9-H-7-니트로플로렌-2-일)-에탄온 옥심-O-tert-부틸페닐
C-4: 1-(9,9-H-7-니트로플로렌-2-일)-에탄온 옥심-O-tert- 에틸부틸페닐
C-5: 1-(9,9-H-7-니트로플로렌-2-일)-에탄온 옥심-O- 부틸페닐
C-6: 1-(9,9-H-7-니트로플로렌-2-일)-에탄온 옥심-O-헵탄-3-일)페닐
C-7: 1-(9,9-H-7-니트로플로렌-2-일)-에탄온 옥심-O-페닐
D: 디펜타에리트리틸헥사키스(3-메르캅토프로미오네이트)(DPMP: SC ORGANIC CHEMICAL CO.,LTD.)
E-1: 프로필렌글리콜모노메틸에테르아세테이트
E-2: 디에틸렌글리콜에틸메틸에테르A: Resin prepared in Preparation Example 1
B: Tripentaerythritol octacrylate (Viscoat#802: Osaka Organic Chemical Industry Co., Ltd.)
C-1: 2,2'4-Tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-biimidazole (CHEMCURE- TCDM: CHEMBRIDGE INTERNATIONAL CORP.)
C-2: Diphenyl (2,4,6-trimethylbenzoyl)-phosphine oxide (IRGACURE-819: BASF)
C-3: 1-(9,9-H-7-nitrofluoren-2-yl)-ethanone oxime-O-tert-butylphenyl
C-4: 1-(9,9-H-7-nitrofluoren-2-yl)-ethanone oxime-O-tert-ethylbutylphenyl
C-5: 1-(9,9-H-7-nitrofluoren-2-yl)-ethanone oxime-O-butylphenyl
C-6: 1-(9,9-H-7-nitrofluoren-2-yl)-ethanone oxime-O-heptan-3-yl)phenyl
C-7: 1-(9,9-H-7-nitrofluoren-2-yl)-ethanone oxime-O-phenyl
D: Dipentaerythritylhexakis(3-mercaptopromionate) (DPMP: SC ORGANIC CHEMICAL CO.,LTD.)
E-1: Propylene glycol monomethyl ether acetate
E-2: Diethylene glycol ethyl methyl ether
<< 실험예Experiment example >>
가로 세로 2 인치의 유리 기판(이글 2000; 코닝사 제조)을 중성 세제, 물 및 알코올로 순차 세정한 후 건조하였다. 이 유리 기판 상에 상기 실시예 및 비교예에서 제조된 감광성 수지 조성물을 각각 스핀 코팅한 다음 클린오븐 중에서 90℃에서 3 분간 프리베이크하였다. 상기 프리베이크한 기판을 상온으로 냉각 후 석영 유리제 포토마스크와의 간격을 150㎛로 하여 노광기 (TME-150RSK; 톱콘 (주) 제조)를 사용하여 60mJ/㎠의 노광량(405㎚ 기준)으로 광을 조사하였다. 이 때의 중합성 수지 조성물에 대한 조사는, 초고압 수은등으로부터의 방사광을, 광학 필터 (LU0400; 아사히 분광 (주) 제조)를 통과시키고, 400㎚ 이하의 광을 커트하여 사용하였다. 이때 포토마스크는 지름이 10㎛인 원형의 투광부(패턴)를 가지며, 당해 패턴의 간격이 100㎛인 포토마스크가 사용되었다. A 2-inch by 2-inch glass substrate (Eagle 2000; manufactured by Corning) was sequentially washed with neutral detergent, water, and alcohol and then dried. The photosensitive resin compositions prepared in Examples and Comparative Examples were spin-coated on this glass substrate and then prebaked at 90°C for 3 minutes in a clean oven. After cooling the prebaked substrate to room temperature, the gap between it and the quartz glass photomask was set to 150㎛, and light was emitted at an exposure dose of 60mJ/cm2 (based on 405nm) using an exposure device (TME-150RSK; manufactured by Topcon Co., Ltd.). investigated. For the irradiation of the polymerizable resin composition at this time, irradiated light from an ultra-high pressure mercury lamp was passed through an optical filter (LU0400; manufactured by Asahi Spectrophoto Co., Ltd.), and light of 400 nm or less was cut out. At this time, the photomask had a circular light transmitting portion (pattern) with a diameter of 10㎛, and a photomask with a spacing of 100㎛ was used.
광조사 후 비이온계 계면활성제 0.12%와 수산화칼륨 0.04%를 함유하는 수계 현상액에 상기 도막을 25℃ 에서 100초간 침지하여 현상하고, 수세 후 오븐 중에서, 220℃에서 20분간 포스트베이크를 실시하였다. 얻어진 막두께는 3㎛이었다. 막두께는 막두께 측정장치(DEKTAK 6M; Veeco사 제조)를 사용하여 측정하였다. 이렇게 얻어진 패턴을 아래와 같이 물성 평가를 실시하고, 그 결과를 하기 표 2에 나타내었다. After light irradiation, the film was developed by immersing it in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25°C for 100 seconds. After washing with water, post-baking was performed in an oven at 220°C for 20 minutes. The obtained film thickness was 3 μm. The film thickness was measured using a film thickness measuring device (DEKTAK 6M; manufactured by Veeco). The pattern obtained in this way was evaluated for physical properties as follows, and the results are shown in Table 2 below.
<물성 평가><Physical property evaluation>
(1) 해상도 평가(1) Resolution evaluation
상기에서 얻어진 패턴의 바닥면으로부터 1.5㎛인 지점에서의 패턴 사이즈를 3차원 형상측정장치(SIS-2000 system; SNU Precision사 제조)를 사용하여 측정하고, 마스크 사이즈와의 차이를 CD-bias로 아래와 같이 산출하여 해상도를 측정하였다. CD-bias는 0에 근접할수록 해상도가 양호한 것으로 평가할 수 있으며, (+)는 패턴이 마스크보다 사이즈가 크고 (-)는 마스크보다 사이즈가 작음을 의미한다.The pattern size at a point 1.5㎛ from the bottom surface of the pattern obtained above was measured using a three-dimensional shape measuring device (SIS-2000 system; manufactured by SNU Precision), and the difference from the mask size was calculated using CD-bias as shown below. The resolution was measured by calculating it together. The closer CD-bias is to 0, the better the resolution. (+) means that the pattern is larger than the mask, and (-) means that the pattern is smaller than the mask.
CD-bias=(형성된 패턴 사이즈)-(형성시 사용한 마스크 사이즈)CD-bias=(formed pattern size)-(mask size used during formation)
(2) 패턴 상하 폭 비(T/B 비) 평가 (2) Evaluation of pattern top-bottom width ratio (T/B ratio)
상기 (1)에서 Dot패턴을 3차원 형상 측정 장치(SIS-2000 Systems; (주)에스엔유프리시젼 제조)을 사용하여, 패턴의 바닥면으로부터 전체 높이의 5%인 지점을 Bottom CD(a), 바닥면으로부터 전체 높이의 95%인 지점을 Top CD(b)로 정의하고, (b)의 길이를 (a)의 길이로 나눈 후 100을 곱한 값(=b/a×100)을 T/B 비로 정의하였다.In (1) above, the dot pattern was measured using a 3D shape measuring device (SIS-2000 Systems; manufactured by SNU Precision Co., Ltd.), and a point 5% of the total height from the bottom surface of the pattern was called Bottom CD (a). The point that is 95% of the total height from the surface is defined as Top CD (b), the length of (b) is divided by the length of (a), and the value multiplied by 100 (=b/a × 100) is the T/B ratio. defined.
(3) 현상밀착력 평가(3) Development adhesion evaluation
현상 밀착성은 지름(size)이 10㎛인 원형 패턴이 각각 1000개가 있는 포토마스크에 의해 막두께가 3㎛로 형성된 패턴을 현미경으로 평가하여 결락된 패턴의 수를 세어 하기 수학식 1에 따라 현상밀착력(%)을 산출하였고, 그 결과를 하기 표 2에 기재하였다.The developing adhesion is evaluated under a microscope on a pattern formed with a film thickness of 3㎛ by a photomask with 1000 circular patterns each having a diameter (size) of 10㎛, and the number of missing patterns is counted. The developing adhesion is determined according to Equation 1 below. (%) was calculated, and the results are shown in Table 2 below.
[수학식 1][Equation 1]
현상밀착력(%) = [1000-(결락된 패턴의 수)]/1000 × 100Development adhesion (%) = [1000-(number of missing patterns)]/1000 × 100
평가Pattern precision
evaluation
표 2를 참조하면, 본 발명의 실시예들에 따른 광중합 개시제가 포함된 실시예들의 경우, 비교예들보다 전체적으로 우수한 화학적, 기계적 특성을 갖는 패턴들이 형성되었다.Referring to Table 2, in the case of Examples containing a photopolymerization initiator according to Examples of the present invention, patterns having overall superior chemical and mechanical properties than the Comparative Examples were formed.
상기 화학식 1로 표시되는 화합물, 비이미다졸계 화합물 및 아세토페논계 화합물을 광중합 개시제로 포함하는 실시예 1 및 2는 가장 우수한 CD-bias, T/B 비 및 현상밀착력을 갖는 것으로 평가되었으며, 상기 화학식 1로 표시되는 화합물이 감광성 수지 조성물에 다소 과량으로 포함된 실시예 3 및 4의 경우 해상도 및 기계적 특성이 다소 저하되었다.Examples 1 and 2 containing the compound represented by Formula 1, a biimidazole-based compound, and an acetophenone-based compound as photopolymerization initiators were evaluated as having the best CD-bias, T/B ratio, and developing adhesion. In Examples 3 and 4, in which the compound represented by Formula 1 was included in a somewhat excessive amount in the photosensitive resin composition, the resolution and mechanical properties were somewhat deteriorated.
또한, 광중합 개시제 중 상기 화학식 1로 표시되는 화합물이 실시예 1보다 다소 적게 첨가된 실시예 5 및 7의 경우 T/B 비 값이 약간 저하되었으며, 광중합 개시제 중 상기 화학식 1로 표시되는 화합물이 실시예 1보다 다소 많이 첨가된 실시예 6의 경우 T/B 비 및 현상 밀착력 특성이 약간 저하되는 것으로 평가되었다.In addition, in Examples 5 and 7, in which a slightly smaller amount of the compound represented by Formula 1 among the photopolymerization initiators was added than in Example 1, the T/B ratio value was slightly lowered, and the compound represented by Formula 1 among the photopolymerization initiators was used In the case of Example 6, where slightly more was added than Example 1, the T/B ratio and development adhesion characteristics were evaluated to be slightly lowered.
또한, 상기 화학식 1로 표시되는 화합물만을 광중합 개시제로 포함하는 실시예 8 및 9의 경우, 이것이 갖는 높은 광효율 및 라디칼 거동 제어 효과로 인해 높은 해상도를 보이나 현상 밀착력은 다소 감소하였다.In addition, in the case of Examples 8 and 9 containing only the compound represented by Formula 1 as a photopolymerization initiator, high resolution was shown due to the high light efficiency and radical behavior control effect, but the developing adhesion was somewhat reduced.
한편, 비교예들은 전체적으로 좋지 않은 CD-bias, T/B 비를 보이므로 해상도가 실시예들에 비해 열등하며, 특히 비교예 2의 경우는 현상 밀착력 또한 매우 좋지 않았다.Meanwhile, the comparative examples showed overall poor CD-bias and T/B ratios, so the resolution was inferior to the examples, and in particular, in the case of Comparative Example 2, the development adhesion was also very poor.
Claims (8)
상기 광중합 개시제는 하기 화학식 1로 표시되는 화합물을 포함하는 감광성 수지 조성물:
[화학식 1]
(화학식 1 중, A는 니트로기 또는 시아노기이고, R1 또는 R2는 각각 독립적으로 수소이고, R3은 탄소수 1 내지 20의 알킬기, 탄소수 6 내지 20 아릴기 또는 탄소수 3 내지 20의 사이클로알킬기, R4는 하기 화학식 2로 표시되는 치환기임)
[화학식 2]
(화학식 2 중, *는 결합부이며, R5, R6 또는 R7는 각각 독립적으로 메틸기 또는 에틸기임).
Alkali soluble resin; polymerizable compounds; photopolymerization initiator; and a solvent,
The photopolymerization initiator is a photosensitive resin composition comprising a compound represented by the following formula (1):
[Formula 1]
(In Formula 1, A is a nitro group or a cyano group, R 1 or R 2 is each independently hydrogen, and R 3 is an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, or a cycloalkyl group with 3 to 20 carbon atoms. , R 4 is a substituent represented by the following formula 2)
[Formula 2]
(In Formula 2, * is a bonding portion, and R 5 , R 6 or R 7 are each independently a methyl group or an ethyl group).
The photosensitive resin composition of claim 1, wherein the photopolymerization initiator further includes at least one selected from the group consisting of acetophenone-based compounds and biimidazole-based compounds.
The photosensitive resin composition of claim 2, wherein the photopolymerization initiator includes the acetophenone-based compound and the biimidazole-based compound at a molar ratio of 1:9 to 9:1.
The photosensitive resin composition of claim 1, wherein the photopolymerization initiator includes a compound represented by Formula 1 in an amount of 20 to 90 parts by weight based on 100 parts by weight of the photopolymerization initiator.
The photosensitive resin composition of claim 1, wherein the photopolymerization initiator is included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of solid content of the photosensitive resin composition.
A photocurable pattern manufactured from the photosensitive resin composition of any one of claims 1 to 5.
The method according to claim 6, wherein the photocuring pattern is a photocuring pattern selected from the group consisting of an array planarization film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern, and a spacer pattern.
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| JP2009075283A (en) * | 2007-09-20 | 2009-04-09 | Jsr Corp | Radiation-sensitive resin composition, spacer for liquid crystal display device and method for producing the same |
| KR102047079B1 (en) * | 2015-03-11 | 2019-12-02 | 동우 화인켐 주식회사 | A colored photo sensitive resin composition, color filter and liquid crystal display device having the same |
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| KR101302508B1 (en) | 2006-02-03 | 2013-09-02 | 주식회사 동진쎄미켐 | Negative photosensitive resin composition, liquid crystal display having that curing product, method of forming a pattern of liquid crystal display using the same |
| KR101418735B1 (en) * | 2007-12-25 | 2014-07-11 | 가부시키가이샤 아데카 | Oxime esters and photopolymerization initiators containing the same |
| US9316906B2 (en) * | 2012-05-03 | 2016-04-19 | Korea Research Institute Of Chemical Technology | Fluorene oxime ester compound, photopolymerization initiator and photoresist composition containing the same |
| JP2017537347A (en) * | 2014-11-12 | 2017-12-14 | サムヤン コーポレーション | Black matrix photoresist composition for liquid crystal display panel |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2009075283A (en) * | 2007-09-20 | 2009-04-09 | Jsr Corp | Radiation-sensitive resin composition, spacer for liquid crystal display device and method for producing the same |
| KR102047079B1 (en) * | 2015-03-11 | 2019-12-02 | 동우 화인켐 주식회사 | A colored photo sensitive resin composition, color filter and liquid crystal display device having the same |
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