KR20180138023A - UV-curable resin composition and optical device using the same - Google Patents
UV-curable resin composition and optical device using the same Download PDFInfo
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- KR20180138023A KR20180138023A KR1020170078050A KR20170078050A KR20180138023A KR 20180138023 A KR20180138023 A KR 20180138023A KR 1020170078050 A KR1020170078050 A KR 1020170078050A KR 20170078050 A KR20170078050 A KR 20170078050A KR 20180138023 A KR20180138023 A KR 20180138023A
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- 239000011342 resin composition Substances 0.000 title claims abstract description 56
- 230000003287 optical effect Effects 0.000 title claims abstract description 45
- 150000001875 compounds Chemical class 0.000 claims abstract description 39
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000010521 absorption reaction Methods 0.000 claims abstract description 28
- 239000003999 initiator Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims description 40
- 238000001723 curing Methods 0.000 claims description 28
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 19
- 239000002096 quantum dot Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 239000004305 biphenyl Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 12
- 235000010290 biphenyl Nutrition 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 8
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- HZAWHDJKNZWAAR-YHARCJFQSA-N 1-methoxy-2-[(e)-2-[4-[4-[(e)-2-(2-methoxyphenyl)ethenyl]phenyl]phenyl]ethenyl]benzene Chemical group COC1=CC=CC=C1\C=C\C1=CC=C(C=2C=CC(\C=C\C=3C(=CC=CC=3)OC)=CC=2)C=C1 HZAWHDJKNZWAAR-YHARCJFQSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 3
- MASVCBBIUQRUKL-UHFFFAOYSA-N POPOP Chemical compound C=1N=C(C=2C=CC(=CC=2)C=2OC(=CN=2)C=2C=CC=CC=2)OC=1C1=CC=CC=C1 MASVCBBIUQRUKL-UHFFFAOYSA-N 0.000 claims description 3
- 238000000016 photochemical curing Methods 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000006267 biphenyl group Chemical group 0.000 claims description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical group C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- 229920001187 thermosetting polymer Polymers 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 19
- 230000001070 adhesive effect Effects 0.000 abstract description 19
- 229910001507 metal halide Inorganic materials 0.000 abstract description 17
- 150000005309 metal halides Chemical class 0.000 abstract description 17
- -1 phenyl compound Chemical class 0.000 abstract description 13
- 230000000052 comparative effect Effects 0.000 description 23
- 238000002834 transmittance Methods 0.000 description 11
- 239000011521 glass Substances 0.000 description 9
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000000306 component Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- 229910001428 transition metal ion Inorganic materials 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 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
- 238000002845 discoloration Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012994 photoredox catalyst Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- UHXOHPVVEHBKKT-UHFFFAOYSA-N 1-(2,2-diphenylethenyl)-4-[4-(2,2-diphenylethenyl)phenyl]benzene Chemical group C=1C=C(C=2C=CC(C=C(C=3C=CC=CC=3)C=3C=CC=CC=3)=CC=2)C=CC=1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 UHXOHPVVEHBKKT-UHFFFAOYSA-N 0.000 description 1
- DDZJGFHXUOWOSL-UHFFFAOYSA-N 2,5-bis(4-phenylphenyl)-1,3-oxazole Chemical compound C=1N=C(C=2C=CC(=CC=2)C=2C=CC=CC=2)OC=1C(C=C1)=CC=C1C1=CC=CC=C1 DDZJGFHXUOWOSL-UHFFFAOYSA-N 0.000 description 1
- CNRNYORZJGVOSY-UHFFFAOYSA-N 2,5-diphenyl-1,3-oxazole Chemical compound C=1N=C(C=2C=CC=CC=2)OC=1C1=CC=CC=C1 CNRNYORZJGVOSY-UHFFFAOYSA-N 0.000 description 1
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
- VFUDMQLBKNMONU-UHFFFAOYSA-N 9-[4-(4-carbazol-9-ylphenyl)phenyl]carbazole Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 VFUDMQLBKNMONU-UHFFFAOYSA-N 0.000 description 1
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 description 1
- QZWMOMOVGDJVSU-UHFFFAOYSA-N Cc1cc(C)c(C(=O)OP(=O)c2ccccc2)c(C)c1 Chemical compound Cc1cc(C)c(C(=O)OP(=O)c2ccccc2)c(C)c1 QZWMOMOVGDJVSU-UHFFFAOYSA-N 0.000 description 1
- 239000004713 Cyclic olefin copolymer Substances 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- XZCJVWCMJYNSQO-UHFFFAOYSA-N butyl pbd Chemical compound C1=CC(C(C)(C)C)=CC=C1C1=NN=C(C=2C=CC(=CC=2)C=2C=CC=CC=2)O1 XZCJVWCMJYNSQO-UHFFFAOYSA-N 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000004054 semiconductor nanocrystal Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
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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
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- 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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/12—Esters of monohydric alcohols or phenols
- C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/13—Phenols; Phenolates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
- C08K5/3417—Five-membered rings condensed with carbocyclic rings
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
- C08K5/353—Five-membered rings
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
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- 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
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Abstract
Description
본 발명은 비페닐계 화합물로서 흡수 파장이 340 ~ 420nm 범위이고, 형광 파장이 360 ~ 440nm 범위인 유기형광체 또는 옥사졸계 화합물로서 흡수 파장이 340 ~ 420nm 범위이고, 형광 파장이 360 ~ 440nm 범위인 유기형광체(A), 광중합성 화합물(B), 흡수 파장이 360 ~ 440nm인 광중합 개시제(C), 및 365 nm 파장을 흡수하였을 때 370 ~ 440 nm 범위에서 발광하는 무기형광체(D)를 포함하는 자외선 경화형 수지 조성물 및 이를 이용하여 제조한 광학 부재에 관한 것이다.The present invention relates to an organic phosphor or an oxazole-based compound having an absorption wavelength in the range of 340 to 420 nm and a fluorescence wavelength in the range of 360 to 440 nm as a biphenyl-based compound and having an absorption wavelength in the range of 340 to 420 nm and a fluorescence wavelength in the range of 360 to 440 nm (A), a photopolymerizable compound (B), a photopolymerization initiator (C) having an absorption wavelength of 360 to 440 nm, and an inorganic phosphor (D) emitting light in a wavelength range of 370 to 440 nm A curable resin composition and an optical member manufactured using the same.
본 발명에 따른 자외선 경화형 수지 조성물은 무기형광체의 사용으로 유기형광체가 석출되어 결정이 생기는 상용성 문제를 개선하고, 광원으로서 메탈 할라이드 램프뿐만 아니라 UV-LE를 사용하였을 때의 경화성능 또한 우수하여, 차광부가 존재하는 광학 기재에 대해 경화 공정의 추가 없이 자외선의 조사 만으로도 차광 영역에 위치하는 수지 조성물을 충분히 경화시킬 수 있어 접착제로서 유용하게 사용될 수 있다.The ultraviolet ray curable resin composition according to the present invention improves the compatibility problem that crystals are formed by precipitation of an organic fluorescent substance by using an inorganic fluorescent material and has excellent curing performance when a metal halide lamp as well as UV-LE is used as a light source, The resin composition located in the light-shielding region can be sufficiently cured by irradiation of ultraviolet light without adding a curing process to the optical substrate in which the light-shielding portion is present, so that it can be usefully used as an adhesive.
자외선 경화형 수지 조성물은 일반적으로 자외선을 조사함으로써 광중합 개시제로부터 활성 라디칼 또는 산 등이 발생해 광중합성 화합물이 중합한다. 그러나, 차광부가 존재하는 광학 기재에서와 같이 자외선이 도달하지 않는 차광 영역에 위치하는 수지 조성물은 경화하지 않는다. 이처럼 차광 영역에 위치하는 미경화된 수지 조성물은 광학 기재와의 접착력을 충분히 발현하지 못하므로 박리문제가 발생하거나, 미경화된 수지 조성물이 차광층으로 침투해 차광층이 변색되는 등 여러가지 불량을 일으킨다.Generally, ultraviolet curable resin composition generates radicals or acids from the photopolymerization initiator upon irradiation with ultraviolet rays to polymerize the photopolymerizable compound. However, the resin composition located in the light-shielding region in which ultraviolet rays do not reach as in the optical substrate in which the light-shielding portion is present does not cure. Since the uncured resin composition located in the light-shielding region can not sufficiently exhibit the adhesive force with the optical substrate, problems such as peeling may occur, or the uncured resin composition penetrates into the light-shielding layer to cause discoloration of the light-shielding layer .
차광영역에 위치하는 수지 조성물을 경화시키는 기술로서, 일본 등록특허 제5299544호는 유기 과산화물과 같은 열중합 개시제와 광중합 개시제를 병용하여 자외선 경화 후에 추가적인 가열 공정을 거쳐 차광 영역의 수지 조성물을 경화시키는 기술을 제시하고 있다. 그러나 가열 공정은 광학 기재 등이 손상을 받는 것이 우려될 뿐만 아니라, 수지를 충분히 경화시키기 위해서는 60분 이상 가열해야 하기 때문에 생산성이 현저히 낮아지게 된다.Japanese Patent No. 5299544 discloses a technique for curing a resin composition in a light-shielding region by using a thermal polymerization initiator such as an organic peroxide in combination with a photopolymerization initiator, followed by an additional heating step after ultraviolet curing, . However, in addition to the fear that the optical substrate or the like is damaged, the heating process requires heating for 60 minutes or more in order to sufficiently cure the resin, so that the productivity is significantly lowered.
또한, 한국 공개특허 제2014-111283호는 자외선을 흡수하여 발광하고, 특정한 흡수 극대 파장과 발광 극대 파장을 갖는 유기 화합물을 함유시키는 기술을 제시하고 있다. 구체적으로, 유기 화합물이 특정 파장대의 자외선을 흡수하면, 해당 유기 화합물로부터 방사 형상으로 특정한 발광 극대 파장을 갖는 광이 나온다. 그 발광된 광이 차광 영역에 도달하기 때문에, 차광 영역에 위치하는 수지 조성물 내 광중합 개시제가 개시되어 중합이 진행됨으로써 수지를 충분히 경화시킬 수 있다. Korean Patent Laid-Open Publication No. 2014-111283 discloses a technique of absorbing ultraviolet light to emit light and containing an organic compound having a specific absorption maximum wavelength and maximum light emission wavelength. Specifically, when an organic compound absorbs ultraviolet rays of a specific wavelength range, light having a specific maximum light emission wavelength emerges radially from the organic compound. Since the emitted light reaches the light-shielding region, a photopolymerization initiator in the resin composition located in the light-shielding region is initiated and the polymerization proceeds, whereby the resin can be sufficiently cured.
그러나 광원으로써 200 ~ 400nm의 넓은 파장대의 광선을 방출하는 메탈 할라이드 램프를 사용할 때에는 차광 영역에 위치하는 수지 조성물을 효과적으로 경화시키는 것이 가능하나, 365nm와 같은 단일 파장의 광선만을 방출하는 UV-LED를 사용하면 해당 경화 효과가 현저히 낮아지는 문제가 있다.However, when using a metal halide lamp that emits light of a wide wavelength range of 200 to 400 nm as a light source, it is possible to effectively cure the resin composition located in the light-shielding region, but using a UV-LED emitting only a single wavelength light such as 365 nm There is a problem that the effect of the curing is remarkably lowered.
한편, 자외선 경화형 수지의 경화에 이용되는 UV 램프는 수은램프 또는 메탈 할라이드 램프에서 UV-LED로 대체되고 있는 추세이다. 수은램프 또는 메탈 할라이드 램프는 소비전력이 크고, 제논(Xe), 수은(Hg)와 같은 환경 유해 물질을 유발하며, 원치 않는 단파장을 방출하여 경화하고자 하는 수지 또는 도료에 황변 현상을 야기하는 문제점이 있다. 반면, UV-LED 장치는 수은램프 또는 메탈 할라이드 램프에 비해 설비의 크기와 전력소모량이 훨씬 작고 원하는 파장대의 UV만을 이용하여 수지를 경화시킬 수 있다. 또한, UV-LED는 환경 유해 물질의 발생이 없어 친환경적이고 비교적 수명이 긴 장점을 갖는다.On the other hand, UV lamps used for curing UV curable resins are being replaced by UV-LEDs in mercury lamps or metal halide lamps. A mercury lamp or a metal halide lamp consumes a large amount of electric power and causes environmental harmful substances such as xenon (Hg) and mercury (Hg), and causes a problem of causing yellowing in the resin or paint to be cured by emitting an unwanted short wavelength have. On the other hand, a UV-LED device is much smaller in size and power consumption than a mercury lamp or a metal halide lamp, and can harden the resin using only UV of a desired wavelength. In addition, the UV-LED has the advantage of being environmentally friendly and having a relatively long life due to the absence of environmentally harmful substances.
이에, 수은램프 또는 메탈 할라이드 램프를 광원으로 하였을 때뿐만 아니라, UV-LED를 광원으로 한 경우에도 경화성능이 우수하여 차광부가 존재하는 광학 기재에 대해 경화 공정의 추가 없이 자외선의 조사만으로도 차광 영역에 위치하는 수지 조성물이 충분히 경화되어 접착제로서의 역할을 수행하고, 나아가 효과적인 경화성능을 발현하기 위해 상용성이 개선된 자외선 경화형 수지 조성물의 제공이 필요한 실정이다.Therefore, even when the mercury lamp or the metal halide lamp is used as a light source, it is excellent in curing performance even when the UV-LED is used as a light source, so that the UV absorber There is a need to provide an ultraviolet ray curable resin composition having improved compatibility in order to sufficiently cure the resin composition to be cured and to serve as an adhesive and to exhibit effective curing performance.
본 발명은 이러한 종래 기술의 문제점을 고려해서 이루어진 것이고, 자외선 경화형 수지 조성물(접착제)를 이용하여 광학 기재를 접합할 때, 그 광학 기재에 차광부가 형성되어 있는 경우라도 액정 표시 장치 등에 손상이 가해지는 일 없이 자외선의 조사만으로도 차광 영역에 위치하는 수지 조성물을 충분히 경화시킬 수 있는 자외선 경화형 접착제를 제공하는 것을 목적으로 한다.DISCLOSURE OF THE INVENTION The present invention has been made in view of the problems of the prior art, and it is an object of the present invention to provide a liquid crystal display device and a liquid crystal display device in which, even when a light shielding portion is formed on an optical substrate when an optical substrate is bonded using an ultraviolet- It is an object of the present invention to provide an ultraviolet curable adhesive which can sufficiently cure a resin composition located in a light-shielding region only by irradiation of ultraviolet light.
본 발명자들은 상기 과제를 해결하기 위해 연구한 결과, 광중합성 화합물, 광중합 개시제를 포함하는 광경화성 수지 조성물에 비페닐계 화합물로서 흡수 파장이 340 ~ 420 nm 범위이고, 형광 파장이 360 ~ 440 nm 범위인 유기형광체 또는 옥사졸계 화합물로서 흡수 파장이 340 ~ 420nm 범위이고, 형광 파장이 360 ~ 440nm 범위인 유기 형광체 및 365 nm 파장을 흡수하였을 때 370 ~ 440 nm 범위에서 발광하는 무기 형광체를 사용함으로써 상기 과제를 해결할 수 있는 것을 발견하고, 본 발명을 완성했다. As a result of studies to solve the above problems, the present inventors have found that a photocurable resin composition comprising a photopolymerizable compound and a photopolymerization initiator has an absorption wavelength in a range from 340 nm to 420 nm and a fluorescence wavelength in a range from 360 nm to 440 nm An organic phosphor having an absorption wavelength in the range of 340 to 420 nm and a fluorescent wavelength in the range of 360 to 440 nm and an inorganic phosphor emitting light in the range of 370 to 440 nm when absorbing the wavelength of 365 nm is used as the organic phosphor or the oxazole- Can be solved, and the present invention has been completed.
따라서, 본 발명의 목적은 메탈 할라이드 램프를 광원으로 하였을 때뿐만 아니라, UV-LED를 광원으로 한 경우에도 경화성능이 우수한 자외선 경화형 수지 조성물을 제공하는데 있다.Accordingly, it is an object of the present invention to provide an ultraviolet curable resin composition having excellent curing performance not only when a metal halide lamp is used as a light source, but also when a UV-LED is used as a light source.
또한, 본 발명의 다른 목적은 상기 자외선 경화형 수지 조성물을 이용하여 제조한 광학 부재를 제공하는데 있다.Another object of the present invention is to provide an optical member manufactured using the ultraviolet-curable resin composition.
위와 같은 과제를 해결하기 위해, 본 발명은 (A) 비페닐계 화합물로서 흡수 파장이 340 ~ 420 nm 범위이고, 형광 파장이 360 ~ 440 nm 범위인 유기형광체이거나 옥사졸계 화합물로서 흡수 파장이 340 ~ 420nm 범위이고, 형광 파장이 360 ~ 440nm 범위인 유기형광체; (B) 광중합성 화합물; (C) 광중합 개시제; 및 (D) 365 nm 파장을 흡수하였을 때 370 ~ 440 nm 범위에서 발광하는 무기형광체를 포함하는 것을 특징으로 하는 자외선 경화형 수지 조성물을 제공한다.In order to solve the above problems, the present invention provides an organic electroluminescence device comprising (A) an organic phosphor having an absorption wavelength in a range of 340 to 420 nm and a fluorescent wavelength in a range of 360 to 440 nm, An organic fluorescent material having a fluorescence wavelength in a range of 360 to 440 nm; (B) a photopolymerizable compound; (C) a photopolymerization initiator; And (D) an inorganic fluorescent substance which emits light in a wavelength range of 370 to 440 nm when the wavelength is absorbed by 365 nm.
또한 본 발명은 상기 광학 기재 및 차광부를 갖는 광학 기재를 상기 광경화성 수지 조성물을 이용하여 접합한 후, 차광부를 갖는 광학 기재를 통해 자외선을 조사함으로써 수지 조성물을 경화시켜 얻은 광학 부재를 제공한다.Further, the present invention provides an optical member obtained by bonding the optical substrate and the optical substrate having the light-shielding portion by using the photo-curing resin composition, and then irradiating ultraviolet rays through the optical substrate having the shielding portion to cure the resin composition.
본 발명에 따른 자외선 경화형 수지 조성물은 메탈 할라이드 램프를 광원으로 하였을 때뿐만 아니라 UV-LED를 광원으로 한 경우에도 경화성능이 우수하여, 차광부가 존재하는 광학 기재에 대해 경화 공정의 추가 없이 자외선의 조사만으로도 차광 영역에 위치하는 수지 조성물을 충분히 경화시킬 수 있어 접착제로서 유용하게 사용될 수 있다. 더욱이 무기형광체는 유기형광체가 석출되어 결정이 생기는 상용성 문제를 개선하여, 유기형광체만을 사용한 경우와 대비하여 경화 성능을 더욱 향상시킬 수 있다.The ultraviolet ray curable resin composition according to the present invention is excellent in curing performance not only when a metal halide lamp is used as a light source but also when a UV-LED is used as a light source, It is possible to sufficiently cure the resin composition located in the light-shielding region, so that it can be usefully used as an adhesive. Furthermore, the inorganic fluorescent substance can solve the compatibility problem of crystal formation by precipitation of the organic fluorescent substance, and can further improve the curing performance as compared with the case of using only the organic fluorescent substance.
따라서, 본 발명에 따른 광경화성 수지 조성물을 이용하여 접합한 차광부를 갖는 광학 기재는 차광 영역에 위치하는 수지 조성물과 광학 기재와의 접착력 불량에 의한 박리문제나, 미경화된 수지 조성물이 차광층으로 침투하여 발생되는 차광층의 변색문제 등 여러가지 불량을 일으키지 않으므로 신뢰성이 더욱 우수해 진다.Therefore, in the optical substrate having the light shielding portion bonded by using the photo-curing resin composition according to the present invention, peeling problems due to poor adhesion between the resin composition located in the light shielding region and the optical substrate, The problem of discoloration of the light-shielding layer caused by penetration does not cause various defects, so that the reliability is further improved.
도 1은 본 발명에 따른 자와선 경화형 수지 조성물을 이용하여 접합한 광학 부재의 배열상태를 나타낸 단면도이다.
도 2는 본 발명의 실험예에서 측정한 차광부 경화 거리의 측정 위치를 나타낸 단면도이다.BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view showing an arrangement state of optical members bonded using a resin composition according to the present invention. FIG.
2 is a cross-sectional view showing a measurement position of a light-shielding portion cured distance measured in an experimental example of the present invention.
이하에서 본 발명을 하나의 구현예로서 보다 상세히 설명한다. Hereinafter, the present invention will be described in more detail as an embodiment.
본 발명은 광학 부재에 손상이 가해지는 일 없이 자외선의 조사만으로도 차광 영역에 위치하는 수지 조성물을 충분히 경화시키기 위해, (A) 비페닐계 화합물로서 흡수 파장이 340 ~ 420nm 범위이고, 형광 파장이 360 ~ 440nm 범위인 유기형광체이거나 옥사졸계 화합물로서 흡수 파장이 340 ~ 420nm 범위이고, 형광 파장이 360 ~ 440nm 범위인 유기형광체; (B) 광중합성 화합물; (C) 광중합 개시제; 및 (D) 365 nm 파장을 흡수하였을 때 370 ~ 440 nm 범위에서 발광하는 무기형광체를 포함하는 자외선 경화형 수지 조성물을 제공한다.In order to sufficiently cure the resin composition located in the light-shielding region by irradiation of ultraviolet light without damaging the optical member, the present invention provides a resin composition comprising (A) a biphenyl-based compound having an absorption wavelength in the range of 340 to 420 nm and a fluorescence wavelength of 360 An organic phosphor having an absorption wavelength in a range of 340 to 420 nm and a fluorescence wavelength in a range of 360 to 440 nm as an oxazole-based compound; (B) a photopolymerizable compound; (C) a photopolymerization initiator; And (D) an inorganic fluorescent material which emits light in a wavelength range of 370 to 440 nm when the wavelength is absorbed by 365 nm.
본 발명에 따른 수지 조성물은 메탈 할라이드 램프를 광원으로 하였을 때뿐만 아니라 UV-LED를 광원으로 한 경우에도 우수한 경화 성능을 갖기에, 광학 기재 및 차광부가 존재하는 광학기재를 접합하는데 유용한 접착제로 사용될 수 있다. 이때, 본 발명에서의 '차광부'는 광학 기재의 가장자리에 흑색 인쇄 처리 등으로 형성되어 광이 도달하지 않는 부분을 의미하는 것이다.The resin composition according to the present invention can be used as an adhesive useful for bonding an optical substrate and an optical substrate in which a light shielding portion exists because it has excellent curing performance not only when a metal halide lamp is used as a light source but also when a UV LED is used as a light source have. Here, the 'light shielding portion' in the present invention means a portion formed by black printing or the like on the edge of the optical substrate and not reaching the light.
이하 각 성분에 대해서 설명한다. Each component will be described below.
종래에는 유기 형광체로서 안트라센 화합물, 쿠마린 화합물, 카르바졸 화합물, 벤조옥사졸 화합물, 스틸벤 화합물, 벤지딘 화합물, 옥사디아졸 화합물을 사용하였지만, 이들은 흡수 파장이 주로 270 ~ 340 nm 범위이므로 365nm와 같이 단일 파장의 광선만을 방출하는 UV-LED를 광원으로 사용하는 경우에는 발광 효과를 보기 어려울 뿐만 아니라 상기 계열에 해당하는 유기 형광체의 자외선 흡수율 및 발광 효율이 높지 않아 그 효과가 충분히 발현되지 않는다는 점에서 여전히 한계가 있다. Conventionally, an anthracene compound, a coumarin compound, a carbazole compound, a benzoxazole compound, a stilbene compound, a benzidine compound and an oxadiazole compound are used as the organic fluorescent material. However, since they have an absorption wavelength mainly in the range of 270 to 340 nm, In the case of using a UV-LED that emits only a wavelength of light as a light source, it is difficult to obtain a luminescent effect, and ultraviolet absorption and luminescent efficiency of the organic phosphor corresponding to the above-mentioned series are not high, .
이에 본 발명에서 사용하는 유기 형광체(A)는 비페닐계 화합물로서 흡수 파장이 340 ~ 420nm 범위이고, 형광 파장이 360 ~ 440nm 범위인 유기형광체이거나 옥사졸계 화합물로서 흡수 파장이 340 ~ 420nm 범위이고, 형광 파장이 360 ~ 440nm 범위인 것을 사용한다.Accordingly, the organic phosphor (A) used in the present invention is an organic phosphor having an absorption wavelength in the range of 340 to 420 nm and a fluorescent wavelength in the range of 360 to 440 nm as the biphenyl-based compound, or an oxazole-based compound having an absorption wavelength in the range of 340 to 420 nm, And a fluorescent light having a wavelength in the range of 360 to 440 nm is used.
이들은 여기 파장이 365nm일 때의 형광 파장이 360 ~ 440nm범위인 것과 동시에 자외선 흡수율 및 발광 효율이 매우 우수한 것으로서, 흡수 파장이 360 ~ 440nm인 광중합 개시제와 병용하면 메탈 할라이드 램프 또는UV-LED의 광을 1차 광원으로, 유기 형광체의 형광을 2차 광원으로 이용할 수 있기 때문에 우수한 경화 성능을 나타내므로 접착제로서 더욱 적합하다.They have a fluorescent wavelength of 360 to 440 nm when excited at a wavelength of 365 nm and an ultraviolet absorptivity and a high luminous efficiency at the same time. When combined with a photopolymerization initiator having an absorption wavelength of 360 to 440 nm, the light of a metal halide lamp or UV- As a primary light source, since fluorescence of the organic fluorescent material can be used as a secondary light source, it exhibits excellent curing performance and is therefore more suitable as an adhesive.
먼저, 본 발명의 비페닐계 화합물은 하기 화학식 1의 구조를 갖는 화합물이 적합하다.First, the biphenyl-based compound of the present invention is preferably a compound having a structure represented by the following formula (1).
[화학식 1] [Chemical Formula 1]
이때, 상기 식에서, R1은 각각 독립적으로 수소, 직쇄상 또는 분기쇄상의 탄소수 1 내지6의 알킬기 또는 알케닐기 또는 알콕시기, 페닐기, 카르바졸릴기를 나타낸다.In the formula, R 1 independently represents hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms or an alkenyl group, alkoxy group, phenyl group or carbazolyl group.
화학식1의 R1에 있어서의 페닐기는 구체적으로 하기 화학식1-1의 구조로 나타낼 수 있다.The phenyl group in R 1 of formula (1) can be represented by the structure of the following formula (1-1).
[화학식1-1][Formula 1-1]
상기 식에서 R2는 수소, 직쇄상 또는 분기쇄상의 탄소수 1 내지6의 알킬기 또는 알케닐기 또는 알콕시기, 디페닐아민기, 디(4-메틸페닐)아민기, 카르바졸릴기를 나타낸다.In the above formula, R 2 represents hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms or an alkenyl group or alkoxy group, a diphenylamine group, a di (4-methylphenyl) amine group or a carbazolyl group.
화학식1의 R1에 있어서의 카르바졸릴기는 구체적으로 하기 화학식1-2의 구조로 나타낼 수 있다.The carbazolyl group in R 1 of formula (1) can be represented by the structure of formula (1-2).
[화학식 1-2][Formula 1-2]
상기 식에서 R3는 수소, 직쇄상 또는 분기쇄상의 탄소수 1 내지6의 알킬기를 나타낸다.In the above formula, R 3 represents hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms.
바람직한 비페닐계 화합물은4,4'-비스(2-메톡시스티릴)바이페닐(4,4'-bis(2-methoxystyryl)biphenyl), 또는 4,4'-비스(2,2-디페닐비닐)바이페닐(4,4'-bis(2,2-diphenylvinyl)biphenyl), 또는 4,4'-비스(2-(9-에틸-9H-카르바졸-3-일)비닐)-1,1'-바이페닐(4,4'-bis(2-(9-ethyl-9H-carbazol-3-yl)vinyl)-1,1'-biphenyl), 또는 4,4'-비스(4-(9H-카르바졸-9-일)스티릴)바이페닐(4,4'-bis(4-(9H -carbazol-9-yl)styryl)biphenyl)을 사용하는 것이다.Preferred biphenyl-based compounds are 4,4'-bis (2-methoxystyryl) biphenyl, 4,4'-bis (2,2-di Bis (2,2-diphenylvinyl) biphenyl or 4,4'-bis (2- (9-ethyl-9H-carbazol- , 1'-biphenyl (4,4'-bis (2- (9-ethyl-9H-carbazol- (9H-carbazol-9-yl) styryl) biphenyl) is used.
더욱 바람직하게는, 하기 화학식 1a 구조의 4,4'-비스(2-메톡시스티릴)바이페닐을 사용하는 것이다.More preferably, 4,4'-bis (2-methoxystyryl) biphenyl having the following formula (1a) is used.
[화학식 1a][Formula 1a]
다음으로, 본 발명의 옥사졸계 화합물로서, 하기 화학식 2의 구조를 갖는 화합물은 다음과 같다.Next, as the oxazole-based compound of the present invention, the compound having the structure of the following formula (2) is as follows.
[화학식 2](2)
이때, 상기 식에서, R4는 수소, 직쇄상 또는 분기쇄상의 탄소수 1 내지6의 알킬기를 나타내고, R5는 수소, 직쇄상 또는 분기쇄상의 탄소수 1 내지6의 알킬기, 페닐기, 디메틸아민기를 나타내고, R6은 수소, 직쇄상 또는 분기쇄상의 탄소수 1 내지6의 알킬기, 탄소수 6내지8의 아릴기, 비페닐기, 나프틸기를 나타내고, n은 1 내지3의 정수를 나타낸다.Wherein R 4 represents hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, R 5 represents hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, a phenyl group, or a dimethylamine group, R 6 represents hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 8 carbon atoms, a biphenyl group or a naphthyl group, and n represents an integer of 1 to 3.
바람직하게는, 2,5-디페닐옥사졸(2,5-Diphenyloxazole), 또는 1,4-디(5-페닐-2-옥사졸릴)벤젠(1,4-di(5-phenyl-2-oxazolyl)benzene), 또는 2,5-비스(4-비페닐릴)옥사졸(2,5-Bis(4-biphenylyl)oxazole)이다.Preferably, 2,5-diphenyloxazole or 1,4-di (5-phenyl-2-oxazolyl) oxazolyl) benzene, or 2,5-bis (4-biphenylyl) oxazole.
더욱 바람직하게는, 하기 화학식 2a 구조의 1,4-디(5-페닐-2-옥사졸릴)벤젠을 사용하는 것이다.More preferably, 1,4-di (5-phenyl-2-oxazolyl) benzene having the following structural formula (2a) is used.
[화학식 2a](2a)
아울러, 상기 유기형광체(A)는 광중합성 화합물 100 중량부에 대해 0.001 ~ 0.1 중량부를 포함하는 것이 바람직하다. 유기형광체가 0.001 중량부 미만인 경우 차광 영역에 위치하는 수지 조성물을 충분히 경화시킬 수 없고, 0.1 중량부 초과인 경우 유기형광체를 자외선 경화형 수지에 충분히 용해시키기에 한계가 있기에 상기 범위 내에서 사용하는 것이 좋다.In addition, the organic phosphor (A) preferably contains 0.001 to 0.1 part by weight based on 100 parts by weight of the photopolymerizable compound. When the amount of the organic fluorescent material is less than 0.001 part by weight, the resin composition located in the light shielding region can not be sufficiently cured. When the amount of the organic fluorescent material is more than 0.1 part by weight, the organic fluorescent material is not sufficiently dissolved in the ultraviolet curable resin. .
다음으로, 상기 광중합성 화합물(B)는 자외선에 의해 중합하는 화합물이라면 제한되지 않으며, 바람직하게는 (메타)아크릴레이트 올리고머(B-1) 및 (메타)아크릴레이트 모노머(B-2)를 포함하는 것이다.Next, the photopolymerizable compound (B) is not limited as long as it is a compound polymerized by ultraviolet rays, and preferably includes a (meth) acrylate oligomer (B-1) and a (meth) acrylate monomer .
상기 (메타)아크릴레이트 올리고머(B-1)로서는 예를 들면, 우레탄 (메타)아크릴레이트 올리고머, 폴리에스테르 (메타)아크릴레이트 올리고머, 폴리이소프렌 또는 폴리부타디엔 골격을 가지는 (메타)아크릴레이트 올리고머, 아크릴 (메타)아크릴레이트 올리고머를 들 수 있다. 이들 중 특히 경화물의 유연성 및 접착력이 우수하고 광학 기재의 접착제로서 요구되는 기타 물성의 밸런스가 우수하다는 관점에서 우레탄 (메타)아크릴레이트 올리고머가 가장 바람직하다.Examples of the (meth) acrylate oligomer (B-1) include urethane (meth) acrylate oligomers, polyester (meth) acrylate oligomers, (meth) acrylate oligomers having polyisoprene or polybutadiene skeleton, (Meth) acrylate oligomer. Among these, a urethane (meth) acrylate oligomer is most preferable from the viewpoint of excellent flexibility and adhesive force of a cured product and excellent balance of other physical properties required as an adhesive for optical substrates.
상기 (메타)아크릴레이트 모노머(B-2)로서는 단관능 (메타)아크릴레이트 모노머, 또는 다관능 (메타)아크릴레이트 모노머 또는 이들의 혼합물을 들 수 있다.Examples of the (meth) acrylate monomer (B-2) include monofunctional (meth) acrylate monomers, polyfunctional (meth) acrylate monomers, and mixtures thereof.
상기 광중합개시제(C)는 흡수 파장이 360 ~ 440 nm인 것으로, 특별히 한정은 되지 않고, 공지의 라디칼중합 개시제 및 양이온 중합 개시제 등이 사용될 수 있다. 구체적으로, 비스(2,4,6-트리메틸벤조일)-페닐포스핀옥사이드(Irgacure 819:BASF사제), 2,4,6-트리메틸벤조일-디페닐-포스핀옥사이드(Irgacure TPO:BASF사제, 에틸(2,4,6-트리메틸벤조일)페닐 포스피네이트(Irgacure TPO-L:BASF사제)을 사용할 수 있다. The photopolymerization initiator (C) has an absorption wavelength of 360 to 440 nm and is not particularly limited, and known radical polymerization initiators and cation polymerization initiators can be used. Specifically, a mixture of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure 819, manufactured by BASF), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Irgacure TPO (2,4,6-trimethylbenzoyl) phenylphosphinate (Irgacure TPO-L: manufactured by BASF) can be used.
아울러, 상기 광중합개시제(C)는 광중합성 화합물 100 중량부에 대해 0.01 ~ 5 중량부를 포함하는 것이 바람직하다. 광중합개시제가 0.01 중량부 미만인 경우 차광 영역에 위치하는 수지 조성물을 충분히 경화시킬 수 없고, 5 중량부 초과인 경우 경화물에 황변이 발생하거나 광중합개시제를 자외선 경화형 수지에 충분히 용해시키기에 한계가 있기에 상기 범위 내에서 사용하는 것이 좋다.In addition, the photopolymerization initiator (C) preferably includes 0.01 to 5 parts by weight based on 100 parts by weight of the photopolymerizable compound. When the amount of the photopolymerization initiator is less than 0.01 part by weight, the resin composition located in the light-shielding region can not be sufficiently cured. When the amount of the photopolymerization initiator is more than 5 parts by weight, yellowing occurs in the cured product or there is a limit in sufficiently dissolving the photopolymerization initiator in the ultraviolet- It is recommended to use it within the range.
상기 무기형광체(D)는 유기형광체가 수지 조성물 내에 과포화되어 있거나 수지 조성물의 보관 온도가 낮은 경우에 발생할 수 있는 유기형광체가 결정화되어 석출되는 문제를 개선하여, 유기형광체만을 사용한 경우와 대비하여 경화 성능을 더욱 향상시킬 수 있는 장점이 있다.The inorganic phosphor (D) improves the problem of crystallization and precipitation of the organic phosphor which may occur when the organic phosphor is supersaturated in the resin composition or when the storage temperature of the resin composition is low, Can be further improved.
이때 본 발명에서 사용하는 무기형광체는 365 nm 파장을 흡수하였을 때 370 ~ 440 nm 범위에서 발광하는 것으로, 무기결정 형광체 또는 QD(Quantum Dot) 를 사용할 수 있다.At this time, the inorganic phosphor used in the present invention emits light in a wavelength range of 370 to 440 nm when absorbing a wavelength of 365 nm, and an inorganic crystal fluorescent material or a QD (Quantum Dot) can be used.
무기결정 형광체는 고체 결정의 무기형광체로, 순수한 결정 그대로 발광하는 순수형과 활성화제로 불리는 미량의 불순물 첨가로 발광하는 활성화형이 있다. 순수형에는 대표적으로 전이금속이온의 염과 전이금속의 착이온염이 있으며, 활성화형은 활성화제의 종류로 분류하였을 때 격자 결함, 전이금속이온 이외의 중금속 이온 또는 원자, 전이금속이온, 전이금속의 착이온이 있다.The inorganic crystal phosphor is an inorganic phosphor of a solid crystal. It has a pure type which emits light as pure crystals and an activated type which emits light by addition of a trace amount of impurities called an activator. In pure form, there are typically transition metal ion salts and complex ionic salts of transition metals. Activated forms are classified into lattice defects, heavy metal ions or atoms other than transition metal ions, transition metal ions, transition metals Of complex ions.
본 발명에서 사용하는 무기결정 형광체는 365 nm 파장을 흡수하였을 때 370 ~ 440 nm 범위에서 발광하는 것이라면 특별히 제한되지 않는다. 바람직한 일 구현예로서, 청색-발광 무기결정 형광체에는 ZnO, (Sr, Mg, Ca)10(PO4)6Cl2:Eu2 +, BaMgAl10O17:Eu2+, BaMg2Al16O27:Eu2 +, 및 (Sr,Ba)Al2O4:Eu2 + 로 이루어진 군으로부터 선택된 1종 이상을 들 수 있다.The inorganic crystal phosphor used in the present invention is not particularly limited as long as it emits light in a wavelength range of 370 to 440 nm when it absorbs a wavelength of 365 nm. In a preferred embodiment, the blue-light-emitting inorganic fluorescent substance crystal is ZnO, (Sr, Mg, Ca ) 10 (PO 4) 6 Cl 2: Eu 2 +, BaMgAl 10 O 17: Eu 2+, BaMg 2 Al 16 O 27 : there may be mentioned at least one selected from the group consisting of Eu 2 +: Eu 2 +, and (Sr, Ba) Al 2 O 4.
또한, 바람직한 다른 구현예로서, QD(Quantum dot)는 양자 제한 효과를 가지는 1 ~ 100 nm의 직경의 반도체 나노 결정을 의미하며, 물질 종류의 변화 없이도 입자의 크기를 조절하여 원하는 파장의 발광을 얻을 수 있다. 광 발광 효율이 높고 발광 파장의 변조가 용이할 뿐만 아니라 기존 발광체보다 색 순도, 광 안정성 등이 높다는 장점이 있어 종래의 무기 벌크 형광체 및 유기형광물질을 대체하는 광 에미터로 각광받고 있다. In another preferred embodiment, the QD (quantum dot) means a semiconductor nanocrystal having a diameter of 1 to 100 nm, which has a quantum confinement effect. By controlling the particle size without changing the kind of the material, . Has high light emitting efficiency and easy modulation of emission wavelength, and is superior in color purity and optical stability to existing light emitting bodies. Therefore, it is widely regarded as an optical emitter replacing conventional inorganic bulk fluorescent substance and organic type mineral.
아울러, QD(Quantum dot)는 II-VI족, I-Ⅲ-VI족 또는 Ⅲ-V족의 나노 반도체 화합물을 포함한 것일 수 있고, 단일 구조 또는 코어/쉘 구조를 가질 수 있다. 바람직하게, QD는 중심에 빛을 내는 코어 성분이 있고, 그 표면에 보호를 위해 쉘이 둘러싸고 있는 코어/쉘 구조를 가지며, 쉘 표면에는 용매에 분산을 위한 리간드 성분이 둘러싸고 있다.In addition, the QD (quantum dot) may include a nano semiconductor compound of group II-VI, I-III-VI, or III-V, and may have a single structure or a core / shell structure. Preferably, the QD has a core-luminescent core component with a core / shell structure surrounding the shell for protection, and the shell surface surrounds a ligand component for dispersion in the solvent.
또한, QD(Quantum dot)는 화학적 습식공정 또는 기상법에 의해 합성될 수 있는데, 이 중 화학식 습식공정은 유기 용매에 전구체 물질을 넣고 입자들을 성장시키는 방법으로, 화학적 습식방법에 의한 양자점의 합성방법은 종래에 알려진 기술을 이용하여 합성할 수 있다.The QD (Quantum dot) can be synthesized by a chemical wet process or a vapor phase process. In the chemical wet process, a precursor material is added to an organic solvent to grow particles, and a method of synthesizing a quantum dot by a chemical wet process Can be synthesized using a conventionally known technique.
본 발명에서 사용하는 QD(Quantum dot)는 365 nm 파장을 흡수하였을 때 370 ~ 440 nm 범위에서 발광하는 것이라면 사용할 수 있다. 예를 들면, 청색-발광 QD(Quantum dot)로서는 Cd계 II-VI족 QD(예로서, CdZnS, CdZnSSe, CdZnSe, CdS, CdSe), 비-Cd계 II-VI족 QD(예로서, ZnSe, ZnTe, ZnS, HgS), 또는 비-Cd계 -V족 QD(예로서, InP, InGaP, InZnP, GaN, GaAs, GaP)을 사용할 수 있다. The QD (Quantum dot) used in the present invention can be used as long as it emits light in the range of 370 to 440 nm when absorbing a wavelength of 365 nm. For example, a blue-emitting QD (quantum dot) may be a Cd-based II-VI QD (e.g., CdZnS, CdZnSSe, CdZnSe, CdS, CdSe) (For example, InP, InGaP, InZnP, GaN, GaAs, GaP) can be used.
또한, 무기형광체는 광중합성 화합물 100 중량부에 대해 0.001 ~ 0.1 중량부를 포함하는 것이 바람직하다. 무기형광체가 0.001 중량부 미만인 경우 차광 영역에 위치하는 수지 조성물을 충분히 경화시킬 수 없고, 0.1 중량부 초과인 경우 무기형광체를 자외선 경화형 수지에 충분히 분산시키기에 한계가 있으며 또한 경화물의 투명성을 확보하기 위해서는 상기 범위 내에서 사용하는 것이 좋다.The inorganic phosphor preferably contains 0.001 to 0.1 part by weight based on 100 parts by weight of the photopolymerizable compound. When the amount of the inorganic fluorescent substance is less than 0.001 part by weight, the resin composition located in the light shielding region can not be sufficiently cured. When the inorganic fluorescent substance is more than 0.1 part by weight, there is a limit to sufficiently dispersing the inorganic fluorescent substance in the ultraviolet curable resin. In order to secure transparency of the cured product It is preferable to use it within the above range.
또한, 상기 기술한 자외선 경화형 수지 조성물은, 필요하다면 본 발명의 수지 조성물에 가소제, 점착부여제, 실란커플링제, 광안정제, 산화방지제, 분산제, 광확산제, 및 소포제로 이루어진 군으로부터 선택된 1종 이상의 첨가제를 임의로 첨가하여 사용하는 것이 가능하다.The ultraviolet ray curable resin composition described above may further contain one kind selected from the group consisting of a plasticizer, a tackifier, a silane coupling agent, a light stabilizer, an antioxidant, a dispersant, a light diffusing agent, It is possible to add the above additives optionally.
본 발명에 따른 자외선 경화형 수지 조성물은 메탈 할라이드 램프를 광원으로 하였을 때뿐만 아니라 UV-LED를 광원으로 한 경우에도 경화성능이 우수하여, 차광부가 존재하는 광학 기재에 대해 경화 공정의 추가 없이 자외선의 조사만으로도 차광 영역에 위치하는 수지 조성물이 충분히 경화되어 접착제로서 유용하게 사용될 수 있다. 따라서, 본 발명에 따른 광경화성 수지 조성물을 이용하여 접합한 차광부를 갖는 광학 기재는 신뢰성이 더욱 우수해 진다.The ultraviolet ray curable resin composition according to the present invention is excellent in curing performance not only when a metal halide lamp is used as a light source but also when a UV-LED is used as a light source, The resin composition located in the light-shielding region is sufficiently cured and can be usefully used as an adhesive. Therefore, the optical substrate having the light-shielding portion bonded by using the photo-curable resin composition according to the present invention is more reliable.
아울러, 본 명세서에 있어서, 광학 기재는 표면에 차광부를 갖지 않는 광학 기재와, 표면에 차광부를 갖는 광학 기재 모두를 포함한다. 표면에 차광부를 갖는 광학 기재에서 차광부는 광학 기재의 한쪽 면 또는 양면에 일부 또는 전부 형성될 수 있다. 또한, 광학 기재를 접합했을 때에 수지 조성물의 자외선 경화가 가능하도록 적어도 접합된 광학 기재의 일부는 차광부가 형성되어 있지 않은 노광부가 있는 것이 바람직하다.Further, in the present specification, the optical substrate includes both an optical substrate having no light-shielding portion on its surface and an optical substrate having a light-shielding portion on its surface. In the optical substrate having the light-shielding portion on its surface, the light-shielding portion may be formed on one or both surfaces of the optical substrate. It is also preferable that at least a part of the optical substrate bonded in order to enable ultraviolet curing of the resin composition when the optical substrate is bonded is an exposure section in which no shielding section is formed.
또한, 광학 기재로서는 투명판, 시트, 터치 패널 및 표시제 등을 예시할 수 있으며, 패널의 표면의 재질로서는 유리, PET, PC, PMMA, PC와 PMMA의 복합체, COC 및 COP가 예시된다.Examples of the optical substrate include a transparent plate, a sheet, a touch panel, a display, and the like. Examples of materials for the surface of the panel include glass, PET, PC, PMMA, complex of PC and PMMA, COC and COP.
또한, 본 발명의 자외선 경화형 접착제를 이용하여 얻어지는 상기 표시 패널 등의 광학 부재는 텔레비전, 소형 게임기, 휴대전화 및 퍼스널 컴퓨터 등의 전자 기기에 장착될 수 있다.The optical member such as the display panel obtained by using the ultraviolet curable adhesive of the present invention can be mounted on an electronic apparatus such as a television, a small game machine, a cellular phone, and a personal computer.
이하, 본 발명을 실시예를 통하여 더욱 상세히 설명한다. 그러나 이들 실시예는 본 발명을 예시하기 위한 것으로, 본 발명의 범위가 이들에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.
실시예Example 1 ~ 2 및 1 to 2 and 비교예Comparative Example 1 ~ 5 1-5
[표 1]에 나타내는 조성으로 이루어지는 광경화성 수지 조성물을 혼합하여 광경화성 접착제를 제조하였다. The photo-curable resin composition having the composition shown in Table 1 was mixed to prepare a photo-curable adhesive.
2) 1,4-디(5-페닐-2-옥사졸릴)벤젠, 흡수 파장 360nm, 형광 파장 419nm
3) 2-(4-비페닐)-5-(4-tert-부틸페닐)-1,3,4-옥사디아졸, 흡수 파장 305nm, 형광 파장 364nm
4) 4,4'-비스(9H-카르바졸-9-일)비페닐, 흡수 파장 318nm, 형광 파장 369nm
5) 이소보닐 아크릴레이트
6) 이소데실 아크릴레이트
7) 비스(2,4,6-트리메틸벤조일)-페닐포스핀옥사이드
8) 청색-발광 QD(ZnSe가 코어 구조이고 ZnS가 쉘 구조인 'ZnSe/ZnS'로서, 365nm 파장을 흡수하였을 때 형광 파장 427nm임)1) 4,4'-bis (2-methoxystyryl) biphenyl, absorption wavelength 361 nm, fluorescence wavelength 411 nm
2) 1,4-di (5-phenyl-2-oxazolyl) benzene, absorption wavelength 360 nm, fluorescence wavelength 419 nm
3) 2- (4-biphenyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole, absorption wavelength 305 nm, fluorescence wavelength 364 nm
4) 4,4'-bis (9H-carbazol-9-yl) biphenyl, absorption wavelength 318 nm, fluorescence wavelength 369 nm
5) Isobornyl acrylate
6) Isodecyl acrylate
7) Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide
8) Blue-emitting QD ('ZnSe / ZnS' in which ZnSe has a core structure and ZnS is a shell structure and has a fluorescence wavelength of 427 nm when it absorbs a wavelength of 365 nm)
실험예Experimental Example : 물성 측정: Measurement of physical properties
이상의 방법으로 얻어진 광경화성 접착제를 이용하여 이하의 물성을 측정하여 그 결과를 하기 [표 2]에 나타내었다.The following properties were measured using the photo-curable adhesive obtained by the above method, and the results are shown in Table 2 below.
<< 차광부의Miners 경화길이 1> Hardening length 1>
도 1과 같이 유리판(75mmⅹ25mmⅹ1mm)의 한쪽 면의 전면에 흑색 인쇄 처리를 실시하여 자외선 차광부를 형성한 기판과, 유리판의 한쪽 면의 절반에 흑색 인쇄 처리를 실시하여 자외선 차광부를 형성한 기판을 준비했다. 이들 기판의 자외선 차광부가 형성된 면 위로 두께 200㎛의 스페이서를 배치하고, 각 실시예 및 비교예에서 얻어진 자외선 경화형 접착제를 도포했다. 그 후, 각 기판에서 자외선 차광부가 형성된 면이 서로 마주 보도록 2장의 기판을 접합했다.As shown in Fig. 1, a substrate on which an ultraviolet light shielding portion was formed by performing black printing on the entire surface of one side of a glass plate (75 mm x 25 mm x 1 mm) and a substrate on which an ultraviolet light shielding portion was formed by performing black printing processing on half of one side of the glass plate was prepared . A spacer having a thickness of 200 mu m was placed on the surface of the substrate on which the ultraviolet light shielding portion was formed, and the ultraviolet curable adhesive obtained in each of the Examples and Comparative Examples was applied. Thereafter, the two substrates were joined so that the surfaces of the respective substrates, on which the ultraviolet light shielding portions were formed, faced each other.
이어서, 한쪽 면의 절반에 흑색 인쇄 처리를 실시한 기판측으로 자외선을 전면에 조사했다. 이 때 광원으로는 메탈 할라이드 램프(UNILAM사제, UV 메탈(Fe) 램프, 조도 150mW/㎠)를 이용하였으며 적산광량은 3,000mJ/㎠이었다. 그 후, 도 2과 같이 흑색 인쇄 처리부의 끝으로부터 접착제의 경화가 진행된 거리(차광부 경화 거리1)를 측정했다.Subsequently, ultraviolet rays were irradiated to the entire surface of the substrate subjected to the black printing process on one half of the surface. In this case, a metal halide lamp (UNILAM, UV metal (Fe) lamp, illuminance of 150 mW / cm 2) was used as a light source, and the accumulated light quantity was 3,000 mJ / cm 2. Thereafter, as shown in Fig. 2, the distance (the light shielding portion curing distance 1) at which the curing of the adhesive proceeded from the end of the black printing processing portion was measured.
각 실시예 및 비교예의 차광부 경화 거리의 측정 결과를 [표 2]에 나타낸다.Table 2 shows the measurement results of the curing distance of the light-shielding portion in each of the examples and comparative examples.
<< 차광부의Miners 경화길이 2> Hardening length 2>
도 1과 같이 유리판(75mmⅹ25mmⅹ1mm)의 한쪽 면의 전면에 흑색 인쇄 처리를 실시하여 자외선 차광부를 형성한 기판과, 유리판의 한쪽 면의 절반에 흑색 인쇄 처리를 실시하여 자외선 차광부를 형성한 기판을 준비하였다. 이들 기판의 자외선 차광부가 형성된 면 위로 두께 200㎛의 스페이서를 배치하고, 각 실시예 및 비교예에서 얻어진 자외선 경화형 접착제를 도포했다. 그 후, 각 기판에서 자외선 차광부가 형성된 면이 서로 마주 보도록 2장의 기판을 접합했다.As shown in Fig. 1, a substrate on which an ultraviolet light shielding portion was formed by performing black printing on the entire surface of one side of a glass plate (75 mm × 25 mm × 1 mm) and a substrate on which an ultraviolet light shielding portion was formed by performing black printing processing on half of one side of the glass plate was prepared . A spacer having a thickness of 200 mu m was placed on the surface of the substrate on which the ultraviolet light shielding portion was formed, and the ultraviolet curable adhesive obtained in each of the Examples and Comparative Examples was applied. Thereafter, the two substrates were joined so that the surfaces of the respective substrates, on which the ultraviolet light shielding portions were formed, faced each other.
이어서, 한쪽 면의 절반에 흑색 인쇄 처리를 실시한 기판측으로 자외선을 전면에 조사했다. 이 때 광원으로는 UV-LED(주은유브이텍사제, 365nm 파장, 조도 500mW/㎠)를 이용하였으며 적산광량은 3,000mJ/㎠이었다. 그 후, 도 2과 같이 흑색 인쇄 처리부의 끝으로부터 접착제의 경화가 진행된 거리(차광부 경화 거리2)를 측정했다.Subsequently, ultraviolet rays were irradiated to the entire surface of the substrate subjected to the black printing process on one half of the surface. At this time, a UV-LED (365 nm wavelength, illuminance 500 mW / cm 2 manufactured by Metaphor Vitech Co., Ltd.) was used as a light source, and the accumulated light amount was 3,000 mJ / cm 2. Thereafter, as shown in Fig. 2, the distance (the light shielding portion curing distance 2) at which the curing of the adhesive proceeded from the end of the black printing processing portion was measured.
각 실시예 및 비교예의 차광부 경화 거리의 측정 결과를 [표 2]에 나타낸다.Table 2 shows the measurement results of the curing distance of the light-shielding portion in each of the examples and comparative examples.
<투과율><Transmittance>
두께 50㎛의 경박 이형필름과 유리판(75mm25mmⅹ1mm)을 준비하였다. 그 중 경박 이형필름면 위로 두께 200㎛의 스페이서를 배치하고, 각 실시예 및 비교예에서 얻어진 자외선 경화형 접착제를 도포했다. 그 후, 경박 이형필름면과 유리판이 서로 마주 보도록 접합했다. 이어서 유리판측으로 UV-LED(주은유브이텍사제, 365nm 파장, 조도 500mW/㎠)을 이용하여 적산광량 3,000mJ/㎠의 자외선을 조사했다. 그 후, 경박 이형필름을 박리함으로써 투과율 측정용 시편을 제작했다. 각 시편의 투과율에 대해 UV-Vis 분광광도계(제품명UV-2600, SHIMADZU제)를 이용하여 400~800㎚의 범위의 투과율을 측정했다. 각 실시예 및 각 비교예의 경화시편에 대한 400㎚에서의 투과율 측정 결과와 400 ~ 800nm에서의 투과율 평균값을 [표 2]에 나타낸다.A thin release film having a thickness of 50 탆 and a glass plate (75 mm 25 mm ⅹ 1 mm) were prepared. Among them, a spacer with a thickness of 200 mu m was placed on the surface of the release film, and the ultraviolet curable adhesive obtained in each of the Examples and Comparative Examples was applied. Thereafter, the thin release film side and the glass plate were bonded so as to face each other. Subsequently, ultraviolet light of 3,000 mJ / cm 2 was irradiated onto the glass plate side using UV-LED (365 nm wavelength, illuminance 500 mW / cm 2 manufactured by Metaphor Vitech Co., Ltd.). Thereafter, a release film was peeled off to prepare a specimen for measuring transmittance. The transmittance of each specimen was measured in a range of 400 to 800 nm using a UV-Vis spectrophotometer (product name: UV-2600, manufactured by SHIMADZU). Table 2 shows the measurement results of the transmittance at 400 nm and the transmittance at 400 to 800 nm for the cured specimens of the respective examples and comparative examples.
상기 [표 2]의 결과를 살펴보면, 비교예 4 및 5의 경우, 비페닐계 화합물로서 흡수 파장이 340 ~ 420nm 범위이고, 형광 파장이 360 ~ 440nm 범위인 유기형광체 또는 옥사졸계 화합물로서 흡수 파장이 340 ~ 420nm 범위이고, 형광 파장이 360 ~ 440nm 범위인 유기형광체를 사용하는 경우, 유기형광체를 포함하지 않은 비교예 1보다 차광부 경화 성능이 매우 향상된 것을 알 수 있었다. 또한, 광원으로 메탈 할라이드 램프를 사용하거나 UV-LED를 사용한 경우 모두 경화성이 우수함을 확인할 수 있었다.As a result of the results of Table 2, in the case of Comparative Examples 4 and 5, as the biphenyl-based compound, an organic fluorescent substance or an oxazole-based compound having an absorption wavelength in the range of 340 to 420 nm and a fluorescent wavelength in the range of 360 to 440 nm It was found that the curing performance of the light-shielding portion was significantly improved as compared with Comparative Example 1, which did not include the organic phosphor, in the case of using an organic phosphor having a wavelength in the range of 340 to 420 nm and a fluorescent wavelength in the range of 360 to 440 nm. In addition, it was confirmed that both the use of a metal halide lamp as a light source and the use of a UV-LED exhibit excellent curability.
아울러, 시인성이 양호한 광학 부재를 얻기 위해 요구되는 경화 시편의 투과율은 400 ~ 800nm 파장 영역에서 80% 이상인 것이 바람직한데, 비교예 4 ~ 5 의 경우 광학 부재에서 요구되는 투과율을 만족시킴을 알 수 있다.In addition, it is preferable that the transmittance of the cured specimen required for obtaining an optical member having good visibility is 80% or more in a wavelength range of 400 to 800 nm, and in Comparative Examples 4 to 5, the transmittance required in the optical member is satisfied .
그러나, 본 발명에 따라 유기형광체와 무기형광체를 모두 사용한 실시예 1, 2의 경우에는 광원으로 메탈 할라이드 램프를 사용하거나 UV-LED를 사용한 경우 모두 비교예 4 ~ 5 보다 차광부 경화 성능이 더욱 우수함을 확인할 수 있다.However, in Examples 1 and 2 using both the organic fluorescent material and the inorganic fluorescent material according to the present invention, a metal halide lamp as a light source or a UV-LED was used, can confirm.
비교예 2 및 비교예 3 의 경우 투과율은 광학 부재에서 요구되는 수준을 만족시키고, 차광부의 경화 길이의 경우 광원으로 메탈 할라이드 램프를 사용하였을 때에는 1.5mm까지 가능하였으나, 광원으로 UV-LED를 사용하였을 때에는 최대 1mm에 불과하여 유기형광체를 함유하지 않은 비교예 1과 비교하였을 때 차광부 경화 효과가 전혀 없거나 미미한 수준임을 알 수 있다.In the case of Comparative Example 2 and Comparative Example 3, the transmittance satisfied the required level in the optical member, and when the metal halide lamp was used as the light source in the case of the hardening length of the light shielding portion, the light transmittance was 1.5 mm or less. The maximum hardness of the light shielding portion is only 1 mm or less, which means that the hardening effect of the light shielding portion is completely or negligible as compared with Comparative Example 1 which does not contain the organic phosphor.
이와 같은 결과를 통해, 본 발명에 따라 광중합성 화합물에 대해 비페닐계 화합물로서 흡수 파장이 340 ~ 420nm 범위이고, 형광 파장이 360 ~ 440nm 범위인 유기형광체 또는 옥사졸계 화합물로서 흡수 파장이 340 ~ 420nm 범위이고, 형광 파장이 360 ~ 440nm 범위인 유기형광체와 흡수 파장이 360 ~ 440nm인 광중합개시제, 및 365 nm 파장을 흡수하였을 때 370 ~ 440 nm 범위에서 발광하는 무기형광체를 소정의 비율로 혼합할 경우, 차광부가 존재하는 광학 기재에 대해 경화 공정의 추가 없이 자외선의 조사만으로도 차광 영역에 위치하는 수지 조성물을 충분히 경화시켜 신뢰성이 우수한 광학 부재를 제공할 수 있음을 알 수 있다.According to the present invention, as the biphenyl-based compound, an organic phosphor or an oxazole-based compound having an absorption wavelength in the range of 340 to 420 nm and a fluorescent wavelength in the range of 360 to 440 nm, , An organic phosphor having a fluorescence wavelength in the range of 360 to 440 nm, a photopolymerization initiator having an absorption wavelength of 360 to 440 nm, and an inorganic phosphor emitting light in a wavelength range of 370 to 440 nm when absorbed at a wavelength of 365 nm are mixed at a predetermined ratio , It can be seen that the resin composition located in the light-shielding region can be sufficiently cured by irradiation of ultraviolet light without adding a curing process to the optical substrate in which the light-shielding portion is present, thereby providing an optical member with excellent reliability.
<도면의 주요 부분에 대한 부호의 설명>Description of the Related Art
10: 유리판10: Glass plate
20: 자외선 차광부 20: Ultraviolet light shielding part
30: 자외선30: ultraviolet ray
40: 자외선 경화형 수지 조성물40: UV curable resin composition
50: 경화된 자외선 경화형 수지 조성물50: Cured UV-curable resin composition
60: 차광부 경화 거리60: Light shielding hardening distance
Claims (13)
(B) 광중합성 화합물;
(C) 광중합 개시제; 및
(D) 365 nm 파장을 흡수하였을 때 370 ~ 440 nm 범위에서 발광하는 무기형광체;
를 포함하는 것을 특징으로 하는 자외선 경화형 수지 조성물.
(A) an organic phosphor having an absorption wavelength in the range of 340 to 420 nm and a fluorescence wavelength in the range of 360 to 440 nm as the biphenyl-based compound, or an organic compound having an absorption wavelength in the range of 340 to 420 nm and a fluorescent wavelength in the range of 360 to 440 nm A phosphor;
(B) a photopolymerizable compound;
(C) a photopolymerization initiator; And
(D) an inorganic fluorescent material which emits light in a wavelength range of 370 to 440 nm when absorbed at a wavelength of 365 nm;
And an ultraviolet curable resin composition.
상기 유기형광체(A)는 자외선을 흡수하여 발광하는 하기 화학식 1의 구조를 갖는 비페닐계 화합물 또는 하기 화학식 2의 구조를 갖는 옥사졸계 화합물인 것을 특징으로 하는 자외선 경화형 수지 조성물.
[화학식 1]
(상기 식에서, R1은 각각 독립적으로 수소, 직쇄상 또는 분기쇄상의 탄소수 1 내지 6의 알킬기 또는 알케닐기 또는 알콕시기, 페닐기, 카르바졸릴기를 나타낸다.)
[화학식 2]
(상기 식에서, R4는 수소, 직쇄상 또는 분기쇄상의 탄소수 1 내지6의 알킬기를 나타내고, R5는 수소, 직쇄상 또는 분기쇄상의 탄소수 1 내지6의 알킬기, 페닐기, 디메틸아민기를 나타내고, R6은 수소, 직쇄상 또는 분기쇄상의 탄소수 1 내지6의 알킬기, 탄소수 6 내지8의 아릴기, 비페닐기, 나프틸기를 나타내고, n은 1 내지 3의 정수를 나타낸다.)
The method according to claim 1,
Wherein the organic fluorescent material (A) is a biphenyl-based compound having a structure of the following formula (1) or an oxazole-based compound having a structure of the following formula (2), which absorbs ultraviolet light to emit light.
[Chemical Formula 1]
(Wherein each R 1 independently represents hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms or an alkenyl group or an alkoxy group, a phenyl group, or a carbazolyl group).
(2)
(Wherein, R 4 is hydrogen, an alkyl group having 1 to 6 carbon atoms of straight or branched chain, R 5 represents a hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms in the chain, a phenyl group, a dimethyl amine, R 6 represents hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 8 carbon atoms, a biphenyl group or a naphthyl group, and n represents an integer of 1 to 3.)
[화학식1-1]
(상기 식에서 R2는 수소, 직쇄상 또는 분기쇄상의 탄소수 1 내지6의 알킬기 또는 알케닐기 또는 알콕시기, 디페닐아민기, 디(4-메틸페닐)아민기, 카르바졸릴기를 나타낸다.)
[화학식 1-2]
(상기 식에서 R3는 수소, 직쇄상 또는 분기쇄상의 탄소수 1 내지6의 알킬기를 나타낸다.)
The ultraviolet-curing resin composition according to claim 2, wherein the phenyl group in Formula 1 is represented by Formula 1-1, and the carbazolyl group in Formula 1 is represented by Formula 1-2.
[Formula 1-1]
(Wherein R 2 represents hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms or an alkenyl group or alkoxy group, a diphenylamine group, a di (4-methylphenyl) amine group or a carbazolyl group.
[Formula 1-2]
(In the above formula, R 3 represents hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms.)
[화학식 1a]
The ultraviolet ray curable resin composition according to claim 2, wherein the formula (1) is 4,4'-bis (2-methoxystyryl) biphenyl represented by the following formula (1a).
[Formula 1a]
[화학식 2a]
The ultraviolet ray curable resin composition according to claim 2, wherein the formula (2) is 1,4-di (5-phenyl-2-oxazolyl) benzene having the following formula (2a).
(2a)
The ultraviolet-curing resin composition according to claim 1, wherein the photopolymerizable compound (B) comprises a (meth) acrylate oligomer (B-1) and a (meth) acrylate monomer (B-2).
(Meth) acrylate oligomer (B-1) of the photopolymerizable compound (B) is a urethane (meth) acrylate oligomer or a polyester (Meth) acrylate oligomer having a skeleton, or an acrylic (meth) acrylate oligomer.
The composition according to claim 6, wherein the (meth) acrylate monomer (B-2) of the photopolymerizable compound (B) is a monofunctional (meth) acrylate monomer or a polyfunctional (meth) acrylate monomer, Wherein the ultraviolet curable resin composition is a thermosetting resin composition.
The ultraviolet-curing resin composition according to claim 1, wherein the photopolymerization initiator (C) has an absorption wavelength of 360 to 440 nm.
상기 광중합개시제(C)는 광중합성 화합물 100 중량부에 대해 0.01 ~ 5 중량부를 포함하고,
상기 무기형광체(D)는 광중합성 화합물 100 중량부에 대해 0.001 ~ 0.1 중량부를 포함하는 것을 특징으로 하는 자외선 경화형 수지 조성물.
The organic electroluminescent device according to claim 1, wherein the organic fluorescent material (A) comprises 0.001 to 0.1 part by weight per 100 parts by weight of the photopolymerizable compound,
The photopolymerization initiator (C) comprises 0.01 to 5 parts by weight based on 100 parts by weight of the photopolymerizable compound,
Wherein the inorganic fluorescent substance (D) comprises 0.001 to 0.1 part by weight based on 100 parts by weight of the photopolymerizable compound.
The ultraviolet ray curable resin composition according to claim 1, wherein the inorganic phosphor (D) is an inorganic crystal phosphor or QD (Quantum Dot) which emits light in a wavelength range of 370 to 440 nm when absorbed at a wavelength of 365 nm.
상기 제 1 항 내지 제 11항 중에서 선택된 어느 한 항에 기재된 광경화성 수지 조성물을 이용하여 접합한 후 차광부를 갖는 광학 기재를 통해 광조사하여 경화시켜 얻은 광학 부재.
An optical substrate and an optical substrate having the light-
An optical member obtained by joining using the photo-curing resin composition according to any one of claims 1 to 11 and then irradiating light through an optical substrate having a light-shielding portion and curing.
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| WO2020242850A1 (en) * | 2019-05-24 | 2020-12-03 | Applied Materials, Inc. | Color conversion layers for light-emitting devices |
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