WO2017002362A1 - Photocurable resin composition, display element sealing agent, liquid crystal sealing agent, liquid crystal display panel and method for producing liquid crystal display panel - Google Patents
Photocurable resin composition, display element sealing agent, liquid crystal sealing agent, liquid crystal display panel and method for producing liquid crystal display panel Download PDFInfo
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- WO2017002362A1 WO2017002362A1 PCT/JP2016/003107 JP2016003107W WO2017002362A1 WO 2017002362 A1 WO2017002362 A1 WO 2017002362A1 JP 2016003107 W JP2016003107 W JP 2016003107W WO 2017002362 A1 WO2017002362 A1 WO 2017002362A1
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- WIPO (PCT)
- Prior art keywords
- compound
- liquid crystal
- resin composition
- photocurable resin
- molecule
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 141
- 239000011342 resin composition Substances 0.000 title claims abstract description 93
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 66
- 238000007789 sealing Methods 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 218
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 claims abstract description 51
- 229940126062 Compound A Drugs 0.000 claims abstract description 38
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 38
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical group C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 claims abstract description 22
- 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 20
- 239000000758 substrate Substances 0.000 claims description 50
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 20
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- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- OEZKDMYTQDZSAZ-UHFFFAOYSA-N 1-hydroxythioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2O OEZKDMYTQDZSAZ-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 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 1
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 description 1
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- 229940076442 9,10-anthraquinone Drugs 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- SEDYRAYQTFQNEI-UHFFFAOYSA-N [K].SCCO Chemical compound [K].SCCO SEDYRAYQTFQNEI-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000011097 chromatography purification Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical compound NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 description 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- GRGBENNNGZARRZ-UHFFFAOYSA-N dodecanedihydrazide Chemical compound NNC(=O)CCCCCCCCCCC(=O)NN GRGBENNNGZARRZ-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- RXFZJKXZSLVQJV-UHFFFAOYSA-N icosa-8,12-dienedihydrazide Chemical compound NNC(=O)CCCCCCC=CCCC=CCCCCCCC(=O)NN RXFZJKXZSLVQJV-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 125000005699 methyleneoxy group Chemical group [H]C([H])([*:1])O[*:2] 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 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
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure Methods 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
- 125000006839 xylylene group Chemical group 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
-
- 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
Definitions
- the present invention relates to a photocurable resin composition, a display element sealant, a liquid crystal sealant, a liquid crystal display panel, and a method for producing a liquid crystal display panel.
- a liquid crystal display panel includes two transparent substrates having electrodes provided on the surface, a frame-shaped sealing member sandwiched between them, and a liquid crystal material sealed in a region surrounded by the sealing member And have.
- the liquid crystal display panel can be manufactured by a liquid crystal dropping method, for example.
- Production of a liquid crystal display panel by a liquid crystal dropping method is as follows: (1) A liquid crystal sealing agent is applied to the inner edge of a transparent substrate to form a frame for filling with liquid crystal; (2) Liquid crystal is dropped into the frame; (3) After superposing two substrates under high vacuum while the liquid crystal sealant is in an uncured state, (4) curing the liquid crystal sealant.
- liquid crystal dropping method photocuring or thermosetting is performed in a state where the uncured liquid crystal sealant and the liquid crystal material are in contact with each other. Therefore, the liquid crystal sealant is required not only to have high curability but also to reduce contamination of the liquid crystal material.
- a photocurable resin composition containing a compound having a (meth) acryloyl group in the molecule and an anthraquinone derivative as a photopolymerization initiator has been proposed (for example, Patent Document 1).
- a photocurable resin composition comprising a photopolymerizable oligomer, a compound B obtained by reacting hydroxythioxanthone as a photopolymerization initiator with a compound having two or more epoxy groups in the molecule.
- a sealing agent for liquid crystal display elements has been proposed that includes a curable resin and a compound obtained by reacting an oxime ester and a polyfunctional isocyanate as a photopolymerization initiator (for example, Patent Document 3).
- composition shown in Patent Document 3 contains a photopolymerization initiator having low light absorption in the visible light region, the curability to light in the visible light region is low. Since the compositions shown in Patent Documents 1 and 2 contain a photopolymerization initiator having an anthraquinone skeleton or a thioxanthone skeleton, the curability to light in the visible light region is good. There is a demand for further reduction of elution. Thus, it is desired to provide a photocurable resin composition that has high curability with respect to light in the visible light region and can highly suppress liquid crystal contamination.
- the present invention has been made in view of the above problems.
- the photocurability is high in visible light curing and can highly suppress liquid crystal contamination. It aims at providing a resin composition.
- a curable compound A having an ethylenically unsaturated double bond in the molecule, an anthraquinone skeleton or thioxanthone skeleton in the molecule, and an NHCO group, and an NHCO group equivalent represented by the formula (I) is The photocurable resin composition containing the compound B which is 350 g / eq or less.
- NHCO group equivalent (g / eq) molecular weight / number of NHCO groups contained in one molecule: Formula (I) [2]
- L 1 each independently represents a single bond, an alkylene group having 1 to 10 carbon atoms, an alkyleneoxy group having 1 to 10 carbon atoms, an alkylenethio group having 1 to 10 carbon atoms, Represents an arylene group having 6 to 10 carbon atoms, an aryleneoxy group having 6 to 10 carbon atoms, or an arylenethio group having 6 to 10 carbon atoms, and X is derived from a compound having at least p isocyanate groups in the molecule.
- thermosetting compound C having an epoxy group in the molecule and a thermosetting agent D, and the thermosetting compound C is different from the curable compound A, [1] to [7 ]
- the photocurable resin composition in any one of.
- the thermosetting agent D is selected from the group consisting of a dihydrazide thermal latent curing agent, an imidazole thermal latent curing agent, an amine adduct thermal latent curing agent, and a polyamine thermal latent curing agent.
- the photocurable resin composition according to [8] which is as described above.
- a display element sealing agent comprising the photocurable resin composition according to any one of [1] to [9].
- a liquid crystal sealing agent comprising the photocurable resin composition according to any one of [1] to [9].
- the liquid crystal sealant according to [11] which is a liquid crystal sealant for a liquid crystal dropping method.
- [13] In the step of forming a seal pattern on one substrate using the liquid crystal sealant according to [11] or [12], and in the state of the seal pattern in an uncured state, or Dropping the liquid crystal on the other substrate paired with the one substrate, superimposing the one substrate and the other substrate through the seal pattern, and curing the seal pattern; A method for manufacturing a liquid crystal display panel.
- [17] including a pair of substrates, a frame-shaped sealing member disposed between the pair of substrates, and a liquid crystal layer filled in a space surrounded by the sealing member between the pair of substrates, A liquid crystal display panel, wherein the seal member is a cured product of the liquid crystal sealant according to [11] or [12].
- the present invention when used as a display element sealant, particularly a liquid crystal sealant, it is an object to provide a photocurable resin composition that has high curability to visible light and can highly suppress liquid crystal contamination.
- photocurable resin composition contains the curable compound A and the compound B, and may further contain the thermosetting compound C and the thermosetting agent D as needed.
- Curable compound A The curable compound A contained in the photocurable resin composition of the present invention is a compound having an ethylenically unsaturated double bond in the molecule.
- the compound having an ethylenically unsaturated double bond in the molecule is preferably a compound having a (meth) acryloyl group in the molecule.
- the number of (meth) acryloyl groups per molecule is 1 or 2 or more.
- the compound having a (meth) acryloyl group in the molecule may be a monomer, an oligomer or a polymer.
- (Meth) acryloyl group means acryloyl group or methacryloyl group
- (meth) acrylate means acrylate or methacrylate.
- the curable compound A does not have an anthraquinone skeleton or a thioxanthone skeleton.
- Examples of compounds having one (meth) acryloyl group in one molecule include (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic acid 2-hydroxyethyl ester. Alkyl esters are included.
- Examples of compounds having two or more (meth) acryloyl groups in one molecule include di (meth) acrylates such as polyethylene glycol, propylene glycol, and polypropylene glycol; di (meth) tris (2-hydroxyethyl) isocyanurate Acrylate; Di (meth) acrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of neopentyl glycol; Diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A Di (meth) acrylate of triol obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of trimethylolpropane; bisphenol A1 Di (meth) acrylate of a diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to the above; tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate; trimethylolprop
- the curable compound A may further have an epoxy group in the molecule.
- the number of epoxy groups per molecule is 1 or 2 or more. If the curable compound A further has not only a (meth) acryloyl group but also an epoxy group in the molecule, the photocurable resin composition containing it can be imparted with photocurability and thermosetting properties. Thereby, the sclerosis
- the compound having a (meth) acryloyl group and an epoxy group in the molecule can be, for example, a (meth) acrylic acid glycidyl ester obtained by reacting an epoxy compound and (meth) acrylic acid in the presence of a basic catalyst. .
- the epoxy compound to be reacted may be a polyfunctional epoxy compound having two or more epoxy groups in the molecule, and suppresses the decrease in the adhesiveness of the cured product of the photocurable resin composition due to excessive increase in the crosslinking density.
- a bifunctional epoxy compound is preferable.
- bifunctional epoxy compounds include bisphenol type epoxy compounds (bisphenol A type, bisphenol F type, 2,2′-diallyl bisphenol A type, bisphenol AD type, hydrogenated bisphenol type, etc.), biphenyl type epoxy compounds, And naphthalene type epoxy compounds. Of these, bisphenol A type and bisphenol F type bisphenol type epoxy compounds are preferred from the viewpoint of good coating properties.
- the bisphenol type epoxy compound has advantages such as excellent coating properties as compared with the biphenyl ether type epoxy compound.
- the compound having a (meth) acryloyl group and an epoxy group in the molecule may be one kind or a combination of two or more kinds.
- a compound A1 having a (meth) acryloyl group in the molecule and not having an epoxy group may be combined with a compound A2 having a (meth) acryloyl group and an epoxy group in the molecule.
- the photocurable resin composition further contains an epoxy compound as the thermosetting compound C, the epoxy compound, and a compound A1 having a (meth) acryloyl group in the molecule and not having an epoxy group, Can improve the compatibility.
- the photocurable resin composition contains the compound B having moderate hydrophilicity, even if the photocurable resin composition contains the compound A1 that is more hydrophobic than the compound A2, the display element of the photocurable resin composition, in particular, Elution to the liquid crystal can be suppressed.
- the content of the compound A2 having a (meth) acryloyl group and an epoxy group in the molecule is not particularly limited, but may be, for example, 30% by mass or more based on the curable compound A.
- the weight average molecular weight of the curable compound A is preferably about 310 to 1,000.
- the weight average molecular weight of the curable compound A can be measured in terms of polystyrene by, for example, gel permeation chromatography (GPC).
- the content of the curable compound A is preferably 40 to 80% by mass, and more preferably 50 to 75% by mass with respect to the photocurable resin composition.
- Compound B contained in the photocurable resin composition of the present invention has an anthraquinone skeleton or thioxanthone skeleton and an NHCO group in the molecule.
- the anthraquinone skeleton or thioxanthone skeleton contained in the compound B can excite by absorbing light in the visible light region well, and can cause a hydrogen abstraction reaction from the curable compound A. Since the NHCO group contained in Compound B exhibits moderate hydrophilicity, the elution of Compound B into the liquid crystal material can be preferably suppressed. Therefore, the compound B can preferably function as a photopolymerization initiator for a photocurable resin composition used as a display element sealant, particularly a liquid crystal sealant.
- the number of anthraquinone skeleton or thioxanthone skeleton per molecule is 1 or 2 or more. Even if the content of Compound B is small, the number of anthraquinone skeletons or thioxanthone skeletons per molecule is preferably 2 or more from the viewpoint of obtaining sufficient curability for light in the visible light region.
- the number of NHCO groups per molecule is 1 or 2 or more. From the viewpoint of highly suppressing the elution of Compound B into the liquid crystal material, the number of NHCO groups per molecule is preferably 2 or more, and more preferably 3 or more.
- Compound B preferably has a burette skeleton (—NHCO (N—) CONH—) or an allophanate skeleton (—NHCO (N—) COO—) from the viewpoint of easily increasing the number of NHCO groups per molecule. .
- Compound B may further have an ethylenically unsaturated double bond in the molecule.
- compound B and curable compound A undergo a polymerization reaction during curing, and elution of compound B into the liquid crystal material is further suppressed.
- Compound B is obtained by reacting “anthraquinone compound b1 having a hydroxy group in the molecule or thioxanthone compound b2 having a hydroxy group in the molecule” with “compound b3 having an isocyanate group in the molecule”.
- Anthraquinone compound b1 having a hydroxy group in the molecule is represented by the following formula (1).
- the “thioxanthone compound b2 having a hydroxy group in the molecule” is represented by the following formula (2).
- L 1 in the formulas (1) and (2) each independently represents a single bond or a divalent organic group.
- the divalent organic group includes an alkylene group having 1 to 10 carbon atoms (for example, a methylene group and an ethylene group), an alkyleneoxy group having 1 to 10 carbon atoms (for example, a methyleneoxy group and an ethyleneoxy group), 10 alkylenethio groups (for example, methylenethio group (—S—CH 2 —), ethylenethio group (—S—CH 2 CH 2 —), etc.), arylene groups having 6 to 10 carbon atoms (for example, phenylene groups), 6 carbon atoms Or an arylenethio group having 6 to 10 carbon atoms (for example, a phenylenethio group).
- a thioether group (—S—) is bonded to an anthraquinone skeleton or a thioxanthone skeleton, it is easy to absorb light on the long wavelength side. Therefore, an alkylenethio group having 1 to 10 carbon atoms or 6 to 10 carbon atoms is preferred. An arylenethio group is preferred.
- M in the formulas (1) and (2) is an integer of 1 or more, preferably 1.
- — (L 1 —OH) may be bonded to any one of the 1st to 8th carbon atoms of the anthraquinone skeleton or thioxanthone skeleton, but is preferably bonded to the 2nd or 7th carbon atom. .
- the compound represented by the formula (1) is preferably represented by the following formula (1 ′); the compound represented by the formula (2) is preferably represented by the following formula (2 ′).
- —L 1 —OH in the formulas (1 ′) and (2 ′) may be bonded to any one of the 1st to 8th carbon atoms of the anthraquinone skeleton or thioxanthone skeleton, but the 2nd or 7th carbon It is preferably bonded to an atom.
- the compound b3 having an isocyanate group in the molecule is a compound having one or more isocyanate groups in the molecule.
- a compound having two or more isocyanate groups in the molecule is preferable in that the NHCO group equivalent of the obtained compound B can be easily adjusted to a certain value or less.
- the number of isocyanate groups per molecule is not particularly limited, but is preferably 2 to 4 and more preferably 2 to 3 from the viewpoint that the NHCO group equivalent of Compound B can be easily kept below a certain level.
- the compound having two or more isocyanate groups in the molecule preferably has an NHCO group in the molecule, and a burette skeleton (—NHCO (N—) CONH—), an allophanate skeleton (—NHCO (N—) COO—) Alternatively, it preferably has a urethane skeleton, and more preferably has a burette skeleton or an allophanate skeleton. That is, a compound having two or more isocyanate groups in the molecule can be represented by, for example, the following formula (3a) or (3b).
- R 1 in formula (3a) and R 2 in formula (3b) are each a linear, branched or cyclic saturated aliphatic hydrocarbon group or aromatic hydrocarbon group which may have an NHCO group. .
- the number of NHCO groups contained in R 1 and R 2 is 0 or 1 or more, and preferably 2 or more.
- R 1 and R 2 preferably include a structure represented by the following formula ( ⁇ ), ( ⁇ ) or ( ⁇ ); and may have a structure represented by the following formula ( ⁇ ) or formula ( ⁇ ). More preferred.
- (R 3 in the formula ( ⁇ ) represents a saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group derived from a polyol described later, and n is an integer of 1 or more)
- the compound having two or more isocyanate groups in the molecule is, for example, a burette body or allophanate body obtained from diisocyanate, or a urethane prepolymer obtained by reacting polyisocyanate and polyol, and having an isocyanate group at the molecular end. It is possible.
- diisocyanates used as raw materials for burettes or allophanates include aliphatic diisocyanates having 1 to 10 carbon atoms such as tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate; cyclohexylene diisocyanate, hydrogenated C6-C15 alicyclic diisocyanates such as xylylene diisocyanate and isophorone diisocyanate; and C6-C15 such as tolylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate Aromatic diisocyanates are included.
- the polyisocyanate used as a raw material for the urethane prepolymer is a polyfunctional aliphatic, alicyclic or aromatic isocyanate, and examples thereof include the aforementioned diisocyanate.
- the polyol used as a raw material for the urethane prepolymer include aliphatic polyols such as ethylene glycol, 1,3-propanediol, polyethylene glycol, dipropylene glycol, and pentaerythritol; 1,4-cyclohexanedimethanol, 1,4- Examples include alicyclic polyols such as cyclohexanediol, hydrogenated bisphenol A, and hydrogenated bisphenol F; aromatic polyols such as phenol A and bisphenol F, and the like.
- Compound B is preferably obtained by reacting “compound represented by formula (1 ′) or formula (2 ′)” with “compound having two or more isocyanate groups in the molecule”; 1 ′) or a compound represented by formula (2 ′) ”and“ a compound represented by formula (3a) or (3b) (preferably R 1 or R 2 has an NHCO group) ” It is more preferable to be obtained.
- reaction scheme shows an example in which compound B is obtained by reacting a compound represented by formula (1 ′) with a compound represented by formula (3b).
- “Hydroxy group-containing compound b4” is a compound having a hydroxy group in the molecule.
- the hydroxy group of the compound having a hydroxy group in the molecule can react with the isocyanate group of the “compound having two or more isocyanate groups in the molecule” to further form —O—CONH—.
- Examples of the compound having a hydroxy group in the molecule include monoalcohols having 1 to 20 carbon atoms such as methanol, ethanol, propanol, butanol, pentanol, hexanol, 1-octadecanol and the like.
- the compound having a hydroxy group in the molecule may further have an ethylenically unsaturated double bond. Thereby, an ethylenically unsaturated double bond can be introduced into the compound B.
- the hydroxy group-containing compound having an ethylenically unsaturated double bond in the molecule include (meth) acrylate substituted with a hydroxy group such as 4-hydroxybutyl acrylate.
- the compound B is represented by following formula (4) or (5).
- L 1 of formula (4) and (5) are the same meaning as L 1 in formula (1) and (2).
- X in the formulas (4) and (5) represents an organic group derived from a compound having at least p isocyanate groups in the molecule.
- the group derived from a compound having at least p isocyanate groups in the molecule is preferably a group derived from a compound having two or more isocyanate groups in the molecule, and is represented by the formula (3a). More preferably, it is a divalent group derived from the compound represented by formula (3b) or a trivalent group derived from the compound represented by formula (3b).
- P in the formulas (4) and (5) represents an integer of 1 to 5, preferably 2 or 3.
- the group represented by —L 1 —OX may be bonded to any one of the 1st to 8th carbon atoms of the anthraquinone skeleton or thioxanthone skeleton, but may be bonded to the 2nd or 7th carbon atom. It is preferable.
- compound B examples include a compound obtained by reacting 2- (2-hydroxyethylthio) -9,10-anthraquinone with a modified product of hexamethylene diisocyanate biuret, 2-hydroxymethylanthraquinone and modified with hexamethylene diisocyanate biuret.
- a compound obtained by reacting with a compound, a compound obtained by reacting 2- (2-hydroxyethylthio) -9,10-anthraquinone with a modified product of hexamethylene diisocyanate allophanate, 2-hydroxythioxanthone and hexamethylene diisocyanate biuret A compound obtained by reacting with a modified product, a compound obtained by reacting 2-hydroxythioxanthone with a modified product of hexamethylene diisocyanate allophanate, 2- (2-hydroxyethylthio) -thioxanthen-9-one;
- Compounds obtained by reacting with a hexamethylene diisocyanate biuret-modified product, compounds obtained by reacting 2- (2-hydroxyethylthio) -thioxanthen-9-one with a hexamethylene diisocyanate allophanate-modified product and these Examples include compounds obtained by further reacting compounds with octadecanol or 4-
- the NHCO group equivalent of Compound B is preferably 350 g / eq or less. If the NHCO group equivalent of Compound B is 350 g / eq or less, the number of NHCO groups contained in Compound B is relatively large, so that the hydrophilicity is moderately increased and the photocurable resin composition is used as a liquid crystal sealant. Elution of the compound B into the liquid crystal material can be suppressed.
- the NHCO group equivalent of Compound B is more preferably 200 to 350 g / eq, and further preferably 230 to 330 g / eq.
- NHCO group equivalent of Compound B is 200 g / eq or more, the moisture resistance of the cured product of the photocurable resin composition is hardly impaired.
- the NHCO group equivalent of compound B is defined by the following formula (I).
- NHCO group equivalent (g / eq) molecular weight / number of NHCO groups contained in one molecule: Formula (I)
- the molecular weight of Compound B is preferably 500 or more and 5000 or less, for example.
- the “molecular weight” of compound B is the “relative molecular mass” of the molecular structure of the main peak when a main peak is detected when high performance liquid chromatography (HPLC: High Performance Liquid Crystal) is performed under the following conditions. When the main peak is not detected, the weight average molecular weight is assumed.
- Main detection peak refers to a peak having the highest intensity (peak having the highest peak height) among all peaks detected at a detection wavelength of 400 nm.
- the weight average molecular weight of Compound B can be measured in terms of standard polystyrene by gel permeation chromatography (GPC).
- the molecular weight of Compound B is more preferably 500 or more and 3000 or less, and further preferably 700 or more and 1500 or less.
- the NHCO group equivalent of compound B can be confirmed by combining high performance liquid chromatography (HPLC) and liquid chromatography mass spectrometry (LC / MS) with NMR measurement or IR measurement. Specifically, the following procedure can be used. 1) A solution in which a photocurable resin composition is dissolved in tetrahydrofuran (THF) is centrifuged by a centrifugal separator to precipitate particle components such as silica particles and thermoplastic resin particles. The obtained solution is filtered through a filter to remove the particle component, thereby obtaining a sample solution. 2) The sample solution obtained in 1) is subjected to high performance liquid chromatography (HPLC) measurement.
- HPLC high performance liquid chromatography
- the HPLC measurement methods and conditions are the same as the HPLC measurement methods and conditions in the measurement of the molecular weight of Compound B.
- the relative molecular mass and the composition formula of the main peak detected by a detector having a wavelength of 400 nm characteristic of the anthraquinone skeleton or thioxanthone skeleton are analyzed by liquid chromatography mass spectrometry (LC / MS ) To measure.
- the LC / MS measurement method and conditions are the same as the LC / MS measurement method and conditions in the measurement of the molecular weight of Compound B. 3)
- NMR measurement or IR measurement is performed on the sample solution obtained in 1).
- Compound B may be one type or a combination of two or more types. For example, a compound having an anthraquinone skeleton in the molecule and a compound having a thioxanthone skeleton in the molecule may be combined.
- the content of compound B is preferably 0.01 to 10% by mass with respect to curable compound A. If the content of Compound B is 0.01% by mass or more, sufficient photocurability is easily obtained. When the content of Compound B is 10% by mass or less, elution into the liquid crystal material is unlikely to occur, and sufficient photocurability is easily obtained.
- the content of the compound B is more preferably 0.1 to 5% by mass with respect to the curable compound A, preferably 0.1 to It is more preferable that it is 3 mass%, and it is especially preferable that it is 0.1 to 2 mass%.
- the content of the compound B is more preferably 0.1 to 6% by mass with respect to the curable compound A, and 0.1% by mass. % Or more and less than 4% by mass.
- thermosetting compound C is preferably an epoxy compound having an epoxy group in the molecule. However, the thermosetting compound C is different from the curable compound A.
- the thermosetting compound C is more preferably an epoxy compound having no (meth) acryloyl group in the molecule.
- the epoxy compound may be any of a monomer, an oligomer or a polymer. Epoxy compounds, for example, have low solubility and diffusibility in liquid crystal when using a photocurable resin composition as a liquid crystal sealant, and not only improve the display characteristics of the resulting liquid crystal panel, but also the moisture resistance of the cured product. Can improve sex.
- the epoxy compound may be an aromatic epoxy compound having a weight average molecular weight of 500 to 10,000, preferably 1,000 to 5,000.
- the weight average molecular weight of the epoxy compound can be measured in terms of polystyrene by gel permeation chromatography (GPC).
- aromatic epoxy compounds include the reaction of aromatic diols typified by bisphenol A, bisphenol S, bisphenol F, bisphenol AD, etc., and diols modified with ethylene glycol, propylene glycol, alkylene glycol, and epichlorohydrin.
- Polyvalent glycidyl ether compounds; xylylene phenol resin glycidyl ether compounds and the like are included.
- cresol novolac type epoxy compound cresol novolac type epoxy compound, phenol novolac type epoxy compound, bisphenol A type epoxy compound, bisphenol F type epoxy compound, triphenolmethane type epoxy compound, triphenolethane type epoxy compound, trisphenol type epoxy compound, dicyclopentadiene type Epoxy compounds, diphenyl ether type epoxy compounds and biphenyl type epoxy compounds are preferred.
- the epoxy compound may be one type or a combination of two or more types.
- the epoxy compound may be liquid or solid.
- a solid epoxy compound is preferable from the viewpoint of easily improving the moisture resistance of the cured product.
- the softening point of the solid epoxy compound is preferably 40 ° C. or higher and 150 ° C. or lower. The softening point can be measured by the ring and ball method defined in JIS K7234.
- the content of the thermosetting compound C is preferably 3 to 20% by mass with respect to the photocurable resin composition.
- the content of the thermosetting compound C with respect to the photocurable resin composition is 3% by mass or more, the moisture resistance of the cured product of the photocurable resin composition can be easily improved.
- the content of the thermosetting compound C with respect to the photocurable resin composition is 20% by mass or less, an excessive increase in the viscosity of the photocurable resin composition can be suppressed.
- the content of the thermosetting compound C is more preferably 3 to 15% by mass, and further preferably 4 to 15% by mass with respect to the photocurable resin composition.
- the content of the thermosetting compound C is preferably 3.8 to 50% by mass, more preferably 5 to 30% by mass with respect to the curable compound A.
- the content of the thermosetting compound C with respect to the curable compound A is 5% by mass or more, the moisture resistance of the cured product and the adhesive strength to the glass substrate can be further enhanced.
- the compatibility with the conductive compound A tends to be further improved.
- thermosetting agent D is a compound that does not cure the thermosetting compound C under normal storage conditions (room temperature, under visible light, etc.), but cures the compound when given heat.
- the photocurable resin composition containing the thermosetting agent D is excellent in storage stability and excellent in thermosetting.
- the thermosetting agent D is preferably an epoxy curing agent.
- Epoxy curing agent is an epoxy curing agent having a melting point of 50 ° C. or more and 250 ° C. or less, although it depends on the heat curing temperature from the viewpoint of enhancing the viscosity stability of the photo-curable resin composition and not impairing the moisture resistance of the cured product
- An epoxy curing agent having a melting point of 100 ° C. or higher and 200 ° C. or lower is more preferable, and an epoxy curing agent having a melting point of 150 ° C. or higher and 200 ° C. or lower is further preferable.
- epoxy curing agents include organic acid dihydrazide thermal latent curing agents, imidazole thermal latent curing agents, dicyandiamide thermal latent curing agents, amine adduct thermal latent curing agents, and polyamine thermal latent curing. Agent is included.
- organic acid dihydrazide thermal latent curing agents include adipic acid dihydrazide (melting point 181 ° C.), 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin (melting point 120 ° C.), 7,11-octa Decadiene-1,18-dicarbohydrazide (melting point 160 ° C.), dodecanedioic acid dihydrazide (melting point 190 ° C.), sebacic acid dihydrazide (melting point 189 ° C.) and the like.
- imidazole-based thermal latent curing agents examples include 2,4-diamino-6- [2′-ethylimidazolyl- (1 ′)]-ethyltriazine (melting point 215 to 225 ° C.) and 2-phenylimidazole (melting point) 137-147 ° C.) and the like.
- Examples of the dicyandiamide-based heat latent curing agent include dicyandiamide (melting point: 209 ° C.).
- the amine adduct thermal latent curing agent is a thermal latent curing agent comprising an addition compound obtained by reacting an amine compound having catalytic activity with an arbitrary compound, and examples thereof include Ajinomoto Fine Techno Co., Ltd.
- Amicure PN-40 (melting point 110 ° C.), Ajinomoto Fine Techno Co., Ltd. Amicure PN-23 (melting point 100 ° C.), Ajinomoto Fine Techno Co., Ltd. Amicure PN-31 (melting point 115 ° C.), Ajinomoto Fine Techno ( Amicure PN-H (melting point 115 ° C.) manufactured by Ajinomoto Fine Techno Co., Ltd. Amycure MY-24 (melting point 120 ° C.), Amicure MY-H (melting point 131 ° C.) manufactured by Ajinomoto Fine Techno Co., etc. It is.
- the polyamine thermal latent curing agent is a thermal latent curing agent having a polymer structure obtained by reacting an amine and an epoxy.
- examples thereof include ADEKA HARDNER EH4339S (softening point 120 to 130, manufactured by ADEKA Corporation).
- Adeka Hardener EH4357S softening point 73 to 83 ° C. manufactured by ADEKA Corporation.
- dihydrazide thermal latent curing agents, imidazole thermal latent curing agents, amine adduct thermal latent curing agents, and polyamine thermal latent curing agents are preferred.
- the epoxy curing agent may be only one type or a combination of two or more types.
- the content of the thermosetting agent D is preferably 3 to 30% by mass, more preferably 3 to 20% by mass, and more preferably 5 to 20% by mass with respect to the photocurable resin composition. Further preferred.
- the photocurable resin composition containing the thermosetting agent D can be a one-component curable resin composition.
- the one-component curable resin composition is excellent in workability because it is not necessary to mix the main agent and the curing agent in use.
- the content of the thermosetting agent D is preferably 3.8 to 75% by mass, more preferably 3.8 to 50% by mass with respect to the curable compound A, and 10 to 40% by mass. More preferably.
- the content of the thermosetting agent D with respect to the curable compound A is 10% by mass or more, the curability of the curable compound A at the time of heating is further enhanced, and when it is 40% by mass or less, liquid crystal contamination is further suppressed. It's easy to do.
- the total content of the thermosetting compound C and the thermosetting agent D is preferably 6 to 50% by mass, more preferably 6 to 35% by mass, and more preferably 6 to 35% by mass with respect to the photocurable resin composition. More preferably, it is 30 mass%.
- the photocurable resin composition of the present invention may further contain thermoplastic polymer fine particles as necessary.
- the thermoplastic polymer fine particles contain a thermoplastic polymer having a softening point temperature measured by the ring and ball method of 50 to 120 ° C., preferably 70 to 100 ° C., and a number average particle size of 0.05 to 5 ⁇ m, preferably 0.8. It can be 1 to 3 ⁇ m.
- the photocurable resin composition containing such thermoplastic polymer fine particles can relieve the shrinkage stress generated in the cured product.
- the number average particle diameter is set to the upper limit value or less, it is possible to prevent the coating stability from being lowered by the thermoplastic polymer fine particles when forming a seal member having a narrow line width.
- the number average particle diameter can be measured with a dry particle size distribution meter.
- thermoplastic polymer fine particles include fine particles obtained by suspension polymerization of a resin containing an epoxy group and a double bond group with a monomer capable of radical polymerization.
- the resin containing an epoxy group and a double bond group include a resin obtained by reacting a bisphenol F type epoxy resin and methacrylic acid in the presence of a tertiary amine.
- radically polymerizable monomers include butyl acrylate, glycidyl methacrylate, and divinylbenzene.
- the content of the thermoplastic polymer fine particles is preferably 5 to 40% by mass, more preferably 7 to 30% by mass with respect to the photocurable resin composition.
- the thermoplastic polymer fine particle can preferably relieve the shrinkage stress during the heat curing of the photocurable resin composition, and can easily form a seal member with a desired line width. .
- the photocurable resin composition of the present invention may further contain a filler as necessary.
- a photocurable resin composition containing a filler may have good viscosity, strength of a cured product, linear expansion, and the like.
- fillers include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium oxide, titanium nitride, aluminum oxide (alumina), zinc oxide, silicon dioxide, potassium titanate, Inorganic fillers such as kaolin, talc, glass beads, sericite activated clay, bentonite, aluminum nitride, silicon nitride are included. Of these, silicon dioxide and talc are preferable.
- the shape of the filler may be a regular shape such as a spherical shape, a plate shape, or a needle shape, or may be an irregular shape.
- the average primary particle diameter of the filler is preferably 1.5 ⁇ m or less, and the specific surface area is preferably 0.5 to 20 m 2 / g.
- the average primary particle diameter of the filler can be measured by a laser diffraction method described in JIS Z8825-1.
- the specific surface area of the filler can be measured by the BET method described in JIS Z8830.
- the content of the filler is preferably 1 to 45% by mass with respect to the photocurable resin composition.
- the content of the filler is more preferably 10 to 30% by mass with respect to the photocurable resin composition.
- the photocurable resin composition of the present invention includes a thermal radical polymerization initiator, a coupling agent such as a silane coupling agent, an ion trapping agent, an ion exchange agent, a leveling agent, a pigment, a dye, a sensitizer, as necessary. Additives such as plasticizers and antifoaming agents may further be included.
- silane coupling agent examples include vinyltrimethoxysilane, ⁇ - (meth) acryloxypropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, and the like.
- the content of the silane coupling agent may be 0.01 to 5% by mass with respect to the curable compound A.
- the content of the silane coupling agent is 0.01% by mass or more, the cured product of the photocurable resin composition tends to have sufficient adhesiveness.
- the photocurable resin composition of the present invention may further contain a spacer for adjusting the gap of the liquid crystal display panel.
- the total content of other components E is preferably 1 to 50% by mass with respect to the photocurable resin composition.
- the total content of other components E is 50% by mass or less, the viscosity of the photocurable resin composition is hardly excessively increased, and the coating stability is not easily impaired.
- the viscosity of the photocurable resin composition of the present invention at 25 ° C. and 2.5 rpm of the E-type viscometer is preferably 200 to 450 Pa ⁇ s, and preferably 300 to 400 Pa ⁇ s. It is more preferable that When the viscosity is in the above range, the applicability of the photocurable resin composition by the dispenser is good.
- the photocurable resin composition of the present invention can be used as, for example, a sealing agent.
- the sealing agent is preferably a display element sealing agent used for sealing display elements such as liquid crystal display elements, organic EL elements, and LED elements.
- the display element sealant is particularly preferably a liquid crystal sealant and more preferably a liquid crystal sealant for a liquid crystal dropping method because the photocurable resin composition of the present invention can satisfactorily suppress liquid crystal contamination. preferable.
- Compound B contained in the photocurable resin composition of the present invention exhibits good light absorption even for light having a long wavelength, so that curing in a short time while reducing damage to the liquid crystal layer due to light. Is possible.
- compound B since compound B contains a relatively large number of NHCO groups per molecule, it has moderate hydrophilicity and can highly suppress elution into the liquid crystal material.
- the display element panel of the present invention includes a pair of substrates, a display element disposed between the pair of substrates, and a seal member for sealing the display element.
- the seal member can be a cured product of the display element sealant of the present invention.
- the display element sealing agent of the present invention is composed of the photocurable resin composition of the present invention.
- Examples of display elements include liquid crystal display elements, organic EL elements, LED elements, and the like.
- a liquid crystal display element is preferable because the photocurable resin composition of the present invention can satisfactorily suppress liquid crystal contamination.
- the liquid crystal display panel of the present invention includes a display substrate, a counter substrate that is paired with the display substrate, a frame-shaped sealing member disposed between the display substrate and the counter substrate, and a space between the display substrate and the counter substrate. And a liquid crystal layer filled in a space surrounded by the seal member.
- the seal member can be a cured product of the liquid crystal sealant of the present invention.
- the liquid crystal sealing agent of the present invention comprises the photocurable resin composition of the present invention.
- the display substrate and the counter substrate are both transparent substrates.
- the material of the transparent substrate can be glass or plastic such as polycarbonate, polyethylene terephthalate, polyethersulfone and PMMA.
- a matrix-like TFT, a color filter, a black matrix, or the like can be disposed on the surface of the display substrate or the counter substrate.
- An alignment film may be further disposed on the surface of the display substrate or the counter substrate.
- the alignment film contains a known organic alignment agent or inorganic alignment agent.
- the liquid crystal display panel is manufactured using the liquid crystal sealant of the present invention.
- a liquid crystal dropping method and a liquid crystal injecting method as a method for manufacturing a liquid crystal display panel, but the liquid crystal display panel of the present invention is preferably manufactured by a liquid crystal dropping method.
- the manufacturing method of the liquid crystal display panel by the liquid crystal dropping method is 1) forming a seal pattern of the liquid crystal sealant of the present invention on one substrate; 2) a step of dropping liquid crystal in a region surrounded by the seal pattern of the substrate or a region of the other substrate facing the region surrounded by the seal pattern when the seal pattern is in an uncured state; 3) a step of superimposing one substrate and the other substrate through a seal pattern; 4) curing the seal pattern.
- the uncured state of the seal pattern means a state in which the curing reaction of the liquid crystal sealant has not progressed to the gel point. For this reason, in the step 2), in order to suppress dissolution of the liquid crystal sealant in the liquid crystal, the seal pattern may be semi-cured by light irradiation or heating.
- One substrate and the other substrate are a display substrate and a counter substrate, respectively.
- step 4 only curing by light irradiation may be performed, but curing by light irradiation may be performed and then curing by heating may be performed. Since the liquid crystal sealant can be cured in a short time by curing by light irradiation, dissolution in the liquid crystal can be suppressed. By combining curing by light irradiation and curing by heating, damage to the liquid crystal layer due to light can be reduced compared to the case of only curing by light irradiation.
- the light to be irradiated is preferably light having a wavelength of 370 to 450 nm. This is because the light having the above wavelength causes relatively little damage to the liquid crystal material and the drive electrode.
- a known light source that emits ultraviolet light or visible light can be used.
- a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a xenon lamp, a fluorescent lamp, or the like can be used.
- the light irradiation energy may be energy that can cure the curable compound A.
- the photocuring time is, for example, about 10 minutes although it depends on the composition of the liquid crystal sealant.
- thermosetting temperature is 120 ° C., for example, although it depends on the composition of the liquid crystal sealant, and the thermosetting time is about 2 hours.
- the liquid crystal sealant of the present invention has reduced dissolution in liquid crystals. Therefore, a liquid crystal display panel having a cured product of the liquid crystal sealant of the present invention is less contaminated with liquid crystals and can have high quality display performance.
- Synthesis and Evaluation of Compound B and Comparative Compound (1) Synthesis (Synthesis Example 1) 2. Hexamethylene diisocyanate biuret modified (manufactured by Mitsui Chemicals, Takenate D-165N, isocyanate equivalent 179.5 g / eq) into a four-necked flask equipped with a stirrer, nitrogen gas inlet tube, reflux condenser, and thermometer. 16 g and 40 g of toluene were added and stirred at 80 ° C.
- the peak with the highest intensity (peak with the highest peak height) among all peaks detected at a detection wavelength of 400 nm was defined as “main peak”, and the presence or absence of the main peak was confirmed.
- compounds B-1 to B-9, compounds R-1 to R-3, R-5 to R-7, 2- (2-hydroxyethylthio) -9,10-anthraquinone, 2-hydroxymethyl- Main peaks were detected for 9,10-anthraquinone (HMAQ) and 2- (2-hydroxyethylthio) -thioxanthen-9-one.
- HMAQ 9,10-anthraquinone
- 2- (2-hydroxyethylthio) -thioxanthen-9-one On the other hand, no main peak was detected for compound R-4.
- Voltage holding ratio of liquid crystal 0.1 g of the above compound and 1 g of liquid crystal (MLC-7021-000, manufactured by Merck & Co., Inc.) were put into a vial and heated at 120 ° C. for 1 hour to obtain a liquid crystal mixture. Next, this liquid crystal mixture is taken out, poured into a glass cell (KSSZ-10 / B111M1NSS05, manufactured by EHC) in which a transparent electrode is formed in advance, a voltage of 1 V is applied, and a voltage holding ratio at 60 Hz is measured by a 6254 type measuring device. It was measured by (Toyo Technica). The case where the voltage holding ratio was 95% or more was marked with ⁇ , the case where it was 90% or more and less than 95%, and the case where it was less than 90%. A higher voltage holding ratio means that the contamination of the liquid crystal is suppressed.
- NI point drop of liquid crystal 0.1 g of the above compound and 1 g of liquid crystal (MLC-7021-000, manufactured by Merck & Co., Inc.) were put into a vial and heated at 120 ° C. for 1 hour to obtain a liquid crystal mixture.
- 10 mg of this liquid crystal mixture was placed in an aluminum open pan (Epolide Service), and the NI point was measured with a DTA-TG apparatus (Seiko Instruments). The measurement was performed by heating the liquid crystal mixture from 55 ° C. to 150 ° C. at a temperature rising rate of 2 ° C./min.
- the case where the amount of change with respect to the NI point of the liquid crystal was less than 2 ° C. was evaluated as ⁇ : the case where it was 2 ° C. or higher and lower than 5 ° C.
- Table 5 shows the measurement results of Experimental Examples 1 to 9, and Table 6 shows the measurement results of Comparative Experimental Examples 1 to 10.
- “molecular weight” in Tables 5 and 6 since the main peak was not detected by HPLC measurement in compound R-4, “weight average molecular weight” was described. Since the main peak of other compounds was detected by HPLC measurement, the “relative molecular mass” (molecular weight measured by LC / MS) corresponding to the apex of the main peak was described.
- compounds B-6 to B-9 of Experimental Examples 6 to 9 having an NHCO group equivalent of 350 g / eq or less are compounds R-5 of Comparative Experimental Examples 7 to 9 having an NHCO group equivalent of more than 350 g / eq. It can be seen that there is less NI point depression than ⁇ R-7.
- Curing compound A-1 A methacrylic acid-modified bisphenol F type epoxy resin (95% partially methacrylic product) was synthesized by the following method. 160 g of liquid bisphenol F type epoxy resin (Epototo YDF-8170C, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 160 g / eq), 0.1 g of p-methoxyphenol as a polymerization inhibitor, 0.2 g of triethanolamine as a catalyst, And 81.7 g of methacrylic acid were charged into the flask, dried air was fed, and the mixture was reacted at 90 ° C. with reflux stirring for 5 hours.
- liquid bisphenol F type epoxy resin Epoto YDF-8170C, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 160 g / eq
- 0.1 g of p-methoxyphenol as a polymerization inhibitor 0.1 g of p-methoxyphenol as a polymer
- thermosetting compound C JER resin 1004 manufactured by Mitsubishi Chemical Corporation (bisphenol A type epoxy resin, epoxy equivalent 875-975 g / eq, molecular weight 1650, softening point 97 ° C.)
- thermosetting agent D ADH (Nippon Kasei Co., Ltd., adipic acid dihydrazide, melting point 177-184 ° C)
- Silica particles S-100 manufactured by Nippon Shokubai Co., Ltd.
- Fine particle polymer F351 thermoplastic resin particles, manufactured by Aika Kogyo Co., Ltd., softening point 120 ° C., average particle diameter 0.3 ⁇ m
- KBM-403 ⁇ -glycidoxypropyltrimethoxysilane, silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd.
- Example 1 As the curable compound A, 430 parts by mass of the synthesized curable compound A-1 and 200 parts by mass of Kyoeisha Chemical Light Acrylate 14EG-A, and as the compound B, 10% of the compound B-1 obtained in Synthesis Example 1 were used. 50 parts by mass of jER resin 1004 manufactured by Mitsubishi Chemical Corporation as thermosetting compound C, 90 parts by mass of ADH manufactured by Nippon Kasei Co., Ltd. as thermosetting agent D, and silica produced by Nippon Shokubai Co., Ltd. as other components E 130 parts by mass of particles S-100, 70 parts by mass of fine polymer F351 manufactured by Aika and 20 parts by mass of silane coupling agent KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd. are converted into a uniform liquid using a three-roll mill. The mixture was sufficiently mixed to obtain a photocurable resin composition.
- Examples 2 to 9, Comparative Examples 1 to 10 A photocurable resin composition was obtained in the same manner as in Example 1 except that the composition shown in Table 7 or 8 was changed.
- the display characteristics of the obtained photocurable resin composition were evaluated by the following methods.
- LCD display panel display characteristics test A 40 mm ⁇ 45 mm glass substrate (RT-DM88-PIN, manufactured by EHC) in which a transparent electrode and an alignment film were formed in advance using a dispenser (manufactured by Musashi Engineering) with the obtained photocurable resin composition
- a 35 mm ⁇ 40 mm square seal pattern cross-sectional area 3500 ⁇ m 2
- a 38 mm ⁇ 43 mm square seal pattern were formed as the main seal.
- a liquid crystal material MLC-7021-000, manufactured by Merck & Co., Inc.
- a pair of glass substrates was bonded together under reduced pressure, and then bonded to the atmosphere. Then, after holding the two bonded glass substrates in a light shielding box for 3 minutes, the main seal was masked with a substrate coated with a square black matrix of 36 mm ⁇ 41 mm, and 3000 mJ / cm 2 of visible light was emitted. The main seal was cured by irradiating the contained light (light having a wavelength of 370 to 450 nm) and further heating at 120 ° C. for 1 hour. Then, a polarizing film was affixed on both surfaces of the obtained liquid crystal cell, and the liquid crystal display panel was obtained.
- a liquid crystal display panel was produced in the same manner as the liquid crystal display panel display characteristic test, and was driven with an applied voltage of 5 V using a DC power source. At that time, when there is no white unevenness in the vicinity of the main seal and the liquid crystal display function is sufficiently exerted, ⁇ : when white unevenness occurs in the vicinity of the main seal over a range of less than 1 mm, ⁇ : 1 mm from the vicinity of the main seal A case where white unevenness occurred over the above range and the device was not driven normally was marked as x. O or more was defined as the present invention.
- the present invention can provide a photocurable resin composition that is highly curable with respect to visible light and can highly suppress liquid crystal contamination when used as, for example, a display element sealant, particularly a liquid crystal sealant.
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Abstract
Description
NHCO基当量(g/eq)=分子量/1分子に含まれるNHCO基の数・・・式(I)
[2] 前記化合物Bが、分子内に3以上のNHCO基を有する、[1]に記載の光硬化性樹脂組成物。
[3] 前記化合物Bが、分子内にビューレット骨格又はアロファネート骨格を有する、[1]又は[2]に記載の光硬化性樹脂組成物。
[4] 前記化合物Bは、下記式(4)又は式(5)で表される、[1]~[3]のいずれかに記載の光硬化性樹脂組成物。
[5] 前記化合物Bが、分子内にエチレン性不飽和二重結合をさらに有し、且つ前記硬化性化合物Aが、アントラキノン骨格又はチオキサントン骨格を有しない、[1]~[4]のいずれかに記載の光硬化性樹脂組成物。
[6] 前記化合物Bの含有量が、前記硬化性化合物Aに対して0.01~10質量%である、[1]~[5]のいずれかに記載の光硬化性樹脂組成物。
[7] 前記硬化性化合物Aが、分子内にエポキシ基をさらに有する、[1]~[6]のいずれかに記載の光硬化性樹脂組成物。
[8] 分子内にエポキシ基を有する熱硬化性化合物Cと、熱硬化剤Dとをさらに含み、且つ前記熱硬化性化合物Cは、前記硬化性化合物Aとは異なる、[1]~[7]のいずれかに記載の光硬化性樹脂組成物。
[9] 前記熱硬化剤Dが、ジヒドラジド系熱潜在性硬化剤、イミダゾール系熱潜在性硬化剤、アミンアダクト系熱潜在性硬化剤、及びポリアミン系熱潜在性硬化剤からなる群より選ばれる1以上である、[8]に記載の光硬化性樹脂組成物。
[10] [1]~[9]のいずれかに記載の光硬化性樹脂組成物からなる、表示素子シール剤。
[11] [1]~[9]のいずれかに記載の光硬化性樹脂組成物からなる、液晶シール剤。
[12] 液晶滴下工法用の液晶シール剤である、[11]に記載の液晶シール剤。
[13] [11]又は[12]に記載の液晶シール剤を用いて、一方の基板にシールパターンを形成する工程と、前記シールパターンが未硬化の状態において、前記シールパターンの領域内、又は前記一方の基板と対になる他方の基板に液晶を滴下する工程と、前記一方の基板と前記他方の基板とを、前記シールパターンを介して重ね合わせる工程と、前記シールパターンを硬化させる工程と、を含む、液晶表示パネルの製造方法。
[14] 前記シールパターンを硬化させる工程は、前記シールパターンに光を照射して前記シールパターンを硬化させる工程を含む、[13]に記載の液晶表示パネルの製造方法。
[15] 前記シールパターンに照射する光は、可視光領域の光を含む、[14]に記載の液晶表示パネルの製造方法。
[16] 前記シールパターンを硬化させる工程は、光が照射された前記シールパターンを加熱して硬化させる工程をさらに含む、[14]又は[15]に記載の液晶表示パネルの製造方法。
[17] 一対の基板と、前記一対の基板の間に配置された枠状のシール部材と、前記一対の基板の間の前記シール部材で囲まれた空間に充填された液晶層とを含み、前記シール部材が、[11]又は[12]に記載の液晶シール剤の硬化物である、液晶表示パネル。 [1] A curable compound A having an ethylenically unsaturated double bond in the molecule, an anthraquinone skeleton or thioxanthone skeleton in the molecule, and an NHCO group, and an NHCO group equivalent represented by the formula (I) is The photocurable resin composition containing the compound B which is 350 g / eq or less.
NHCO group equivalent (g / eq) = molecular weight / number of NHCO groups contained in one molecule: Formula (I)
[2] The photocurable resin composition according to [1], wherein the compound B has 3 or more NHCO groups in the molecule.
[3] The photocurable resin composition according to [1] or [2], wherein the compound B has a burette skeleton or an allophanate skeleton in the molecule.
[4] The photocurable resin composition according to any one of [1] to [3], wherein the compound B is represented by the following formula (4) or formula (5).
[5] Any of [1] to [4], wherein the compound B further has an ethylenically unsaturated double bond in the molecule, and the curable compound A does not have an anthraquinone skeleton or a thioxanthone skeleton. The photocurable resin composition described in 1.
[6] The photocurable resin composition according to any one of [1] to [5], wherein the content of the compound B is 0.01 to 10% by mass with respect to the curable compound A.
[7] The photocurable resin composition according to any one of [1] to [6], wherein the curable compound A further has an epoxy group in the molecule.
[8] A thermosetting compound C having an epoxy group in the molecule and a thermosetting agent D, and the thermosetting compound C is different from the curable compound A, [1] to [7 ] The photocurable resin composition in any one of.
[9] The thermosetting agent D is selected from the group consisting of a dihydrazide thermal latent curing agent, an imidazole thermal latent curing agent, an amine adduct thermal latent curing agent, and a polyamine thermal latent curing agent. The photocurable resin composition according to [8], which is as described above.
[10] A display element sealing agent comprising the photocurable resin composition according to any one of [1] to [9].
[11] A liquid crystal sealing agent comprising the photocurable resin composition according to any one of [1] to [9].
[12] The liquid crystal sealant according to [11], which is a liquid crystal sealant for a liquid crystal dropping method.
[13] In the step of forming a seal pattern on one substrate using the liquid crystal sealant according to [11] or [12], and in the state of the seal pattern in an uncured state, or Dropping the liquid crystal on the other substrate paired with the one substrate, superimposing the one substrate and the other substrate through the seal pattern, and curing the seal pattern; A method for manufacturing a liquid crystal display panel.
[14] The method for manufacturing a liquid crystal display panel according to [13], wherein the step of curing the seal pattern includes a step of irradiating the seal pattern with light to cure the seal pattern.
[15] The method for manufacturing a liquid crystal display panel according to [14], wherein the light applied to the seal pattern includes light in a visible light region.
[16] The method for manufacturing a liquid crystal display panel according to [14] or [15], wherein the step of curing the seal pattern further includes a step of heating and curing the seal pattern irradiated with light.
[17] including a pair of substrates, a frame-shaped sealing member disposed between the pair of substrates, and a liquid crystal layer filled in a space surrounded by the sealing member between the pair of substrates, A liquid crystal display panel, wherein the seal member is a cured product of the liquid crystal sealant according to [11] or [12].
本発明の光硬化性樹脂組成物は、硬化性化合物Aと、化合物Bとを含み、必要に応じて熱硬化性化合物Cと、熱硬化剤Dとをさらに含みうる。 1. Photocurable resin composition The photocurable resin composition of this invention contains the curable compound A and the compound B, and may further contain the thermosetting compound C and the thermosetting agent D as needed.
本発明の光硬化性樹脂組成物に含まれる硬化性化合物Aは、分子内にエチレン性不飽和二重結合を有する化合物である。分子内にエチレン性不飽和二重結合を有する化合物は、分子内に(メタ)アクリロイル基を有する化合物であることが好ましい。1分子あたりの(メタ)アクリロイル基の数は、1又は2以上である。分子内に(メタ)アクリロイル基を有する化合物は、モノマー、オリゴマー又はポリマーのいずれであってもよい。(メタ)アクリロイル基は、アクリロイル基又はメタクリロイル基を意味し、(メタ)アクリレートは、アクリレート又はメタクリレートを意味する。但し、硬化性化合物Aは、アントラキノン骨格又はチオキサントン骨格を有しない。 1-1. Curable compound A
The curable compound A contained in the photocurable resin composition of the present invention is a compound having an ethylenically unsaturated double bond in the molecule. The compound having an ethylenically unsaturated double bond in the molecule is preferably a compound having a (meth) acryloyl group in the molecule. The number of (meth) acryloyl groups per molecule is 1 or 2 or more. The compound having a (meth) acryloyl group in the molecule may be a monomer, an oligomer or a polymer. (Meth) acryloyl group means acryloyl group or methacryloyl group, and (meth) acrylate means acrylate or methacrylate. However, the curable compound A does not have an anthraquinone skeleton or a thioxanthone skeleton.
本発明の光硬化性樹脂組成物に含まれる化合物Bは、分子内にアントラキノン骨格又はチオキサントン骨格と、NHCO基とを有する。 1-2. Compound B
Compound B contained in the photocurable resin composition of the present invention has an anthraquinone skeleton or thioxanthone skeleton and an NHCO group in the molecule.
NHCO基当量(g/eq)=分子量/1分子に含まれるNHCO基の数・・・式(I) That is, the NHCO group equivalent of Compound B is preferably 350 g / eq or less. If the NHCO group equivalent of Compound B is 350 g / eq or less, the number of NHCO groups contained in Compound B is relatively large, so that the hydrophilicity is moderately increased and the photocurable resin composition is used as a liquid crystal sealant. Elution of the compound B into the liquid crystal material can be suppressed. The NHCO group equivalent of Compound B is more preferably 200 to 350 g / eq, and further preferably 230 to 330 g / eq. When the NHCO group equivalent of Compound B is 200 g / eq or more, the moisture resistance of the cured product of the photocurable resin composition is hardly impaired. The NHCO group equivalent of compound B is defined by the following formula (I).
NHCO group equivalent (g / eq) = molecular weight / number of NHCO groups contained in one molecule: Formula (I)
(HPLC測定条件)
装置:waters製 Acquity TM UPLC H-Class system
カラム:Acquity UPLC BEH C18、2.1mmID×100mm 粒子径:1.7μm
移動相:A:アセトニトリル
B:5mM酢酸アンモニウム水溶液
A/B = 60/40(0~4分)
95/5(4~9分)
95/5(9~10分)
流速:0.4mL/分
PDA検出器:測定波長:190~500nm、抽出波長:400nm Specifically, Compound B is dissolved in THF (tetrahydrofuran) to prepare a sample solution, and high performance liquid chromatography (HPLC) measurement is performed under the following measurement conditions. And the presence or absence of the main peak (main detection peak) is confirmed in the peak detected with the detection wavelength of 400 nm. “Main peak (main detection peak)” refers to a peak having the highest intensity (peak having the highest peak height) among all peaks detected at a detection wavelength of 400 nm.
(HPLC measurement conditions)
Equipment: Acquity TM UPLC H-Class system made by waters
Column: Acquity UPLC BEH C18, 2.1 mm ID × 100 mm Particle size: 1.7 μm
Mobile phase: A: Acetonitrile B: 5 mM ammonium acetate aqueous solution A / B = 60/40 (0-4 minutes)
95/5 (4-9 minutes)
95/5 (9-10 minutes)
Flow rate: 0.4mL / min PDA detector: Measurement wavelength: 190-500nm, Extraction wavelength: 400nm
(LC/MS測定条件)
装置:waters製 Acquity TM H-Class system / SQ Detector
カラム:Acquity UPLC BEH C18、2.1mmID×100mm 粒子径:1.7μm
移動相:A:アセトニトリル
B:5mM酢酸アンモニウム水溶液
A/B = 60/40(0~4分)
95/5(4~9分)
95/5(9~10分)
流速:0.4mL/分
イオン化:ESI(エレクトロスプレーイオン化)、正・負イオン測定
PDA検出器:測定波長:190~500nm、抽出波長:400nm Next, the relative molecular mass corresponding to the peak apex of the detected main peak is measured by liquid chromatography mass spectrometry (LC / MS).
(LC / MS measurement conditions)
Equipment: Acquity TM H-Class system / SQ Detector made by waters
Column: Acquity UPLC BEH C18, 2.1mmID × 100mm Particle size: 1.7μm
Mobile phase: A: Acetonitrile B: 5 mM ammonium acetate aqueous solution A / B = 60/40 (0-4 minutes)
95/5 (4-9 minutes)
95/5 (9-10 minutes)
Flow rate: 0.4 mL / min Ionization: ESI (electrospray ionization), positive / negative ion measurement PDA detector: Measurement wavelength: 190-500 nm, Extraction wavelength: 400 nm
1)光硬化性樹脂組成物をテトラヒドロフラン(THF)に溶解させた溶液を、遠心分離機により遠心分離し、シリカ粒子や熱可塑性樹脂粒子等の粒子成分を沈降させる。得られた溶液をフィルターで濾過して粒子成分を除去し、試料液を得る。
2)前記1)で得られた試料液について、高速液体クロマトグラフフィー(HPLC)測定を行う。HPLCの測定方法・条件は、化合物Bの分子量の測定におけるHPLCの測定方法・条件と同様である。
次いで、HPLC測定において、アントラキノン骨格又はチオキサントン骨格に特徴的な波長400nmの検出器で検出されたメインピークの、ピーク頂点に対応する相対分子質量と組成式を、液体クロマトグラフィー質量分析(LC/MS)により測定する。LC/MSの測定方法・条件は、化合物Bの分子量の測定におけるLC/MSの測定方法・条件と同様である。
3)一方、前記1)で得られた試料液について、NMR測定又はIR測定を行う。それにより、アントラキノン骨格又はチオキサントン骨格やNHCO基に特徴的なスペクトルの有無を確認し、化学構造を特定する。
4)前記2)で得られた分子量と前記3)で得られたNHCO基の数とを、前述の式(I)に当てはめて、NHCO基当量(g/eq)を求める。 The NHCO group equivalent of compound B can be confirmed by combining high performance liquid chromatography (HPLC) and liquid chromatography mass spectrometry (LC / MS) with NMR measurement or IR measurement. Specifically, the following procedure can be used.
1) A solution in which a photocurable resin composition is dissolved in tetrahydrofuran (THF) is centrifuged by a centrifugal separator to precipitate particle components such as silica particles and thermoplastic resin particles. The obtained solution is filtered through a filter to remove the particle component, thereby obtaining a sample solution.
2) The sample solution obtained in 1) is subjected to high performance liquid chromatography (HPLC) measurement. The HPLC measurement methods and conditions are the same as the HPLC measurement methods and conditions in the measurement of the molecular weight of Compound B.
Next, in HPLC measurement, the relative molecular mass and the composition formula of the main peak detected by a detector having a wavelength of 400 nm characteristic of the anthraquinone skeleton or thioxanthone skeleton are analyzed by liquid chromatography mass spectrometry (LC / MS ) To measure. The LC / MS measurement method and conditions are the same as the LC / MS measurement method and conditions in the measurement of the molecular weight of Compound B.
3) On the other hand, NMR measurement or IR measurement is performed on the sample solution obtained in 1). Thereby, the presence or absence of a spectrum characteristic of the anthraquinone skeleton or thioxanthone skeleton or NHCO group is confirmed, and the chemical structure is specified.
4) The molecular weight obtained in 2) above and the number of NHCO groups obtained in 3) above are applied to the above formula (I) to obtain the NHCO group equivalent (g / eq).
また、化合物Bが、分子内にチオキサントン骨格を有する化合物である場合、化合物Bの含有量は、硬化性化合物Aに対して0.1~6質量%であることがより好ましく、0.1質量%以上4質量%未満であることがさらに好ましい。 In particular, when the compound B is a compound having an anthraquinone skeleton in the molecule, the content of the compound B is more preferably 0.1 to 5% by mass with respect to the curable compound A, preferably 0.1 to It is more preferable that it is 3 mass%, and it is especially preferable that it is 0.1 to 2 mass%.
Further, when the compound B is a compound having a thioxanthone skeleton in the molecule, the content of the compound B is more preferably 0.1 to 6% by mass with respect to the curable compound A, and 0.1% by mass. % Or more and less than 4% by mass.
熱硬化性化合物Cは、分子内にエポキシ基を有するエポキシ化合物であることが好ましい。但し、熱硬化性化合物Cは、硬化性化合物Aとは異なるものである。熱硬化性化合物Cは、分子内に(メタ)アクリロイル基を有さないエポキシ化合物であることがより好ましい。エポキシ化合物は、モノマー、オリゴマー又はポリマーのいずれであってもよい。エポキシ化合物は、例えば光硬化性樹脂組成物を液晶シール剤として用いた際に、液晶に対する溶解性や拡散性が低く、得られる液晶パネルの表示特性を良好とするだけでなく、硬化物の耐湿性を高めうる。 1-3. Thermosetting compound C
The thermosetting compound C is preferably an epoxy compound having an epoxy group in the molecule. However, the thermosetting compound C is different from the curable compound A. The thermosetting compound C is more preferably an epoxy compound having no (meth) acryloyl group in the molecule. The epoxy compound may be any of a monomer, an oligomer or a polymer. Epoxy compounds, for example, have low solubility and diffusibility in liquid crystal when using a photocurable resin composition as a liquid crystal sealant, and not only improve the display characteristics of the resulting liquid crystal panel, but also the moisture resistance of the cured product. Can improve sex.
熱硬化剤Dは、通常の保存条件下(室温、可視光線下等)では熱硬化性化合物Cを硬化させないが、熱を与えられると当該化合物を硬化させる化合物である。熱硬化剤Dを含有する光硬化性樹脂組成物は、保存安定性に優れ、且つ熱硬化性に優れる。熱硬化剤Dは、エポキシ硬化剤であることが好ましい。 1-4. Thermosetting agent D
The thermosetting agent D is a compound that does not cure the thermosetting compound C under normal storage conditions (room temperature, under visible light, etc.), but cures the compound when given heat. The photocurable resin composition containing the thermosetting agent D is excellent in storage stability and excellent in thermosetting. The thermosetting agent D is preferably an epoxy curing agent.
1-5-1.熱可塑性ポリマー微粒子
本発明の光硬化性樹脂組成物は、必要に応じて熱可塑性ポリマー微粒子をさらに含んでいてもよい。熱可塑性ポリマー微粒子は、環球法により測定される軟化点温度が50~120℃、好ましくは70~100℃の熱可塑性ポリマーを含み、且つ数平均粒子径が0.05~5μm、好ましくは0.1~3μmでありうる。そのような熱可塑性ポリマー微粒子を含む光硬化性樹脂組成物は、硬化物に発生する収縮応力を緩和できる。また、数平均粒子径を上限値以下とすることにより、線幅の細いシール部材を形成する際に、熱可塑性ポリマー微粒子によって、塗工安定性が低下することを防ぐことができる。数平均粒子径は、乾式粒度分布計で測定されうる。 1-5. Other ingredients E
1-5-1. Thermoplastic polymer fine particles
The photocurable resin composition of the present invention may further contain thermoplastic polymer fine particles as necessary. The thermoplastic polymer fine particles contain a thermoplastic polymer having a softening point temperature measured by the ring and ball method of 50 to 120 ° C., preferably 70 to 100 ° C., and a number average particle size of 0.05 to 5 μm, preferably 0.8. It can be 1 to 3 μm. The photocurable resin composition containing such thermoplastic polymer fine particles can relieve the shrinkage stress generated in the cured product. Moreover, when the number average particle diameter is set to the upper limit value or less, it is possible to prevent the coating stability from being lowered by the thermoplastic polymer fine particles when forming a seal member having a narrow line width. The number average particle diameter can be measured with a dry particle size distribution meter.
本発明の光硬化性樹脂組成物は、必要に応じて充填剤をさらに含んでいてもよい。充填剤を含む光硬化性樹脂組成物は、粘度や硬化物の強度、及び線膨張性等が良好でありうる。 1-5-2. Filler The photocurable resin composition of the present invention may further contain a filler as necessary. A photocurable resin composition containing a filler may have good viscosity, strength of a cured product, linear expansion, and the like.
本発明の光硬化性樹脂組成物の、E型粘度計の25℃、2.5rpmにおける粘度は、200~450Pa・sであることが好ましく、300~400Pa・sであることがより好ましい。粘度が上記範囲にあると、光硬化性樹脂組成物のディスペンサーによる塗布性が良好となる。 1-6. Physical Properties of Photocurable Resin Composition The viscosity of the photocurable resin composition of the present invention at 25 ° C. and 2.5 rpm of the E-type viscometer is preferably 200 to 450 Pa · s, and preferably 300 to 400 Pa · s. It is more preferable that When the viscosity is in the above range, the applicability of the photocurable resin composition by the dispenser is good.
本発明の表示素子パネルは、一対の基板と、該一対の基板の間に配置される表示素子と、該表示素子を封止するシール部材とを含む。シール部材を、本発明の表示素子シール剤の硬化物とし得る。本発明の表示素子シール剤は、本発明の光硬化性樹脂組成物からなる。 2. Liquid crystal display panel and manufacturing method thereof The display element panel of the present invention includes a pair of substrates, a display element disposed between the pair of substrates, and a seal member for sealing the display element. The seal member can be a cured product of the display element sealant of the present invention. The display element sealing agent of the present invention is composed of the photocurable resin composition of the present invention.
1)一方の基板に、本発明の液晶シール剤のシールパターンを形成する工程と、
2)シールパターンが未硬化の状態において、該基板のシールパターンで囲まれた領域内、又はシールパターンで囲まれた領域に対向する他方の基板の領域に、液晶を滴下する工程と、
3)一方の基板と他方の基板とをシールパターンを介して重ね合わせる工程と、
4)シールパターンを硬化させる工程とを含む。 The manufacturing method of the liquid crystal display panel by the liquid crystal dropping method is
1) forming a seal pattern of the liquid crystal sealant of the present invention on one substrate;
2) a step of dropping liquid crystal in a region surrounded by the seal pattern of the substrate or a region of the other substrate facing the region surrounded by the seal pattern when the seal pattern is in an uncured state;
3) a step of superimposing one substrate and the other substrate through a seal pattern;
4) curing the seal pattern.
(1)合成
(合成例1)
攪拌機、窒素ガス導入管、還流冷却管、温度計を備えた4つ口フラスコ中へ、ヘキサメチレンジイソシアネートビウレット変性体(三井化学社製、タケネートD-165N、イソシアネート当量179.5g/eq)3.16gと、トルエン40gとを加えて80℃で撹拌した。次いで、2-(2-ヒドロキシエチルチオ)-9,10-アントラキノン2.50g(8.80×10-3モル)をトルエン100gに溶解させた溶液を加え、ジブチル錫を触媒として1滴添加した後、そのまま窒素雰囲気下80℃で1時間撹拌した。
薄層クロマトグラフィー(TLC)にて、2-(2-ヒドロキシエチルチオ)-9,10-アントラキノンの消失を確認した後、4-ヒドロキシブチルアクリレート(東京化成工業社製)1.27gをトルエン5gに溶解させた溶液をさらに滴下して加え、大気下80℃で1時間撹拌した。反応終了後、4つ口フラスコを室温にて放冷し、析出した結晶成分を分離した。得られた結晶成分を再びトルエンと混合し、100℃で1時間撹拌した後、再度氷冷して不純成分を除去した。回収した結晶成分をオーブンで十分に乾燥させて、化合物B-1を得た。 1. Synthesis and Evaluation of Compound B and Comparative Compound (1) Synthesis (Synthesis Example 1)
2. Hexamethylene diisocyanate biuret modified (manufactured by Mitsui Chemicals, Takenate D-165N, isocyanate equivalent 179.5 g / eq) into a four-necked flask equipped with a stirrer, nitrogen gas inlet tube, reflux condenser, and thermometer. 16 g and 40 g of toluene were added and stirred at 80 ° C. Next, a solution prepared by dissolving 2.50 g (8.80 × 10 −3 mol) of 2- (2-hydroxyethylthio) -9,10-anthraquinone in 100 g of toluene was added, and 1 drop was added using dibutyltin as a catalyst. Thereafter, the mixture was stirred as it was at 80 ° C. for 1 hour in a nitrogen atmosphere.
After confirming disappearance of 2- (2-hydroxyethylthio) -9,10-anthraquinone by thin layer chromatography (TLC), 1.27 g of 4-hydroxybutyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 5 g of toluene. The solution dissolved in was further added dropwise and stirred at 80 ° C. for 1 hour in the atmosphere. After completion of the reaction, the four-necked flask was allowed to cool at room temperature, and the precipitated crystal component was separated. The obtained crystal component was again mixed with toluene, stirred at 100 ° C. for 1 hour, and then ice-cooled again to remove impure components. The recovered crystal component was sufficiently dried in an oven to obtain Compound B-1.
攪拌機、窒素ガス導入管、還流冷却管、温度計を備えた4つ口フラスコ中へ、2-ヒドロキシメチルアントラキノン(純正化学社製)0.5g(2.1×10-3モル)とトルエン20gとを加えて90℃で撹拌した後、ジブチル錫を触媒として1滴添加した。次いで、ヘキサメチレンジイソシアネートビウレット変性体(三井化学社製、タケネートD-165N、イソシアネート当量179.5g/eq)0.45gをトルエン10gに溶解させた溶液を20分かけて滴下した後、そのまま窒素雰囲気下80℃で2時間撹拌した。反応終了後、4つ口フラスコを氷浴で冷却し、析出した結晶成分を分離した。得られた結晶成分を再びトルエンと混合し、90℃で1時間撹拌した後、再度氷冷して不純成分を除去した。回収した結晶成分をオーブンで十分に乾燥させて、化合物B-2を得た。 (Synthesis Example 2)
Into a four-necked flask equipped with a stirrer, nitrogen gas introduction tube, reflux condenser, and thermometer, 0.5 g (2.1 × 10 −3 mol) of 2-hydroxymethylanthraquinone (manufactured by Junsei Kagaku) and 20 g of toluene After stirring at 90 ° C., 1 drop of dibutyltin was added as a catalyst. Next, a hexamethylene diisocyanate biuret modified product (manufactured by Mitsui Chemicals, Takenate D-165N, isocyanate equivalent 179.5 g / eq) 0.45 g dissolved in toluene 10 g was added dropwise over 20 minutes, and then a nitrogen atmosphere as it was The mixture was stirred at 80 ° C. for 2 hours. After completion of the reaction, the four-necked flask was cooled in an ice bath, and the precipitated crystal components were separated. The obtained crystal component was again mixed with toluene, stirred at 90 ° C. for 1 hour, and then ice-cooled again to remove impure components. The recovered crystal component was sufficiently dried in an oven to obtain Compound B-2.
攪拌機、窒素ガス導入管、還流冷却管、温度計を備えた4つ口フラスコ中へ、2-(2-ヒドロキシエチルチオ)-9,10-アントラキノン5.00g1.76×10-2モル)とトルエン150gとを加えて80℃で撹拌した後、ジブチル錫を触媒として1滴添加した。次いで、ヘキサメチレンジイソシアネートビウレット変性体(三井化学社製、タケネートD-165N、イソシアネート当量179.5g/eq)3.79gをトルエン10gに溶解させた溶液を30分かけて滴下した。滴下終了後、窒素雰囲気下80℃で3時間撹拌した後、イソプロピルアルコール10.6gを添加し、そのまま2時間撹拌した。反応終了後、4つ口フラスコを氷浴で冷却し、結晶成分を分離した。得られた結晶成分を再びトルエンと混合し、100℃で1時間撹拌した後、再度氷冷して不純成分を除去した。回収した結晶成分をオーブンで十分に乾燥し、化合物B-3を得た。 (Synthesis Example 3)
2- (2-hydroxyethylthio) -9,10-anthraquinone (5.00 g, 1.76 × 10 −2 mol) into a four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a thermometer After adding 150 g of toluene and stirring at 80 ° C., 1 drop of dibutyltin was added as a catalyst. Subsequently, a solution prepared by dissolving 3.79 g of a hexamethylene diisocyanate biuret modified product (manufactured by Mitsui Chemicals, Takenate D-165N, isocyanate equivalent 179.5 g / eq) in 10 g of toluene was dropped over 30 minutes. After completion of the dropwise addition, the mixture was stirred at 80 ° C. for 3 hours under a nitrogen atmosphere, and then 10.6 g of isopropyl alcohol was added and the mixture was stirred as it was for 2 hours. After completion of the reaction, the four-necked flask was cooled in an ice bath to separate the crystal component. The obtained crystal component was again mixed with toluene, stirred at 100 ° C. for 1 hour, and then ice-cooled again to remove impure components. The recovered crystal component was sufficiently dried in an oven to obtain Compound B-3.
攪拌機、窒素ガス導入管、還流冷却管、温度計を備えた4つ口フラスコ中へ、2-(2-ヒドロキシエチルチオ)-9,10-アントラキノン3.0g(1.06×10-2モル)とトルエン100gとを加えて110℃で撹拌した後、ジブチル錫を触媒として1滴添加した。次いで、ヘキサメチレンジイソシアネートビウレット変性体(三井化学社製、タケネートD-165N、イソシアネート当量179.5g/eq)2.95gをトルエン10gに溶解させた溶液を30分かけて滴下した。
薄層クロマトグラフィー(TLC)にて、2-(2-ヒドロキシエチルチオ)-9,10-アントラキノンの消失を確認した後、1-オクタデカノール(東京化成工業社製)1.43gをトルエン10gに溶解させた溶液をさらに滴下して加え、窒素雰囲気下110℃で2時間撹拌した。反応終了後、4つ口フラスコを氷浴で冷却し、析出した結晶成分を分離した。得られた結晶成分を再びトルエンと混合し、100℃で1時間撹拌した後、再度氷冷して不純成分を除去した。ろ過により回収した結晶成分をオーブンで十分に乾燥させて、化合物B-4を得た。 (Synthesis Example 4)
Into a four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a thermometer, 3.0 g (1.06 × 10 −2 mol) of 2- (2-hydroxyethylthio) -9,10-anthraquinone And 100 g of toluene were added and stirred at 110 ° C., and 1 drop of dibutyltin was added as a catalyst. Subsequently, a solution prepared by dissolving 2.95 g of a hexamethylene diisocyanate biuret modified product (manufactured by Mitsui Chemicals, Takenate D-165N, isocyanate equivalent 179.5 g / eq) in 10 g of toluene was added dropwise over 30 minutes.
After confirming the disappearance of 2- (2-hydroxyethylthio) -9,10-anthraquinone by thin layer chromatography (TLC), 1.43 g of 1-octadecanol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 10 g of toluene. The solution dissolved in was further added dropwise and stirred at 110 ° C. for 2 hours under a nitrogen atmosphere. After completion of the reaction, the four-necked flask was cooled in an ice bath, and the precipitated crystal components were separated. The obtained crystal component was again mixed with toluene, stirred at 100 ° C. for 1 hour, and then ice-cooled again to remove impure components. The crystal component recovered by filtration was sufficiently dried in an oven to obtain Compound B-4.
攪拌機、窒素ガス導入管、還流冷却管、温度計を備えた4つ口フラスコ中へ、2-(2-ヒドロキシエチルチオ)-9,10-アントラキノン5.0g(1.76×10-2モル)とトルエン150gとを加えて、80℃で撹拌した後、ジブチル錫を触媒として1滴添加した。次いで、ヘキサメチレンジイソシアネートアロファネート変性体(三井化学社製、タケネートD-178NL、イソシアネート当量216.1g/eq)3.98gをトルエン10gに溶解させた溶液を30分かけて滴下した後、そのまま窒素雰囲気下80℃で2時間撹拌した。反応終了後、4つ口フラスコを氷浴で冷却し、析出した結晶成分を分離した。得られた結晶成分を再びトルエンと混合し、100℃で1時間撹拌した後、再度氷冷して不純成分を除去した。回収した結晶成分をオーブンで十分に乾燥し、化合物B-5を得た。 (Synthesis Example 5)
Into a four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a thermometer, 5.0 g (1.76 × 10 −2 mol) of 2- (2-hydroxyethylthio) -9,10-anthraquinone ) And 150 g of toluene were added and stirred at 80 ° C., and 1 drop of dibutyltin was added as a catalyst. Next, a hexamethylene diisocyanate allophanate modified product (manufactured by Mitsui Chemicals, Takenate D-178NL, isocyanate equivalent 216.1 g / eq) of 3.98 g dissolved in 10 g of toluene was added dropwise over 30 minutes, and then a nitrogen atmosphere as it was The mixture was stirred at 80 ° C. for 2 hours. After completion of the reaction, the four-necked flask was cooled in an ice bath, and the precipitated crystal components were separated. The obtained crystal component was again mixed with toluene, stirred at 100 ° C. for 1 hour, and then ice-cooled again to remove impure components. The recovered crystal component was sufficiently dried in an oven to obtain Compound B-5.
攪拌機、窒素ガス導入管、還流冷却管、温度計を備えた4つ口フラスコ中へ、2-(2-ヒドロキシエチルチオ)-9,10-アントラキノン1.0g(3.52×10-3モル)と酢酸エチル70gとを加えて70℃で撹拌した後、ジブチル錫を触媒として1滴添加した。次いで、ヘキサメチレンジイソシアネート(東京化成工業社製)0.28gを酢酸エチル10gに溶解させた溶液を10分かけて滴下した後、そのまま窒素雰囲気下70℃で1時間撹拌した。反応終了後、4つ口フラスコを室温にて放冷し、析出した結晶成分を分離した。得られた結晶成分を再び酢酸エチルと混合し、80℃で1時間撹拌した後、氷冷して不純成分を除去した。回収した結晶成分をオーブンで十分に乾燥させて、化合物R-1を得た。 (Synthesis Example 6)
2- (2-hydroxyethylthio) -9,10-anthraquinone 1.0 g (3.52 × 10 −3 mol) into a four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a thermometer And 70 g of ethyl acetate were added and stirred at 70 ° C., and 1 drop of dibutyltin was added as a catalyst. Next, a solution prepared by dissolving 0.28 g of hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) in 10 g of ethyl acetate was added dropwise over 10 minutes, and then stirred at 70 ° C. for 1 hour in a nitrogen atmosphere. After completion of the reaction, the four-necked flask was allowed to cool at room temperature, and the precipitated crystal component was separated. The obtained crystal component was again mixed with ethyl acetate, stirred at 80 ° C. for 1 hour, and then cooled with ice to remove impure components. The recovered crystal component was sufficiently dried in an oven to obtain Compound R-1.
攪拌機、窒素ガス導入管、還流冷却管、温度計を備えた4つ口フラスコ中へ、2-(2-ヒドロキシエチルチオ)-9,10-アントラキノン10.0g(3.52×10-2モル)とメチルイソブチルケトン150gとを加えて80℃で撹拌した後、ジブチル錫を触媒として1滴添加した。次いで、ジシクロヘキシルメタン4,4'-ジイソシアナート(東京化成工業社製)5.53gをメチルイソブチルケトン25gに溶解させた溶液を30分かけて滴下した後、そのまま窒素雰囲気下80℃で3時間撹拌した。反応終了後、4つ口フラスコを氷浴で冷却し、析出した結晶成分を分離した。得られた結晶成分を再びトルエンと混合し、100℃で1時間撹拌した後、再度氷冷して、不純成分を除去した。回収した結晶成分をオーブンで十分に乾燥させて、化合物R-2を得た。 (Synthesis Example 7)
Into a four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a thermometer, 10.0 g (3.52 × 10 −2 mol) of 2- (2-hydroxyethylthio) -9,10-anthraquinone And 150 g of methyl isobutyl ketone were added and stirred at 80 ° C., and 1 drop of dibutyltin was added as a catalyst. Next, a solution prepared by dissolving 5.53 g of dicyclohexylmethane 4,4′-diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) in 25 g of methyl isobutyl ketone was added dropwise over 30 minutes, and then, as it was at 80 ° C. for 3 hours in a nitrogen atmosphere. Stir. After completion of the reaction, the four-necked flask was cooled in an ice bath, and the precipitated crystal components were separated. The obtained crystal component was again mixed with toluene, stirred at 100 ° C. for 1 hour, and then ice-cooled again to remove impure components. The recovered crystal component was sufficiently dried in an oven to obtain Compound R-2.
攪拌機、窒素ガス導入管、還流冷却管、温度計を備えた4つ口フラスコ中へ、2-(2-ヒドロキシエチルチオ)-9,10-アントラキノン5.0g(1.76×10-2モル)とトルエン150gとを加えて80℃で撹拌した後、ジブチル錫を触媒として1滴添加した。次いで、1,1-(ビスアクリロイルオキシメチル)エチルイソシアネート(昭和電工社製、カレンズBEI)5.25g(2.20×10-2モル)をトルエン10gに溶解させた溶液を30分かけて滴下後、そのまま窒素雰囲気下80℃で2時間撹拌した。反応終了後、エバポレーターを用いてトルエンを留去した。残渣にトルエン70gと酢酸エチル20gを加えて均一溶解し、超純水40gにて10回洗浄した。水洗後、再度エバポレーターを用いて溶媒を留去し、化合物R-3を得た。 (Synthesis Example 8)
Into a four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a thermometer, 5.0 g (1.76 × 10 −2 mol) of 2- (2-hydroxyethylthio) -9,10-anthraquinone ) And 150 g of toluene were added and stirred at 80 ° C., and 1 drop of dibutyltin was added as a catalyst. Next, a solution prepared by dissolving 5.25 g (2.20 × 10 −2 mol) of 1,1- (bisacryloyloxymethyl) ethyl isocyanate (produced by Showa Denko KK, Karenz BEI) in 10 g of toluene was added dropwise over 30 minutes. Thereafter, the mixture was stirred as it was at 80 ° C. for 2 hours under a nitrogen atmosphere. After completion of the reaction, toluene was distilled off using an evaporator. To the residue, 70 g of toluene and 20 g of ethyl acetate were added and dissolved uniformly, and washed 10 times with 40 g of ultrapure water. After washing with water, the solvent was distilled off again using an evaporator to obtain Compound R-3.
攪拌機、窒素ガス導入管、還流冷却管、温度計を備えた4つ口フラスコ中へ、2-(2-ヒドロキシエチルチオ)-9,10-アントラキノン3.43g(1.21×10-2モル)と1液型ポリウレタン樹脂(三井化学社製、タケネートM-631N、NCO%=4.58%、重量平均分子量17000、溶剤:酢酸エチル/メチルエチルケトン)12.15gを加えて80℃で撹拌した後、さらにメチルエチルケトン30gを添加して均一な溶解液とした。次いで、トルエンに溶解させたジブチル錫を触媒として滴下し、窒素雰囲気下80℃で2時間撹拌した。反応終了後、4つ口フラスコを氷浴で冷却し、析出した結晶成分を分離した。得られた結晶成分を再びトルエンと混合し、100℃で1時間撹拌した後、再度氷冷して不純成分を除去した。回収した結晶成分をオーブンで十分に乾燥させて、化合物R-4を得た。 (Synthesis Example 9)
Into a four-necked flask equipped with a stirrer, a nitrogen gas introduction tube, a reflux condenser, and a thermometer, 3.43 g (1.21 × 10 −2 mol) of 2- (2-hydroxyethylthio) -9,10-anthraquinone And 12.15 g of one-component polyurethane resin (Mitsui Chemicals, Takenate M-631N, NCO% = 4.58%, weight average molecular weight 17000, solvent: ethyl acetate / methyl ethyl ketone) and stirred at 80 ° C. Further, 30 g of methyl ethyl ketone was added to obtain a uniform solution. Next, dibutyltin dissolved in toluene was added dropwise as a catalyst, and the mixture was stirred at 80 ° C. for 2 hours in a nitrogen atmosphere. After completion of the reaction, the four-necked flask was cooled in an ice bath, and the precipitated crystal components were separated. The obtained crystal component was again mixed with toluene, stirred at 100 ° C. for 1 hour, and then ice-cooled again to remove impure components. The recovered crystal component was sufficiently dried in an oven to obtain Compound R-4.
5.6g(0.0225モル)の2-クロロチオキサントンと、2.6g(0.0225モル)の2-メルカプトエタノールのカリウム塩とを、20mlのN,N-ジメチルアセトアミド中で、100℃で18時間攪拌した。次いで、得られた反応混合物を、2N塩酸に添加し、酢酸エチルで抽出した。抽出物を慣用の後処理及びクロマトグラフィー精製後、3.5gの2-(2-ヒドロキシエチルチオ)-チオキサンテン-9-オンを得た。 (Synthesis Example 10)
5.6 g (0.0225 mol) 2-chlorothioxanthone and 2.6 g (0.0225 mol) 2-mercaptoethanol potassium salt in 100 ml at 20 ° C. in 20 ml N, N-dimethylacetamide. Stir for 18 hours. The resulting reaction mixture was then added to 2N hydrochloric acid and extracted with ethyl acetate. After conventional work-up and chromatographic purification of the extract, 3.5 g of 2- (2-hydroxyethylthio) -thioxanthen-9-one was obtained.
攪拌機、窒素ガス導入管、還流冷却管、温度計を備えた4つ口フラスコ中へ、合成例10で合成した2-(2-ヒドロキシエチルチオ)-チオキサンテン-9-オン5.00g(1.74×10-2モル)とトルエン50gとを加えて80℃で撹拌した後、ジブチル錫を触媒として1滴添加した。次いで、ヘキサメチレンジイソシアネートビウレット変性体(三井化学社製、タケネートD-165N、イソシアネート当量179.5g/eq)2.08gをトルエン10gに溶解させた溶液を30分かけて滴下し、そのまま窒素雰囲気下80℃で3時間撹拌した。
薄層クロマトグラフィー(TLC)にて、2-(2-ヒドロキシエチルチオ)-チオキサントンの消失を確認した後、4-ヒドロキシブチルアクリレート(東京化成工業社製)0.84gをトルエン5gに溶解させた溶液をさらに滴下して加え、大気下80℃で1時間撹拌した。反応終了後、4つ口フラスコを室温にて放冷し、析出した固体成分を分離した。回収した固体成分をオーブンで十分に乾燥し、化合物B-6を得た。 (Synthesis Example 11)
2- (2-hydroxyethylthio) -thioxanthen-9-one synthesized in Synthesis Example 10 into a four-necked flask equipped with a stirrer, a nitrogen gas introduction tube, a reflux condenser, and a thermometer (1 g) .74 × 10 −2 mol) and 50 g of toluene were added and stirred at 80 ° C., and 1 drop of dibutyltin was added as a catalyst. Next, a hexamethylene diisocyanate biuret modified product (Mitsui Chemicals, Takenate D-165N, isocyanate equivalent 179.5 g / eq) 2.08 g dissolved in toluene 10 g was added dropwise over 30 minutes and left under a nitrogen atmosphere. Stir at 80 ° C. for 3 hours.
After confirming the disappearance of 2- (2-hydroxyethylthio) -thioxanthone by thin layer chromatography (TLC), 0.84 g of 4-hydroxybutyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 5 g of toluene. The solution was further added dropwise and stirred at 80 ° C. for 1 hour in the atmosphere. After completion of the reaction, the four-necked flask was allowed to cool at room temperature, and the precipitated solid component was separated. The collected solid component was sufficiently dried in an oven to obtain Compound B-6.
攪拌機、窒素ガス導入管、還流冷却管、温度計を備えた4つ口フラスコ中へ、合成例10で合成した2-(2-ヒドロキシエチルチオ)-チオキサンテン-9-オン5.00g(1.74×10-2モル)とトルエン50gとを加えて80℃で撹拌した後、ジブチル錫を触媒として1滴添加した。次いで、ヘキサメチレンジイソシアネートビウレット変性体(三井化学社製、タケネートD-165N、イソシアネート当量179.5g/eq)3.74gをトルエン10gに溶解させた溶液を30分かけて滴下した。滴下終了後、窒素雰囲気下80℃で3時間撹拌した後、イソプロピルアルコール1.04gを添加し、そのまま2時間撹拌した。反応終了後、4つ口フラスコを室温で放冷し、固体成分を分離した。回収した固体成分をオーブンで十分に乾燥し、化合物B-7を得た。 (Synthesis Example 12)
2- (2-hydroxyethylthio) -thioxanthen-9-one synthesized in Synthesis Example 10 into a four-necked flask equipped with a stirrer, a nitrogen gas introduction tube, a reflux condenser, and a thermometer (1 g) .74 × 10 −2 mol) and 50 g of toluene were added and stirred at 80 ° C., and 1 drop of dibutyltin was added as a catalyst. Subsequently, a solution obtained by dissolving 3.74 g of a hexamethylene diisocyanate biuret modified product (manufactured by Mitsui Chemicals, Takenate D-165N, isocyanate equivalent 179.5 g / eq) in 10 g of toluene was dropped over 30 minutes. After completion of the dropwise addition, the mixture was stirred at 80 ° C. for 3 hours in a nitrogen atmosphere, and then 1.04 g of isopropyl alcohol was added and stirred as it was for 2 hours. After completion of the reaction, the four-necked flask was allowed to cool at room temperature to separate the solid components. The collected solid component was sufficiently dried in an oven to obtain Compound B-7.
攪拌機、窒素ガス導入管、還流冷却管、温度計を備えた4つ口フラスコ中へ、合成例10で合成した2-(2-ヒドロキシエチルチオ)-チオキサンテン-9-オン5.00g(1.74×10-2モル)とトルエン50gとを加えて80℃で撹拌した後、ジブチル錫を触媒として1滴添加した。次いで、ヘキサメチレンジイソシアネートビウレット変性体(三井化学社製、タケネートD-165N、イソシアネート当量179.5g/eq)2.08gをトルエン10gに溶解させた溶液を30分かけて滴下し、そのまま窒素雰囲気下80℃で3時間撹拌した。
薄層クロマトグラフィー(TLC)にて、2-(2-ヒドロキシエチルチオ)-チオキサントンの消失を確認した後、1-オクタデカノール(東京化成工業社製)1.57gをトルエン5gに溶解させた溶液をさらに滴下して加え、大気下80℃で1時間撹拌した。反応終了後、4つ口フラスコを室温にて放冷し、析出した固体成分を分離した。回収した固体成分をオーブンで十分に乾燥し、化合物B-8を得た。 (Synthesis Example 13)
2- (2-hydroxyethylthio) -thioxanthen-9-one synthesized in Synthesis Example 10 into a four-necked flask equipped with a stirrer, a nitrogen gas introduction tube, a reflux condenser, and a thermometer (1 g) .74 × 10 −2 mol) and 50 g of toluene were added and stirred at 80 ° C., and 1 drop of dibutyltin was added as a catalyst. Next, a hexamethylene diisocyanate biuret modified product (Mitsui Chemicals, Takenate D-165N, isocyanate equivalent 179.5 g / eq) 2.08 g dissolved in toluene 10 g was added dropwise over 30 minutes and left under a nitrogen atmosphere. Stir at 80 ° C. for 3 hours.
After confirming the disappearance of 2- (2-hydroxyethylthio) -thioxanthone by thin layer chromatography (TLC), 1.57 g of 1-octadecanol (Tokyo Chemical Industry Co., Ltd.) was dissolved in 5 g of toluene. The solution was further added dropwise and stirred at 80 ° C. for 1 hour in the atmosphere. After completion of the reaction, the four-necked flask was allowed to cool at room temperature, and the precipitated solid component was separated. The collected solid component was sufficiently dried in an oven to obtain Compound B-8.
攪拌機、窒素ガス導入管、還流冷却管、温度計を備えた4つ口フラスコ中へ、合成例10で合成した2-(2-ヒドロキシエチルチオ)-チオキサンテン-9-オン5.00g(1.74×10-2モル)とトルエン50gとを加えて80℃で撹拌した後、ジブチル錫を触媒として1滴添加した。次いで、ヘキサメチレンジイソシアネートアロファネート変性体(三井化学社製、タケネートD-178NL、イソシアネート当量216.1g/eq)4.51gをトルエン10gに溶解させた溶液を30分かけて滴下し、そのまま窒素雰囲気下80℃で3時間撹拌した。反応終了後、4つ口フラスコを室温で放冷し、固体成分を分離した。回収した固体成分をオーブンで十分に乾燥し、化合物B-9を得た。 (Synthesis Example 14)
2- (2-hydroxyethylthio) -thioxanthen-9-one synthesized in Synthesis Example 10 into a four-necked flask equipped with a stirrer, a nitrogen gas introduction tube, a reflux condenser, and a thermometer (1 g) .74 × 10 −2 mol) and 50 g of toluene were added and stirred at 80 ° C., and 1 drop of dibutyltin was added as a catalyst. Next, a solution in which 4.51 g of hexamethylene diisocyanate allophanate modified product (Mitsui Chemicals, Takenate D-178NL, isocyanate equivalent 216.1 g / eq) was dissolved in 10 g of toluene was dropped over 30 minutes, and the solution was left under a nitrogen atmosphere. Stir at 80 ° C. for 3 hours. After completion of the reaction, the four-necked flask was allowed to cool at room temperature to separate the solid components. The collected solid component was sufficiently dried in an oven to obtain Compound B-9.
攪拌機、窒素ガス導入管、還流冷却管、温度計を備えた4つ口フラスコ中へ、合成例10で合成した2-(2-ヒドロキシエチルチオ)-チオキサンテン-9-オン5.00g(1.74×10-2モル)と酢酸エチル50gとを加えて80℃で撹拌した後、ジブチル錫を触媒として1滴添加した。次いで、ヘキサメチレンジイソシアネート(東京化成工業社製)1.46gを酢酸エチル10gに溶解させた溶液を10分かけて滴下した後、そのまま窒素雰囲気下70℃で1時間撹拌した。反応終了後、4つ口フラスコを室温にて放冷し、析出した固体成分を分離した。回収した固体成分をオーブンで十分に乾燥し、化合物R-5を得た。 (Synthesis Example 15)
2- (2-hydroxyethylthio) -thioxanthen-9-one synthesized in Synthesis Example 10 into a four-necked flask equipped with a stirrer, a nitrogen gas introduction tube, a reflux condenser, and a thermometer (1 g) .74 × 10 −2 mol) and 50 g of ethyl acetate were added and stirred at 80 ° C., and 1 drop of dibutyltin was added as a catalyst. Next, a solution prepared by dissolving 1.46 g of hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) in 10 g of ethyl acetate was added dropwise over 10 minutes, and then the mixture was stirred as it was at 70 ° C. for 1 hour in a nitrogen atmosphere. After completion of the reaction, the four-necked flask was allowed to cool at room temperature, and the precipitated solid component was separated. The collected solid component was sufficiently dried in an oven to obtain Compound R-5.
攪拌機、窒素ガス導入管、還流冷却管、温度計を備えた4つ口フラスコ中へ、合成例10で合成した2-(2-ヒドロキシエチルチオ)-チオキサンテン-9-オン5.00g(1.74×10-2モル)とメチルイソブチルケトン50gとを加えて80℃で撹拌した後、ジブチル錫を触媒として1滴添加した。次いで、ジシクロヘキシルメタン4,4'-ジイソシアナート(東京化成工業社製)2.28gをメチルイソブチルケトン25gに溶解させた溶液を30分かけて滴下した後、そのまま窒素雰囲気下80℃で3時間撹拌した。反応終了後、4つ口フラスコを室温にて放冷し、析出した固体成分を分離した。回収した固体成分をオーブンで十分に乾燥し、化合物R-6を得た。 (Synthesis Example 16)
2- (2-hydroxyethylthio) -thioxanthen-9-one synthesized in Synthesis Example 10 into a four-necked flask equipped with a stirrer, a nitrogen gas introduction tube, a reflux condenser, and a thermometer (1 g) .74 × 10 −2 mol) and 50 g of methyl isobutyl ketone were added and stirred at 80 ° C., and then 1 drop of dibutyltin was added as a catalyst. Next, a solution prepared by dissolving 2.28 g of dicyclohexylmethane 4,4′-diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) in 25 g of methyl isobutyl ketone was added dropwise over 30 minutes, and then kept at 80 ° C. for 3 hours under a nitrogen atmosphere. Stir. After completion of the reaction, the four-necked flask was allowed to cool at room temperature, and the precipitated solid component was separated. The collected solid component was sufficiently dried in an oven to obtain Compound R-6.
攪拌機、窒素ガス導入管、還流冷却管、温度計を備えた4つ口フラスコ中へ、合成例10で合成した2-(2-ヒドロキシエチルチオ)-チオキサンテン-9-オン5.00g(1.74×10-2モル)とメチルイソブチルケトン50gとを加えて80℃で撹拌した後、ジブチル錫を触媒として1滴添加した。次いで、1,1-(ビスアクリロイルオキシメチル)エチルイソシアネート(昭和電工社製、カレンズBEI)4.58g(1.91×10-2モル)をトルエン10gに溶解させた溶液を30分かけて滴下後、そのまま窒素雰囲気下80℃で2時間撹拌した。反応終了後、エバポレーターを用いてトルエンを留去した。残渣にトルエン70gと酢酸エチル20gを加えて均一溶解し、超純水40gにて10回洗浄した。水洗後、再度エバポレーターを用いて溶媒を留去し、化合物R-7を得た。 (Synthesis Example 17)
2- (2-hydroxyethylthio) -thioxanthen-9-one synthesized in Synthesis Example 10 into a four-necked flask equipped with a stirrer, a nitrogen gas introduction tube, a reflux condenser, and a thermometer (1 g) .74 × 10 −2 mol) and 50 g of methyl isobutyl ketone were added and stirred at 80 ° C., and then 1 drop of dibutyltin was added as a catalyst. Next, a solution prepared by dissolving 4.58 g (1.91 × 10 −2 mol) of 1,1- (bisacryloyloxymethyl) ethyl isocyanate (produced by Showa Denko KK, Karenz BEI) in 10 g of toluene was added dropwise over 30 minutes. Thereafter, the mixture was stirred as it was at 80 ° C. for 2 hours under a nitrogen atmosphere. After completion of the reaction, toluene was distilled off using an evaporator. To the residue, 70 g of toluene and 20 g of ethyl acetate were added and dissolved uniformly, and washed 10 times with 40 g of ultrapure water. After washing with water, the solvent was distilled off again using an evaporator to obtain Compound R-7.
(実験例1~9、比較実験例1~10)
合成例1~5及び合成例11~14で得られた化合物B-1~B-9、合成例6~9及び合成例15~17で得られた化合物R-1~R-7、2-(2-ヒドロキシエチルチオ)-9,10-アントラキノン、2-ヒドロキシメチル-9,10-アントラキノン(HMAQ)、及び合成例10で得られた2-(2-ヒドロキシエチルチオ)-チオキサンテン-9-オンの分子量、液晶の電圧保持率及び液晶のN-I点降下を、以下の方法で評価した。 (2) Evaluation (Experimental Examples 1-9, Comparative Experimental Examples 1-10)
Compounds B-1 to B-9 obtained in Synthesis Examples 1 to 5 and Synthesis Examples 11 to 14, Compounds R-1 to R-7 obtained in Synthesis Examples 6 to 9 and Synthesis Examples 15 to 17, 2- (2-hydroxyethylthio) -9,10-anthraquinone, 2-hydroxymethyl-9,10-anthraquinone (HMAQ), and 2- (2-hydroxyethylthio) -thioxanthene-9 obtained in Synthesis Example 10 The molecular weight of ON, the voltage holding ratio of the liquid crystal, and the NI point drop of the liquid crystal were evaluated by the following methods.
1)高速液体クロマトグラフィー(HPLC)測定
上記化合物について、それぞれテトラヒドロフラン(THF)に溶解した試料液を調製し、下記測定条件で高速液体クロマトグラフフィー(HPLC)測定を行った。
(HPLC測定条件)
装置:waters製 Acquity TM UPLC H-Class system
カラム:Acquity UPLC BEH C18、2.1mmID×100mm 粒子径:1.7μm
移動相:A:アセトニトリル
B:5mM酢酸アンモニウム水溶液
A/B = 60/40(0~4分)
95/5(4~9分)
95/5(9~10分)
流速:0.4mL/分
PDA検出器:測定波長:190~500nm、抽出波長:400nm (Molecular weight)
1) High performance liquid chromatography (HPLC) measurement About the said compound, the sample solution melt | dissolved in tetrahydrofuran (THF) was prepared, respectively, and the high performance liquid chromatography (HPLC) measurement was performed on the following measurement conditions.
(HPLC measurement conditions)
Equipment: Acquity TM UPLC H-Class system made by waters
Column: Acquity UPLC BEH C18, 2.1mmID × 100mm Particle size: 1.7μm
Mobile phase: A: Acetonitrile B: 5 mM ammonium acetate aqueous solution A / B = 60/40 (0-4 minutes)
95/5 (4-9 minutes)
95/5 (9-10 minutes)
Flow rate: 0.4mL / min PDA detector: Measurement wavelength: 190-500nm, Extraction wavelength: 400nm
メインピークが検出された化合物について、検出されたメインピークのピーク頂点に対応する相対分子質量を、液体クロマトグラフィー質量分析(LC/MS)により測定した。
(LC/MS測定条件)
装置:waters製 Acquity TM H-Class system / SQ Detector
カラム:Acquity UPLC BEH C18、2.1mmID×100mm 粒子径:1.7μm
移動相:A:アセトニトリル
B:5mM酢酸アンモニウム水溶液
A/B = 60/40(0~4分)
95/5(4~9分)
95/5(9~10分)
流速:0.4mL/分
イオン化:ESI(エレクトロスプレーイオン化)、正・負イオン測定
PDA検出器:測定波長:190~500nm、抽出波長:400nm 2) Liquid Chromatography Mass Spectrometry (LC / MS) Measurement For compounds in which the main peak was detected, the relative molecular mass corresponding to the peak apex of the detected main peak was measured by liquid chromatography mass spectrometry (LC / MS). did.
(LC / MS measurement conditions)
Equipment: Acquity TM H-Class system / SQ Detector made by waters
Column: Acquity UPLC BEH C18, 2.1mmID × 100mm Particle size: 1.7μm
Mobile phase: A: Acetonitrile B: 5 mM ammonium acetate aqueous solution A / B = 60/40 (0-4 minutes)
95/5 (4-9 minutes)
95/5 (9-10 minutes)
Flow rate: 0.4 mL / min Ionization: ESI (electrospray ionization), positive / negative ion measurement PDA detector: Measurement wavelength: 190-500 nm, Extraction wavelength: 400 nm
0.1gの上記化合物と、1gの液晶(MLC-7021-000、メルク社製)とをバイアル瓶に投入し、120℃で1時間加熱して液晶混合物を得た。次いで、この液晶混合物を取り出して、透明電極が予め形成されたガラスセル(KSSZ-10/B111M1NSS05、EHC社製)に注入し、電圧1Vを印加し、60Hzでの電圧保持率を6254型測定装置(東陽テクニカ製)により測定した。
電圧保持率が95%以上である場合を◎、90%以上95%未満である場合を○、90%未満である場合を×とした。
電圧保持率が高いほど、液晶の汚染性が抑制されていることを意味する。 (Voltage holding ratio of liquid crystal)
0.1 g of the above compound and 1 g of liquid crystal (MLC-7021-000, manufactured by Merck & Co., Inc.) were put into a vial and heated at 120 ° C. for 1 hour to obtain a liquid crystal mixture. Next, this liquid crystal mixture is taken out, poured into a glass cell (KSSZ-10 / B111M1NSS05, manufactured by EHC) in which a transparent electrode is formed in advance, a voltage of 1 V is applied, and a voltage holding ratio at 60 Hz is measured by a 6254 type measuring device. It was measured by (Toyo Technica).
The case where the voltage holding ratio was 95% or more was marked with ◎, the case where it was 90% or more and less than 95%, and the case where it was less than 90%.
A higher voltage holding ratio means that the contamination of the liquid crystal is suppressed.
0.1gの上記化合物と、1gの液晶(MLC-7021-000、メルク社製)とをバイアル瓶に投入し、120℃で1時間加熱して液晶混合物を得た。次いで、この液晶混合物を、アルミ製オープンパン(エポリードサービス社製)に10mg入れ、DTA-TG装置(セイコーインスツル社製)によりN-I点を測定した。測定は、昇温速度2℃/minで、55℃から150℃まで液晶混合物を加熱して行った。
液晶のN-I点に対する変化量が2℃未満である場合を◎、2℃以上5℃未満の場合を○、5℃以上である場合を×とした。 (NI point drop of liquid crystal)
0.1 g of the above compound and 1 g of liquid crystal (MLC-7021-000, manufactured by Merck & Co., Inc.) were put into a vial and heated at 120 ° C. for 1 hour to obtain a liquid crystal mixture. Next, 10 mg of this liquid crystal mixture was placed in an aluminum open pan (Epolide Service), and the NI point was measured with a DTA-TG apparatus (Seiko Instruments). The measurement was performed by heating the liquid crystal mixture from 55 ° C. to 150 ° C. at a temperature rising rate of 2 ° C./min.
The case where the amount of change with respect to the NI point of the liquid crystal was less than 2 ° C. was evaluated as ◎: the case where it was 2 ° C. or higher and lower than 5 ° C.
(硬化性化合物A)
硬化性化合物A-1:
以下の方法で、メタアクリル酸変性ビスフェノールF型エポキシ樹脂(95%部分メタアクリル化物)を合成した。
160gの液状ビスフェノールF型エポキシ樹脂(エポトートYDF-8170C、新日鉄住金化学社製、エポキシ当量160g/eq)、重合禁止剤として0.1gのp-メトキシフェノール、触媒として0.2gのトリエタノールアミン、及び81.7gのメタアクリル酸をフラスコ内に仕込み、乾燥空気を送り込んで90℃で還流攪拌しながら5時間反応させた。得られた化合物を、超純水にて20回洗浄し、メタアクリル酸変性ビスフェノールF型エポキシ樹脂(硬化性樹脂A-1)を得た。
共栄社化学製ライトアクリレート14EG-A:
下記式で表されるポリエチレングリコールジアクリレート(分子量600)
Curing compound A-1:
A methacrylic acid-modified bisphenol F type epoxy resin (95% partially methacrylic product) was synthesized by the following method.
160 g of liquid bisphenol F type epoxy resin (Epototo YDF-8170C, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 160 g / eq), 0.1 g of p-methoxyphenol as a polymerization inhibitor, 0.2 g of triethanolamine as a catalyst, And 81.7 g of methacrylic acid were charged into the flask, dried air was fed, and the mixture was reacted at 90 ° C. with reflux stirring for 5 hours. The obtained compound was washed 20 times with ultrapure water to obtain a methacrylic acid-modified bisphenol F type epoxy resin (curable resin A-1).
Kyoeisha Chemical Light Acrylate 14EG-A:
Polyethylene glycol diacrylate represented by the following formula (molecular weight 600)
合成例1~5及び合成例11~14で得られた化合物B-1~B-9
(比較用化合物)
合成例6~9及び合成例15~17で得られた化合物R-1~R-7
2-(2-ヒドロキシエチルチオ)-9,10-アントラキノン
2-ヒドロキシメチル-9,10-アントラキノン(HMAQ)
合成例10で得られた2-(2-ヒドロキシエチルチオ)-チオキサンテン-9-オン (Compound B)
Compounds B-1 to B-9 obtained in Synthesis Examples 1 to 5 and Synthesis Examples 11 to 14
(Comparative compound)
Compounds R-1 to R-7 obtained in Synthesis Examples 6 to 9 and Synthesis Examples 15 to 17
2- (2-hydroxyethylthio) -9,10-anthraquinone 2-hydroxymethyl-9,10-anthraquinone (HMAQ)
2- (2-Hydroxyethylthio) -thioxanthen-9-one obtained in Synthesis Example 10
三菱化学社製jER樹脂1004(ビスフェノールA型エポキシ樹脂、エポキシ当量875~975g/eq、分子量1650、軟化点97℃) (Thermosetting compound C)
JER resin 1004 manufactured by Mitsubishi Chemical Corporation (bisphenol A type epoxy resin, epoxy equivalent 875-975 g / eq, molecular weight 1650, softening point 97 ° C.)
日本化成社製ADH(アジピン酸ジヒドラジド、融点177~184℃) (Thermosetting agent D)
ADH (Nippon Kasei Co., Ltd., adipic acid dihydrazide, melting point 177-184 ° C)
シリカ粒子S-100((株)日本触媒製)
微粒子ポリマーF351(熱可塑性樹脂粒子、アイカ工業社製、軟化点120℃、平均粒子径0.3μm)
信越化学工業社製KBM-403(γ-グリシドキシプロピルトリメトキシシラン、シランカップリング剤) (Other components E)
Silica particles S-100 (manufactured by Nippon Shokubai Co., Ltd.)
Fine particle polymer F351 (thermoplastic resin particles, manufactured by Aika Kogyo Co., Ltd., softening point 120 ° C., average particle diameter 0.3 μm)
KBM-403 (γ-glycidoxypropyltrimethoxysilane, silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd.
硬化性化合物Aとして、上記合成した硬化性化合物A-1を430質量部及び共栄社化学製ライトアクリレート14EG-Aを200質量部と、化合物Bとして合成例1で得られた化合物B-1を10質量部と、熱硬化性化合物Cとして三菱化学社製jER樹脂1004を50質量部と、熱硬化剤Dとして日本化成社製ADHを90質量部と、その他成分Eとして(株)日本触媒製シリカ粒子S-100を130質量部、アイカ社製微粒子ポリマーF351を70質量部、及び信越化学工業社製シランカップリング剤KBM-403を20質量部とを三本ロールミルを用いて均一な液となるように十分に混合して、光硬化性樹脂組成物を得た。 (Example 1)
As the curable compound A, 430 parts by mass of the synthesized curable compound A-1 and 200 parts by mass of Kyoeisha Chemical Light Acrylate 14EG-A, and as the compound B, 10% of the compound B-1 obtained in Synthesis Example 1 were used. 50 parts by mass of jER resin 1004 manufactured by Mitsubishi Chemical Corporation as thermosetting compound C, 90 parts by mass of ADH manufactured by Nippon Kasei Co., Ltd. as thermosetting agent D, and silica produced by Nippon Shokubai Co., Ltd. as other components E 130 parts by mass of particles S-100, 70 parts by mass of fine polymer F351 manufactured by Aika and 20 parts by mass of silane coupling agent KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd. are converted into a uniform liquid using a three-roll mill. The mixture was sufficiently mixed to obtain a photocurable resin composition.
表7又は8に示される組成に変更した以外は実施例1と同様にして光硬化性樹脂組成物を得た。 (Examples 2 to 9, Comparative Examples 1 to 10)
A photocurable resin composition was obtained in the same manner as in Example 1 except that the composition shown in Table 7 or 8 was changed.
得られた光硬化性樹脂組成物を、ディスペンサー(ショットマスター、武蔵エンジニアリング製)を用いて、透明電極と配向膜が予め形成された40mm×45mmガラス基板(RT-DM88-PIN、EHC社製)上に、メインシールとして35mm×40mmの四角形のシールパターン(断面積3500μm2)と、その外周に38mm×43mmの四角形のシールパターンとを形成した。
次いで、貼り合せ後のパネル内容量に相当する液晶材料(MLC-7021-000、メルク社製)を、メインシールの枠内にディスペンサーを用いて精密に滴下した。次いで、対になるガラス基板を減圧下で貼り合せた後、大気開放して貼り合わせた。そして、貼り合わせた2枚のガラス基板を3分間遮光ボックス内で保持した後、メインシールを36mm×41mmの四角形のブラックマトリックスを塗布した基板でマスクした状態で、3000mJ/cm2の可視光を含む光(波長370~450nmの光)を照射し、さらに120℃で1時間加熱して、メインシールを硬化させた。その後、得られた液晶セルの両面に偏光フィルムを貼り付けて、液晶表示パネルを得た。 (LCD display panel display characteristics test)
A 40 mm × 45 mm glass substrate (RT-DM88-PIN, manufactured by EHC) in which a transparent electrode and an alignment film were formed in advance using a dispenser (manufactured by Musashi Engineering) with the obtained photocurable resin composition On the top, a 35 mm × 40 mm square seal pattern (cross-sectional area 3500 μm 2 ) and a 38 mm × 43 mm square seal pattern were formed as the main seal.
Next, a liquid crystal material (MLC-7021-000, manufactured by Merck & Co., Inc.) corresponding to the internal volume of the panel after bonding was precisely dropped into the main seal frame using a dispenser. Next, a pair of glass substrates was bonded together under reduced pressure, and then bonded to the atmosphere. Then, after holding the two bonded glass substrates in a light shielding box for 3 minutes, the main seal was masked with a substrate coated with a square black matrix of 36 mm × 41 mm, and 3000 mJ / cm 2 of visible light was emitted. The main seal was cured by irradiating the contained light (light having a wavelength of 370 to 450 nm) and further heating at 120 ° C. for 1 hour. Then, a polarizing film was affixed on both surfaces of the obtained liquid crystal cell, and the liquid crystal display panel was obtained.
液晶表示パネル表示特性テストと同様にして液晶表示パネルを作製し、直流電源を用いて5Vの印加電圧で駆動させた。その際に、メインシール近傍の白ムラがなく、液晶表示機能が十分に発揮できている場合を○;メインシール近傍に1mm未満の範囲にわたり白ムラが発生する場合を△;メインシール近傍から1mm以上の範囲にわたり白ムラが発生して正常に駆動しない場合を×とした。〇以上を本発明とした。 (Display characteristics test when the LCD panel is energized)
A liquid crystal display panel was produced in the same manner as the liquid crystal display panel display characteristic test, and was driven with an applied voltage of 5 V using a DC power source. At that time, when there is no white unevenness in the vicinity of the main seal and the liquid crystal display function is sufficiently exerted, ○: when white unevenness occurs in the vicinity of the main seal over a range of less than 1 mm, Δ: 1 mm from the vicinity of the main seal A case where white unevenness occurred over the above range and the device was not driven normally was marked as x. O or more was defined as the present invention.
Claims (17)
- 分子内にエチレン性不飽和二重結合を有する硬化性化合物Aと、
分子内にアントラキノン骨格又はチオキサントン骨格と、NHCO基とを有し、式(I)で表されるNHCO基当量が350g/eq以下である化合物Bと、を含む、光硬化性樹脂組成物。
NHCO基当量(g/eq)=分子量/1分子に含まれるNHCO基の数・・・式(I) A curable compound A having an ethylenically unsaturated double bond in the molecule;
A photocurable resin composition comprising: an compound having an anthraquinone skeleton or a thioxanthone skeleton in the molecule and an NHCO group, and an NHCO group equivalent represented by the formula (I) being 350 g / eq or less.
NHCO group equivalent (g / eq) = molecular weight / number of NHCO groups contained in one molecule: Formula (I) - 前記化合物Bが、分子内に3以上のNHCO基を有する、請求項1に記載の光硬化性樹脂組成物。 The photocurable resin composition according to claim 1, wherein the compound B has 3 or more NHCO groups in the molecule.
- 前記化合物Bが、分子内にビューレット骨格又はアロファネート骨格を有する、請求項1に記載の光硬化性樹脂組成物。 The photocurable resin composition according to claim 1, wherein the compound B has a burette skeleton or an allophanate skeleton in the molecule.
- 前記化合物Bは、下記式(4)又は式(5)で表される、請求項1に記載の光硬化性樹脂組成物。
L1は、それぞれ独立に単結合、炭素数1~10のアルキレン基、炭素数1~10のアルキレンオキシ基、炭素数1~10のアルキレンチオ基、炭素数6~10のアリーレン基、炭素数6~10のアリーレンオキシ基又は炭素数6~10のアリーレンチオ基を表し、
Xは、分子内に少なくともp個のイソシアネート基を有する化合物から誘導される有機基を表し、
pは、1~5の整数を表す) The said compound B is a photocurable resin composition of Claim 1 represented by following formula (4) or Formula (5).
L 1 each independently represents a single bond, an alkylene group having 1 to 10 carbon atoms, an alkyleneoxy group having 1 to 10 carbon atoms, an alkylenethio group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, Represents an aryleneoxy group having 6 to 10 carbon atoms or an arylenethio group having 6 to 10 carbon atoms,
X represents an organic group derived from a compound having at least p isocyanate groups in the molecule;
p represents an integer of 1 to 5) - 前記化合物Bが、分子内にエチレン性不飽和二重結合をさらに有し、且つ
前記硬化性化合物Aが、アントラキノン骨格又はチオキサントン骨格を有しない、請求項1に記載の光硬化性樹脂組成物。 The photocurable resin composition according to claim 1, wherein the compound B further has an ethylenically unsaturated double bond in the molecule, and the curable compound A does not have an anthraquinone skeleton or a thioxanthone skeleton. - 前記化合物Bの含有量が、前記硬化性化合物Aに対して0.01~10質量%である、請求項1に記載の光硬化性樹脂組成物。 The photocurable resin composition according to claim 1, wherein the content of the compound B is 0.01 to 10% by mass with respect to the curable compound A.
- 前記硬化性化合物Aが、分子内にエポキシ基をさらに有する、請求項1に記載の光硬化性樹脂組成物。 The photocurable resin composition according to claim 1, wherein the curable compound A further has an epoxy group in the molecule.
- 分子内にエポキシ基を有する熱硬化性化合物Cと、
熱硬化剤Dとをさらに含み、且つ
前記熱硬化性化合物Cは、前記硬化性化合物Aとは異なる、請求項1に記載の光硬化性樹脂組成物。 A thermosetting compound C having an epoxy group in the molecule;
The photocurable resin composition according to claim 1, further comprising a thermosetting agent D, wherein the thermosetting compound C is different from the curable compound A. - 前記熱硬化剤Dが、ジヒドラジド系熱潜在性硬化剤、イミダゾール系熱潜在性硬化剤、アミンアダクト系熱潜在性硬化剤、及びポリアミン系熱潜在性硬化剤からなる群より選ばれる1以上である、請求項8に記載の光硬化性樹脂組成物。 The thermosetting agent D is at least one selected from the group consisting of a dihydrazide-based thermal latent curing agent, an imidazole-based thermal latent curing agent, an amine adduct-based thermal latent curing agent, and a polyamine-based thermal latent curing agent. The photocurable resin composition according to claim 8.
- 請求項1に記載の光硬化性樹脂組成物からなる、表示素子シール剤。 A display element sealant comprising the photocurable resin composition according to claim 1.
- 請求項1に記載の光硬化性樹脂組成物からなる、液晶シール剤。 A liquid crystal sealant comprising the photocurable resin composition according to claim 1.
- 液晶滴下工法用の液晶シール剤である、請求項11に記載の液晶シール剤。 The liquid crystal sealant according to claim 11, which is a liquid crystal sealant for a liquid crystal dropping method.
- 請求項11に記載の液晶シール剤を用いて、一方の基板にシールパターンを形成する工程と、
前記シールパターンが未硬化の状態において、前記シールパターンの領域内、又は前記一方の基板と対になる他方の基板に液晶を滴下する工程と、
前記一方の基板と前記他方の基板とを、前記シールパターンを介して重ね合わせる工程と、
前記シールパターンを硬化させる工程と、を含む、液晶表示パネルの製造方法。 Using the liquid crystal sealant according to claim 11 to form a seal pattern on one substrate;
In the uncured state of the seal pattern, dropping the liquid crystal on the other substrate that is paired with the one substrate in the region of the seal pattern;
Superimposing the one substrate and the other substrate through the seal pattern;
And a step of curing the seal pattern. - 前記シールパターンを硬化させる工程は、前記シールパターンに光を照射して前記シールパターンを硬化させる工程を含む、請求項13に記載の液晶表示パネルの製造方法。 The method of manufacturing a liquid crystal display panel according to claim 13, wherein the step of curing the seal pattern includes a step of irradiating the seal pattern with light to cure the seal pattern.
- 前記シールパターンに照射する光は、可視光領域の光を含む、請求項14に記載の液晶表示パネルの製造方法。 15. The method for manufacturing a liquid crystal display panel according to claim 14, wherein the light applied to the seal pattern includes light in a visible light region.
- 前記シールパターンを硬化させる工程は、光が照射された前記シールパターンを加熱して硬化させる工程をさらに含む、請求項14に記載の液晶表示パネルの製造方法。 The method for manufacturing a liquid crystal display panel according to claim 14, wherein the step of curing the seal pattern further includes a step of heating and curing the seal pattern irradiated with light.
- 一対の基板と、
前記一対の基板の間に配置された枠状のシール部材と、
前記一対の基板の間の前記シール部材で囲まれた空間に充填された液晶層とを含み、
前記シール部材が、請求項11に記載の液晶シール剤の硬化物である、液晶表示パネル。 A pair of substrates;
A frame-shaped sealing member disposed between the pair of substrates;
A liquid crystal layer filled in a space surrounded by the seal member between the pair of substrates,
A liquid crystal display panel, wherein the seal member is a cured product of the liquid crystal sealant according to claim 11.
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