CN111372952B - Photopolymerization initiator, sealing agent for display element, vertical conduction material, display element, and compound - Google Patents
Photopolymerization initiator, sealing agent for display element, vertical conduction material, display element, and compound Download PDFInfo
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- CN111372952B CN111372952B CN201980005877.0A CN201980005877A CN111372952B CN 111372952 B CN111372952 B CN 111372952B CN 201980005877 A CN201980005877 A CN 201980005877A CN 111372952 B CN111372952 B CN 111372952B
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- meth
- display element
- acrylate
- liquid crystal
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 105
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 51
- 239000003999 initiator Substances 0.000 title claims abstract description 45
- 238000007789 sealing Methods 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 title abstract description 9
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 84
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000002835 absorbance Methods 0.000 claims abstract description 12
- 125000003277 amino group Chemical group 0.000 claims abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical group C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000565 sealant Substances 0.000 claims description 65
- 229920005989 resin Polymers 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- 239000010419 fine particle Substances 0.000 claims description 13
- 239000004020 conductor Substances 0.000 claims description 4
- 238000011109 contamination Methods 0.000 abstract description 21
- 230000009257 reactivity Effects 0.000 abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 102
- 239000004593 Epoxy Substances 0.000 description 70
- -1 4- (N, N-dimethylamino) benzoyloxy group Chemical group 0.000 description 50
- 239000000126 substance Substances 0.000 description 27
- 239000000047 product Substances 0.000 description 23
- 239000000758 substrate Substances 0.000 description 20
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 13
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 11
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 11
- 150000002148 esters Chemical class 0.000 description 11
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- 229910052719 titanium Inorganic materials 0.000 description 11
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- 230000000052 comparative effect Effects 0.000 description 9
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- 238000003786 synthesis reaction Methods 0.000 description 9
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 8
- 239000006087 Silane Coupling Agent Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 150000007524 organic acids Chemical class 0.000 description 8
- 238000001723 curing Methods 0.000 description 7
- 238000000016 photochemical curing Methods 0.000 description 7
- 239000003505 polymerization initiator Substances 0.000 description 7
- 238000012719 thermal polymerization Methods 0.000 description 7
- 229920001187 thermosetting polymer Polymers 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 5
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
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- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
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- 238000013461 design Methods 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 125000006850 spacer group Chemical group 0.000 description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
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- 125000004663 dialkyl amino group Chemical group 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
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- 150000003254 radicals Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- ANHLDZMOXDYFMQ-UHFFFAOYSA-N 2-hydroxythioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(O)=CC=C3SC2=C1 ANHLDZMOXDYFMQ-UHFFFAOYSA-N 0.000 description 2
- UDXXYUDJOHIIDZ-UHFFFAOYSA-N 2-phosphonooxyethyl prop-2-enoate Chemical compound OP(O)(=O)OCCOC(=O)C=C UDXXYUDJOHIIDZ-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- UGJDXRVQCYBXAJ-UHFFFAOYSA-N 4-(dimethylamino)benzoyl chloride Chemical compound CN(C)C1=CC=C(C(Cl)=O)C=C1 UGJDXRVQCYBXAJ-UHFFFAOYSA-N 0.000 description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- YPCHGLDQZXOZFW-UHFFFAOYSA-N [2-[[4-methyl-3-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]carbonylamino]phenyl]carbamoyloxymethyl]-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound CC1=CC=C(NC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C)C=C1NC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C YPCHGLDQZXOZFW-UHFFFAOYSA-N 0.000 description 2
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- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
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- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
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- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 2
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- 229920000233 poly(alkylene oxides) Polymers 0.000 description 2
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
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- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
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- ILBBNQMSDGAAPF-UHFFFAOYSA-N 1-(6-hydroxy-6-methylcyclohexa-2,4-dien-1-yl)propan-1-one Chemical compound CCC(=O)C1C=CC=CC1(C)O ILBBNQMSDGAAPF-UHFFFAOYSA-N 0.000 description 1
- CSCSROFYRUZJJH-UHFFFAOYSA-N 1-methoxyethane-1,2-diol Chemical compound COC(O)CO CSCSROFYRUZJJH-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
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- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- RUVNKAUVVBCURD-UHFFFAOYSA-N 2-[[4-[2-[4-(oxiran-2-ylmethoxy)-3-prop-2-enylphenyl]propan-2-yl]-2-prop-2-enylphenoxy]methyl]oxirane Chemical compound C=1C=C(OCC2OC2)C(CC=C)=CC=1C(C)(C)C(C=C1CC=C)=CC=C1OCC1CO1 RUVNKAUVVBCURD-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- VNGJZOHDGNDTPE-UHFFFAOYSA-N 3,5-bis(dimethylamino)benzoyl chloride Chemical compound CN(C=1C=C(C(=O)Cl)C=C(C1)N(C)C)C VNGJZOHDGNDTPE-UHFFFAOYSA-N 0.000 description 1
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
- C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
- C07D335/12—Thioxanthenes
- C07D335/14—Thioxanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
- C07D335/16—Oxygen atoms, e.g. thioxanthones
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
Abstract
The purpose of the present invention is to provide a photopolymerization initiator that has excellent reactivity with light having a long wavelength. Further, an object of the present invention is to provide a sealing agent for a display element, which contains the photopolymerization initiator, has excellent curability with respect to light having a long wavelength, and has excellent low liquid crystal contamination when used in a liquid crystal display element; and a vertical conduction material and a display element using the sealing agent for a display element. Further, another object of the present invention is to provide a compound constituting the photopolymerization initiator. The photopolymerization initiator is a compound having a thioxanthone group optionally substituted with a hydroxyl group and an amino group, and has an absorbance at a wavelength of 420nm of 0.10 or more when dissolved in acetonitrile to a concentration of 0.1 mg/mL.
Description
Technical Field
The present invention relates to a photopolymerization initiator having excellent reactivity with light having a long wavelength. The present invention also relates to a sealing agent for a display element, which contains the photopolymerization initiator, has excellent curability with respect to light having a long wavelength, and has excellent low liquid crystal contamination when used in a liquid crystal display element; and a vertical conduction material and a display element using the sealing agent for a display element. The present invention also relates to a compound constituting the photopolymerization initiator.
Background
In recent years, as a method for manufacturing a liquid crystal display element such as a liquid crystal display unit, a liquid crystal dropping method called a dropping method using a photo-thermal curable sealing agent as disclosed in patent documents 1 and 2 has been used from the viewpoint of shortening the tact time and optimizing the amount of liquid crystal used.
In the one drop fill process, first, a frame-shaped seal pattern is formed on one of two transparent substrates with electrodes by dispensing. Next, in a state where the sealant is not cured, fine droplets of liquid crystal are dropped onto the entire inner surface of the frame of the transparent substrate, another transparent substrate is immediately bonded, and the sealing portion is irradiated with light such as ultraviolet light to perform precuring. Then, the liquid crystal is heated during annealing to perform main curing, thereby producing a liquid crystal display element. The one-drop fill process is currently the mainstream of a method for manufacturing a liquid crystal display element, and can manufacture a liquid crystal display element with extremely high efficiency if bonding of substrates is performed under reduced pressure.
However, in the modern day in which various mobile devices with liquid crystal panels such as mobile phones and portable game machines are widespread, miniaturization of the devices is the most demanding issue. As a method for downsizing the device, narrowing of the frame of the liquid crystal display portion, for example, an operation of disposing the position of the sealing portion under the black matrix (hereinafter, also referred to as narrow frame design) is performed.
However, in the narrow-frame design, since the sealant is disposed directly below the black matrix, if the one-drop process is performed, light irradiated when photocuring the sealant is blocked, and there is a problem that light cannot reach the inside of the sealant and curing becomes insufficient. If the curing of the sealant is insufficient in this manner, uncured sealant components elute into the liquid crystal, and the curing reaction due to the eluted sealant components proceeds in the liquid crystal, thereby causing a problem of contamination of the liquid crystal.
In addition, although ultraviolet irradiation is generally performed as a method of photocuring a sealant, there is a problem that, particularly in a liquid crystal dropping process, since the sealant is cured after dropping a liquid crystal, the liquid crystal is deteriorated by irradiation with ultraviolet rays. Therefore, in order to prevent deterioration of liquid crystal due to ultraviolet rays, photo-curing is performed using light having a long wavelength in the visible light region via a cut filter or the like. As a method of photocuring a sealant by using light of a long wavelength, a method of using a sensitizer having high sensitivity to light of a long wavelength in combination with a photopolymerization initiator is conceivable. For example, patent documents 3 and 4 disclose photocurable resin compositions in which a photopolymerization initiator and a sensitizer are combined. However, when these photocurable resin compositions are used as a sealing agent for a liquid crystal display element, there is a problem that the total amount of the photopolymerization initiator and the sensitizer becomes large in order to sufficiently perform photocuring by light of a long wavelength, and thus liquid crystal contamination may occur.
Documents of the prior art
Patent literature
Patent document 1: japanese patent laid-open No. 2001-133794
Patent document 2: international publication No. 02/092718
Patent document 3: japanese laid-open patent publication No. 2017-125033
Patent document 4: international publication No. 2017/130594
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide a photopolymerization initiator that has excellent reactivity with light having a long wavelength. Further, an object of the present invention is to provide a sealing agent for a display element, which contains the photopolymerization initiator, has excellent curability with respect to light having a long wavelength, and has excellent low liquid crystal contamination when used in a liquid crystal display element; and a vertical-conduction material and a display element using the sealing agent for a display element. Further, another object of the present invention is to provide a compound constituting the photopolymerization initiator.
Means for solving the problems
The photopolymerization initiator is a compound having a thioxanthone group optionally substituted with a hydroxyl group and an amino group, and has an absorbance at a wavelength of 420nm of 0.10 or more when dissolved in acetonitrile to a concentration of 0.1 mg/mL.
The present invention will be described in detail below.
The inventor finds that: the compound having a thioxanthone group and an amino group, which are optionally substituted with a hydroxyl group, and having a high absorbance at 420nm is excellent in reactivity to light having a long wavelength in the visible light region, and hardly generates a residue which causes liquid crystal contamination after light irradiation. Thus, the present inventors have found that: by using this compound as a photopolymerization initiator, a sealing agent for a display element which is excellent in curability with respect to light having a long wavelength and is excellent in low liquid crystal contamination when used for a liquid crystal display element can be obtained, and the present invention has been completed.
The photopolymerization initiator of the present invention is a compound having a thioxanthone group optionally substituted with a hydroxyl group and an amino group.
The curable resin composition has excellent photocurability even when a small amount of the photopolymerization initiator of the present invention is blended, because the compound having a thioxanthone group optionally substituted with a hydroxyl group and an amino group is a compound showing the absorbance described later. Therefore, when the curable resin composition is used as a sealant for a liquid crystal display element, the liquid crystal display element is excellent in low liquid crystal contamination.
In the photopolymerization initiator of the present invention, the thioxanthone group has the following effects: the dehydrogenation, cleavage, or the like is performed by light irradiation to generate radicals, thereby promoting the polymerization reaction of the polymerizable compound. In the photopolymerization initiator of the invention, the amino group has the following functions: the thioxanthone group exhibits a sensitizing effect by energy transfer or the like by light irradiation.
In the present specification, the "thioxanthone group" refers to a 9-oxo-9H-thioxanthone group.
The amino group is preferably a primary amino group or a dialkylamino group, more preferably a dialkylamino group, and still more preferably a dimethylamino group, from the viewpoint of providing a photopolymerization initiator having more excellent reactivity to light having a long wavelength.
The photopolymerization initiator of the present invention preferably has a 4- (N, N-dialkylamino) benzoyloxy group, and more preferably has a 4- (N, N-dimethylamino) benzoyloxy group as a group containing the dialkylamino group.
The photopolymerization initiator of the present invention preferably has a hydroxyl group, and more preferably has 2 or more hydroxyl groups in 1 molecule, from the viewpoint of low liquid crystal contamination.
The molecular weight of the photopolymerization initiator of the present invention is preferably 200 or more, and more preferably 400 or more, from the viewpoint of low liquid crystal contamination.
The preferable upper limit of the molecular weight of the photopolymerization initiator of the present invention is not particularly limited, but the substantial upper limit is 3 ten thousand.
In the present specification, the "molecular weight" is a molecular weight determined from a structural formula for a compound having a specific molecular structure, but may be expressed by a number average molecular weight for a compound having a wide distribution of polymerization degrees and a compound having no specific modification site. In the present specification, the "number average molecular weight" is a value determined by measuring with Gel Permeation Chromatography (GPC) using tetrahydrofuran as a solvent and converting into polystyrene. Examples of the column used for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko K.K.).
The photopolymerization initiator of the present invention has an absorbance at a wavelength of 420nm of 0.10 or more when dissolved in acetonitrile to give a concentration of 0.1 mg/mL. When the absorbance at a wavelength of 420nm is 0.10 or more, the photopolymerization initiator of the present invention can be suitably used for a sealant for a display element which is cured by light having a long wavelength in the visible light region, and the like.
The absorbance is more preferably 0.15 or more.
The absorbance can be measured by using a spectrophotometer under the condition that the optical path length is 1 cm. Examples of the spectrophotometer include U-3900 (manufactured by Hitachi High-Tech Science Corporation).
Specifically, the photopolymerization initiator of the present invention is preferably a compound represented by the following formula (1-1) or (1-2), and more preferably a compound represented by the following formula (2-1), (2-2) or (2-3). Further, a compound represented by the following formula (2-1), (2-2) or (2-3) is also one aspect of the present invention.
In the formulae (1-1) and (1-2), R 1 Is C1-20 alkylene optionally substituted by hydroxy or C1-20 (poly) alkyleneoxy optionally substituted by hydroxy, R 2 Each independently is a hydrogen atom or an amino group, and at least 1R 2 Is an amino group.
As the above-mentioned R 2 The amino group is preferably a primary amino group, a dimethylamino group, or a diethylamino group.
Further, a sealing agent for a display element containing a curable resin and the photopolymerization initiator of the present invention is also one aspect of the present invention.
The sealing agent for a display element of the present invention contains the photopolymerization initiator of the present invention, and therefore, has excellent curability against light of a long wavelength and also has excellent low liquid crystal contamination when used in a liquid crystal display element. That is, the sealant for a display element of the present invention is suitably used for a liquid crystal display element as a sealant for a liquid crystal display element.
The content of the photopolymerization initiator of the present invention in the sealant for display elements of the present invention is preferably 0.01 part by weight in terms of the lower limit and 5 parts by weight in terms of the upper limit, based on 100 parts by weight of the curable resin. When the content of the photopolymerization initiator of the present invention is in this range, the obtained sealant for display elements is more excellent in curability against light of long wavelength, and is more excellent in the effect of satisfying both curability against light of long wavelength and low liquid crystal contamination when used in a liquid crystal display element. The lower limit of the content of the photopolymerization initiator of the present invention is more preferably 0.5 parts by weight, and the upper limit is more preferably 3 parts by weight.
The sealant for a display element of the present invention contains a curable resin.
The curable resin preferably contains a (meth) acrylic compound.
Examples of the (meth) acrylic compound include a (meth) acrylate compound, an epoxy (meth) acrylate, and a urethane (meth) acrylate. Among them, epoxy (meth) acrylates are preferable. From the viewpoint of reactivity, the (meth) acrylic compound preferably has 2 or more (meth) acryloyl groups in the molecule.
In the present specification, the "(meth) acrylic" refers to an acrylic or a methacrylic, the "(meth) acrylic compound" refers to a compound having a (meth) acryloyl group, and the "(meth) acryloyl group" refers to an acryloyl group or a methacryloyl group. The "(meth) acrylate" refers to an acrylate or a methacrylate. The "epoxy (meth) acrylate" is a compound obtained by reacting all epoxy groups in an epoxy compound with (meth) acrylic acid.
Examples of the monofunctional compound among the above-mentioned (meth) acrylate compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethyl carbitol (meth) acrylate, 2-trifluoroethyl (meth) acrylate, 2, 3-tetrafluoropropyl (meth) acrylate, 1h, 5h-octafluoropentyl (meth) acrylate, imide (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, 2- (meth) acryloyloxyethyl phosphate, glycidyl (meth) acrylate, and the like.
Examples of the 2-functional compound among the (meth) acrylate compounds include 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2-n-butyl-2-ethyl-1, 3-propanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide addition bisphenol a di (meth) acrylate, propylene oxide addition bisphenol a di (meth) acrylate, ethylene oxide addition bisphenol F di (meth) acrylate, dimethylol dicyclopentadienyl di (meth) acrylate, ethylene oxide-modified isocyanurate di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl) acrylate, and dimethylol di (meth) acrylate, polyether diol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, polybutadiene diol di (meth) acrylate, and the like.
Examples of the 3-or more-functional compound in the (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, glycerol tri (meth) acrylate, propylene oxide-added glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri (meth) acryloyloxyethyl phosphate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.
Examples of the epoxy (meth) acrylate include those obtained by reacting an epoxy compound with (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.
Examples of the epoxy compound to be used as a raw material for synthesizing the epoxy (meth) acrylate include bisphenol a type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, 2' -diallyl bisphenol a type epoxy compounds, hydrogenated bisphenol type epoxy compounds, propylene oxide-added bisphenol a type epoxy compounds, resorcinol type epoxy compounds, biphenyl type epoxy compounds, thioether type epoxy compounds, diphenyl ether type epoxy compounds, dicyclopentadiene type epoxy compounds, naphthalene type epoxy compounds, phenol novolac type epoxy compounds, o-cresol novolac type epoxy compounds, dicyclopentadiene novolac type epoxy compounds, biphenol aldehyde type epoxy compounds, naphthol novolac type epoxy compounds, glycidyl amine type epoxy compounds, alkyl polyol type epoxy compounds, rubber-modified epoxy compounds, glycidyl ester compounds, and the like.
Examples of commercially available products of the bisphenol A type epoxy compounds include jER828EL, jER1004 (both manufactured by Mitsubishi chemical corporation), EPICLON 850CRP (manufactured by DIC corporation), and the like.
Examples of commercially available products of the bisphenol F type epoxy compounds include jER806 and jER4004 (both manufactured by Mitsubishi chemical corporation).
Examples of commercially available products of the bisphenol S type epoxy compounds include EPICLON EXA1514 (available from DIC).
Examples of commercially available products of the 2,2' -diallylbisphenol A type epoxy compound include RE-810NM (manufactured by Nippon chemical Co., ltd.).
Examples of commercially available products of the above-mentioned hydrogenated bisphenol epoxy compounds include EPICLON EXA7015 (available from DIC).
Examples of commercially available products of the above propylene oxide-added bisphenol A type epoxy compounds include EP-4000S (manufactured by ADEKA).
Examples of commercially available products of the above resorcinol type epoxy compounds include EX-201 (manufactured by Nagase ChemteX Corporation).
Examples of the commercially available biphenyl-type epoxy compound include jER YX-4000H (manufactured by Mitsubishi chemical corporation).
Examples of commercially available products of the thioether-type epoxy compounds include YSLV-50TE (manufactured by NIPPON STEEL Chemical & Material Co., ltd.).
Examples of commercially available diphenyl ether type epoxy compounds include YSLV-80DE (NIPPON STEEL Chemical & Material Co., ltd.).
Examples of commercially available products of the dicyclopentadiene type epoxy compounds include EP-4088S (manufactured by ADEKA).
Examples of the commercially available naphthalene epoxy compound include EPICLON HP4032 and EPICLON EXA-4700 (both available from DIC).
Examples of commercially available products of the phenol novolac type epoxy compounds include EPICLON-770 (available from DIC).
Examples of the commercially available product of the o-cresol novolac-type epoxy compound include EPICLON-670-EXP-S (DIC).
Examples of commercially available products of the dicyclopentadiene phenol-based epoxy compound include EPICLON HP7200 (available from DIC).
Examples of the commercially available products of the above-mentioned diphenolaldehyde type epoxy compounds include NC-3000P (manufactured by Nippon chemical Co., ltd.).
Examples of commercially available products of the naphthol phenol type epoxy compounds include ESN-165S (NIPPON STEEL Chemical & Material Co., ltd.).
Examples of commercially available products of the above glycidyl amine type epoxy compound include jER630 (manufactured by Mitsubishi chemical corporation), EPICLON 430 (manufactured by DIC corporation), and TETRAD-X (manufactured by Mitsubishi gas chemical corporation).
Examples of commercially available products of the above-mentioned alkyl polyol type epoxy compound include ZX-1542 (NIPPON STEEL Chemical & Material Co., ltd., manufactured by Ltd.), EPICLON 726 (manufactured by DIC), EPOLIGHT 80MFA (manufactured by Kyoho Chemical Co., ltd.), DENACOL EX-611 (manufactured by Nagase ChemteX Corporation), and the like.
Examples of commercially available products of the rubber-modified epoxy compound include YR-450, YR-207 (both NIPPON STEEL Chemical & Material Co., ltd.), EPOLEAD PB (manufactured by Daiiluol Co., ltd.), and the like.
Examples of commercially available products of the glycidyl ester compounds include DENACOL EX-147 (manufactured by Nagase ChemteX Corporation).
Examples of other commercially available products of the epoxy compounds include YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by NIPPON STEEL Chemical & Material Co., ltd.), XAC4151 (manufactured by Asahi Kasei corporation), jER1031, jER1032 (all manufactured by Mitsubishi Chemical corporation), EXA-7120 (manufactured by DIC corporation), and TEPIC (manufactured by Nissan Chemical Co., ltd.).
Examples of commercially available products of the above epoxy (meth) acrylate include epoxy (meth) acrylate manufactured by Daicel-Allnex LTD., epoxy (meth) acrylate manufactured by Ninghamu chemical industries, epoxy (meth) acrylate manufactured by Kyowa chemical Corporation, and epoxy (meth) acrylate manufactured by Nagase ChemteX Corporation.
Examples of the epoxy (meth) acrylate produced by Daicel-Allnex LTD.C. include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, EBECRYL3800, EBECRYL6040, and EBECRYL RDX 63182.
Examples of the epoxy (meth) acrylate manufactured by Ninghamu chemical industries include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD and EMA-1020.
Examples of the EPOXY (meth) acrylate manufactured by Kyoeisha chemical company include EPOXESTER M-600A, EPXY ESTER 40EM, EPXY ESTER 70PA, EPXY ESTER 200PA, EPXY ESTER 80MFA, EPXY ESTER 3002M, EPXY ESTER 3002A, EPXY ESTER 1600A, EPXY ESTER 3000M, EPXY ESTER 3000A, EPXY ESTER 200EA, and EPXY ESTER 400 EA.
Examples of the epoxy (meth) ACRYLATE produced by Nagase ChemteX Corporation include DENACOL ACRYLATE DA-141, DENACOL ACRYLATE DA-314, and DENACOLACRYLATE DA-911.
The urethane (meth) acrylate can be obtained, for example, by reacting an isocyanate compound with a (meth) acrylic acid derivative having a hydroxyl group in the presence of a catalytic amount of a tin-based compound.
Examples of the isocyanate compound include isophorone diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4, 4' -diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1, 5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene Diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethylxylylene diisocyanate, 1,6, 11-undecane triisocyanate and the like.
Further, as the isocyanate compound, an isocyanate compound having a chain extended by a reaction of a polyol and an excess amount of the isocyanate compound may be used.
Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, and the like.
Examples of the (meth) acrylic acid derivative having a hydroxyl group include hydroxyalkyl mono (meth) acrylates, mono (meth) acrylates of diols, mono (meth) acrylates or di (meth) acrylates of triols, epoxy (meth) acrylates, and the like.
Examples of the hydroxyalkyl mono (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
Examples of the diol include ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, and polyethylene glycol.
Examples of the trihydric alcohol include trimethylolethane, trimethylolpropane, glycerol, and the like.
Examples of the epoxy (meth) acrylate include bisphenol a type epoxy acrylates and the like.
Examples of commercially available products among the urethane (meth) acrylates include urethane (meth) acrylates manufactured by east asia synthesis, urethane (meth) acrylates manufactured by Daicel-Allnex ltd., urethane (meth) acrylates manufactured by kokusho industries, urethane (meth) acrylates manufactured by seiko chemical industries, and urethane (meth) acrylates manufactured by coyokko chemical companies.
Examples of the urethane (meth) acrylates produced by Toyo Synthesis Co.Ltd include M-1100, M-1200, M-1210 and M-1600.
Examples of the urethane (meth) acrylate produced by Daicel-Allnex LTD.can include EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL 8808402, EBECRYL8803, EBECRYL8804, EBECRYL8807 and EBECRYL 9260.
Examples of the urethane (meth) acrylates produced by the above-mentioned Generals include Art Resin UN-330, art Resin SH-500B, art Resin UN-1200TPK, art Resin UN-1255, art Resin UN-3320HB, art Resin UN-7100, art Resin UN-9000A and Art Resin UN-9000H.
Examples of the urethane (meth) acrylates produced by Mitsuoku chemical industries include U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U-6LPA, U-10H, U-15HA, U-108A, U-122P, U-324A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4000, UA-4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, and UA-W2A.
Examples of the urethane (meth) acrylates produced by Kyoeisha chemical company include AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-3061, and UA-306T.
The curable resin preferably contains an epoxy compound for the purpose of improving the adhesiveness and the like of the obtained sealant for a display element. Examples of the epoxy compound include epoxy compounds that are raw materials for synthesizing the above epoxy (meth) acrylate, and partially (meth) acrylic acid-modified epoxy compounds.
In the present specification, the partially (meth) acrylic-modified epoxy compound refers to a compound having 1 or more epoxy groups and 1 or more (meth) acryloyl groups in each molecule, and can be obtained by reacting a part of the epoxy groups of an epoxy compound having 2 or more epoxy groups in 1 molecule with (meth) acrylic acid, for example.
When the curable resin contains the (meth) acrylic compound and the epoxy compound or when the curable resin contains the partially (meth) acrylic-modified epoxy compound, the ratio of (meth) acryloyl groups in the total of (meth) acryloyl groups and epoxy groups in the curable resin is preferably 30 mol% or more and 95 mol% or less. When the ratio of the (meth) acryloyl group is in this range, the resultant sealant for a display element is more excellent in adhesiveness while suppressing the occurrence of liquid crystal contamination when used in a liquid crystal display element.
The curable resin preferably has-OH, -NH-group, or-NH-group from the viewpoint of suppressing liquid crystal contamination 2 Hydrogen bonding units such as radicals.
The curable resins may be used alone or in combination of 2 or more.
The sealant for a display element of the present invention may contain a thermal polymerization initiator within a range not to impair the object of the present invention.
Examples of the thermal polymerization initiator include azo compounds and organic peroxides. Among them, a macromolecular azo compound is preferable.
The thermal polymerization initiators may be used alone, or 2 or more of them may be used in combination.
In the present specification, the "macromolecular azo compound" refers to a compound having an azo group, which generates a radical capable of curing a (meth) acryloyloxy group by heat, and has a number average molecular weight of 300 or more.
The number average molecular weight of the macromolecular azo compound has a preferred lower limit of 1000 and a preferred upper limit of 30 ten thousand. When the number average molecular weight of the macromolecular azo compound is in this range, the resultant sealant for a display element can be easily mixed with a curable resin while suppressing liquid crystal contamination when used in a liquid crystal display element. The number average molecular weight of the macromolecular azo compound is preferably 5000 at the lower limit, 10 ten thousand at the upper limit, 1 ten thousand at the lower limit, and 9 ten thousand at the upper limit.
Examples of the macromolecular azo compound include compounds having a structure in which a plurality of polyalkylene oxide, polydimethylsiloxane, or other units are bonded via an azo group.
The polymer azo compound having a structure in which a plurality of polyalkylene oxide units and the like are bonded to each other via an azo group is preferably a compound having a polyethylene oxide structure.
Specific examples of the macromolecular azo compound include a polycondensate of 4,4 '-azobis (4-cyanovaleric acid) and a polyalkylene glycol, and a polycondensate of 4,4' -azobis (4-cyanovaleric acid) and a polydimethylsiloxane having a terminal amino group.
Examples of commercially available products of the above-mentioned macromolecular azo compounds include VPE-0201, VPE-0401, VPE-0601, VPS-0501 and VPS-1001 (all manufactured by Fuji film and Wako pure chemical industries, ltd.).
Examples of the azo compound which is not a polymer include V-65 and V-501 (both manufactured by Fuji film and Wako pure chemical industries, ltd.).
Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, peroxydicarbonate, and the like.
The content of the thermal polymerization initiator is preferably 0.05 parts by weight in the lower limit and 10 parts by weight in the upper limit, based on 100 parts by weight of the curable resin. When the content of the thermal polymerization initiator is 0.05 parts by weight or more, the thermosetting property of the sealant for a display element of the present invention is further improved. When the content of the thermal polymerization initiator is 10 parts by weight or less, the sealant for a display element of the present invention is more excellent in storage stability and low in liquid crystal contamination when used in a liquid crystal display element. The lower limit of the content of the thermal polymerization initiator is more preferably 0.1 part by weight, and the upper limit is more preferably 5 parts by weight.
The sealant for a display element of the present invention may contain a thermosetting agent.
Examples of the heat-curing agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyphenol compounds, and acid anhydrides. Among them, organic acid hydrazide is suitably used.
The thermosetting agent may be used alone, or 2 or more of them may be used in combination.
Examples of the organic acid hydrazide include sebacic dihydrazide, isophthalic dihydrazide, adipic dihydrazide, malonic dihydrazide and the like.
Examples of commercially available organic acid hydrazides include organic acid hydrazides manufactured by Otsuka chemical corporation, and organic acid hydrazides manufactured by Ajinomoto Fine-Techno Co., inc.
Examples of the organic acid hydrazide manufactured by Otsuka chemical company include SDH and ADH.
Examples of the organic acid hydrazide manufactured by Ajinomoto Fine-Techno Co., inc. include Amicure VDH, amicure VDH-J, amicure UDH, and Amicure UDH-J.
The lower limit of the content of the thermosetting agent is preferably 1 part by weight and the upper limit is preferably 50 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the thermosetting agent is in this range, the thermosetting property can be further improved without deteriorating the coatability and the like of the obtained sealing agent for display elements. The more preferable upper limit of the content of the thermal curing agent is 30 parts by weight.
The sealant for a display element of the present invention preferably contains a filler for the purpose of increasing viscosity, improving adhesiveness by a stress dispersion effect, improving a linear expansion coefficient, and the like.
As the filler, an inorganic filler or an organic filler can be used.
Examples of the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate, and the like.
Examples of the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles.
The fillers may be used alone, or 2 or more of them may be used in combination.
The lower limit of the content of the filler in 100 parts by weight of the sealant for display element of the present invention is preferably 10 parts by weight, and the upper limit is preferably 70 parts by weight. When the content of the filler is in this range, the effect of improving the adhesiveness and the like can be further improved without deteriorating the coating property and the like. The lower limit of the content of the filler is more preferably 20 parts by weight, and the upper limit is more preferably 60 parts by weight.
The sealant for a display element of the present invention preferably contains a silane coupling agent. The silane coupling agent mainly functions as an adhesion aid for satisfactorily adhering the sealant to a substrate or the like.
As the silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and the like are suitably used. These compounds have an excellent effect of improving adhesion to a substrate or the like, and chemically bond with a curable resin, whereby the curable resin can be inhibited from flowing out into a liquid crystal when the obtained sealant for a display element is used for a liquid crystal display element.
The silane coupling agents may be used alone, or 2 or more kinds thereof may be used in combination.
The preferable lower limit of the content of the silane coupling agent in 100 parts by weight of the sealant for display elements of the present invention is 0.1 part by weight, and the preferable upper limit is 10 parts by weight. When the content of the silane coupling agent is within this range, the effect of improving the adhesion while suppressing the occurrence of liquid crystal contamination when the obtained sealant for a display element is used for a liquid crystal display element becomes more excellent. The lower limit of the content of the silane coupling agent is more preferably 0.3 parts by weight, and the upper limit is more preferably 5 parts by weight.
The sealing agent for a display element of the present invention may contain a light-screening agent. By containing the light-shading agent, the sealant for a display element of the present invention can be suitably used as a light-shielding sealant.
The sealing agent for display elements of the present invention contains the photopolymerization initiator of the present invention which is excellent in reactivity with light of a long wavelength, and therefore, even when the sealing agent contains the light-shielding agent, curability with respect to light of a long wavelength is excellent.
Examples of the light-shading agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Among them, a substance having high insulation properties is preferable, and titanium black is more preferable.
The above titanium black can exhibit a sufficient effect without being surface-treated, but titanium black having a surface treated with an organic component such as a coupling agent, or surface-treated titanium black such as titanium black coated with an inorganic component such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, or magnesium oxide may be used. Among them, titanium black treated with an organic component is preferable in that the insulating property can be further improved.
Further, since a display element produced using the sealant for a display element of the present invention containing the titanium black as a light-shielding agent has sufficient light-shielding properties, it is possible to realize: a display element having high contrast without light leakage and excellent image display quality.
Examples of commercially available products of the titanium black include 12S, 13M-C, 13R-N, 14M-C (all manufactured by Mitsubishi corporation), and Tilack D (manufactured by Gibber chemical Co., ltd.).
The lower limit of the specific surface area of the titanium black is preferably 13m 2 A preferred upper limit of 30 m/g 2 A more preferred lower limit is 15m 2 The upper limit is 251n2/g.
The volume resistance of the titanium black is preferably 0.5 Ω · cm at the lower limit, 3 Ω · cm at the upper limit, 1 Ω · cm at the lower limit, and 2.5 Ω · cm at the upper limit.
The primary particle size of the light-shading agent is not particularly limited as long as it is not more than the distance between the substrates of the display element, and the lower limit is preferably 1nm and the upper limit is preferably 5000nm. By setting the primary particle size of the light-shielding agent to the above range, the light-shielding property can be further improved without deteriorating the drawing property and the like of the obtained sealing agent for a display element. The lower limit of the primary particle size of the light-shading agent is more preferably 5nm, the upper limit is more preferably 200nm, the lower limit is more preferably 10nm, and the upper limit is more preferably 100nm.
The primary PARTICLE size of the light-shading agent can be measured by dispersing the light-shading agent in a solvent (water, organic solvent, etc.) using NICOMP 380ZLS (manufactured by part SIZING SYSTEMS).
The preferable lower limit of the content of the above-mentioned light-shading agent in 100 parts by weight of the sealant for a display element of the present invention is 5 parts by weight, and the preferable upper limit is 80 parts by weight. By setting the content of the light-shading agent within this range, it is possible to exhibit more excellent light-shielding properties without reducing the adhesiveness of the obtained sealant for a display element to a substrate, the strength after curing, and the drawing properties. The content of the light-shading agent is more preferably 10 parts by weight at the lower limit, more preferably 70 parts by weight at the upper limit, still more preferably 30 parts by weight at the lower limit, and still more preferably 60 parts by weight at the upper limit.
The sealing agent for a display element of the present invention may further contain additives such as a reactive diluent, a thixotropic agent, a spacer, a curing accelerator, an antifoaming agent, a leveling agent, and a polymerization inhibitor, if necessary.
Examples of a method for producing the sealant for a display element of the present invention include a method in which a curable resin, a photopolymerization initiator, and a silane coupling agent added as needed are mixed using a mixer.
Examples of the mixer include a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roll mixer.
The conductive fine particles are mixed in the sealing agent for a display element of the present invention, whereby a vertical conduction material can be produced. The vertically conducting material comprising the sealing agent for display elements of the present invention and conductive fine particles is also one aspect of the present invention.
As the conductive fine particles, metal balls, fine particles in which a conductive metal layer is formed on the surface of resin fine particles, or the like can be used. Among these, fine particles having a conductive metal layer formed on the surface of the resin fine particles are preferable because they can be electrically connected without damaging the transparent substrate or the like due to the excellent elasticity of the resin fine particles.
A display element using the sealant for a display element of the present invention or the vertically conducting material of the present invention is also one aspect of the present invention.
The display element of the present invention is preferably a liquid crystal display element, and more preferably a narrow-frame-edge liquid crystal display element. Specifically, the width of the frame portion around the liquid crystal display unit is preferably 2mm or less.
In addition, when a liquid crystal display device of narrow bezel design is manufactured as the display device of the present invention, the application width of the sealant for display devices of the present invention is preferably 1mm or less.
As a method for manufacturing a liquid crystal display element as a display element of the present invention, a liquid crystal dropping method is suitably used, and specifically, a method including the following steps, for example, is exemplified.
First, the following steps are performed: forming a frame-shaped seal pattern by applying the sealant for a display element of the present invention to one of 2 transparent substrates having an electrode such as an ITO thin film and an alignment film by screen printing, dispenser application, or the like; then, the following steps are performed: in the present invention, a sealant for a display element is uncured, and droplets of liquid crystal are applied dropwise to a frame of a seal pattern of a substrate and overlapped with another transparent substrate under vacuum; then, the following steps are performed: the liquid crystal display element can be obtained by performing the above-described methods of the respective steps by irradiating a seal pattern portion of the sealant for a display element of the present invention with light of a long wavelength through a cut filter or the like to photocure the sealant. In addition to the step of photocuring the sealant, a step of heating and thermosetting the sealant may be performed.
Effects of the invention
According to the present invention, a photopolymerization initiator having excellent reactivity with light having a long wavelength can be provided. Further, the present invention can provide a sealing agent for a display element, which contains the photopolymerization initiator, has excellent curability with respect to light having a long wavelength, and has excellent low liquid crystal contamination when used in a liquid crystal display element; and a vertical-conduction material and a display element using the sealing agent for a display element. Further, according to the present invention, a compound constituting the photopolymerization initiator can be provided.
Drawings
FIG. 1 is a ` H-NMR spectrum of the compound represented by the formula (2-1) obtained in Synthesis example 1.
FIG. 2 is an absorption spectrum of the compound represented by the formula (2-1) obtained in Synthesis example 1.
Fig. 3 is a cross-sectional view schematically showing a liquid crystal display element produced using each of the display element sealants obtained in examples and comparative examples in a state where no light shielding portion is present.
Fig. 4 is a cross-sectional view schematically showing a liquid crystal display element produced using each of the display element sealants obtained in examples and comparative examples in a state in which a light shielding portion is present.
Detailed Description
The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.
(Synthesis example 1)
(preparation of Compound represented by formula (2-1))
To 100 parts by weight of methylene chloride, 10 parts by weight of 4- (dimethylamino) benzoyl chloride and 0.5 part by weight of pyridine as a catalyst were added, 1 part by weight of glycidol was added dropwise under an atmosphere of 0 ℃, and the mixture was allowed to cool and stirred at room temperature overnight. Methylene chloride was removed from the obtained reaction liquid, thereby obtaining a reaction product.
To 100 parts by weight of N, N-dimethylformamide were added 10 parts by weight of the obtained reaction product and 5 parts by weight of 2-hydroxy-9H-thioxanthen-9-one, and the mixture was reacted in the presence of potassium carbonate as a basic catalyst while stirring at 120 ℃ for 48 hours. N, N-dimethylformamide was removed from the obtained reaction solution, and purification was performed by column chromatography, thereby obtaining a compound represented by the above formula (2-1).
The structure of the compound represented by the above formula (2-1) is defined by 1 H-NMR、 13 C-NMR and FT-IR. Subjecting the obtained compound represented by the formula (2-1) 1 The H-NMR spectrum is shown in FIG. 1.
The compound represented by the formula (2-1) thus obtained was dissolved in acetonitrile to give a concentration of 0.1 mg/mL. The obtained acetonitrile solution was measured for an absorption spectrum in a range of 300nm to 800nm under a condition of an optical path length of 1cm using a spectrophotometer (manufactured by Hitachi High-Tech Science Corporation, U-3900). As a result, it was confirmed that: the compound represented by the formula (2-1) has an absorbance at 420nm of 0.10 or more. The absorption spectrum of the compound represented by the formula (2-1) thus obtained is shown in FIG. 2.
(Synthesis example 2)
(preparation of Compound represented by the formula (2-2))
The compound represented by the above formula (2-2) was obtained in the same manner as in synthesis example 1, except that 2-hydroxy-9H-thioxanthen-9-one was changed to 2, 7-dihydroxy-9H-thioxanthen-9-one.
The structure of the compound represented by the above formula (2-2) is defined by 1 H-NMR、 13 C-NMR and FT-IR.
The compound represented by the formula (2-2) thus obtained was dissolved in acetonitrile to give a concentration of 0.1 mg/mL. The obtained acetonitrile solution was measured for an absorption spectrum in a range of 300nm to 800nm under a condition of an optical path length of 1cm using a spectrophotometer (manufactured by Hitachi High-Tech Science Corporation, U-3900). As a result, it was confirmed that: the compound represented by the formula (2-2) has an absorbance at 420nm of 0.10 or more.
(Synthesis example 3)
(preparation of Compound represented by formula (2-3))
The procedure of synthesis example 1 was repeated except for changing 4- (dimethylamino) benzoyl chloride to 3, 5-bis- (dimethylamino) benzoyl chloride, to obtain a compound represented by the above formula (2-3).
The structure of the compound represented by the above formula (2-3) is defined by 1 H-NMR、 13 C-NMR and FT-IR.
The compound represented by the formula (2-3) thus obtained was dissolved in acetonitrile to give a concentration of 0.1 mg/mL. The obtained acetonitrile solution was measured for an absorption spectrum in a range of 300nm to 800nm under a condition of an optical path length of 1em by using a spectrophotometer (manufactured by Hitachi High-Tech Science Corporation, U-3900). As a result, it was confirmed that: the compound represented by the formula (2-3) has an absorbance at 420nm of 0.10 or more.
(examples 1 to 7 and comparative examples 1 to 4)
The respective materials were mixed with a planetary mixer (manufactured by Thinky corporation, "12354\1243192 \\\3224444tazar"), and then further mixed with a three-roll mill in accordance with the mixing ratios described in table 1, thereby preparing sealants for display elements of examples 1 to 7 and comparative examples 1 to 4.
< evaluation >
The following evaluations were made with respect to each of the sealing agents for display elements obtained in examples and comparative examples. The results are shown in Table 1.
(photo-curing)
1 part by weight of spacer particles (Micropearl SI-H050, manufactured by Water chemical industries, ltd.) was dispersed in 100 parts by weight of each of the sealing materials for display elements obtained in examples and comparative examples. Next, the sealant was filled in a syringe for dispensing ("PSY-10E" manufactured by Musashi Engineering inc., and subjected to defoaming treatment, and then coated on a glass substrate using a dispenser ("SHOTMASTER 300") to form a sealant. Glass substrates of the same size were bonded to the substrates under a reduced pressure of 5Pa by a vacuum bonding apparatus. The sealant portion of the attached glass substrate was irradiated with 100mW/cm using a metal halide lamp 2 For 10 seconds. The light irradiation is performed through a cut-off filter (400 nm cut-off filter) for cutting off light having a wavelength of 400nm or less.
FT-IR measurement of the sealant was performed using an infrared spectrometer (FTS 3000, manufactured by BIORAD), and the amount of change in the peak value derived from the (meth) acryloyl group before and after light irradiation was measured. Photocurability was evaluated by setting "x" to a value of 85% or more reduction of the peak value derived from a (meth) acryloyl group after light irradiation, "o" to a value of 70% or more reduction and less than 85%, a value of 60% or more reduction and less than 70%, and a value of 60% or less reduction of the peak value derived from a (meth) acryloyl group after light irradiation.
(Low liquid Crystal contamination)
1 part by weight of spacer particles (Micropearl SI-H050, manufactured by Water chemical industries, ltd.) was dispersed in 100 parts by weight of each of the sealing materials for display elements obtained in examples and comparative examples. Next, the sealant in which the spacer particles were dispersed was applied to the substrate with the polished alignment film and the transparent electrode by a dispenser so that the line width reached 1 mm.
Subsequently, minute droplets of liquid crystal (JC-5004 LA, manufactured by Chisso Corporation) were applied dropwise to the entire inner surface of the frame of the sealant of the substrate with the transparent electrode, and the color filter substrate with the transparent electrode was immediately bonded. Then, the sealant portion was irradiated with 100mW/cm using a metal halide lamp 2 The resultant was cured for 30 seconds, and further heated at 120 ℃ for 1 hour to obtain a liquid crystal display element. The light irradiation is performed through a cut-off filter (400 nm cut-off filter) for cutting off light having a wavelength of 400nm or less.
In the liquid crystal display element, the liquid crystal display element (without light-shielding portion) in which the sealant was completely irradiated with light and the liquid crystal display element (with light-shielding portion) in which the sealant was applied to the black matrix of the color filter substrate so as to occupy 50% of the line width were manufactured by controlling the application position of the sealant by a dispenser. Fig. 3 is a cross-sectional view schematically showing a liquid crystal display element manufactured in a state where a light shielding portion is not present using each of the sealing agents for display elements obtained in examples and comparative examples, and fig. 4 is a cross-sectional view schematically showing a liquid crystal display element manufactured in a state where a light shielding portion is present using each of the sealing agents for display elements obtained in examples and comparative examples. As shown in fig. 3, the state where there is no light shielding portion on the sealant 1 is a state where the sealant 1 is completely illuminated, while, as shown in fig. 4, the state where there is a light shielding portion on the sealant 1, the sealant 1 in the portion in contact with the liquid crystal 3 is shielded by the black matrix 2 and light hardly reaches.
The resultant liquid crystal display element was visually observed to find the liquid crystal alignment disorder (display unevenness) after applying a voltage of 1000 hours at 80 ℃ after performing a 100-hour operation test.
The low liquid crystal contamination was evaluated by "x" in the case where no display unevenness was observed in the liquid crystal display element at all, "o" in the case where a slightly light display unevenness was observed in the vicinity of the sealant (peripheral portion) of the liquid crystal display element, "Δ" in the case where a significantly severe display unevenness was present in the peripheral portion, and "x" in the case where the significantly severe display unevenness was spread not only in the peripheral portion but also in the central portion.
Note that the liquid crystal display elements evaluated as "cyc" and "smal" are levels that have no practical problem at all, the liquid crystal display element evaluated as "Δ" is a level that may have a problem depending on the display design, and the liquid crystal display element evaluated as "x" is a level that cannot withstand practical use.
[ Table 1]
Industrial applicability
According to the present invention, a photopolymerization initiator having excellent reactivity with light having a long wavelength can be provided. Further, according to the present invention, it is possible to provide a sealing agent for a display element which has excellent curability with respect to light having a long wavelength and is excellent in low liquid crystal contamination when used in a liquid crystal display element, and a vertical conduction material and a display element using the sealing agent for a display element. Further, according to the present invention, a compound constituting the photopolymerization initiator can be provided.
Description of the reference numerals
1. Sealing agent
2. Black matrix
3. Liquid crystal display device
Claims (4)
1. A sealing agent for a display element, which comprises a curable resin and a photopolymerization initiator, wherein the photopolymerization initiator is a compound having a thioxanthone group optionally substituted with a hydroxyl group and an amino group, and the photopolymerization initiator has an absorbance at a wavelength of 420nm of 0.10 or more when dissolved in acetonitrile to a concentration of 0.1mg/mL,
the photopolymerization initiator is a compound represented by the following formula (2-2) or (2-3),
2. the sealant for a display element according to claim 1, which is used for a liquid crystal display element.
3. A vertically conducting material comprising the sealing agent for display element according to claim 1 or 2 and conductive fine particles.
4. A display element formed using the sealant for a display element according to claim 1 or 2 or the vertically conducting material according to claim 3.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2018-076174 | 2018-04-11 | ||
| JP2018076174 | 2018-04-11 | ||
| PCT/JP2019/015089 WO2019198631A1 (en) | 2018-04-11 | 2019-04-05 | Photopolymerization initiator, sealant for display elements, vertical conduction material, display element, and compound |
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| CN111372952A CN111372952A (en) | 2020-07-03 |
| CN111372952B true CN111372952B (en) | 2023-03-07 |
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| CN115004093A (en) * | 2020-02-06 | 2022-09-02 | 三井化学株式会社 | Photothermally curable resin composition, liquid crystal sealing agent comprising same, liquid crystal display panel, and method for producing same |
| CN112079813B (en) * | 2020-08-18 | 2021-05-25 | 新丰博兴聚合材料有限公司 | UV LED photoinitiator and preparation method thereof |
| KR20230078950A (en) * | 2020-09-30 | 2023-06-05 | 세키스이가가쿠 고교가부시키가이샤 | Thioxanthone compound, photopolymerization initiator, curable resin composition, display element composition, liquid crystal display element sealant, upper and lower conduction material, and liquid crystal display element |
| KR20220057097A (en) | 2020-10-29 | 2022-05-09 | 주식회사 엘지에너지솔루션 | Battery module and battery pack including the same |
| WO2023176778A1 (en) * | 2022-03-16 | 2023-09-21 | 積水化学工業株式会社 | Curable resin composition and method for manufacturing semiconductor component |
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| CN111372952A (en) | 2020-07-03 |
| TW201943738A (en) | 2019-11-16 |
| JP6655219B1 (en) | 2020-02-26 |
| TWI801554B (en) | 2023-05-11 |
| WO2019198631A1 (en) | 2019-10-17 |
| JPWO2019198631A1 (en) | 2020-04-30 |
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